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    • 专利摘要:
    PHOTOPOLYMERIZABLE COMPOSITION, PHOTOPOLYMERIZABLE INKJET INK, AND INK CARTRIDGE. Provide a non-aqueous photopolymerizable composition, which contains: a polymerizable monomer; a polymerization initiator; and a polyether-modified polysiloxane compound represented by the following general formula (1): (CH3)3Si-O-[Si(CH3)2-O]a-[Si(CH3)(X)-O]b-Si( CH3)3 where X represents R(C2H4O)c(C3H6O)dR', R is a single bond or an alkylene group, R? is a hydrogen atom or an alkyl group, and each of a through d denotes an average degree of polymerization including a case where both c and d are 0.
    公开号:BR112015007572B1
    申请号:R112015007572-0
    申请日:2013-09-27
    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 composition, a photopolymerizable inkjet ink, and an ink cartridge that houses the ink. Background of the technique
    [0002] Light-curing compositions and light-curing inkjet inks using (meth)acrylic acid esters have been well known (see PTL 1).
    [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 sensitivity, which causes allergic skin reactions through contact with them. The conventional technique has not yet provided any solution to this problem.
    [0004] Based on the studies conducted so far, the present inventors have discovered some esters of (meth)acrylic acid and (meth)acrylamide, which have no problem in skin sensitization. As for one of the examples thereof, an inkjet ink containing methacrylate as a main component is proposed, as methacrylate has less toxicity in terms of skin sensitization than acrylate, as disclosed in Japanese Patent Application No. 2010-278177, and PTL 2. In order to further improve performances, it has been desired to improve the strength of a cured coating film to improve the durability of the same against abrasions or the like, and to reduce a viscosity so that it can be ejected by inkjet without any problem even when an ink increases its viscosity as a result of the various formulated materials, such as a pigment, and additives, in it. To reduce the viscosity of an ink, water can be mixed in it, and a light-curing aqueous inkjet ink, which water is mixed in, is known. As described later, however, such ink is not penetrated and dries to a non-absorbent base. The use of such an ink requires a step to evaporate water in order to increase the speed or achieve efficiency of a process. Furthermore, a heat source is desired to be provided. Therefore, it is not preferable in view of energy savings. In the case where the light curing composition is used as a coating material used for brush coating, an organic solvent can be used in it. However, the organic solvent is evaporated and released into the atmosphere. In view of a possible influence on the environment, the use of the organic solvent is preferably as small as possible. In the case where the light curing composition is used as an inkjet ink, if an organic solvent mixed in it is highly volatile, the ink in a nozzle through which the ink is ejected increases its viscosity due to vaporization of the organic solvent , which can cause a blast problem. Therefore, such ink is not preferable.
    [0005] By virtue of these points mentioned above, the present inventors invented technologies disclosed in Japanese Patent Application No. 2012-46301 and 2012-113970. Considering an objective of improving a coating film strength under the situation where polymerization reactivity is more or less sacrificed as the materials are formulated in view of the reduction in skin sensitization, it is very important to further improve the scratch resistance of a surface of a coating film using a different method of accelerating a polymerization reaction for the purpose of protecting housing surfaces or molded articles using light-curing composition, which is an important task along with a task to achieve excellent appearance, such as high gloss, achieved by uniformly forming a surface of a coating film without any unevenness.
    [0006] Furthermore, if a solid coating film is produced using the light curing composition, not by printing a certain image pattern, not only an inkjet system, but also a method such as spray coating, and brush coating can be used. However it is difficult to provide a coating film, which has no skin sensitization problem, and has high strength and excellent appearance regardless of a coating system. Patent Literature Citation List
    [0007] PTL 1: Open-filed Japanese Patent Application (JP-A) No. 2004-526820
    [0008] PTL 2: JP-A No. 2012-140593 Invention Summary Technical problem
    [0009] The present invention desires to provide a photopolymerizable composition, which has no skin sensitization problem, which achieves both low viscosity and improved strength of a cured coating film, and also achieves an improvement in the appearance of the cured coating film. Solution to Problem
    [00010] As the means to solve the aforementioned problems, the non-aqueous photopolymerizable composition of the present invention containing:
    [00011] a polymerizable monomer;
    [00012] a polymerization initiator; and
    [00013] a polyether-modified polysiloxane compound represented by the following general formula (1): <General Formula (1)> (CH3)sSi-O-[Si(CH3)2-O]a-[Si(CH3)( X) "Gib-Si (CH3)3
    [00014] where X represents R(C2H4O)c(C3H6O)d-R', R is a single bond or an alkylene group, R' is a hydrogen atom or an alkyl group, and each of a through d denotes one average degree of polymerization including a case where both c and d are 0. Advantageous Effects of the Invention
    [00015] The present invention can provide a photopolymerizable composition, which has no skin sensitization problem, achieves both low viscosity and improved strength of a cured coating film, and also achieves an improvement in the appearance of the cured coating film.
    [00016] In addition, the light curing composition is easily handled, as the odor thereof is weak, and a coated product obtained using the light curing composition has no skin sensitization problem even if a small amount of an uncured monomer component is maintained, and does not cause skin sensitization even when touched with hands or fingers. Appropriately, high security can be guaranteed. Brief Description of Drawings
    [00017] FIG. 1 is a schematic diagram illustrating an example of an ink bag of an ink cartridge.
    [00018] FIG. 2 is a schematic diagram illustrating an example of the ink cartridge housing the ink pouch. Description of Modalities (Non-aqueous light curing composition)
    [00019] The non-aqueous photopolymerizable composition of the present invention contains at least polymerizable monomer, a polymerization initiator, and a polyether-modified polysiloxane compound represented by the following general formula (1), and may additionally contain other components, if necessary. <General Formula (1)> (CH3)3Si-O-[Si(CH3)2-O]a-[Si(CH3)(X)-O]b-Si(CH3)3
    [00020] In the above formula, X represents R(C2H4O)c(C3H6O)d-R', R is a single bond or an alkylene group, R' is a hydrogen atom or an alkyl group, and each from a to d denotes an average degree of polymerization including a case where both c and d are 0. <Polymerizable monomer>
    [00021] The photopolymerizable composition (may be referred to as "ink" hereinafter) is a composition prepared by mixing a polymerization initiator in addition to methacrylic acid ester and/or acrylic acid ester that serves as a negative polymerizable monomer for the skin sensitization, to produce a viscosity that can be ejected by inkjet. As a countermeasure to a problem that such a photopolymerizable composition cannot form a coating film that is smooth and having excellent appearance, the present inventors have found that the leveling of the photopolymerizable composition is improved by mixing therewith the polyether-modified polysiloxane compound represented by General Formula (1) to thereby form a coating film that is smooth and has excellent appearance as well as improves coating film strength.
