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    • 专利摘要:
    PHOTOPOLIMERIZABLE INK JET INK, INK CARTRIDGE AND PRINTER. A light-curing inkjet ink including: a light-curing monomer having a Stimulation Index (SI value) less than 3, where the Stimulation Index indicates the extent of sensitization as measured by a skin sensitization test based on local lymph node; and an aromatic phenol compound having two hydroxyl groups on the molecule thereof.
    公开号:BR112013029528B1
    申请号:R112013029528-7
    申请日:2012-05-10
    公开日:2021-01-19
    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 light-curable inkjet ink, an ink cartridge that houses the ink and a printer on which the ink cartridge is mounted. BACKGROUND TECHNIQUE
    [0002] Photopolymerizable monomers used in photopolymerizable inkjet inks are, for example, methacrylic acid ester compounds, acrylate amide compounds, cation polymerizable oxetane compounds and epoxy compounds. Among these, methacrylic acid ester compounds and acrylic amide compounds are preferred since they are available in large quantities, inexpensive, easily obtainable, and capable of being used in combination with a radical polymerizable photopolymerization initiator which is inexpensive and commonly used between polymerization initiators.
    [0003] However, many of methacrylic acid ester compounds and acrylic amide compounds have toxicity. Although some of them are relatively mild in oral toxicity and skin irritation, those with low viscosity used in inkjet inks are not safe materials for skin sensitization where they come into contact with the skin to cause allergy.
    [0004] The present inventor has carried out extensive studies and has previously found some safe materials in skin sensitization. As a result of further studies, the present inventor previously found that there were some methacrylic acid ester compounds and acrylic amide compounds usable as photopolymerizable monomers and having a Stimulation Index (SI value) less than 3 where the Stimulation Index indicates the extent of sensitization as measured by a skin sensitization test based on LLNA (Local Lymph Node Assay). However, when these compounds are formulated in order to obtain practically usable curing property, the curing property of the resulting inks becomes inferior to those of commonly used photopolymerizable inkjet inks. Thus, a photoradical polymerization initiator has to be incorporated in a larger than usual amount. It has been found that such a larger amount of the incorporated photoradical polymerization initiator prevents the resulting inks from showing sufficient storage stability in high temperature environments such as summer.
    [0005] In addition, the present inventor has previously discovered a photopolymerizable inkjet ink that is negative for skin sensitization, improves the coated film in its curing property, allows possible curing failures in the coated film to be visually confirmed, and facilitates quality control in the production process. Specifically, the light-curing inkjet ink contains: one or more types of light-curing monomers each having an SI value of less than 3; a self-cleaving light curing initiator; a polymerization initiator to extract hydrogen; and an amine compound that serves as a polymerization accelerator. However, even this light-curing inkjet ink is difficult to obtain sufficient storage stability as described above.
    [0006] As widely known, the storage stability of the photopolymerizable inkjet ink can be improved by the addition of a material called polymerization initiator. Examples of useful useful polymerization inhibitors include phenol compounds and quinone compounds such as methoquinone and benzoquinone, and aromatic secondary amine compounds such as diphenyl amine and phenothiazine (see, for example, PTLs 1 and 2).
    [0007] However, even when such a polymerization inhibitor known as methoquinone is added to the newly discovered compound, above, it is not possible to prevent the resulting inks from thickening or solidifying as a result of polymerization. In addition, it has been found that aromatic secondary amine compounds such as phenothiazine cannot be used due to their considerable coloring properties, although they have higher polymerization inhibiting effects.
    [0008] In addition, many of the light-curing monomers having an SI value of less than 3 have high viscosity like inkjet inks, and the addition of a polymerization initiator increases the viscosity inks. Therefore, it is important to take appropriate measures to reduce the viscosity inks. Here, it is easy to reduce their viscosity by incorporating a diluting solvent in them. However, the use of the diluent solvent is not desirable since it volatilizes to be released into the air to provide adverse effects to the environment. Therefore, the incorporation of a solvent in paints should be avoided. Alternatively, water can be incorporated into paints containing water-soluble monomers to reduce its viscosity. In that case, when non-permeable base materials such as plastic materials are used, it may not be possible to achieve the effect that water penetrates the non-permeable base materials to lead to dryness. Thus, in an attempt to obtain a high speed printing process, it is necessary to volatilize water instantly for drying. To do this, a heat source must be provided in many cases, which is not preferred in terms of energy savings. List of citations Patent literature PTL 1: Japanese patent application open (JP-A) no. 04-164975. PTL 2: JP-A no. 2005-290035. Summary of the invention Technical problem
    [0009] An object of the present invention is to provide a photopolymerizable inkjet ink that is safe in skin sensitization and good in storage stability at elevated temperatures. Solution to the problem
    [00010] Means for solving problems are as follows. Specifically, a photopolymerizable inkjet ink of the present invention contains: a photopolymerizable monomer having a Stimulation Index (SI value) less than 3, where the Stimulation Index indicates the extent of sensitization as measured by a skin sensitization test (LLNA); and an aromatic phenol compound having two hydroxyl groups on the molecule thereof. Advantageous effects of the invention
    [00011] The present invention can provide a photopolymerizable inkjet ink that is safe in skin sensitization and good in storage stability at elevated temperatures. Brief description of the drawings
    [00012] Figure 1 schematically illustrates an ink bag exemplary of an ink cartridge.
    [00013] Figure 2 schematically illustrates an ink cartridge that houses an ink bag.
