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    • 专利摘要:
    light-curing inkjet ink, ink cartridge, and inkjet engraving device. a photopolymerizable inkjet ink including: at least one selected from the group consisting of negative (meth) acrylic acid esters for skin sensitization and negative (meth) acrylamides for skin sensitization; and at least one selected from the group consisting of vinyl negative ethers for skin sensitization, negative t-butyl methacrylate for skin sensitization, negative n-pentyl methacrylate for skin sensitization and negative n-hexyl methacrylate for skin sensitization.
    公开号:BR112013028897B1
    申请号:R112013028897-3
    申请日:2012-05-10
    公开日:2020-12-15
    发明作者:Takao Hiraoka
    申请人:Ricoh Company, Ltd；
    IPC主号:
    专利说明:

    Technical Field
    The present invention relates to a photopolymerizable inkjet ink, an ink cartridge that houses the photopolymerizable inkjet ink and an inkjet recording device containing the ink cartridge mounted thereon. Background of the technique
    Photopolymerizable inkjet inks containing (meth) acrylic acid esters and photopolymerizable inkjet inks containing (meth) acrylic acid and vinyl ethers in combination are widely known (see, for example, PTL 1).
    However, many of the monomers used in such conventional photopolymerizable inkjet inks are toxic. Although esters of (meth) acrylic acid are inexpensive and easily obtainable, most of them exhibit high skin sensitization, which is an allergy-causing property on the skin kept in contact with them. Conventional technique has shown no solution to this problem.
    The present inventors have previously conducted studies on this problem and have discovered some esters of (meth) acrylic acid and (meth) acrylamides negative for skin sensitization. However, in an attempt to produce an ink with a practical level of curing property from these compounds, the resulting ink disadvantageously becomes more viscous than commonly used inkjet inks. Thus, an ejection head capable of being heated to a temperature high enough to reduce ink viscosity should be used to use ink for inkjet printing. In addition, the head's internal pressure must be increased considerably to eject the ink, making it difficult to eject the ink steadily. Citation List Patent Literature
    PTL 1: Japanese Patent Application filed in Open (JP-A) No. 2004-526820 Summary of the Invention Technical problem
    An object of the present invention is to provide a photopolymerizable inkjet ink which does not involve skin sensitization and which has low viscosity and improved healing properties; a photopolymerizable cartridge; and an inkjet recording device containing the ink cartridge mounted thereon. Solution to the Problem
    Means for solving the problems are as follows. Specifically, a photopolymerizable ink jet ink of the present invention includes: at least one selected from the group consisting of negative (meth) acrylic acid ester for skin sensitization and negative (meth) acrylamide for skin sensitization; and at least one selected from the group consisting of vinyl ether negative for skin sensitization, negative t-butyl methacrylate for skin sensitization, negative n-pentyl methacrylate for skin sensitization and negative n-hexyl methacrylate for skin sensitization . Advantageous Effects of the Invention
    The present invention can provide: a photopolymerizable inkjet ink which does not involve skin sensitization and which has low viscosity and an improved healing property; an ink cartridge that houses the light-curing inkjet ink; and an inkjet recording device containing the ink cartridge mounted thereon. Brief Description of Drawings
    FIG. 1 schematically illustrates an exemplary ink pouch for an ink cartridge.
    FIG. 2 schematically illustrates an ink cartridge that houses an ink pouch.
    FIG. 3 schematically illustrates an exemplary inkjet recording device. Description of Achievements (Light Curing Inkjet Ink)
    A photopolymerizable inkjet ink of the present invention includes: at least one selected from the group consisting of negative (meth) acrylic acid esters for skin sensitization and negative (meth) acrylamides for skin sensitization; and at least one selected from the group consisting of vinyl negative ethers for skin sensitization, negative t-butyl methacrylate for skin sensitization, negative n-pentyl methacrylate for skin sensitization and negative n-hexyl methacrylate for skin sensitization . The photopolymerizable inkjet ink of the present invention can include a photo-radical polymerization initiator and, if necessary, include other ingredients.
    No materials have yet been identified that can be used for the light-curable inkjet ink (hereinafter referred to as "ink") which do not cause skin sensitization and can sufficiently reduce the viscosity of the ink and confer healing properties enough ink when used individually. Then, using combinations of negative monomers for skin sensitization, the present inventors examined favorable balances between a monomer having high viscosity, but good healing property, and a monomer having good healing property, but low viscosity. As a result, they found that vinyl ether, t-butyl methacrylate, n-pentyl methacrylate and n-hexyl methacrylate as light-curing monomers have sufficiently low and negative viscosity for skin sensitization and have been successful in preparing an ink with low viscosity and enhanced healing property by combining the above light-curing monomers with negative (meth) acrylic acid for skin sensitization and / or negative (meth) acrylamide for skin sensitization, both of which the present inventors have previously discovered.
    Here, the photopolymerizable monomer that does not cause skin sensitization refers to at least one of the following compounds (1) to (3): (1) a compound having a Stimulation Index (SI - Stimulation Index) of less than 3, where the Stimulation Index indicates the extent of sensitization, as measured by a skin sensitization test based on the LLNA (Local Lymph Node Assay - Local Lymph Node assay); (2) a compound rated "negative for skin sensitization" or "no skin sensitization" in its MSDS (Material Safety Data Sheet); and (3) a compound rated "negative for skin sensitization" or "no skin sensitization" in the literature [for example, Contact Dermatitis 8: 223-235 (1982)].
