• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    PHOTOPOLIMERIZABLE COMPOSITION, PHOTOPOLIMERIZABLE INK JET INK, AND INK CARTRIDGE. Provide a light-curing composition, which includes light-curing monomers containing glycerol dimethacrylate, dipentaerythritol hexa-acrylate modified by caprolactone, and diethylene glycol dimethacrylate, where an amount of the glycerol dimethacrylate in the photopolymerizable monomers is greater than 25% by weight.
    公开号:BR112014028699B1
    申请号:R112014028699-0
    申请日:2013-05-17
    公开日:2021-01-12
    发明作者:Takao Hiraoka
    申请人:Ricoh Company, Ltd.；
    IPC主号:
    专利说明:

    Technical Field
    [0001] The present invention relates to a photopolymerizable composition, a photopolymerizable inkjet ink, and an ink cartridge that houses the ink. Knowledge Technique
    [0002] Light-curing compositions and light-curing inkjet inks using (meth) acrylic acid esters have been well known (see PTL 1 etc.).
    [0003] However, many of the monomers used in conventional light-curing compositions and light-curing inkjet inks are toxic. Especially, most esters of (meth) acrylic acid, which are readily available at low cost, have high toxicity in terms of skin sensitivity, which causes allergic reactions with skin contact with them. The conventional technique has yet to provide a solution to this problem.
    [0004] Printing inks using glycerol dimethacrylate are known (see PTL 2).
    [0005] However, there is no description of skin sensitization associated with glycerol dimethacrylate and other monomers used in combination. Citation List Patent Literature PTL 1: Japanese Patent Application filed open (JP-A) No. 2004-526820 PTL 2: Japanese Patent (JP-B) No. 3947754 Summary of the Invention Technical Problem
    [0006] The present invention wishes to solve the various problems mentioned previously in the art and achieve the following objective. An object of the present invention is to provide a photopolymerizable composition, which has no skin sensitization problem, and provides a coating film having excellent film resistance. Solution to the Problem
    [0007] The means to solve the previous problems are as follows,
    [0008] The photopolymerizable composition of the present invention contains: photopolymerizable monomers containing glycerol dimethacrylate, dipentaerythritol hexa-acrylate modified by caprolactone, and diethylene glycol dimethacrylate, in which the amount of dimeracrylate glycerol in the photopolymerizable monomers is greater than 25% by weight. Advantageous Effects of the Invention
    [0009] The present invention can solve the various problems mentioned previously in the art, achieve the aforementioned objective, and can provide a photopolymerizable composition, which has no skin sensitivity problem, and provides a coating film having excellent film resistance.
    [00010] Furthermore, printed matter obtained using the photopolymerizable composition of the present invention has no problem of skin sensitivity even if an uncured monomer component remains, and skin sensitivity is not caused even when the printed matter is touched with the hands or fingers. Appropriately, safe coated matter and printed matter can be provided. Brief Description of Drawings
    [00011] FIG. 1 is a schematic diagram illustrating an example of an ink pouch for an ink cartridge.
    [00012] FIG. 2 is a schematic diagram illustrating an example of an ink cartridge that houses an ink pouch. Description of Modalities (Light-curing composition)
    [00013] The photopolymerizable composition of the present invention contains at least photopolymerizable monomers, and may contain other additional components, such as a photoradical polymerization initiator, a polymerization accelerator, and a colorant, if necessary. <Light-curing monomers>
    [00014] The photopolymerizable monomers contain at least glycerol dimethacrylate, dipentaerythritol hexacrylate modified by caprolactone, and diethylene glycol dimethacrylate, which are negative for skin sensitivity, and may additionally contain other photopolymerizable monomers, if necessary.
    [00015] An amount of the glycerol dimethacrylate in the photopolymerizable monomers is 25% by weight or greater.
    [00016] The present invention will be specifically explained hereinafter.
    [00017] The present inventors have discovered that it is possible to provide a photopolymerizable composition that can be ejected by inkjet, can be cured by applying appropriate light, and can provide a more solid coating film than that disclosed in the Patent Application Japanese No. 2012-46301, when the photopolymerizable composition contains, as photopolymerizable monomers having a viscosity in the range, in which they can be ejected as an inkjet, and being negative for skin sensitivity, glycerol dimethacrylate, diethylene glycol dimethacrylate, and dipentaerythritol hexa-acrylate modified by caprolactone, all of which have a very small SI value that indicates a level of sensitization, that is, 1.2 or less, compared to methacrylate disclosed in Japanese Patent Application No. 2010-278177, and an amount of the glycerol dimethacrylate in the photopolymerizable monomer is 25% by weight or greater. Note that the details of an SI value will be described later.
    [00018] As a result of the studies conducted by the present inventors, they discovered several (meth) acrylic acids and (meth) acrylamides, which do not have a skin sensitivity problem. As an example of them, an inkjet ink using methacrylate, as a main component, is disclosed in Japanese Patent Application No. 2010-278177 based on the fact that methacrylate is low in toxicity in terms of skin sensitivity compared with acrylate. However, to further improve performance, it is desired that a level of skin sensitivity is decreased, and a viscosity is decreased so as not to adversely affect inkjet ejection even when viscosity is increased by mixing with various materials such as a pigment and additives.
    [00019] Note that the reduction in viscosity can be easily achieved by adding a dilution solvent, but the use of a solvent is not desirable considering the environment, as the solvent is evaporated and released into the air. In addition, a photopolymerizable aqueous inkjet ink containing water has been known in the art. As described later, however, this paint cannot be expected to achieve the desired penetration and drying with a non-permeable base. Therefore, it is necessary to provide a step to evaporate water to speed up the processing speed or improve efficiency, for which a heat source is needed. Therefore, such an ink is not desirable in terms of energy savings.
    [00020] To solve the problems described above, the present inventors disclosed a photopolymerizable inkjet ink, which can provide a rigid coating film and have no skin sensitivity problem in Japanese Patent Application No. 2012-46301. However, for the purpose of protecting a surface of a molded article or housing, there is a need for strength under more severe conditions and thus the further improvement in strength of a coating film than that disclosed in Japanese Patent Application No 2012-46301 is desired.
    [00021] In addition, if a solid-coated film is produced, not a pattern in a certain way, not just inkjet printing, but methods such as spray coating and brush coating, can be used. However, it is difficult to obtain a highly solid coating film without a problem of skin sensitivity.
    [00022] A printing ink using glycerol dimethacrylate, which is one of (meth) acrylic esters having no skin sensitivity problem discovered by the present inventors, has already been known in the art (see JP-B No. 3947754).
    [00023] In this disclosure, however, there is no description on the skin sensitivity of glycerol dimethacrylate and other monomers used in combination. Although details are described later, when glycerol dimethacrylate is added to an ink in an amount from 10% by mass to 21% by mass, as disclosed in JP-B No. 3947754, as well as (meth) acrylic acid ester having no skin sensitivity problem discovered by the present inventors, a coating film resistance does not improve more than the result disclosed in Japanese Patent Application No. 2012-46301.
    [00024] Here, the photopolymerizable monomer negative for skin sensitivity refers to a compound that satisfies at least one of the following skin sensitivity assessments (1) to (2).
    [00025] (1) A compound having a Stimulus Index (SI value) of less than 3, where the Stimulus Index indicates the level of sensitization as measured by a skin sensitivity test based on LLNA (Local Test lymph nodes).
    [00026] (2) A compound rated “negative for skin sensitivity” or “non-skin sensitive” in its material safety data sheet (MSDS).
