• 专利附录
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    • 专利摘要:
    photopolymerizable composition, photopolymerizable ink, composition container, imaging method or cured product, imaging device or cured product, and image or cured product. a photopolymerizable composition, which contains: a monofunctional monomer having a viscosity of 5 mpa.s or less at 25°C; one or more polyfunctional monomers including glycerol dimethacrylate; and a polymer free of a hydrophilic functional group, wherein a mass ratio (a/b) of an amount (a) of the polymer free of a hydrophilic functional group to an amount (b) of the polyfunctional monomer is greater than 0. 80 but it's 3 or less.
    公开号:BR112016028322B1
    申请号:R112016028322-8
    申请日:2015-06-01
    公开日:2021-08-03
    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 ink, a composition container, a method of forming a cured product or image, a cured product or image forming device, and a cured product or image. Knowledge Technique
    [0002] Conventionally, a light curing ink jet ink composed of a light curing composition containing a light curing monomer (eg (meth)acrylate) is well known (see eg PTL 1). Furthermore, it is also known that various properties can be provided to a cured product or image by blending a polymer component with the light-curing composition (see, for example, PTL 2).
    [0003] One of the advantages obtained by mixing the polymer component with the photopolymerizable composition is that sufficient adhesion can be ensured for a type of a base material (for example, a plastic material), in which the photopolymerizable composition does not easily penetrate, and which is relatively smooth so that it is difficult to guarantee the adhesion of a cured product or image. Not only when the light-curing composition in which the polymer component is mixed is used in a coating method such as spray coating, and bar coating, but also when the light-curing composition is used as a light-curing inkjet ink, in However, the use of the polymer component in the light-cured inkjet ink significantly increases the viscosity of the light-cured inkjet ink, and so there is a problem where it is difficult to achieve low viscosity suitable for use in a system. inkjet unless a light-curing monomer, which has sufficiently low viscosity, is used.
    [0004] Furthermore, many of the photopolymerizable monomers used in conventional photopolymerizable compositions are toxic. Especially most monomers with sufficiently low viscosity among (meth)acrylate which is cheap and readily available are highly toxic in terms of skin sensitivity which causes allergic reactions as it is touched by the skin. Suitably, it is still difficult to achieve a photopolymerizable composition, which has no skin sensitization problem, and has sufficiently low viscosity even when a polymer component is mixed into it.
    [0005] Among the problems mentioned above, the reduction in the viscosity of the light curing composition can be easily achieved by mixing a diluted solvent. However, you should avoid mixing a solvent into the light-curing composition, considering a potential effect of an applied solvent with the environment releasing the evaporated solvent into the air. Also, another idea is a method where a water-soluble monomer is used, and the viscosity of a resulting light-curing composition is reduced by mixing water in it. As a dry permeation effect cannot be expected from a base material such as a plastic film, glass, and a metal material, water needs to be evaporated to dry when an increase in the speed of a printing process is attempted. To this end, a heating device, such as a heat source, needs to be provided. Therefore, the use of such a light-curing composition is not preferable in view of energy savings.
    [0006] In view of the above, the present inventors have diligently conducted research to solve the aforementioned problems. As a result of this, the present inventors have proposed a photopolymerizable inkjet ink, which contains at least one selected from the group consisting of tert-butyl methacrylate, n-pentyl methacrylate, and n-hexyl methacrylate, and glycerol dimethacrylate, and additionally contains a polymer or copolymer composed of at least one selected from the group consisting of styrene, a styrene derivative, acrylic acid ester, and acrylic acid (see PTL 3). According to this proposal, a light-curing inkjet ink, which has no skin sensitization problem, has a viscosity that is low enough not to cause any inkjet ejection problem, and exhibits excellent adhesion to a plastic material .
    [0007] However, adhesion has not been sufficient for the use of a cured product or image that requires water resistance, after immersing the image or the cured product, specially formed in a non-permeable base, such as a plastic material , in water. Patent Literature Citation List
    [0008] PTL 1: Japanese Patent Application Filed (JP-A) No. 2004-526820
    [0009] PTL 2: Japanese Patent Application Publication (JP-B) No. 07-10894
    [00010] PTL 3: Japanese Patent Application Filed (JP-A) No. 2013-249357 Invention Summary Technical Problem
    [00011] The present invention seeks to provide a light-curing composition that has excellent water resistance, such that the adhesion of a cured image or product formed from the light-cured composition to a non-permeable base material is desirably maintained even when the cured image or product is immersed in water. Solution to Problem
    [00012] As the means to solve the aforementioned problems, the photopolymerizable composition of the present invention contains: a monofunctional monomer having a viscosity of 5 mPa.s or less at 25°C; one or more polyfunctional monomers including glycerol dimethacrylate; and a polymer free of a hydrophilic functional group, in which a mass ratio (A/B) of an amount (A) of the polymer free of a hydrophilic functional group to an amount (B) of the polyfunctional monomers is greater than 0.80 but 3 or less. Advantageous Effects of the Invention
    [00013] The present invention provides a light-curing composition that has excellent water resistance, such that the adhesion of a cured image or product formed from the light-cured composition to a non-permeable base material is desirably maintained even when the cured image or product is immersed in water. Brief Description of Drawings
    [00014] FIG. 1 is a schematic diagram illustrating an example of an ink cartridge as a composition container.
    [00015] FIG. 2 is a schematic diagram illustrating the ink cartridge of FIG. 1 as the composition container including an ink cartridge housing.
    [00016] FIG. 3 illustrates an example of an imaging device and/or cured product (inkjet recording device). Description of Achievements (Light-curing composition)
    [00017] The photopolymerizable composition of the present invention contains at least one monofunctional monomer having a viscosity of 5 mPa.s or less at 25°C (may be referred to as a low viscosity monofunctional monomer, hereinafter), tert-butyl methacrylate , one or more polyfunctional monomers including glycerol dimethacrylate, and a polymer free of a hydrophilic functional group, and may additionally contain other components as needed.
    [00018] The present inventors have diligently conducted research to solve the aforementioned problems. As a result, the present inventors have come to the following knowledge, on the basis of which the present invention has been achieved. In the case where a light-curing composition is used as a light-curing inkjet ink, a monofunctional monomer having a viscosity of 5 mPa.s or less at 25°C by itself is an essential component for reducing a viscosity of the light-curing composition to the band that can be ejected by the inkjet.
    [00019] Note that a low viscosity monofunctional monomer viscosity alone preferably is 3 mPa.s or less at 25°C, more preferably about 1 mPa.s or less at 25°C.
    [00020] Viscosity can be measured by means of a cone-plate rotor viscometer, VISCOMETER TV-22, manufactured by Toki Sangyo Co., Ltd., using a corn rotor (1°34' x R24) at speed 50 rpm rotary, with constant temperature circulation water temperature adjustment to 25°C.