    In relation to (1) above, the compound having an SI value of less than 3 is considered to be negative for skin sensitization, as described in the literature, for example, "Functional Material" (Kino Zairyoii) 2005, September, Vol. 25 , No. 9, page 55. The lower SI value means less skin sensitization. Thus, in the present invention, a monomer or an oligomer having a lower SI value is preferably used. The SI value of the monomer or oligomer used is less than 3, preferably 2 or less, more preferably 1.6 or less. <(Met) Acrylic Acid and (Met) Acrylamide Ester>
    Examples of the (meth) acrylic acid or (meth) acrylamide ester which are negative for skin sensitization, cheap and easily obtainable include polyethylene glycol dimethacrylates represented by the General Formula (1) below, Y-butyrolactone methacrylate, trimethacrylate trimethylolpropane, tricyclodecanedimethanol dimethacrylate, caprolactone modified dipentaerythritol hexa-acrylate, polypropylene glycol diacrylate [CH2 = CH-CO- (OC3H6) n-OCOCH = CH2 (n is 12), where n is the average degree of polymerization], neopentyl glycol hydroxypivalate diacrylates modified with caprolactone, polyethoxylated tetramethylol tetra acrylate, ethylene oxide modified bisphenol A diacrylate, neopentyl glycol dimethacrylate, acrylamide hydroxyethyl and stearyl acrylate. These can be used individually or in combination.

    In General Formula (1), n is an integer from 9 to 14, where n is the average degree of polymerization.
    The amount of at least one (meth) acrylic acid ester that is negative for skin sensitization and (meth) acrylamide negative for skin sensitization is preferably 10% by mass to 90% by mass, more preferably 40% by mass to 60% by weight in relation to the total amount of monomers.
    When the quantity of them is excessively small, the photocure reaction does not proceed satisfactorily. As a result, there may be degradation in the quick drying performance and strength of a coated film, which are advantageous characteristics of photopolymerizable inks. In contrast, when the quantity of these is excessively large, several materials other than these monomers are incorporated only in small quantities. In particular, limitation is imposed on the amounts of a dye and a polymerization initiator, which are important materials. In this case, it becomes difficult to form a coated film having a sufficiently high density hue and obtain quick drying performance and resistance of a coated film, which are advantageous characteristics of light-curable inks. However, this is not true in the case of the formation of a colorless film or a light-colored film that requires only a small amount of a colorant and the use of electron beams as a light source with which the polymerization reaction can proceed. without polymerization initiator.
    Specifically, other (meth) acrylates, (meth) acrylamides and vinyl ethers, which have little skin sensitization when used individually or which have not been confirmed for skin sensitization, could be used in combination, as long as the amount of them falls within a range such that it does not cause any problems such as paints. Specifically, the following are exemplified: ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Y-butyrolactone acrylate, isobornyl (meth) acrylate, formalized trimethylol mono (meth) acrylate , polytetramethylene glycol di (meth) acrylate, trimethylolpropane (meth) acrylate benzoate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol diacrylates , [CH2 = CH-CO- (OC2H4) n-OCOCH = CH2 where n is 4], [CH2 = CH-CO- (OC2H4) n-OCOCH = CH2 where n is 9], [CH2 = CH-CO- (OC2H4) n-OCOCH = CH2 where n is 14] and [CH2 = CH-CO- (OC2H4) n- OCOCH = CH2 where n is 23], dipropylene glycol di (meth) acrylate, di (meth) acrylate tripropylene glycol, polypropylene glycol dimethacrylate [CH2 = C (CH3) -CO- (OC3H6) n -OCOC (CH3) = CH2, where n is 7)], 1,3-butanediol di (meth) acrylate, diacrylate 1,4-butanediol, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neop diacrylate entyl glycol, tricyclodecanedimethanol diacrylate, propylene oxide modified di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipentaerythritol hex (meth) acrylate, (meth) acryloyl morpholine, 2-hydroxypropyl (meth) acrylamide, propylene oxide modified tetramethylolmethane tetra (meth) acrylate, dipentaerythritol hydroxy (meth) acrylate, hydroxyipenta (meth) acrylate modified dipentaerythritol acrylate, titr (meth) acrylate tritrate, tetra (meth) acrylate, tetra (meth) acrylate trimethylpropane, ethylene oxide modified trimethylpropane tri (meth) acrylate, propylene oxide modified trimethylpropane tri (meth) acrylate, caprolactone modified tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri (meth) acrylate, tri (meth) acrylate met) tris (2-hydroxyethyl) isocyanurate acrylate, neopentyl glycol diacrylate, ethoxylated neopentyl glycol di (meth) acrylate, pro-oxide modified neopentyl glycol di (meth) acrylate pilene, propylene oxide modified glyceryl tri (meth) acrylate, polyester di (meth) acrylate, polyester tri (meth) acrylate, polyester tetra (meth) acrylate, polyester (p) (meth) acrylate, poly (meth) ) polyester acrylate, N-vinylcaprolactam, N-vinylpyrrolidone, N-vinylformamide, polyurethane di (meth) acrylate, polyurethane tri (meth) acrylate, polyurethane tetra (meth) acrylate, polyurethane penta (meth) acrylate, poly (meth) polyurethane acrylate, cyclohexane dimethanol divinyl ether, dimethanol cyclohexane monovinyl ether, hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, diethylene glycol ether divinyl, dicyclopentadiene vinyl ether, tricyclodecane vinyl ether, benzyl vinyl ether and ethyloxetanomethyl vinyl ether. These can be used individually or in combination. <T-Butyl methacrylate, n-pentyl methacrylate and n-hexyl methacrylate>
    Examples of vinyl ether negative for skin sensitization include triethylene glycol divinyl ether, hydroxybutyl vinyl ether and ethyl vinyl ether. Among them, triethylene glycol divinyl ether is preferred, as it has sufficiently low viscosity and has a boiling point to be easily manipulated under common temperature and pressure.
    As described above, when at least one vinyl ether, t-butyl methacrylate, n-pentyl methacrylate and n-hexyl methacrylate having sufficiently low viscosity was used, the paint obtained may have reduced viscosity and enhanced curing properties, while it is negative for skin sensitization when compared to an ink containing none of them.