    [00014] Figure 3 schematically illustrates an exemplary printer of the present invention. Description of modalities Light-curing inkjet ink
    [00015] A photopolymerizable inkjet ink of the present invention contains: a photopolymerizable monomer having a Stimulation Index (SI value) less than 3, where the Stimulation Index indicates the extent of sensitization as measured by a sensitization test of the skin (LLNA); and an aromatic phenol compound having two hydroxyl groups on the molecule thereof. The actual light-curing ink preferably contains at least one selected from the group consisting of a photopolymerization initiator and an amine compound serving as a polymerization accelerator; and if necessary, it contains other ingredients.
    [00016] The present inventor has found that by incorporating the aromatic phenol compound having two hydroxyl groups into its molecule in a photopolymerizable inkjet ink (hereinafter referred to as "ink") containing a safe photopolymerizable monomer having a SI value less than 3 where the SI value indicates the extent of sensitivity as measured by the skin sensitization test (LLNA), the resulting ink can show good storage stability even at elevated temperatures.
    [00017] Notably, the “LLNA” is the skin sensitization test defined as the OECD 429 test guideline. As described in the literature (for example, “Functional material” (Kino Zairyou) 2005, September, vol. 25, no. 9, page 55), the compound having a Stimulation Index (SI value) less than 3, where the Stimulation Index indicates the extent of skin sensitization, is judged to be negative for skin sensitization. In addition, compounds rated “negative for skin sensitization” or “no skin sensitization” in their MSDS (Material Safety Data Sheet) and / or literature (eg van der Walle HB and others, Contact dermatitis , 1982, 8 (4), 223-235) each has the SI value above which is less than 3, and therefore are covered by the present invention. The lower SI value means lower skin sensitization. Thus, in the present invention, a monomer or oligomer having a lower SI value is preferably used. The SI value of the monomer or oligomer used is preferably 2 or lower, more preferably 1.6 or lower. Aromatic phenol compound having two hydroxyl groups in the same molecule
    [00018] The aromatic phenol compound having two hydroxyl groups in its molecule is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of the same include hydroquinone, methyl hydroquinone, tert-butyl hydroquinone, 2,5-di-tert-butyl hydroquinone, 2,2'-methylenebis (4-methyl-6-tert-butyl phenol), 2,2'- methylenobis (4-ethyl-6-tert-butyl phenol) and 2,2'-methylenebis [6- (1-methylcyclohexyl-p-cresol)]. These can be used individually or in combination.
    [00019] Among them, hydroquinone, methyl hydroquinone, tert-butyl hydroquinone, and 2,5-di-tert-butyl hydroquinone are preferred since they are particularly excellent in storage stability at elevated temperatures.
    [00020] An adequate amount of the phenol aromatic compound having two hydroxyl groups in the molecule of the same varies with properties required for paints depending on its applications. When the amount of the phenol aromatic compound having two hydroxyl groups in the molecule thereof is too small, satisfactory effects cannot be obtained in some cases, whereas when it is too large, the curing property of the resulting ink can be degraded. Thus, the amount of the phenol aromatic compound having two hydroxyl groups in the same molecule contained in the paint is preferably 0.001 parts by mass to 1 part by mass per 100 parts by mass of the photopolymerizable monomer. However, the amount of the phenol aromatic compound having two hydroxyl groups in its molecule is necessarily limited to that range. In particular, considering a generally known mechanism of showing storage stability in which the aromatic phenol compound having hydroxyl groups in the molecule retains radicals generated in paints to form stable radicals, the amount of the phenol aromatic compound having two hydroxyl groups in its molecule it is preferably larger to improve storage stability. However, a greater amount of the aromatic phenol compound having two hydroxyl groups in the molecule of the same is not preferred to obtain sufficient curing property. Therefore, the amount of the phenol aromatic compound having two hydroxyl groups in the molecule of the same must be appropriately determined considering the required curing property. Light-curing monomer
    [00021] The photopolymerizable monomer that does not involve problems in skin sensitization, which is cheap and easily obtainable, is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of the same include polyethylene glycol dimethacrylates represented by the following general formula (1) where n is almost equal to 2, 9 or 14, y-butyrolactone methacrylate, trimethylol propane trimethacrylate, dimethanol tricyclodecane dimethacrylate, modified dipentaerythritol hexaacrylate. caprolactone, polypropylene glycol diacrylate [CH2 = CH-CO- (OC3H6) n-OCOCH = CH2 (n is almost equal to 12)], caprolactone modified neopentyl glycol hydroxypivalate diacrylates, polyethoxylated bisaccharide tetramethylol tetraacrylate, diacrylate A modified by ethylene oxide, neopentyl glycol dimethacrylate, stearyl acrylate, 1,4-butanediol dimethacrylate, hydroxy ethyl acrylamide, acryloyl morpholine, t-butyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, ethylene oxide modified phenol, isostearyl acrylate, ethylene oxide modified trimethylol propane trimethacrylate, stearyl methacrylate, dimethacryl glycerin, triethylene glycol divinyl ether and isobutyl vinyl ether. These can be used individually or in combination.
    [00022] Among them, polyethylene glycol dimethacrylates represented by the following general formula (1) are preferred where n is almost equal to 2, 9 or 14, y-butyrolactone methacrylate, trimethylol propane trimethacrylate, tricyclodecane dimethacrylate dimethanol, hexaacrylate hexane caprolactone-modified dipentaerythritol, polypropylene glycol diacrylate [CH2 = CH-CO- (OC3H6) n-OCOCH = CH2 (n is almost equal to 12)], caprolactone-modified neopentyl glycol hydroxypivalate diameters, tetramethyl polyethane tetraacrylate, polyetethoxymethyl tetraacrylate, bisphenol A diacrylate modified by ethylene oxide, neopentyl glycol dimethacrylate, stearyl acrylate, 1,4-butanediol dimethacrylate, hydroxy ethyl acrylamide, n-pentyl methacrylate, n-hexyl methacrylate, phenol acrylate modified by oxide modified ethylene, isostearyl acrylate, trimethylol propane trimethacrylate modified by ethylene oxide, stearyl methacrylate and glycerin dimethacrylate, as they are excellent lenses in storage stability at elevated temperatures.