    [00022] Here, the negative light curing monomer for skin sensitization refers to a compound that satisfies at least one of the following skin sensitization assessments (1) to (3). (1) A compound having a Stimulation Index (SI value) of less than 3, where the Stimulation Index indicates the level of sensitization as measured by the LLNA-based skin sensitization test (Local Lymph Node Assay) . (2) A compound assessed as “negative to skin sensitization” or “no skin sensitization” in its Material Safety Data Sheet (MSDS). (3) A compound rated “skin sensitizing negative” or “no skin sensitizing” in the literature [eg, Contact Dermatitis 8 223235(1982) ] .
    [00023] 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) September 2005, Vol. 25, No. 9, p. 55. The lower the SI value means the lower the skin sensitization. Thus, in the present invention, a monomer having a lower SI value is preferably used. The SI value of the monomer used preferably is less than 3, more preferably 2 or less, even more preferably 1.6 or less.
    [00024] Among the (meth)acrylic acid esters, which are readily available polymerizable monomers at low cost, those negative for skin sensitization have low polymerization reactivity. In order to provide sufficient curing property for a photopolymerizable monomer resulting in practical use, an amount of the polymerization initiator is preferably 10 parts by mass or greater with respect to 100 parts by mass of the polymerizable monomer. When an excessive amount of polymerization initiator is mixed, other strength, such as lightfastness, deteriorates. Suitably the amount thereof is preferably 20 parts by mass or less.
    [00025] In order to improve the leveling of the light-curing composition to improve an appearance of a resulting coating surface, an amount of the polyether-modified polysiloxane compound represented by General Formula (1) is preferably 0.1 parts by mass or greater, more preferably 0.1 parts by mass to 4 parts by mass, with respect to 100 parts by mass of the polymerizable monomer. When the amount of it is too small, a sufficient effect cannot be achieved. When the amount of the same is excessively large, the polyether-modified polysiloxane compound can inhibit photocuring. Suitably, the amount of the polyether-modified polysiloxane compound is even more preferably 0.1 part by mass to 1 part by mass.
    [00026] Examples of the negative monomer for skin sensitization include caprolactone-modified dipentaerythritol hexaacrylate (negative: rated on MSDS), polyethoxylated tetramethylol methane tetraacrylate (1.7), ethylene oxide-modified bisphenol A diacrylate (1 .2), hydroxypivalic acid neopentyl glycol diacrylate modified by caprolactone (0.9), hydroxyethyl acrylamide (not: evaluated on MSDS), polypropylene glycol diacrylate [CH2=CH-CO-(OC3H6)n-OCOCH=CH2(n = 12 )] (1.5), tricyclodecane dimethanol dimethacrylate (1.3), polyethylene glycol dimethacrylate [CH2=CH-CO-(OC2H4)n-OCOCH=CH2(n=14)] (1.6), polyethylene glycol dimethacrylate [CH2=CH-CO-(OC2H4)n-OCOCH=CH2(n = 9)] (1,3), diethylene glycol dimethacrylate (1,1), trimethylol propane trimethacrylate (1.9), trimethylol propane trimethacrylate modified by ethylene oxide (1.0), y-butyrolactone methacrylate (2.1), stearyl acrylate (2.7), neopentyl glycol dimethacrylate (2.0), 1,4-butanediol dimethacrylate (2.6), glycerol dimethacrylate lato (1,2), triethylene glycol divinyl ether (no: evaluated in MSDS), t-butyl methacrylate (negative: evaluated in literature), n-pentyl methacrylate (negative: evaluated in literature), and n-hexyl methacrylate (negative : evaluated in the literature). Among these, diethylene glycol dimethacrylate is particularly preferable as it has low viscosity, is easily used for an inkjet ink, and has excellent curing property. For the use of a photopolymerization composition necessary to form a solid coating film, caprolactone-modified dipentaerythritol hexaacrylate, and ethylene oxide-modified trimethylol propane trimethacrylate are preferably used in combination, as they do not have a sufficiently low viscosity per themselves, but they are particularly excellent in curing properties, and are excellent in dark stability.
    [00027] In addition to the negative monomer for skin sensitization, in addition, the following (meth)acrylate, and (meth)acrylamide, which may have a skin sensitization problem as used alone, or which is a compound in which skin sensitization has not been confirmed, they can be used in combination, provided they do not adversely affect a resulting light-curing composition.
    [00028] Examples of such (meth)acrylate and (meth)acrylamide include ethylene glycol di(meth)acrylate, hydroxy pivalic acid neopentyl glycol di(meth)acrylate, y-butyrolactone acrylate, isobornyl(meth)acrylate, trimethylol propane mono( formulated meth)acrylate, polytetramethylene (meth)acrylic benzoate, diethylene glycol diacrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate [CH2=CH-CO-(OC2H4) n -OCOCH=CH2 (n = 4)], CH2=CH-CO-(OC2H4)n-OCOCH=CH2 (n = 9)], CH2=CH-CO-(OC2H4)n-OCOCH=CH2 (n = 14 )], CH2=CH-CO-(OC2H4)n-OCOCH=CH2 (n = 23)], dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol dimethacrylate [CH2=C(CH3) -CO-(OCsH6)n-OCOC(CH3)=CH2 (n = 7)], 1,3-dibutanediol diacrylate, 1,4-dibutanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, oxide-modified bisphenol A di(meth)acrylate of propylene, polyethylene glycol di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, (meth)acryloyl morpholino, 2-hydroxypropyl(meth)acrylamide, tetramethylol methane tetra(meth)acrylate modified by propylene oxide, dipentaerythritol hydroxypenta(meth) acrylate, dipentaerythritol hydroxy penta(meth)acrylate modified by caprolactone, ditrimethylol propane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, trimethylol propane triacrylate, trimethylol propane triacrylate modified by modified by propylene oxide, trimethylol propane tri(meth)acrylate modified by caprolactone, pentaerythritol tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate modified by propylene oxide, glyceryl tri(meth) propylene oxide modified acrylate, polyester di(meth)acrylate, polyester tri(meth)acrylate, polyester tetra(meth)acrylate, polyester penta(meth)acrylate, polyester poly(meth)acrylate, N-vinyl cap rolactam, N-vinyl pyrrolidone, N-vinyl formamide, polyurethane di(meth)acrylate, polyurethane tri(meth)acrylate, polyurethane tetra(meth)acrylate, polyurethane penta(meth)acrylate, and polyurethane poly(meth)acrylate. <Photoradical polymerization initiator>
    [00029] With the photopolymerizable composition (ink) of the present invention, a photoradical polymerization initiator is preferably used. (meth)acrylic ester and (meth)acrylamide are known to also have ionic polymerization properties. Ionic polymerization initiators are typically expensive and also generate small amounts of strong acid and strong base even in the state where there is any light irradiation. Therefore, special care must be taken, such as imparting acid or alkaline resistance to an ink supply channel within an inkjet coating system. Appropriately, there is a limitation in choosing a member that constitutes an inkjet coating system.