    [00027] With respect to (1) above, the compound having an SI value of less than 3 is considered negative for skin sensitivity as described in the literature, for example, “Functional Material” (Kino Zairyou) 2005, September , Vol. 25, No. 9, p. 55. The lower SI value means less skin sensitivity. Thus, in the present invention, a monomer or an oligomer having a lower SI value is preferably used. The SI value of the monomer used is preferably less than 3, more preferably 2 or less, even more preferably 1.6 or less.
    [00028] When diethylene glycol dimethacrylate, dipentaerythritol hexa-acrylate modified by caprolactone, and glycerol dimethacrylate, which are negative monomers for skin sensitivity and readily available, are determined as Compound (A1), Compound (A2), and Compound (A3 ), respectively, amounts of Compound (A1) and Compound (A2) are appropriately adjusted, provided that an amount of Compound (A3) in the photopolymerizable monomer is 25% by weight or greater. It is preferred that the amount of Compound (A1) is 25% by mass to 70% by mass, the amount of Compound (A2) is 5% by mass to 50% by mass, and the amount of Compound (A3) is 25%. by mass to 40% by mass. In addition, it is more preferred in terms of no skin sensitivity, excellent coating film resistance, and inkjet ejection that the amount of Compound (A1) is 25% by mass to 70% by mass, the amount of Compound (A2) is 5 wt% to 40 wt%, and the amount of Compound (A3) is 25 wt% to 40 wt%. << Other light curing monomers >>
    [00029] The following (meth) acrylate, (meth) acrylamide, and vinyl ether, which may have a skin sensitivity problem as used alone, or which is a compound in which skin sensitivity has not been confirmed, may be used as other light-curing monomers, together with the light-curing monomers mentioned above, provided that they do not adversely affect a resulting light-curing composition.
    [00030] Examples of other photopolymerizable monomers include ethylene glycol di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, y-butyrolactone acrylate, isobornyl (meth) acrylate, trimethylol propane mono (meth) acrylate, polytetramethylene glycol (meth) acrylate, trimethylol propane (meth) acrylic benzoate, diethylene glycol diacrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate [CH2 = CH-CO- (OC2H4 ) n-OCOCH = CH2 (n = 4)], CH2 = CH-CO- (OC2H4) n-OCOCH = CH2 (n = 9)], CH2 = CH-CO- (OC2H4) n-OCOCH = CH2 (n = 14)], CH2 = CH-CO- (OC2H4) n-OCOCH = CH2 (n = 23)], dipropylene glycol di (met) acrylate, tripropylene glycol di (met) acrylate, polypropylene glycol dimethacrylate [CH2 = C ( CH3) -CO- (OC3H6) n-OCOC (CHs) = CH2 (n = 7)], 1,3-dibutanediol diacrylate, 1,4-dibutanediol di (meth) acrylate, 1,6-hexanediol di (met) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tricyclodecane dimethanol daily crylate, bisphenol A modified by propylene oxide di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, (meth) acryloyl morpholine, 2-hydroxypropyl (meth) acrylate, tetramethylol methane tetra (meth) acrylate modified by propylene oxide, dipentaerythritol hydroxypenta (meth) acrylate, dipentaerythritol hydroxypenta (meth) acrylate modified by caprolactone, ditrimethylol propane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylol propane triacrylate, trimethylol propane triloxymethyl ethanol triloxymethyl triloxide propylate ) propylene oxide modified acrylate, caprolactone modified trimethylol propane tri (meth) acrylate, tri (meth) acrylate pentaerythritol, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethoxylated di (meth) acrylate, neopentyl glycol propylene oxide modified (met) acrylate, propylene oxide modified tri (meth) acrylate, di (met) acrylate polyester, tri (met) acrylate polyester, tetra (met) acrylate polyester to, polyester penta (meth) acrylate, polyester poly (meth) acrylate, N-vinyl caprolactam, N-vinyl pyrrolidone, N-vinyl formamide, polyurethane di (meth) acrylate, polyurethane tri (meth) acrylate, polyurethane tetra (met) acrylate, polyurethane penta (meth) acrylate, polyurethane poly (meth) acrylate, cyclohexane dimethanol divinyl ether, cyclohexane dimethanol monovinyl ether, hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, diethylene glycol divinyl ether, dicyclopentadiene vinyl ether, tricyclodecane ether, benzyl vinyl ether, and ethyloxtacene methyl vinyl ether.
    [00031] Examples of vinyl ether negative for skin sensitivity include, unlike those listed above, triethylene glycol divinyl ether, hydroxybutyl vinyl ether, and ethyl vinyl ether. Among these, triethylene glycol divinyl ether is preferable since its viscosity is low enough, and its boiling point is not excessively low, and so it is easily manipulated at normal temperature and normal pressure. Other vinyl ethers can also be used if needed. <Other Components> << Photoradical polymerization initiator >>
    [00032] The ink of the present invention preferably contains a photoradical polymerization initiator. The photoradical polymerization initiator is not selected appropriately depending on the intended purpose without any limitation, but the photoradical polymerization initiator is preferably selected from those negative for skin sensitivity.
    [00033] The photoradical polymerization initiator negative for skin sensitivity is appropriately selected depending on the intended purpose without any limitation, provided that its compounds that satisfy any of the skin sensitivity assessments (1) to (2), and examples thereof include 1-hydroxy-cyclohexylphenyl ketone, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) butan-1-one, and 2,4-diethyl thioxanthone. These can be used alone or in combination.
    [00034] The (meth) acrylic acid ester, the (meth) acryl amide, and the vinyl ether are known to also have cationic polymerization properties. Photocathonic polymerization initiators are generally expensive and generate a small amount of strong acid even in the state where they are not irradiated with light. Thus, it is necessary to take special care such as transmitting acid resistance to the ink supply channel of a printer, imposing limitations on the choice of the constituent members of the printer.
    [00035] In contrast, the photopolymerizable composition of the present invention can use a photoradical polymerization initiator which is inexpensive and does not generate strong acid. Thus it is possible to produce a light-curing composition at low cost, and it is also easy to select the constituent members of a printer. Needless to say, when using a very high energy source such as electron beams, α rays, β rays, y rays or X rays, the polymerization reaction proceeds without a polymerization initiator. This is a matter known conventionally, and not described in detail in the present invention.
    [00036] The photoradical polymerization initiator includes, for example, a polymerization autocleaving photoinitiator and a hydrogen abstraction polymerization initiator.
    [00037] Examples of the polymerization autocleaving photoinitiator include 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one , 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2- methylpropionyl) benzyl] phenyl} -2-methyl-1-propan-1-one, phenyl glycoxyl acid methyl ester, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1,2-dimethylamino- 2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) butan-1-one, oxide bis (2,4,6-trimethylbenzoyl) phenylphosphine, bis (2,6-dimethoxybenzolyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoylphosphine oxide, 1,2-octanodion- [ 4- (phenylthio) -2- (o-benzoyloxime)], ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) and [ 4- (methylphenylthio) phenyl] phenylmethanone. Examples of the hydrogen abstraction polymerization initiator include: benzophenone compounds such as benzophenone, methylbenzophenone, methyl-2-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl sulfide and phenylbenzophenone; and thioxanthone compounds such as 2,4-diethyloxyantone, 2-chlorothioxanthone, isopropyloxanthone and 1-chloro-4-propyloxanthone. << Curing accelerator >>
    [00038] In addition, amine can be used as a polymerization accelerator in combination with the polymerization accelerator.
    [00039] Examples of the polymerization accelerator include p-dimethylaminobenzoate, 2-ethylhexyl p-dimethylaminobenzoate, methyl p-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate and butoxyethyl p-dimethylaminobenzoate. <<Coloring>>
    [00040] The light-curing composition does not need to contain a colorant, but it can contain a colorant, if necessary. The colorant is appropriately selected from conventional inorganic pigments, organic pigment, and various color pigments (for example, a black pigment, a yellow pigment, a magenta pigment, a cyan pigment, and a white pigment) depending on the purpose intended without any limitation.
