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    • 专利摘要:
    toner, developer and image-forming device. provide a toner that includes a binder resin and a dye, where the toner has a glass transition temperature by differential scanning calorimetry (dsc) of 20 ° c or greater and less than 50 ° c, an endothermic peak temperature per dsc of 50 ° c or greater and less than 80 ° c and an amount of compressive strain at 50 ° c by a thermomechanical analysis of 5% or less.
    公开号:BR102013015398B1
    申请号:R102013015398
    申请日:2013-06-18
    公开日:2020-01-21
    发明作者:Yamashita Hiroshi；Sekiguchi Satoyuki；Chiba Susumu；Sugimoto Tsuyoshi
    申请人:Ricoh Co Ltd；
    IPC主号:
    专利说明:

    Description of the Related Art
    In recent years, a toner is required to have a small particle diameter and high temperature resistant displacement property for a high quality output image, low temperature fixing property for energy saving, and heat resistant storage stability. for sustainability in a high temperature and high humidity environment during toner storage and transport. In particular, energy consumption during fixation is responsible for the majority of energy consumption in an imaging method, and the improvement of the fixation property at low temperature is very important.
    Conventionally, a toner prepared by a kneading and spraying method has been used, where a toner composition obtained by melting and uniformly dispersing a dye, a release agent and so on in a binder resin is pulverized and classified. It is difficult to reduce a particle diameter of the toner prepared by the kneading and spraying method, and at the same time, there have been problems such as the insufficient quality of an image emitted from it and high energy fixation due to its irregular shape and its wide distribution particle diameter. Also, when a release agent (wax) is added in order to improve the holding capacity, the toner prepared by the kneading and spraying method is cracked at a wax interface during spraying, and as a result, the wax exists predominantly in a toner surface. Thus, while a release effect is obtained, adhesion of the toner to a carrier, a photoconductor and a cleaning blade (film) is likely to occur, and the overall performance has not been satisfactory.
    In order to solve the problems of the toner by the method of kneading and spraying, several methods of manufacturing toner by a method of polymerization are proposed. A toner that is prepared by the polymerization method has a small particle diameter and an acute particle size distribution, and it is possible to encapsulate a release agent.
    As the method of manufacturing toner by the polymerization method, for example, a method for manufacturing toner from a polyester elongation product modified by urethane was proposed for the purpose of improving the fixing property at low temperature and the high temperature resistant displacement property (see Japanese Open Deposited Patent Application (JP-A) No. 11-133665).
    Also, a toner having superior powder fluidity and superior transfer property like a toner that has a small particle diameter and at the same time has superior heat resistant storage stability, superior low temperature fixation property and displacement property superior high temperature resistant has been proposed (see JP-A No. 2002-287400 and JP-A No. 2002-351143).
    In addition, a toner manufacturing method that includes an aging step has been proposed to produce a toner binder that has a stable molecular weight distribution and that obtains both the low temperature fixing property and the high temperature resistant displacement property. (see Japanese Patent (JP-B) No. 2579150 and JP-A No. 2001-158819).
    However, these proposed technologies cannot satisfy the low temperature fastening property of a higher level required in recent years.
    Thus, for the purpose of obtaining the property of fixing at low temperature of a higher level, for example, a toner composed of a resin (a) has been proposed which does not include a poly5 hydroxycarboxylic acid skeleton composed of an optically active monomer and a resin (b) that has a polyhydroxycarboxylic acid backbone composed of an optically active monomer, where resin (a) is a polyester resin having crystallinity (see JP-A No. 2011-59603).
    In addition, a toner that includes a block copolymer composed of a crystalline polyester block and a non-crystalline polyester block as a core and a non-crystalline polyester resin as an outer shell (see JP-A No. 2002-300848 ).
    According to these proposals, the fixation at low temperature of the toners can be achieved since the crystalline polyester resin melts quickly compared to the non-crystalline polyester resin. However, even through the crystalline polyester resin that corresponds to an island in a sea - island separation structure melts the non - crystalline polyester resin that corresponds to the sea as a majority does not melt. Since fixation cannot occur until the crystalline polyester resin and the non-crystalline polyester resin melts to some degree, these proposed techniques cannot satisfy the high-temperature low-temperature fixing property.
    Appropriately, it has been desired to propose a toner which does not cause film formation and has superior low temperature fixing properties, superior high temperature resistant displacement properties and superior heat resistant storage stability.
    SUMMARY OF THE INVENTION
    The present invention aims to provide a toner that does not cause any occurrence of film formation and has superior low temperature fixing property, superior high temperature resistant displacement property and superior heat resistant storage stability.
    A toner of the present invention as a means of solving the above problems includes a binder resin and a dye, wherein the toner has a differential scanning calorimetry (DSC) glass transition temperature of 20 ° C or greater and less than 50 ° C. ° C, an endothermic peak temperature by differential scanning calorimetry (DSC) of 50 ° C or greater and less than 80 ° C and an amount of compressive strain at 50 ° C by a thermomechanical analysis of 5% or less.
    The present invention can solve conventional problems and provide a toner that does not cause any occurrence of film formation and has superior low temperature fixing property, superior high temperature resistant displacement property and superior heat resistant storage stability. BRIEF DESCRIPTION OF THE DRAWINGS
    FIG. 1 is a schematic diagram illustrating an example of an image forming apparatus of the present invention.
    FIG. 2 is a schematic diagram illustrating another example of an image forming apparatus of the present invention.
    FIG. 3 is a schematic diagram illustrating an example of an imaging apparatus set of the present invention.
    FIG. 4 is a partially enlarged schematic diagram of the imaging apparatus illustrated in FIG. 3.
    DETAILED DESCRIPTION OF THE INVENTION (Toner)
    A toner of the present invention includes a binder resin and a dye, and it additionally includes other components as needed.
    <Binder resin>
    The binder resin preferably includes a resin that has a crystalline portion.
    The resin that has a crystalline portion is not particularly restricted, and it can be appropriately selected according to the purpose. Examples of the same include a crystalline resin and a copolymer that includes at least partly a crystalline portion.
    The binding resin is not particularly restricted as long as it has a crystalline portion, and can be selected appropriately according to the purpose. However, it preferably includes: a crystalline resin A; a non-crystalline resin B; and a resin E that has a crystalline portion C and a non-crystalline portion D in a molecule thereof.
    The toner of the present invention has a low glass transition temperature Tg by differential scanning calorimetry (DSC method) compared to a conventional toner. However, due to the crystallinity of the crystalline resin A included in the toner, the deformation of the toner at a temperature above the glass transition temperature Tg is suppressed. Thus a quantity of compressive strain (TMA amount of compressive strain) at ° C by thermomechanical analysis is reduced. Properly toner can maintain heat-resistant storage stability.
    Still crystalline resin A melts at a melting temperature along with that of the endothermic peak mp, which is crystalline resin A included melting of non-crystalline resin glass transition melting with etching. Thus a peak d in the toner crystallizes, and
    A, the resin
    B which has a low temperature of possible display
    Tg also softens even a viscosity of which it is capable compared to a temperature property at a very high level.
    Additionally, the crystalline C and the resin portion E of adhering to a conventional low-setting toner medium that has the non-crystalline portion D in a molecule thereof, which is included in the toner, has a molecular skeleton similar to each of the resin crystalline A and non-crystalline resin B and has an affinity (compatibility) with both crystalline resin A and non-crystalline resin B. Thus, it acts as a bond between crystalline resin A and non-crystalline resin B. As a result , thermal deformation becomes difficult due to the crystalline structure of crystalline resin A despite a low glass transition temperature Tg of non-crystalline resin B, and it is possible to maintain the heat resistant storage stability of the toner. Yet, 5 despite a very low melt viscosity and high temperature resistant displacement property can degrade only with crystalline resin A, the melt viscosity can be maintained with non-crystalline resin B to a degree that a high displacement 10 temperature is not caused.
    The glass transition temperature Tg of the toner by the DSC method is 20 ° C or more and less than 50 ° C, and is preferably 20 ° C to 40 ° C, and more preferably 30 ° C to 40 ° C in view low temperature fixing property.
    When the glass transition temperature is less than 20 ° C there are cases where the heat-resistant storage stability degrades even though the crystalline portion is present in the toner. When it is 50 C or less, the melting of the non-crystalline portion is insufficient with respect to the melting of the crystalline portion in the toner, and there are cases in which the low temperature fixing property is lower. The glass transition temperature within the preferable range is advantageous since both the low temperature fastening property and the heat-resistant storage stability of the toner can be achieved.
    A peak endothermic temperature mp of toner by the DSC method is 50 ° C or more and less than 80 ° C, and is preferably 55 ° C to 70 ° C. When the endothermic peak temperature is less than 50 ° C, crystalline resin A melts in a high-temperature toner storage environment, and there are cases where the toner has degraded the heat-resistant storage stability. When it is 80 ° C or more, non-crystalline resin B softens, but crystalline resin A is likely to melt only at a high temperature. Thus, there are cases where the toner's low-temperature fixing property degrades.
    Toner is not particularly restricted, and it can be selected appropriately for the purpose. However, a Q2 / Q1 ratio of an endothermic quantity Q2 of a second DSC heating to an endothermic quantity Q1 of a first DSC heating due to the melting of the crystalline portion (e.g., crystalline resin A and crystalline portion C of resin E ) is preferably 0 or more and less than 0.3. The endothermic quantity Q1 is not particularly restricted, and it can be selected appropriately according to the purpose. However, it is preferably greater than 10 J / g and more preferably 20 J / g or more, and an upper limit thereof is preferably 100 J / g or less.
    When the Q2 / Q1 ratio is 0.3 or greater, the compatibility between the crystalline portion and the non-crystalline portion in the toner during heating in the fixture is insufficient, and there are cases in which the low temperature fixing property and the high-temperature resistant toner displacement may be less.
    When the endothermic quantity Q1 is 10 J / g or less, an amount of the crystalline portion present in the toner is reduced. The deformation of the toner in an expected high temperature storage environment of the toner cannot be suppressed, and the heat-resistant storage stability of the toner can degrade.
    Here, the glass transition temperature Tg of the toner, the endothermic peak temperature mp of the toner and the endothermic amounts (Ql, Q2) of the toner by the DSC method can be measured as follows.
    A measurement object is stored in an isothermal environment having a temperature of 45 ° C and a humidity of 20% relative humidity or less for 24 hours in order to have constant initial conditions of the crystalline portion and the non-crystalline portion. It is then stored at a temperature of 23 ° C or less, and Tg, mp, Ql s Q2 are measured within 24 hours. By this operation, a thermal history effect in a high temperature storage environment can be reduced, and the condition of the crystalline portion and the non-crystalline portion of the toner can be uniformized.
    First, 5 mg of a particulate toner are sealed in a simple T-ZERO sealing pan, manufactured by TA Instruments, and a measurement is made using a differential scanning calorimeter (DSC) (manufactured by TA
    Instruments, Q2000). With regard to measurement, under a nitrogen stream, the toner is heated as a first heating from -20 ° C to 200 ° C at a heating rate of 10 ° C / min, maintained for 5 minutes, then heated to -20 ° C at a cooling rate of 10 ° C / min, held for 5 minutes, and then heated as a second heat to 200 ° C at a heating rate of 10 ° C / min. Thermal changes are measured, and graphs of endothermic quantity - exothermic and temperature are created. A temperature at a characteristic tipping point at this point is defined as the glass transition temperature Tg.
    As the glass transition temperature Tg, a value obtained by a midpoint method in the analysis programs of the device that uses the graph of the first heating can be used.
    In addition, the endothermic peak temperature mp can be calculated as a maximum peak temperature using a device analysis program that uses the graph of the first heating.
    In addition, Q1 can be calculated as a quantity of heat of fusion of the crystalline component using a program of analysis of the apparatus that uses the graph of the first heating.
    In addition, Q2 can be calculated as a quantity of heat of fusion of the crystalline component that uses a
    analysis program of the device using the second heating. 15 An amount deformation compressive toner a 50 ° C per analysis thermomechanical (amount TMA of
    compressive strain) is 5% or less, and preferably 1% to 4%. When the amount of compressive strain TMA exceeds 5%, the toner deforms and melts in an expected high temperature storage environment of the toner, and there are cases where the toner has degraded the heat resistant storage stability. The amount of compressive strain TMA within the preferable range is advantageous since both the low-temperature fastening property and the heat-resistant storage stability of the toner can be achieved.
    In the present invention, by incorporating into the toner the resin E that has the crystalline portion C and the non-crystalline portion D in a molecule thereof, resin E acts as a bond between crystalline resin A and non-crystalline resin B, and the TMA amount of compressive strain can be adjusted to a low value compared to a case where E resin is not included. Thus, through the analysis that the toner has the amount of compressive strain TMA of 5% or less, it is possible to provide that the toner includes resin E.
    Here, the amount of compressive strain TMA can be measured, for example, by using 0.5 15 g of the toner formed in a tablet by a tablet molding machine (manufactured by Shimadzu Corporation) that has a diameter of 3 mm with a thermomechanical measuring device (EXSTAR7000, manufactured by SII NanoTechnology Inc.). The tablet is heated to 2 ° C / min from 0 C to 20 180 ° C under a stream of nitrogen, and the measurement is performed in a compressed module. A compressive force at this point is 100 mN. The amount of compressive strain at 50 ° C is read from a graph obtained from a sample temperature and a compression offset (strain ratio), and this value is referred to as the amount of compressive strain TMA.
    toner is not particularly restricted, and it can be appropriately selected according to the purpose.
    However, a relative crystallinity obtained from an area of the crystalline portion and an area of the non-crystalline portion by the X-ray diffraction method is preferably 10% to 50%, and more preferably 20% to 40%. When the relative crystallinity is less than 10%, the 10 toner has a decreased amount of the crystalline portion present in it. As a result, deformation of the toner in an expected high temperature storage environment of the toner cannot be suppressed, and there are cases where the toner has degraded the heat resistant storage stability. When it exceeds 50%, the melt viscosity is greatly decreased during fixing, and there are cases where the high temperature resistant displacement property and the low temperature fixing property of the toner degrade.
    Here, the relative crystallinity of the toner can be measured using, for example, a crystallinity analysis X-ray diffractometer (X'PERT MRD, manufactured by Philips) as follows.
    First, the toner as a target sample is ground by a pestle to prepare a sample powder, and the sample powder obtained is applied evenly to a sample fixer. Next, the sample fixer is defined on the 5-ray diffractometer for crystalline analysis, and a measurement is made to obtain the diffraction spectrum.
    Among the diffraction peaks obtained, a peak in a range of 20 ° <2Θ <25 ° is considered to be an endothermic peak derived from the crystalline portion. In addition, a wide peak 10 well spread across the measurement area is considered to be a component derived from the non-crystalline portion. For each peak, an integrated area of the diffraction spectrum for which a background is subtracted is calculated. An area value derived from the crystalline portion is considered to be Sc, and an area value derived from the non-crystalline portion is considered to be Sa. From Sc / Sa, the relative crystallinity can be calculated. The measurement conditions of the X-ray diffraction method are as follows.
    [Measuring conditions]
    - Voltage kV: 45 kV
    - Current: 40 mA
    MPSS
    Higher
    Gonio
    - Scan mode: continuous
    - Starting angle: 3
    - Final angle: 35 °
    - Angle step: 0.02 °
    - Lucid-beam optics
    - Divergence gap: div gap 1/2
    - Diflexion beam optics
    - Anti-spatter gap: as fixed 1/2
    - Reception slot: Prog recording slot << Crystalline resin A >>
    Crystalline resin A is not particularly restricted, and it can be selected appropriately according to the purpose. However, polyester resins are preferable as they melt sharply during fixation and have sufficient flexibility and durability even at low molecular weight. Among polyester resins, aliphatic polyester resins are particularly preferable as they have superior acute melting properties and high crystallinity.
    Aliphatic polyester resins can be obtained by condensation polymerization of a polyhydric alcohol and a polycarboxylic acid or a derivative thereof such as polycarboxylic acid, polycarboxylic acid anhydride and polycarboxylic acid ester.
    - Polyhydric alcohol Polyhydric alcohol is not particularly restricted, and can be sectioned appropriately according to the purpose. Examples of the same include diols and trihydric alcohols or larger.
    Examples of diols include saturated aliphatic diols. Examples of the saturated aliphatic diols include saturated aliphatic diols and branched saturated aliphatic diols. Among these, linear saturated aliphatic diols are preferable, and linear saturated aliphatic diols having 2 to 12 carbon atoms are more preferable. When the saturated aliphatic diols are branched, the crystallinity of the crystalline polyester resin decreases, which can result in a decreased melting point. When the number of carbon atoms in the saturated aliphatic diols exceeds 12, such material cannot be readily available. Thus, the number of carbon atoms is preferably 12 or less.
    Examples of the saturated aliphatic diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10 -decanediol, 1,11undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14tetradecanediol, 1,18-octadecanediol and 1,14 eicosanodecanediol. These can be used alone or in combination of two or more.
    Among these, ethylene glycol, 1,4-butanediol, 1,6hexanediol, 1,8-octanediol, 1,10-decanediol, and 1,125 dodecanediol are particularly preferable since the crystalline polyester resin has high crystallinity and superior acute melting property .
    Examples of trihydric alcohols or higher include glycerin, trimethylolethane, trimethylolpropane, and 10 pentaerythritol. These can be sweated alone or in combination of two or more.
    - Polycarboxylic acid Polycarboxylic acid is not particularly restricted, and it can be selected appropriately according to the purpose. Examples of the same include bivalent carboxylic acid and trivalent or higher carboxylic acid.
    Examples of bivalent carboxylic acid include: saturated aliphatic dicarboxylic acids such as oxalic acid, succinic acid, glutaric acid, adipic acid, submeric acid, azelaic acid, sebacic acid, 1,9nonanedicarboxylic acid, 1,10-decanodicarboxylic acid, 1, 12-dodecanedicarboxylic acid, 1,14tetradecanedicarboxylic acid and 1,18 octadecanedicarboxylic acid; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, malonic acid and mesaconic acid; and anhydrides thereof and lower alkyl esters (1 to 3 carbon atoms). These can be used alone or in combination of two or more.
    Examples of trivalent or higher carboxylic acid include 1,2,4-benzene tricarboxylic acid, 1,2,5-benzene tricarboxylic acid, 1,2,4-naphthalene 10 tricarboxylic acid, anhydrides thereof and lower alkyl esters (1 to 3 carbon atoms) carbon). These can be used alone or in combination of two or more.
    Here, like polycarboxylic acid, in addition to saturated aliphatic dicarboxylic acid and aromatic dicarboxylic acid, a dicarboxylic acid that has a sulfonic acid group, a dicarboxylic acid that has a double bond and so on can be included.
    The crystalline polyester resin is preferably obtained by condensation polymerization of a saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms and a linear saturated aliphatic diol having 2 to 12 carbon atoms. That is, the crystalline polyester resin preferably includes a structural unit derived from a saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms and a structural unit derived from a saturated aliphatic diol having 2 to 12 atoms of carbon. As a result, the crystalline polyester resin obtained has high crystallinity and superior acute melting property, and the toner can exhibit the superior low temperature fixing property.
    The crystallinity, molecular structure and so on of the crystalline polyester resin can be confirmed by an NMR measurement, differential scanning calorimetry (DSC) measurement, X-ray diffraction measurement, a GC / MS measurement, an LC measurement / MS, an infrared (IR) absorption spectrum measurement and so on.
    A melting point of crystalline resin A is not particularly restricted, and can be appropriately selected according to the purpose. However, it is preferably 50 ° C to 80 ° C. When the melting point is less than 50 ° C, crystalline resin A is likely to melt at a low temperature, which can result in degraded heat-resistant storage stability of the toner. When it exceeds 80 ° C, heating during fixing insufficiently melts the crystalline resin
    A, which can result in degraded low temperature holding properties of the toner.