    [00030] In contrast, the photopolymerizable composition (ink) of the present invention can use a photoradical polymerization initiator which is inexpensive and does not generate strong acid or strong base. Therefore, it is possible to produce a photopolymerization composition at low cost, and it is also easy to elect a member that constitutes an inkjet coating system. Note that in the case where a light source with very high energy, such as electron beams, a-rays, β-rays, Y-rays or X-rays, a polymerization reaction can proceed without the polymerization initiator. This is a conventionally known matter, and has a problem, such as installing it is very expensive and maintaining it is complicated. Therefore, it is not particularly described in detail in the present specification.
    [00031] The photoradical polymerization initiator includes, for example, a self-cleaving photopolymerization initiator and a hydrogen abstraction polymerization initiator. Unlike those used in the Examples, any of the following compounds can be used in combination.
    [00032] Examples of the self-cleaving photopolymerization initiator include 2,2-dimethoxy-1,2-diphenyletan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-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 oxide, bis(2,6-dimethoxybenzolyl)-2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoylphosphine 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.
    [00033] 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.
    [00034] Furthermore, amine can be used in combination as a polymerization accelerator.
    [00035] Examples of the polymerization accelerator include: an aromatic amine compound such as ethyl-p-dimethylaminobenzoate, 2-ethyl-hexyl-p-dimethylaminobenzoate, methyl p-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate and butoxyethyl-p-dimethylaminobenzoate; and a non-aromatic amine compound, such as N-methyldiethanol amine. <Other Components>
    [00036] Examples of the other components include a colorant, a polymerization inhibitor, a surfactant, and a high molecular weight pigment dispersant that contains a polar group. - Colorant -
    [00037] The light-curing composition can be made transparent without containing a colorant, and can contain a colorant if necessary. In the case where a clear or white photopolymerizable composition is desirable, it is preferred that less colored materials are selected for the aforementioned materials, such as the polymerization initiator, and the polymerization accelerator, and the materials mentioned below other than the colorant.
    [00038] As for the colorant in the case where the light curing composition is colored, any of the conventional inorganic pigments or organic pigments can be used.
    [00039] As for pigment black, carbon black produced by an oven method or a channel method can be used.
    [00040] Examples of the yellow pigment include pigments from the Pigment Yellow series, such as Pigment Yellow 1, Pigment Yellow 2, Pigment Yellow 3, Pigment Yellow 12, Pigment Yellow 13, Pigment Yellow 14, Pigment Yellow 16, Pigment Yellow 17, Pigment Yellow 73, Pigment Yellow 74, Pigment Yellow 75, Pigment Yellow 83, Pigment Yellow 93, Pigment Yellow 95, Pigment Yellow 97, Pigment Yellow 98, Pigment Yellow 114, Pigment Yellow 120, Pigment Yellow 128, Pigment Yellow 129, Pigment Yellow 138 , Pigment Yellow 150, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 155, and Pigment Yellow 180.
    [00041] Examples of magenta pigment include Pigment Red series pigments such as Pigment Red 5, Pigment Red 7, Pigment Red 12, Pigment Red 48(Ca), Pigment Red 48(Mn), Pigment Red 57(Ca), Pigment Red 57:1, Pigment Red 112, Pigment Red 122, Pigment Red 123, Pigment Red 168, Pigment Red 184, Pigment Red 202, and Pigment Violet 19.
    [00042] Examples of cyan pigment include Pigment Blue series pigments such as Pigment Blue 1, Pigment Blue 2, Pigment Blue 3, Pigment Blue 15, Pigment Blue 15:3, Pigment Blue 15:4, Pigment Blue 16, Pigment Blue 22, Pigment Blue 60, Blue Vat 4, and Blue Vat 60.
    [00043] Examples of the white pigment or clear filler to modify physical properties include: sulfuric acid salts of alkaline earth metals such as barium sulfate; alkaline earth metal carbonic acid salts such as calcium carbonate; silica such as fine powdered silicic acid and synthetic silicic acid salts; calcium silicate; alumina; alumina hydrate; titanium oxide; zinc oxide; baby powder; and clay.
    [00044] In addition, various inorganic or organic pigments can optionally be used considering, for example, physical properties of the light curing composition. - Polymerization inhibitor -
    [00045] Examples of the polymerization inhibitor include 4-methoxy-1-naphthol, methylhydroquinone, hydroquinone, t-butylhydroquinone, di-t-butylhydroquinone, methoquinone, 2,2'-dihydroxy-3,3' -di(α-methylcyclohexyl)-5,5'-dimethyldiphenylmethane, p-benzoquinone, di-t-butylbutyl diphenylamine, 9,10-di-n-butoxyanthracene, 4,4'-[1,10-dioxo- 1,10-decandiylbis(oxy)]bis[2,2,6,6-tetramethyl]-1-piperidinyloxy. surfactant
    [00046] Examples of the surfactant include polyether containing a higher fatty acid ester, an amino group, a carboxyl group, or a hydroxyl group, and a polyether containing a fluoroalkyl compound, an amino group, a carboxyl group, or a hydroxyl group. (Cartridge)
    [00047] The inkjet ink of the present invention can be housed in a container, and can be used as an ink cartridge. With this form, users do not need to directly touch the ink during operations such as changing the ink, and so they are not concerned about staining their fingers, hands or clothes. In addition, it is possible to avoid the interfusion of foreign matter such as dust in the paint.
    [00048] The container is not particularly limited, and the shape, structure, size and material of the same can be selected appropriately depending on the intended purpose. For example, the container preferably is selected from those having an ink pouch formed from a laminated aluminum film, or a resin film.
    [00049] The ink cartridge will be described with reference to FIGs. 1 and 2. FIG. 1 is a schematic diagram illustrating an example of the ink pouch 241 of the ink cartridge, and FIG. 2 is a schematic diagram illustrating the ink cartridge 200 housing the ink pouch 241 of FIG. 1 in the cartridge housing 244 thereof.
    [00050] As illustrated in FIG. 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 242 is sealed by a fusion connection. . At the time of use, a needle attached to the main body of the device is inserted into an ink outlet 243 formed from a rubber member to supply ink to the device. The ink pouch 241 is formed from a roll-up member, such as a non-air permeable aluminum laminated film. As illustrated in FIG. 2, ink pouch 241 typically is housed in a plastic cartridge housing 244 which is then detachably mounted in use for various ink jet recording devices such as ink cartridge 200.
    [00051] The ink cartridge of the present invention is preferably detachably mounted on the ink jet recording devices. As a result of this, ink replenishment or replacement can be simplified, and workability can be improved.