    [00041] Examples of the black pigment include carbon black produced by an oven method or a channel method.
    [00042] Examples of the yellow pigment include pigments from the Yellow Pigment Series, such as Yellow Pigment 1, Yellow Pigment 2, Yellow Pigment 3, Yellow Pigment 12, Yellow Pigment 13, Yellow Pigment 14, Yellow Pigment 16, Yellow Pigment 17, Pigment Yellow 73, Pigment Yellow 74, Pigment Yellow 75, Pigment Yellow 83, Pigment Yellow 93, Pigment Yellow 95, Pigment Yellow 97, Pigment Yellow 98, Pigment Yellow 114, Pigment Yellow 120, Pigment Yellow 128, Pigment Yellow 129, Pigment Yellow 138 , Yellow Pigment 150, Yellow Pigment 151, Yellow Pigment 154, Yellow Pigment 155, and Yellow Pigment 180.
    [00043] Examples of the magenta pigment include pigments from the Red Pigment series, such as Pigment Red 5, Pigment Red 7, Pigment Red 12, Pigment Red 48 (Ca), Pigment Red 48 (Mn), Pigment Red 57 (Ca), Pigment Red 57: 1, Pigment Red 112, Pigment Red 122, Pigment Red 123, Pigment Red 168, Pigment Red 184, Pigment Red 202, and Pigment Violet 19.
    [00044] Examples of cyan pigment include Pigment Blue series pigment, such as Pigment Blue 1, Pigment Blue 2, Pigment Blue 3, Pigment Blue 15, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 16, Pigment Blue 22, Pigment Blue 60, Vat Blue 4, and Vat Blue 60.
    [00045] Examples of the white pigment include: sulfuric acid salts of alkaline earth metals such as barium sulfate; carbonic acid salts of alkaline earth metals such as calcium carbonate; silica such as fine silicic acid powder and synthetic silicic acid salts, calcium silicate; alumina; alumina hydrate; titanium oxide; zinc oxide; baby powder; and clay.
    [00046] In addition, various organic or inorganic pigments can be used optionally considering, for example, physical properties of the photopolymerizable composition.
    [00047] Additionally, polymerization inhibitor, a surfactant, and a pigment dispersing agent can be used optionally.
    [00048] Examples of the polymerization inhibitor include 4-methoxy-1-naphthol, methylhydroquinone, hydroquinone, t-butylhydroquinone, di-t-butylhydroquinone, methoquinone, 2,2'-dihydroxy-3,3 ' -di (α- methylcyclohexyl) -5,5'-dimethyldiphenylmethane, p-benzoquinone, di-t-butylbutyl diphenylamine, 9,10-di-n-butoxy anthracene, 4,4 '- [1,10-dioxo- 1,10-decandiilbis (oxy)] bis [2,2,6,6-tetramethyl] -1-piperidinyloxy.
    [00049] Examples of the surfactant include polyether-containing higher fatty acid ester, an amino group, a carboxyl group, or a hydroxyl group, a polydimethylsiloxane compound containing, in its side or terminal chain, polyether, an amino group, a carboxyl group , or a hydroxyl group, and a fluoroalkyl compound containing polyether, an amino group, a carboxyl group, and a hydroxyl group.
    [00050] Examples of the equipment dispersing agent include a polymer compound that contains polar group.
    [00051] (Inkjet ink)
    [00052] The inkjet ink (may be referred to as a "ink" hereinafter) of the present invention contains the photopolymerizable composition of the present invention, and may additionally contain another component, if necessary.
    [00053] The light-curing composition of the present invention can be used as a coating agent for spray coating, or brush coating, or it can be used as an inkjet ink.
    [00054] The physical properties of the inkjet ink are selected in an appropriate manner depending on the intended purpose without any limitation, but they are desirably matched to the specifications required for an inkjet ejection head for use. Various ejection heads are on the market from various manufacturers, and among these, there are ejection heads having a temperature adjustment function over a wide temperature range. Considering such market trends, the paint viscosity at a temperature of 25 ° C is preferably 2 mPa-s to 150 mPa-s. In the case where the paint is ejected at 25 ° C, the paint viscosity is preferably 5 mPa-s to 18 mPa-s. As mentioned earlier, it is possible to use the temperature adjustment function of the ejection head. In the case where the viscosity of the paint is very high at 25 ° C, the viscosity of the paint can be reduced optionally by heating the head. Assuming that the heating condition is 45 ° C to 60 ° C, in the case mentioned above, the paint viscosity from 45 ° C to 60 ° C is preferably 2 mPa-s to 20 mPa-s, more preferably 5 mPa • sa 18 mPa • s.
    [00055] Appropriately, the low viscosity of the paint can be achieved as long as the viscosity of the paint drops to either a range of 5 mPa-s to 18 mPa-s at 25 ° C, or a range of 2 mPa-s 20 mPa-s at 45 ° C to 60 ° C.
    [00056] (Ink cartridge)
    [00057] The ink cartridge of the present invention contains the photopolymerizable inkjet ink of the present invention and a container, and can additionally contain other members, such as an ink pouch, if necessary.
    [00058] The ink of the present invention can be housed in a container, and used as an ink cartridge. With this form, users do not need to directly touch the ink during jobs such as changing the ink, so they do not worry about staining their fingers, hands or clothes. In addition, it is possible to avoid the interference of foreign matter such as dust in the paint.
    [00059] The container is not particularly limited, and its shape, structure, size and material can be selected in an appropriate manner depending on the intended purpose. For example, the container is preferably selected from that having an ink pouch formed from a laminated aluminum film, or a resin film.
    [00060] The ink cartridge will be described with reference to FIGs. 1 and 2. FIG. 1 is a schematic diagram illustrating an example of an ink pouch (241) of the ink cartridge of the present invention. FIG. 2 is a schematic diagram illustrating the ink cartridge (200) in which the ink pouch (241) of FIG. 1 is housed in a cartridge case (244) which is an example of the container.
    [00061] As illustrated in FIG. 1, the ink pouch (241) is filled with ink by injecting ink from an ink inlet (242). After removing air present inside the ink pouch (241), the ink inlet (242) is sealed by a fusion connection. At the time of use, a needle attached to the main body of the device is inserted into an ink outlet (243) formed by a rubber member to supply ink to the device through it. The ink pouch (241) is formed of a wrapping member such as a laminated aluminum film not permeable to air. As illustrated in FIG. 2, the ink pouch (241) is typically housed in a plastic cartridge case (244), which is then detachably mounted in use for various inkjet engraving devices such as the ink cartridge (200).
    [00062] The ink cartridge of the present invention is preferably detachably mounted to inkjet engraving devices. As a result of this, refilling or changing the ink can be simplified, and the workability can be improved.
    [00063] A coating base (recording medium) is selected appropriately depending on the intended purpose without any limitation. Examples of it include paper, plastic, metal, ceramics, glass, and a material composed of the materials listed above.
    [00064] As an absorbent base, such as wood-free paper, you can expect a penetrating and drying effect, an aqueous ink or an oil ink, which is not a quick-drying ink, can be used for such a base. On the other hand, it is not practical to use a quick-drying ink for a non-absorbent base, such as glass lining paper, a plastic film, a molded article of plastic, ceramics, glass, and metal.
