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    • 专利摘要:
    LIGHT-CURING INK FOR INK JET. To provide a photopolymerizable inkjet ink, which contains photopolymerizable monomers containing at least one selected from the group of compounds (A) below, compounds which are negative for skin sensitization and at least one selected from the group of compounds (B ) below, compounds which are negative for skin sensitization, wherein the group of compounds (A) is a group of compounds consisting of caprolatone-modified dipentaerythritol hexaacrylate, polyethoxylated tetramethylol methane tetraacrylate, modified ethylene oxide diacrylate with bisphenol A, caprolactone modified hydroxy pivalic acid neopentyl glycol diacrylate, polypropylene glycol diacrylate [CH2=CH-CO-(OC3H6)n-OCOCH=CH2 (#12)], hydroxyethyl acrylamide, trimethylol propane trimethacrylate and tricyclodecane dimethanol dimethacrylate and the group of compounds (B) is a group of compounds consisting of phenol acrylate modified with ethylene oxide, acrylates of isostearyl, ethylene oxide modified trimethylol propane trimethacrylate, stearyl methacrylate and glycerine dimethacrylate.
    公开号:BR112014011047B1
    申请号:R112014011047-6
    申请日:2012-10-30
    公开日:2021-05-11
    发明作者:Takao Hiraoka
    申请人:Ricoh Company, Ltd；
    IPC主号:
    专利说明:

    Technical Field
    [0001] The present invention relates to a photopolymerizable ink for inkjet. Previous Technique
    [0002] Light cure ink jet inks using meth(acrylic acid) esters and light cure ink jet inks using a combination of meth(acrylic acid esters) and vinyl ethers have been widely known (see PTL 1 etc.) .
    [0003] However, many of the monomers used in conventional light curing inkjet inks are toxic. Especially, most (meth)acrylic acid esters, which are readily available at low cost, have high toxicity in terms of skin sensitization, which causes allergic reactions to the skin having contact with them. Conventional technique has not provided any solution to this problem. List of Quotes Patent Literature
    [0004] PTL 1: Open Japanese Patent Application (JP-A)
    [0005] No. 2004 - 526820 Invention Summary Technical problem
    [0006] The present invention aims to solve the aforementioned problems in the art and achieve the following objective. An object of the present invention is to provide a photopolymerizable ink jet ink, which has no skin sensitization problem and obtains both low viscosity and improved curing property. Solution to Problem
    [0007] As a result of the studies conducted by the present inventors, they found several (meth)acrylic acids and (meth)acrylamide, which do not have a skin sensitization problem. When an ink is produced by using these monomers and providing the curing property to a practical use level, however, a resulting ink has been found to have high viscosity compared to commonly used inkjet inks. Therefore, this ink cannot be ejected as inkjets without using an ejection heat capable of heating to a temperature high enough to make the ink low in viscosity. In addition, it is necessary to adjust the considerably high internal head pressure to eject the ink. As a result, there is a problem with the aforementioned ink in that stable ejection performances cannot easily be obtained.
    [0008] The present inventors have conducted diligent studies to solve the various aforementioned problems and achieve the aforementioned objective and the studies have led to the following conclusions. Based on these findings, the present invention has been carried out. Namely, the conclusions of the present inventors are that a photopolymerizable ink jet ink, containing at least one selected from the group of compounds (A) below, compounds which are negative for skin sensitization and at least one selected from the group of compounds (B) below, compounds which are negative for skin sensitization, do not have a skin sensitization problem and both low viscosity and improved curing property can be obtained.
    [0009] The present invention is based on the findings of the present inventors and means for solving the aforementioned problems are as follows.
    [0010] A photopolymerizable inkjet ink containing photopolymerizable monomers, containing at least one selected from the group of compounds (A) below, compounds which are negative for skin sensitization and at least one selected from the group of compounds (B ) below, compounds which are negative for skin sensitization, where the group of compounds (A) is a group of compounds consisting of caprolatone modified dipentaerythritol hexaacrylate, polyethoxylated tetramethylol methane tetraacrylate, bisphenol A diacrylate modified with ethylene oxide, caprolactone-modified hydroxypivalic acid neopentyl glycol diacrylate, polypropylene glycol diacrylate [CH2=CH—CO—(OC3H6)n—OCOCH=CH2 (n^12)], hydroxyethyl acrylamide, trimethylol propane trimethacrylate and dimethacrylate of tricyclodecane dimethanol and the group of compounds (B) is a group of compounds consisting of ethylene oxide modified phenolacrylate, isostearyl acrylates, t trimethylol propane rimmethacrylate modified with ethylene oxide, stearyl methacrylate and glycerin dimethacrylate. Advantageous Effects of the Invention
    [0011] The present invention can provide a photopolymerizable ink jet ink, which has no skin sensitization problem and obtains both low viscosity and improved curing property.
    [0012] Furthermore, the printed matter produced with the ink of the present invention has no problem of skin sensitization, even if an uncured monomer component is retained and therefore safe and skin sensitization is not caused, even when the material printed is played with your hands or fingers. As a result, a secure printed matter can be provided. Brief Description of Drawings
    [0013] Figure 1 is a schematic diagram illustrating an example of an ink pouch of the ink cartridge of the present invention.
    [0014] Figure 2 is a schematic diagram illustrating an example of the ink cartridge of the present invention housing an ink pouch.
    [0015] Figure 3 is a schematic diagram illustrating an example of the ink jet recording device (printer) of the present invention. Description of Modalities (Light-curing Inkjet Ink)
    [0016] The photopolymerizable ink jet ink (may also be referred to only as "ink" hereinafter) of the present invention contains at least photopolymerizable monomers and may further contain other components, such as a photoradical polymerization initiator, a polymerization accelerator and a colorant if necessary. <Photopolymerizable Monomers>
    [0017] The photopolymerizable monomers contain at least one selected from the group of compounds (A) below, compounds which are negative for skin sensitization and at least one selected from the group of compounds (B) below, compounds which are negative for skin sensitization and may further contain at least one selected from the group of compounds (C) below and other photopolymerizable monomers, if necessary.