    [00023] In the general formula (1), n is almost equal to 2, 9 or 14.
    [00024] Notably, when using a mixture containing two or more polyethylene glycol dimethacrylates each represented by the general formula (1), the average of the numbers indicated by "n", which are calculated through analysis as a measurement of their molecular weights, preferably is comprised in the range of 9 to 14.
    [00025] In addition, other (meth) acrylates, (meth) acrylamides and compounds can be used in combination, as long as the amount of them is comprised in such a range that does not create any problems like paints even if in a way they cause problems in skin sensitization when used individually or have not been confirmed for skin sensitization.
    [00026] Examples of the same include ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, y-butyrolactone acrylate, isobornyl acrylate, formalized trimethylol propane mono (meth) acrylate, di ( met) polytetramethylene glycol acrylate, trimethylol propane (meth) acrylate, diethylene glycol diacrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol diacrylates [CH2 = CH-CO - (OC2H4) n-OCOCH = CH2 where n is almost equal to 4], [CH2 = CH-CO- (OC2H4) n-OCOCH = CH2 where n is almost equal to 9], [CH2 = CH-CO- ( OC2H4) n-OCOCH = CH2 where n is almost equal to 14], and [CH2 = CH-CO- (OC2H4) n-OCOCH = CH2 where n is almost equal to 23], di (methyl) arylated dipropylene glycol, tripropylene glycol di (meth) acrylate, polypropylene glycol dimethacrylate [CH2 = C (CH3) -CO- (OC3H6) n -OCOC (CH3) = CH2 where n is almost equal to 7)], 1,3- butandiol, 1,4-butandiol diacrylate, 1,6-hexanediol di (meth) acrylate, 1-di (meth) acrylate , 9-nonanediol, neopentyl glycol di (meth) acrylate, tricyclodecanedimethanol diacrylate, propylene oxide adduct di (meth) acrylate bisphenol A, di (meth) polyethylene glycol acrylate, dipentaerythriol hexa (meth) acrylate, methacryl morpholine, 2-hydroxy propyl methacrylamide, tetramethylol tetramethacrylate methane modified by ethylene oxide, hydroxypenta (meth) dipentaerythritol acrylate, hydroxypenta (meth) acrylate dipetraerythritol acrylate, tetra (meth) acrylate, tetra (meth) acrylate and pentaerythritol acrylate, trimethylol propane triacrylate, ethylene oxide modified trimethylol triacrylate, propylene oxide modified trimethylol propane triacrylate, caprolactone modified tri (meth) acrylate tri (meth) acrylate trimethylol acrylate, tri (pyrethyl acrylate) tri (meth) tris (2-hydroxyethyl) isocyanurate, neopentyl glycol diacrylate, ethoxylated neopentyl glycol di (meth) acrylate, neopentyl gly (di) acrylate propoxylated ol, propoxylated glycerol tri (meth) acrylate, polyester di (meth) acrylate, polyester tri (meth) acrylate, polyester tetra (meth) acrylate, polyester penta (meth) acrylate, poly (meth) acrylate polyester, vinyl caprolactam, vinyl pyrrolidone, N-vinyl formamide, polyurethane di (met) acrylate, polyurethane tri (meth) acrylate, polyurethane tetra (meth) acrylate, polyurethane penta (meth) acrylate, poly (meth) acrylate polyurethane, N-dimethyl aminoethyl acrylamide, N-isopropyl acrylamide, N-dimethyl acrylamide, N-diethyl acrylamide and N-dimethyl amino propyl acrylamide.
    [00027] The quantity of these photopolymerizable monomers in the ink is not particularly limited and can be appropriately selected depending on the intended purpose. It is preferably 50% by mass to 100% by mass, more preferably 80% by mass to 100% by mass. Although incorporating a coloring substance and other additives into the paint can provide the paint with various functions, the polymerization reaction of the monomers can be inhibited depending on the amount of the paint. Thus, it is not preferred to incorporate an unnecessarily excessive amount of a coloring substance and other additives. Light curing initiator
    [00028] The ink can also contain a light curing initiator. The photopolymerization initiator is preferably a self-cleaving photopolymerization initiator or a photopolymerization initiator which extracts hydrogen. The photopolymerization initiator used is preferably negative for skin sensitization similar to photopolymerizable monomers. In addition, the following formulas, which somehow sensitize the skin when used individually or which have not been confirmed for skin sensitization, would be used as long as the amount of them is included in such a range that does not create any problem with paints. Self-cleaving light curing initiator
    [00029] The self-cleaving light curing initiator is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of the same 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 glyoxylic 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-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) butan-1-one, bis (2,4,6 -trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzolyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl phosphine oxide, 1,2-octanedion- [4- (phenylthio ) -2- (o-benzoyloxime)], ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) and [4- (methylphenylthio ) phenyl] phenylmethanone. These can be used individually or in combination.
    [00030] In particular, 2-dimethyl amino-2- (4-methyl benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one is preferred since it has good curing performance. In addition, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one is preferred since it is inexpensive. Hydrogen extraction photopolymerization initiator
    [00031] The hydrogenation polymerization initiator is not particularly limited and can be appropriately selected depending on the intended purpose. Examples of the same include: thioxanthone compounds such as 2,4-diethylthioxanthone, 2-chlorothioxanthone, isopropyl thioxanthone and 1-chloro-4-propyl thioxanthone; and benzophenone compounds such as benzophenone, methyl benzophenone, methyl-2-benzoyl benzoate, 4-benzoyl-4'-methyl diphenyl sulfide and phenyl benzophenone. These can be used individually or in combination.
    [00032] With the increased demands for environmental protection awareness, recent interest has focused on LED light sources as light sources for curing light-curable inks since LED light sources have higher energy efficiency than conventional mercury lamps and metal halide lamps and save energy. However, the wavelength of practical problem-free LED light sources is 365 nm or greater. Thus, when current LED light sources are used, it is difficult to expect benzophenone compounds to serve satisfactorily as an initiator, judging from their specific absorption spectra. For this reason, thioxanthone compounds are more suitable. Among them, chlorine-free 2,4-diethyl thioxanthone and isopropyl thioxanthone are preferred from the point of view of environmental protection. Polymerization accelerator
    [00033] The polymerization accelerator is not particularly limited, as long as it is an amine compound, and can be appropriately selected depending on the intended purpose. Examples of the same include benzoic acid ester compounds containing a group of N, N'-dimethyl amino, such as ethyl p-dimethyl amino benzoate, 2-ethyl hexyl p-dimethyl amino benzoate, methyl p-dimethyl amino benzoate, 2- dimethyl amino ethyl benzoate and butoxy ethyl p-dimethyl amino benzoate. These can be used individually or in combination.
    [00034] Among them, ethyl p-dimethyl amino benzoate is preferred since it is inexpensive, easily obtainable and has the highest viscosity-reducing effect.
    [00035] The amine compound serves as a source to supply hydrogen to the photopolymerization initiator to extract hydrogen. In particular, a benzoic acid ester compound having an N, N-dimethyl amino group can more efficiently accelerate the curing reaction.
    [00036] When the quantity of the light curing initiators (the self-cleaving light curing starter and / or the hydrogen-extracting light curing starter) and the polymerization accelerator is too small, the light curing reaction hardly proceeds so that sufficient curing does not can be obtained in some cases. When it is too large, the polymerization reaction proceeds, however the degree of polymerization does not increase so that the cured product can be brittle, or the light curing initiator can excessively increase the viscosity of the ink to cause failure in the ink jet ejection.
    [00037] Therefore, the total amount of the photopolymerization initiators and the polymerization accelerator is preferably 1 part by mass to 50 parts by mass, particularly preferably 10 parts by mass to 35 parts by mass, per 100 parts by mass of the photopolymerizable monomer. When high energy light sources such as α rays, β rays, y rays, X rays or electron beams are used, the polymerization reaction proceeds without a photopolymerization initiator or polymerization accelerator. This is a widely known issue, and these high energy light sources have not been commonly used yet as they demand a high cost for their safety and for the maintenance of necessary facilities. Thus, the explanation in detail for the same is not given here. Other ingredients