    [00052] As a base coat, paper, plastic, metal, ceramic, glass, or a composite material thereof can be used. As an absorbent base, such as wood-free paper, a penetration and drying effect can be expected, an aqueous ink or an oil ink, which is not a quick-drying ink, can be used for such a base. On the other hand, it is practical to use a fast drying ink for a low-absorbing base or a non-absorbent base, such as glass overlay paper, a plastic film, a molded article of plastic, ceramic, glass, metal, and rubber .
    [00053] The ink of the present invention does not particularly restrict a base to be used. As the ink is cured immediately after application of light, however, the aforementioned non-absorbent base is particularly preferable. Among these, plastic films and plastic molded articles formed from polyethylene, polypropylene, polyethylene terephthalate, polycarbonate, an ABS resin, polyvinyl chloride, polystyrene, other polyesters, polyamide, vinyl-based materials, and composite materials thereof are suitable . Examples
    [00054] The present invention will be explained concretely through the Examples and Comparative Examples hereinafter, but the Examples should not be interpreted as limiting the scope of the present invention. <SI Value Assessment Method>
    [00055] According to the skin sensitization test based on the LLNA (Local Lymph Node Assay), the SI value was measured as described below. [Test Material] <<Positive Control>> a-Hexylcinnamaldehyde (HCA; product of Wako Pure Chemical Industries, Ltd.) was used as the positive control. <<Vehicle>>
    [00056] As a vehicle, a mixture containing acetone (product of Wako Pure Chemical Industries, Ltd.) and olive oil (product of Fudimi Pharmaceutical Co., Ltd.) in a volume ratio of 4/1 was used. <<Used animals>>
    [00057] Prior to being treated with the test substances, the positive control or the vehicle control, female mice were acclimated for 8 days including 6 days quarantine. No abnormalities were found in all animals during the quarantine/acclimatization period.
    [00058] Based on the body weights measured 2 days before the start of sensitization, they were categorized into 2 groups (4 mice/group) by the stratified random sampling method of body weight so that each individual's body weight was within ± 20% of the mean body weight of all individuals. Each animal was 8 to 9 weeks old at the time of onset of sensitization. Animals that will remain after categorization were excluded from the test.
    [00059] The animals were individually identified by applying oil paint to their tail throughout the testing period, and also their cages were labeled for identification. <<Accommodation environment>>
    [00060] During the housing period including the quarantine/acclimatization period, the animals were housed in an animal space with a barrier system, which was defined as follows: temperature from 21 °C to 25 °C, relative humidity of 40 % to 70%, air circulation frequency from 10 times/hour to 15 times/hour, and 12-hour lighting cycle (light from 7:00 to 19:00 hours).
    [00061] The housing cages used were those made of polycarbonate, and four animals were housed in each cage.
    [00062] Animals were given solid ad libitum diet for MF laboratory animals (product of Oriental Yeast Co., Ltd.). Further, using a water supply bottle, they were given free tap water in which sodium hypochlorite (PURELOX, product of OYALOX Co., Ltd.) was added so that the chlorine concentration was about 5 ppm . Bed used was SUNFLAKE (fir, steves obtained with a power planer) (product of Charles River Inc.). Diet and feeding equipment was sterilized with an autoclave (121 °C, 30 min) prior to use.
    [00063] 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 animal environment), and the water supply bottle and support were replaced by new ones at the time of categorization. [Test Method] <<Group Composition>>
    [00064] The group composition used for measuring the SI value is shown in Table 1.
    [Preparation] <<Test Substance>>
    [00065] 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 prepared in this way was placed in a light-shielded hermetic container (made of glass).
    <<Positive Control Substance>>
    [00066] 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 prepare in this way a 25.0% w/v solution. The solution prepared in this way was placed in a light-shielded hermetic container (made of glass). <<BrdU>>
    [00067] 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 prepared in this way was sterilized by filtration with a sterile filtration filter and placed in a sterilized container. <<Day of Preparation and Storage Period»
    [00068] The preparation of the Positive Control was done the day before the start of sensitization, and stored in a cool place except in use. Vehicle and test substance preparations were made 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. [Awareness and Administration of BrdU] <<Awareness>>
    [00069] Each (25 μL) of the test substance preparations, the Positive Control preparations and the vehicle preparations were applied to both atria of each animal using a micropipette. This treatment was performed once a day for three consecutive days. <<BrdU Administration>>
    [00070] About 48 hours after the final sensitization, the preparation of BrdU (0.5 mL) was administered intraperitoneally once to each animal. [Observation and Examination] <<General Conditions >>
    [00071] All animals used for the test were observed one or more times a day from the day of the start of sensitization until the day of removal of the lymph node transferred from the animal environment). Notably, the observation day was counted from the start day of sensitization which is considered as Day 1. <<Body Weight Measurement>>
    The body weight of each animal was measured on the day of initiation of sensitization and on the day of removal of the auricular lymph node (i.e. the day when the animals were transferred from the animal environment). Also, the mean of body weights and their standard error were calculated for each group. <<Auricular Lymph Node Removal and Mass Measurement of It>>
    [00073] About 24 hours after administration of BrdU, the animals were allowed to undergo euthanasia, and their auricular lymph nodes were sampled. The tissue surrounding each auricular lymph node was removed, and the auricular lymph nodes of both atria were collectively weighed. Furthermore, the mean weights of the auricular lymph nodes and their standard error were calculated for each group. After measuring the weights, each subject's auricular lymph nodes were stored in a frozen state using a BIOMEDICAL FREEZER set at -20°C. <<BrdU Admission Measurement>>
    [00074] After returning to room temperature, the auricular lymph nodes were kneaded with the gradual addition of physiological saline solution, and suspended in it. The suspension thus obtained was filtered and then dispensed into the wells of a 96-well microplate, with 3 wells being used per individual. Suspensions used in this way were measured for BrdU admission 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 multiple plate bed (FLUOSTAR OPTIMA, product of BMG LABTECH Inc.) was used to measure the absorbance of each well (OD: 370 nm to 492 nm, BrdU inlet), and the average absorbance of the 3 wells for each subject was used as the BrdU measurement for the subject. [Evaluation of Results] <<Calculation of Stimulation Index (SI)>>
    [00075] As shown in the following formula, the BrdU intake measurement for each subject was divided by the average of the BrdU intake 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. Notably, the SI value has been rounded to the second decimal place and shown to the first decimal place.
    [Example 1]
    [00076] An ink of Example 1 having a viscosity of 8 mPa-s at 25°C was obtained by mixing the materials of sequence (a) to (d) with the mixing ratio as shown in Table 3-1.