    The amount of at least one vinyl ether negative for skin sensitization, negative t-butyl methacrylate for skin sensitization, negative n-pentyl methacrylate for skin sensitization and negative n-hexyl methacrylate for skin sensitization is preferably , 10 wt% to 90 wt%, more preferably 40 wt% to 60 wt% with respect to the total amount of monomers.
    The above monomers all have a sufficiently low viscosity, but do not have very high polymerization reactivity. Thus, when their quantity is excessively small, it may be difficult for the resulting ink to have reduced viscosity to the point where good ejection performance can be obtained. When the quantity of them is excessively large, the photocure reaction does not proceed satisfactorily and the fast drying performance, which is an advantageous characteristic of photopolymerizable inks, cannot be obtained in some cases. <Photo-radical polymerization initiator>
    The ink of the present invention preferably contains a photo-radical polymerization initiator.
    More preferably, the photo-radical polymerization initiator is negative for skin sensitization.
    The (meth) acrylic acid ester, (meth) acrylamide and vinyl ether are also known to have cationic polymerization properties.
    Photocationic polymerization initiators are generally expensive and generate a trace amount of a strong acid, even in the state where they are not irradiated with light. Thus, it is necessary to take special care, such as giving acid resistance to the ink supply channel of a printer, imposing limitations on the choice of the constituent elements of the printer. In contrast, the ink of the present invention can contain the photo-radical polymerization initiator which is inexpensive and does not generate strong acid. Thus, it is possible to produce ink at a low cost and it is also easy to choose the constituent elements of a printer. Needless to say, when using a very high energy light source, such as electron beams, α-rays, β-rays, Y-rays or X-rays, polymerization reactions proceed without a polymerization initiator. This is a conventionally known subject and is not described in detail in the present invention.
    The photo-radical polymerization initiator is, for example, a self-cleaving photopolymerization initiator and a hydrogen capture polymerization initiator.
    Examples of the self-cleaving photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-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- {4- [4- (2-hydroxy-2-methylpropionyl ) benzyl] phenyl} -2-methyl-1-propan-1-one, phenylglyoxylic acid methyl ester, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl - 2-dimethylamino-1- (4-morpholinophenyl) butanone-1,2-dimethyl-amino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, 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-acetyloxy) methanone and [4- (methylphenylthio) phenyl] phenylmethanone. These can be used individually or in combination.
    Examples of the hydrogen capture polymerization initiator include compounds such as benzophenone, methyl-2-benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide and phenylbenzophenone; and thioxanthone compounds, such as 2,4-diethyloxyantone, 2-chlorothioxanthone, isopropyloxanthone and 1-chloro-4-propyloxanthone. These can be used individually or in combination.
    Also, an amine can additionally be used as a polymerization accelerator and examples of the amine include ethyl p-dimethylaminobenzoate, 2-ethylhexyl p-dimethylaminobenzoate, methyl p-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate and p-dimethylaminobenzoate butoxyethyl.
    The amount of photo-radical polymerization initiator is preferably 1 wt% to 25 wt% in relation to the total amount of the paint. <Other Ingredients>
    If necessary, a colorant can be incorporated into the ink. The colorant usable for the ink can be a known inorganic or organic pigment.
    As for black pigments, those such as carbon black produced using the oven method or the channel method can be used.
    As for yellow pigments, for example, pigments in the Pig series. Yellow can be used: Pig. Yellow 1, Pig. Yellow 2, Pig. Yellow 3, Pig. Yellow 12, Pig. Yellow 13, Pig. Yellow 14, Pig. Yellow 16, Pig. Yellow 17, Pig. Yellow 73, Pig. Yellow 74, Pig. Yellow 75, Pig. Yellow 83, Pig. Yellow 93, Pig. Yellow 95, Pig. Yellow 97, Pig. Yellow 98, Pig. Yellow 114, Pig. Yellow 120, Pig. Yellow 128, Pig. Yellow 129, Pig. Yellow 138, Pig. Yellow 150, Pig. Yellow 151, Pig. Yellow 154, Pig. Yellow 155 and Pig. Yellow 180.
    As for magenta pigments, for example, pigments in the Pig series. Red can be used: Pig. Red 5, Pig. Red 7, Pig. Red 12, Pig. Red 48 (Ca), Pig. Red 48 (Mn), Pig. Red 57 (Ca), Pig. Red 57: 1, Pig. Red 112, Pig. Red 122, Pig. Red 123, Pig. Red 168, Pig. Red 184, Pig. Red 202 and Pig. Violet 19.
    As for cyan pigments, for example, pigments in the Pig series. Blue can be used: Pig. Blue 1, Pig. Blue 2, Pig. Blue 3, Pig. Blue 15, Pig. Blue 15: 3, Pig. Blue 15: 4, Pig. Blue 16, Pig. Blue 22, Pig. Blue 60, Vat Blue 4 and Vat Blue 60.
    As for white pigments, for example, sulfuric acid salts of alkaline earth metals, such as barium sulphate, carbonic acid salts of alkaline earth metals, such as calcium carbonate, silica, such as fine powdered silicic acid and salts of synthetic silicic acid, calcium silicate, alumina, alumina hydrate, titanium oxide, zinc oxide, talc and clay.
    In addition, various inorganic or organic pigments can be optionally used considering, for example, the physical properties of the paint.
    The amount of the colorant is preferably 1% by weight to 15% by weight in relation to the total amount of the paint.
    In addition, a polymerization inhibitor, a surfactant or a polar group containing polymeric pigment dispersing agent can be optionally used. 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. Examples of the surfactant include higher fatty acid surfactants, silicone surfactants and fluorotensive agents. (Cartridge)
    An inkjet cartridge of the present invention includes: the photopolymerizable inkjet ink of the present invention described above; and a container which houses the light-curable ink jet ink. With this form, users do not have to directly touch the paint during tasks such as changing the paint, so they do not have to worry about staining their fingers, hands or clothes. In addition, it is possible to avoid the interference of foreign matter, such as dust, with the paint.