    A mass average molecular weight of crystalline resin A is not particularly restricted, and it can be appropriately selected according to the purpose. However, it is preferably from 3,000 to 50,000 and more particularly 5,000 to 25,000.
    The average molecular weight of crystalline resin A can be measured, for example, by gel permeation chromatography (GPC).
    A glass transition temperature of crystalline resin A is not particularly restricted, and it can be selected appropriately according to the purpose. However, it is preferably from 50 ° C to 70 ° C.
    The glass transition temperature of crystalline resin A can be measured, for example, by differential scanning calorimetry (DSC method).
    A content of crystalline resin A in the toner is not particularly restricted, and it can be selected appropriately according to the purpose. However, it is preferably 3% by mass to 30% by mass, and more preferably 5% by mass and 20% by mass. When the content is less than 3% by mass, there are cases where the toner has degraded the heat resistant storage stability and the low temperature fixing property. When it exceeds 30% by mass, there are cases where film formation occurs, which results in displacement property resistant to degraded high temperature.
    << Non-crystalline resin B »
    Crystalline resin B is not particularly restricted, and it can be selected appropriately according to the purpose. Examples of the same include a resin that has a repeating unit derived from a compound obtained by condensation of lactic acid dehydration such as resin that has a polyhydroxycarboxylic acid skeleton and non-crystalline polyester resin as it has superior affinity with paper as a primary recording medium and the toner has superior heat-resistant storage stability. Among these, a resin that has a skeleton of polyhydroxycarboxylic acid with racemized lactic acid composed of L-lactic acid and D-lactic acid as a raw material is particularly preferable since the toner has superior low temperature fixing properties.
    The resin having a polyhydroxycarboxylic acid backbone has an optical purity X (%) in terms of the monomer component represented by the following formula, preferably 90% or less.
    X (%) = | X (form L) - X (form D) |
    Here, in the formula, ο X (form L) represents a ratio (%) of a form L in terms of lactic acid monomer, and ο X (form D) represents a ratio (%) of a form D in terms of monomer of lactic acid.
    Here, a method for measuring optical purity X is not particularly restricted, and it can be selected appropriately according to the purpose. For example, a polymer or toner having a polyester skeleton is added to a mixed solvent of pure water, 1-N sodium hydroxide and isopropyl alcohol, which is heated and stirred at 70 ° C for hydrolysis. It is then filtered to remove a solid content in the liquid and then neutralized by the addition of a sulfuric acid, and an aqueous solution that includes at least any of L-lactic acid and D-lactic acid decomposed from resin. polyester is obtained. The aqueous solution is measured by 20 high performance liquid chromatography (HPLC) using a chiral ligand exchange type column, SUMICHIRAL AO-5000 (manufactured by Sumika Chemical Analysis Service, Ltd.), and a peak area derived from from Llatic acid S (L) and a peak area derived from acid
    D-lactic S (D) are calculated. From the peak areas, the
    purity optics X can to be obtained as if Follow. X (form L) g. __Ό - 100 x S (L) / (S (L) + S (D)) X (form D) g. __Ό - 100 x S (D) / (S (L) + S (D)) Optical purity X g, __O - | X (form L) - X (form D)
    Here, the L form and the D form used as the raw materials are optical isomers, and the optical isomer has identical physical properties and different chemical properties from optical properties. Thus, their reactivities are the same when they are polymerized, and the component ratios of the monomers are identical to the component ratios of the monomers in the polymer.
    Optical purity of 90% or less is preferable as solvent solubility and resin transparency improve.
    Ο X (form D) and ο X (form L) of the monomers which form the resin that has a polyhydroxycarboxylic acid backbone have the same ratio as the D form and the L form of the monomers used to form the backbone resin of polyhydroxycarboxylic acid. Thus, the optical purity X (%) in terms of the monomer components of the resin having a polyhydroxycarboxylic acid backbone like the non-crystalline resin B can be controlled using appropriate amounts of monomers of form L and form D in combination.
    A method for making the resin having a polyhydroxycarboxylic acid backbone is not particularly restricted, and so far known conventional methods can be used. For example, the method for making the resin having a polyhydroxycarbonyl acid backbone can be a starch fermentation method such as corn as a raw material to obtain lactic acid, followed by direct dehydration condensation of lactic acid or followed by formation of lactic acid in cyclic dimeric lactate and synthesis by ring opening polymerization in the presence of a catalyst. Among these, the manufacturing method by ring-opening polymerization is preferable since it can control the molecular weight with a quantity of an initiator and complete the reaction in a short period of time.
    Não non-crystalline polyester resin is not particularly restricted, and it can be selected appropriately according to the purpose. However, an unmodified polyester resin is preferable. Não unmodified polyester resin is a polyester resin obtained by condensation polymerization of a polyhydric alcohol, a polycarboxylic acid or a derivative thereof such as polycarboxylic acid, polycarboxylic acid anhydride and polycarboxylic acid ester, and is a polyester not modified by a 5-isocyanate compound and so on.
    polyhydric alcohol is not particularly restricted, and it can be selected appropriately according to the purpose. Examples of these include a diol.
    Examples of the diol include alkylene oxide (2 to 3 carbon atoms) (average number of moles 1 to 10) bisphenol A adduct such as polyoxypropylene (2.2) -2,2-bis (4hydroxyphenyl) propane and polyoxyethylene ( 2.2) -2,2-bis (4hydroxyphenyl) propane; ethylene glycol, propylene glycol;
    alkylene oxide (2 to 3 carbon atoms) (average number of moles from 1 to 10) adduct such as hydrogenated bisphenol A and hydrogenated bisphenol A. These can be used alone or in combination.
    polycarboxylic acid is not particularly restricted, and it can be selected appropriately according to the purpose. Examples of these include dicarboxylic acid.
    Examples of dicarboxylic acid include: adipic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, maleic acid, and succinic acid substituted by an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 atoms of carbon such as dodecenylsuccinic acid and octylsuccinic acid. These can be used alone or in combination of two or more.
    The non-crystalline polyester resin can include at least one of a trivalent or higher carboxylic acid and a trihydrous or higher alcohol at one end of the resin chain for the purpose of adjusting an acid value and a hydroxyl value.
    Examples of the trivalent or higher carboxylic acid include trimellitic acid, pyromellitic acid and acid anhydrides thereof.
    Examples of trihydric alcohol or higher include glycerin, pentaerythritol and trimethylolpropane.
    An average mass molecular weight of the non-crystalline resin B is not particularly restricted, and it can be selected appropriately according to the purpose.
    However, it is preferably 3,000 to 30,000, more preferably 5,000 to 20,000.
    The mass average molecular weight of the non-crystalline resin B can be measured, for example, by gel permeation chromatography (GPC).
    A glass transition temperature of the non-crystalline resin B is not particularly restricted, and it can be selected appropriately according to the purpose. However, it is preferably from 40 ° C to 70 ° C. when the glass transition temperature is less than 40 ° C, the heat-resistant storage stability degrades, which can cause film formation. When it exceeds 70 ° C, there are cases where the low temperature fastening property degrades.
    The glass transition temperature of the non-crystalline resin B can be measured by differential scanning calorimetry (DSC method).
    A content of non-crystalline resin B in the toner is not particularly restricted, and can be selected appropriately according to the purpose. However, it is preferably from 30% by mass to 90% by mass, and more preferably 50% by mass up to 85% by mass.
    «Resin E»
    Resin E is not particularly restricted as long as it has the crystalline portion C and the non-crystalline portion D in a molecule thereof, and it can be selected appropriately according to the purpose. Examples of the same include a copolymer of a repeat unit derived from a crystalline monomer and a repeat unit derived from a non-crystalline monomer; a copolymer of a repeat unit derived from a crystalline oligomer and a repeat unit derived from a non-crystalline oligomer; a copolymer of a repeat unit derived from a crystalline polymer and a repeat unit derived from a non-crystalline polymer; and combinations thereof. Among these, the copolymer of the repeating unit derived from a non-crystalline polymer is particularly preferable in view of the compatibility of resin E with crystalline resin A and non-crystalline resin B.
    A copolymerization modality in the copolymer is not particularly restricted, and can be selected appropriately according to the purpose. However, block copolymerization is preferable.
    Examples of the crystalline polymer in the repeat unit derived from the crystalline polymer include crystalline resin A.
    Examples of the non-crystalline polymer in the repeat unit derived from the non-crystalline polymer include non-crystalline resin B.
    A method for copolymerization is not particularly restricted, and can be selected appropriately according to the purpose. Examples of the same include any of the following methods (1) to (3).
    (1) A non-crystalline resin prepared in advance by polymerization reaction and a crystalline resin prepared in advance by polymerization reaction are dissolved or dispersed in an appropriate solvent and then reacted with an elongation agent that has two or more functional groups that react with a hydroxyl group or a carboxylic acid at an end 10 of a polymer chain such as an isocyanate group and epoxy group for copolymerization.
    (2) A non-crystalline resin prepared in advance by polymerization reaction and a crystalline resin prepared in advance by polymerization reaction are kneaded, and a copolymer is prepared by transesterification reaction thereof under reduced pressure.
    (3) Using a hydroxyl group of a crystalline resin prepared in advance by polymerization reaction as a polymerization initiator component, a ring-opening polymerization of a non-crystalline resin is carried out from one end of a resin polymer chain crystalline for copolymerization.
    - Crystalline portion C Crystalline portion C preferably includes a common backbone composed of a monomer unit of the same type as crystalline resin A as it improves the affinity (compatibility) between crystalline resin A and resin E and provides storage resistance resistant to superior heat and superior low temperature fixing properties of the toner.
    As the skeleton of the crystalline portion C composed of the monomer unit, that similar to crystalline resin A can be used, but aliphatic polyester is particularly preferable. The aliphatic polyester can be selected appropriately for that similar to crystalline resin A.
    A mass ratio (A / C) of a mass (g) of crystalline resin A to a mass (g) of crystalline portion C of resin E is not particularly restricted, and it can be selected appropriately according to the purpose. However, it is preferably 0.5 to 3.0, more preferably 0.6 to 2.0; and even more preferably 0.8 to 1.2. The mass ratio (A / C) within the most preferable range is advantageous since both the low temperature fastening property and the heat resistant storage stability of the toner can be obtained.
    - Non-crystalline portion D Non-crystalline portion D preferably includes a common backbone composed of a monomer unit of the same type as non-crystalline resin B as it improves the affinity (compatibility) between non-crystalline resin B and resin E and provides superior heat-resistant storage stability and toner low-temperature holding property.
    As the skeleton of the non-crystalline portion D composed of the monomer unit, that similar to the non-crystalline resin B can be used, but the polyhydroxycarboxylic acid skeleton is particularly preferable. The resin that has a polyhydroxycarboxylic acid skeleton can be selected appropriately from that similar to non-crystalline resin B.
    A mass ratio (B / D) of a mass (g) of the non-crystalline resin B to a mass (g) of the non-crystalline portion D of resin E is not particularly restricted, and it can be selected appropriately according to the purpose . However, it is preferably 0.5 to 10.0, more preferably 1.0 to 5.0, and even more preferably 1.5 to 2.5. The mass ratio (B / D) within the most preferable range is advantageous since both the low temperature fastening property and the heat-resistant storage stability of the toner can be achieved.
    A mass average molecular weight of resin E is not particularly restricted, and it can be selected appropriately according to the purpose. However, it is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.
    The average molecular weight of resin E can be measured, for example, by gel permeation chromatography 10 (GPC).
    A glass transition temperature of resin E is not particularly restricted, and can be selected appropriately according to the purpose. However, it is preferably 30 ° C to 70 ° C, and more preferably 40 ° C 15 to 60 ° C.
    The glass transition temperature of resin E can be measured, for example, by differential scanning calorimetry (DSC method).
    A mass ratio (C / D) of a mass (g) of the crystalline portion C and a mass (g) of the non-crystalline portion D in resin E is not particularly restricted, and it can be appropriately selected according to the purpose. However, it is preferably 0.25 to 2.5, and more preferably 0.3 to 1.5. When the mass ratio is outside the preferable numerical range, the bonding effect of resin E with crystalline resin A and non-crystalline resin B decreases, and there are cases where the low temperature fastening property and storage-resistant stability toner heat degrade.
    A content of resin E in the toner is not particularly restricted, and it can be selected appropriately according to the purpose. However, it is preferably 1 wt% to 30 wt%, and a further 10 preferably 5 wt% to 15 wt%. When the content is less than 1% by mass, the binding effect of resin E with crystalline resin A and non-crystalline resin B decreases, and there are cases where the low temperature fixing property and storage stability heat-resistant toner degrade. Content that exceeds 30% by mass impairs the toner 's sharp melting property, which can result in the degraded low temperature fixing property of the toner.
    <Coloring>
    The dye is not particularly restricted, and it can be selected appropriately according to the purpose. Examples of these include carbon black, nigrosine dye, black iron, naphthol yellow S, Hansa yellow (10G, 5G, G) cadmium yellow, yellow iron oxide, yellow ocher, chrome yellow, titanium yellow, polyazole yellow, yellow Oil , Hansa yellow (GR, A, RN, R), yellow pigment L, benzidine yellow (G, GR), permanent yellow (NCG), Vulcan Fast yellow (5G, R), lake 5 tartrazine, lake quinoline yellow, anthrax yellow BGL, isoindolinone yellow, colcothar, red conductor, conductive vermilion, cadmium red, cadmium red mercury, antimony vermilion, permanent red 4R, red for, red Fiser, red for-chloro-ortho10 nitroaniline, scarlet Lithol Fast G, scarlet Brilliant fast, BS bright carmine, permanent red (F2R, F4R, FRL, FRLL, F4RH), scarlet Fast VD), Vulcan Fast B ruby, bright scarlet G, ruby Lithol GX, permanent red F5R, bright carmine 6B, scarlet pigment 3B, burgundy 5B , 15 toluidine brown, burgundy per keep F2K, burgundy helium BL, burgundy 10B, light brown BON, medium brown BON, lake eosin, lake rhodamine B, lake rhodamine Y, alizarin red, thioindigo red B, thioindigo brown, oil red, quinacridone red, pyrazolone red, polyazole , 20 chrome vermilion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkaline blue lake, peacock blue lake, Victoria blue lake, metal-free phthalocyanine blue, phthalocyanine blue, Fast Sky blue, indanthrene blue (RS, BC), indigo, ultramarine, Prussian blue, anthraquinone blue, Fast B violet, methyl violet lake, cobalt violet, manganese violet, dioxane violet, anthraquinone violet, chromium green, zinc green, chromium oxide, viridian, emerald green, green pigment B, naphthol green B, green gold, acid green lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc oxide and lithopone. These can be used alone or in combination of two or more.
    A dye content is not particularly restricted, and it can be selected appropriately according to the purpose. However, with respect to 100 parts by weight of the toner, it is preferably 1 part by weight to 15 parts by weight, and more preferably 3 parts by weight to 10 parts by weight.
    dye can also be used as a masterbatch combined with a resin.
    Examples of the resin include: non-crystalline polyester resin B, and polymers of styrene or substituents thereof such as polystyrene, poly-p-chloro-styrene and polyvinyl toluene; styrene copolymers such as styrene-p-chloro-styrene copolymer, styrene-propylene copolymer, styrene-vinyl-toluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer acrylate, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, 5-styrene-methyl methyl chloroacrylate copolymer, styrene copolymer ketone, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer and 10-styrene-maleic ester copolymer; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, an epoxy resin, a polyol epoxy resin, polyurethane, polyamide, polyvinyl butyral, poly-acrylic acid, rosin, modified rosin, 15 a terpene resin, an alicyclic or aliphatic hydrocarbon resin and an aromatic petroleum resin. These can be used alone or in combination of two or more.
    The masterbatch can be obtained by mixing and kneading the resin for the masterbatch and the dye with an application of a high shear force. At this time, an organic solvent can be used in order to improve the interaction between the dye and the resin for the masterbatch. In addition, it is preferable to produce the masterbatch by a so-called discharge method. The discharge method is to knead an aqueous paste of a dye with a resin and an organic solvent to migrate the dye to the resin and then to remove the water and the organic solvent. With this method, a moist cake of the dye can be used directly, and there is no need for drying. In mixing and kneading, a high shear dispersion apparatus such as a three-roller mill is preferably used.
    Other components>
    The other components are not particularly restricted, and they can be selected appropriately and according to the purpose. Examples of these include a release agent, a charge control agent, an external additive, a fluidity-enhancing agent, a cleaning-enhancing agent and a magnetic material.
    - Release agent The release agent is not particularly restricted, and it can be selected appropriately according to the purpose. However, waxes are preferable.
    Examples of waxes include natural waxes, synthetic waxes and other waxes. Examples of natural waxes include: vegetable waxes such as carnauba wax, cotton wax, Japanese wax and rice wax; animal waxes such as beeswax and lanolin; mineral waxes such as ozokerite and ceresin; and petroleum waxes such as paraffin, microcrystalline wax and petrolatum.
    Examples of synthetic waxes include: synthetic hydrocarbon waxes such as Fischer wax — tropsch, polyethylene and polypropylene; synthetic waxes based on oil and fat such as esters, ketones and ethers; and hydrogenated wax.
    Examples of other waxes include: fatty acid amide compounds such as 12-hydroxystearic amide, stearic amide, phthalic anhydride imide and dormant hydrocarbons; polyacrylate homopolymers or copolymers such as a low molecular weight crystalline polymeric resin such as poly-n-stearyl methacrylate and poly-n-lauryl ethacrylate (for example, a n-stearyl acrylate - ethyl methacrylate copolymer and so on) and one crystalline polymeric resin that has a long alkyl group on its side chain.
    These release agents can be used alone or in combination with two or more.
    Among these, paraffin wax, microcrystalline wax and hydrocarbon wax such as Fischer-tropsch wax, polyethylene wax and polypropylene wax are preferable.
    A melting point of the release agent is not particularly restricted, and it can be selected appropriately according to the purpose. However, it is preferably from 60 ° C to 80 ° C. When the melting point is less than 60 ° C, the release agent is likely to melt at a low temperature, which can degrade heat-resistant storage stability. When the melting point exceeds 80 ° C, the release agent does not melt substantially and causes a high temperature displacement during fixation even though the resin melts and is in a region of fixation temperature. How
    result, there are cases in what a defect of image 15 occurs. Agent content in release is not particularly restricted, and him Can be selected
    appropriately according to the purpose. However, with respect to 100 parts by weight of the toner, it is 20 preferably from 2 parts by weight to 10 parts by weight, and more preferably 3 parts by weight to 8 parts by weight. When the content is less than 2 parts by mass, there are cases where the high temperature resistant displacement property and the low temperature fixation property during fixation degrade. When it exceeds 10 parts by mass, there are cases where heat-resistant storage stability degrades or image blurring occurs easily. The most preferable content within range 5 is advantageous in view of improving the high image quality and improving the fixation stability.
    - Load control agent The load control agent is not particularly restricted, and it can be selected appropriately according to the purpose. Examples thereof include nigrosine dyes, triphenylmethane dyes, complex metal dyes containing chromium, molybdic acid chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salt (including fluorine-modified quaternary ammonium salts), alkyl amides, elemental phosphorus or phosphorus compound, elemental tungsten or tungsten compounds, fluorine surfactants, salicylic acid metal salts and salicylic acid derivative metal salts.
    Commercial products can be used as the charge control agent, and examples of commercial products include: BONTRON 03 of nigrosine dyes, BONTRON P-51 of quaternary ammonium salt, BONTRON S-34 of azo dye containing metal, E- 82 of oxinaftóic acid metal complex, E-84 of salicylic acid metal complex, and E-89 of methane condensate (all manufactured by Orient Chemical Industries Co. Ltd.); TP-302 and TP-415 of quaternary ammonium salt molybdenum complexes (all manufactured by Hodogaya Chemical Co., Ltd.); LRA-901, and LR147 as a boron complex (manufactured by Carlit Japan Co. Ltd.); copper phthalocyanine, perylene, quinacridone, azo pigments and other polymeric compounds that have a functional group such as sulfonic acid group, carboxyl group 10 and quaternary ammonium salt. These can be used alone or in combination of two or more.
    charge control agent can be kneaded fused together with the masterbatch and resin and then dissolved or dispersed. In addition, it can be added directly to the organic solvent during dissolution or dispersion, or it can be added externally to a toner surface after toner-based particles are prepared.