    [00065] The photopolymerizable composition and inkjet ink of the present invention are cured immediately by applying light, and thus can be used in the aforementioned non-absorbent base, as well as an absorbent base. Among the non-absorbent bases, the photopolymerizable composition and the inkjet ink of the present invention are used appropriately for a plastic film or plastic article formed of polyethylene, polypropylene, polyethylene terephthalate, an ABS resin, polyvinyl chloride, polystyrene , other polyesters, polyamide, vinyl-based materials, or a material composed of it, but the base is not particularly limited. Examples
    [00066] The present invention will be explained concretely through the Examples hereinafter, but Examples are not to be construed as limiting the scope of the present invention. <IS Value Assessment Method>
    [00067] According to the skin sensitivity test based on LLNA (Local Lymph Node Assay), the SI value was measured in the manner described below. [Test Material] << Positive Control >>
    [00068] a-Hexylcinamaldehyde (HCA; product of Wako Pure Chemical Industries, Ltd.) was used as the positive control. << Vehicle >>
    [00069] As a vehicle, a mixture containing acetone (product of Wako Pure Chemical Industries, Ltd.) and olive oil (product of Fudimi Pharmaceutical Co., Ltd.) in a volume ratio of 4/1 was used. << Animals used >>
    [00070] Before being treated with test substances, positive control or vehicle control, female mice were acclimated for 8 days including a 6-day quarantine. No abnormalities were found in all animals during the quarantine / acclimatization period. Based on body weights measured 2 days before the start of sensitization, they are categorized into 2 groups (4 mice / group) by the stratified body weight random sampling method so that each individual's body weight was within ± 20% of the average body weight of all individuals. Each animal was 8 weeks old to 9 weeks old at the time of initiation of sensitization. The animals that remain after categorization were excluded from the test.
    [00071] The animals were identified individually by applying oil paint to their tail during the test period, and their cages were also marked for identification.
    [00072] << Accommodation Environment >>
    [00073] Through the housing period including the quarantine / acclimatization period, the animals were housed in an animal environment with a barrier system, which was defined as follows: 21 ° C to 25 ° C temperature, 40% at 70% in relative humidity, 10 moments / hour to 15 moments / hour in air circulation frequency, and 12 hours in dark - light cycle (light from 7:00 am to 7:00 pm).
    [00074] The housing cages used were those made of polycarbonate, and four animals were housed in each cage.
    [00075] The animals were given a solid diet at will for MF laboratory animals (product of Oriental Yeast Co., Ltd.). Also, using a water supply bottle, they were given tap water at will in which sodium hypochlorite (PURELOX, product of OYALOX Co., Ltd.) was added so that the chlorine concentration was about 5 ppm. The stratification used was SUNFLAKE (fir tree, stendos obtained with a powder planer) (product of Charles River Inc.). The food and diet equipment was sterilized with an autoclave (121 ° C, 30 min) before use.
    [00076] The cage and the stratification were replaced by new ones at the time of categorization and removal of the auricular lymph node (that is, the moment when the animals were transferred from the animal environment), and the water supply bottle and the rack was replaced by new ones at the time of categorization. [Test Method] << Composition of the Group >>
    [00077] The composition of the group used to measure the SI value is shown in Table 1. Table 1

    << Test Substance >>
    [00078] Table 2 shows the amount of test substance. The test substance was weighed in a measuring vial, and the volume of the test substance was adjusted to 1 mL with a vehicle. The solution prepared in this way was placed in an airtight container shielded against light (made of glass). Table 2
    << Positive control substance >>
    [00079] About 0.25 g of HCA was precisely weighed, and a vehicle was added to the HCA to have a volume of 1 mL, in order to prepare a 25.0% w / v solution. The solution prepared in this way was placed in an airtight container shielded against light (made of glass).
    [00080] <<BrdU>>
    [00081] In a measuring flask, 200 mg of 5-bromo-2'-deoxyuridine (BrdU, product of NACALAI TESQUE, INC.) Was accurately weighed. Then, physiological saline solution (product of OTSUKA PHARMACEUTICAL CO., LTD.) Was added to the measuring flask, and dissolved through the application of ultrasonic waves. The volume of the resulting solution was adjusted to 20 ml to prepare a 10 mg / ml solution (BrdU preparation). The solution prepared in this way was sterilized through filtration with a sterile filtration filter and placed in a sterile container. << Preparation Day and Storage Period »
    [00082] The positive control preparation was prepared the day before the sensitization started, and stored in a cold place except in use. The vehicle and test substance preparations were prepared on the day of sensitization. The BrdU solution was prepared 2 days before administration and stored in a cold place until the day of administration. BrdU Awareness and Administration] << Awareness >>
    [00083] Each (25 μL) of the test substance preparations, the positive control preparation and the vehicle was applied to both auricles of each animal using a micropipette. This treatment was carried out once a day for three consecutive days. << BrdU Administration >>
    [00084] About 48 hours after the final sensitization, the preparation of BrdU (0.5 mL) was administered intraperitoneally once for each animal. [Observation and Examination] << General Conditions >>
    [00085] All animals used for the test were observed once or more times on the day from the beginning of sensitization to the day of removal of the auricular lymph node (that is, the day when the animals were transferred from the animal room). Notably, the observation day was counted from the day the sensitization started and was considered Day 1. << Measurement of Body Weights >>
    [00086] The body weight of each animal was measured on the day the sensitization started and on the day the auricular lymph node was removed (ie the day when the animals were transferred from the animal environment). In addition, the mean body weights and standard error were calculated for each group. << Removal of atrial lymph node and mass measurement >>
    [00087] About 24 hours after BrdU administration, the animals were euthanized, and their auricular lymph nodes were sampled. The tissue surrounding each atrial lymph node was removed, and the atrial lymph nodes from both atria were collectively weighed. In addition, the mean weights of the auricular lymph nodes and their standard error were calculated for each group. After measuring the weights, the auricular lymph nodes of each individual were stored in a frozen state using a MEDIUM BIO FREEZER set to -20 ° C.
    [00088] << Measurement of BrdU Admission >>
    [00089] After returning to room temperature, the auricular lymph nodes were crushed with the gradual addition of physiological saline, and suspended in it. The suspension obtained in this way was filtered and then dispensed into the wells of a 96-well microplate, with 3 wells being used per individual. The suspensions obtained in this way were measured for the admission of BrdU by the ELISA method. The reagents used were those from a commercially available kit (Cell Proliferation ELISA, BrdU colorimetric, Cat. No. 1647229, product of Roche Diagnostics Inc.). A multi-plate reader (FLUOSTAR OPTIMA, product of BMG LABTECH Inc.) was used to measure the absorbance of each well (OD: 370 nm at 492 nm, the BrdU inlet), and the mean absorbance of 3 wells for each individual was used as the BrdU measurement for the individual. [Evaluation of Results] << Calculation of Stimulus Index (SI) >>
    [00090] As shown in the following formula, the measurement of BrdU intake for each individual was divided by the average of BrdU intake measurements in the vehicle control group to calculate the SI value for the individual. The SI value of each test group was the average of the individuals' SI values. In addition, the standard error of SI values was calculated for each test group. Notably, the SI value has been rounded to the second decimal place and shown to the first decimal place. <evaluation>
    [00091] The light-curing composition and ink of Example 1 were subjected to viscosity measurements (mPa ^ s) at 25 ° C, 45 ° C, and 60 ° C, and the strength of the coating film. The results are shown in Table 3. <<Visit>>
    [00092] The viscosity at 25 ° C, 45 ° C, 60 ° C was measured with a cone and plate rotary viscometer (product of TOKI SANGYO CO., LTD.) With the circulating water temperature that is constantly defined to 25 ° C, 45 ° C and 60 ° C. The temperature of 25 ° C is the temperature generally considered to be the ambient temperature. The temperature of 45 ° or 60 ° C is the temperature defined considering the specification of a commercially available inkjet ejection head, such as GEN4 (product of Ricoh Printing Systems, Ltd.), which can be heated. In the case where low viscosity was achieved without heating up to 60 ° C, the viscosity measurement at 60 ° C was omitted. << Coating Film Strength »
    [00093] The strength of the coating film was assessed as follows. Specifically, to a commercially available polycarbonate film (LUPILON E-2000, manufactured by Mitsubishi Engineering-Plastics Corporation, thickness: 100 μm), the light-curing composition and ink were applied by brushing or inkjet printing. The photopolymerizable composition applied and the paint were cured by applying light at a light dose of 0.2 mW / cm2 using an LH6 UV irradiation device (product from Fusion Systems Japan Co., Ltd.). The resulting solid coating film was subjected to zero hardness assessment according to a pencil method as specified in JIS-K-5600-5-4. The pencil hardness includes 2H, H, F, HB, B, and 2B in that order of the hardest.