    [00077] a: (meth)acrylic acid ester
    [00078] a1: diethylene glycol dimethacrylate 95
    [00079] (2G (1.1), manufactured by Shin-Nakamura Chemical Co., Ltd.)
    [00080] a2: caprolactone dipentaerythritol hexaacrylate 5
    [00081] (TMPT-3EO(3,1), manufactured by Shin-Nakamura Chemical Co., Ltd.)
    [00082] a3: trimethylol propane trimethacrylate modified by ethylene oxide 0
    [00083] b: polymerization initiator
    [00084] b1: 1-hydroxycyclohexylphenyl ketone 20
    [00085] c: polyether-modified polysiloxane compound
    [00086] c1: (CH3)Si-O-[Si(CH3)2-O]a—[Si(CH3)(X) -O]b-Si(CH3)3 0.1
    [00087] d: (meth)acrylic acid ester other than (a) (a) (meth)acrylic acid ester negative for skin sensitization (b) photoradical polymerization initiator (c) polyether-modified polysiloxane compound
    [00088] The details of a1 through a3, b1 through b4, c1 through c7, and d1 through d3 in Tables 3 through 5 are as follows. The numeric value in parentheses described after each product name is the SI value in the LLNA test in (1). The description "no" after each product name means that the product is assessed as "skin sensitizing negative" or "no skin sensitization" in the MSDS (Material Safety Data Sheet) described in the sensitization assessment of the skin above (2). Similarly, the description “yes” after each product name means that the product is rated “skin sensitizing positive” or “skin sensitizing” on the MSDS.
    [00089] [(a) Negative (meth)acrylic acid ester for skin sensitization]
    [00090] a1: diethylene glycol dimethacrylate, 2G (1.1), manufactured by Shin-Nakamura Chemical Co., Ltd.
    [00091] a2: caprolactone-modified hexaacrylate dipentaerythritol, DPCA 60 (not: rated on MSDS), manufactured by NIPPON KAYAKU Co., Ltd.
    [00092] a3: ethylene oxide-modified trimethylol propanetrimethacrylate, TMPT-3EO(1.0), manufactured by Shin-Nakamura Chemical Co., Ltd.
    [00093] [(b) Photoradical polymerization initiator]
    [00094] b1: 1-hydroxycyclohexyl phenyl ketone, Irgacure184 (not: rated on MSDS), manufactured by BASF
    [00095] b2: 2-hydroxy-2-methyl-1-phenylpropan-1-one, Darocur1173 (not: rated on MSDS), manufactured by BASF
    [00096] b3: 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methyl-1-propan-1-one, Irgacure127 (no: evaluated in MSDS ), manufactured by BASF
    [00097] b4: oligo[2-hydroxy-2-methyl-1{4-(1-methylvinyl)phenyl}propanone], ESACURE KIP150 (not: evaluated on MSDS), manufactured by Lamberti
    [00098] [(c) Polysiloxane Compound (Polyether Modified)]
    [00099] c1: polyether-modified polysiloxane represented by the General Formula, (CH3)3Si-O-[Si(CH3)2-O]a-[Si(CH3)(X)-O]b-Si(CH3)3 , KF353, manufactured by Shin-Etsu Chemical Co., Ltd.
    [000100] c2: polyether-modified polysiloxane represented by the General Formula, (CH3)3Si-O-[Si(CH3)2-O]a-[Si(CH3)(X)-O]b-Si(CH3)3 , KF351A, manufactured by Shin-Etsu Chemical Co., Ltd.
    [000101] c3: polyether-modified polysiloxane represented by the General Formula, (CH3)3Si-O-[Si(CH3)2-O]a-[Si(CH3)(X)-O]b-Si(CH3)3 , KF352A, manufactured by Shin-Etsu Chemical Co., Ltd.
    [000102] c4: polyether-modified polysiloxane represented by the General Formula, (CH3)3Si-O-[Si(CH3)2-O]a-[Si(CH3)(X)-O]b-Si(CH3)3 , BYK-UV3510, manufactured by BYK Japan KK
    [000103] c5: polyether-modified polysiloxane represented by the General Formula, (CH3)3Si-O-[Si(CH3)2-O]a-[Si(CH3)(X)-O]b-Si(CH3)3 , BYK-377, manufactured by BYK Japan KK
    [000104] c6: polysiloxane represented by the General Formula, (CH3)3Si-O-[Si(CH3)2-O]a-Si(CH3)3, KF-96H-12500cs, manufactured by Shin-Etsu Chemical Co., Ltd.
    [000105] c7: polysiloxane represented by the General Formula, (CH3)3Si-O-[Si(CH3)2-O]a-Si(CH3)2(-ROH), X-22-170BX, manufactured by Shin-Etsu Chemical Co., Ltd.
    [000106] [(d) Skin sensitization of (meth)acrylic acid ester of which is Positive or Unknown]
    [000107] d1: trimethylol propane triacrylate, M309 (marked as R43, which indicates that it is a skin sensitizing material under the hazard classification in European Union Directive 67/548/EEC), manufactured by TOAGOSEI CO., LTD.
    [000108] d2: hexamethylene diacrylate, A-HD-N (marked as R43, which indicates that it is a skin sensitizing material, under the hazard classification in European Union Directive 67/548/EEC), manufactured by Shin-Nakamura Chemical Co., Ltd.
    [000109] d3: vinyloxyethoxyethyl acrylate, VEEA (marked as R43, which indicates that it is a skin sensitizing material under the hazard classification in European Union Directive 67/548/EEC), manufactured by NIPPON SHOKUBAI CO., LTD.
    [000110] Each paint was subjected to viscosity measurements (mPa*s) at 25°C, 45°C, and 60°C, and flatness of the same, which indicates the smoothness of a coating film, was evaluated. The results are shown in Table 3.
    [000111] The viscosity of each paint was measured by a cone and plate type rotating viscometer (manufactured by TOKI SANGYO CO., LTD.) with the water circulation temperature being set constantly at 25°C, 45°C, or 60°C. The temperature of 25°C is the set temperature considering typical ambient temperature, and the temperature of 45°C or 60°C is the set temperature considering the specification of a commercially available heatable inkjet head, such as GEN 4, manufactured by Ricoh Industry Company, Ltd.
    [000112] The light curing composition prepared with the predetermined formulation was used as it was for the evaluation performed by brush coating. For evaluation as inkjet ink, the light curing composition was manipulated as follows. After filtering the ink (light-curing composition) through a membrane filter that was formed from a fluororesin had a pore size of 5 µm, the aluminum pouch having a shape illustrated in FIG. 1 has been loaded with the ink, and hermetically sealed to prevent the inclusion of air bubbles. As illustrated in FIG. 2, the hermetically sealed pouch containing the wire ink housed in a plastic cartridge. This cartridge was mounted in a casing adapted to house it. In coating, an ink flow channel was provided from the cartridge to a GEN4 head (manufactured by Ricoh Industry Company, Ltd.) Then, ink was blasted from the head to produce a solid coating film. Note that in both cases of brush coating and inkjet printing, the conditions were adjusted so that the solid coating film had an average thickness of about 40 µm.