    A load control agent's content is not particularly restricted, and it can be selected appropriately according to the purpose. However, with respect to 100 parts by weight of the toner, it is preferably from 0.1 part by weight to 10 parts by weight, and more preferably 0.2 part by weight up to 5 parts by weight. When the content exceeds 10 parts by mass, the charge property of the toner is relatively large, this weakens an effect of the main charge control agent and increases the electrostatically attractive force with a developing roller, which can result in reduced fluidity of a developer and reduced image density.
    - External additive As the external additive, other than fine oxide particles 10, inorganic particles or hydrophobized inorganic particles can be used in combination. However, hydrophobized primary particles preferably have an average particle diameter of 1 nm to 100 nm, and inorganic particles having an average particle diameter of 5 nm to 70 nm are more preferable.
    In addition, it is preferable to include at least one type of inorganic particles that have an average particle diameter of hydrophobized primary particles of 20 nm or less and at least one type of inorganic particles of 30 nm or more. In addition, a specific BET surface area is preferably 20 m 2 / g to 500 m 2 / g.
    external additive is not particularly restricted, and it can be selected appropriately according to the purpose. Examples of these include silica particles, hydrophobic silica, fatty acid metal salts (for example, zinc stearate, zinc stearate and so on), metal oxides (for example, titania, alumina, tin oxide, oxide antimony and so on) and fluoropolymers. These can be used alone or in combination of two or more.
    Examples of the external additive include silica particles, hydrophobized silica particles, titania particles, hydrophobized titanium oxide particles and 10 alumina particles.
    Commercial products can be used as silica particles, and examples of commercial products include R972, R974, RX200, RY200, R202, R805, R812 (all manufactured by Nippon Aerosil Co. Ltd.).
    Commercial products can be used as titania particles, and examples of commercial products include: P-25 (manufactured by Nippon Aerosil Co. Ltd.); STT30 and STT-65C-S (all manufactured by Titan Kogyo, Ltd.);
    TAF-140 (manufactured by Fuji Titanium Industry Co., Ltd.); and 20 MT-150W, MT-500B, MT-600B and MT-150A (all manufactured by
    Tayca Corporation).
    Commercial products can be used as fine particles of hydrophobized titanium oxide and examples of commercial products include T-805 (manufactured by Nippon Aerosil Co. Ltd.); STT-30A and STT-65S-S (all manufactured by Titan Kogyo, Ltd.); TAF-500T and TAF-1500T (all manufactured by Fuji Titanium Industry Co., Ltd.); MT-100S and MT-100T (all manufactured by Tayca Corporation);
    and IT-S (manufactured by Ishihara Sangyo Kaisha Ltd.).
    The fine particles of hydrophobized oxide, the particles of hydrophobized silica, the particles of hydrophobized titania and the particles of hydrophobized alumina can be obtained, for example, by treating the hydrophilic fine particles with a silane coupling agent such as methyltrimethoxysilane , methyltriethoxysilane and octyltrimethoxysilane.
    In addition, inorganic particles treated with silicone oil obtained by processing inorganic particles with silicone oil with heating according to the need are favorable.
    Examples of silicone oil include dimethylsilicone oil, methylphenylsilicone oil, chlorophenylsilicone oil, methylhydrogen silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil, polyether-modified silicone oil, silicone oil modified alcohol, amino modified silicone oil, epoxy modified silicone oil, epoxy polyether modified silicone oil, phenol modified silicone oil, carboxyl modified silicone oil, mercapto modified silicone oil, silicone modified by methacryl and silicone oil modified by α-methylstyrene.
    Examples of inorganic particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, zinc oxide, tin oxide, silica sand, clay , mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, colcotar, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide and silicon nitride. These
    can be used alone or in combination in two or more. Among these, dioxide in titanium and silica are particularly preferable s. Content from external additive no it is particularly restricted, and He can to be selected appropriately according how purpose. At the however , with relation to 100 parts in mass of toner, it is
    preferably from 0.1 part by mass to 5 parts by mass, and more preferably 0.3 part by mass to 3 parts by mass.
    A particle diameter of primary particles of inorganic particles is not particularly restricted, it can be appropriately selected according to the purpose. However, it is preferably 100 nm or 5 min, and more preferably 3 nm to 70 nm. When the average particle diameter is less than 3 nm, the inorganic particles are incorporated into the toner, and there are cases where their functions are not effectively displayed. A diameter that exceeds 100 nm can cause 10 non-uniform scratches on a photoconductor surface.
    - Fluidity-enhancing agent The fluidity-enhancing agent is not particularly restricted as long as it improves hydrophobicity through surface treatment and prevents degradation of fluidity and loading properties under high humidity, and it can be appropriately selected according to the purpose. Examples thereof include a silane coupling agent, a silylation agent, a silane coupling agent that has a fluorinated alkyl group, an organic titanate coupling agent, an aluminum based coupling agent, silicone oil and modified silicone oil. It is particularly preferable that silica and titanium oxide as the external additive are subjected to surface treatment through the flow-improving agent and used as hydrophobic silica and hydrophobic titanium oxide.
    - Cleaning capacity improving agent The cleaning capacity improving agent is not particularly restricted as long as it is added to the toner for removal in a photoconductor and an intermediate transfer member after transfer, and it can be appropriately selected according to the purpose. Examples of the same include: fatty acid metal salt such as zinc stearate, calcium stearate and stearic acid; and fine polymer particles manufactured by polymerization in soap-free emulsion such as 15 fine polymethyl methacrylate particles and fine polystyrene particles. The fine polymer particles preferably have a relatively narrow particle size distribution, and the average volumetric particle diameter thereof is more preferably 20 0.01 µm at 1 pm.
    - Magnetic material The magnetic material is not particularly restricted, and it can be selected appropriately according to the purpose. Examples of it include iron powder, magnetite and ferrite. Among these, a white material is preferable in view of the color tone.
    <Toner manufacturing method>
    Toner manufacturing method is not particularly restricted, and it can be selected appropriately according to the purpose. However, a method of dispersing an oil phase which includes crystalline resin A, non-crystalline resin B, resin E and dye and which additionally includes other components such as release agent as required in an aqueous medium for granulation to be preferable. Favorable examples of the toner manufacturing method include a dissolution-suspension method.
    The dissolution-suspension method preferably includes the preparation of an aqueous medium, the preparation of an oil phase which includes a toner material, the emulsification or dispersion of the toner material and the removal of an organic solvent.
    - Preparation of the aqueous medium (aqueous phase) The aqueous medium can be prepared, for example, by dispersing resin particles in an aqueous medium. An added amount of the resin particles in the aqueous medium is not particularly restricted, and it can be selected appropriately according to the purpose. However, with respect to 100 parts by weight of the aqueous medium, it is preferably 0.5 parts by weight to 10 parts by weight.
    The aqueous medium is not particularly restricted, and it can be selected appropriately according to the purpose. Examples of this include water, a water-miscible solvent, and mixtures thereof. These can be used alone or in combination of two or more. Among these, water is preferable.
    The water-miscible solvent is not particularly restricted, and it can be selected appropriately according to the purpose. Examples of these include alcohols, dimethylformamide, tetrahydrofuran, celosolves and lower ketones. Alcohols are not particularly restricted, and they can be selected appropriately according to their purpose. Examples of these include methanol, isopropanol and ethylene glycol. Lower ketones are not particularly restricted, and they can be selected appropriately according to their purpose.
    Examples of these include acetone and methyl ethyl ketone.
    - Preparation of the oil phase An oil phase that includes the toner material can be prepared by dissolving or dispersing in a organic solvent a toner material that includes crystalline resin A, non-crystalline resin Bea resin E, which include the dye and which additionally include other components such as the release agent as needed.
    The organic solvent is not particularly restricted, and it can be selected appropriately according to the purpose. However, the organic solvent that has a melting point of less than 150 ° C is preferably for easy removal.
    The organic solvent that has a melting point of less than 150 ° C is not particularly restricted, and it can be selected appropriately according to the purpose. Examples of these include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,215 dichloroethane, 1,1,2-trichloroethane, trichlorethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone and methyl isobutyl ketone. These can be used alone or in combination of two or more.
    Among these, ethyl acetate, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform and carbon tetrachloride are preferable, and ethyl acetate is more preferable.
    - Emulsification or dispersion 53
    Emulsification or dispersion of the toner material can be carried out by dispersing the oil phase which includes the toner material in the aqueous medium.
    A method for steadily forming the dispersion liquid in the aqueous medium is not particularly restricted, and it can be selected appropriately according to the purpose. Examples of the same include a method of adding an oil phase prepared by dissolving or dispersing a toner material in a solvent in an aqueous medium phase and dispersing it through a shear force.
    A dispersion machine for dispersion is not particularly restricted, and it can be selected appropriately according to the purpose. Examples of the same include a low speed shear disperser, a high speed shear disperser, a frictional disperser, a high pressure jet disperser and an ultrasonic disperser. Among these, the high speed shear disperser is preferable as it allows the control of a diameter of
    dispersion particle (oil droplets) to 2 pm for 20 pm.When the disperser shear High
    speed is used, conditions such as rotational speed, dispersion time and dispersion temperature are not particularly restricted, and they can be selected appropriately according to the purpose.
    The rotational speed is not particularly restricted, and it can be selected appropriately according to the purpose. However, it is preferably 1,000 rpm at 30,000 rpm, and more preferably 5,000 rpm at 20,000 rpm.
    dispersion time is not particularly restricted, and it can be selected appropriately according to the purpose. However, for a batch operation, it is preferably 0.1 minute to 5 minutes.
    The dispersion temperature is not particularly restricted, and it can be selected appropriately according to the purpose. However, under increased pressure, it is preferably 0 ° C to 150 ° C, and more preferably 40 ° C to 98 ° C. Here, in general, dispersion is easier when the dispersion temperature is higher.
    An amount of the aqueous medium used in emulsifying or dispersing the toner material is not particularly restricted, and it can be selected appropriately according to the purpose. However, with respect to 100 parts by weight of the toner material, it is preferably 50 parts by weight to 2,000 parts by weight, and more preferably 100 parts by weight to 1,000 parts by weight.
    The amount of aqueous medium used of less than 50 parts by weight can result in poor dispersion of the 5 toner materials, and toner-based particles that have a predetermined particle diameter cannot be obtained. The amount used that exceeds 2,000 parts by mass can result in high production costs.
    When the oil phase that includes the toner material is emulsified or dispersed, it is preferable to use a dispersant in view of stabilizing the dispersant such as oil droplets to form them in a desired shape as well as narrowing the size distribution of particle.
    The dispersant is not particularly restricted, and it can be selected appropriately according to the purpose. Examples of the same include a surfactant, an inorganic compound dispersant which is hardly soluble in water and a polymeric protective colloid. These can be used alone or in combination of two or more. Among these, the surfactant is particularly preferable.
    Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant and an amphoteric surfactant.
    Examples of the anionic surfactant include alkylbenzene sulfonate, α-olefinsulfonate, phosphoric acid esters and anionic surfactants that contain a fluoroalkyl group. Among these, anionic surfactants that contain a fluoroalkyl group are preferable. Examples of anionic surfactants containing a fluoroalkyl group that includes fluoroalkyl carboxylic acids that have 2 to 10 carbon atoms and metal salts thereof, perfluorooctanesulfonylglutamate disodium, 3- [ω-fluoroalkyl (C6 to Cll) oxy) -1-alkylsulfonates (C3 or C4) sulfonates, sodium 3- [ωfluoroalkanoyl (C6 to C8) -N-ethylamino) -1-propanesulfonates, fluoroalkyl acids (Cll to C20) carboxylic acids and metal salts thereof, (C7 to C13) perfluoroalkylcarboxylic acids and metal salts thereof, perfluoroalkyl (C4 to C12) sulfonates and metal salts thereof, perfluorooctanesulfonic acid dimethanol amide, N-propyl-N- (2hydroxyethyl) perfluorooctanesulfone amide, perfluoroalkyl salts (C6 to CIO) sulfonamide propyltrim perfluoroalkyl salts (C6 to CIO) -N-ethylsulfonylglycine and monoperfluoroalkyl (C6 to C16) ethylphosphates. These can be used alone or in combination of two or more.
    Commercial products can be used as surfactants that contain a fluoroalkyl group. Examples of commercial products include: SURFLON S-lll, S-112 and S-113 (manufactured by Asahi Glass Co. Ltd.); FLUORAD FC-93, FC-95, FC-98 and FC-129 (manufactured by Sumitomo 3M Ltd.); UNIDYNE DS-101 and DS-102 (manufactured by Daikin Industries, Ltd.); MEGAFACE F-110, F-120, F-113, F-191, F-812 and F-833 (manufactured by DIC Corporation); EFTOP EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201 and 204 (manufactured by Tochem Products Inc.); and FTERGENT F-100 and F-150 (manufactured by Neos Company Ltd.). These can be used alone or in combination of two or more.
    Examples of the cationic surfactant include amine salt surfactants, cationic quaternary ammonium salt surfactants and cationic surfactants that contain a fluoroalkyl group. Examples of the amine salt surfactants include alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives and imidazoline. Examples of the quaternary ammonium salt cationic surfactants include alkyl trimethyl ammonium salts, dialkyldimethyl ammonium salts, alkylldimethylbenzyl ammonium salts, pyridinium salts, alkylisoquinolinium salts and benzethium chloride. Examples of cationic surfactants that contain a fluoroalkyl group include a primary, secondary or tertiary aliphatic amine that has a fluoroalkyl group, an aliphatic quaternary ammonium salt such as perfluoroalkyl salt (C6
    CIO) sulfonamidepropyltrimethyl ammonium, a benzalkonium salt, benzethonium chloride, a pyridinium salt and an imidazolinium salt. These can be used alone or in combination of two or more.
    Commercial products can be used as cationic surfactants, and examples of commercial products include: SURFLON S-121 (manufactured by Asahi Glass Co. Ltd.); FLUORAD FC-135 (manufactured by Sumitomo 3M Ltd.); UNIDYNE DS-202 (manufactured by Daikin Industries, Ltd.), MEGAFACE F-150 and F-824 (manufactured by DIC Corporation); EFTOP EF-132 (manufactured by Tochem Products Inc.); and FTERGENT F-300 (manufactured by Neos Company Ltd.). These can be used alone or in combination of two or more.
    Examples of the nonionic surfactant include derivatives of fatty acid amide and derivatives of polyhydric alcohol.
    Examples of the amphoteric surfactant include alanine, dodecildi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethyl ammonium betaine.
    - Removal of organic solvent A method for removing organic solvent from the dispersion liquid as an emulsified slurry is not particularly restricted, and it can be selected appropriately according to the purpose. Examples of this include: a method of evaporating the organic solvent in the oil droplets by gradually heating the entire reaction system; and a method of removing the organic solvent in the oil droplets by spraying the dispersion liquid in a dry atmosphere.
    Once the organic solvent is removed, toner-based particles are formed. The toner-based particles can be subjected to washing and drying and additionally for classification. Sorting can be done by removing a portion of 10 fine particles in a liquid using a cyclone, a decanter, a centrifuge and so on, or a sorting operation can be performed after drying.
    The toner-based particles obtained can be mixed with particles such as external additive and charge control agent above. At this time, the application of a mechanical impact can suppress the departure of particles such as external additive from a surface of the toner-based particles.
    A method for applying mechanical impact is not particularly restricted, and it can be selected appropriately according to the purpose. Examples of this include: a method of applying an impact to the mixture using a blade that rotates at high speed;
    and a method for having the mixture collide against a collision plate by positioning the mixture in a high speed flow stream for acceleration.
    An apparatus used for the method is not particularly restricted, and it can be selected appropriately according to the purpose. Examples of this include ANGMILL (manufactured by Hosokawa Micron Co. Ltd.), a refurbished type I mill apparatus with reduced grinding air pressure (manufactured by Nippon
    Pneumatic Mfg. Co., Ltd.), HYBRIDIZATION SYSTEM (manufactured by Nara Kikai Seisakusho Co., Ltd.), KRYPTON SERIES (manufactured by Kawasaki Heavy Industries, Ltd.) and an automatic pestle.
    A shape, a size and so on of the toner of the present invention are not particularly restricted, and they can be selected appropriately according to the purpose. However, it is preferably 3 pm to 7 pm. still, a ratio (Dv / Dn) of a numerical average particle diameter Dn to the volumetric average particle diameter
    Toner dv is preferably 1.2 or less. In addition, it is preferable to include 1% per number to 10% per number of particles having a particle diameter of 2 pm or less.
    The color of the toner is not particularly restricted, and it can be selected appropriately according to the purpose. It can be at least one type selected from a black toner, a cyan toner, a magenta toner and a yellow toner, and the toners of the respective colors can be obtained by appropriately selecting a type of dye.
    << Calculation method and analysis method of various toner properties and toner components »
    A glass transition temperature Tg, an acid value, a hydroxyl value, a molecular weight and a melting point of crystalline resin A, non-crystalline resin B and resin E which has crystalline portion C and non-crystalline portion D in a molecule of them are not particularly restricted, and they can be selected appropriately according to the purpose. These can be measured by themselves. However, these can be separated from a real toner using gel permeation chromatography (GPC) and so on, and a value of
    SP, Tg, molecular weight, melting point and a mass ratio of the components of the separate components can be calculated by analysis techniques described later.
    Here, the separation of components by GPC can be carried out, for example, using the following method.
    In a GPC measurement with THE (tetrahydrofuran) as a mobile phase, an eluate is fractionated by a fraction collector, etc., and over the entire area of an evasive curve, fractions that correspond to a desired molecular weight portion are collected.
    The eluate is collected, concentrated and dried by an evaporator, and a solid content is dissolved in a deuterated solvent such as deuterated chloroform and THE deuterated. Then, a 1 H-NMR measurement is performed, and from an integration ratio of each element, it is possible to calculate the ratio of monomers that make up the resin in the eluted component.
    Yet, as another method, after the eluate is concentrated and then hydrolyzed by sodium hydroxide and so on. A product of its decomposition is subjected to qualitative and quantitative analyzes by high speed liquid chromatography (HPLC) and so on. In this way, the constitutional monomer ratio can be calculated.
    «Method for separating the toner component»
    An example of a method of separating components in toner analysis is described below.
    First, 1 g of the toner is placed in 100 mL and tetrahydrofuran (THE) and dissolved by stirring for 30 minutes under a condition of 25 ° C, and a solution in which soluble components are dissolved is obtained.
    This is filtered through a membrane filter that has openings of 0.2 pm, and material soluble in THE in the toner is obtained.
    This is then dissolved in THE as a sample for measuring GPC and injected into a GPC used to measure molecular weights of the resins described above.
    Meanwhile, a fraction collector is arranged in an eluate exit from the GPC. An eluate is fractionated at each predetermined count, and an eluate is obtained every 5% as an air ratio from the beginning of the evasion of an evasion curve (rise of the curve).
    Then, for each evasion, 30 mg of the sample is dissolved in 1 ml of deuterated chloroform, which 0.05% by volume of tetramethylsilane (TMS) is added as a referenced substance.
    The solution is filtered in a glass tube for NMR measurement that has a diameter of 5 mm, and that uses a nuclear magnetic resonator (manufactured by JEOL Ltd., JNMAL400), integrations are performed 128 times at a temperature of 23 ° C to 25 ° C to obtain a spectrum.
    The monomer compositions and the composition ratio of crystalline resin A, non-crystalline resin B, resin
    And so on included in the toner can be obtained from the peak integration ratio of the obtained spectrum.