    The container is not particularly limited and the shape, structure, size and material of the container can be appropriately selected depending on the intended purpose. For example, the container is preferably selected from those having at least one ink bag formed from an aluminum laminate film or a resin film.
    The ink cartridge will be described with reference to Figs. 1 and 2. Fig. 1 schematically illustrates an example of an ink pouch 241 from an ink cartridge. Fig. 2 schematically illustrates an ink cartridge 200 containing the ink pouch 241 shown in FIG. 1 and a cartridge case 244 which houses the ink pouch 241.
    As illustrated in FIG. 1, the ink bag 241 is filled with the ink by injecting the ink from an ink inlet 242. After removing the air present inside the ink bag 241, the ink inlet 242 is sealed by joining by Fusion. 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 element to supply ink to the device through it. The ink bag 241 is formed of a wrapping element, such as a laminated aluminum film not permeable to air. As illustrated in Fig. 2, the ink bag 241 is typically housed in a plastic cartridge case 244 which is then releasably assembled when in use with various inkjet engraving devices, such as the cartridge 200 ink.
    The ink cartridge of the present invention is preferably releasably mounted on inkjet engraving devices. The ink cartridge can simplify refilling and changing the ink to improve operability. (Inkjet engraving device)
    An inkjet engraving device of the present invention includes an inkjet unit and the ink cartridge of the present invention described above; and, if necessary, it also includes other units, such as a control unit. - Ink blasting unit -
    The ink jet unit is a unit configured to apply a stimulus to the ink of the present invention to make the ink jet and thereby form an image. The ink jet unit is not particularly limited and examples of these include ink jet heads.
    The inkjet print heads cover any one of a piezoelectric inkjet head, a thermal inkjet head and an electrostatic inkjet head. The piezoelectric inkjet head is configured to eject ink droplets by deformation of a vibration plate that forms the wall surface of an ink flow channel to change the internal volume of the ink flow channel using an element piezoelectric as a pressure generating unit configured to compress the ink within the ink flow channel (see JP-A No. 02-51734). The thermal inkjet head is configured to generate air bubbles by heating an ink inside an ink flow channel using a heating element (see document JP-A No. 61-59911). The electrostatic inkjet head is configured to eject ink droplets by deformation of a vibration plate with electrostatic force generated between an electrode and a vibration plate facing the electrode and which forms the wall surface of an electrode channel. ink flow to change the internal volume of the ink flow channel (see document JP-A No. 06-71882).
    The stimulus can be generated, for example, by a stimulus generation unit. The stimulus is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of these include application of heat (temperature), pressure, vibration and light. These can be used individually or in combination. Among them, heat and pressure are preferred.
    The stimulus generating unit is, for example, a heating device, a pressure device, a piezoelectric element, a vibration generator, an ultrasonic wave oscillator and an electric light. Specific examples of the stimulus generating unit include: piezoelectric actuators, such as a piezoelectric element; thermal actuators using phase transition resulting from boiling of film liquid caused by the use of an electric heating converter, such as a heating element; memory-shaped alloy drives that use a metal phase transition resulting from a change in temperature; and electrostatic actuators that use electrostatic force.
    The embodiment where the inkjet ink is ejected is not particularly limited and varies depending on the stimulus applied. In the case where the stimulus is corresponding to the recording signals, it is applied to the ink present in a recording head using, for example, a thermal head, to cause foaming of the ink by the applied thermal energy and the pressure of the resulting foam is used to eject drops of ink from the nozzle openings of the recording head. In the case where the stimulus is "pressure", there is a method by which tension is applied to a piezoelectric element that adheres to a position called a pressure chamber in the ink flow channel inside the recording head, in order to bend the element piezoelectric and the reduction in the volume of the pressure chamber caused by the bent piezoelectric element initiates the ink droplets ejection from the nozzle openings of the recording head.
    The control unit is not particularly limited, as long as it can control the operation of each unit and can be properly selected depending on the intended purpose. Examples of it include devices such as a sequencer and a computer.
    Here, Fig. 3 schematically illustrates an exemplary inkjet engraving device.
    The inkjet recording device illustrated in Fig. 3 forms a color image as follows.
    Specifically, printing units 3 (that is, printing units 3a, 3b, 3c and 3d for respective colors (for example, yellow, magenta, cyan and black)) eject colored inks (yellow, magenta, cyan and black) on a base material to be printed 2 (which is transported from left to right in Fig. 3) fed from a feed roller of base material 1 and light (UV rays) is applied from UV light sources ( curing light sources) 4a, 4b, 4c and 4d to the corresponding colored inks for curing. Each of the printing units 3a, 3b, 3c and 3d has a heating mechanism on an ink ejection portion of the same and a cooling mechanism on a supporting portion of the base material (i.e., a portion above or below the base material in Fig. 3). The heating mechanism serves to heat a paint with a high viscosity in order to decrease its viscosity. The cooling mechanism serves to cool the base material to about room temperature in a contact or non-contact manner, if necessary. In the case where the ink is heated for ejection, when the printing area of the previously printed color is small and the transport speed of the base material is low, the base material is naturally cooled and kept around room temperature for subsequent printing . However, when the print area of the previously printed color is large and the transport speed of the base material is high, the temperature of the base material increases, potentially causing behavioral variation between the respective colored inks, such as wetting and diffusion. of the ink droplets that have been blasted onto the base material or the previously blasted ink, thus adversely affecting image formation. Thus, if necessary, the cooling mechanism can be provided to keep the base material around room temperature.
    The base material 2 used is, for example, paper, a film, a metal or a composite material thereof. The base material 2 shown in Fig. 3 is a roll, but it can be a sheet.