    [00021] The viscosity of the light-curing composition can be kept sufficiently low by using the low-viscosity monofunctional monomer, even when a polymer component is mixed with the light-curing inkjet ink. However, the use of the low viscosity monofunctional monomer alone as a light curing monomer in the light curing composition cannot provide sufficient curing ability. It is the perception that excellent curing and practicality can be achieved by containing in the photopolymerizable composition one or more polyfunctional monomers containing glycerol dimethacrylate, which are negative for skin sensitization, inexpensive, and readily available. <Skin Sensitization>
    [00022] In the present specification, the negative photopolymerizable monomer for skin sensitization refers to a compound that satisfies at least one of the following (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 rated as negligible skin sensitization in the literature “Contact Dermatitis 1982(8) 223225.”(3) A compound evaluated as “no skin sensitization” or “skin sensitization negative” on MSDS (chemical material safety data sheet).
    [00023] With respect to the above in (1), the compound having an SI value of less than 3 is considered to be negative for skin sensitization as described in the literature, for example, "Functional Material" (Kino Zairyou ) September, 2005, Vol. 25, No. 9, p. 55. The lowest SI value means less skin sensitization. In the present invention, therefore, a photopolymerizable monomer having a lower SI value is preferably used. The SI value is preferably less than 3, more preferably 2 or less, and even more preferably 1.6 or less. <Low viscosity monofunctional monomer having Viscosity of 5 mPa.s or less by itself at 25°C>
    [00024] The low viscosity monofunctional monomer having a viscosity of 5 mPa.s or less at 25°C by itself is not particularly limited, but is preferably any one of tert-butyl methacrylate, n-pentyl methacrylate, and n-hexyl methacrylate, which are cheap, readily available, skin-sensitizing negative photopolymerizable monomers. Tert-butyl methacrylate is the monofunctional photopolymerizable monomer represented by the following structural formula.

    [00025] An amount of the low viscosity monofunctional monomer is appropriately selected depending on the intended purpose without any limitation, but the amount thereof is preferably 85 parts by mass to 96 parts by mass with respect to 100 parts by mass of a total amount of photopolymerizable monomers. When the amount of the low viscosity monofunctional monomer is in the range of 85 parts by mass to 96 parts by mass, the viscosity of the photopolymerizable composition can be made low enough even when a required amount of the polymer free of a hydrophilic functional group is mixed, and gives a suitable viscosity range for a light-curing ink. <Polyfunctional light-curing monomers>
    [00026] Polyfunctional photopolymerizable monomers contain at least glycerol dimethacrylate, which is negative for skin sensitization, is inexpensive, and is readily available. The use of glyceroldimethacrylate can impart a photopolymerizable composition with excellent curing capacity.
    [00027] As for the polyfunctional photopolymerizable monomers, it is preferred that, in addition to glycerol dimethacrylate, tricyclodecane dimethanol dimethacrylate, which is negative for skin sensitization, inexpensive, and readily available, to be contained in view of an improvement in curing capacity .
    [00028] An amount of the polyfunctional photopolymerizable monomers is appropriately selected depending on the intended purpose without any limitation, but the amount thereof is preferably 4 parts by mass to 25 parts by mass, more preferably 5 parts by mass to 15 parts by mass, with respect to 100 parts by mass of a total amount of the light curing monomers. When the amount of polyfunctional photopolymerizable monomers is in the range of 4 parts by mass to 25 parts by mass, a resulting photopolymerizable composition can form a coating film having a certain strength even in the case where the photopolymerizable composition contains a colorant. In the case where the amount of glycerol dimethacrylate is 1 part by mass, furthermore, the amount of the low viscosity monofunctional monomer is preferably 5 parts by mass to 30 parts by mass, more preferably 10 parts by mass to 25 parts by mass .
    [00029] The photopolymerizable composition of the present invention may contain other photopolymerizable monomers different than the low viscosity monofunctional monomer and the polyfunctional photopolymerizable monomers.
    [00030] The other photopolymerizable monomers mentioned above can be monofunctional or polyfunctional monomers. As for the other photopolymerizable monomers mentioned above, compounds that have a skin sensitization problem to a certain degree for single use, or a skin sensitizing compound which has not been confirmed, can be used in addition to a negative sensitizing compound of the skin, so long as a resulting photopolymerizable composition does not have a skin sensitization problem.
    [00031] The other photopolymerizable monomers mentioned above are appropriately selected depending on the intended purpose without any limitation. Examples thereof include n-pentyl(meth)acrylate, n-hexyl(meth)acrylate, ethylene glycol di(meth)acrylate, hydroxyl pivalic acid neopentyl glycol di(meth)acrylate, gamma-butyrolactone acrylate, isobornyl(meth)acrylate, formalized trimethylol propane mono(meth)acrylate, polytetramethylene glycol di(meth)acrylate, trimethylol propane (meth)acrylic acid benzoate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate [CH2=CH-CO-(OC2H4)n-OCOCH= CH2(n is almost equal to 9), CH2=CH-CO-(OC2H4)n-OCOCH=CH2 (n is almost equal to 14), CH2=CH-CO-(OC2H4)n-OCOCH=CH2 (n is almost equal to 23)], dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol dimethacrylate [CH2=C(CHa)-CO-(OC3H6H6)n-OCOC(CH3)=CH2 (n is almost equal to 7)], 1,3-butanediol diacrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di( meth)acrylate, tricyclodecane dimethanol diacrylate, bisphenol A modified by propylene oxide di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, (meth)acryloyl morpholine, 2-hydroxypropyl(meth)acrylamide, modified by propylene oxide tetramethylol methane tetra(meth)acrylate , dipentaerythritol hydroxypenta(meth)acrylate, dipentaerythritol hydroxypenta(meth)acrylate modified by caprolactone, ditrimethylol propane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, trimethylol propane triacrylate, trimethylol propane triacrylate(trimethylol propane modified by propane trimethylol oxide meth)acrylate modified by propylene oxide, trimethylol propane tri(meth)acrylate modified by caprolactone, pentaerythritol tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, neopentyl glycol di(meth)acrylate, modified by propylene oxide neopentyl glycol di(meth)acrylate, glyceryl tri(meth)acrylate modified by propylene oxide, polyester di(meth)acrylate, polyester tri(meth)acrylate, polyester tetra(meth)acrylate lacto, polyester penta(meth)acrylate, polyester poly(meth)acrylate, N-vinyl caproformamide, 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, triethylene glycol divinyl ether, cyclohexane dimethanol divinyl ether, cyclohexane dimethanol monovinyl ether, diethylene glycol divinyl ether, dicyclopentadiene vinyl ether, tricyclodecane vinyl ether, benzyl vinyl ether, ethyl oxetane methyl vinyl ether, triethylene glycol divinyl ether, and ethyl vinyl ether. These can be used alone, or in combination.<Free Hydrophilic Functional Group Polymer>
    [00032] A term "a hydrophilic functional group" in the polymer free of a hydrophilic functional group typically means, for example, a substituent having polarity, such as a hydroxyl group, a carboxyl group, a phosphonic acid group, a sulfonic acid group , and an amino group.