    From these results, for example, an extract collected in a fraction in which crystalline resin A is responsible for 90% or more can be treated as crystalline resin A. Similarly, an extract collected in a fraction in which crystalline resin B is responsible for 90% or more can be treated as crystalline resin B. Also similarly, an extract collected in a fraction in which resin E is responsible for 90% or more can be treated like resin E.
    Toner of the present invention does not cause film formation and has superior properties such as low temperature setting property, high temperature resistant displacement property and heat resistant storage stability. Thus, the toner of the present invention can be used favorably in various fields, can be used favorably used for electrophotographic imaging, and can be used favorably by a developer of the present invention, a toner container used in the present invention, a cartridge method used in the present invention, an imaging apparatus of the present invention and an imaging method used in the present invention described below.
    (Developer)
    A developer of the present invention includes the toner of the present invention, and it includes other components such as a carrier selected appropriately as needed.
    Thus, it has superior transfer property, loading property and so on, and it is possible to form a high quality image in a stable manner. Here, the developer can be a one-component developer or a two-component developer. However, the two-component developer is preferable as it improves life when it is used for a high-speed 15 printer compatible with information processing speed in recent years.
    When the developer is used as a component developer, the variation in toner particle diameter is small even after the toner is balanced, and in addition, 20 does not cause film to form on a developer roll or spindle on a limb such as the blades which fine tune the toner, and stable and favorable developing property and images can be achieved after a long period of shaking in the developer.
    When the developer is used as a two-component developer, the variation of the toner particle diameter is small when the toner in the developer is balanced over a long period of time, and images and the stable and favorable development property can be achieved after long-term agitation in a developing apparatus.
    <Carrier>
    The bearer is not particularly restricted, and he can be selected appropriately according to the purpose. However, the carrier preferably includes a core material and a layer of resin that coats the core material.
    - Core material A core material is not particularly restricted, and it can be selected appropriately according to the purpose. Examples of it include a manganese - strontium material from 50 emu / g to 90 emu / g and a manganese - magnesium material from 50 emu / g to 90 emu / g. still, to guarantee the image density, it is preferable to use a material of high magnetization such as iron powder of 100 emu / g or greater and magnetite of 75 emu / g to 120 emu / g. In addition, it is preferable to use a low magnetizing material such as copper-zinc of 30 emu / g to 80 emu / g as it can facilitate a developer impact as a chain of magnetic particles for the photoconductor and is advantageous for high image quality . These can be used alone or in combination of two or more.
    A mean volumetric particle diameter of the core material is not particularly restricted, and it can be selected appropriately according to the purpose. However, it is preferably 10 pm to 150 pm, and more preferably 40 pm to 100 pm. When the average volumetric particle diameter is less than 10 pm, fine powder 10 increases in the carrier particles, and magnetization by a particle can decrease. This can result in carrier spreading. When it exceeds 150 pm, the specific surface area decreases, which can result in toner scattering. In a full color print 15 that has many solid portions, the reproduction of the solid portions can degrade in particular.
    Toner can be mixed with the carrier when it is used for a two-component developer.
    A carrier's content in the two-component developer is not particularly restricted, and it can be selected appropriately according to the purpose. However, it is preferably 90 parts by weight to 98 parts by weight, and more preferably 93 parts by weight to 97 parts by weight with respect to 100 parts by weight of the two component developer.
    <Toner container>
    A toner container used in the present invention contains the toner or developer of the present invention in a container.
    The container is not is particularly restricted, and he Can be selected appropriately a deal with O purpose. Examples favorable include one container that includes a main body of container in toner and a cover. One size, one shape, a structure, a material and
    so on the main toner container body are not particularly restricted, and they can be selected appropriately according to the purpose. For example, as the shape, a cylinder is preferable, and some particularly preferable ones have a spiral shaped roughness formed on an internal surface of the same, which is capable of transferring a toner as content to an output side by rotation, where a part or the entire spiral portion has a bellows function.
    A material in the main body of the toner container is not particularly restricted, and some with high accuracy in size are preferable. Favorable examples of these include resins, including polyester resins, polyethylene resins, polypropylene resins, polystyrene resins, polyvinyl chloride resins, poly-acrylic acid, polycarbonate 5 resins, ABS resins, polyacetal resins and so on are favorable.
    toner container allows for easy storage, transportation and so on and is superior in terms of handling, and it can be detachably mounted 10 on a process cartridge, image forming apparatus and so on of the present invention described later and favorably used for toner replacement.
    <Process cartridge »
    A process cartridge used in the present invention includes: an electrostatic imaging support member that supports an electrostatic imaging; and a developing unit that reveals the electrostatic imaging supported on the electrostatic imaging support member that uses a toner to form a visible image, and additionally includes other units selected appropriately as needed.
    The developer unit includes: developer container which contains the toner or developer of the present invention;
    and a developer support member which supports and carries the toner or developer in the developer container; and it may additionally include a layer thickness regulating member for regulating a layer thickness of the supported toner and so on.
    The other units are not particularly restricted, and they can be selected appropriately according to the purpose. Favorable examples of these include a loading unit and a cleaning unit 10 described later.
    The process cartridge can be detachably mounted on various imaging devices, and preferably it is detachably mounted on an image apparatus of the present invention 15 described below.
    (Image formation method and image formation apparatus)
    An imaging method used in the present invention includes: an electrostatic imaging step 20; a disclosure step; a transfer step; and a fixation step, and it additionally includes other steps selected appropriately according to the need such as neutralization step, cleaning step, recycling step and control step.
    The imaging apparatus of the present invention includes an electrostatic imaging support member; an electrostatic imaging training unit; a developing unit; a transfer unit; and a clamping unit, and it additionally includes other units selected appropriately according to the need such as the neutralization unit, the cleaning unit, the recycling unit and the control unit.
    <Electrostatic Imaging Stage and Electrostatic Imaging Unit>
    The electrostatic imaging step is a step to form an electrostatic imaging on the electrostatic imaging support member.
    A material, shape, structure and size of the electrostatic imaging support member (may also be referred to as an electrophotographic photoconductor, photoconductor or image support member) are not particularly restricted, and can be appropriately selected up to here some acquaintances. However, the shape is preferably a drum, and like the material, an inorganic photoconductor of amorphous silicon, selenium and so on and an organic photoconductor (OPC) of polysilane, phthalopolymethine and so on are exemplified.
    The electrostatic imaging is formed by uniformly loading a surface of the member of an electrostatic imaging support followed by exposure in the image direction, and it can be performed via the electrostatic imaging unit.
    The electrostatic imaging unit includes, for example, a charger that uniformly charges the surface of the electrostatic imaging support member and an exposure device that performs an image-oriented exposure on the surface of the imaging support member electrostatic.
    Loading can be done via the application /
    of a voltage on the surface of the electrostatic imaging support member using the charger.
    The charger is not particularly restricted, and can be selected appropriately according to the purpose.
    However, examples of the same include: a contact charger equipped with an electrically conductive or semiconductor roller, brush, film, rubber blade and so on, which are known here by themselves; and a non-contact charger that uses corona discharge such as corotron and scorotron.
    In addition, it is preferable that the charger is arranged on an electrostatic imaging support member in a contact or non-contact state - and charges a surface of the electrostatic imaging support member by applying direct current and current voltages. alternating overlapping.
    It is preferable that the charger is a charging roll arranged close to the electrostatic imaging support member through a gap ribbon in a non-contact manner and applies superimposed DC and alternating current voltages on the charging roll to charge the surface of the electrostatic imaging support member.
    The exposure can be carried out, for example, by exposing in the image direction a surface of the electrostatic imaging support member using the exposure device.
    The display device is not particularly restricted as long as it can expose in the image direction an image to be formed on the surface of the electrostatic imaging support member charged through the charger, and it can be selected appropriately according to the purpose. Examples of the same include various display devices such as the optical duplicating system, rod lens arrangement system, laser optical system and liquid crystal blocker optical system.
    Here, in the present invention, a backlight system which exposes towards the image from the rear side of the electrostatic imaging support member can be adopted.
    <Development stage and development unit>
    The development step is a step to develop the electrostatic imaging using the toner of the present invention to form a visible image.
    The visible image is formed, for example, by developing the electrostatic latent image using the toner of the present invention, and can be realized by the developing unit.
    The development unit is not particularly restricted as long as the development is carried out using the toner of the present invention, for example, and some known ones can be appropriately selected. For example, a favorable developer unit contains the toner of the present invention or a developer and includes a developer device capable of transmitting the developer to the electrostatic imaging in a contact or non-contact manner.
    developing device can employ a system of
    revelation dry or a system in wet revelation. 0 5 device in revelation can to be a device in revelation for Single color, or a device in
    development for multiple colors. Examples of the same include a developer device that contains a stirrer for friction and agitation to load the developer and a roller of a rotating magnet.
    toner and carrier are mixed and agitated in the developer, for example. The toner is rubbed off in this way and held on a surface of the rotating magnet roll like a chain of magnetic particles, and a magnetic brush is formed. The magnet roll is arranged close to the electrostatic imaging support member, and so a portion of the toner that makes up the magnetic brush formed on the surface of the magnetic roller moves to the surface of the electrostatic imaging support member 20 due to a electrically attractive force. As a result, the electrostatic imaging is revealed by the toner, and a visible image is formed on the surface of the electrostatic imaging support member.
    <Transfer step and transfer unit>
    The transfer step is a step to transfer the visible image to a recording medium. A preferable aspect employs an intermediate transfer member. The visible image is primarily transferred on the intermediate transfer member, and the visible image is transferred on a secondary basis in the recording medium. A more preferable aspect employs a toner of two or more colors, or preferably a full color toner 10, such as toner and includes a primary transfer step in which the visible image is transferred on the intermediate transfer member to form a transfer image composite and a secondary transfer step in which the composite transfer image is transferred on the recording medium.
    The transfer can be carried out, for example, by loading the visible image using the transfer charger, and it can be carried out via the transfer unit. Like the transfer unit, an aspect that includes a primary transfer unit that transfers the visible image on the intermediate transfer member to form the composite transfer image and a secondary transfer unit that transfers the composite transfer image to the recording medium it's preferable.
    Here, the intermediate transfer member is not particularly restricted, and it can be selected appropriately so far from transfer members known for the purpose, and examples thereof include a transfer belt.
    The transfer unit (the primary transfer unit, the secondary transfer unit) 10 preferably includes a transfer device which peels and loads the visible image formed on the electrostatic imaging support member to the side of the recording medium. There can be one transfer unit or there can be two or more transfer units.
    Examples of the transfer device include a corona transfer device via corona discharge, a transfer belt, a transfer roller, a pressure transfer roller and an adhesive transfer device.
    Here, the recording medium is not particularly restricted, and it can be selected appropriately so far from known recording paper.
    <Fixing step and fixing unit>
    The fixing step and a fixing step of the visible image transferred to the recording medium using a fixing unit. It can be performed each time the toner of a respective color is transferred in the recording medium, or it can be performed once at the same time when the toners of the respective colors are laminated.
    The fixing unit is not particularly restricted, and it can be appropriately selected according to the purpose. However, a pressurization and heating unit known until now is
    preferable. Examples gives unity of pressurization and heating include an combination of a roll in heating and a roll in pressure and a combination of one heating roller, a pressure roller and a belt without
    end.
    The fixing unit preferably includes: a heating body equipped with a heating element; a film which is in contact with the heating body; and a pressure member which is pressed against the heating body through the film. It is preferably a unit that passes the recording medium in which an unfixed image is formed between the film and the pressure member to be fixed by heating. Usually, heating in the pressurizing and heating unit is preferably at 80 ° C to 200 ° C.
    Other steps and other units>
    - Neutralization stage and neutralization unit -
    The neutralization step is a step to apply a neutralization polarization to the electrostatic imaging support member for neutralization, and it can be performed favorably by a neutralization unit.
    The neutralization unit is not particularly restricted as long as it can apply neutralization polarization to the electrostatic imaging support member. It can be selected appropriately from neutralization devices known to date, and examples of it include a neutralization lamp.
    - Cleaning step and cleaning unit -
    The cleaning step is a step to remove the toner that remains in the electrostatic imaging support member, and it can be performed favorably through a cleaning unit.
    The cleaning unit is not particularly restricted as long as it can remove the electrophotographic toner that remains in the electrostatic imaging support member. It can be selected appropriately from cleaners known so far, and examples of it include a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, a blade cleaner, a brush cleaner and a 5 wiper. continuous sheet.
    - Recycling step and recycling unit de Recycling step is a step to recycle the toner removed by the cleaning step to the development unit, and it can be performed favorably by a recycling unit.
    The recycling unit is not particularly restricted, and it can be selected appropriately according to the purpose. Examples of the same include transport units known so far.
    - Control step and control unit The control step is a step to control the above steps, and it can be performed favorably by a control unit.
    The control unit is not particularly restricted as long as it can control operations for each of the units, and it can be selected appropriately according to the purpose. Examples of it include devices such as sequencer and computer.
    An implementation aspect of the training and imaging method used in the present invention by the imaging apparatus of the present invention is explained with reference to FIG. 1. An image forming apparatus 100 illustrated in FIG. 1 is equipped with: a photoconductive drum 10 as the electrostatic imaging support member (hereinafter referred to as a photoconductor 10); a loading roller 20 as the loading unit; an exposure apparatus 30 as the exposure unit; a developing apparatus 40 as the developing unit; an intermediate transfer member 50; a cleaning device 60 such as the cleaning unit that includes a cleaning blade; and a neutralization lamp 70 as the neutralization unit.
    The intermediate transfer member 50 is an endless belt, and is designed to be movable in the direction of an arrow in the figure by three (3) rollers 51 which are arranged within and stretch the member. A portion of the three rollers 51 also functions as a transfer bias roll 20 which is capable of applying a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. The intermediate transfer member 50 has a transfer blade cleaning 90 for the nearby intermediate transfer member, and it also has a transfer roller 80 as the transfer unit capable of applying a transfer bias to transfer (secondary transfer) a visible image (toner image) to a recording medium 95 arranged facing him. Around the intermediate transfer member 50, a corona charger 58 for transmitting a charge on a visible image on this intermediate transfer member 50 is arranged between a contact portion 10 of the electrostatic imaging support member 10 and the intermediate transfer member and a contact portion of the intermediate transfer member 50 and the recording medium 95 in a direction of rotation of the intermediate transfer member 50.
    The developer 40 is composed of: a developer belt 41 as a developer support member; and a 45K black developer unit, a 45Y yellow developer unit, a 45M magenta developer unit and a 45C cyan developer unit attached to a periphery of this 41 development belt. Here, the 45K black developer unit is equipped with a unit containing 42K developer, a 43K developer supply roller and a 44K developer roller. The 45Y yellow developer unit is equipped with a unit containing 42Y developer, a 43Y developer supply roller and a 44Y developer roller. The 45M magenta developer unit is equipped with a unit containing 42M developer, a 3M developer 4 supply roller and a 4M developer roller. The 45C cyan developer unit is equipped with a unit containing 42C developer, a 43C developer supply roller and a 44C developer roller. In addition, the developing belt 41 is an endless belt rotatively stretched by a plurality of belt rolls, and a portion thereof is in contact with the electrostatic imaging support member 10.
    In the imaging apparatus 100 shown in FIG. 1, for example, the loading roller 20 uniformly loads the photoconductive drum 10. The display apparatus 30 performs an image-oriented exposure on the photoconductive drum 10 to form an electrostatic latent image. The electrostatic latent image formed in the photoconductive drum 10 is developed by supplying a toner from the developer 40, and a visible image (toner image) is formed. The visible image (toner image) is transferred from the roller 51 to the intermediate transfer member 50 by an applied voltage (primary transfer), and is additionally transferred on transfer paper 95 (secondary transfer). As a result, a transfer image is formed on the recording medium 95. Here, a residual toner on the photoconductor 10 is removed by the cleaning device 60, and the charge on the photoconductor 10 is neutralized by the neutralization lamp 70.
    Another aspect of implementing the imaging method used in the present invention by the imaging apparatus of the present invention is explained with reference to FIG. 2. An image forming apparatus 100 10 illustrated in FIG. 2 has the same configuration and the same operational effect as the image forming apparatus 100 illustrated in FIG. 1 except that the former is not equipped with the development belt 41 of the latter and that the black development unit 45K, the development unit 15 yellow 45Y, the magenta development unit 45M and the cyan development unit 45C are arranged around photoconductor 10 in order to face it directly. Here, elements in FIG. 2 which are the same as those in FIG. 1 are indicated by the same signs.
    Another aspect of implementing the imaging method used in the present invention by the imaging apparatus of the present invention is explained with reference to FIG. 3. An image forming apparatus set illustrated in FIG. 3 is a set of color imaging apparatus. This imaging apparatus set is equipped with a copy machine main body 150, a paper feed table 200, a scanner 300 and an automatic document feeder (ADF) 400.
    In the copier main body 150, an intermediate transfer member 50 as an endless belt is arranged in a central portion thereof. The intermediate transfer member 50 is stretched by 10 support rollers 14, 15 and 16, and is rotatable in a clockwise direction in FIG. 3. Near the support roll
    15, an intermediate transfer member cleaning device 17 is arranged to remove residual toner in the intermediate transfer member 50. Along 15 a transport direction of the intermediate transfer member 50 stretched by the support roller 14 and the transfer roller. support 15, a developing device assembly 120 is arranged, in which four (4) imaging units 18 of yellow, cyan, magenta and black are arranged 20 in parallel, facing the intermediate transfer member. Next to the developing device assembly 120, an exposure apparatus 21 is arranged. On one side of the intermediate transfer member 50 opposite the side on which the
    revelation 120 is arranged, a device in transfer secondary 22 is arranged. On the device in transfer secondary 22, a transfer belt secondary 24
    how an endless belt is stretched by a pair of rollers 23, and a recording medium (transfer paper) carried on the secondary transfer belt 24 and the intermediate transfer member 50 can contact each of these. Next to the secondary transfer device 22, an attachment device 25 is arranged. The fixture 25 is equipped with a fixing belt 26 as an endless belt and a pressure roller 27 arranged to be pressed through the fixing belt.
    Here, in the image forming apparatus as a whole, a sheet reversing apparatus 28 is arranged close to the secondary transfer apparatus 22 and the fixing apparatus 25 in order to invert the transfer paper to form images on both sides of the paper transfer.
    In the following, the formation of a complete color image (color copy) using the developing device set 120 is explained. That is, first, a document is positioned on a document table 130 of the automatic document feeder (ADF) 400. Alternatively, the automatic document feeder 400, the document is positioned on a contact glass 32 on the scanner 300, and the automatic document feeder 400 is closed.
    A start switch (not shown) is pressed. The scanner 300 is activated after the document is transported to the contact glass 32 in case the document is positioned in the automatic document feeder 400, or immediately if the document is positioned in the contact glass 32, and a first travel body 33 and the second travel body 34 travels. At this time, a light from 10 of a light source is radiated by the first travel body 33, and at the same time, the light reflected from one surface of the document is reflected by a mirror on the second travel body 34. A light is received by a reading sensor 36 through an image forming lens 15 35. In this way, the color document (color image) is read as black, yellow, magenta and cyan image information.