    [00038] The other ingredients are not particularly limited and can be appropriately selected depending on the intended purpose. Examples of the same include coloring substances: higher fatty acid esters having, for example, a polyether, an amino group, a carboxyl group, and / or a hydroxyl group on the side chain or at the end thereof; polydimethyl siloxane compounds having, for example, a polyether, an amino group, a carboxyl group, and / or a hydroxyl group on the side chain or at the end thereof; surfactants such as fluoroalkyl compounds having, for example, a polyether, an amino group, a carboxyl group, and / or a hydroxyl group; and polymeric pigment dispersing agents containing polar group. These can be used individually or in combination. Colorant
    [00039] The colorant of the ink is not particularly limited and can be appropriately selected from known inorganic pigments and organic pigments considering, for example, physical properties of the ink.
    [00040] With respect to black pigments, those such as carbon black produced by the oven method or channel method can be used. These can be used individually or in combination.
    [00041] With respect to yellow pigments, for example, the following 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. These can be used individually or in combination.
    [00042] With respect to magenta pigments, for example, the following 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. These can be used individually or in combination.
    [00043] With respect to cyan pigments, for example, the following 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. These can be used individually or in combination.
    [00044] With respect to white pigments, for example, sulfuric acid salts of alkaline earth metals such as barium sulfate, carbonic acid salts of alkaline earth metals such as calcium carbonate, silica as fine silicic acid powder and silicic acid salts synthetic, calcium silicate, alumina, alumina hydrate, titanium oxide, zinc oxide, talc and clay. These can be used individually or in combination. Cartridge
    [00045] An inkjet cartridge of the present invention includes at least the photopolymerizable inkjet ink described above of the present invention.
    [00046] In other words, the ink of the present invention can be suitably used as an ink cartridge where the ink is housed in a container. With this form, users do not have to directly touch the paint during jobs such as changing the paint, so they are not concerned with getting their fingers, hands or clothes dirty. In addition, it is possible to avoid the interference of foreign matter as dust in the paint.
    [00047] The container is not particularly limited, and its shape, structure, size and material can be appropriately selected depending on the intended purpose. For example, the container is preferably selected from those having an ink bag formed from an aluminum laminate film, or a resin film.
    [00048] The ink cartridge will be described with reference to figures 1 and 2. Figure 1 schematically illustrates an example of an ink bag 241 from an ink cartridge. Figure 2 schematically illustrates an ink cartridge 200 containing the ink bag 241 shown in figure 1 and a cartridge case 244 housing the ink bag 241.
    [00049] As illustrated in figure 1, the ink bag 241 is filled with ink by injecting the ink from an ink inlet 242. After removing air present inside the ink bag 241, the ink inlet 242 is sealed by 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 element to supply ink to the device through it. The ink bag 241 is formed of a wrapping element such as a non-air permeable aluminum laminate film. As illustrated in Figure 2, the ink bag 241 is typically housed in a plastic cartridge case 244, which is then mounted loosely in use on various inkjet engraving devices such as ink cartridge 200.
    [00050] The ink cartridge of the present invention is preferably loosely mounted on inkjet engraving devices (for example, a printer). The ink cartridge can simplify refilling and changing the ink to improve workability. Printer
    [00051] A printer of the present invention includes at least the ink cartridge described above of the present invention mounted thereon.
    [00052] Here, figure 3 schematically illustrates an exemplary printer.
    [00053] The printer illustrated in figure 3 forms a color image as follows. Specifically, printing units 3 (i.e., printing units 3a, 3b, 3c and 3d having ink cartridges 200a, 200b, 200c and 200d 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 transferred from left to right in figure 3) fed from a base material feed roller 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.
    [00054] The base material 2 used is, for example, paper, a film, a metal or a composite material thereof. The base material 2 shown in figure 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.
    [00055] When UV rays are applied to each of the colored inks for each printing process, the colored inks are satisfactorily cured. For high speed printing, UV light sources 4a, 4b and 4c can be reduced in output energy or can be omitted, so that the UV light source 4d is made to apply a sufficient dose of UV rays to an image composite impression formed of a plurality of colors. By doing so, energy savings and cost savings can also be realized.
    [00056] In figure 3, reference numeral 5 indicates a processing unit and reference numeral 6 indicates a take-up reel for printed products. EXAMPLES
    [00057] The present invention will be described in more detail below by means of Examples and Comparative Examples. However, the present invention is not to be construed as being limited to the Examples. Examples 1 to 480
    [00058] Mixtures of Preparation Examples 1 to 120 were prepared by mixing the following photopolymerizable monomers A1 to A23 (i.e., (meth) acrylic acid compounds or acrylamide compounds each being negative for skin sensitization or having a value SI less than 3) with at least one of the following self-cleaving light curing primers B1-1 and B1-2, the following B2-1 and B2-2 hydrogen extracting light curing initiator, and the following polymerization accelerator B3 in the compositions and the quantities (parts by mass) shown in tables 1 to 12. Next, 100 parts by mass of each of the mixtures were mixed with 0.1 part by mass of each of the following C1 to C4 phenol aromatics having two hydroxyl groups in the molecule shown in tables 13-1 to 18-2, to thereby produce inks (light-curable inkjet inks) of examples 1 to 480.
    [00059] Notably, the units of the quantities of the photopolymerizable monomers, the photopolymerization initiators, and the aromatic phenol compound having two hydroxyl groups in the molecule shown in tables 1 to 12 are "parts by mass". Comparative examples 1 to 240
    [00060] The paints of comparative examples 1 to 240 were produced in the same way as in each of examples 1 to 480, except that 0.1 part by mass of the aromatic phenol compound C1, C2, C3 or C4 having two hydroxyl groups in the molecule it was changed to 0.1 part by mass of each of the following aromatic compounds of phenol C5 and C6 having a hydroxyl group in the molecule of the same as shown in tables 13-1 to 18-2.
    [00061] Notably, the units of the quantities of the photopolymerizable monomers, the photopolymerization initiators, and the aromatic phenol compound having a hydroxyl group in the molecule shown in tables 1 to 12 are "parts by mass."
    [00062] The following compounds were used as A1 to A23 (light-curing monomers), B1-1 to B2-2 (light-curing initiators), B3 (polymerization accelerator), C1 to C4 (aromatic phenol compounds having two hydroxyl groups in their molecule) and C5 and C6 (aromatic phenol compounds having a hydroxyl group in their molecule) shown in tables 1 to 18-2.
    [00063] The value in parentheses after each of A1 to A23 is "SI value" and the description "negative" or "none" after each of A1 to A23 means that the compound is rated as "negative for skin sensitization" or " no skin sensitization ”in the MSDS (Material Safety Data Sheet) or literature (for example, van der Walle HB et al., Contact Dermatitis, 1982, 8 (4), 223-235). The “negative” or “none” description is equivalent to the SI value less than 3. Light-curing monomers
    [00064] A1: neopentyl glycol dimethacrylate (2.0) ("NPG", product of Shin-Nakamura Chemical Co., Ltd.).
    [00065] A2: polyethylene glycol dimethacrylate represented by the following general formula (1) (n is almost equal to 9) (1.3) (“LIGHT ESTER 9EG,” product of KYOEISHA CHEMICAL CO., LTD.).