    [000113] After about 1 minute of coating, the printed solid coating film produced on commercially available polycarbonate film (Lupilon E-2000, manufactured by Mitsubishi Engineering-Plastics Corporation, thickness: 100 µm) was light cured having a strip of wavelength corresponding to the UVA region, in the illuminance of 0.2 W/cm2, with the light dose of each one of 1200 (mJ/cm2). The resulting coating film was provided for coating film strength evaluation and flatness evaluation.
    [000114] The coating film strength was evaluated by evaluating the scratch hardness of the solid coating film cured by applying light according to the pencil method as specified in JIS-K-5600-5-4. Pencil hardness includes 2H, H, F, HB, B, 2B to 6B in this order from the hardest. As for the leveling, which indicates the smoothness of the coating film, the evaluation was carried out through visual observation. A case where significant irregularities were observed on the surface was rated as C, a case where the coating film having a smooth surface was formed was rated as A, and one case in between was rated as B.
    [000115] Note that, in the case where the light curing composition is used as an inkjet ink, the ink's physical properties are preferably matched with the specifications necessary for an inkjet head to use. Various inkjet heads are on the market from various manufacturers, and among these there are inkjet heads having a temperature adjustment function over a wide temperature range. Considering such market trends, the ink viscosity at the temperature of 25°C is preferably from 2 mPa-s to 150 mPa-s. In the case where the ink is ejected at 25°C, the ink viscosity is more preferably 5 mPa-s to 18 mPa-s. As mentioned earlier, it is possible to use the eject head temperature adjustment function. In the case where the ink viscosity is very high at 25°C, the ink viscosity can be optionally reduced by heating the head. Assuming the heating condition is 45°C or 60°C, in the case mentioned above, the ink viscosity at 45°C or 60°C preferably is 5 mPa-s to 18 mPa-s.








    * 1: carbon black “#10” manufactured by Mitsubishi Chemical Corporation mixed with a dispersing agent “Solsperse 32000” manufactured by Lubrizol Japan Co. are blended in a weight ratio of 3/1 * 2: Viscosity measurement was not performed, as the ink can be ejected at a lower temperature than the described temperature. *3: As curing was insufficient at 1200 mJ/cm2 illuminance, curing was performed at 2000 mJ/cm2. Note that as it was difficult to cure the 40 µm coating film at one time, the film having a thickness of 10 µm was cured and laminated to form a 40 µm film. * 4: The assessment cannot be performed as it has not been homogeneously dissolved. [Examples 2 to 8, Comparative Examples 1 to 2]
    [000116] Each of the paints of Examples 2 to 8 and the paints of Comparative Examples 1 to 2 similarly was obtained by mixing the materials from (a) to (d) with the mixing ratio as shown in Table 3-1.
    [000117] Each of the paints obtained was subjected to measurements of viscosity measurements (mPa*s) at 25°C, 45°C, and 60°C, and leveling of the same, which indicates the smoothness of a coating film, was evaluated in the same way as in Example 1. The results are shown in Table 3-1. [Examples 9 to 16, Comparative Examples 3 to 4]
    [000118] Each of the paints of Examples 9 to 16 and the paints of Comparative Examples 3 to 4 similarly were obtained by mixing the materials (a) to (d) with the mixing ratio (unit for numerical value: parts by mass ) as shown in Table 3-2.
    [000119] Each of the paints obtained was subjected to measurements of viscosity measurements (mPa*s) at 25°C, 45°C, and 60°C, and leveling of the same, which indicates the smoothness of a coating film, was evaluated in the same way as in Example 1. The results are shown in Table 3-2 [Examples 17 to 24, Comparative Example 5]
    [000120] Each of the paints of Examples 17 to 24 and Comparative Example 5 similarly was obtained by mixing the materials (a) to (d) with the mixing ratio (unit for numerical value: parts by mass) as shown in Table 4-1.
    [000121] Each of the paints obtained was subjected to measurements of viscosity measurements (mPa*s) at 25°C, 45°C, and 60°C, and leveling of the same, which indicates the smoothness of a coating film, was evaluated in the same way as in Example 1. The results are shown in Table 4-1 [Examples 25 to 31]
    [000122] Each of the paints of Examples 25 to 31 similarly was obtained by mixing the materials (a) to (d) with the mixing ratio (unit to numerical value: parts by mass) as shown in Table 4-2.
    [000123] Each of the paints obtained was subjected to measurements of viscosity measurements (mPa*s) at 25°C, 45°C, and 60°C, and leveling of the same, which indicates the smoothness of a coating film, was evaluated in the same way as in Example 1. The results are shown in Table 4-2 [Examples 32 to 36, Comparative Examples 6 to 7]
    [000124] Each of the paints of Examples 32 to 36 and the paints of Comparative Examples 6 to 7 similarly were obtained by mixing the materials (a) to (d) with the mixing ratio (unit for numerical value: parts by mass ) as shown in Table 5-1.
    [000125] Each of the paints obtained was subjected to measurements of viscosity measurements (mPa*s) at 25°C, 45°C, and 60°C, and leveling of the same, which indicates the smoothness of a coating film, was evaluated in the same way as in Example 1. The results are shown in Table 5-1 [Examples 37 to 42, Comparative Examples 8 to 9]
    [000126] Each of the paints of Examples 37 to 42 and the paints of Comparative Examples 8 to 9 similarly were obtained by mixing the materials (a) to (d) with the mixing ratio (unit for numerical value: parts by mass ) as shown in Table 5-2.
    [000127] Each of the paints obtained was subjected to measurements of viscosity measurements (mPa*s) at 25°C, 45°C, and 60°C, and leveling of the same, which indicates the smoothness of a coating film, was evaluated in the same way as in Example 1. The results are shown in Table 5-2
    [000128] As it has been made clear from Examples 1 to 36, it has been confirmed that the leveling is improved as well as the coating film strength by adding the polyether modified polysiloxane compound to the light curing composition, so that an appearance of a coating film is enhanced. As for the coating film strength, the cases where the improvement of the same can be improved irrespective of the mixing ratio are confirmed, and the case where the coating film strength is improved with a certain mixing ratio. Monomer materials selected under consideration of skin sensitization tend to be difficult to pass through a polymerization reaction, and there is a limitation in accelerating the polymerization reaction, which is critical to exhibiting sufficient coating film strength. Therefore, it is desired to improve the coating film strength using various other methods in combination. However, an effect to improve the coating film strength, which is achieved by adding a small amount of the polyether-modified polysiloxane compound as an additive, is quite effective.