    [0018] Group of compounds (A): a group of compounds consisting of caprolatone-modified dipentaerythritol hexaacrylate, polyethoxylated tetramethylol methane tetraacrylate, ethylene oxide-modified bisphenol A diacrylate, caprolactone-modified hydroxypivalic acid neopentyl glycol diacrylate, polypropylene glycol diacrylate [CH2=CH—CO—(OC3H6)n—OCOCH=CH2 (n=12)], hydroxyethyl acrylamide, trimethylol propane trimethacrylate and tricyclodecane dimethanol dimethacrylate.
    [0019] Compound group (B): a group of compounds consisting of phenol acrylate modified with ethylene oxide, isostearyl acrylates, trimethylol propane trimethacrylate modified with ethylene oxide, stearyl methacrylate and glycerin dimethacrylate.
    [0020] Compound group (C): a group of compounds consisting of triethylene glycol divinyl ether, hydroxybutyl vinyl ether, ethyl vinyl ether, t-butyl methacrylate, n-pentyl methacrylate and n-hexyl methacrylate.
    [0021] Note that "n~12" in the description of polypropylene glycol diacrylate CH2=CH-CO-(OC3H6)n-OCOCH=CH2 (n«12)] means that the average value of "n" is 12 across compounds having different "n" values are present as a mixture in polypropylene glycol diacrylate.
    [0022] The present invention will be explained in detail hereafter.
    [0023] Conventionally, there has not been a photopolymerizable monomer that can be used as a material for a photopolymerizable inkjet ink and is negative for skin sensitization and that can obtain sufficiently low viscosity and sufficient curing property when used alone. With monomers that are negative for skin sensitization, a method is studied to mix the monomer having excellent curing property but having high viscosity and the monomer having low viscosity but having insufficient curing property with a desirable balance and using blending.
    [0024] As a result, the group of compounds (B) was found to be photopolymerizable monomers being negative for skin sensitization and having low viscosity. Thus, both low viscosity and improved curing property have been successfully obtained by using the group of compounds (B) in combination with the group of compounds (A), which is previously discovered and compounds which are negative for skin sensitization and have the desirable curing property but having high viscosity.
    [0025] An amount of the group of compounds (A) in the photopolymerizable monomers is not appropriately selected depending on the intended purpose, without any limitation, but is preferably 5% by mass to 95% by mass, more preferably 10% by mass to 50% by mass. An amount of the group of compounds (B) in the photopolymerizable monomers is not appropriately selected depending on the intended purpose, without any limitation, but is preferably 5% by mass to 95% by mass, more preferably 10% by mass to 85% by mass.
    [0026] A mixing ratio (A)/(B) (mass ratio) of the group of compounds (A) and the group of compounds (B) is not properly selected depending on the intended purpose, without any limitation, but it is preferably 5/95 to 95/5, more preferably 15/85 to 85/15.
    [0027] Here, the negative light curing monomer for skin sensitization refers to a compound that is rated at least one of the following skin sensitization ratings from (1) to (3): (1) a compound has an Index of Stimulation (SI Value) 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); (2) a compound assessed as "negative to skin sensitization" or "no skin sensitization" on its MSDS (Material Safety Data Sheet); and (3) a compound evaluated as "skin sensitizing negative" or "no skin sensitization" in the literature [e.g., Contact Dermatitis 8 223-235 (1982)].
    [0028] With respect to the above (1), the compound having an SI value of less than 3 is considered negative for skin sensitization, as described in the literature, eg "Functional Material" {Kino Zairyou) 2005, September , Vol. 25, No. 9, p. 55. The lower the SI value, the lower the 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. <<Group of Compounds (C)>> As for the group of compounds (C), skin sensitizing negative vinyl ethers are used and examples of the group of compounds (C) include a group of compounds consisting of divinyl ether of triethylene glycol, hydroxybutyl vinyl ether, ethyl vinyl ether, t-butyl methacrylate, n-pentyl methacrylate and n-hexyl methacrylate.
    [0029] The ink of the present invention preferably contains as a photopolymerizable monomer, at least one selected from the group of compounds (C), compounds which are negative for skin sensitization.
    [0030] At least one selected from the group of compounds is not properly selected, depending on the intended purpose, without any limitation, but among the group of compounds (C), triethylene glycol divinyl ether is preferable because it has sufficiently low viscosity, it has a boiling point that is not excessively low and easily manipulated under ambient temperature and pressure. Furthermore, t-butyl methacrylate, n-pentyl methacrylate and n-hexyl methacrylate are also preferable because they are negative for skin sensitization and have sufficiently low viscosity. An amount of the group of compounds (C) in the photopolymerizable monomers is not properly selected depending on the intended purpose, without any limitation, but is preferably 10% by mass to 90% by mass, more preferably 40% by mass to 60% by mass. <<Another Light-curing Monomer>>
    [0031] In addition to these, the following (meth)acrylates (meth)acrylamides and vinyl ethers can be used in combination with other photopolymerizable monomers, even if through them there is a problem of skin sensitization to some degree, when used alone or its skin sensitization is not confirmed as long as an ink as a whole does not have a problem.