    [00033] In the present specification, the phrase "free from a hydrophilic functional group" associated with the polymer free from a hydrophilic functional group means an acid value, a saponification value, or a hydroxyl value of the polymer as measured by JIS K0070 “Test methods for acid value, saponification value, ester value, iodine value, hydroxyl value, and unsaponifiable matter of chemical products” or a method in accordance with their standard is 1 mg/g or less. Among these, it is preferred that the acid value of the polymer free of a functional hydrophilic group is 1 mg KOH/g or less.
    [00034] The polymer free of a hydrophilic functional group is preferably a polymer having excellent solubility for the photopolymerizable monomer that constitutes the photopolymerizable composition, more preferably a polymer having a chain structure rather than a dense crosslinking structure, and having the weight weight average molecular weight of 1,000,000 or less, and even more preferably a polymer having a weight average molecular weight of 4,400 to 450,000.
    [00035] Polymer free from a hydrophilic functional group, which has a chain structure and weight average molecular weight of 1,000,000 or less, is preferable, so that the polymer can be easily dissolved into the photopolymerizable monomer.
    [00036] Furthermore, the polymer is preferably a material with low crystallinity having flexibility in order to improve solubility. In addition, practically, a polymer that is cheap and readily available is more preferable.
    [00037] Weight average molecular weight can be measured, for example, by standard polystyrene molecular weight conversion using high speed liquid chromatography (“Waters 2695 (main body)” and “Waters 2414 (detector), manufactured by Nihon Waters KK), with which columns of three series Shodex GPC KF-806L (cut molecular weight: 2 x 107, separation range: 100 to 2 x 107, number of theoretical plates: 10,000 plates per column, filler material: copolymer of styrene-divinylbenzene, filler particle diameter: 10μm) are used, and tetrahydrofuran is used as an eluent.
    [00038] Examples of the polymer free of a hydrophilic functional group include a polymer or copolymer composed of at least one monomer selected from the groups consisting of a vinyl monomer, such as styrene, and a styrene derivative, and a monomer of (meth)acrylate. Among these, polystyrene, ethyl polymethacrylate, and a styrene-butyl methacrylate copolymer are particularly preferred.
    [00039] Mixing the polymer free of a hydrophilic functional group in the photopolymerizable composition, excellent water resistance, such that an image or cured product thereof formed in a non-permeable base material, such as plastic, glass, and a metal material , desirably maintains adhesion even when immersed in water.
    [00040] The polymer free of a hydrophilic functional group has a molecular weight significantly higher than those previously mentioned photopolymerizable monomers, and thus it is difficult for such polymer to pass through the skins, and the polymer typically does not give rise to skin sensitization.
    [00041] In the present invention, a mass ratio (A/B) of an amount (A) of the free polymer of a hydrophilic functional group to an amount (B) of the polyfunctional monomers is greater than 0.80 but 3 or less , preferably 1.3 to 3.
    [00042] The photopolymerizable composition having a mass ratio (A/B) of more than 0.80 but 3 or less is advantageous, as it has excellent water resistance, such that the adhesion of an image or cured product thereof formed on a non-permeable base material can be desirably maintained, is achieved. When the mass ratio (A/B) is 3 or less, the resulting light cure composition can be used for inkjet.<Light cure initiator>
    [00043] The photopolymerizable initiator is suitably selected depending on the intended purpose without any limitation, but is preferably a photoradical polymerization initiator.
    [00044] As for the photoradical polymerization initiator, a negative photoradical polymerization initiator for skin sensitization is preferable.
    [00045] (Met)acrylate, (meth)acryl amide, derivatives thereof, and a vinyl ether compound are known to have ionic polymerization properties. Not only are these ionic polymerization initiators typically expensive, these initiators generate a slight amount of strong acid or strong alkali even in the state where they are not irradiated with light. Therefore, special care must be taken, such as imparting acid resistance or alkali resistance to a coating member of a light-curing composition, or a section in an inkjet system in contact with a liquid, which imposes a limitation on a choice of coating member to use, or members making up the inkjet system.
    [00046] In contrast, the photopolymerizable composition of the present invention can use a photoradical polymerization initiator that is inexpensive and does not generate strong acid or strong alkali. Therefore, it is possible to produce a light-curing composition at low cost, and it is also easy to select the coating member or members making up the inkjet system.
    [00047] Note that when a high-energy light source, such as electron beams, alpha rays, beta rays, gamma rays, and X-rays, is used, a polymerization reaction proceeds without a polymerization initiator, although that there is a disadvantage that a large cost is required for installation or maintenance of equipment. This is a conventionally known matter, and is not described in detail in the present specification.
    [00048] Examples of the photoradical light curing initiator include a self-cleaving light curing initiator, and a hydrogen abstracting light curing initiator.
    [00049] Examples of the self-cleavage photopolymerizable initiator include 2,2-dimethoxy-1,2-diphenyletan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl ]phenyl}-2-methyl-1-propan-1-one, oligo[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone, phenyl glyoxylic acid methyl ester, 2-methyl -1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1,2-dimethylamino-2-(4-methylbenzyl) -1-(4-morpholin-4-yl-phenyl)butan-1-one, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4 oxide -trimethyl-pentylphosphine, 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), [4-(methylphenylthio)phenyl]phenylmethanone, and oligo[2-hydroxy-2-methyl-1-[4-(1- methylvinyl)phenyl]propanone. These can be used alone, or in combination.
    [00050] Examples of the photopolymerizable hydrogen abstraction initiator include: a compound based on benzophenone, such as benzophenone, methyl benzophenone, methyl-2-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl sulfide, and phenyl benzophenone; and a thioxanthone-based compound, such as 2,4-diethylthioxanthone, 2-chlorothioxanthone, isopropylthioxanthone, and 1-chloro-4-propylthioxanthone. These can be used alone, or in combination.
    [00051] An amount of light curing initiator is appropriately selected depending on the intended purpose without any limitation, but the amount thereof is preferably 2 parts by mass to 10 parts by mass with respect to 100 parts by mass of a total amount of the light curing monomers for the use. When the amount of light curing initiator is in the range of 2 parts by mass to 10 parts by mass, the strength of a coating film of the resulting light curing composition can be maintained at a certain strength or greater. <<Polymerization Accelerator>>
    [00052] An amine compound can be used as a polymerization accelerator in combination with the photopolymerizable initiator in the photopolymerizable composition of the present invention.
    [00053] Examples of the amine compound include ethyl-p-dimethylamino benzoate, 2-ethyl-hexyl-p-dimethylamino benzoate, methyl-p-dimethylamino benzoate, 2-dimethylaminoethyl benzoate, and butoxyethyl-p-dimethylamino benzoate. These can be used alone, or in combination.
    [00054] The photopolymerizable composition of the present invention may contain no colorant to form a clear liquid, or may contain a colorant to form a colored liquid. Note that, in case clear liquid is formed, or it is desired to maintain a color tone of a colorant itself as much as possible, it is preferred that materials for use, other than the following colorant, have as little color as is possible. <Coloring>
    [00055] As for the colorant, an inorganic pigment, or an organic pigment can be used. Note that various inorganic pigments or organic pigments can be used depending on requirements considering the physical properties of a resulting paint.