    [00094] In the case where the viscosity of the photopolymerizable composition is excessively high, the photopolymerizable composition can be used as a coating agent, but it cannot be used as an inkjet ink. As shown in Table 3, the photopolymerizable compositions according to the present invention have variations in viscosity values, but most of them can also be used as an inkjet ink.
    [00095] As for handling inkjet ink, an aluminum packaging pouch having a shape illustrated in FIG. 1 was loaded with ink, and hermetically sealed to prevent the inclusion of air bubbles. The hermetically sealed packaging pouch containing the ink was housed in a plastic cartridge as illustrated in FIG. 2. This cartridge has been assembled for a cover adapted to accommodate it. In the coating, an ink flow channel was provided for a GEN4 head (product of Ricoh Printing Systems, Ltd.). The ink was blasted through the ink flow channel to form a solid coated film on the film.
    [00096] In either a brush coating case and an inkjet printing case, the conditions have been adjusted so that a solid coating film has an average thickness of about 30 μm. The resulting solid coating film was irradiated with light from the wavelength region that corresponds to the UVA region, with the light dose each being 400 (mJ / cm2), 800 (mJ / cm2), and 1,200 (mJ / cm2), in order to cure the solid coating film. The resulting coating film was provided for the evaluation of the resistance of the coating film (the same in the order of the examples).
    [00097] Example 1
    [00098] As shown in Table 3, 65 parts of Component A1 [diethylene glycol dimethacrylate ("2G" manufactured by Shin-Nakamura Chemical Co., Ltd.)], 10 parts of Component A2 component [caprenta lactone-modified dipentaerythritol hexacrylate (“DPCA-60” manufactured by NIPPON KAYAKU Co., Ltd.)], 25 parts of Component A3 [glycerol dimethacrylate (“701” manufactured by Shin-Nakamura Chemical Co., Ltd.)], and 15 parts of Component B1 [1-hydroxy-cyclohexylphenyl ketone] as a photopolymerization initiator were used to prepare a photopolymerizable composition and an ink jet ink of Example 1 in this way.
    [00099] In the case where the light-curing composition and the paint were applied by the brushing coating, they were used as they were. Like inkjet ink, they were handled in the following way. An aluminum packaging pouch having a shape illustrated in FIG. 1 was loaded with ink, and hermetically sealed to prevent the inclusion of air bubbles. The hermetically sealed packaging pouch containing the ink was housed in a plastic cartridge as illustrated in FIG. 2. This cartridge has been assembled for a cover adapted to accommodate it. In the coating, an ink flow channel was provided from the cartridge to a GEN4 head (product from Ricoh Printing Systems, Ltd.). The ink was blasted onto a recording medium (LUPILON E-2000, manufactured by Mitsubishi Engineering-Plastics Corporation, thickness: 100 μμm) through the ink flow channel at an ejection temperature of 60 ° C to form a solid coating film . The conditions were adjusted so that the solid coating film had an average thickness of about 30 μm. in both cases of brush coating and inkjet printing, the conditions were adjusted so that the solid coating film had an average thickness of about 30 μm. In the predetermined method, the prepared solid coating film was irradiated to light from the region of wavelength that corresponds to the UVA region, with the light dose being each of 400 (mJ / cm2), 800 (mJ / cm2) , and 1,200 (mJ / cm2), in order to cure the solid coating film. The resulting coating film was provided for the evaluation of coating film strength (the same in each of the Examples and Comparative Examples).
    [000100] In each of the Examples and Comparative Examples, all materials were mixed with the mixing ratio (value was represented by the parts by mass) presented and each column by examples in Table 3, in order to obtain a photopolymerizable composition.
    [000101] Note that where there is a case where a photopolymerizable composition can be used as a coating agent for brushing coating and also as an inkjet paint, and a case where a photopolymerizable composition can be used only as a coating agent, which are also shown in Table 3. Example 2
    [000102] The strength of the coating film was evaluated in the same way as in Example 1, provided that raw materials of an ink, such as the (meth) acrylate monomer component, and the polymerization intimidator, were changed for those represented in Table 3 to prepare a light-curing composition and ink of Example 2 as shown in Table 3. The results are shown in Table 3. Example 3
    [000103] The resistance of the coating film was evaluated in the same way as in Example 1, provided that raw materials of a paint, such as the (meth) acrylate monomer component, and the polymerization intimidator, were changed for those represented in Table 3 to prepare a photopolymerizable composition and the ink of Example 3 as shown in Table 3. The results are shown in Table 3. Example 4
    [000104] The strength of the coating film was evaluated in the same way as in Example 1, provided that raw materials of a paint, such as the (meth) acrylate monomer component, and the polymerization intimidator, were changed for those represented in Table 3 to prepare a photopolymerizable composition and the ink of Example 4 as represented in Table 3. The results are shown in Table 3. Example 5
    [000105] The strength of the coating film was evaluated in the same way as in Example 1, provided that raw materials of a paint, such as the (meth) acrylate monomer component, and the polymerization intimidator, were changed for those represented in Table 3 to prepare a photopolymerizable composition and the ink of Example 5 as shown in Table 3. The results are shown in Table 3. Example 6
    [000106] The strength of the coating film was evaluated in the same way as in Example 1, provided that raw materials of a paint, such as the (meth) acrylate monomer component, and the polymerization intimidator, were changed for those represented in Table 3 to prepare a photopolymerizable composition and the paint of Example 6 as shown in Table 3. The results are shown in Table 3. Example 7
    [000107] The resistance of the coating film was evaluated in the same way as in Example 1, provided that raw materials of a paint, such as the (meth) acrylate monomer component, and the polymerization intimidator, were changed for those represented in Table 3 to prepare a photopolymerizable composition and the ink of Example 7 as represented in Table 3. The results are shown in Table 3. Example 8
    [000108] The resistance of the coating film was evaluated in the same way as in Example 1, provided that raw materials of an ink, such as the (meth) acrylate monomer component, and the polymerization intimidator, were changed for those represented in Table 3 to prepare a photopolymerizable composition and the paint of Example 8 as shown in Table 3. The results are shown in Table 3. Comparative Example 1
    [000109] The strength of the coating film was evaluated in the same way as in Example 1, provided that raw materials of a paint, such as the (meth) acrylate monomer component, and the polymerization intimidator, were changed for those represented in Table 3 to prepare a photopolymerizable composition and the ink of Comparative Example 1 as represented in Table 3. The results are shown in Table 3. Comparative Example 2
    [000110] The strength of the coating film was evaluated in the same manner as in Example 1, provided that raw materials of a paint, such as the (meth) acrylate monomer component, and the polymerization intimidator, were changed for those represented in Table 3 to prepare a photopolymerizable composition and the ink of Comparative Example 2 as represented in Table 3. The results are shown in Table 3. Comparative Example 3
    [000111] The strength of the coating film was evaluated in the same way as in Example 1, provided that raw materials of a paint, such as the (meth) acrylate monomer component, and the polymerization intimidator, were changed for those represented in Table 3 to prepare a photopolymerizable composition and the ink of Comparative Example 3 as represented in Table 3. The results are shown in Table 3. Comparative Example 4
    [000112] The strength of the coating film was evaluated in the same way as in Example 1, provided that raw materials of an ink, such as the (meth) acrylate monomer component, and the polymerization intimidator, were changed for those represented in Table 3 to prepare a photopolymerizable composition and the ink of Comparative Example 4 as represented in Table 3. The results are shown in Table 3. Comparative Example 5
    [000113] The strength of the coating film was evaluated in the same way as in Example 1, provided that raw materials of a paint, such as the (meth) acrylate monomer component, and the polymerization intimidator, were changed for those represented in Table 3 to prepare a photopolymerizable composition and the ink of Comparative Example 5 as shown in Table 3. The results are shown in Table 3.