    [0032] Examples of other photopolymerizable monomers include ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate hydroxypivalic acid, y-butyrolactone acrylates, isobornyl (meth)acrylates, trimethylol mono(meth)acrylates formulated propane, polytetra methylene glycol di(meth)acrylates, trimethylol propane (meth)acrylic acid benzoate, diethylene glycol diacrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene diacrylates glycol [CH2=CH-CO-(OC2H4)n-OCOCH=CH2 (n«4)], [CH2=CH-CO-(OC2H4)n-OCOCH=CH2 (n«9)], [CH2=CH- CO- (OC2H4)n-OCOCH=CH2 (n«14)], [CH2=CH-CO-(OC2H4)n-OCOCH=CH2 (n«23)], dipropylene glycol di(meth)acrylate, di( tripropylene glycol meth)acrylate, polypropylene glycol di(meth)acrylate [CH2=C(CH3) —CO— (OC3H6)n-OCOC (CH3)=CH2 (n-7)], di(meth)acrylates of 1 ,3-butanediol, 1,4-butanediol diacrylate, 1,6-hexane di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, di(meth)acrylate of neopentyl glycol, tricyclodecane dimethanol diacrylate, bisphenol A di(meth)acrylates modified with propylene oxide, polyethylene glycol oil di(meth)acrylates, dipentaerythritol hexa(meth)acrylates, morpholine (meth)acrylol, 2— hydroxypropyl(meth)acrylamide, tetramethylol methane tetra(meth)acrylates modified with propylene oxide, hydroxypenta(meth)acrylate dipentaerythritol, hydroxypenta(meth)acrylate modified dipentaerythritol with caprolactone, tetra(meth)acrylates of propane, tetra( pentaerythritol meth)acrylate, trimethylol propane triacrylate, trimethylol propane triacrylate modified with ethylene oxide, trimethylol propane tri(meth)acrylate modified with propylene oxide, trimethylol propane tri(meth)acrylate modified with caprolactone, tri(meth) )pentaerythritol acrylate, tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate, prooxide modified neopentyl glycol di(meth)acrylate pylene, propylene oxide modified glyceryl tri(meth)acrylates, polyester di(meth)acrylate, polyester tri(meth)acrylate, polyester tetra(meth)acrylate, polyester penta(meth)acrylate, poly(meth)acrylate ) polyester acrylate, N-vinyl caprolactam, N-vinyl pyrrolidone N-vinyl formamide, polyurethane di(meth)acrylate, polyurethane tri(meth)acrylate, polyurethane tetra(meth)acrylate, polyurethane penta(meth)acrylate , polyurethane poly(meth)acrylate, cyclohexane dimethanol divinyl ether, cyclohexane dimethanol monovinyl ether, hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, diethylene glycol divinyl ether, dicyclopentadiene vinyl ether, tricyclodecane ether vinyl, benzyl vinyl ether and ethyl xtacene methyl vinyl ether. <<Photo-radical Polymerization Initiator>>
    [0033] The ink of the present invention preferably contains a photo-radical polymerization initiator. The photoradical polymerization initiator is not properly selected depending on the intended purpose, without any limitation, but the photoradical polymerization initiator is preferably selected from those negatives for skin sensitization.
    [0034] The negative photoradical polymerization initiator for skin sensitization is appropriately selected depending on the intended purpose, without any limitation as long as they are composed of any of the skin sensitization assessments (1) to (3) and their examples include: 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)butan-1-one, 2-methyl-1-[4-methylthio)phenyl]-2- morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1, and 2,4-diethyl thioxanthone. These can be used alone or in combination.
    [0035] The (meth)acrylic acid ester, the (meth)acrylamide and the vinyl ether are known to have cationic polymerization property, equally. Examples of photocationic polymerization in general are expensive and generate a trace amount of strong acid, even in the state where they are not irradiated with light. Thus, it is necessary to take special care, such as transmitting acid resistance to the ink supply channel of a printer, imposing a limitation on the choice of the constituent elements of the printer. In contrast, the ink of the present invention may contain the photoradical polymerization initiator which is inexpensive and does not generate strong acid. Thus, it is possible to produce an ink at 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, the polymerization reaction proceeds without a polymerization initiator. This is a matter conventionally known and not described in detail in the present invention.
    [0036] The photoradical polymerization initiator includes, for example, a self-cleaving polymerization initiator and a polymerization initiator with hydrogen abstraction.
    [0037] Examples of the self-cleaving polymerization initiator include: 2,2-dimethoxy-1,2-diphenyletan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan- 1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-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-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)butan-1-one, bis( 2,4,6-trimethylbenzoyl)phenylphosphine, bis(2,6-dimethoxyibenzolyl)-2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoylphosphine oxide, 1,2-octanadion-[4- (phenylthio)-2-(o-benzoyloxime)], ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(0-acetyloxime) and [4- (methylphenylthio)phenyl]phenylmethanone.
    [0038] Examples of the hydrogen abstraction polymerization initiator include benzophenone compounds such as benzophenone, methylbenzophenone, methyl-2-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl sulfide and phenylbenzophenone; and thioxanthone compounds such as 2,4-diethylthioxanthone, 2-chlorothioxanthone, isopropylthioxanthone and 1-chloro-4-propylthioxanthone. «Polymerization Accelerator»
    [0039] Amines can be used as a polymerization accelerator in combination with a photoradical polymerization initiator. Examples of the polymerization accelerator include p-dimethylaminobenzoate, 2-ethylhexyl p-dimethylaminobenzoate, methyl p-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate and butoxyethyl p-dimethylaminobenzoate. <<Dye>>
    [0040] The ink can contain a dye as desired. The colorant is suitably selected from conventional inorganic pigments, organic pigment and various color pigments (eg black pigments, yellow pigments, magenta pigments, cyan pigments and white pigments) depending on the intended purpose, without any limitation.
    [0041] As for black pigments, those such as carbon black produced by the kiln method or the channel method can be used.
    [0042] As for the yellow pigments, for example, the following Yellow series pigments 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.
    [0043] As for magenta pigments, for example, the following pigments from the Pigs series. Reds 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.
    [0044] As for cyan pigments, for example, the pigments of the Blue Series, below, 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, Blue Vat 4 and Blue Vat 60.
    [0045] As for the white pigment, 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, such as fine powder of silicic acid, calcium silicate, alumina, alumina hydrate, titanium oxide, zinc oxide, talc and clay.
    [0046] In addition, various inorganic or organic pigments optionally can be used, considering, for example, the physical properties of the paint.