    [000129] As in Examples 17 to 36, the same effect can be obtained with a different kind of polyether-modified polysiloxane compound, and therefore an optimal polyether-modified polysiloxane compound can be selected to match with various required specifications, different from flatness and the resistance of coating film. As in Comparative Examples 6 and 7, however, in the case where the polyether-modified polysiloxane compound has a different molecular structure, the solubility of the same may be poor, or a leveling or film strength enhancing effect may be insufficient. Therefore, it is important that the polyether-modified polysiloxane compound represented by the General Formula of (CH3)3Si-O-[Si(CH3)2-O]a-[Si(CH3)(X)-O]b-Si( CH3)3 (provided that, X=-R(C2H4O)c(C3H6O)d-R', R is a single bond or an alkylene group, R' is a hydrogen atom or an alkyl group, and each of a through d denotes the average degree of polymerization) is used.
    [000130] As is clear from Examples 37 to 39, even when a different type of compound is used as the polymerization initiator, the same effect can be achieved. Therefore, an optimal compound can be selected as the polymerization initiator to match various required specifications, rather than flatness and coating film strength. However, the use of 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methyl-1-propan-1-one, which is marked with a trademark an "Xn" symbol that indicates a health hazard, an "N" symbol mark that indicates an environmental hazard, and a "R48/22" risk phrase that indicates acute lethal effect, and a "R50/53" risk phrase that indicates acute aquatic toxicity and long-term adverse effect on the hazard classification of EU directive 67/548/EEC, preferably is kept to a minimum. The use of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, or oligo[2-hydroxy-2-methyl-1{4-(1-methylvinyl)phenyl}propanone ], which are not marked with a symbol mark or risk phrase in the aforementioned hazard classification, is preferable.
    [000131] Example 40 is the case where a large amount of the polyether modified polysiloxane compound is mixed. The leveling improvement can be confirmed because of mixing, but the coating film strength is reduced. In view of the coating film strength, it is not preferable to mix an excessive amount of the polyether modified polysiloxane compound. In the case where the coating film strength is not important, however, a mixing amount of the film can be optimized to match various required specifications, such as leveling.
    [000132] As is clear from Example 41, even in the case where the light curing composition contains the colorant, it has been confirmed that the leveling and coating film strength are improved in an appropriate manner by selecting the curing conditions.
    [000133] As in Examples 5 to 8, and 17 to 36, even when the mixing ratio of the polymerization initiator is reduced, the coating film strength can be maintained by appropriately adjusting a mixing amount of the dipentaerythritol hexa-acrylate modified by caprolactone, which is a polyfunctional acrylate having high polymerization reactivity, and selecting optimal irradiation conditions. Therefore, reducing the amount of mixing of the polymerization initiator, which is more expensive than the monomer that is a major component, can achieve cost savings for producing the light-curing composition.
    [000134] As in Example 42, in the case where monomer material which is not negative for skin sensitization is used, such monomer material has excellent polymerization reactivity, and therefore the mixing amount of the polymerization initiator can be reduced , which is great. In this case, it was also confirmed that the use of the polyether-modified polysiloxane compound in the light-curing composition improves the leveling and appearance of a resulting coating film. Considering the safety of operators, the use of a material, which is not negative for skin sensitization, is not preferable, and therefore the use of such material is kept to a minimum.
    [000135] Note that, ethylene oxide modified trimethylol propanetrimethacrylate is represented by the General Formula [CH3CH2C-{(O-CH2CH2)n-OCOC(CH3)=CH2}3]. With respect to the length “n” of the ethylene oxide segment, the higher value of “n” means a higher molecular weight, which increases viscosity. Therefore, such ethylene oxide-modified trimethylol propanetrimethacrylate is difficult to be used as a material for an inkjet ink, and also increases a molecular weight between crosslink formed during curing to reduce crosslink density. As a result, it is difficult to achieve sufficient coating strength. Therefore, the value of n is preferably as small as possible. On the other hand, trimethylol propanetrimethacrylate, where the value of n is 0 (n = 0), is a compound marked with an “N” symbol that denotes environmental hazard and marked with a risk phrase “R51/53” that denotes acute aquatic toxicity and long-term adverse effect on classification according to European Union Directive 67/548/EEC. Considering a possible influence on the environment, therefore, the use of trimethylol propanetrimethacrylate is preferably avoided. The ethylene oxide-modified trimethylol propanetrimethacrylate used in the Examples has 1 as the value of n (n = 1), which is not particularly a problem in a viscosity as a raw material mixed in an inkjet ink. The photopolymerizable composition to which this ethylene oxide-modified trimethylol propanetrimethacrylate is mixed has sufficient film coating strength and no skin sensitization problems, and is not classified as a material that exhibits environmental hazard, or acute aquatic toxicity and adverse effect long term. Suitably, as for ethylene oxide-modified trimethylol propanetrimethacrylate, which of n = 1 is particularly preferable.
    [000136] In all Examples and Comparative Examples, no significant difference was observed between inkjet printing and brush coating. Also, the inclusion of air bubbles in an ink channel in an inkjet system should be avoided, as the inclusion of air bubbles adversely affects ink ejection. However, in all Comparative Examples and Examples, it was not necessary to take any consideration in the operating process by which air bubbles can be easily included, such as ink charging. Furthermore, all photopolymerizable compositions have very weak odor, which any particular consideration must be taken in handling them. Note that the siloxane compound is a substance disclosed as a cosmetic material in the “Guideline for Labeling Name Preparation, Japan Cosmetic Industry Association” and therefore the skin sensitization of the siloxane compound is sufficiently low compared to several typically used products in a light-curing composition.