    [00056] Examples of the black pigment include carbon black produced by an oven method or a channel method.
    [00057] Examples of the yellow pigment include pigments of 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.
    [00058] Examples of magenta pigment include pigments from the series Pigment Red, 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.
    [00059] Examples of the cyan pigment include pigments of the Pigment Blue series, 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.
    [00060] Examples of the white pigment 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 silicic acid powder and synthetic silicic acid salts; calcium silicate; alumina; alumina hydrate; titanium oxide; zinc oxide; baby powder; and clay. <Other Components>
    [00061] Examples of the other components mentioned above include: a polymerization inhibitor; a polyether containing higher fatty acid ester, an amino group, a carboxyl group, or a hydroxyl group; a polydimethylsiloxane compound containing a polyether residue, an amino group, a carboxyl group, or a hydroxyl group on a side or terminal chain thereof; a surfactant, such as a fluoroalkyl compound containing a polyether residue, an amino group, a carboxyl group, or a hydroxyl group; and a polar group-containing polymer pigment dispersing agent. In the case where a material containing a hydrophilic functional group is used from among the aforementioned components, the use of the material in an amount of 5% by mass or less can guarantee the water resistance of a resulting photopolymerizable composition. <<Polymerization inhibitor>>
    [00062] Examples of the polymerization inhibitor include 4-methoxy-1-naphthol, methyl-hydroquinone, hydroquinone, tert-butyl-hydroquinone, di-tert-butyl-hydroquinone, methoquinone, 2,2'-dihydroxy-3, 3'-di(alpha-methylcyclohexyl)-5,5'-dimethyl diphenylmethane, p-benzoquinone, di-tert-butyldiphenylamine, 9,10-di-n-butoxyyanthracene, and 4,4'-[1.10 -dioxo-1,10-decanediylbis(oxy)bis][2,2,6,6-tetramethyl]-1-piperidinyloxy. These can be used alone, or in combination.
    [00063] The photopolymerizable composition of the present invention may contain an organic solvent, but the photopolymerizable composition is preferably free of an organic solvent, if possible. When the composition is free of an organic solvent, especially in the case of a composition free of a volatile organic solvent (volatile organic compounds (VOC) free composition), safety of a place where the composition is manipulated is improved, and environmental pollutions can be avoided.
    [00064] The term "organic solvent" means a typical unreactive organic solvent, such as ether, ketone, xylene, ethyl acetate, cyclohexanone, and toluene, and is to be distinguished from a reactive monomer. Furthermore, "free from" organic solvent means that the composition substantially does not contain the organic solvent, and the organic solvent content is preferably 0.1% by mass or less. <Use>
    [00065] Use of the photopolymerizable composition of the present invention is appropriately selected depending on the intended purpose without any limitation, provided that it is used in a field where a photopolymerizable composition is typically used. For example, the light curing composition can be applied to a molding resin, a coating agent, an adhesive, an insulating material, a release agent, a coating material, a sealing material, various strength materials, and various optical materials.
    [00066] In addition, the photopolymerizable composition of the present invention can also be used as a solid-forming material to form a three-dimensional solid object, as well as an ink to form two-dimensional characters, images, or design coating films for various types of a base. (Light-curing paint)
    [00067] The photopolymerizable ink of the present invention contains the photopolymerizable composition of the present invention.
    [00068] The photopolymerizable ink is preferably for use in inkjet printing.
    [00069] The viscosity of the light curing ink at 25°C is preferably 2 mPa.s to 150 mPa.s, more preferably 3 mPa.s to 18 mPa.s.
    [00070] As for the inkjet ejection head, there is a head which has a large ejection power compatible with a highly viscous ink, and a head having a temperature control function over a wide range. In the case where an inkjet ejection head temperature control function can be used, the inkjet ejection head is heated to reduce the ink viscosity as necessary if the ink viscosity is too high at 25°C. Assuming the heating condition is 60°C, the viscosity of the light curing composition at 60°C is preferably 2 mPa.s to 20 mPa.s, more preferably 3 mPa.s to 18 mPa.s.
    [00071] Viscosity is measured by means of a cone-plate rotor viscometer, VISCOMETER TV-22, manufactured by Toki Sangyo Co., Ltd., using a corn rotor (1°34 ' x R24) at rotary speed of 50 rpm, with constant temperature circulation water temperature adjustment to 25°C or 60°C. As for the adjustment of the circulating water temperature, VISCOMATE VM-150III is used. The temperature of 25°C is specified based on a typical ambient temperature environment, and the temperature of 60°C is specified based on a specification for a commercially available heatable inkjet ejection head, such as GEN4, manufactured by Ricoh Industry Company, Ltd.
    [00072] The static surface tension of the light curing ink at 25°C is preferably 20 mN/m to 40 mN/m, more preferably 28 mN/m to 35 mN/m.
    [00073] Static surface tension is measured at 25°C by means of a static surface tensiometer (CBVP-Z, manufactured by Kyowa Interface Science Co., Ltd.). Static surface tension is specified based on a specification for a commercially available inkjet ejection head, such as GEN4, manufactured by Ricoh Industry Company, Ltd. (Composition container)
    [00074] The composition container of the present invention contains a container, and the composition of the present invention housed in the container.
    [00075] The composition container of the present invention contains the photopolymerizable ink of the present invention, and a container, and may additionally contain other members, such as a composition pouch, as necessary. With this form, users do not need to directly touch the composition during operations such as changing a composition, and therefore, there is no need to worry about staining their fingers, hands or clothes. In addition, it is possible to avoid the interfusion of foreign matter, such as dust, into the composition.
    [00076] The container is not particularly limited, and a shape, structure, size, and material thereof are appropriately selected depending on the intended purpose. For example, a container containing a composition pouch formed from a laminated aluminum film, or a resin film, is preferred.
    [00077] The ink cartridge as an example of the composition container is explained with reference to FIGs. 1 and 2. FIG. 1 is a schematic diagram illustrating an example of an ink pouch 241 of an ink cartridge, and FIG. 2 is a schematic diagram illustrating an ink cartridge 200, in which the ink pouch 241 of FIG. 1 is housed in a cartridge housing 244.
    [00078] As illustrated in FIG. 1, the ink pouch 241 is filled with ink by injecting the ink from an ink inlet 242. Upon removal of the air present inside the ink bag 241, the ink inlet 242 is sealed by fusion bonding. At the time of use, a needle attached with 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 laminate film. As illustrated in FIG. 2, the ink pouch 241 typically is housed in a plastic cartridge housing 244, and the resultant is used as the ink cartridge 200, which is detachably mounted in use for various cured product or imaging devices ( inkjet recording devices).
    [00079] The ink cartridge is preferably detachably mounted in a cured product or image forming device (inkjet recording device). As a result of this, ink replenishment or replacement can be simplified, and workability can be improved. (Method for Imaging or Cured Product and Cured Product or Imaging Device)
    [00080] The method for forming a cured product or image of the present invention contains at least one application step, and one curing step, and may additionally contain other steps as necessary.