    [00066] A3: Polyethylene glycol dimethacrylate represented by the general Formula (1) (n is almost equal to 14) (1.6) (“LIGHT ESTER 14EG,” product of KYOEISHA CHEMICAL CO., LTD.).
    [00067] A4: y-Butyrolactone methacrylate (2.1) (“GBLMA,” product of OSAKA ORGANIC CHEMICAL INDUSTRY, LTD.)
    [00068] A5: trimethylol propane trimethacrylate (1.9) (“SR350,” product of Sartomer Co.).
    [00069] A6: Tricyclodecanedimethanol dimethacrylate (1.3) (“DCP,” product of Shin-Nakamura Chemical Co., Ltd.)
    [00070] A7: caprolactone-modified dipentaerythritol hexaacrylate (“negative” rated on MSDS) (“DPCA60,” product of NIPPON KAYAKU Co. Ltd.).
    [00071] A8: caprolactone-modified neopentyl glycol hydroxypivalate diacrylate (0.9) (“HX620,” product of NIPPON KAYAKU Co. Ltd.).
    [00072] A9: polyethoxylated tetramethylol methane tetraacrylate (1.7) (“ATM35E,” product of Shin-Nakamura Chemical Co., Ltd.).
    [00073] A10: Bisphenol A diacrylate modified by ethylene oxide (1.2) (“BPE10,” product of DAI-ICHI KOGYO SEIYAKU CO., LTD.).
    [00074] A11: hydroxy ethyl ethyl amide ("none": MSDS) ("HEAA," product of KOHJIN Co., Ltd.).
    [00075] A12: stearyl acrylate (2.7) (“STA,” product of OSAKA ORGANIC CHEMICAL INDUSTRY, LTD.).
    [00076] A13: 1,4-Butanediol dimethacrylate (2.6) ("SR214," product of Sartomer Co.).
    [00077] A14: polypropylene glycol diacrylate [CH2 = CH-CO- (OC3H6) n-OCOCH = CH2 (n is almost equal to 12)] (1.5) (“M-270,” product of Toagosei Chemical CO., LTD.).
    [00078] A15: t-butyl methacrylate ("negative": literature) ("LIGHT ESTER TB" product of KYOEISHA CHEMICAL CO., LTD.).
    [00079] A16: n-pentyl methacrylate ("negative": literature) ("n-AMYL METHACRYLATE," product of Toyo Science Corp.).
    [00080] A17: n-hexyl methacrylate ("negative": literature) ("n-HEXYL METHACRYLATE," product of TOKYO CHEMICAL INDUSTRY CO., LTD.).
    [00081] A18: ethylene oxide modified phenol acrylate (0.7) (“M102,” product of Toagosei Chemical CO., LTD.).
    [00082] A19: isostearyl acrylate (1.4) ("S1800A," product of Shin-Nakamura Chemical Co., Ltd.).
    [00083] A20: ethylene oxide-modified trimethylol propane trimethacrylate (1.0) (“TMPT3EO,” product of Shin-Nakamura Chemical Co., Ltd.).
    [00084] A21: stearyl methacrylate (1.2) ("S," product of Shin-Nakamura Chemical Co., Ltd.).
    [00085] A22: glycerin dimethacrylate (1.2) ("701," product of Shin-Nakamura Chemical Co., Ltd.).
    [00086] A23: polyethylene glycol dimethacrylate represented by General Formula (1) (n is almost equal to 2) (1.1) (“2G,” product of Shin-Nakamura Chemical Co., Ltd.) Self-curing initiators cleavage
    [00087] B1-1: 2-Methyl 1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (“Irgacure907,” product of BASF Co.)
    [00088] B1-2: 2-Dimethylamino-2- (4-methyl benzyl) -1- (4-morpholin-4-yl-phenyl) - butan-1-one (“Irgacure379,” product of BASF Co.) . Hydrogen extraction photopolymerization initiators
    [00089] B2-1: 2,4-Diethyltoxanthone ("DETX-S," product of NIPPON KAYAKU Co. Ltd.).
    [00090] B2-2: Isopropyloxanthone (“Esacure ITX,” product of Lamberti Co.). Polymerization accelerator
    [00091] B3: ethyl p-dimethylaminobenzoate ("Darocur EDB," product of Ciba Specialty Chemicals K.K.). Aromatic phenol compound having two hydroxyl groups in the same molecule
    [00092] C1: Hydroquinone ("HYDROQUINONE," product of Seiko Chemical Co., Ltd.).
    [00093] C2: Methyl hydroquinone ("MH," product of Seiko Chemical Co., Ltd.).
    [00094] C3: tert-Butylhydroquinone ("TBH," product of Seiko Chemical Co., Ltd.).
    [00095] C4: 2,5-Di-tert-butylhydroquinone ("NONFLEX ALBA," product of Seiko Chemical Co., Ltd.). Aromatic compound of phenol having a hydroxyl group in its molecule
    [00096] C5: Methoquinone ("METHOQUINONE," product of Seiko Chemical Co., Ltd.).
    [00097] C6: 4-Methoxy-1-naphthol ("MNT," product of KAWASAKI KASEI CHEMICALS LTD.).
    [00098] Each of the paints from Examples 1 to 480 and Comparative Examples 1 to 240 was placed in a container, which was then hermetically sealed in the dark and left to stand at 70 ° C for 1 week. In the mode described below, the ink was evaluated for “viscosity change rate at 60 ° C” and “inkjet property”. Notably, since the evaluation of the storage stability of an ink at ordinary temperature requires observation of a considerably long term and complicated evaluation process, the paints were subjected to the acceleration test at 70 ° C.
    [00099] In addition, mixtures of Preparation Examples 1 to 120 and the inks of Examples 1 to 480 and Comparative Examples 1 to 240 were subjected to “curing light dose measurement” and “observation of the appearance of uncoated films cured and cured ”in the manner described below. Rate of change in viscosity at 60 ° C
    [000100] Before and after being subjected to the acceleration test, each of the paints from examples 1 to 480 and comparative examples 1 to 240 was measured in relation to the viscosity at 60 ° C (mPa.S) and the value obtained was used to calculate the rate of change (%) in viscosity at 60 ° C from the following equation. Viscosity at 60 ° C was measured with a cone-type rotary viscometer (TV.22L, product of TOKI SANGYO CO., LTD.) With the circulating water temperature being constantly adjusted to 60 ° C. The temperature of 60 ° C is a temperature adjusted considering the specification of a commercially available inkjet ejection head capable of being heated, such as GEN4 (product of Ricoh Printing Systems, Ltd.).
    [000101] Rate of change (%) = [1 - (viscosity after the acceleration test / viscosity before the acceleration test)] x 100
    [000102] The results are collectively shown in tables 13-1 to 18-2. All inks from Comparative Examples 1 to 240 frozen after the acceleration test. Here, "freezing" described in tables 13-1 to 18-2 means a state where part or all of the paint has turned into a solid state after the acceleration test and the paint cannot be measured in relation to viscosity. In other words, it means that the ink had considerably poor storage stability.
    [000103] In contrast, the rates of change in the Examples were up to + 3.2%, indicating that the inks in the Examples had high storage stability at elevated temperatures. Inkjet Property Assessment
    [000104] An aluminum bag having a shape illustrated in figure 1 was loaded with each of the paints of examples 1 to 480 and comparative examples 1 to 240 before and after the acceleration test, and hermetically sealed in order to avoid inclusion of bubbles of air. The hermetically sealed bag containing the ink was housed in a plastic cartridge as illustrated in figure 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 an inkjet head (GEN4, product of Ricoh Printing Systems, Ltd.). next, each of the inks in examples 1 to 480 and comparative examples 1 to 240 before and after the acceleration test was ejected through the ink flow channel to form a solid coated film (ie, a uniform and fully coated film) in a commercially available polyethylene terephthalate film (product name: COSMOSHINE A4300, product of TOYOBO CO., LTD.) so that the solid coated film has a thickness of approximately 10 μm.
    [000105] As a result, the inks in examples 1 to 480 could be ejected without any specific problem both before and after the acceleration test. The solid coated films formed from the paints of example 1 to 480 both before and after the acceleration test were cured without any problem. Specifically, by applying a dose of light twice or less than that required to cure the initial solid coated films formed from the paints of example 1 to 480 before the acceleration test, the solid coated films formed from the paints of example 1 to 480 after the acceleration tests were cured to be in a non-adherent state that was judged by touching them with a finger.
    [000106] The inks of comparative examples 1 to 240 partially or totally frozen after the acceleration test to lose properties such as inkjet inks. Thus, these inks could not be evaluated for inkjet property. Also, their curing properties have not been evaluated since they could not form the solid coated film described above.
    [000107] Measurement of the curing light dose required for the disappearance of adhesion, and observation of the appearance of cured and uncured coated films.
    [000108] Each of the mixtures of Preparation Examples 1 to 120 shown in tables 1 to 12 was measured in relation to the curing light dose required for the disappearance of adhesion as follows.
    [000109] An aluminum bag having a shape illustrated in figure 1 was loaded with each of the mixtures of Preparation Examples 1 to 120, and hermetically sealed in order to avoid the inclusion of air bubbles. The hermetically sealed bag containing the mixture was housed in a plastic cartridge as illustrated in figure 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 an inkjet head (GEN4, product of Ricoh Printing Systems, Ltd.). The mixture was then ejected through the ink flow channel to form a solid coated film (ie a uniform and fully coated film) on a commercially available polyethylene terephthalate film (product name: COSMOSHINE A4300, product of TOYOBO CO., LTD.) So that the solid coated film is approximately 10 μm thick, so an uncured film has been formed.
    [000110] The film not cured in this way was irradiated with light using a UV curing device (LH6, product of Fusion UV Systems Co.) with the dose of light being changed in stages to 1,000 mJ / cm2, 500 mJ / cm2 , 300 mJ / cm2, 100 mJ / cm2, 50 mJ / cm2, 20 mJ / cm2, 10 mJ / cm2 and 5 mJ / cm2. After irradiation of the predetermined light dose above, the condition of the coated film was confirmed by touching it with a finger. The coated film that had lost adhesion was considered to be cured. The minimum light dose required for the coated film to be cured was used as the required light cure dose for the coated film to lose adhesion. The dose of curing light required for the coated film to have lost adherence is shown as a “dose of curing light” in Tables 1 to 12.
    [000111] In addition, the uncured coated film was irradiated with the curing light dose required for the coated film to lose adhesion to prepare a cured coated film. The cured and uncured coated films prepared above were observed for appearance. The results are shown in tables 1 to 12.
    [000112] Likewise, the paints of examples 1 to 480 and comparative examples 1 to 240, each containing each of the mixtures of Preparation examples 1 to 120 together with the aromatic phenol compound having two hydroxyl groups on the same molecule ( either from C1 to C4) or the aromatic phenol compound having a hydroxyl group in the molecule thereof (C5 or C6) were measured in relation to the curing light dose, and the appearance of cured and uncured coated films made from each ink was observed.
    [000113] Although the results are not shown in Tables 1 to 12, they were comparable to the results shown in Tables 1 to 12 (those of the mixtures of Preparation Examples 1 to 120); that is, they remained unchanged. Table 1