    Then, the black, yellow, magenta and cyan image information is transmitted to the respective imaging units 18 (an imaging unit for black, an imaging unit for yellow, an imaging unit for magenta and an imaging unit for cyan) in the developing device set 120, and black, yellow, magenta and cyan toner images are formed in the respective imaging units. That is, the imaging units 18 (the imaging unit for black, an imaging unit for yellow, an imaging unit for magenta, and an imaging unit for cyan) in the set of developing device 120 are respectively equipped with, as illustrated in FIG. 4: electrostatic imaging support members. 10 (one 10K electrostatic imaging support member for 10K black, one 10Y yellow electrostatic imaging support member, one 10M magenta electrostatic imaging support member and one 10C cyan electrostatic imaging support member ); charging apparatus 160, which uniformly charges 15 electrostatic imaging support members 10; display devices that perform an image sense exposure of the electrostatic imaging support members that correspond to the respective color image based on color image information 20 (L in FIG. 4) and form electrostatic latent images that correspond to the respective image colored in the electrostatic imaging support member; developing devices 61 which reveal electrostatic latent images using the respective color toners (a black toner, a yellow toner, a magenta toner and a cyan toner) and form toner images of the respective color toners; transfer chargers 62 for transferring the toner images to the intermediate transfer member 50;
    cleaning devices 63; and neutralization devices
    64, and is capable of forming single color images of the respective colors based on the information (a black image, a yellow image, a magenta image and a cyan image). The black image, the yellow image, the magenta image and the cyan image formed in this way, that is, the black image formed on the electrostatic imaging support member for black 10K, the yellow image formed on the imaging support member electrostatic to yellow 10Y, the magenta image formed on the support member 15 of electrostatic imaging to magenta 10M and the cyan image formed on the electrostatic imaging support member to cyan 10C are sequentially transferred on the intermediate transfer member 50 which is moved rotatingly through the support rollers 20 14, 15 and 16 (primary transfer). Then, the black image, the yellow image, the magenta image and the cyan image are overlaid on the intermediate transfer member
    50, and a composite color image (color transfer image) is formed.
    Meanwhile, at the table feed in 200 paper, one of the feed rollers of paper 142 is selectively rotated to feed a paper in recording) The from one of the paper cassettes 144 provided in
    multiple stages on a paper bench 143. The sheet is separated one by one by separation rollers 145 and sent to a feed path 14 6. It is transported by the transport rollers 147 and guided to a feed path 148 in the main body copy machine 10 150. It stops when it reaches a registration roller 49.
    Alternatively, a manual paper feed roller
    153 is rotated to feed a sheet (recording paper) into a manual feed tray 54, separated one by one by a manual separation roller 154 and fed into a manual feed path 53, and is stopped similarly when it reaches the registration roller 49. Here, registration roller 49 is usually grounded in use, or a bias can be applied in use to remove paper dust from the sheet. Then, the registration roller 49 is rotated to 20 to match the timing of the composite color image (color transfer image) formed on the intermediate transfer member 50, the sheet (embossing paper) is sent between the intermediate transfer member 50 and the secondary transfer device 22, and the composite color image (color transfer image) is transferred on the slide (recording paper) by the secondary transfer device 22 (secondary transfer). In this way, the color image is transferred and formed on the sheet (recording paper). Here, a residual toner in the intermediate transfer member 50 after image transfer is cleaned by the intermediate transfer member cleaning device 17.
    The sheet (recording paper) on which the color image was transferred and formed is transported by the secondary transfer device 22 and sent to the fixture 25, and the composite color image (color transfer image) is fixed on the sheet ( embossing paper) by heat and pressure in the fixture 25. Next, the sheet (embossing paper) is switched by a switch claw 55, unloaded by an unloading roller 56 and stacked in an unloading tray 57. Alternatively , the sheet is switched by the switch claw 55, inverted by a sheet reversing apparatus 28 and guided again to a transfer position. Then, an image is also recorded on a rear side, and it is unloaded by the discharge roller 56 and stacked in the discharge tray 57.
    As the toner of the present invention which does not cause film formation to occur and has superior low temperature fixing property, high temperature resistant displacement property and heat resistant storage stability is used in the imaging method and the apparatus image formation of the present invention used in the present invention, a high quality image can be formed efficiently.
    Examples
    In the following, the present invention is further described in detail with reference to the Examples, which however should not be construed as limiting the scope of the present invention. Methods for measuring various physical property values of resins are used in the 15 Examples and Comparative Examples are described below.
    <Measurement of the numerical mean molecular weight Mn and the mean molecular weight Mw>
    A numerical average molecular weight and a mass average molecular weight of a resin were measured by GPC 20 (gel permeation chromatography) as follows.
    First, a column was stabilized in a heat chamber at 40 ° C, and tetrahydrofuran (THE) as a solvent was drained on the column at temperature at a flow rate of 1 ml / min. Then, 50 pL to 200 pL of a THF sample solution of the resin having a sample concentration adjusted to 0.05 wt% to 0.6 wt% was injected, and a measurement was made. In the sample molecular weight measurement, the sample molecular weight distribution was calculated from a relationship between log values and a number of counts on a calibration curve created from various types of standard monodisperse polystyrene samples. Like standard polystyrene samples to create the calibration curve, those having a mass average molecular weight of 6 x 10 2 , 2.1 x 10 3 , 4 x 10 3 , 1.75 x 10 4 , 5.1 x 10 4 , 1, 1 x 10 5 , 3.9 x 10 5 , 8.6 x 10 5 , 2 x 10 6 , 4.48 x 10 6 , manufactured by Pressure Chemical Co. or manufactured by Tosoh Corporation, and at least about 10 samples of standard polystyrene were used. An IR (refractive index) detector was used for a detector.
    Glass transition temperature Tg>
    A glass transition temperature Tg of a resin was measured using a differential scanning calorimeter (DSC) (Q2000, manufactured by TA Instruments).
    First, 5 mg of a toner was sealed in a simple T-ZERO sealing pan, manufactured by TA Instruments, which was set in the device. With regard to measurement, under a stream of nitrogen, the toner was heated as a first heating from -20 ° C to 200 ° C at a heating rate of 10 ° C / min, maintained for 5 minutes, then cooled until -20 ° C at a cooling rate of 10 ° C / min, held for 5 minutes, and then heated as a second heat to 200 ° C at a heating rate of 10 ° C / min. In this way, thermal changes were measured.
    As the glass transition temperature Tg, a value obtained by a midpoint method in the device analysis programs that uses the graph of the first heating was used.
    (Example of Synthesis of Crystalline Resin 1)
    - Synthesis of Crystalline Resin 1 A four-necked 5 L flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer and a thermo coupler was loaded with sebacic acid and 1,4-butanediol such that a molar ratio of a hydroxyl group and a caboxyl group (OH / COOH) was 1.2. It was reacted at 180 ° C for 10 hours together with titanium tetraisopropoxide (500 ppm by mass with respect to the resin component). Then it was reacted for 3 hours at an elevated temperature of 200 ° C and further reacted for 2 hours at a pressure of 8.3 kPa. In this way, [Crystalline Resin 1] was obtained.
    The obtained [Crystalline Resin 1] had a mass average molecular weight of 15,000, an Mw / Mn of 3.0, a melting point of 62 ° C and a glass transition temperature of 55 ° C.
    [Crystalline Resin 1] was measured by an X-ray diffraction method (crystallinity analysis X-ray diffractometer, X'PERT MRD, manufactured by Philips) to determine whether crystallinity is present or absent. An endothermic peak was observed in a range of 20 ° C <2Θ <25 ° from a diffraction peak of a 10 diffraction spectrum obtained, and it was confirmed to have crystallinity.
    The measurement conditions of the ray diffraction method
    X are described below.
    [Measuring conditions]
    - Voltage kV: 45 kV
    - Current: 40 mA
    MPSS
    Higher
    Gonio
    - Scan mode: continuous
    - Starting angle: 3
    - Final angle: 35 °
    - Angle step: 0.02 °
    - Lucid-beam optics
    - Divergence gap: div gap 1/2
    - Diflexion beam optics
    - Anti-spatter gap: as fixed 1/2
    - Reception slot: Prog recording slot (Crystalline Resin Synthesis Example 2)
    - Synthesis of Crystalline Resin 2 -
    A four-necked 5 L flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer and a thermo coupler was charged with 10 terephthalic acid, 1.5 - pentanediol and 1.4 - butanediol such that a molar ratio (OH / COOH) of a hydroxyl group and a caboxyl group was 1.2; that an acid component was composed of 100 mol% of terephthalic acid, and that an alcohol component was composed of 50 mol% of 1,5-pentanediol and 15 50 mol% of 1,4-butanediol. It was reacted at 180 ° C for hours together with titanium tetraisopropoxide (500 ppm by mass with respect to the resin component). Then it was reacted for 3 hours at an elevated temperature of 200 ° C and further reacted for 2 hours at a pressure of 8.3 kPa. In this way, [Crystalline Resin 2] was obtained.
    The obtained [Crystalline Resin 2] had a mass average molecular weight of 12,000, an Mw / Mn of 4.0, a melting point of 69 ° C and a glass transition temperature of 58 ° C.
    A diffraction spectrum of [Crystalline Resin 2] was measured by an X-ray diffraction method in the same way as the crystalline resin of Synthesis Example 1, and an endothermic peak was observed in a range of 20 ° C <2Θ <25 .
    Thus, it was confirmed to have crystallinity.
    (Example of Synthesis of Crystalline Resin 3)
    - Synthesis of Crystalline Resin 3 A four-necked 5 L flask equipped with a nitrogen inlet tube, a dehydration tube, a 10 shaker and a thermo coupler was charged with terephthalic acid, 1,6-hexanediol and 1,4- butanediol such that a molar ratio (OH / COOH) of a hydroxyl group and a caboxyl group was 1.2; that an acid component was composed of 100 mol% of terephthalic acid, and that an alcohol component was composed of 50 mol% of 1,6-hexanediol and 50 mol% of 1,4-butanediol. It was reacted at 180 ° C for 10 hours together with titanium tetraisopropoxide (500 ppm by mass with respect to the resin component). Then it was reacted for 3 hours at an elevated temperature of 200 ° C and 20 additionally reacted for 2 hours at a pressure of 8.3 kPa. In this way, [Crystalline Resin 3] was obtained.
    The obtained [Crystalline Resin 3] had a mass average molecular weight of 13,000, a Mw / Mn of 4.2, a melting point of 84 ° C and a glass transition temperature of 52 ° C.
    A diffraction spectrum of [Crystalline Resin 3] was measured by an X-ray diffraction method in the same way as the crystalline resin of Synthesis Example 1, and an endothermic peak was observed in a range of 20 C <2Θ <25. Thus, it was confirmed to have crystallinity.
    (Example of Synthesis of Crystalline Resin 4)
    - Synthesis of Crystalline Resin 4 A four-necked 5 L flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer and a thermo coupler was loaded with adipic acid, 1,6-hexanediol and 1,4-butanediol such that a molar ratio (OH / COOH) of a hydroxyl group and a caboxyl group was 1.2; that an acid component was composed of 10 0 mol in terephthalic acid, and that an alcohol component was composed of 50 mol% of 1,6-hexanediol and 50 mol% of 1,4-butanediol. It was reacted at 180 ° C for 10 hours together with titanium tetraisopropoxide (500 ppm by mass with respect to the resin component). Then it was reacted for 3 hours at an elevated temperature of 200 ° C and further reacted for 2 hours at a pressure of 8.3 kPa. In this way, [Crystalline Resin 4] was obtained.
    The [Crystalline Resin 4] obtained had a mass average molecular weight of 14,000, an Mw / Mn of 3.5, a melting point of 49 ° C and a glass transition temperature of 42 C.
    A diffraction spectrum of [Crystalline Resin 4] was measured by an X-ray diffraction method in the same way as the crystalline resin of Synthesis Example 1, and an endothermic peak was observed in a range of 20 ° C <2Θ <25 . Thus, it was confirmed to have crystallinity.
    (Example of Synthesis of Crystalline Resin 5)
    - Synthesis of Crystalline Resin 5 A four-necked 5 L flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer and a thermo coupler was loaded with sebacic acid and 1,4-butanediol such that a molar ratio ( OH / COOH) of a hydroxyl group and a caboxyl group was 1.05. It was reacted at 180 ° C for 10 hours together with titanium tetraisopropoxide (500 ppm by mass with respect to the resin component). It was reacted for 5 hours at an elevated temperature of 200 ° C and additionally reacted for 4 hours at a pressure of 4.0 kPa. In this way, [Crystalline Resin 5] was obtained.
    The [Crystalline Resin 5] obtained had a mass average molecular weight of 30,000, an Mw / Mn of 2.0, a melting point of 65 ° C and a glass transition temperature of 57 C.
    A diffraction spectrum of [Crystalline Resin 5] was measured by an X-ray diffraction method in the same way as the crystalline resin in Synthesis Example 1, and a peak
    100 endothermic was observed in a range of 20 C <2Θ Thus, it was confirmed to have crystallinity.
    Table 1-1
    ---- Acid component Alcohol component Molar ratio(OH / COOH) Crystalline Resin 1 Sebaceous acid Sebaceous acid 1.4butanediol 1.2 Crystalline Resin 2 Terephthalic acid Terephthalic acid 1.4-butanediol 1.2 Crystalline Resin3 Terephthalic acid Terephthalic acid 1.4butanediol 1.2 Crystalline Resin 4 Adipic acid Adipic acid 1.4-butanediol 1.2 Crystalline Resin 5 Adipic acid Sebaceous acid 1.4butanediol 1.05 Crystalline Resin 6 PLACCEL H polycaprolactone, manufactured by Daicel Corporation
    Table 1-2
    Mass average molecular weight Mw Mw / Mn Point ofFusion Glass transition temperature Crystalline Resin 1 15,000 3.0 62 ° C 55 ° C Crystalline Resin 2 12,000 4.0 69 ° C 58 ° C Crystalline Resin 3 13,000 4.2 84 ° C 52 ° C Crystalline Resin 4 14,000 3.5 49 ° C 42 ° C Crystalline Resin 5 30,000 2.0 65 ° C 57 ° C Resin 10,000 3.0 60 ° C 52 ° C
    101
    Crystalline __________ L _ — __________________ : ____ L _____._____ J ------------— (Example of Synthesis of Non-crystalline Resin 1)
    - Synthesis of non-crystalline resin 1 A four-necked 5 L flask equipped with a nitrogen inlet tube, a dehydration tube, a shaker and a thermo coupler was loaded with 100 parts by mass of L-lactate and D-lactate with a molar ratio (L lactate: D-lactate) of 75:25. Along with 1 part by mass of ethylene glycol and 2-ethylhexanoate tin (200 ppm by mass with respect to the resin component) as a catalyst, it was reacted at 190 ° C for 4 hours. Then it was reacted at a reduced temperature of 170 ° C and a pressure of 8.3 kPa for 1 hour. In this way, [Non-Crystalline Resin 1] was obtained.
    A diffraction spectrum of [Non-Crystalline Resin 1] obtained was measured by the X-ray diffraction method in the same way as the crystalline resin of Synthesis Example 1, and a wide peak spread across an entire measurement area was observed. Thus, it was confirmed that it has no crystallinity.
    (Example of Synthesis of Non-crystalline Resin 2)
    - Synthesis of non-crystalline resin 2 A reactor equipped with a cooling tube, a stirrer and a nitrogen tube was charged with acid
    102 and propylene glycol terephthalic such that a molar ratio (OH / COOH) of a hydroxyl group to a carboxyl group was 1.3, with titanium tetraisopopóxido (PP 200 m by mass with respect to resin component). Then, it was reacted at 200 ° C for 4 hours and then heated for 2 hours at 230 ° C, and a reaction was carried out until there was no effluent water. The reaction continued at a reduced pressure of 10 mm Hg to 15 mm Hg for 5 hours. In this way, [Non-Crystalline Resin 2] was obtained.
    A diffraction spectrum of [Non-Crystalline Resin 2] obtained was measured by the X-ray diffraction method in the same way as the crystalline resin of Synthesis Example 1, and a wide peak spread across an entire measurement area was observed. Thus, it was confirmed that it has no crystallinity.
    (Example of Synthesis of Non-crystalline Resin 3)
    - Synthesis of non-crystalline resin 3 A four-necked 5 L flask equipped with a nitrogen inlet tube, a dehydration tube, a shaker and a thermo coupler was loaded with 100 parts by mass of L-lactate and D-lactate with a molar ratio (Llactate: D-lactate) of 90:10. Along with 5 parts by mass of adduct propylene oxide of 2 mol of bisphenol A and 2 tin ethylhexanoate (200 ppm by weight with respect to
    103 resin component) as a catalyst, it was reacted at 190 ° C for 6 hours and then reacted for 2 hours at a reduced temperature of 180 ° C and a pressure of 8.3 kPa. In this way, [Non-Crystalline Resin 3] was obtained.
    A diffraction spectrum of [Non-Crystalline Resin 3] obtained was measured by the X-ray diffraction method in the same way as the crystalline resin in Synthesis Example 1, and a wide peak spread across an entire measurement area was observed. Thus, it was confirmed that it has no crystallinity.
    (Example of Synthesis of Non-crystalline Resin 4)
    - Synthesis of non-crystalline resin 4 A four-necked 5 L flask equipped with a nitrogen inlet tube, a dehydration tube, a shaker and a thermo coupler was loaded with 100 parts by mass of L-lactate and D-lactate with a molar ratio (Llactate: D-lactate) of 90:10. Along with 1 part by mass of ethylene glycol and tin 2-ethylhexanoate (200 ppm by mass with respect to the resin component) as a catalyst, it was reacted at 190 ° C for 4 hours and then it was further reacted by 1 hour at a reduced temperature of 170 ° C and a pressure of 8.3 kPa. In this way, [Non-Crystalline Resin 4] was obtained.
    104
    A diffraction spectrum of [Non-Crystalline Resin 4] obtained was measured by the X-ray diffraction method in the same way as the crystalline resin of Synthesis Example 1, and a wide peak spread across an entire measurement area was observed. Thus, it was confirmed that it has no crystallinity.
    (Example of Synthesis of Non-crystalline Resin 5)
    - Synthesis of non-crystalline resin 5 A four-necked 5 L flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer and a thermo coupler was loaded with 100 parts by mass of L-lactate and D-lactate with a molar ratio (L lactate: D-lactate) of 70:30. Along with 5 parts by mass of hexanediol and tin 2-ethylhexanoate (200 ppm by mass with respect to the resin component) as a catalyst, it was reacted at 190 ° C for 4 hours and then it was reacted additionally for 1 hour at a reduced temperature of 170 ° C and a pressure of 8.3 kPa. In this way, [Non-Crystalline Resin 5] was obtained.
    A diffraction spectrum of [Non-Crystalline Resin 5] obtained was measured by the X-ray diffraction method in the same way as the crystalline resin in Synthesis Example 1, and a wide peak spread across an area of
    105 measurement was observed. Thus, it was confirmed that it has no crystallinity.
    (Example of Synthesis of Non-crystalline Resin 6)
    - Synthesis of non-crystalline resin 6 5 A four-necked 5 L flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer and a thermo coupler was loaded with 100 parts by mass of L-lactate and D-lactate with a molar ratio (Llactate: D-lactate) of 93: 7. Along with 0.5 part by mass 10 of ethylene glycol and tin 2-ethylhexanoate (200 ppm by mass with respect to the resin component) as a catalyst, it was reacted at 190 ° C for 6 hours and then it was additionally reacted for 2 hours at a reduced temperature of 180 ° C and a pressure of 8.3 kPa.
    In this way, [Non-Crystalline Resin 6] was obtained.
    A diffraction spectrum of [Non-Crystalline Resin 6] obtained was measured by the X-ray diffraction method in the same way as the crystalline resin in Synthesis Example 1, and a wide peak spread across an entire measurement area was observed. Thus, it was confirmed that it has no crystallinity.
    (Synthesis example of non-crystalline resin 7)
    - Synthesis of non-crystalline resin 7 106
    A four-necked flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer and a thermo coupler was loaded with: adduct ethylene oxide of 2 moles of bisphenol A; isophthalic acid, and adipic acid, with a molar ratio of adduct ethylene oxide of 2 moles of bisphenol A to adduct ethylene oxide of 2 moles of bisphenol A (adduct ethylene oxide of 2 moles of bisphenol A / oxide of adduct ethylene of 3 moles of bisphenol A) of 80/20, with a molar ratio of isophthalic acid to adipic acid (isophthalic acid / adipic acid) of 80/20 and a molar ratio (OH / COOH) of hydroxyl group for carboxyl group of 1.3. Together with titanium tetraisopropoxide (300 ppm by mass with respect to the resin component), it was reacted at normal pressure and at 230 ° C for 8 hours and then it was further reacted at a reduced pressure of 10 mm Hg to 15 mm of Hg for 4 hours. In this way, [Non-Crystalline Resin 7] was obtained.