    [00081] The cured product or image forming device of the present invention contains at least one application unit, and one curing unit, and may additionally contain other units as required.
    [00082] The method for forming a cured product or image of the present invention can be properly performed by the cured product or image forming device of the present invention, the application step can be performed by the application unit, the curing step can be performed by the healing unit, and the other steps mentioned above can be performed by the other units mentioned above. <Application Step and Application Unit>
    [00083] The application step is a step containing the application of the light curing composition of the present invention, or the light curing paint of the present invention on a base material, and the application step is performed by the application unit.
    [00084] The application method is appropriately selected depending on the intended purpose without any limitation, but the application method is preferably an inkjet ejection system, or a coating system. Among these, the inkjet ejection system is particularly preferable.
    [00085] The inkjet ejection system is selected appropriately depending on the intended purpose without any limitation. As for an ejection head drive system, a piezoelectric element actuator using PZT or the like, an on-demand head that uses an actuator that uses a system where thermal energy is operated, or an actuator that uses electrostatic force, or a Continuous act head of a load control type can be used.
    [00086] The coating method is appropriately selected depending on the intended purpose without any limitation, and examples thereof include blade coating, gravure coating, gravure displacement coating, wire bar coating, bar coating, roller coating , knife coating, air knife coating, comma coating, U-coating, AKKU coating, smooth coating, microengraving coating, reverse roll coating, 4 or 5 roll coating, dip coating, coating by curtain, slide coating, and dye coating. Among these, wire rod coating, and roller coating are preferred. <Base material>
    [00087] As for the base material, an absorbent base material, such as wood-free paper, can expect a permeation drying effect, and so it is practical for use in an aqueous paint or an oil-based paint, which is not quick-drying on such a base material. In the case of a non-permeable base material, such as coated paper, synthetic paper, a plastic film, a plastic molded product, ceramic, glass, and metal, on the other hand, it is practical to use a quick-drying ink on it. , and is preferably for the photopolymerizable ink of the present invention, which is immediately cured with light irradiation.
    [00088] The photopolymerizable composition of the present invention, or the photopolymerizable ink of the present invention is particularly suitably used with the non-permeable base material.
    [00089] As for a plastic material, such as a film, and a molded product, among the non-permeable base materials, for example, polyethylene, polypropylene, polyethylene terephthalate, polycarbonate, an ABS resin, polyvinyl chloride, is preferred, polystyrene, polyester, polyamide, a vinyl-based material, or a material composed of the above materials.
    [00090] There is a casing where a corona treatment is performed on the plastic material in order to activate a surface of the same to improve adhesion. Even when corona treatment is carried out, however, there are not many polar functional groups present on the surface of the same, and the surface of the same is inactive. Therefore, it is typically difficult to form an image or coating film on it, and to exhibit excellent adhesion. However, an image or coating film can be formed on the plastic material and excellent adhesion thereof can be achieved using the photopolymerizable composition of the present invention, or the photopolymerizable ink of the present invention.
    [00091] Furthermore, an inorganic base material, such as metal, ceramic, and glass, is quite active as long as a surface thereof is clean, and adhesion of a coating film is relatively excellent. However, such a clean surface is polluted through the adsorption of impurities, leaving only them in the atmosphere. Therefore, it is typically difficult for the inorganic base material to achieve excellent adhesion, similarly to the plastic material.
    [00092] Among these various materials, polypropylene and polyethylene terephthalate are typical base materials that are especially difficult to achieve adhesion. Since these materials are widely used for general purpose, it is highly desirable to assess adhesion to these materials. If adhesion to these materials can be achieved, adhesion to the other materials mentioned above can also be achieved.
    [00093] The average thickness of an image before curing or a cured product is preferably 5 µm to 20 µm. The average thickness of 5 µm to 20 µm is advantageous, as a resulting image or cured product, which is formed in a non-permeable base material, has excellent water resistance, such that adhesion can be desirably maintained after being immersed in water. . <Healing Stage and Healing Unit>
    [00094] The curing step is a step containing irradiating a film applied to the base material with active energy rays to cure the film, and is performed by the curing unit.
    [00095] Examples of the curing unit include a UV radiation device.
    [00096] Healing is preferably carried out through irradiation with ultraviolet (UV) rays as the active energy rays. UV rays as active energy rays are selected appropriately depending on the intended purpose without any limitation, but it is preferably light having a wavelength of 350 nm to 450 nm.
    [00097] As for the irradiation with active energy rays, it is preferred that a sufficient dose of active energy rays is applied to cure the film with consideration for potential thermal damage applied to the base material.
    [00098] The radiation dose of the active energy rays is selected appropriately depending on the intended purpose without any limitation, but it is preferably from 1000 mJ/cm2 to 2000 mJ/cm2. When the radiation dose is within the preferable range mentioned above, a cure reaction is sufficiently carried out.
    [00099] A light source of ultraviolet ray radiation is appropriately selected depending on the intended purpose without any limitation, and examples thereof include a lamp (eg a metal halide lamp, a xenon lamp, an arc lamp carbon, a chemical lamp, a low pressure mercury lamp, and a high pressure mercury lamp), and an ultraviolet ray emitting semiconductor element (eg, a UV light emitting diode (UV LED) ,and a UV light-emitting semiconductor laser). For example, UV ray radiation can be carried out using a commercially available product, such as H lamp, D lamp, V lamp, manufactured by Noblelight Fusion. <Other Steps and Other Units>
    [000100] Examples of the other steps mentioned above and the other units mentioned above include a transport step and a transport unit, and a control step and a control unit.
    [000101] FIG. 3 is a schematic diagram illustrating an example of the cured product or image forming device (inkjet recording device) of the present invention used in the method for forming an image or cured product of the present invention.
    [000102] FIG. 3 illustrates an embodiment where a color print is formed by printing a print base material 2 (carried from left to right in FIG. 3) with each color (yellow, magenta, cyan, or black) ejected from of a printing unit 3 (consisting of color 3a, 3b, 3c, and 3d printing units (for example, yellow, magenta, cyan, and black)), and radiating with light (UV light) each time printed with each color, using UV light sources (light sources for curing) 4a, 4b, 4c, and 4d to cure the ink. Each of the printing units 3a, 3b, 3c, 3d is equipped with a heating system in an ink ejection section, so as to reduce the ink viscosity when the ink viscosity is excessively high, and equipped with an ink ejection system. cooling in a base material holding section (a section that is on the upper or lower side of the base material in FIG. 3) in order to optionally cool the base material in a direct or indirect manner. In the case where a printing area of the color, which is printed first, is small and the base material transport speed is low, the base material is kept around room temperature by natural cooling for the color printed later. In the case where a printing area of the color, which is printed first, is large, or the base material transport speed is fast, however, the base material temperature is increased. Therefore, it is preferred that a refrigeration system is optionally provided to maintain the temperature of the base material to about room temperature.