    [000114] In Table 1, "tp" means "transparent." Table 2


    [000115] In Table 2, "tp" means "transparent." Table 3


    [000116] In Table 3, "tp" means "transparent." Table 4


    [000117] In Table 4, "tp" means "transparent." Table 5


    [000118] In Table 5, "tp" means "transparent" and "tw" means "cloudy in white." Table 6


    [000119] In Table 6, "tp" means "transparent" and "tw" means "cloudy in white." Table 7


    [000120] In Table 7, "tp" means "transparent" and "tw" means "cloudy in white." Table 8


    [000121] In Table 8, "tp" means "transparent" and "tw" means "cloudy in white." Table 9


    [000122] In Table 9, "tp" means "transparent" and "tw" means "cloudy in white." Table 10


    [000123] In Table 10, "tp" means "transparent" and "tw" means "cloudy in white." Table 11

    [000124] In Table 11, "tp" means "transparent" and "tw" means "cloudy in white." Table 12


    [000125] In Table 12, "tp" means "transparent" and "tw" means "cloudy in white." Table 13-1
    *Ex. of Prep. means "Preparation example," and the mixture prepared in each Preparation example was used to prepare the paints of the Examples described in the same row. Table 13-2

    *Ex. of Prep. means "Preparation example," and the mixture prepared in each Preparation example was used to prepare the inks of the Examples and comparative examples described in the same row. Table 14-1

    *Ex. of Prep. means "Preparation example," and the mixture prepared in each Preparation example was used to prepare the paints of the Examples described in the same row. Table 14-2

    *Ex. of Prep. means "Preparation example," and the mixture prepared in each Preparation example was used to prepare the inks of the Examples and comparative examples described in the same row. Table 15-1

    *Ex. of Prep. means "Preparation example," and the mixture prepared in each Preparation example was used to prepare the paints of the Examples described in the same row. Table 15-2

    *Ex. of Prep. means "Preparation Example," and the mixture prepared in each Preparation Example was used to prepare the inks of the Examples and Comparative Examples described in the same row. Table 16-1

    *Ex. of Prep. means "Preparation example," and the mixture prepared in each Preparation example was used to prepare the paints of the Examples described in the same row. Table 16-2

    *Ex. of Prep. means "Preparation Example," and the mixture prepared in each Preparation Example was used to prepare the inks of the Examples and Comparative Examples described in the same row. Table 17-1
    * Prep. means "Preparation example," and the mixture prepared in each Preparation example was used to prepare the paints of the Examples described in the same row. Table 17-2