    [000137] The embodiments of the present invention, for example, are as follows: <1> A non-aqueous photopolymerizable composition containing: a polymerizable monomer; a polymerization initiator; and a polyether-modified polysiloxane compound represented by the following general formula (1): <General Formula (1)> (CH3)3Si-O-[Si(CH3)2-O]a-[Si(CH3)(X) -O]b-Si(CH3)3 where X represents R(C2H4O)c(C3H6O)d-R', R is a single bond or an alkylene group, R' is a hydrogen atom or an alkyl group, and each a through d denotes an average degree of polymerization including a case where both c and d are 0 . < 2> The non-aqueous photopolymerizable composition according to <1>, wherein the polymerizable monomer is negative for skin sensitization. <3> The non-aqueous photopolymerizable composition according to <2>, wherein the polymerizable monomer contains diethylene glycol dimethacrylate. <4> The non-aqueous photopolymerizable composition according to any one of <1> to <3>, wherein an amount of the polyether-modified polysiloxane compound represented by General Formula (1) is 0.1 parts by mass or greater with to 100 parts by mass of the polymerizable monomer. <5> The non-aqueous photopolymerizable composition according to any one of <1> to <4>, wherein the polymerizable monomer additionally contains caprolactone-modified hexaacrylate dipentaerythritol. <6> The non-aqueous photopolymerizable composition according to any one of <1> to <5>, wherein the polymerization initiator is 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1 -one, or oligo[2-hydroxy-2-methyl-1{4-(1-methylvinyl)phenyl}propanone]. <7> The non-aqueous photopolymerizable composition according to any one of <1> to <6>, wherein an amount of the polymerization initiator is 10 parts by mass or greater with respect to 100 parts by mass of the polymerizable monomer. < 8> An inkjet ink, containing: the light curing composition according to any one of <1> to <7>. < 9> An ink cartridge, containing: < inkjet ink according to <8>; and a container. Reference Signs List 200 ink cartridge 241 ink bag 242 ink in 243 ink output 244 cartridge casing
    权利要求:
    Claims (8)
    [0001]
    1. Non-aqueous photopolymerizable composition characterized in that it comprises: a polymerizable monomer comprising diethylene glycol dimethacrylate; a polymerization initiator; and a polyether-modified polysiloxane compound represented by the following general formula (1): <General Formula (1)> (CH3)3Si-O-[Si(CH3)2-O]a-[Si(CH3)(X) -O]b-Si(CH3)3 where X represents R(C2H4O)c(C3H6O)d-R', R is a single bond or an alkylene group, R' is a hydrogen atom or an alkyl group, and each a through d denotes an average degree of polymerization including a case where both c and d are 0.
    [0002]
    2. Non-aqueous photopolymerizable composition according to claim 1, characterized in that an amount of the polyether-modified polysiloxane compound represented by the General Formula (1) is 0.1 parts by mass or greater with respect to 100 parts in polymerizable monomer mass.
    [0003]
    3. Non-aqueous photopolymerizable composition according to claim 1 or 2, characterized in that the polymerizable monomer additionally comprises dipentaerythritol hexaacrylate modified by caprolactone.
    [0004]
    4. Non-aqueous photopolymerizable composition according to any one of claims 1 to 3, characterized in that the polymerization initiator is 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1- one, or oligo[2-hydroxy-2-methyl-1{4-(1-methylvinyl)phenyl}propanone].
    [0005]
    5. Non-aqueous photopolymerizable composition according to any one of claims 1 to 4, characterized in that an amount of the polymerization initiator is 10 parts by mass or greater with respect to 100 parts by mass of the polymerizable monomer.
    [0006]
    6. Inkjet ink characterized by the fact that it comprises: the light curing composition as defined in any one of claims 1 to 5.
    [0007]
    7. Inkjet ink according to claim 6, characterized in that the inkjet ink has a viscosity of 5 mPa-s to 18 mPa-s at 25°C.
    [0008]
    8. Ink cartridge (200) characterized in that it comprises: the inkjet ink as defined in claim 6 or 7; and a container (241).
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    同族专利:
    公开号 | 公开日
    RU2603639C1|2016-11-27|
    KR20150052222A|2015-05-13|
    EP2904020A1|2015-08-12|
    CA2887113A1|2014-04-10|
    CN104704010A|2015-06-10|
    JP2014088539A|2014-05-15|
    IN2015KN00604A|2015-07-17|
    WO2014054763A1|2014-04-10|
    EP2904020A4|2015-11-04|
    CA2887113C|2017-01-03|
    CN104704010B|2019-05-07|
    US20150232676A1|2015-08-20|
    BR112015007572A2|2019-12-10|
    JP6255695B2|2018-01-10|
    US9758683B2|2017-09-12|
    KR101670198B1|2016-10-27|
    EP2904020B1|2017-12-06|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    IT1243985B|1990-10-12|1994-06-28|Enichem Sintesi|UV STABILIZERS SILICONES CONTAINING REACTIVE GROUPS.|
    US6013330A|1997-02-27|2000-01-11|Acushnet Company|Process of forming a print|
    US6335382B1|1998-05-08|2002-01-01|Nagase-Ciba Ltd.|Ultraviolet-curable adhesive for bonding optical disks|
    GB2371551B|2001-01-29|2003-07-30|Sericol Ltd|A printing ink|
    US6767980B2|2002-04-19|2004-07-27|Nippon Shokubai Co., Ltd.|Reactive diluent and curable resin composition|
    JP4876379B2|2003-09-02|2012-02-15|セイコーエプソン株式会社|Water-based ink|
    US7105585B2|2003-09-25|2006-09-12|Flint Ink Corporation|UV cure ink jet ink for nonporous substrates|
    WO2006046698A1|2004-10-29|2006-05-04|Dainippon Ink And Chemicals, Inc.|Active energy ray-curable inkjet recording ink|
    JP4967378B2|2005-03-29|2012-07-04|セイコーエプソン株式会社|Ink composition|
    TWI419929B|2005-07-15|2013-12-21|Dainippon Ink & Chemicals|Ultraviolet curable resin composition and optical information recording media|
    CN101305061B|2005-11-11|2011-07-27|东洋油墨制造株式会社|Active energy ray-curable ink-jet ink|
    JP3936724B1|2006-06-16|2007-06-27|有限会社アプライドダイヤモンド|Method for producing ultrafine diamond particle dispersion|
    JP5159102B2|2006-12-14|2013-03-06|アシザワ・ファインテック株式会社|Vertical media stirring mill|
    US20110033650A1|2007-06-29|2011-02-10|Dic Corporation|Ultraviolet-curable composition for light-transmission layer and optical disk|
    JP5236238B2|2007-09-28|2013-07-17|富士フイルム株式会社|White ink composition for inkjet recording|
    JP5014299B2|2008-09-30|2012-08-29|ハニー化成株式会社|Composition for UV-curable cationic electrodeposition coating with good scratch resistance and coating film thereof|
    JP5293961B2|2009-05-28|2013-09-18|Ｔｄｋ株式会社|LED drive circuit|
    JP5668908B2|2009-12-28|2015-02-12|セイコーエプソン株式会社|Radiation curable ink composition, inkjet recording method and recorded matter|
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    法律状态:
    2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-20| B06I| Publication of requirement cancelled [chapter 6.9 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |
    2019-12-03| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-02-23| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-05-11| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 27/09/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2012-222728|2012-10-05|
    JP2012222728|2012-10-05|
    JP2013-077468|2013-04-03|
    JP2013077468A|JP6255695B2|2012-10-05|2013-04-03|Non-aqueous photopolymerizable composition, inkjet ink, and ink cartridge|
    PCT/JP2013/077012|WO2014054763A1|2012-10-05|2013-09-27|Photopolymerizable composition, photopolymerizable inkjet ink, and ink cartridge|
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