    A diffraction spectrum of [Non-Crystalline Resin 7] obtained was measured by the X-ray diffraction method in the same way as the crystalline resin in Synthesis Example 1, and a wide peak spread across an entire measurement area was observed. Thus, it was confirmed that it has no crystallinity.
    107
    Table 2-1
    Acid component Amount of acidic component Alcohol component Quantity ofalcohol component (OH / COOH) Non-cristali resin 1 L-lactate(75) Dlacta to (25) 100 pieces in bulk Ethylene glycol1 part by mass Non-cristali resin in 2 Terephthalic acid CO Propylene glycol(1.3) Non-cristali resin in 3 L-lactate(90) Dlacta to (10) 100 pieces in bulk Propylene oxideadduct of 2 moles of bisphenol A5 parts in bulk Non-cristali resin at 4 L-lactate(90) Dlacta to (10) 100 pieces in bulk Ethylene glycol1 part by mass Non-cristali resin at 5 L-lactate(70) Placta to (30) 100 pieces in bulk Hexanodi ol5 parts in bulk Non-cristali resin at 6 L-lactate(93) Dlacta to(7) 100 pieces in bulk Ethylene glycol0.5 part by mass Non-cristali resin at 7 Isophthalic acid o Adipi acid COPO ofadduct of2 moles of bisphenol A Adduct EO of 2molesfrom bisfen ol A (1.3)
    Table 2-2
    Mass average molecular weight Mw Mw / Mn Glass transition temperature Tg Resin not 20,000 3.2 48 ° C
    108
    crystalline 1 Resin notcrystalline 2 7,000 3.5 62 ° C Resin notcrystalline 3 13,000 3.3 51 ° C Resin notcrystalline 4 22,000 2.8 53 ° C Resin notcrystalline 5 10,000 3.5 42 ° C Resin notcrystal clear 6 45,000 3.1 55 ° C Resin notcrystalline 7 8,000 3.2 58 ° C
    (Example of Synthesis of Resin E 1)
    - Synthesis of Resin E 1 A four-necked 5 L flask equipped with a nitrogen inlet tube, a dehydration tube, a 5 agitator and a thermo coupler was loaded with: 300 parts by mass of [Crystalline Resin 1]; 700 parts by mass of [Non-crystalline resin 1]; and 200 ppm by weight of titanium tetraisopropoxide as a catalyst. It was reacted at 180 ° C for 4 hours, and then it was reacted at a pressure of 8.3 kPa for 1 hour with its temperature reduced to 170 ° C. In this way, [Resin E 1] which has a crystalline portion C and a non-crystalline portion D in a molecule of it was obtained.
    (Example of Synthesis of Resin E 2)
    - Synthesis of Resin E 2 A four-necked 5 L flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer and a thermocouple was loaded with: 300 parts
    109 by mass of [Crystalline Resin 1]; 700 parts by mass of [Non-crystalline resin 2]; and 200 ppm by weight of titanium tetraisopropoxide as a catalyst. It was reacted at 180 ° C for 4 hours, and then it was reacted at a pressure of 8.3 kPa for 1 hour with its temperature reduced to 170 ° C. In this way, the [Resin E 2] which has a crystalline portion C and a non-crystalline portion D in a molecule of the same was obtained.
    (Example of Synthesis of Resin E 3)
    - Synthesis of E 3 Resin A four-necked 5 L flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer and a thermo coupler was loaded with: 300 parts by mass of [Crystalline Resin 2]; 700 parts by mass of 15 [Non-crystalline resin 1]; and 200 ppm by weight of titanium tetraisopropoxide as a catalyst. It was reacted at 180 ° C for 4 hours, and then it was reacted at a pressure of 8.3 kPa for 1 hour with its temperature reduced to 170 ° C. In this way, [Resin E 3] which has a crystalline portion C and a non-crystalline portion D in a molecule of the same was obtained.
    (Example of Synthesis of Resin E 4)
    - Synthesis of Resin E 4 110
    A four-necked 5 L flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer and a thermo coupler was loaded with: 300 parts by mass of [Crystalline Resin 1]; 700 parts by mass of 5 [Non-crystalline resin 3]; and 200 ppm by weight of titanium tetraisopropoxide as a catalyst. It was reacted at 180 ° C for 4 hours, and then it was reacted at a pressure of 8.3 kPa for 1 hour with its temperature reduced to 170 ° C. In this way, [Resin E 4] which has a crystalline portion C and a non-crystalline portion D in a molecule of the same was obtained.
    (Example of Synthesis of Resin E 5)
    - Synthesis of Resin E 5 A four-necked 5 L flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer and a thermo coupler was loaded with: 300 parts by mass of [Crystalline Resin 1]; 700 parts by mass of [Non-crystalline resin 4]; and 200 ppm by weight of titanium tetraisopropoxide as a catalyst. It was reacted at 180 ° C for 4 hours, and then it was reacted at a pressure of 8.3 kPa for 1 hour with its temperature reduced to 170 ° C. In this way, [Resin E 5] which has a crystalline portion C and a non-crystalline portion D in a molecule of the same was obtained.
    Ill (Example of Synthesis of Resin E 6)
    - Synthesis of Resin E 6 A four-necked 5 L flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer and a thermo coupler was loaded with: 300 parts by mass of [Crystalline Resin 1]; 700 parts by mass of [Non-crystalline resin 5]; and 200 ppm by weight of titanium tetraisopropoxide as a catalyst. It was reacted at 180 ° C for 4 hours, and then it was reacted at a pressure of 8.3 kPa for 1 hour with its temperature reduced to 170 ° C. In this way, [Resin E 6] which has a crystalline portion C and a non-crystalline portion D in a molecule of the same was obtained.
    (Example of Synthesis of Resin E 7)
    - Synthesis of Resin E 7 A four-necked 5 L flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer and a thermo coupler was loaded with: 300 parts by mass of [Crystalline Resin 1]; 700 parts by mass of 20 [Non-crystalline resin 6]; and 200 ppm by weight of titanium tetraisopropoxide as a catalyst. It was reacted at 180 ° C for 4 hours, and then it was reacted at a pressure of 8.3 kPa for 1 hour with its temperature reduced to 170 ° C. In this way, [Resin E 7] which has a
    112 crystalline portion C and a non-crystalline portion D in a molecule thereof were obtained.
    (Example of Synthesis of Resin E 8)
    - Synthesis of Resin E 8 A four-necked 5 L flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer and a thermo coupler was loaded with: 300 parts by weight of [Crystalline Resin 3]; 700 parts by mass of [Non-crystalline resin 1]; and 200 ppm by weight of titanium tetraisopropoxide as a catalyst. It was reacted at 180 ° C for 4 hours, and then it was reacted at a pressure of 8.3 kPa for 1 hour with its temperature reduced to 170 ° C. In this way, [Resin E 8] which has a crystalline portion C and a non-crystalline portion D in a molecule of the same was obtained.
    (Example of Synthesis of Resin E 9)
    - Synthesis of Resin E 9 A four-necked 5 L flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer and a thermo coupler was loaded with: 300 parts by mass of [Crystalline Resin 4]; 700 parts by mass of [Non-crystalline resin 1]; and 200 ppm by weight of titanium tetraisopropoxide as a catalyst. It was reacted at 180 ° C for 4 hours, and then it was reacted in a
    113 pressure of 8.3 kPa for 1 hour with its temperature reduced to 170 ° C. In this way, [Resin E 9] which has a crystalline portion C and a non-crystalline portion D in a molecule of the same was obtained.
    (Example of Synthesis of Resin E 10)
    - Synthesis of Resin E 10 A four-necked 5 L flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer and a thermo coupler was loaded with: 700 parts by mass of [Crystalline Resin 1]; 300 parts by mass of [Non-crystalline resin 1]; and 200 ppm by weight of titanium tetraisopropoxide as a catalyst. It was reacted at 180 ° C for 4 hours, and then it was reacted at a pressure of 8.3 kPa for 1 hour with its temperature reduced to 170 ° C. In this way, [Resin E 10] which has a crystalline portion C and a non-crystalline portion D in a molecule of the same was obtained.
    (Example of Synthesis of Resin E 11)
    - Synthesis of Resin E 11 A four-necked 5 L flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer and a thermo coupler was loaded with: 180 parts by mass of [Crystalline Resin 1]; 820 parts by mass of [Non-crystalline resin 1]; and 200 ppm by weight of
    114 titanium tetraisopropoxide as a catalyst. It was reacted at 180 ° C for 4 hours, and then it was reacted at a pressure of 8.3 kPa for 1 hour with its temperature reduced to 170 ° C. In this way, [Resin E 11] which has a crystalline portion C and a non-crystalline portion D in a molecule of the same was obtained.
    (Example of Synthesis of Resin E 12)
    - Synthesis of Resin E 12 A four-necked 5 L flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer and a thermo coupler was loaded with: 820 parts by mass of [Crystalline Resin 1]; 180 parts by mass of [Non-crystalline resin 1]; and 200 ppm by weight of titanium tetraisopropoxide as a catalyst. It was reacted at 180 ° C for 4 hours, and then it was reacted at a pressure of 8.3 kPa for 1 hour with its temperature reduced to 170 ° C. In this way, the [Resin E 12] which has a crystalline portion C and a non-crystalline portion D in a molecule of the same was obtained.
    Table 3-1
    Crystalline portion C Mixing amount Non-crystalline portion D Mixing amount Mass ratio C / D ResinE 1 Crystalline resin 1 300 pieces in bulk Non-crystalline resin 1 700 piecesin large scale 30/70
    115
    ResinE 2 Crystalline resin 1 300 piecesin large scale Non-crystalline resin 2 700 parts in bulk 30/70 ResinE 3 Crystalline resin 2 300 piecesin large scale Non-crystalline resin 1 700 parts in bulk 30/70 ResinE 4 Crystalline resin 1 300 piecesin large scale Non-crystalline resin 3 700 piecesin large scale 30/70 ResinE 5 Crystalline resin 1 300 pieces in bulk Non-crystalline resin 4 700 piecesin large scale 30/70 ResinE 6 Crystalline resin 1 300 pieces in bulk Non-crystalline resin 5 700 piecesin large scale 30/70 ResinE 7 Crystalline resin 1 300 piecesin large scale Non-crystalline resin6 700 parts in bulk 30/70 ResinE 8 Crystalline resin3 300 piecesin large scale Non-crystalline resin 1 700 piecesin large scale 30/70 ResinE 9 Crystalline resin 4 300 pieces in bulk Non-crystalline resin 1 700 piecesin large scale 30/70 ResinE 10 Crystalline resin 1 700 piecesin large scale Non-crystalline resin 1 300 piecesin large scale 70/30 ResinE 11 Crystalline resin 1 180 pieces in bulk Non-crystalline resin 1 820 pieces in bulk 18/82 ResinE 12 Crystalline resin 1 820 piecesin large scale Non-crystalline resin 1 180 pieces in bulk 82/18
    Table 3-2
    Mass average molecular weight Mw Mw / Mn Glass transition temperature Tg Resin E 1 25,000 2.3 42 ° C Resin E 2 15,000 2.8 44 ° C Resin E 3 28,000 2.5 42 ° C Resin E 4 23,000 2.9 46 ° C Resin E 5 28,000 2.7 48 ° C Resin E 6 16,000 3.1 35 ° C Resin E 7 48,000 2.8 53 ° C Resin E 8 26,000 3.1 44 ° C Resin E 9 25,000 2.8 40 ° C Resin E 10 18,000 2.5 4 6 ° C Resin E 11 26,000 2.4 41 ° C Resin E 12 17,000 2, 6 48 ° C
    116 (Example 1) <Preparing the toner>
    - Preparation of the masterbatch (MB) First, 1,200 parts by weight of water, 500 parts by weight of carbon black (PRINTEX 35, manufactured by Evonik Degussa Japan Co. Ltd., oil absorption DBP = 42 mL / 100 mg, pH = 9.5) and 500 parts by mass of [Non-crystalline resin 1] were added by the HENSCHEL mixer (manufactured by Nippon Coke & Engineering Co. Ltd.). Then, a mixture obtained was kneaded using two rollers at 150 C for 30 minutes, rolled for cooling and sprayed by a sprayer. In this way, [Masterbatch 1] was obtained.
    - Preparation of wax dispersion liquid
    A container equipped with a stirring rod and a thermometer was loaded with: 50 parts by weight of paraffin wax (hydrocarbon wax, HNP-9, manufactured by Nippon Seiro Co., Ltd., melting point = 75 ° C, SP value = 8.8) as [Release Agent]; and 450 parts by weight of ethyl acetate. It was heated to 80 ° C with stirring, maintained at 80 ° C for 5 hours and then cooled to 30 ° C for 1 hour. Using a bead mill (ULTRA VISCO MILL, manufactured by Aimex Co., Ltd.) packaged for 80% of the volume with 0.5 mm zirconia beads, it was dispersed by running 3 passes under the conditions of a
    117 1 kg / h liquid feed and a 6 m / min disk peripheral speed. In this way, [Wax Dispersion Liquid 1] was obtained.
    - Preparation of crystalline resin dispersion liquid A container equipped with a stirring rod and a thermometer was loaded with 50 parts by weight of [Crystalline Resin 1] and 450 parts by weight of ethyl acetate. It was heated to 80 ° C with stirring, maintained at 80 ° C for 5-10 hours and then cooled to 30 ° C for 1 hour. Using a bead mill (ULTRA VISCO MILL, manufactured by Aimex Co., Ltd.) packaged for 80% of the volume with 0.5 mm zirconia beads, it was dispersed by running 3 passes under the conditions of a feed rate of liquid of 1 kg / h and 15 a peripheral speed of a disk of 6 m / min. In this way, [Crystalline Resin Dispersion Liquid 1] (concentration of solid content of 10% by mass) was obtained.
    - Preparation of the oil phase 20 A container was loaded with: 500 parts by weight of [Wax Dispersion Liquid 1]; 1,000 pieces in bulk
    of [Dispersion Liquid in Crystalline Resin I]; 450 bulk parts of [Resin no crystalline 1]; 300 parts in mass of [Resin E 1]; and 100 pieces in pasta in
    118 [Masterbatch 1]. It was mixed using a TK HOMOMIXER (manufactured by Primix Corporation) at 10,000 rpm for 60 minutes. In this way, the [Oil Phase 1] was obtained.
    - Preparation of the aqueous phase -
    A milky liquid was obtained by mixing and stirring:
    990 parts by mass of water; 10 parts by weight of a 50% by weight aqueous solution of sodium dodecyl sulfate (manufactured by Tokyo Chemical Co. Ltd.); 5 parts by weight of sodium chloride (manufactured by Tokyo Chemical Co.
    Ltd.); and 100 parts by weight of ethyl acetate. This was considered to be [Ease Aqueous 1].
    - Emulsification and desolvation -
    To the container containing [Oil Phase 1], 1,200 parts by mass of [Aqueous Phase 1] were added. It was then mixed using a TK HOMOMIXER (manufactured by Primix Corporation) at a rotary speed of 13,000 rpm for 20 minutes. In this way, [Emulsified Fluid Paste 1] was obtained.
    [Emulsified Fluid Paste 1] was placed in a container equipped with a stirrer and a thermometer for desolvation at 30 ° C for 8 hours, followed by aging at 45 ° C for 4 hours. In this way, [Slurry 1] was obtained.
    - Washing and Drying -
    119
    After 100 parts by mass of [Slurry 1] were subjected to vacuum filtration, a filter cake was washed and dried as follows.
    (1) To the filter cake, 100 parts by mass of ion exchange water were added, which was mixed by TK HOMOMIXER (rotary speed of 12,000 rpm for 10 minutes) followed by filtration.
    (2) To the filter cake of (1), 100 parts by mass of a 10% by weight aqueous sodium hydroxide solution were added, which was mixed by TK HOMOMIXER (rotary speed of 12,000 rpm for 30 minutes) followed by filtration vacuum.
    (3) To the filter cake of (2), 100 parts by mass of 10% by weight hydrochloric acid were added, which was mixed by TK HOMOMIXER (rotary speed of 12,000 rpm for 10 minutes) followed by filtration.
    (4) To the filter cake of (3), 300 parts by mass of ion exchange water were added, which was mixed by TK HOMOMIXER (rotary speed of 12,000 rpm for 30 minutes) followed by filtration.
    The operations from (1) to (4) were repeated twice, and in this way, [Filter Cake 1] was obtained.
    [Filter cake 1] obtained was dried in a wind dryer at 45 ° C for 48 hours and sieved with a mesh that
    120 has openings of 75 pm. In this way, the [Toner 1] of Example 1 was obtained.
    (Example 2)
    - Toner preparation -
    The [Toner 2] of Example 2 was obtained in the same way as in Example 1 except that [Non-crystalline resin 1] and [Resin E 1] in Example 1 were changed to [Non-crystalline resin 2] and [Resin And 2], respectively.
    (Example 3)
    - Preparation of toner The [Toner 3] of Example 3 was obtained in the same way as in Example 1 except that [Non-crystalline resin 1] and [Resin E 1] in Example 1 were changed to [Non-crystalline resin 2] and [Resin E 3], respectively.
    (Example 4)
    - Toner preparation -
    The [Toner 4] of Example 4 was obtained in the same way as in Example 1 except that [Non-crystalline Resin 1] and [Resin E 1] in Example 1 were changed to [Non-crystalline Resin 3] and [ Resin E 4], respectively.
    (Example 5)
    - Toner preparation -
    The [Toner 5] of Example 5 was obtained in the same way as in Example 1 except that the amount of mixing of the
    121 materials in the Preparation of the oil phase in Example 1 were changed as follows.
    - Preparation of the oil phase A container was loaded with: 500 parts by weight of [Wax Dispersion Liquid 1]; 3,000 parts by mass of [Crystalline Resin Dispersion Liquid 1]; 450
    parts en masse [Resin not crystalline 1]; 100 parts in pasta of [Resin AND 1] ; and 100 pieces in pasta of [Masterbatch 1]. Was mixed using a TK HOMOMIXER
    (manufactured by Primix Corporation) at 10,000 rpm for 60 minutes. In this way, the [Oil Phase 5] was obtained.
    (Example 6)
    - Toner preparation - [Toner 6] from Example 6 was obtained in the same way as in Example 1 except that the amount of mixing of the materials in the Preparation of the oil phase in Example 1 was changed as follows.
    - Preparation of the oil phase -
    One container was loaded with: 500 parts by weight of [Wax Dispersion Liquid 1]; 500 parts by mass of [Crystalline Resin Dispersion Liquid 1]; 600 parts by mass of [Non-crystalline resin 1]; 100 parts by mass of [El Resin]; and 100 parts by mass of [Masterbatch 1]. It was mixed using a TK HOMOMIXER (manufactured by Primix
    122
    Corporation) at 10,000 rpm for 60 minutes. In this way, the [Oil Phase 6] was obtained.
    (Example 7)
    - Preparation of toner 5 The [Toner 7] of Example 7 was obtained in the same way as in Example 1 except that [Non-crystalline resin 1] and [Resin E 1] in Example 1 were changed to [Non-crystalline resin 4 ] and [Resin E 5], respectively.
    (Example 8)
    - Preparation of toner 0 [Toner 8] of Example 6 was obtained in the same manner as in Example 1 except that [Crystalline Resin Dispersion Liquid 5] (10% mass concentration of solid content) was prepared with [Crystalline Resin 1] in Example 15 replaced by [Crystalline Resin 5] and that the amount of mixing of the materials in the Preparation of the oil phase in Example 1 was changed as follows.
    - Preparation of the oil phase A container was loaded with: 500 parts by weight of [Wax Dispersion Liquid 1]; 5,500 parts by mass of [Crystalline Resin Dispersion Liquid 5]; 200 parts by mass of [Non-crystalline resin 1]; 100 parts by mass of [Resin E 1]; and 100 parts by mass of [Masterbatch 1]. It was mixed using a TK HOMOMIXER
    123 (manufactured by Primix Corporation) at 10,000 rpm for 60 minutes. In this way, [Oil Phase 8] was obtained.