    [0047] In addition, a polymerization initiator, a higher fatty acid, silicone or fluorine surfactant, or a polymeric pigment dispersing agent containing a polar group can optionally be used. Examples of the polymerization initiator include: 4-methoxy-1-naphthol, methylhydroquinone, hydroquinone, t-butylhydroquinone, di-t-butylhydroquinone, methoquinone, 2,2'-dihydroxy-3,3'-di (α-methylcyclohexyl)-5,5'-dimethyldiphenyl methane, p-benzoquinone, di-t-butyldiphenylamine, 9,10-di-n-butoxy anthracene, 4,4'-[1,10-dioxo- 1,10-decandylbis(oxy)]bis[2,2,6,6-tetramethyl]-1-piperidinyloxy.
    [0048] The physical properties of the ink are appropriately selected depending on the intended purpose, without any limitation, but are desirably matched with the specification required for an inkjet ejection head as used. Various ejection heads are on the market from numerous manufacturers and among them there are ejection heads having a temperature adjustment function over a wide temperature range. Considering these market trends, the ink viscosity at a temperature of 25°C is preferably 2 mPa.s to 150 mPa.s. In the case where the ink is ejected at 25°C, the ink viscosity is preferably 5 mPa.s to 18 mPa.s. As mentioned before, it is possible to use the ejection head temperature adjustment function. In the case where the ink viscosity is too high at 25°C, its viscosity can be reduced by heating the head, optionally. Assuming the heating condition is 60°C, in the aforementioned case, the ink viscosity at 60°C is preferably 2 mPa.s to 20 mPa.s, more preferably 5 mPa.s to 18 mPa.s,
    [0049] Consequently, low ink viscosity can be obtained as long as the ink viscosity falls in a range of 5 mPa.s to 18 mPa.s, at 25°C or a range of 2 mPa.s to 20 mPa.s , at 60°C.
    [0050] The light dose required for curing is selected appropriately depending on the intended purpose, without any limitation, but less energy is more preferable in view of energy savings. When ink is intended to cure with very weak light radiation, the ink is reacted with light that has leaked from a light source or internal illumination light to cure at a gas-liquid ink interface in an inkjet nozzle of the ejection head, which can cause nozzle clogging. It is often the case that this problem can be avoided by optimizing a printer design, but in any case it is not preferable for the ink to have high reactivity for curing. Therefore, the light dose required for curing is preferably 5 mJ/cm2 to 10,000 mJ/cm2, more preferably 10 mJ/cm2 to 1000 mJ/cm2 and even more preferably 10 mJ/cm2 to 200 mJ/ cm2.
    [0051] When the light dose required for curing is within the aforementioned preferable range, it can be said that the curing property of the ink is improved. (Cartridge)
    [0052] The ink cartridge of the present invention contains the photopolymerizable ink jet ink of the present invention and a container and may further contain other elements such as an ink pouch, if necessary.
    [0053] The ink of the present invention is housed in the container, which can be used as an ink cartridge. With this form, users do not have to directly touch the ink during tasks such as changing ink and thus are not related to staining their fingers, hands or clothes. Furthermore, it is possible to prevent the interfusion of foreign matter, such as dust, into the ink.
    [0054] The container is not particularly limited and the shape, structure, size and material can be selected appropriately depending on the intended purpose. For example, the container is preferably selected from those having at least one paint pouch formed from an aluminum laminate film or resin film.
    [0055] The ink cartridge will be described with reference to figures 1 and 2. Figure 1 is a schematic diagram illustrating an example of an ink bag 241 of an ink cartridge. Figure 2 is a schematic diagram illustrating an ink cartridge 200 containing the ink bag 241 illustrated in Figure 1 and a cartridge case 244, which is an example of the container and housing the ink bag 241.
    [0056] As shown in Figure 1, the ink bag 241 is filled with ink by injecting the ink from an ink inlet 242. After removing the air present inside the ink bag 241, the ink inlet ink 242 is sealed through the fusion bond. At the time of use, a needle attached to the main body of the device is inserted into an ink outlet 243 formed from a rubber element to supply ink to the device. The ink pouch 241 is formed from a wrapping element, such as a non-air permeable aluminum laminated film. As illustrated in Figure 2, ink pouch 241 is housed, typically in a plastic cartridge case 244, which is then detachably mounted in use with various inkjet recording devices, such as ink cartridge 200.
    [0057] The ink cartridge of the present invention is preferably mounted detachably in the inkjet recording devices. The ink cartridge can simplify ink refilling and changing to improve workability. (Inkjet Recording Device)
    [0058] The inkjet recording device of the present invention contains at least one ink application unit configured to apply a light-curing inkjet ink to a base material to be printed and may further contain other units such as a ink curing unit configured to cure ink on the base stock to be printed, if necessary.
    [0059] The light curing ink jet ink is the light curing ink jet ink of the present invention. Furthermore, the ink application unit preferably contains the ink cartridge of the present invention mounted thereon.
    [0060] Figure 3 is a schematic diagram illustrating an example of the ink jet recording device (printer) of the present invention.
    [0061] Figure 3 illustrates an example that forms a color image as follows. Specifically, print units 3 (ie print units 3a, 3b, 3c and 3d for respective colors (eg yellow, magenta, cyan and black) eject color inks (yellow, magenta, cyan and black) onto a media of base to be printed 2 (which is driven from left to right in figure 3 and may be referred to as "base" hereinafter) fed from a base material feed roller 1 and light (UV rays) is applied from the UV light sources (curing light sources) 4a, 4b, 4c and 4d to the corresponding color inks for curing. Each of the 3a, 3b, 3c and 3d printing units has a heating mechanism in an ink ejection portion and a cooling mechanism in a supporting portion of the base (ie, a portion above or below the base in Figure 3) The heating mechanism serves to heat a paint with a high viscosity so as to lower its viscosity. Coolant serves to cool the base to approximately tempera environment in a contact or non-contact manner, if necessary. In the case where the ink is heated for ejection, when the print area of the previously printed color is small and the base transport speed is low, the base material is naturally cooled and kept at approximately room temperature in the subsequent printing. However, when the print area of the previously printed color is large and the base transport speed is high, the base increases in temperature at temperature to potentially cause variation between the respective color inks in behaviors such as moisture and dispersion of the ink droplets that have been blasted onto the base or previously blasted ink, thereby adversely affecting image formation. Thus, if necessary, the cooling mechanism can be provided to maintain a base at approximately room temperature.