    [000103] As for printing base material 2, paper, plastic, metal, ceramic, glass, or a material composition thereof is used. Although the printing base material 2 in the form of a roll is illustrated in FIG. 3, the printing base material 2 may be in the form of a sheet. Furthermore, the printing can be not only one-sided printing, but two-sided printing as well.
    [000104] In high speed printing, high curing capability can be achieved by applying ultraviolet rays each time each color is printed. Energy savings and cost savings can be realized, for example, by decreasing the output of 4a, 4b, 4c UV ray sources or omitting the UV ray sources to apply a sufficient dose of UV rays with 4d at once after printing of a plurality of colors. Alternatively, to realize energy savings and cost savings, LED light sources, which have recently been used practically for printing photopolymerizable inks, can be used instead of conventionally used light sources such as high-pressure mercury lamps and metal halide lamps.
    [000105] In FIG. 3, reference numeral 5 denotes a processing unit and reference numeral 6 denotes a take-up roll for printed products. (Image or cured product)
    [000106] The image or cured product of the present invention is obtained by the method containing the application of the light-curing composition of the present invention, or the light-curing ink of the present invention to a base material, and curing the light-curing composition, the light-curing ink, or the light-curing inkjet ink.
    [000107] As for the base material, at least one selected from the group consisting of paper, plastic, metal, glass, and a material composed of the following materials is used.
    [000108] Examples of the image include letters, symbols, shapes, any combination thereof, and a solid image.
    [000109] As the light-curing composition of the present invention, or the light-curing ink of the present invention is used for the cured image or product, the cured image or product has excellent water resistance, such that the cured image or product formed in a material of non-permeable base desirably maintains adhesion even after immersion in water.
    [000110] Examples of the present invention are explained hereinafter, but the present invention is not limited to these examples in any way. <SI Value Assessment Method>
    [000111] According to the Local Lymph Node Assay (LLNA) skin sensitization test, the SI value was measured as follows.- Test Material - <<Positive Control>>
    [000112] As for a positive control, alpha-hexylcinnamaldehyde (HCA, manufactured by Wako Pure Chemical Industries, Ltd.) was used. <<Vehicle>>
    [000113] As for the vehicle, a mixed liquid prepared by mixing acetone (manufactured by Wako Pure Chemical Industries, Ltd.) and olive oil (manufactured by Fudimi Pharmaceutical Co., Ltd.) in a volume ratio (acetone:oil olive) of 4:1 was used. <<Used Animals>>
    [000114] Prior to 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 with all animals during the quarantine/acclimatization period.
    [000115] 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 the body weight of each individual was within plus or minus 20%. Each animal was 8 weeks old to 9 weeks old at the time of onset of sensitization. Animals that remain after categorization were excluded from the test.
    [000116] The animals were individually identified by applying oil paint on their tail during the test period, and also their cages were marked for identification. <<Accommodation environment>>
    [000117] During the housing period including the quarantine/acclimatization period, the animals were housed in an animal environment with a barrier system, which was defined as follows: 21°C to 25°C temperature, 40% to 70% relative humidity, 10 times/hour up to 15 times/hour at a circulating air frequency, and a 12-hour interval lighting cycle (7:00 to 19:00 lighting).
    [000118] As for the housing cages, casings made of polycarbonate were used. Four animals were housed in each cage.
    [000119] The animals used were given solid feed ad libitum to MF laboratory animals (product of Oriental Yeast Co., Ltd.). Also, with the use of a water supply bottle, the animals used were given tap water ad libitum in which sodium hypochlorite (PURELOX, product of OYALOX Co., Ltd.) was added so that the chlorine concentration was added. of about 5 ppm. Beds used were SUNFLAKE (fir, shavings obtained with a planing machine) (product of Charles River Inc.). Feeding and all feeding equipment were sterilized with an autoclave (121°C, 30 min) prior to use.
    [000120] The housing cage and the bed were replaced with new ones at the time of categorization and the removal of the auricular lymph node (i.e., the time the animals were transferred from the animal environment), and the supply bottle for water and support were replaced with new ones at the time of categorization. - Test Method - <<Group Composition>>
    [000121] The group compositions used in measuring the SI value are shown in Table 1.
    - Preparation - <<Test Substance>>
    [000122] 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 subjected to 1 ml with the vehicle. The test substance prepared in this way was placed in an airtight container protected from light (made of glass).
    <<Positive Control Substance>>
    [000123] About 0.25 g of HCA was accurately weighed, and the vehicle was added to the HCA to have the volume of 1 mL, to thereby prepare a 25.0 w/v% solution. The positive control substance preparation thus prepared was placed in a light-shielded, airtight container (made of glass). <<BrdU>>
    [000124] In a measuring vial, 200 mg of 5-bromo-2'-deoxyuridine (BrdU, product of NACALAI TESQUE, INC.) was accurately weighed in a measuring vial. Then, physiological saline solution (product of OTSUKAPHARMACEUTICAL CO., LTD.) was added to the measuring flask, and dissolved by applying ultrasonic waves. Next, the volume of the resulting solution was adjusted to 20 ml to prepare a 10 mg/ml solution (BrdU preparation). The BrdU preparation was sterilized by filtration with a sterilized filtration filter and placed in a sterilized container. <Day of Preparation and Storage Period»
    [000125] The positive control preparation was prepared the day before the start of sensitization, and stored in a cool place except for use. Vehicle and test substance preparations were prepared on the day of sensitization. The preparation of BrdU was done 2 days before administration and stored in a cold place until the day of administration.- Sensitization and Administration of BrdU -<<Sensibilization>>
    [000126] Each of the test substance preparations, the positive control preparation, and the vehicle was applied to both atria of each used animal for 25 mL. For application, a micropipette was used. This process was performed once a day for three consecutive days.<<BrdU administration>>
    [000127] About 48 hours after the final sensitization, the preparation of BrdU (0.5 mL) was administered intraperitoneally once for each of the animals used.- Observation and Examination - <<General Conditions>>
    [000128] All animals used for the test were observed once or more times a day from the day of initiation of sensitization until the day of auricular lymph node removal (i.e., the day when the animals were transferred from the animal environment). Note that the day of observation was counted from the day of the start of sensitization being considered as Day 1. <<Body Weight Measurement>>
    [000129] The body weight of each of the animals used was measured on the day of initiation of sensitization and on the day of auricular lymph node removal (i.e. the day when the animals were transferred from the animal environment). Also, the mean body weight and its standard error were calculated for each group. <<Auricular Lymph Node Removal and Weight Measurement >>
    [000130] About 24 hours after administration of BrdU, the used 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 from 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 ear lymph nodes were stored in a frozen state using a BIO MEDICAL FREEZER set at -20°C. <<BrdU Admission Measurement >>