    (Example 9)
    - Toner preparation - [Toner 9] from Example 9 was obtained in the same manner as in Example 1 except that the amount of mixing of the materials in the Preparation of the oil phase in Example 1 was changed as follows.
    - Preparation of the oil phase -
    One container was loaded with: 500 parts by weight of [Wax Dispersion Liquid 1]; 700 parts by mass of [Crystalline Resin Dispersion Liquid 1]; 450 parts by mass of [Non-crystalline resin 1]; 330 parts by mass of [Resin E 1]; and 100 parts by mass of [Masterbatch 1]. It was mixed using a TK HOMOMIXER (manufactured by Primix Corporation) at 10,000 rpm for 60 minutes. In this way, [Oil Phase 9] was obtained.
    (Example 10)
    - Toner preparation -
    The [Toner 10] of Example 10 was obtained in the same manner as in Example 1 except that the amount of mixing of the materials in the Preparation of the oil phase in Example 1 was changed as follows.
    - Preparation of the oil phase -
    124
    One container was loaded with: 500 parts by weight of [Wax Dispersion Liquid 1]; 1,200 parts by mass of [Crystalline Resin Dispersion Liquid 1]; 450
    parts en masse [Resin not crystalline 1]; 280 parts in 5 mass of [Resin AND 1]; and 100 pieces in pasta of [Masterbatch 1]. Was mixed using a TK HOMOMIXER
    (manufactured by Primix Corporation) at 10,000 rpm for 60 minutes. In this way, the [Oil Phase 10] was obtained.
    (Example 11)
    - Preparation of toner The [Toner 11] of Example 11 was obtained in the same way as in Example 1 except that [Non-crystalline resin 1] and [Resin E 1] in Example 1 were changed to [Non-crystalline resin 7] and [Resin E 2], respectively.
    (Example 12)
    - Toner preparation -
    The [Toner 12] of Example 12 was obtained in the same way as in Example 1 except that [Resin E 1] in Example 1 was replaced by [Resin E 10] and the amount of mixture of materials in the Preparation of the oil phase in Example 1 was changed as follows.
    - Preparation of the oil phase -
    One container was loaded with: 500 parts by weight of [Wax Dispersion Liquid 1]; 1,000 pieces in bulk
    125 of [Crystalline Resin Dispersion Liquid 1]; 600 parts by mass of [Non-crystalline resin 1]; 150 parts by mass of [Resin E 10]; and 100 parts by mass of [Masterbatch 1]. It was mixed using a TK HOMOMIXER (manufactured by Primix Corporation) at 10,000 rpm for 60 minutes. In this way, the [Oil Phase 12] was obtained.
    (Example 13)
    - Toner preparation -
    The [Toner 13] in Example 13 was obtained in the same way as in Example 1 except that [E1 Resin] in Example 1 was replaced by [E1 Resin] and the amount of mixing of the materials in the Preparation of the oil phase in Example 1 has been changed as follows.
    - Preparation of the oil phase -
    One container was loaded with: 500 parts by weight of [Wax Dispersion Liquid 1]; 800 parts by mass of [Crystalline Resin Dispersion Liquid 1]; 370 parts by mass of [Non-crystalline resin 1]; 400 parts by mass of [Resin E 11]; and 100 parts by mass of [Masterbatch 1]. It was mixed using a TK HOMOMIXER (manufactured by Primix Corporation) at 10,000 rpm for 60 minutes. In this way, [Oil Phase 13] was obtained.
    (Example 14)
    - Preparation of toner 126 [Toner 14] of Example 14 was obtained in the same way as in Example 1 except that [Resin E 1] in Example 1 was replaced by [Resin E 12] and that the amount of mixing of the materials in Preparation of the oil phase in Example 5 was changed as follows.
    - Preparation of the oil phase -
    One container was loaded with: 500 parts by weight of [Wax Dispersion Liquid 1]; 1,000 parts by mass of [Crystalline Resin Dispersion Liquid 1]; 620 parts by mass of [Non-crystalline resin 1]; 130 parts by mass of [Resin E 12]; and 100 parts by mass of [Masterbatch 1]. It was mixed using a TK HOMOMIXER (manufactured by Primix Corporation) at 10,000 rpm for 60 minutes. In this way, the [Oil Phase 14] was obtained.
    (Example 15)
    - Toner preparation - [Toner 15] from Example 15 was obtained in the same way as in Example 1 except that [Resin E 1] in Example 1 was replaced by [Resin E 2].
    (Example 16)
    - Toner preparation -
    The [Toner 16] in Example 16 was obtained in the same way as in Example 1 except that the amount of mixing of the
    127 materials in the Preparation of the oil phase in Example 1 were changed as follows.
    - Preparation of the oil phase A container was loaded with: 500 parts by weight of [Wax Dispersion Liquid 1]; 500 parts by mass of [Crystalline Resin Dispersion Liquid 1]; 400 parts by mass of [Non-crystalline resin 1]; 400 parts by mass of [El Resin]; and 100 parts by mass of [Masterbatch 1]. It was mixed using a TK HOMOMIXER (manufactured by Primix Corporation) at 10,000 rpm for 60 minutes. In this way, the [Oil Phase 16] was obtained.
    (Example 17)
    - Preparation of toner - [Toner 17] of Example 17 was obtained in the same manner as in Example 1 except that the amount of mixing of the materials in the Preparation of the oil phase in Example 1 was changed as follows.
    - Preparation of the oil phase -
    One container was loaded with: 500 parts by weight of [Wax Dispersion Liquid 1]; 1,500 parts by weight of [Crystalline Resin Dispersion Liquid 1], 100 parts by weight of [Non-crystalline Resin 1], 600 parts by weight of [Resin E 1]; and 100 parts by mass of [Masterbatch 1]. It was mixed using a TK HOMOMIXER
    128 (manufactured by Primix Corporation) at 10,000 rpm for 60 minutes. In this way, [Oil Phase 17] was obtained.
    (Comparative Example 1)
    - Toner preparation -
    The [Toner 18] of Comparative Example 1 was obtained in the same manner as in Example 1 except that the amount of mixing of the materials in the Preparation of the oil phase in Example 1 was changed as follows.
    - Preparation of the oil phase -
    One container was loaded with: 500 parts by weight of [Wax Dispersion Liquid 1]; 2,000 parts by mass of [Crystalline Resin Dispersion Liquid 1]; 650 parts by mass of [Non-crystalline resin 1]; and 100 parts by mass of [Masterbatch 1]. It was mixed using a TK
    HOMOMIXER (manufactured by Primix Corporation) at 10,000 rpm for 60 minutes. In this way, [Oil Phase 18] was obtained.
    (Comparative Example 2)
    - Toner preparation -
    The [Toner 19] of Comparative Example 2 was obtained in the same way as in Example 1 except that [Non-crystalline resin 1] and [Resin E 1] in Example 1 were replaced by [Non-crystalline resin 5] and [Resin
    And 6], respectively.
    (Comparative Example 3)
    129
    - Toner preparation - [Toner 20] from Comparative Example 3 was obtained in the same way as in Example 1 except that [Non-crystalline resin 1] and [Resin E 1] in Example 1 were replaced by [Non-crystalline resin 6] and [Resin
    And 7], respectively.
    (Comparative Example 4)
    - Toner preparation -
    The [Toner 21] of Comparative Example 4 was obtained in the same way as in Example 1 except that [Non-crystalline resin 1] and [Resin E 1] in Example 1 were replaced by [Non-crystalline resin 3] and [Resin
    And 8], respectively.
    (Comparative Example 5)
    - Toner preparation -
    The [Toner 22] of Comparative Example 5 was obtained in the same way as in Example 1 except that [Crystalline Resin 1] and [Resin E 1] in Example 1 were replaced by [Crystalline Resin 4] and [Resin E 9 ], respectively.
    (Comparative Example 6)
    - Toner preparation -
    The [Toner 23] of Comparative Example 6 was obtained in the same way as in Example 1 except that [Resin
    130 crystalline 1] and [Non-crystalline resin 1] in Example 1 were replaced by [Crystalline resin 6] (polycaprolactone, PLACCEL H, manufactured by Daicel Corporation, highly crystalline aliphatic polyester resin 5) and [Non-crystalline resin 7] , respectively.
    (Comparative Example 7)
    - Toner preparation -
    The [Toner 24] of Comparative Example 7 was obtained in the same way as in Example 1 except that the amount of mixing of the materials in the Preparation of the oil phase in Example 1 was changed as follows.
    - Preparation of the oil phase -
    One container was loaded with: 500 parts by weight 15 of [Wax Dispersion Liquid 1]; 650 parts by mass of [Non-Crystalline Resin 1]; 200 parts by mass of [Resin E 1]; and 100 parts by mass of [Masterbatch 1]. It was mixed using a TK HOMOMIXER (manufactured by Primix Corporation) at 10,000 rpm for 60 minutes. In this way, the [Oil Phase 19] 20 was obtained.
    (Comparative Example 8)
    - Toner preparation The [Toner 25] of Comparative Example 8 was obtained in the same way as in Example 1 except that the amount of
    131 mixture of materials in the Preparation of the oil phase in
    Example 1 was changed as follows.
    - Preparation of the oil phase A container was loaded with: 500 parts by weight of [Wax Dispersion Liquid 1]; 3,000 parts by mass of [Crystalline Resin Dispersion Liquid 1]; 600 parts by mass of [El Resin]; and 50 parts by mass of carbon black (PRINTEX35, manufactured by Evonik Degussa
    Japan Co. Ltd. DBP oil absorption = 42 mL / 100 mg, pH = 10 9.5). It was mixed using a TK HOMOMIXER (manufactured by
    Primix Corporation) at 10,000 rpm for 60 minutes. In this way, the [Oil Phase 20] was obtained.
    (Comparative Example 9)
    - Preparation of toner - the [Toner 26] of Comparative Example 9 was obtained in the same way as in Example 1 except that the amount of mixing of the materials in the Preparation of the oil phase in Example 1 was changed as follows.
    - Preparation of the oil phase -
    One container was loaded with: 500 parts by weight of [Wax Dispersion Liquid 1]; 900 parts by mass of [Resin E 1]; and 50 parts by mass of carbon black (PRINTEX35, manufactured by Evonik Degussa Japan Co. Ltd. oil absorption DBP = 42 mL / 100 mg, pH = 9.5). Was
    132 mixed using a TK HOMOMIXER (manufactured by Primix Corporation) at 10,000 rpm for 60 minutes. In this way, the [Oil Phase 21] was obtained.
    Then, for each of the toners obtained, a glass transition temperature Tg of the toner, an endothermic peak temperature mp of the toner, a Q2 / Q1 ratio of an endothermic quantity Ql in the first DSC heating to an endothermic quantity Q2 in the second heating of DSC by melting a crystalline portion (crystalline resin A and crystalline portion C of resin E) in the toner, an amount of compressive deformation TMA of the toner, and a relative crystallinity of the toner were measured as follows. The results were shown in Table 4.
    <Measurements of the glass transition temperature Tg of the toner, endothermic peak temperature mp of the toner and endothermic quantities (Ql, Q2)>
    A measuring object is stored in an isothermal environment having a temperature of 45 C and a humidity of 20 20% relative humidity or less for 24 hours in order to have constant initial conditions of the crystalline portion and the non-crystalline portion. It is then stored at a temperature of 23 ° C or less, and Tg, mp, Ql and Q2 are measured within 24 hours. For this operation, an effect of
    133 thermal history in a high temperature storage environment can be reduced, and the condition of the crystalline portion and the non-crystalline portion of the toner can be uniformized.
    First, 5 mg of a particulate toner are sealed in a simple T-ZERO sealing pan, manufactured by TA Instruments, and a measurement is made using a differential scanning calorimeter (DSC) (manufactured by TA
    Instruments, Q2000). With respect to measurement, under a stream of nitrogen, the toner is heated as a first heating from -20 ° C to 200 ° C at a heating rate of 10 ° C / min, maintained for 5 minutes, then heated to -20 ° C at a cooling rate of 10 ° C / min, held for 5 minutes, and then heated as a 15 second heat to 200 ° C at a heating rate of 10 ° C / min. Thermal changes are measured, and graphs of endothermic quantity - exothermic and temperature are created. A temperature at a characteristic tipping point at this point is defined as the glass transition temperature Tg.
    Like the glass transition temperature Tg, a value obtained by a midpoint method in the device analysis programs that uses the graph of the first heating can be used.
    134
    Furthermore, the endothermic peak temperature mp can be calculated as a maximum peak temperature using a device analysis program that uses the first heating graph.
    In addition, Q1 can be calculated as a quantity of heat of fusion of the crystalline component that uses a device analysis program that uses the graph of the first heating.
    In addition, Q2 can be calculated as a quantity of heat of fusion of the crystalline component that uses an analysis program of the apparatus that uses the second heating.
    <Amount of compressive strain TMA>
    The amount of compressive strain TMA was measured using 0.5 g of the toner formed in a tablet by a tablet molding machine (manufactured by Shimadzu Corporation) that has a diameter of 3 mm with a thermomechanical measuring device ( EXSTAR7000, manufactured by SII NanoTechnology Inc.). The tablet is heated at 2 ° C / min from 0 C to 180 C under a stream of nitrogen, and the measurement is performed in a compressed module. A compressive force at this point is 100 mN. The amount of compressive strain at 50 C is read from a graph obtained from a temperature of
    135 sample and a compression displacement (strain rate), and this value is referred to as the amount of compressive strain TMA.
    <Measurement of toner crystallinity by the X-ray diffraction method>
    A crystallinity of the toner by an X-ray diffraction method was measured using a crystallinity analysis X-ray diffractometer (X'PERT MRD, manufactured by Philips).
    First, the toner as a target sample is ground by a pestle to prepare a sample powder, and the sample powder obtained is applied evenly to a sample fixer. Next, the sample fixator is defined in the crystalline analysis X-ray diffractometer, and a measurement was made to obtain the diffraction spectrum.
    Among the diffraction peaks obtained, a peak in a range of 20 ° <2Θ <25 ° is considered to be an endothermic peak derived from the crystalline portion. In addition, a wide peak well spread across the measurement area is considered to be a component derived from the non-crystalline portion. For each peak, an integrated area of the diffraction spectrum for which a background is subtracted and calculated.
    An area value derived from the crystalline portion is considered to be Sc, and an area value derived from the crystalline portion
    136 non-crystalline is considered as Sa. From Sc / Sa, the relative crystallinity can be calculated.
    The measurement conditions of the ray diffraction method
    X are as follows.
    [Measuring conditions]
    - Voltage kV: 45 kV
    - Current: 40 mA
    MPSS
    Higher
    Gonio
    - Scan mode: continuous
    - Starting angle: 3
    - Final angle: 35 °
    - Angle step: 0.02 °
    - Lucid-beam optics
    - Divergence gap: div gap 1/2
    - Diflexion beam optics
    - Anti-spatter gap: as fixed 1/2
    - Reception slot: prog recording slot (Developer preparation)
    - Carrier preparation -
    To 100 parts by mass of toluene, 100 parts by mass of silicone resin (direct organo silicone, manufactured by Shin-Etsu Chemical Co., Ltd.), 5 parts by mass of γ
    137 (2-aminoethyl) aminopropyltrimethoxysilane and 10 parts by weight of carbon black were added. They were dispersed by a homomixer for 20 minutes, and in this way, a resin layer coating solution was prepared.
    Next, the [Carrier] was prepared by applying a resin layer coating solution to a surface of 1,000 parts by mass of spherical magnetite having a particle diameter of 50 10 pm using a bed-type coating device fluidized.
    - Preparation of the developer The [Developers] were prepared by 5 parts by weight of the [Toners] and were respectively mixed with 15 95 parts by weight of [Carrier] using a spherical mill.
    Then, using the [Toners] and [Developers] thus prepared, several properties were evaluated as follows. The results are shown in Table 4.
    2Q <Low temperature fastening property and high temperature resistant property>
    Using a refurbished imaging device that a copy machine fixture unit (MF2200, manufactured by Ricoh Company, Ltd.) that uses a
    138
    TEFLON (trademark) as a fixing roller has been refurbished so that a temperature of the fixing roller can be varied, a copy test was performed on TYPE 6200 paper (manufactured by Ricoh Company, Ltd.).
    By varying the temperature of the clamping roller, a travel temperature at low temperature (minimum holding temperature) and a travel temperature at high temperature (maximum holding temperature) were obtained under the following evaluation conditions, and based on The following criteria, a low temperature fixation property and a high temperature resistant property were evaluated. Specifically, a low temperature shift and a high temperature shift were determined visually by confirming whether or not an image shifted in one location a rotation in front of the fixation roller from a fixed image portion on the paper. It was not considered good (NG) when the displacement of an image was confirmed. A lower temperature at which no low temperature displacement occurred was defined as the minimum holding temperature, and a higher temperature at which no high temperature displacement occurred was defined as the maximum holding temperature.
    139
    As conditions for assessing the minimum fixing temperature, a linear paper feed speed was 120 mm / sec to 150 mm / sec, a surface pressure was 1.2 kgf / cm 2 , and a narrowing width was 3 mm .
    As conditions for assessing the minimum fixing temperature, a linear paper feed speed was 50 mm / sec, the surface pressure was 2.0 kgf / cm 2 , and a narrowing width was 4.5 mm.
    [Criteria for evaluating the fixation property at 10 low temperature]
    A: The minimum fixing temperature was 105 ° C or less.
    B: The minimum fixing temperature exceeded 105 ° C and was less than 115 ° C.
    F: The minimum fixing temperature has exceeded 115 ° C.
    [Criteria for assessing the high temperature fastening property]
    A: The minimum fixing temperature was 165 ° C or more.
    B: The minimum fixing temperature exceeded 150 ° C and was less than 165 ° C.
    F: The maximum fixing temperature was less than
    150 ° C.
    <Heat-resistant storage stability>
    A 50 mL glass container was filled with each toner, and it was placed in a thermostatic bath at
    140
    50 ° C and left per 20 hours. THE follow, the toner was cold up until an temperatureenvironment (25 ° C). an penetration (mm) was measure of a deal with a test in penetration (JIS K2235-1991), and the stability in
    heat resistant storage was assessed based on the following criteria. Here, a high penetration value indicates superior heat-resistant storage stability of the toner.
    [Rating criteria]
    AA: The penetration was 20 mm or more.
    THE: THE penetration was in 15 mm or more and less of what 20 mm. B: THE penetration was in 10 mm or more and less of what 15 mm. 15 F: THE penetration was smaller of than 10 mm.
    <Film Formation>
    Using an image forming device (MF2800, manufactured by Ricoh Company, Ltd.), a test chart that includes solid portions, semitone portions, thick lines, 20 and the like was printed. After printing on 10,000 sheets and 100,000 sheets, a surface of the photoconductor was visually observed, and whether or not toner (mainly the release agent) adhered to the photoconductor was evaluated based on the following criteria.
    141
    After printing on 10,000 sheets and 100,000 sheets, whether abnormal images or not such as uneven image and image that disintegrates in the solid portions and semitone portions of images, and whether or not abnormal images such as voids 5 in thick lines and lines were assessed based on the following criteria.
    [Rating criteria]
    AA: Toner adhesion to the photoconductor has not been confirmed after printing 100,000 sheets.
    A: Toner adhesion to the photoconductor has not been confirmed after printing 10,000 sheets. The adhesion of toner to the photoconductor was confirmed after printing 100,000 sheets, but it was not a level that the abnormality was observed in the images.
    B: The adhesion of toner to the photoconductor was confirmed after printing 10,000 sheets, but it was not a level that the abnormality was observed in the images. The adhesion of toner to the photoconductor was confirmed after printing 100,000 sheets, and it was at a level that the abnormality was observed 20 in the images.