    [0062] The base material 2 used is, for example, paper, a film, a metal or a composite material. 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.
    [0063] When UV rays are applied to each of the colored inks for each printing process, the colored inks are cured satisfactorily. In order to obtain high speed printing, UV light sources 4a, 4b and 4c can be reduced in output power or can be omitted, so that the UV light source 4d is made to apply a sufficient dose of rays UV to a composite printed image formed from a plurality of colors. Furthermore, to realize energy savings and cost savings, LED light sources, which have recently been used practically for printing light curing inks, can be used in place of conventionally used light sources such as mercury lamps. in high pressure and metal halide lamps. In figure 3, the reference numeral 5 denotes a processing unit and the reference numeral 6 denotes a winding roll for printed products. Examples
    [0064] The present invention will be described below by way of Examples, which should not be construed as limiting the present invention thereto. Examples 1 to 19
    [0065] The materials from the groups of compounds (A) to (C) below were mixed in the mixing ratio (unit for numerical value was parts by mass) of the corresponding columns of Examples and Comparative Examples, shown in Table 3 to thus obtain paints.
    [0066] Compound Group (A): (meth)acrylic acid ester and/or (meth)acrylamide, which are negative for skin sensitization (high viscosity, but excellent curing property).
    [0067] Compound Group (B): (meth)acrylic acid ester and/or (meth)acrylamide, which are negative for skin sensitization (low viscosity).
    [0068] Compound Group (C): triethylene glycol divinyl ether, t-butyl methacrylate, n-pentyl methacrylate and n-hexyl methacrylate, each of which is negative for skin sensitization (of sufficiently low viscosity) .
    [0069] Compound Group (D): photoradical polymerization initiator, negative for skin sensitization.
    [0070] The details of A1 to A8, B1 to B5, C1 to C4 and D1 4 D4 in Table 3 are as follows. The value in parentheses after each product name is "SI value" as measured by the LLNA test described in the Skin Sensitization Assessment (1). The description "skin sensitization negative" or "no skin sensitization" after each product name means that the product is assessed as "skin sensitizing negative" or "no skin sensitization" on the MSDS (Material Safety Data Sheet ) described in the skin sensitization assessment (2) or the literature described in the skin sensitization assessment (3) and MSDS or literature used for the standard of assessment and test method used will also be represented.
    [0071] The SI value valuation method will be described in detail below.
    [0072] A1: caprolactone-modified dipentaerythritol hexaacrylate, DPCA-60, manufactured by NIPPON KAYAKU Co. Ltd. (skin sensitization negative, evaluated on MSDS, test method: OECD test guidelines 406)
    [0073] A2: polyethoxylated tetramethylol methane tetraacrylate, ATM-35E (1.7), manufactured by Shin - Nakamura Chemical Co., Ltd.
    [0074] A3: ethylene oxide modified bisphenol A diacrylate, BPE-10 (1.2) manufactured by dai-ichi Kogyo Seiyaku Co., Ltd.
    [0075] A4: caprolactone-modified neopentyl glycol hydroxypivalate diacrylate, HX-620 (0.9), manufactured by NIPPON KAYAKU Co. Ltd.
    [0076] A5: polypropylene glycol diacrylate
    [0077] [CH2=CH-CO-(OC3H6)n-OCOCH=CH2 (n«12)], M-270 (1.5), manufactured by Toagosei Chemical Co., LTD.
    [0078] A6: hydroxyethyl acrylamide, HEAA, manufactured by KOHJIN Co., Ltd. (no skin sensitization, evaluated on MSDS, test method: OECD test guidelines 429).
    A7: trimethylol propane tri(meth)acrylates, SR350 (1.9, manufactured by Sartomer Co.
    [0080] A8: Tricyclodecane dimethanol di(meth)acrylates, DCP (1.3), manufactured by Shin - Nakamura Chemical Co., Ltd.
    [0081] B1: ethylene oxide-modified phenol acrylates, M-102 (0.7), manufactured by Toagosei Chemical CO., LTD.
    [0082] B2: isostearyl acrylates, S-1800A (1.4), manufactured by Shin - Nakamura Chemical Co., Ltd.
    [0083] B3: Ethylene oxide-modified trimethylol propane trimethacrylate, TMPT-3EO (1.0), manufactured by Shin - Nakamura Chemical Co., Ltd.
    [0084] B4: Stearyl methacrylate, S (1,2) manufactured by Shin - Nakamura Chemical Co., Ltd.
    [0085] B5: Glycerin dimethacrylate, 701 (1.2) manufactured by Shin - Nakamura Chemical Co., Ltd.
    [0086] C1: triethylene glycol divinyl ether, manufactured by BASF (skin sensitization negative, evaluated on MSDS, test method: OECD test guidelines 406).
    [0087] C2: t-butyl methacrylate, Light Ester TB, manufactured by KYOEISHA CHEMICAL CO., LTD. (Negative for skin sensitization, evaluated in the literature: Contact Dermtitis 8 223- 235 (1982), test method: maximization).
    [0088] C3 n-pentyl methacrylate, manufactured by Tokyo Science Corp. (Negative for skin sensitization, evaluated in the literature: Contact Dermtitis 8 223- 235 (1982), test method: maximization).
    [0089] C4: n-hexime methacrylate, TOKYO CHEMICAL INDUSTRY CO., LTD, (skin sensitization negative, evaluated in literature: Contact Dermtitis 8 223- 235 (1982), test method: maximization).