    [000114] The details from A1 to A3 and B1 to B3 in Table 3 are as follows. The value in parentheses after each product name is “SI value” as measured by the LLNA test described in the skin sensitivity assessment above (1). The description “no skin sensitivity” or “negative for skin sensitivity” after each product name means that the product is rated as “no skin sensitivity” or “negative for skin sensitivity” in the MSDS (Sheet Material Safety Data) described in the skin sensitivity assessment above (2).
    [000115] A1: diethylene glycol dimethacrylate, 2G (1.1), manufactured by Shin-Nakamura Chemical Co., Ltd.
    [000116] A2: caprolactone-modified hexa-acrylate dipentaerythritol, DPCA-60 (negative for skin sensitivity, evaluated in MSDS, test method: OECD 406 test guide line) manufactured by NIPPON KAYAKU Co., Ltd.
    [000117] A3: glycerol dimethacrylate, 701 (1.2), manufactured by Shin-Nakamura Chemical Co., Ltd.
    [000118] As a comparative compound, the following A4 was used.
    [000119] A4: trimethylol propane trimethyl acrylate modified by ethylene oxide, TMPT-3EO (1.0), manufactured by Shin-Nakamura Chemical Co., Ltd. [Polymerization initiator and polymerization accelerator]
    [000120] B1: 1-hydroxy-cyclohexylphenyl ketone, IRGACURE 184 (without skin sensitivity, evaluated in MSDS, test method: OECD 406 test guide line), manufactured by BASF
    [000121] B2: 2-dimethylamino-2- (4-methylbenzyl) -1-
    [000122] (4-morpholin-4-yl-phenyl) butan-1-one, IRGACURE 379 (without skin sensitivity, evaluated in MSDS, test method: OECD 406 test guide line), manufactured by BASF
    [000123] B3: an equimolar mixture of 2,4-diethyl thioxanthone, KAYACURE DETX-S (1.4), manufactured by NIPPON KAYAKU Co., Ltd., and 2-dimethylhexyl p-dimethylaminobenzoate, ESCALOL 507 (without sensitivity of skin, rated on MSDS, test method: OECD 406 test guide line), manufactured by ISP Japan. Table 3-1





    [000124] In Tables 3-1 and 3-2, * 1 denotes carbon black “# 10” manufactured by Mitsubishi Chemical Corporation mixed with a dispersing agent “SOLSPERSE 32000” manufactured by Lubrizol Japan Co. are mixed in the weight ratio 3/1; * 2 denotes that the ink can be ejected at a lower temperature than the temperature described and thus the viscosity measurement was not performed; * 3 denotes that the coating film was not cured (liquid remained or became sticky); and * 4 denotes that it had high viscosity and could not be ejected by the inkjet.
    [000125] As in Comparative Examples 1 and 2, or Comparative Examples 3 and 4, even when glycerol dimethacrylate was used instead of trimethylol propane trimethacrylate modified by ethylene oxide, there was no change particularly in the viscosity and strength of the coating film, unless the amount of glycerol dimethacrylate in the photopolymerizable monomer reached 25% by weight. Comparing Comparative Example 5 and Example 1, Example 1, in which the amount of glycerol dimethacrylate was 25% by mass, improved the strength of the coating film.
    [000126] Furthermore, as in Example 6, when the amount of glycerol dimethacrylate (A3) was increased, similarly to Example 1, the resistance of the coating film was improved more than Comparative Example 5. Additionally, it was discovered from Examples 1, 2 and 3 that when the amount of glycerol dimethacrylate (A3) was 25% by mass or greater, a coating film in which the strength was improved or had a certain strength with less light dose can be obtained adjusting the amount of diethylene glycol dimethacrylate (A1) and the amount of caprolactone-modified dipentaerythritol hexa-acrylate (A2).
    [000127] It was confirmed from the above that the three-component monomers including glycerol dimethacrylate, dipentaerythritol hexa-acrylate modified by caprolactone, and diethylene glycol dimethacrylate can improve the strength of coating film more than the three-component monomers including trimethylol ethylene oxide-modified trimethacrylate propane, caprolactone-modified dipentaerythritol hexa-acrylate, and diethylene glycol dimethacrylate disclosed by Japanese Patent Application No. 2012-46301 when the amount of dimeracrylate glycerol in the photopolymerizable monomer was 25% by weight or greater.
    [000128] It was confirmed from Examples 3 and 4 that the coating film resistance was not decreased by a certain level or more of the light was, even when the amount of polymerization initiator was reduced. Since the polymerization initiator is more expensive than monomers, it is possible to save a cost of the photopolymerizable composition.
    [000129] Furthermore, although not shown in the table, Comparative Examples 4 and 5 and Examples 1 and 6 were subjected to an evaluation of the odor function of a coating film. Odor of the coating films of Comparative Examples 4 and 5 and Examples 1 and 6 were compared with those of the coating films of Comparative Examples 4 and 5 and Examples 1 and 6 in each of which the polymerization initiator was increased to 20 parts by mass with identical monomer composition, and that of the coating films of Comparative Examples 4 and 5 and Examples 1 and 6 in each of which the film was cured with a light dose of 800 mJ / cm2 and 1,200 mJ / cm2. As a result, it was confirmed that the coating films of Comparative Examples 4 and 5 and Examples 1 and 6, in each of which the amount of polymerization initiator was 15 parts by mass, reduced odor that distinguishes the polymerization initiator under any condition of cure.
    [000130] Similarly, it was confirmed from the comparison between Example 3 and Comparative Example 4 that a very light characteristic odor for the polymerization initiator was felt from the coating film of Example 4, in which the amount of initiator polymerization was reduced, and it was effective in adjusting the amount of glycerol dimethacrylate in the photopolymerizable monomer to 25% by weight or greater for reducing the odor of the coating film.
    [000131] As the photopolymerizable composition of Example 5 had high viscosity, it was evaluated only as a coating agent. However, it has been confirmed that the resistance of the coating film can be improved by applying less light dose by adjusting the mixing ratio of three components of glycerol dimethacrylate, dipentaerythritol hexa-acrylate modified by caprolactone, and diethylene glycol dimethacrylate.
    [000132] It has been confirmed from Examples 6, 7 and 8 that a coating film of a certain strength can be obtained using 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl ) butan-1-one (B2) as a photoradical polymerization initiator even when a pigment was continued, although the resistance of the coating film containing the pigment was less than that of the coating film that did not contain the pigment.
    [000133] In all Comparative Examples and Examples exclusive to Example 5, solid coating films were produced by two methods including brush coating and inkjet printing, but the resistance of the coating film did not change depending on the production method. Suitably, a suitable method for producing a coating film can be selected depending on a requirement.
    [000134] The modalities of the present invention are as follows:
    [000135] <1> A photopolymerizable composition, including: photopolymerizable monomers containing glycerol dimethacrylate, dipentaerythritol hexa-acrylate modified by caprolactone, and diethylene glycol dimethacrylate, in which a quantity of glycerol dimethacrylate in the monomers is greater than 25% by weight.