    In addition, the base material can be subjected to double-sided printing as well as single-sided printing.
    When UV rays are applied to each of the colored inks for each printing process, the colored inks are cured satisfactorily. In order to achieve high speed printing, UV light sources 4a, 4b and 4c may have reduced output power or may be omitted, so that the UV light source 4d is made to apply a sufficient dose of UV rays to a composite printed image formed of a plurality of colors. In addition, for the purpose of saving energy and reducing costs, LED light sources, which have recently been used in a practical way for printing with light-curable inks, can be used instead of conventionally used light sources, such as mercury lamps high-pressure lamps and metal halide lamps.
    In Fig. 3, reference numeral 5 denotes a processing unit and reference numeral 6 denotes a take-up roll for printed products. Examples
    The present invention will be described below by way of Examples, which should not be construed as limiting the present invention to them. (Examples 1 to 17)
    The materials (A) to (C) below were mixed together in the quantities of the corresponding columns of the Examples shown in Table 3 to thereby obtain inks. In Table 3, the units of material quantities (A) to (C) are part (s) by mass. (A) Ether of (meth) acrylic acid and / or (meth) acrylamide, each of which is negative for skin sensitization. (B) Triethylene glycol divinyl ether, t-butyl methacrylate, n-pentyl methacrylate and / or n-hexyl methacrylate, each of which is negative for skin sensitization. (C) Negative photo-radical polymerization initiator for skin sensitization. A1 to A14, B1 to B4 and C1 to C4 shown in Table 3 are as follows. The value in parentheses after each product name is the "SI value", as measured by the LLNA test described in (1) above. The description "negative" or "none" after each product name means that the product is rated "negative for skin sensitization" or "no skin sensitization" in the MSDS (Material Safety Data Sheet) ) described in (2) above or in the literature described in (3) above. The method of calculating the SI value will be described in detail below. A1: Dipentaerythritol hexa-acrylate modified with caprolactone "DPCA-60" (rated "negative" in MSDS), product of NIPPON KAYAKU Co. Ltda. (test method: OECD test, guideline 406) A2: Polyethoxylated tetramethylolmethane tetra-acrylate "ATM-35E" (1.7), product of Shin.Nakamura Chemical Co., Ltda. A3: Bisphenol A diacrylate modified with ethylene oxide "BPE-10" (1.2), product of DAI-ICHI KOGYO SEIYAKU CO., LTDA. A4: Neopentyl glycol hydroxypivalate diacrylate modified with caprolactone "HX-620" (0.9), product of NIPPON KAYAKU Co. Ltda. A5: Hydroxyethylacrylamide "HEAA" ("none"), product of KOHJIN Co., Ltda. (test method: OECD test, guideline 429) A6: Polypropylene glycol diacrylate [CH2 = CH-CO- (OC3H6) n-OCOCH = CH2 (n is 12)] "M-270" (1.5), product from Toagosei Chemical Co., LTDA. A7: Tricyclodecanedimethanol dimethacrylate "DCP" (1.3), product of Shin-Nakamura Chemical Co., Ltda. A8: Polyethylene glycol dimethacrylate represented by Formula (1) (n is 14) "LIGHT ESTER 14EG" (1.6), product of KYOEISHA CHEMICAL CO., LTDA. A9: Polyethylene glycol dimethacrylate represented by Formula (1) (n is 9) "LIGHT ESTER 9EG" (1.3), product of KYOEISHA Chemical Co., LTDA. A10: Trimethylolpropane trimethacrylate "SR350" (1.9), product of Sartomer Co. A11: Y-butyrolactone methacrylate "GBLMA" (2.1), product of OSAKA ORGANIC CHEMICAL INDUSTRY, LTDA. A12: Stearyl acrylate "STA" (2.7), product of OSAKA ORGANIC CHEMICAL INDUSTRY, LTDA. A13: Neopentyl glycol dimethacrylate "NPG" (2.0), product of Shin-Nakamura Chemical Co., Ltda. A14: 1,4-Butanediol dimethacrylate "SR214" (2.6), product of Sartomer Co. 81: Triethylene glycol divinyl ether (rated "negative" in MSDS) (test method: OECD test, guideline 406), product of BASF Co. 82: "LIGHT ESTER TB" t-butyl methacrylate (rated "negative" in the literature) (test method: the maximization method), product of KYOEISHA CHEMICAL CO., LTDA. 83: "n -AMYL METHACRYLATE" n-pentyl methacrylate (rated "negative" in the literature) (test method: the maximization method), product of Toyo Science Corp. 84: N-hexyl methacrylate "HEXYL METHACRYLATE" (rated "negative" in the literature) (method: the maximization method), product of and TOKYO CHEMICAL INDUSTRY CO., LTDA. C1: 2-Dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one (rated "none" in the MSDS) (test method: OECD test, guideline 406) C2: 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (rated "none" in the MSDS) (test method: OECD test, guideline 406) C3: 2-Benzyl -2-dimethylamino-1- (4-morpholinophenyl) -1- butanone (rated "none" in the MSDS) (test method: OECD test, guideline 406) C4: equimolar mixture of 2,4-diethyl-thioxanthone (1.4) and 2-ethyl-p-dimethylaminobenzoate (rated "none" in the MSDS) (test method: OECD test, guideline 406)
    Measurement method <A for SI value>
    According to the skin sensitization test based on the LLNA (Local Lymph Node Assay - Local Lymph Node assay), the SI value was measured as described below. [Test Materials] <Positive Control>
    a-Hexylcinamaldehyde (HCA; product of Wako Pure Chemical Industries, Ltd.) was used as a positive control. <Vehicle>
    The vehicle used was a mixture containing the acetone listed below and olive oil in a 4: 1 volume ratio. • Acetone (product of Wako Pure Chemical Industries, Ltda.) • Olive oil (product of Fudimi Pharmaceutical Co., Ltda.) <Animals Used>
    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 were divided into two groups (4 mice / group) using the stratified body weight random sampling method, so that the body weight of each individual 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 onset of sensitization. The animals remaining after classification were excluded from the test.