    [0090] D1: 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl) butan-1-one (no skin sensitization, evaluated on MSDS, test method: guidelines Test Code 406).
    [0091] D2: 2-methyl-1-[4-methylthio)phenyl]-2-morpholinopropan-1-one (no skin sensitization, evaluated in MSDS, test method: OECD test guidelines 406).
    [0092] D3: 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (no skin sensitization, evaluated in MSDS, test method: OECD Test Guideline 406).
    [0093] D4: Equimolar mixture of 2,4-diethyl thioxanthone (1,4) and p-dimethylamino benzoic acid (no skin sensitization, evaluated in MSDS, test method: OECD Test Guideline 406). < SI Value Measurement Method >
    [0094] According to the skin sensitization test based on the LLNA (Local Lymph Node Assay), the SI value was measured in the manner described below. [Test Material] << Positive Control >>
    [0095] a-hexylcinnamaldehyde (UCA: product of Wako Pure Chemical Industries, Ltd.) was used as the positive control. << Vehicle >>
    [0096] The vehicle used was a mixture containing the acetone listed below and olive oil in a 4/1 volume portion.
    [0097] Acetone (product of Wako Pure Chemical Industries, Ltd.).
    [0098] Olive oil (product of Fudimi Pharmaceutical Co., Ltd.). << Animals used >>
    [0099] Before being treated with the test substances, the positive control or the 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 sensitization initiation, they were categorized into 2 groups (4 mice/group) by the random sampling method stratified by body weight, so that each individual's body weight was within ± 20 % of the average body weight of all individuals. Each animal was 8 weeks to 9 weeks old at the time of initiation of sensitization. The animals remaining after categorization were excluded from the test.
    [00100] The animals were individually identified by the application of oil paint for their history throughout the testing period and also their cages were labeled for identification. < < Accommodation environment >>
    [00101] For the entire period of housing, including the quarantine/acclimatization period, the animals were housed in a vivarium with a barrier system, which was adjusted as follows: 21° C to 25° C in temperature, 40% to 70 % in relative humidity, 10 times/hour to 15 times/hour in air circulation frequency and 12 hours in light cycle (illumination from 7:00 to 19:00).
    [00102] The housing cages used were made of polycarbonate and four animals were housed in each cage.
    [00103] The animals were given a solid MF laboratory animal free diet (product of Oriental Yeast Co., Ltd.). Also, using a water supply bottle, they were given tap water at will, in which sodium hypochlorite (PURELOX, product of OYALOX Co., Ltd.) had been added so that the chlorine concentration was about 5 ppm. The bed used was SUNFLAKE (fir tree, wood chips, obtained with an electric planer) (product and Charles River Inc.). Feeding equipment and diet were sterilized with an autoclave (121°C, 30 minutes) prior to use.
    [00104] The cage and bed were replaced with new ones at the time of categorization and removal of the auricular lymph node (i.e., the time when the animals were transferred from the vivarium) and the water supply bottle and shelf were replaced by new ones at the time of organization. [Test Method] < < Group Membership >>
    [00105] The composition of the group used for measuring the Si value is shown in Table 1. Table 1
    [Preparation] < < Test Substance >>
    [00106] Table 2 shows the amount of the test substance. The test substance was weighed into a measuring flask 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 Substance>>
    [00107] About 0.25 g of HCA was accurately 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 >>
    [00108] In a measuring vial, 200 mg of 5-bromo-2'-deoxyuridine (BrdU, product of NACALAI TESQUE, INC.) was accurately weighed. Then, physiological saline solution (product of OTSUKA PHARMACEUTICAL CO., LTD.) was added to the measuring flask and dissolved 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 filtration with a sterilized filter filter and placed in a sterilized container. < < Preparation Day and Storage Period >>
    [00109] The positive control preparation was prepared the day before sensitization initiation and stored in a cool place except in use. Vehicle and test substance preparations were prepared on the day of sensitization. The BrdU solution was prepared 2 days before administration and stored in a cold place until the day of administration. [BrdU Awareness and Management] < < Awareness >>
    [00110] Each 25 μl of the test substance preparations, the positive control preparation or the vehicle was applied to both atria of each animal using a micropipette. This treatment was performed once a day for three consecutive days. < < Administration of BrdU >>
    [00111] About 48 hours after the final sensitization, the BrdU preparation (0.5 ml) was administered intraperitoneally once in each animal. [Observation and Examination] << General Conditions >>
    [00112] All animals used for the test were observed one or more times a day from the day of initiation of sensitization until the day of auricular lymph node removal (i.e., the day the animals were transferred from the vivarium). Notably, the day of observation was counted from the day of initiation of sensitization, being considered as Day 1. <<Body Weight Measurement>>
    [00113] The body weight of each animal was measured on the day of initiation of sensitization and on the day of auricular lymph node removal (i.e. the day the animals were transferred from the vivarium). Also, the mean of body weights and their standard error were calculated for each group. <<Auricular Lymph Nodule Removal and Mass Measurement>>
    [00114] About 24 hours after administration of BrdU, the animals were allowed to be euthanized and their auricular lymph nodes were sampled. The tissue surrounding each atrial lymph node was removed and the atrial lymph nodes from both atria were collectively weighed. Also, the mean of the auricular lymph node weights and their standard error were calculated for each group. After measuring the weights, each subject's ear lymph nodes were stored in a frozen state using a BIO MEDICAL FREEZER set to -20%C. <<BrdU Input Measurement>>
    [00115] After returning to room temperature, the auricular lymph nodes were crushed with the gradual addition of physiological saline solution and suspended therein. The suspension thus obtained was filtered and then distributed into the wells of a 96-well microplate, with 3 wells being used per individual. The suspensions thus distributed were measured for BrdU entry by the ELISA method. The reagents used were those from a commercially available kit (Cell Proliferation ELISA, BrdU colorimetric, Cat. No. 1647229, product of Roche Diagnostics Inc.). A multiplate reader (FLUOSTAR OPTIMA, product of BMG LABTECH Inc.) was used for measuring the absorbance of each well (OD: 370 nm to 492 nm, BrdU input) and the average absorbance of the 3 wells for each subject was used as the BrdU measurement for the subject. [Results assessment] <<Calculation of Stimulation Index (SI)>>
    [00116] As shown in the formula below, the BrdU input measurement for each subject was divided by the average of the BrdU input measurements in the vehicle control group to calculate the SI value for the subject. The SI value of each test group was the mean of the individuals' SI values. Also, the standard error of the SI values was calculated for each test group. Notably, the SI value has been rounded to the second decimal and shown to the first decimal.