    [000136] <2> The photopolymerizable composition according to <1>, wherein the amount of glycerol dimethacrylate in the photopolymerizable monomers is from 25% by weight to 40% by weight, an amount of caprolactone-modified hexa-acrylate in the monomers photopolymerizable is 5% by mass to 50% by mass, and an amount of diethylene glycol dimethacrylate in the photopolymerizable monomers is 25% by mass to 70% by mass.
    [000137] <3> The photopolymerizable composition according to <2>, wherein the amount of caprolactone-modified hexa-acrylate dipentaerythritol in the photopolymerizable monomers is from 5% by weight to 40% by weight.
    [000138] <4> The photopolymerizable composition according to any one of <1> to <3>, additionally including a photoradical polymerization initiator.
    [000139] <5> The photopolymerizable composition according to <4>, wherein the photoradical polymerization initiator is 1-hydroxy-cyclohexylphenyl ketone, 2-dimethylamino-2- (4-methylbenzyl) -1- (4- morfolin-4-yl-phenyl) butan-1-one, 2,4-diethyl thioxanthone, or any combination thereof.
    [000140] <6> The photopolymerizable composition according to any one of <1> to <5>, additionally including a colorant.
    [000141] <7> An inkjet ink, including: the light-curing composition according to any of <1> to <6>.
    [000142] <8> An ink cartridge, including: the photopolymerizable inkjet ink according to <7>; and a container, in which the light-curable inkjet ink is housed in the container. Reference Signal List 200: ink cartridge 241: ink pouch 242: ink inlet 243: ink outlet 244: cartridge case
    权利要求:
    Claims (8)
    [0001]
    1. Light-curing composition, characterized by the fact that it comprises: light-curing monomers containing glycerol dimethacrylate, dipentaerythritol hexa-acrylate modified by caprolactone, and diethylene glycol dimethacrylate, in which an amount of dimeracrylate glycerol in the photopolymerizable monomers by weight is 40% by weight% of 40% by weight% of 40% by weight. in large scale.
    [0002]
    2. Light-curing composition according to claim 1, characterized by the fact that an amount of caprolactone-modified hexa-acrylate dipentaerythritol in the light-curing monomers is from 5% by weight to 50% by weight, and an amount of diethylene glycol dimethacrylate in light-curing monomers is 25% by weight to 70% by weight.
    [0003]
    3. Photopolymerizable composition according to claim 2, characterized by the fact that the amount of dipentaerythritol hexa-acrylate modified by caprolactone in the photopolymerizable monomers is from 5% by weight to 40% by weight.
    [0004]
    Photopolymerizable composition according to any one of claims 1 to 3, characterized in that it additionally comprises a photoradical polymerization initiator.
    [0005]
    5. Light-curing composition according to claim 4, characterized by the fact that the photoradical polymerization initiator is 1-hydroxy-cyclohexylphenyl ketone, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin -4-yl-phenyl) butan-1-one, 2,4-diethyl thioxanthone, or any combination thereof.
    [0006]
    6. Light-curing composition according to any one of claims 1 to 5, characterized in that it additionally comprises a colorant.
    [0007]
    7. Photopolymerizable inkjet ink characterized by the fact that it comprises: the photopolymerizable composition as defined in any one of claims 1 to 6.
    [0008]
    8. Ink cartridge characterized by the fact that it comprises: the light-curing ink of light-curing ink as defined in claim 7; and a container, in which the light-curable inkjet ink is housed in the container.
    类似技术:
    公开号 | 公开日 | 专利标题
    BR112014028699B1|2021-01-12|light-curing composition, light-curing inkjet ink, and ink cartridge
    BR102013013568B1|2021-06-22|light-curing inkjet ink, ink cartridge, and inkjet printing device
    BR112015007572B1|2021-05-11|light-curing composition, light-curing inkjet ink, and ink cartridge
    BR112014021597B1|2021-07-06|light-curing inkjet ink and ink cartridge
    BR112014011047B1|2021-05-11|light curing ink jet ink
    EP2801595B1|2018-07-25|Photopolymerizable inkjet ink, ink cartridge, photopolymerizable composition, and coated matter
    BR112013028897B1|2020-12-15|PHOTOPOLIMERIZABLE INK JET INK, INK CARTRIDGE, AND INK JET ENGRAVING DEVICE
    BR112016028322B1|2021-08-03|PHOTOPOLYMERIZABLE COMPOSITION, PHOTOPOLYMERIZABLE INK, COMPOSITION CONTAINER, IMAGE FORMATION METHOD OR CURED PRODUCT, IMAGE FORMATION DEVICE OR CURED PRODUCT, AND IMAGE OR CURED PRODUCT
    US9624392B2|2017-04-18|Photopolymerizable inkjet ink, ink cartridge, photopolymerizable composition, and coated matter
    US9988478B2|2018-06-05|Photopolymerizable composition, photopolymerizable ink jet ink, and ink cartridge
    BR112015006911B1|2021-06-01|PHOTOPOLYMERIZABLE COMPOSITION, PHOTOPOLYMERIZABLE INKJET INK, AND INK CARTRIDGE
    US9150743B2|2015-10-06|Photopolymerizable composition, photopolymerizable ink jet ink, ink cartridge, and coated matter
    同族专利:
    公开号 | 公开日
    US20160297912A1|2016-10-13|
    CN104302681A|2015-01-21|
    IN2014KN02413A|2015-05-01|
    RU2580834C1|2016-04-10|
    EP2850114B1|2017-03-15|
    US20150126636A1|2015-05-07|
    WO2013172480A1|2013-11-21|
    EP2850114A1|2015-03-25|
    US9399717B2|2016-07-26|
    BR112014028699A2|2017-06-27|
    JP6160229B2|2017-07-12|
    CN104302681B|2016-08-17|
    JP2013256659A|2013-12-26|
    EP2850114A4|2015-09-30|
    US9777095B2|2017-10-03|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US5266441A|1989-07-29|1993-11-30|Canon Kabushiki Kaisha|Image forming medium and image forming method|
    JPH0469311A|1990-07-06|1992-03-04|Kanebo Ltd|Composition polymerizable and curable with visible light|
    EP0722098B1|1993-09-30|2003-01-29|Grapac Japan Co., Inc.|Lens manufacturing method, lensed article manufacturing method, lensed article, and partition-forming resin composition|
    US5736609A|1995-06-30|1998-04-07|Mitsui Toatsu Chemicals, Inc.|Sulfur-containing urethane-based resin composition, its resin, and optical element and lens comprising resin|
    US6114404A|1998-03-23|2000-09-05|Corning Incorporated|Radiation curable ink compositions and flat panel color filters made using same|
    JP2000347397A|1999-06-04|2000-12-15|Jsr Corp|Radiation sensitive resin composition and its use for interlayer dielectric|
    GB2371551B|2001-01-29|2003-07-30|Sericol Ltd|A printing ink|
    CN1310707C|2002-01-29|2007-04-18|西巴特殊化学品控股有限公司|Process for the production of strongly adherent coatings|
    JP4197447B2|2003-03-31|2008-12-17|富士フイルム株式会社|Method for manufacturing organic electroluminescent device and organic electroluminescent device|
    JP2004359843A|2003-06-05|2004-12-24|Nippon Shokubai Co Ltd|Actinic-radiation-curing composition|
    JP2005078941A|2003-08-29|2005-03-24|Fuji Photo Film Co Ltd|Manufacturing method of organic electroluminescent element and organic electroluminescent element|
    JP4674053B2|2004-03-31|2011-04-20|理想科学工業株式会社|Non-aqueous inkjet ink|
    DE102004034416A1|2004-07-15|2006-02-02|"Stiftung Caesar" |Liquid, radiation-curing compositions|