    The animals were identified individually by applying oil paint on their tail throughout the test period and their cages were also labeled for identification. <Accommodation Environment>
    During the entire housing period, including the quarantine / acclimatization period, the animals were housed in an animal room with a barrier system, which was adjusted as follows: temperature from 21 ° C to 25 ° C, relative humidity of 40 % to 70%, air circulation frequency from 10 times / hour to 15 times / hour and lighting cycle of 12 hours (lighting from 7:00 am to 7:00 pm). The housing cages used were those made of polycarbonate and four animals were housed in each cage.
    The animals received an ad libitum solid diet for laboratory animals MF (product of Oriental Yeast Co., Ltda.). In addition, using a water supply bottle, running water ad libitum was provided, into which sodium hypochlorite (PURELOX, a product of OYALOX Co., Ltd.) had been added, so that the chlorine concentration was about 5 ppm. The forage used was SUNFLAKE (spruce, shavings obtained with an electric planer (product from Charles River Inc.). The diet and feeding equipment were sterilized with an autoclave (121 ° C, 30 min) before use.
    The cage and forage were replaced with new ones at the time of classification and removal of the auricular lymph node (that is, at the time when the animals were transferred from the animal room) and the water supply bottle and shelf were replaced with new ones at the time classification. [Test Method A] <Group Composition>
    The group composition used to measure the SI value is shown in Table 1. Table 1
    [Preparation] <Test Substance>
    Table 2 shows the amount of the 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 thus prepared was placed in an airtight container protected from light (made of glass). Table 2
    <Positive Control>
    0.25 g of HCA was precisely weighed and a vehicle was added to the HCA to have the volume of 1 ml to thereby prepare a 25.0% w / v solution. The solution thus prepared was placed in an airtight container protected from light (made of glass). <BrdU>
    200 mg of 5-bromo-2'-deoxyuridine (BrdU, product of NACALAI TESQUE, INC.) Were precisely weighed in a measuring flask. Then, physiological saline solution (product of OTSUKA PHARMACEUTICAL CO.) Was added to the measuring bottle and dissolved by applying ultrasonic waves. The volume of the resulting solution was adjusted to 20 ml to prepare a 10 mg / ml solution (BrdU preparation). The solution thus prepared was sterilized by means of filtration with a sterile filtration filter and placed in a sterile container. <Preparation Day and Storage Period>
    The positive control preparation was prepared the day before sensitization started and stored in a cold place, except when in use. The vehicle and test substance preparations were made on a sensitization day. 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>
    Each (25 μL) one of the test substance preparations, positive control preparation and 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>
    About 48 hours after the final sensitization, the BrdU preparation (0.5 mL) was administered intraperitoneally once to each animal. [Observation and Examination] <General Conditions>
    All animals used in the test were observed once or more times a day, from the day of initiation of sensitization to the day of removal of the auricular lymph node (that is, the day when the animals were moved from the animal room). Specifically, the observation day was counted as the day of initiation of awareness and was considered Day 1. <Measuring Body Weights>
    The body weight of each animal was measured on the day the sensitization started and on the day of removal of the auricular lymph node (that is, the day when the animals were transferred from the animal room). In addition, the average body weights and the respective standard errors were calculated for each group. <Removal of Auricular Lymph Node and Mass Measurement>
    About 24 hours after BrdU administration, the animals were euthanized and their auricular lymph nodes were collected. The tissue surrounding each atrial lymph node was removed and the atrial lymph nodes in both atria were weighed at once. In addition, the mean weights of the atrial lymph nodes and the respective standard error were calculated for each group. After measuring the weights, the ear lymph nodes of each individual were stored in a frozen state using a BIO MEDICAL FREEZER freezer set to -20 ° C. <Measurement of BrdU uptake>
    After returning to room temperature, the auricular lymph nodes were crushed with the gradual addition of physiological saline and suspended in it. The suspension thus obtained was filtered and then distributed in the wells of a 96 well microplate, with 3 wells being used per individual. The suspensions thus distributed were measured for BrdU uptake using the ELISA method. The reagents used were those from a commercially available kit (Cell Proliferation ELISA, colorimetric BrdU, cat. No. 1647229, product of Roche Diagnostics Inc.). A Multiplate Reader (FLUOSTAR OPTIMA, a product of BMG LABTECH Inc.) was used to measure the absorbance of each well (OD: 370 nm at 492 nm, BrdU uptake) and the mean absorbance of the 3 wells for each individual was used. as a measure of BrdU for the individual. [Evaluation of Results] <Stimulation Index Calculation (SI)>
    As shown in the following formula, the BrdU uptake measurement for each individual was divided by the average of the BrdU uptake measurements in the vehicle control group to calculate the SI value for the individual. The SI value for each test group was the average of the individuals' SI values. Also, the standard error of the SI values was calculated for each test group. Specifically, the SI value has been rounded to the second decimal place and shown to the first decimal place.

    The viscosity (mPa.s) for each of the paints prepared above was measured at 25 ° C and 60 ° C and the light dose required for curing (mJ / cm2).
    The results are shown in Table 3.
    Viscosities at 25 ° C and 60 ° C were measured with a rotary plate-type viscometer (product of TOKI SANGYO CO., LTDA.) With the water circulation temperature being constantly adjusted to 25 ° C and 60 ° C . The temperature of 25 ° C is a temperature generally considered to be the ambient temperature. The temperature of 60 ° C is a defined temperature considering the specification of a commercially available inkjet ejection head capable of being heated, such as GEN4 (product of Ricoh Printing Systems, Ltda.).