    F: The adhesion of toner to the photoconductor was confirmed after printing 10,000 sheets, and it was at a level that the abnormality was seen in the images.
    Table 4-1
    142
    Example 1 Example 2 Example 3 Example 4 Example 5 Crystalline resin A No. 1 1 2 1 1 Non-crystalline resin B No. 1 2 1 3 1 Resin And Resin EAt the. El E2 E3 E4 El Crystalline portion C No. 1 1 2 1 1 Non-crystalline portionD No. 1 2 1 3 1 Reason formass (C / D) 0.43 0.43 0.43 0.43 0.43 Crystalline resin content A (mass%) 10 10 10 10 30 Non-crystalline resin B content (% by mass) 50 50 50 50 50 E resin content (% by mass) 30 30 30 30 10 Crystalline C content (% by mass) 9.0 9.0 9.0 9.0 3.0 Crystalline portion content D (% by mass) 21.0 21.0 21.0 21.0 7.0 Mass ratio (A / C) 1.1 1, 1 1.1 1.1 10.0 Mass ratio (B / D) 2.4 2.4 2.4 2.4 7.1 Glass transition temperature Tg (° C) of toner 35 33 38 37 34 Peak endothermic temperature mp (° C) of toner 60 57 68 59 60 Endothermic quantity Ql of the crystalline portion (crystalline resin A and crystalline portion C) in the toner (J / g) 30 15 15 25 50 Endothermic quantity Q2 of the crystalline portion (crystalline resin A and crystalline portion C) in the toner (J / g) 3 2 4 8 10 Q2 / Q1 ratio 0.10 0.13 0.27 0.32 0.20 Amount of compressive form TMA 2 3 4 3 3
    143
    toner (%)Relative crystallinity of toner (%) 38 28 16 27 52 Low temperature fastening property Temperatureminimum fixation(° C) 100 105 110 110 105 Evaluation THE THE B B THE High-resistant displacement propertytemperature Temperaturemaximum fixation(° C) 180 170 180 170 160 Evaluation THE THE THE THE B Stability ofheat resistant storage AA THE THE AA AA Film formation AA THE ΆΆ THE THE
    Table 4-2
    Example 6 Example 7 Example 8 Example 9 Example 10 Crystalline resin A No. 1 1 5 1 1 Non-crystalline resin B No. 1 4 1 1 1 Resin E Resin EAt the. El E5 El El El Crystalline portion C No. 1 1 1 1 1Non-crystalline portion D No. 1 4 1 1 1 Reason formass (C / D) 0.43 0.43 0.43 0.43 0.43 Crystalline resin content A (mass%) 5 10 55 7 12 Non-crystalline resin B content (% by mass) 65 50 25 50 50 E resin content (% by mass) 10 30 10 33 28 Crystalline C content (% by mass) 3.0 9.0 3.0 9.9 8.4 Crystalline D content (% in 7.0 21.0 7.0 23, 1 19.6
    144
    pasta)Mass ratio (A / C) 1.7 1.1 18.3 0.7 1.4 Mass ratio (B / D) 0, 9 2.4 3, 6 2.2 2.6 Glass transition temperature Tg (° C) of toner 36 42 28 34 36 Peak endothermic temperature mp (° C) of toner 58 58 62 60 60 Endothermic quantity Ql of the crystalline portion (crystalline resin A and crystalline portion C) in the toner (J / g) 10 27 80 20 35 Endothermic quantity Q2 of the crystalline portion (crystalline resin A and crystalline portion C) in the toner (J / g) 2 3 50 2 5 Q2 / Q1 ratio 0.20 0.11 0.63 0.10 0.14 TMA amount of compressive deformation of toner (%) 3 2 3 4 2 Relative crystallinity of toner (%) 8 29 65 28 42 Low temperature fastening property Temperatureminimum fixation(° C) 110 110 105 105 105 Evaluation B B THE THE THE High-resistant displacement propertytemperature Temperaturemaximum fixation(° C) 180 180 170 180 170 Evaluation THE THE THE THE THE Stability ofheat resistant storage THE AA THE THE ΆΆ Film formation AA AA THE AA THE
    Table 4-3
    Example11 Example12 Example13 Example14 Crystalline resin A No. 1 1 1 1 Non-crystalline resin B No. 7 1 1 1 E resin | Resin E No. E2 E10 Eli E12
    145
    Crystalline portion C No. 1 1 1 1Non-crystalline portion D No. 2 1 1 1 Reason formass (C / D) 0.43 2.3 0.22 4.6 Crystalline resin content A (mass%) 10 10 8 10 Non-crystalline resin B content (% by mass) 50 65 42 67 E resin content (% by mass) 30 15 40 13 Crystalline C content (% by mass) 9, 0 10.5 7.2 10.7 Crystalline portion content D (% by mass) 21.0 4.5 32.8 2.3 Mass ratio (A / C) 1.1 1.0 1.1 0, 9 Mass ratio (B / D) 2.4 14.4 1.3 28.6 Glass transition temperature Tg (° C) of toner 35 35 33 35 Peak endothermic temperature mp (° C) of toner 60 60 60 60 Endothermic quantityQ1 of the crystalline portion (crystalline resin A and crystalline portion C) in the toner (J / g) 30 35 25 40 Endothermic quantityQ2 of the crystalline portion (crystalline resin A and crystalline portion C) in the toner (J / g) 3 3 2 3 Q2 / Q1 ratio 0.10 0.09 0, 08 0.08 TMA amount of compressive deformation of toner (%) 3 2 3 2 Relative crystallinity of toner (%) 35 40 25 44 Fixing propertylowtemperature Minimum fixing temperature (° C) 105 100 105 105 Evaluation THE THE THE THE Property Temperature 175 180 180 170
    146
    high temperature resistant displacement maximum fixing (° C) Evaluation THE THE THE THE Heat-resistant storage stability THE AA THE AA Film formation THE AA ΆΆ THE
    Table 4-4
    Example15 Example16 Example17 Crystalline resin A No. 1 1 1 Non-crystalline resin B No. 1 1 1 Resin E Resin E No. E2 El El Crystalline portion C No. 1 1 1Non-crystalline portion D No. 2 1 1 Reason formass (C / D) 0.43 0.43 0.43 Crystalline resin content A (mass%) 10 5 15 Non-crystalline resin B content (% by mass) 50 45 15 E resin content (% by mass) 30 40 60 Crystalline C content (% by mass) 9.0 12.0 18.0 Crystalline D content (% by mass) 21.0 28.0 42.0 Mass ratio (A / C) 0.9 0.4 0.8 Mass ratio (B / D) 2.4 0.7 0.4 Glass transition temperature Tg (° C) of toner 38 34 36 Peak endothermic temperature mp (° C) of toner 61 59 61 Endothermic quantityQ1 of the crystalline portion (crystalline resin A and crystalline portion C) in 27 25 45
    147
    toner (J / g) Endothermic quantityQ2 of the crystalline portion (crystalline resin A and crystalline portion C) in the toner (J / g) 3 2 5 Q2 / Q1 ratio 0.11 0.08 0.11 TMA amount of compressive deformation of toner (%) 4 4 3 Relative crystallinity of toner (%) 33 28 46 Down fastening propertytemperature Minimum fixing temperature (° C) 105 110 105 Evaluation THE B THE High temperature resistant displacement property Maximum fixing temperature (° C) 170 180 170 Evaluation THE THE THE Heat-resistant storage stability THE THE THE Film formation THE AA THE
    Table 4-5
    ExampleComparative 1 ExampleComparative 2 Comparative Example 3 Comparative Example 4 ExampleComparative 5 Crystalline resin A No. 1 1 1 3 4 Resin notcrystalline B No. 1 5 6 1 1 ResinAND Resin EAt the. - E6 E7 E8 E9 Crystalline portion at C No. - 1 1 3 4Non-crystalline portion at D No.5 6 1 1 Mass ratio(CD) - 0.43 0.43 0.43 0.43 Crystalline resin content A (% by | mass) 20 10 10 10 10
    148
    Non-crystalline resin B content (% by mass) 70 50 50 50 50 Resin contentE (% by mass) 0 30 30 30 30 Crystalline C content (% by mass) 0.0 9.0 9.0 9, 0 9, 0 Crystalline portion content D (% by mass) 0.0 21.0 21.0 21.0 21.0 Mass ratio(B.C) - 1.1 1, 1 1.1 1.1 Mass ratio (B / D)2.4 2.4 2.4 2.4 Glass transition temperature Tg (° C) of toner 38 18 52 36 34 Peak endothermic temperature mp (° C) of toner 58 57 59 82 48 Endothermic quantity Q1 of the crystalline portion (crystalline resin A andcrystalline C) in the toner (J / g) 30 20 25 25 20 Endothermic quantity Q2 of the crystalline portion (crystalline resinA and portioncrystalline C) in the toner (J / g) 20 4 7 7 4 Q2 / Q1 ratio 0.67 0.20 0.28 0.28 0.20 TMA amount of compressive deformation of toner (%) 10 9 2 2 8 Relative crystallinity of toner (%) 42 25 27 28 23 Property oflow temperature fixation Minimum fixture temperature(° C) 120 105 120 105 120 Evaluation F THE F THE F
    149
    Property ofthen move resistant tohigh temperature Maximum fixing temperature(° C) 135 155 175 145 170 Evaluation F B THE F THE Stability ofresistant storageheat B F AA F AA Film formation F F AA B THE
    Table 4-6
    Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Crystalline resin A No. 6 - 1 - Non-crystalline resin B No. 7 1 - - Resin E Resin EAt the. El El El El Crystalline portion C No. 1 1 1 1Non-crystalline portion D No. 1 1 1 1 Reason forpasta(CD) 0.43 0.43 0.43 0.43 Crystalline resin content A (mass%) 10 0 30 0 Non-crystalline resin B content (% by mass) 50 70 0 0 E resin content (% by mass) 30 20 60 90 Crystalline C content (% by mass) 9.0 6.0 18.0 27.0 Crystalline portion content D (% by mass) 21.0 14.0 55.0 63.0 Mass ratio (A / C) 1.1 0.0 0.5 0, 0 Mass ratio (B / D) 2.4 5.0 0.0 0.0
    150
    Glass transition temperature Tg (° C) of toner 35 38 54 38 Peak endothermic temperature mp (° C) of toner 60 58 60 59 Q1 endothermic quantity of the crystalline portion(crystalline resin A and crystalline portion C) in the toner (J / g) 8 3 50 30 Endothermic quantity Q2 of the crystalline portion(crystalline resin A and crystalline portion C) in the toner (J / g) 1 0 30 6 Q2 / Q1 ratio 0.13 0.00 0.60 0.20 TMA amount of compressive deformation of toner (%) 7 8 3 8 Relative crystallinity of toner (%) 12 8 55 28 Property oflow temperature fixation Temperatureminimum fixation(° C) 105 120 120 125 Evaluation THE F F F Property ofhigh-resistance displacementtemperature Temperaturemaximum fixation(° C) 160 170 130 150 Evaluation B THE F F Stability ofheat resistant storage F F Ά F Film formation B B F THE
    From the results in Table 4, the toners in the
    Examples 1 to 17 were superior in terms of all assessment items, that is, low temperature fastening property, high resistant displacement property
    151 temperature, heat-resistant storage stability and film formation, compared to the toners of Comparative Examples 1 to 9.
    Aspects of the present invention are as follows:
    <1> A toner, which includes:
    a binder resin; and a dye, wherein the toner has a glass transition temperature by differential scanning calorimetry (DSC) of 20 ° C or greater and less than 50 ° C, a DSC endothermic peak temperature of 50 ° C or greater and less than 80 ° C and an amount of compressive strain at 50 ° C by a thermomechanical analysis of 5% or less.
    <2> The toner according to <1>, wherein the binder resin includes a resin that has a crystalline portion.
    <3> The toner according to <2>, wherein an endothermic quantity Q1 of a first DSC heating due to fusion of the crystalline portion and a Q2 / Q1 ratio with Q2 being an endothermic quantity Q2 of a second DSC heating satisfy the following formulas (1) and (2):
    <Q2 / Q1 <0.3 ... (1)
    Q1> 10 J / g ... (2) <4> Toner according to any of <2> to <3>, where a relative crystallinity obtained from an area
    152 of the crystalline portion and an area of a non-crystalline portion by the X-ray diffraction method is 10% at
    50%.
    toner according to any of <1>
    where the glass transition temperature of the toner is 30 ° C to
    40 ° C.
    <6> Toner according to any of <1> to <5>, wherein the binding resin includes: a crystalline resin A, a non-crystalline resin B and a resin E that includes a crystalline portion C and a non-crystalline portion crystalline D in a molecule thereof, and in which crystalline resin A, non-crystalline resin B, crystalline portion C and non-crystalline portion D have a mass A (g), a mass B (g), a mass C (g ) and a mass D (g), respectively.
    <7> The toner according to <6>, wherein the crystalline resin A and the crystalline portion C of resin E include a common skeleton composed of a monomer unit of an identical type;
    wherein the non-crystalline resin B and the non-crystalline portion D of resin E include a common backbone composed of a monomer unit of an identical type; or where crystalline resin A and crystalline portion C of resin E include a common skeleton composed of a
    153 monomer unit of an identical type, and the non-crystalline resin B and the non-crystalline portion D of resin E include a common backbone composed of a monomer unit of an identical type.
    <8> Toner according to any of <6> to <7>, wherein both the non-crystalline resin B and the non-crystalline portion D of resin E include a polyhydroxycarboxylic acid backbone.
    <9> 0 toner according to any of <6> to <8>, wherein a content of crystalline resin A is 3% by weight to 30% by weight.
    <10> Toner according to any of <6> to <9>, where an E resin content is from 1% by weight to 30% by weight.
    <11> The toner according to any of <6> to <10>, where both crystalline resin A and crystalline portion C of resin E are aliphatic polyester.
    <12> Toner according to any of <6> to <11>, where a mass ratio (A / C) of mass A to mass C is 20 from 0.5 to 3.0.
    <13> The toner according to any of <6> to <12>, where a mass ratio (B / D) of mass B to mass D is 0.5 to 10.0.
    154 <14> The toner according to any of <6> to <13>, where a mass ratio (C / D) of mass C to mass D is 0.25 to 2.5.
    <15> A developer, which includes toner according to any of <1> to <14>.
    <16> An imaging device, which includes:
    an electrostatic imaging support member;
    an electrostatic imaging formation unit that forms an electrostatic imaging on the electrostatic imaging support member;
    a development unit that forms a visible image by developing the electrostatic imaging with a toner;
    a transfer unit which transfers the visible image on a recording medium; and a fixing unit fixes a transfer image transferred on the recording medium, in which the toner according to any one of <1> to <14> is mounted like the toner.
    <17> An imaging method, which includes:
    an electrostatic imaging formation step where an electrostatic imaging is formed on an electrostatic imaging support member;
    155 a development step where a visible image is formed by developing the electrostatic latent image with a toner;
    a transfer step where the visible image is transferred on a recording medium, and a fixation step where a transfer image transferred on the recording medium is fixed, where the toner is the toner according to any of <1 > to <14>.
    权利要求:
    Claims (5)
    [1]
    1. Toner characterized by the fact that it comprises:
    a binder resin; and a dye, in which the toner comprises a crystalline resin A, a non-crystalline resin B, in which the crystalline resin A is a polycondensate between a linear saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms and a linear saturated aliphatic diol which has 2 to 12 carbon atoms, where the non-crystalline resin B is a resin that has a polyhydroxycarboxylic acid backbone or a polyester resin that has a bisphenol backbone, where the relative crystallinity obtained from a area of the crystalline portion and an area of a non-crystalline portion by the X-ray diffraction method is 10% to 50%, and the toner has a glass transition temperature by differential scanning calorimetry of 20 ° C or greater and less than 50 ° C, an endothermic peak temperature by differential scanning calorimetry of 50 ° C or greater and less than 80 ° C and an amount of compressive strain at 50 ° C and a f compressive budget of 0.1 N (100 mN) by a thermomechanical analysis of 5% or less.
    Petition 870190103134, of 10/14/2019, p. 29/38
    [2]
    2. Toner according to claim 1, characterized by the fact that a Q1 endothermic amount of a first differential scanning calorimetry heating due to the fusion of the crystalline portion and a Q2 / Q1 to Q2 ratio being an endothermic Q2 amount of one second calorimetry heating of differential scanning satisfy the following formulas (1) and (2):
    0 <Q2 / Q1 <0.3 ... (1)
    Q1> 10 J / g ... (2).
    2/5
    [3]
    3/5 where crystalline resin A and crystalline portion C of resin E comprise a common backbone composed of a monomer unit of an identical type, and the resin does not
    crystalline B and the portion not crystalline D from resin AND understand one common skeleton composed of a unity in monomer of one type identical. 6. Toner, in a deal with the claim 4 or 5,
    characterized by the fact that both the non-crystalline resin B and the non-crystalline portion D of resin E comprise a polyhydroxycarboxylic acid backbone.
    7. Toner according to any one of claims 4 to 6, characterized in that the content of crystalline resin A is from 3% by weight to 30% by weight.
    8. Toner according to any one of claims 4 to 7, characterized in that the content of resin E is from 1% by weight to 30% by weight.
    9. Toner according to any one of claims 4 to 8, characterized in that both crystalline resin A and crystalline portion C of resin E are aliphatic polyester.
    10. Toner according to any one of claims 4 to 9, characterized in that a mass ratio (A / C) of the mass (g) of the crystalline resin A to the mass (g) of the crystalline portion C of the resin And it's 0.5 to 3.0.
    Petition 870190103134, of 10/14/2019, p. 31/38
    3. Toner according to claim 1 or 2, characterized by the fact that the glass transition temperature of the toner is from 30 ° C to 40 ° C.
    [4]
    4 to 11, characterized by the fact that a mass ratio (C / D) of the mass (g) of the crystalline portion C to the mass (g) of the non-crystalline portion D of resin E is 0.25 to 2.5.
    13. Developer characterized by the fact that it comprises toner as defined in any of claims 1 to 12.
    14. Imaging apparatus characterized by the fact that it comprises:
    an electrostatic imaging support member;
    an electrostatic imaging formation unit that forms an electrostatic imaging on the electrostatic imaging support member;
    a developing unit that forms a visible image by developing the electrostatic imaging with a toner;
    a transfer unit which transfers the visible image on a recording medium; and a fixing unit that fixes a transfer image transferred to the recording medium,
    Petition 870190103134, of 10/14/2019, p. 32/38
    4 to 10, characterized by the fact that a mass ratio (B / D) of the mass (g) of the non-crystalline resin B to the mass (g) of the non-crystalline portion D of resin E is 0.5 to 10, 0.
    12. Toner according to any of the claims
    4/5
    11. Toner according to any of the claims
    4. Toner according to any one of claims 1 to 3, characterized in that the binding resin comprises a crystalline resin A, a non-crystalline resin B and a resin E comprising a crystalline portion C and a non-crystalline portion D in a molecule of it.
    5. Toner according to claim 4, characterized in that the crystalline resin A and the crystalline portion C of resin E comprise a common skeleton composed of a monomer unit of an identical type;
    wherein the non-crystalline resin B and the non-crystalline portion D of resin E comprise a common backbone composed of a monomer unit of an identical type; or
    Petition 870190103134, of 10/14/2019, p. 30/38
    [5]
    5/5 wherein the toner, as defined in any of claims 1 to 12, is assembled like the toner.
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    同族专利:
    公开号 | 公开日
    BR102013015398A2|2015-08-11|
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    US20130337374A1|2013-12-19|
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    法律状态:
    2015-08-11| B03A| Publication of an application: publication of a patent application or of a certificate of addition of invention|
    2018-12-04| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-07-16| B07A| Technical examination (opinion): publication of technical examination (opinion)|
    2019-11-19| B09A| Decision: intention to grant|
    2020-01-21| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 18/06/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2012136935A|JP6011051B2|2012-06-18|2012-06-18|Toner, developer, and image forming apparatus|
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