    US20060093955A1|2004-11-01|2006-05-04|Kohichi Ohshima|Image forming method, and image forming apparatus and process cartridge using the image forming method|
    JP3947754B1|2006-01-20|2007-07-25|株式会社セイコーアドバンス|UV curable printing ink|
    US20080124555A1|2006-11-29|2008-05-29|3M Innovative Properties Company|Polymerizable composition comprising perfluoropolyether urethane having ethylene oxide repeat units|
    JP5340549B2|2007-02-19|2013-11-13|富士フイルム株式会社|Ink composition, inkjet recording method, and printed matter|
    US8361605B2|2007-04-24|2013-01-29|Mitsui Chemicals, Inc.|Photosensitive resin composition, dry film, and processed product made using the same|
    EP2028241A1|2007-08-09|2009-02-25|Seiko Epson Corporation|Photocurable ink composition, ink cartridge, inkjet recording method and recorded matter|
    JP5176432B2|2007-08-27|2013-04-03|Ｊｎｃ株式会社|Method for forming cured film|
    JP5125345B2|2007-09-19|2013-01-23|日立化成工業株式会社|Liquid crystal display|
    JP2009122478A|2007-11-16|2009-06-04|Chisso Corp|Coloring liquid for color filter|
    JP2010202736A|2009-03-02|2010-09-16|Seiko Epson Corp|Photocurable ink composition, method for inkjet recording, recorded matter, ink set, ink cartridge, and recording apparatus|
    JP2011132382A|2009-11-25|2011-07-07|Toyo Ink Sc Holdings Co Ltd|Inkjet ink for color filter|
    JP2011173405A|2010-01-27|2011-09-08|Seiko Epson Corp|Inkjet recording system and recording method|
    JP5990868B2|2010-04-09|2016-09-14|株式会社リコー|Film production method and film by ink jet method|
    JP5843215B2|2010-10-08|2016-01-13|株式会社リコー|Inkjet recording method|
    US8652728B2|2010-10-18|2014-02-18|Konica Minolta Business Technologies, Inc.|Toner for electrostatic latent image development and production method thereof|
    JP5737141B2|2010-12-14|2015-06-17|株式会社リコー|Active energy ray-curable ink for inkjet, ink container, image forming apparatus and image forming method|
    JP2012140550A|2011-01-04|2012-07-26|Ricoh Co Ltd|Ultraviolet-curable ink and inkjet recording method|
    JP5879689B2|2011-02-07|2016-03-08|株式会社リコー|Photopolymerizable inkjet black ink, ink cartridge, inkjet printer, printed matter, and manufacturing method|
    JP5966482B2|2011-03-25|2016-08-10|株式会社リコー|Ink jet recording method and ink jet recording apparatus|
    JP5803582B2|2011-05-12|2015-11-04|株式会社リコー|Photopolymerizable inkjet ink, ink cartridge, printer|
    JP5874194B2|2011-05-16|2016-03-02|株式会社リコー|Photopolymerizable inkjet ink, ink cartridge, printer|
    JP5803583B2|2011-11-07|2015-11-04|株式会社リコー|Photopolymerizable inkjet ink|
    RU2580834C1|2012-05-18|2016-04-10|Рикох Компани, Лтд.|Photopolymerizable composition, photopolymerizable inkjet ink and ink cartridges|
    JP6142506B2|2012-05-29|2017-06-07|セイコーエプソン株式会社|Inkjet ink composition, ink container, and inkjet recording method|
    JP6123529B2|2013-07-05|2017-05-10|株式会社リコー|Photopolymerizable inkjet ink, ink cartridge, and inkjet recording apparatus|JP5803583B2|2011-11-07|2015-11-04|株式会社リコー|Photopolymerizable inkjet ink|
    RU2580834C1|2012-05-18|2016-04-10|Рикох Компани, Лтд.|Photopolymerizable composition, photopolymerizable inkjet ink and ink cartridges|
    JP6277772B2|2013-04-23|2018-02-14|株式会社リコー|Photopolymerizable composition, photopolymerizable inkjet ink, ink cartridge, coated product|
    JP6299274B2|2013-05-07|2018-03-28|株式会社リコー|Photopolymerizable composition, photopolymerizable inkjet ink, ink cartridge, coated product|
    JP6497006B2|2013-09-27|2019-04-10|株式会社リコー|Active energy ray-curable composition, cured product thereof, container containing the composition, and inkjet discharge apparatus including the container|
    JP6255864B2|2013-10-04|2018-01-10|株式会社リコー|Photopolymerizable composition, photopolymerizable inkjet ink, ink cartridge|
    JP6780227B2|2015-03-17|2020-11-04|株式会社リコー|Active energy ray-curable composition|
    US10995226B2|2015-06-22|2021-05-04|Ricoh Company, Ltd.|Active-energy-ray-curable composition, active-energy-ray-curable ink composition, composition stored container, two-dimensional or three-dimensional image forming apparatus, method for forming two-dimensional or three-dimensional image, cured product, and laminated cured product|
    US10414150B2|2015-07-08|2019-09-17|Ricoh Company, Ltd.|Active-energy-ray-curable composition, composition stored container, two-dimensional or three-dimensional image forming apparatus, method for forming two-dimensional or three-dimensional image, and cured product|
    JP2017025124A|2015-07-15|2017-02-02|株式会社リコー|Active-energy-ray-curable composition|
    US10227497B2|2015-07-21|2019-03-12|Ricoh Company, Ltd.|Active energy ray curable composition, active energy ray curable ink, inkjet ink, stereoscopic modeling material, active energy ray curable composition container, two-dimensional or three dimensional image forming apparatus, two-dimensional or three-dimensional image forming method, cured product, and processed product|
    US9988539B2|2015-11-12|2018-06-05|Ricoh Company, Ltd.|Active-energy-ray-curable composition, active-energy-ray-curable ink, composition stored container, two-dimensional or three-dimensional image forming apparatus, two-dimensional or three-dimensional image forming method, cured material, and structure|
    JP2017088805A|2015-11-16|2017-05-25|株式会社リコー|Active energy ray curable composition, active energy ray curable ink, composition accommodation container, method and device for forming 2-dimensional or 3-dimensional image and molding processed article|
    JP2017088830A|2015-11-17|2017-05-25|株式会社リコー|Active energy ray curable compound, active energy ray curable ink, composition accommodation container, image formation method, image formation device, cured article, image formation article|
    JP6900172B2|2016-01-06|2021-07-07|三洋化成工業株式会社|Active energy ray-curable resin composition|
    EP3243845A1|2016-05-13|2017-11-15|Ricoh Company, Ltd.|Active energy ray curable composition, cured product, composition storage container, two-dimensional or three-dimensional image forming apparatus, and two-dimensional or three-dimensional image forming method|
    US10611920B2|2016-07-15|2020-04-07|Ricoh Company, Ltd.|Curable composition, curable ink, method for forming two-dimensional or three-dimensional images, apparatus for forming two-dimensional or three-dimensional images, cured product, structural body, and processed product|
    US10577514B2|2017-03-21|2020-03-03|Ricoh Company, Ltd.|Curable composition and cured matter|
    US11028280B2|2018-03-19|2021-06-08|Ricoh Company, Ltd.|Composition, cured product, composition stored container, image forming apparatus, and image forming method|
    法律状态:
    2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-20| B06I| Publication of requirement cancelled [chapter 6.9 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |
    2020-02-11| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-10-13| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-01-12| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 17/05/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2012-113970|2012-05-18|
    JP2012113970|2012-05-18|
    PCT/JP2013/064423|WO2013172480A1|2012-05-18|2013-05-17|Photopolymerizable composition, photopolymerizable inkjet ink, and ink cartridge|
    [返回顶部]