    The curing property of the paints was assessed as follows. Specifically, each ink was ejected onto a commercially available polyethylene terephthalate (PET) film (product name: COSMOSHINE A4300, product of TOYOBO CO., LTDA.) And irradiated with light using an UV irradiation device LH6 (product of Fusion Systems Japan Co., Ltd.).
    An aluminum bag having the shape illustrated in Fig. 1 was loaded with the ink and hermetically sealed, in order to avoid the inclusion of air bubbles. The hermetically sealed bag containing the ink was housed in a plastic cartridge, as shown in Fig. 2. This cartridge was mounted in a case adapted to accommodate it. In the case, an ink flow channel was provided from the cartridge to a GEN4 head (a product of Ricoh Printing Systems, Ltd.). The ink was ejected through the ink flow channel to form, on the film, a solid coated film (that is, a uniform and fully coated film) with a thickness of about 10 μm and a size of 2.5 cm x 2.5 cm.
    The solid coated film thus formed was irradiated with light from the wavelength region corresponding to the UVA region, with the light dose being gradually changed to 1,000, 500, 200, 100, 50, 20 and 10 (mJ / cm2). If the solid coated film went to the non-viscous state it was judged by touching it with the finger and the solid coated film was judged to be cured when it became the non-viscous state. The minimum dose of integrated light required for the solid coated film to be judged to be cured is shown as the radiation dose required for curing in Table 3. Inks that require less integrated light dose have better curing properties.
    Specifically, the physical properties of the ink preferably conform to the requirement specification of the used inkjet ejection head. Many manufacturers place several ejection heads on the market. Some of them have a function of adjusting the temperature over a wide range. In view of this, the paint viscosity is preferably from 2 mPa.s to 150 mPa.s at 25 ° C. Considering the ejection of the paint at 25 ° C, its viscosity is, more preferably, 5 mPa.s to 18 mPa.s. However, even when the ink viscosity at 25 ° C is very high, the temperature adjustment function of the ejection head mentioned above can optionally be used to heat the head so that the ink viscosity is reduced. When the heating temperature is 60 ° C, the paint viscosity at 60 ° C is preferably 2 mPa.s to 20 mPa.s, more preferably 5 mPa.s to 18 mPa.s.
    The dose of light required for curing is preferably less in terms of saving energy. However, ink that is cured with a considerably low level of light irradiation will be cured by reacting with ambient light or the light that comes out of the curing light source through the gas-liquid interface of a head blasting nozzle. ejection, causing concerns about the occurrence of nozzle clogging. This problem can be solved by designing an appropriate printer in many cases, but for a much better ink curing property, this is not preferred. Considering this, the dose of light required for curing the inks is preferably from 5 mJ / cm2 to 10,000 mJ / cm2, more preferably 10 mJ / cm2 to 1000 mJ / cm2, even more preferably 10 mJ / cm2 to 200 mJ / cm2. Table 3
    *: Carbon Black # 10 (product of the Corporation), which is in the form of a mixture with polymeric dispersing agent S32000 (product of Lubrizol Japan Co.) with the mass ratio of S32000: Carbon Black # 10 of 3: 1 . The amount of carbon black above is that of Carbon Black # 10 in the mixture.
    From the comparison between Examples 1, 2, 6, 7 and 8 using different low viscosity ingredients or using low viscosity ingredients in combination, it was confirmed that all the inks in these Examples could be ejected without any problem by adjusting the head to a adequate temperature and the solid coated films obtained could be cured by irradiation with light.
    The ink in Example 2 is superior to other inks in terms of having low viscosity and improved curing properties. The ink to be used can be appropriately selected from them, depending on the properties required for the desired image quality and image surface properties, as well as various requirements, such as process cost and compatibility with the printer's printing process used.
    From the comparison between Examples 2, 3, 4 and 5 using different polymerization initiators, the ink of Example 2 is superior to the other paints in terms of curing properties; however, similarly, the paint to be used can be properly selected from them, depending on the various requirements, as described above.
    From the comparison between Example 9 using acrylate and methacrylate in combination, Example 10 using acrylate and acrylamide in combination and Example 11 using acrylate, methacrylate and acrylamide in combination, all of these inks can exhibit viscosity sufficiently low and high curing property; however, similarly, the paint to be used can be properly selected from them, depending on the various requirements, as described above.
    From the comparison between Examples 1 and 12 using different acrylates, both paints can exhibit almost the same viscosity and curing property; however, similarly, the paint to be used can be properly selected from them, depending on the various requirements, as described above.
    The inks of Examples 13 and 14 that do not use acrylate could be blasted without any problems similar to those of the other Examples and the solid coated films obtained could be cured by irradiation with light. The paint to be used can be properly selected from them, depending on the various requirements, as described above.
    The inks of Examples 15, 16 and 17 containing a colorant could be ejected by adjusting the head to an appropriate temperature and the obtained solid coated films could be cured by means of irradiation with light.