    [00117] Each of the paints prepared above was measured for viscosities (mPa-s) at 25°C and 60°C and the required light dose for curing (mJ/cm2). The results are shown in Table 3.
    [00118] Viscosities at 25°C and 60°C were measured with a rotary plate-cone viscometer (product of TOKI SANGYO CO., LTD.) with the circulating water temperature being constantly adjusted to 25°C and 60°C °C. A temperature of 25°C is a general temperature considered to be room temperature. The 60°C temperature is an established temperature considering the specification of an inkjet ejection head such as GEN4 (product of Ricoh Printing Systems, Ltd.) that can be heated.
    [00119] The curing property of the inks was evaluated as follows. Specifically, each ink was blasted onto a commercially available polyethylene terephthalate (PET) film and light-irradiated using an LH6 UV irradiation device (product of Fusion Systems Japan Co., Ltd.).
    [00120] An aluminum pouch, having a shape illustrated in figure 1, was loaded with the paint and hermetically sealed in order to prevent the inclusion of air bubbles. 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 hold it. In the kit, an ink flow channel was provided from the cartridge to a GEN4 head (product of Ricoh Printing Systems, Ltd.) Ink was blasted through the ink flow channel to form a coated solid film over the film.
    [00121] The coated solid 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 coated solid film, transformed to the non-tacky state, was judged by touching it with a finger and the coated solid film was judged to be cured when it comes to the non-tacky state. The minimum integrated light dose required to cure the coated solid film is shown as the light dose required for curing. Inks that require less integrated light dose have better curing property.

    Table 3-2

    *1: unable to assess since ejection could not be performed *2: #10 carbon black, manufactured by Mitsubishi Chemical Corporation, which is in the form of a blend with an S32000 polymer dispersing agent, manufactured by Lubrizol Japan Co. , with a mass ratio of 3/1 (carbon black 210/s32000). The above carbon black amount is #10 carbon black blend amount in the aforementioned blend.
    [00122] It was confirmed from the comparison between Comparative Example 1 and Example 1 that the ink could not be ejected due to its high viscosity, when the ink was composed only of compounds from the group of compounds (A), but in the case where the The ink contained the relatively low viscous compounds of the compound group (B), the ink was ejected without a problem by adjusting the head to the proper temperature and the solid image obtained could be cured by light irradiation.
    [00123] It was confirmed from the comparison between Examples 1 to 6 that viscosity and cure property could be controlled by appropriately adjusting the blend formulation, even in the case where different acrylates or acrylamide were included in the compound group (A ), or in the case where different acrylates or methacrylates have been included in the group of compounds (B). Since the properties required for an ink are not limited to viscosity and cure property and are diverse, such as image quality, various properties of image coated films, cost and adaptability to a device's printing process Inkjet recording, composites can be selected appropriately to meet various requirements depending on the situation.
    [00124] It was also confirmed that, the compound group (A) and the compound group (B) in the paint were mainly methacrylate compounds, such as Examples 7 to 9, or in the case where acrylamide or acrylate were still contained in combination , the curing property of the ink was less desirable compared to those of Examples 1 to 6, but the ink could be ejected as jets without any problem by setting the head to the proper temperature, and the solid image obtained could be cured by light irradiation. .
    [00125] It was confirmed that the viscosity and curing property of the paint could be controlled when different types of polymerization initiator were used, as in Examples 1, 10 to 12. Similar to the above, compounds can be selected appropriately to satisfy various requirements depending on the situation.
    [00126] It was confirmed that even in the case where a compound or a combination of compounds from the compound group (C) were used, as in Examples 13 to 17, the ink could be ejected as ink jets without problems by adjusting from heat to the proper temperature and the solid image obtained could be cured by light irradiation. Especially in the case where t-butyl methacrylate, n-pentyl methacrylate or n-hexyl methacrylate is used in place of vinyl ether, both low viscosity and high curing property of the paint could be obtained, but methacrylate also has odor single. Taking this issue into consideration, as mentioned above, compounds can be appropriately selected to meet various requirements, depending on the situation.
    [00127] It was confirmed that even in the case where the ink contained a dye, as in Examples 18 and 19, provided that the ink contains the relatively low viscosity compound of the compound group (B) or still contains the compound group (C), the ink could be ejected by adjusting the heat to the proper temperature and the solid image obtained could be cured by light irradiation.