    [000131] After returning the auricular lymph nodes to room temperature, the auricular lymph nodes were joined 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. The suspensions thus dispensed were measured for BrdU admission by the ELISA method. 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 to measure the absorbance of each well (OD: 370 nm to 492 nm, BrdU inlet), and the mean absorbance of 3 wells for each individual was used as the BrdU measurement for the individual.- Results Evaluation - <<Calculation of Stimulation Index (SI)>>
    [000132] As shown in the following formula, the BrdU uptake measurement for each subject was divided by the mean of the BrdU uptake 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. In addition, the standard error of the SI values was calculated for each test group. Notably, the SI value has been rounded to the second decimal place and shown to the first decimal place.SI = (Average of BrdU admission ts measurements for each individual (three-well mean)) / (Average of ts measurements of BrdU admission of BrdU in the vehicle control group (mean 4 animals)) (Examples 1 to 10 and Comparative Examples 1 to 2)
    [000133] Each of the photopolymerizable compositions was prepared by mixing the following materials (A) to (E) in the amounts (values were based on parts by mass) represented in each column of the respective Examples and Comparative Examples in the following tables 3 to 8. (A) tert-butyl methacrylate, which is a negative monofunctional light-curing monomer for skin sensitization (B) glycerol dimethacrylate, which is a negative polyfunctional light-curing monomer for skin sensitization (C) tricyclodecane dimethanol dimethacrylate, which is a light-curing monomer negative polyfunctional for skin sensitization (D) negative photoradical polymerization initiator for skin sensitization (E) polymer component
    [000134] In tables 3 to 8, the details of (A), (B), (C), (D1) to (D2), (E1) to (E5), and carbon black are as described below. The numerical value in the parenthesis at the end is the SI value in the LLNA test in (1) mentioned above, "negative" or "not" means that the compound is rated as "mild or mild skin sensitization" in the literature "Contact Dermatitis 1982(8)223-225" in (2) mentioned above, or the compound is assessed as "negative to skin sensitization" or "no skin sensitization" in MSDS (Material Safety Data Sheet) in ( 3) mentioned above. (A): t-butyl methacrylate, “Acryester TB” manufactured by MITSUBISHI RAYON CO., LTD. (negative), evaluated with the literature (test method: maximization method, viscosity at 25°C: 0.9 mPa.s). Viscosity was measured by means of a cone-plate rotor viscometer, VISCOMETER TV-22, manufactured by Toki Sangyo Co., Ltd., using a corn rotor (1°34' x R24) at the rotational speed of 50 rpm , with constant temperature circulating water temperature adjustment to 25°C.(B): glycerol dimethacrylate, “701” manufactured by Shin-Nakamura Chemical Co., Ltd. (SI value: 1.2)(C) : tricyclodecane dimethanol dimethacrylate, "DCP" manufactured by Shin-Nakamura Chemical Co., Ltd. (SI value: 1.3)- Light-curing initiator -(D1): 1-hydroxy-cyclohexylphenylketone, "Irgacure184” manufactured by BASF (no), evaluated with MSDS (test method: OECD test guideline 406)(D2): 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)butan- 1-one, "Irgacure 379" manufactured by BASF (no), evaluated with MSDS (test method: OECD test guideline 406) - Polymer Component -(E1): polystyrene, weight average molecular weight: 4400, "VS1063 ” manufactured by SEIKO PMC CORPORATION (va Acid lor: 0 mg KOH/g, in the hydrophilic functional group)(E2): ethyl polymethacrylate, weight average molecular weight: 300,000 to 450,000, "E5001" manufactured by Negami Chemical Industrial Co., Ltd. (acid value: 0 mg KOH/g, in the hydrophilic functional group)(E3): styrene-butyl methacrylate copolymer, weight average molecular weight: 200,000 to 300,000, "M6701" manufactured by Negami Chemical Industrial Co., Ltd. (acid value: 0 mg of KOH/g, in the hydrophilic functional group)(E4): styrene - acrylic acid - α- methylstyrene copolymer, weight average molecular weight: 4,600, "JONCRYL 586" manufactured by BASF (acid value: 108 mg of KOH /g, presence of hydrophilic functional groups) (E5): ethyl polymethacrylate, weight average molecular weight: 700,000 to 1,300,000, "E5000" manufactured by NegamiChemical Industrial Co., Ltd. (acid value: 0 mg KOH/g, no. hydrophilic functional group) - Carbon black -
    [000135] An amount of carbon black was represented as an amount of the same in a state where an S32000 polymer dispersing agent manufactured by Lubrizol Japan Co. was blended with #10 carbon black manufactured by Mitsubishi Chemical Corporation at a ratio in mass (carbon black:dispersing agent) of 3:1. <Adhesion Test>
    [000136] As for the test for adhesion between a cured coating film of each prepared light curing composition, and a base material, a commercially available polypropylene film (P2161, manufactured by TOYOBO CO., LTD., thickness: 60 µm ) and a commercially available polyethylene terephthalate film (E5100, manufactured by TOYOBO CO., LTD., thickness: 100 µm), which were common film materials widely used as wrapping materials or industrial materials, and were poorly adhesive materials, were used as a base material.
    [000137] The light-curing composition was applied to a corona treated surface of each of these films by bar coating or inkjet printing, followed by irradiation of the applied composition with UV rays from the UVA region at 3 W/cm2, and at 200 mJ/cm2, by means of an LH6 UV radiation device available from Noblelight Fusion once, or a few times to cure the coating film. The resulting solid coating film was subjected to adhesion evaluation by a cross-cut method specified in JIS-K-5600-5-6 before and after immersing the coating film in 40°C hot water for 24 hours. Note that, in the JIS standard, adhesion to the base material is collectively referred to as a term “adhesiveness,” but these terms (adhesion and adhesiveness) are technically the same meanings.
    [000138] In the JIS standard, test results are classified into 6 stages, ie, “0,” “1,” “2,” “3,” “4,” and “5,” where “0” is a state in which no peeling is observed when a tape is peeled off after adhering the tape to the 25 square cuts (5 x 5) provided in the coating film, and "5" is a state in which significant peeling is observed, and "1" to "4" are intermediate states between "0" and "5." In this test, however, the squares remaining unpeeled, outside the 25 squares, were counted, and the adhesion was evaluated based on the following criteria, which was represented along with the number of remaining squares, for the purpose of performing relative evaluation plus need. In the evaluation process, any slight peeling on the intersecting part of the cuts, which tends to be more strongly influenced by the resistance in time when the knife was inserted, etc. was ignored. Note that after being immersed in hot water, the moisture attached with the test coating film was wiped off with a clean cloth, and then the coating film was provided for the adhesion test.- Evaluation Criteria -A: The number of squares remaining was 25 B: The number of squares remaining was 24 or less <Coating Film Production by Inkjet System or Bar Coating>
    [000139] Note that, the production of the coating film by an inkjet system was carried out as follows.
    [000140] The paint was sealed in an aluminum pouch as shown in FIG. 1 so as not to include any blisters, and the pouch was housed in a plastic ink cartridge such as that illustrated in FIG. 2. In a housing, which was designed to house the aforementioned ink cartridge, an ink flow channel was provided from the ink cartridge to the GEN 4 head manufactured by Ricoh Industry Company Ltd. A solid coating film was formed by ejecting ink as ink jets using the device mentioned above. Note that, the desired amount of ink droplets was adjusted to give the average thickness similar to that of the coating film produced by the bar coating.