    Aspects of the present invention are as follows. <1> The photopolymerizable inkjet ink including: at least one selected from the group consisting of negative (met) acrylic acid esters for skin sensitization and negative (met) acrylamides for skin sensitization; and at least one selected from the group consisting of vinyl negative ethers for skin sensitization, negative t-butyl methacrylate for skin sensitization, negative n-pentyl methacrylate for skin sensitization and negative n-hexyl methacrylate for skin sensitization . <2> The light-curing inkjet ink according to <1>, in which at least one selected from the group consisting of negative (meth) acrylic acid esters for skin sensitization and negative (meth) acrylamides for skin sensitization skin is at least one selected from the group consisting of polyethylene glycol dimethacrylates represented by the General Formula (1) below, Y-butyrolactone methacrylate, trimethylol propane trimethacrylate, tricyclodecanedimethanol dimethacrylate, diacyl acrylate, modified caprentacritol hexate acrylate, diacritolized acrylate acrylate polypropylene glycol [CH2 = CH.CO- (OC3H6) n-OCOCH = CH2 (n is 12), where n is the average degree of polymerization], caprolactone-modified neopentyl glycol hydroxypivalate diacrylates, polyethoxylated tetramethylol tetra acrylate , bisphenol A diacrylate modified with ethylene oxide, neopentyl glycol dimethacrylate, hydroxyethyl acrylamide and stearyl acrylate:
    where n is an integer from 9 to 14, where n is the average degree of polymerization. <3> The light-curing inkjet ink according to <1> or <2>, where the vinyl ether negative for skin sensitization is divinyl ether of triethylene glycol. <4> The photopolymerizable inkjet ink according to any of <1> to <3>, including a photo-radical polymerization initiator. <5> The light-curing inkjet ink according to <4>, in which the photo-radical polymerization initiator is negative for skin sensitization. <6> An ink cartridge including: light-curing inkjet ink according to any of <1> to <5>; and a container which houses the light-curable ink jet ink. <7> An inkjet recording device including: <ink cartridge according to <6>; and an inkjet unit configured to apply a stimulus to the photopolymerizable inkjet ink to cause blasting of the photopolymerizable inkjet ink to thereby form an image.
    Reference Symbol List 1: Base material feed roller 2: Base material to be printed 3: Printing unit 3a: Printing unit for color ink 3b: Printing unit for color ink 3c: Printing unit for a 3d color ink: Printing unit for a color ink 4a: UV light source 4b: UV light source 4c: UV light source 4d: UV light source 5: Processing unit 6: Winding roller for printed products 200: Ink cartridge 241: Ink bag 242: Ink inlet 243: Ink outlet 244: Cartridge case
    权利要求:
    Claims (7)
    [0001]
    1. Light-curing ink jet ink characterized by the fact that it comprises: at least one selected from the group consisting of negative (meth) acrylic acid esters for skin sensitization and negative (meth) acrylamides for skin sensitization; and at least one selected from the group consisting of vinyl negative ethers for skin sensitization, negative t-butyl methacrylate for skin sensitization, negative n-pentyl methacrylate for skin sensitization and negative n-hexyl methacrylate for skin sensitization , wherein the amount of at least one negative (meth) acrylic acid for skin sensitization or negative (meth) acrylamide for skin sensitization is 10% by mass to 90% by weight relative to the total amount of monomers, and where a compound is negative for skin sensitization if it has a Stimulation Index of less than 3, where the Stimulation Index indicates the extent of sensitization as measured by a skin sensitization test based on the Lymph Node assay Place.
    [0002]
    2. Light-curing inkjet ink according to claim 1, characterized by the fact that at least one selected from the group consisting of negative (meth) acrylic acid esters for skin sensitization and (meth) acrylamides negative for Skin sensitization is at least one selected from the group consisting of polyethylene glycol dimethacrylates represented by the General Formula (1) below, y-butyrolactone methacrylate, trimethylolpropane trimethacrylate, tricyclodecanedimethanol dimethacrylate, dipentaerythrolone hexa-acrylate, modified dipentaerythritolone acrylate, modified dipentaerythrolate acrylate polypropylene glycol diacrylate [CH2 = CH.CO- (OC3H6) n-OCOCH = CH2 (n is 12), where n is the average degree of polymerization], neopentyl glycol hydroxypivalate diacrylates modified with caprolactone, tetramethylol tetraacrylate polyethoxylated methane, bisphenol A diacrylate modified with ethylene oxide, neopentyl glycol dimethacrylate, hydroxyethyl acrylamide and stearyl acrylate:
    [0003]
    3. Light-curing inkjet ink according to claim 1 or 2, characterized by the fact that vinyl ether negative for skin sensitization is divinyl ether of triethylene glycol.
    [0004]
    4. Photopolymerizable inkjet ink according to any one of claims 1 to 3, characterized in that it also includes a photo-radical polymerization initiator.
    [0005]
    5. Photopolymerizable inkjet ink, according to claim 4, characterized by the fact that the photo-radical polymerization initiator is negative for skin sensitization.
    [0006]
    6. Ink cartridge characterized by the fact that it comprises: the photopolymerizable ink jet ink as defined in claims 1 to 5; and a container which houses the light-curable ink jet ink.
    [0007]
    7. Inkjet engraving device characterized in that it comprises: the ink cartridge as defined in claim 6; and an inkjet unit configured to apply a stimulus to the photopolymerizable inkjet ink to cause blasting of the photopolymerizable inkjet ink to thereby form an image.
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    同族专利:
    公开号 | 公开日
    JP2012251123A|2012-12-20|
    KR20140004227A|2014-01-10|
    EP2707442A4|2015-08-26|
    WO2012153867A1|2012-11-15|
    JP5803582B2|2015-11-04|
    EP2707442B1|2017-11-08|
    EP2707442A1|2014-03-19|
    US20140327719A1|2014-11-06|
    CN103517953B|2015-12-23|
    US9428665B2|2016-08-30|
    CN103517953A|2014-01-15|
    RU2013155183A|2015-06-20|
    CA2834998A1|2012-11-15|
    CA2834998C|2016-04-19|
    RU2570671C2|2015-12-10|
    KR101580026B1|2015-12-23|
    BR112013028897A2|2017-01-31|
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    法律状态:
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-07-23| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-09-15| B09A| Decision: intention to grant|
    2020-12-15| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 10/05/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2011-107318|2011-05-12|
    JP2011107318|2011-05-12|
    JP2011240605A|JP5803582B2|2011-05-12|2011-11-01|Photopolymerizable inkjet ink, ink cartridge, printer|
    JP2011-240605|2011-11-01|
    PCT/JP2012/062568|WO2012153867A1|2011-05-12|2012-05-10|Photopolymerizable inkjet ink, ink cartridge, and inkjet recording device|
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