    [00128] Modalities of the present invention are, for example, as follows: < 1> Light curing ink jet ink, containing: < light curing monomers containing at least one selected from the group of compounds (A) below, compounds which are negative for skin sensitization and at least one selected from the group of compounds (B) below, compounds which are negative for skin sensitization, where the group of compounds (A) is a group of compounds consisting of hexaacrylate. caprolatone-modified dipentaerythritol, polyethoxylated tetramethylol methane tetraacrylate, ethylene oxide-modified bisphenol A diacrylate, caprolactone-modified hydroxypivalic acid neopentyl glycol diacrylate, polypropylene glycol diacrylate [CH2=CH—CO—(OC3H6)n—OCOCH= CH2 (n=12)], hydroxyethyl acrylamide, trimethylol propane trimethacrylate and tricyclodecane dimethanol dimethacrylate; and < the group of compounds (B) is a group of compounds consisting of phenol acrylate modified with ethylene oxide, isostearyl acrylates, trimethylol propane trimethacrylate modified with ethylene oxide, stearyl methacrylate and glycerin dimethacrylate. The photopolymerizable ink jet ink according to claim 1, wherein an amount of the group of compounds (A) in the photopolymerizable monomers is 10% by mass to 50% by mass. The photopolymerizable ink jet ink according to any one of claims 1 or 2, wherein an amount of the compound group (B) in the photopolymerizable monomers is 10% by mass to 85% by mass. A photopolymerizable ink jet ink according to any one of claims 1 to 3, wherein a mixing ratio of the group of compounds (A) and the group of compounds (B), which is expressed by a ratio of (A)/(B) mass is 15/85 to 85/15. The photopolymerizable inkjet ink according to any one of claims 1 to 4, wherein the photopolymerizable monomers further contain at least one selected from the group of compounds (C) below, compounds which are negative for sensitization of the skin, where the Group of compounds (C) is a group of compounds consisting of triethylene glycol divinyl ether, hydroxybutyl vinyl ether, ethyl vinyl ether, t-butyl methacrylate, n-pentyl methacrylate, and n-methacrylate hexyl. The photopolymerizable ink jet ink according to any one of claims 1 to 5, further comprising a photoradical polymerization initiator. The photopolymerizable ink jet ink according to claim 6, wherein the photoradical polymerization initiator is at least selected from the group consisting of 2-dimethylamino-2-(4-methylbenzyl)-1-( 4-morpholin-4-yl-phenyl)butan-1-one, 2-methyl-1-[4-methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4 - morpholinophenyl)butanone-1, and 2,4-diethyl thioxanthone. An ink cartridge, containing: - the light curing ink jet ink as defined in any one of claims 1 to 7; and - a container housing the light curing ink jet ink. An inkjet recording device comprising: - photopolymerizable inkjet ink as defined in any one of claims 1 to 7; and - an ink application unit configured to apply the light curing ink jet ink to a base material to be printed.
    [00129] Reference Signal List 1. base material feed roller 2. base material to be printed 3. printing unit 3a. printing unit 3b. printing unit for one color ink 3c. printing unit for a colored 3d ink. printing unit for one color ink 4a. UV light source 4b. 4c UV light source. 4d UV light source. 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 (9)
    [0001]
    1. Light-curing ink jet ink characterized in that it comprises: light-curing monomers containing at least one selected from the group of compounds (A) below, compounds which are negative for skin sensitization, at least one selected from the group of compounds (B) below, compounds which are negative for skin sensitization and at least one selected from the group of compounds (C) below, compounds which are negative for skin sensitization, wherein the group of compounds (A) ) is a group of compounds consisting of caprolatone modified dipentaerythritol hexaacrylate, polyethoxylated tetramethylol methane tetraacrylate, ethylene oxide modified bisphenol A diacrylate, caprolactone modified hydroxy pivalic acid neopentyl glycol diacrylate, polypropylene glycol diacrylate [CH2= CH—CO—(OC3H6)n—OCOCH=CH2 (n^12)], hydroxyethyl acrylamide, trimethylol propane trimethacrylate and tricyclodecane dimethacrylate dimethanol; the group of compounds (B) is a group of compounds consisting of phenolacrylate modified with ethylene oxide, isostearyl acrylate and glycerin dimethacrylate; the group of compounds (C) is a group of compounds consisting of triethylene glycol divinyl ether, hydroxybutyl vinyl ether, ethyl vinyl ether, t-butyl methacrylate, n-pentyl methacrylate and n-hexyl methacrylate; wherein the ink viscosity at the temperature of 25°C is 2 mPa.s to 150 mPa.s, wherein the ink viscosity at the temperature of 60°C is 2 mPa.s to 20 mPa.s; and wherein it further comprises a photoradical polymerization initiator, the polymerization initiator being 2,4-diethyl thioxanthone.
    [0002]
    2. Light curing ink for inkjet according to claim 1, characterized in that an amount of the compound group (A) in the light curing monomers is 10% by mass to 50% by mass.
    [0003]
    3. Light curing ink for inkjet according to any one of claims 1 or 2, characterized in that an amount of the compound group (B) in the light curing monomers is from 10% by mass to 85% by mass.
    [0004]
    4. Light curing ink for inkjet according to any one of claims 1 to 3, characterized in that a mixing ratio of the group of compounds (A) and the group of compounds (B), which is expressed by a mass ratio of (A)/(B), is 15/85 to 85/15.
    [0005]
    5. Light-curing ink jet ink, according to claim 1, characterized in that the compound of the group of compounds (A) is dipentaerythritol hexaacrylate modified with caprolactone.
    [0006]
    6. Light-curing ink jet ink, according to claim 1, characterized in that the compound of the group of compounds (B) is phenolacrylate modified with ethylene oxide.
    [0007]
    7. Photopolymerizable inkjet ink according to claim 1, characterized in that the compound of group (C) is one of triethylene glycol divinyl ether, t-butyl methacrylate, n-pentyl methacrylate and methacrylate of n-hexyl, and the amount of the compounds of the compound group (C) in the light-curing monomers is 40% by mass to 60% by mass.
    [0008]
    8. Ink cartridge characterized in that it comprises: light-curing ink for inkjet as defined in claims 1 to 7; and a container housing the light curing inkjet ink.
    [0009]
    9. Inkjet recording device, characterized in that it comprises light curing ink for inkjet as defined in claims 1 to 7; and an ink application unit configured to apply the light curing ink jet ink to a base material to be printed.
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    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-08-13| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-12-08| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|
    2021-03-09| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-04-13| B09X| Decision of grant: republication|
    2021-05-11| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 30/10/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2011-243072|2011-11-07|
    JP2011243072A|JP5803583B2|2011-11-07|2011-11-07|Photopolymerizable inkjet ink|
    PCT/JP2012/078555|WO2013069580A1|2011-11-07|2012-10-30|Photopolymerizable inkjet ink|
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