    * Prep. means "Preparation Example," and the mixture prepared in each Preparation Example was used to prepare the inks of the Examples and Comparative Examples described in the same row. Table 18-1
    * Prep. means "Preparation example," and the mixture prepared in each Preparation example was used to prepare the paints of the Examples described in the same row. Table 18-2

    The mixture prepared in each Preparation Example was used to prepare the inks of the Examples and Comparative Examples described in the same row.
    [000126] It was found that the inks containing mixtures of Preparation Examples 1 to 40, each containing the self-cleaving photopolymerization initiator only as the photopolymerization initiator, together with the phenol aromatic compound having two hydroxyl groups in the molecule of the same (any one from C1 to C4) have good storage stability (examples 1 to 160).
    [000127] It was found that the inks containing the mixtures of Preparation Examples 1 to 40, each containing the self-cleaving photopolymerization initiator only as the photopolymerization initiator, together with the aromatic phenol compound having only one hydroxyl group in its molecule (C5 to C6) it freezes; that is, they do not have sufficient storage stability (comparative examples 1 to 80).
    [000128] As described above, the present inventor previously discovered a photopolymerizable inkjet ink that is negative for skin sensitization, improves the coated film in ura property, allows possible curing failures in the coated film to be visually confirmed, and facilitates quality control in the production process. specifically, the photopolymerizable inkjet ink contains: one or more types of photopolymerizable monomers each having an SI value of less than 3; a self-cleaving light curing initiator; a polymerization initiator to extract hydrogen; and an amine compound that serves as a polymerization accelerator. When mixtures of Preparation Examples 41 to 120 each containing, as in the paint described above, the self-cleaving photopolymerization initiator, the hydrogen-extracting polymerization initiator, and the amine compound serving as a polymerization accelerator as initiators of photopolymerization were mixed with the phenol aromatic compound having two hydroxyl groups in the molecule of the same (any one from C1 to C4), it was verified that the obtained inks present good storage stability similar to the mixtures of Preparation Examples 1 to 40 each containing the self-cleaving light curing initiator only as the light curing initiator (examples 161 to 480). however, when they were mixed with the aromatic phenol compound having only one hydroxyl group in its molecule (C5 or C6), it was found that all the obtained paints freeze; that is, they do not have sufficient storage stability (Comparative Examples 81 to 240). Example 481
    [000129] An ink of example 481 was produced in the same way as in Example 60, except that the amount of the aromatic phenol compound having two hydroxyl groups in the molecule of the same C3 was changed from 0.1 parts by mass of 0.01 parts by mass per 100 parts by mass of the mixture of Preparation Example 20.
    [000130] The ink thus produced was measured against the rate of change in viscosity at 60 ° C in the same manner as described above. The rate of change of the paint was + 2.2%, indicating good storage stability. Example 482
    [000131] An ink of Example 482 was produced by adding 0.1 parts by mass of the aromatic phenol compound having two hydroxyl groups on the molecule of the same C7 [2,2'-methylenebis (4-methyl-6-tert-butyl) phenol) (NONFLEX MBP, product of Seiko Chemical Co., Ltd.)] to 100 parts by mass of the mixture of Preparation Example 20.
    [000132] The ink thus produced was measured against the rate of change in viscosity at 60 ° C in the same manner as described above. The paint change rate was + 3.0%, indicating good storage stability. Example 483
    [000133] An ink of example 483 was produced by adding 0.1 parts by mass of the aromatic phenol compound having two hydroxyl groups on the molecule of the same C8 [2,2'-methylenebis (4-ethyl-6-tert-butyl) phenol) (NONFLEX MBP, product of Seiko Chemical Co., Ltd.)] to 100 parts by mass of the mixture of Preparation Example 20.
    [000134] The ink thus produced was measured against the rate of change in viscosity at 60 ° C in the same manner as described above. The rate of change of the paint was + 3.2%, indicating good storage stability. Example 484
    [000135] An ink of example 484 was produced by adding 0.1 parts by mass of the aromatic phenol compound having two hydroxyl groups on the molecule of the same C9 [2,2'-methylenebis (6- (1-methylcyclohexyl-p -cresol) (NONFLEX MBP, product of Seiko Chemical Co., Ltd.) to 100 parts by mass of the mixture of Preparation Example 20.
    [000136] The ink thus produced was measured against the rate of change in viscosity at 60 ° C in the same manner as described above. The paint change rate was + 2.9%, indicating good storage stability. Preparation example 121
    [000137] A mixture of Preparation Example 121 was prepared in the same manner as in Preparation Example 20, except that 40 parts by weight of A20 and 10 parts by weight of A24 [diethylene glycol diacrylate (SR230, product of Sartomer Co. ]) were added instead of 50 parts per mass of A20. Example 485
    [000138] An ink of Example 485 was produced by adding 0.1 parts by mass of the aromatic phenol compound having two hydroxyl groups on the molecule of the same C1 to 100 parts by mass of the mixture of Preparation Example 121.
    [000139] The ink thus produced was measured against the rate of change in viscosity at 60 ° C in the same manner as described above. The paint change rate was + 1.9%, indicating good storage stability. Preparation example 122
    [000140] A mixture of Preparation Example 122 was prepared in the same manner as in Example 20, except that 40 parts by mass of A20 and 10 parts by mass of A25 [trimethylol propane triacrylate (M-309, product of Toagosei Chemical Co ., Ltd.)] instead of 50 parts per mass of A20. Example 486
    [000141] An ink of example 486 was produced by adding 0.1 parts by mass of the aromatic phenol compound having two hydroxyl groups on the molecule of the same C1 to 100 parts by mass of the mixture of preparation example 122.
    [000142] The ink thus produced was measured against the rate of change in viscosity at 60 ° C in the same manner as described above. The paint change rate was + 2.1%, indicating good storage stability.
    [000143] Aspects of the present invention are as follows: 1. Light-curing inkjet ink including: A light-curing monomer having a Stimulation Index less than 3, where the Stimulation Index indicates the extent of sensitization as measured by the test of skin sensitization based on a local lymph node test; and An aromatic phenol compound having two hydroxyl groups on its molecule. 2. Light-curing ink jet ink, according to 1, in which the aromatic phenol compound having two hydroxyl groups in its molecule is at least one selected from the group consisting of hydroquinone, methyl hydroquinone, tert-butyl hydroquinone and 2,5-di-tert-butyl hydroquinone. 3. Light-curing inkjet ink, according to 1 or 2, also including: at least one selected from the group consisting of a self-cleaving light-curing initiator, a hydrogen-extracting light-curing initiator, and an amine compound serving as a polymerization accelerator. 4. Photopolymerizable inkjet ink, according to 3, in which the hydrogen-extracting photopolymerization initiator is a compound of thioxanthone. 5. Light-curable ink jet ink, according to 3 or 4, wherein the amine compound is a benzoic acid ester compound containing an N, N-dimethyl amino group. 6. Photopolymerizable inkjet ink, according to any one from 1 to 5, in which the photopolymerizable monomer is at least one selected from the group consisting of polyethylene glycol dimethacrylates represented by the following general formula (1), y methacrylate -butyrolactone, trimethylol propane trimethacrylate, tricyclodecane dimethacrylate dimethanol, caprolactone modified dipentaerythritol hexaacrylate, polypropylene glycol diacrylate [CH2 = CH-CO- (OC3H6) n-OCOCH = CH2 (n) is equal to 12 days] hydroxypivalate of caprolactone-modified neopentyl glycol, methane tetraacrylate, polyethoxylated tetramethylol, bisphenol A modified ethylene oxide, neopentyl glycol dimethacrylate, 1,4-butanediol acrylate dimethylacrylate, stearyl acrylate, hydroxy acrylate, acrylate, ethyl acetate, acrylate butyl, n-pentyl methacrylate, n-hexyl methacrylate, ethylene oxide modified phenol acrylate, isostearyl acrylate, t trimethacrylate rimethylol propane modified by ethylene oxide, stearyl methacrylate, glycerin dimethacrylate:
    Where n is almost equal to 2, 9 or 14. 7. Ink cartridge, including: light-curing inkjet ink according to any one from 1 to 6; and a container, which houses the light-curing inkjet ink. 8. Printer, including: The light-curing inkjet ink according to either 1 to 6, or the ink cartridge according to 7, or both.
    [000144] The present invention can provide: a photopolymerizable inkjet ink safe in skin sensitization and good in storage stability at high temperatures; an ink cartridge housing the ink; and a printer containing the ink cartridge mounted thereon.
    [000145] Also in light-curing inkjet ink, curing failures can easily be determined visually, requiring no dangerous actions like inserting fingers into operating printers or providing printers with expensive detectors.
    [000146] In addition, printed products obtained by using the ink of the present invention are safe in skin sensitization even if uncured monomers remain. The printed products do not sensitize the skin, for example, the fingers and hands that have been placed in contact with them. In this way, the present ink can provide safe printed products. List of reference signs: 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 printing for a 3d colored ink: printing unit for a colored ink 4a: UV light source 4b: UV light source 4c: UV light source 4d: UV light source 5: processing unit 6: take-up roller for products 200: ink cartridge 241: ink bag 242: ink input 243: ink output 244: cartridge case
    权利要求:
    Claims (9)
    [0001]
    1. Light-curing inkjet ink characterized by the fact that it comprises: at least one light-curing monomer having a stimulation index less than 3, where the stimulation index indicates the extent of sensitization as measured by the skin sensitization test based on in local lymph node test; and at least one aromatic phenol compound having two hydroxyl groups on the molecule thereof, wherein the photopolymerizable monomer is at least one of polyethylene glycol dimethacrylate represented by the following general Formula (1), where n is 2, 9 or 14 ,
    [0002]
    2. Light-curing ink jet ink according to claim 1, characterized by the fact that the aromatic phenol compound having two hydroxyl groups in its molecule is at least one selected from the group consisting of hydroquinone, methyl hydroquinone, tert-butyl hydroquinone and 2,5-di-tert-butyl hydroquinone.
    [0003]
    3. Light-curing inkjet ink, according to claim 1 or 2, characterized by the fact that it also comprises: at least one selected from the group consisting of a self-cleaving light-curing initiator, an extracting light-curing initiator hydrogen, and an amine compound serving as a polymerization accelerator.
    [0004]
    4. Light-curing inkjet ink according to claim 3, characterized by the fact that the hydrogen-extracting photopolymerization initiator is a compound of thioxanthone.
    [0005]
    Photopolymerizable inkjet ink according to claim 3 or 4, characterized in that the amine compound is a benzoic acid ester compound containing an N, N-dimethyl amino group.
    [0006]
    6. Light-curing ink jet ink according to claim 3, characterized in that the self-cleaving light curing initiator comprises 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4 -yl-phenyl) -butan-1-one, or the self-cleaving photopolymerization initiator is 2- methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, and a photopolymerization initiator Extracting hydrogen is composed of thioxanthone, and an amine compound serving as a polymerization accelerator is a benzoic acid ester compound having an NN-dimethylamino group.
    [0007]
    7. Light-curing ink jet ink according to claim 1 or 2, characterized in that it comprises a self-cleaving light curing initiator comprising 2-dimethyl amino-2- (4-methyl benzyl) - 1- ( 4-morpholin-4-yl-phenyl) -butan-1-one, a hydrogen-extracting photopolymerization initiator comprising a thioxanthone compound, and a benzoic acid ester compound containing an N, N-dimethylamino group as an accelerator of polymerization.
    [0008]
    8. Photopolymerizable inkjet ink according to claim 1 or 2, characterized by the fact that the photopolymerizable monomer is at least one of polyethylene glycol dimethacrylate represented by the General Formula (1), where n is 2, 9 or 14, trimethylolpropane trimethacrylate, caprolactone modified dipentaerythritol hexaacrylate, t-butyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, ethylene oxide modified phenol acrylate and trimethyl oxide ethyl acetate acetate.
    [0009]
    9. Light-curing ink jet ink according to claim 1 or 2, characterized in that the light-curing monomer is at least one of caprolactone-modified dipentaerythritol hexaaxrilate, t-butyl methacrylate, and phenol acrylate modified by ethylene oxide.
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    同族专利:
    公开号 | 公开日
    US9493663B2|2016-11-15|
    CN103547640A|2014-01-29|
    BR112013029528A2|2017-01-24|
    KR101580027B1|2015-12-23|
    RU2570666C2|2015-12-10|
    EP2710081A4|2015-05-06|
    WO2012157690A1|2012-11-22|
    CN103547640B|2016-04-13|
    CA2835165A1|2012-11-22|
    EP2710081A1|2014-03-26|
    US20140125744A1|2014-05-08|
    CA2835165C|2016-07-05|
    JP2012255137A|2012-12-27|
    RU2013156237A|2015-06-27|
    US20150232677A1|2015-08-20|
    US9068094B2|2015-06-30|
    KR20140016383A|2014-02-07|
    JP5994357B2|2016-09-21|
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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| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|
    2020-11-10| B09A| Decision: intention to grant|
    2021-01-19| 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
    JP2011-111757|2011-05-18|
    JP2011111757|2011-05-18|
    PCT/JP2012/062573|WO2012157690A1|2011-05-18|2012-05-10|Photopolymerizable inkjet ink, ink cartridge, and printer|
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