    [000141] In the bar coating process, the average thickness of the coating film was adjusted by selecting a commercially available wire winding bar.
    [000142] Note that, the average thickness of the coating film in both the inkjet system and the bar coating means a thickness of the film in a non-dry state before UV radiation.










    <Pencil Hardness Test>
    [000143] The pencil hardness test performed in Examples 1 and 4 as an evaluation of coating film strength was performed using a polyethylene terephthalate film (A4300, manufactured by TOYOBO CO., LTD., thickness: 188 µm) as a base material, and measured 1 day after formation of a cured coating film according to JIS K5600-5-4 scratch hardness (pencil method), for the purpose of ensuring the accuracy of the evaluation regardless of insufficient adhesion.
    [000144] As for the pencil, a set of wooden drawing pencils (manufactured by Mitsubishi Pencil Co., Ltd.) of the following hardness was used. 6B, 5B, 4B, 3B, 2B, B, HB, F, H , 2H, 3H, 4H, 5H, 6H

    [000145] It was confirmed from the results of Tables 3 to 9 that, as seen from the comparison between Comparative Example 1 and Example 1, the adhesion was deteriorated after being immersed in hot water when the polymer component containing groups hydrophilic functional groups, and in the case of the polymer component free of a hydrophilic functional group, adhesion can be maintained even after immersion in hot water, appropriately adjusting the conditions to produce the coating film, eg, the dose of UV radiation, and the average thickness of the coating film before curing, and the water resistance of the coating film can be improved.
    [000146] Furthermore, it was confirmed from the comparison between Comparative Example 2 and Example 2, and the comparison between Examples 1, 2, and 5 that as long as the mass ratio (A/B) of the quantity ( A) from the polymer free of a hydrophilic functional group to the amount (B) of the polyfunctional monomers was greater than 0.80 but 3 or less, adhesion can be maintained even after immersing in hot water, properly adjusting the conditions to produce the coating film, for example, the dose of UV radiation, and the average thickness of the coating film before curing, and the water resistance of the coating film can be improved. In addition, it was confirmed that the water resistance of the coating film produced under the wider production conditions could be improved as the mass ratio (A/B) was higher. Especially, in Example 5, it was confirmed that the water resistance of the coating film can be improved over the wide range of conditions such that the average thickness of the coating film before curing was 6 µm to 20 µm, and the large range of conditions, such that the UV radiation dose was 1000 mJ/cm2 to 2000 mJ/cm2. Although not represented in the tables, a coating film having a thickness of 20 µm before curing was formed by spray coating in Example 5, and similar results were obtained.
    [000147] As can be seen from the comparison between Example 1 and Example 3, furthermore, it has been confirmed that the water resistance of the coating film can be similarly suitable, even though a type of light curing initiator for use is different.
    [000148] As can be seen from the comparison between Example 1 and Example 4, it was confirmed that the water resistance of the coating film was similarly improved even when tricyclodecane dimethanol dimethacrylate was added additionally as a polyfunctional monomer, in addition to glycerol dimethacrylate. The coating film strength was HB pencil hardness in Example 1, but the coating film strength was F pencil hardness in Example 4. It was confirmed that the coating film strength was improved when tricyclodecane dimethanol dimethacrylate was added further.
    [000149] As seen from the comparison between Examples 5, 6, and 7, furthermore, it was confirmed that the water resistance of the coating film can be similarly improved with various types of polymers, as long as they are free polymers. a hydrophilic functional group. Furthermore, it was confirmed that the water resistance of the coating film could be similarly improved even when various types of polymers were used in combination as in Example 9. When polymer having a large weight average molecular weight was used as in Example 10, excellent results were obtained, but it was as necessary to heat until dissolved, where excellent solubility was obtained at room temperature in all other examples. Therefore, the weight average molecular weight of the polymer component for use is preferably not excessively large, in view of the energy savings and simplicity of the process. A type of a polymer for use, or combination of polymers, is appropriately selected under consideration of solubility at the time of production of the photopolymerizable composition, and various other properties required for the coating film.
    [000150] Although they are not represented in the Tables, it was confirmed that the water resistance of the coating film was similarly improved in each of these Examples, even when polycarbonate (“Panlite 1151N” manufactured by TEIJIN LIMITED), ABS (“ABS -1100-N1-G" manufactured by Sekisui Seikei, Ltd.), polyvinyl chloride ("HP-319" manufactured by Sekisui Seikei, Ltd.), polystyrene ("PS-2000-W1-G" manufactured by Sekisui Seikei, Ltd.), an acrylic plate (“SUMIPEX AS” manufactured by SUMIKA ACRIL CO., LTD.), glass (general sliding glass for physical and chemical experiments), aluminum (common aluminum plate), or stainless steel (plate stainless steel) was used as the base material other than polypropylene and polyethylene terephthalate.
    [000151] As seen from Example 8, it was confirmed that the water resistance of the coating film could be improved even when carbon black was contained as a colorant. Although they are not represented in the table, the same results were obtained when each of a yellow pigment “Toner Yellow HG” manufactured by Clariant Japan KK, a magenta pigment “CINQUASIA MAGENTA L 4540” manufactured by BASF, and a cyan pigment “ Lionogen Blue LX-8091” manufactured by TOKYOCOLOR CO., LTD. was mixed instead of carbon black under the same conditions as those for carbon black.
    [000152] Note that, it was confirmed in all Examples that the coating film after light irradiation was desirably cured without sticking, as it was touched with fingers. (Examples 11 to 20 and Comparative Examples 3 to 4)
    [000153] Each of the photopolymerizable compositions was prepared by mixing the materials in the amounts (values were based on parts by mass) represented in each column of the respective Examples and Comparative Examples in the following tables 10 to 15.
    [000154] The components represented in the following tables 10 to 15 are as follows. (A) component: n-pentyl methacrylate (trade name: "n-AmilMethacrylate" manufactured by Toyo Science Corp. (negative), reviewed with the literature ( test method: maximization method, viscosity at 25°C: 1 mPa.s)(B) to (E) components: same as above Carbon black: same as above










    [000155] Embodiments of the present invention are, for example, as in the sequence:<1> A photopolymerizable composition, containing: a monofunctional monomer having a viscosity of 5 mPa.s or less at 25 °C; one or more polyfunctional monomers including glycerol dimethacrylate; and a polymer free of a hydrophilic functional group, wherein a mass ratio (A/B) of an amount (A) of the polymer free of a hydrophilic functional group to an amount (B) of the polyfunctional monomers is greater than 0.80 but 3 or less.< 2> The light-curing composition according to <1>, wherein the mass ratio (A/B) is 1.3 to 2.< 3> The light-curing composition according to <1> or < 2>, wherein the polyfunctional monomers additionally contain tricyclodecane dimethanol dimethacrylate.< 4> The photopolymerizable composition according to any one of <1> to <3>, wherein the polymer free of a hydrophilic functional group has a weight average molecular weight from 4400 to 450,000.< 5> The photopolymerizable composition according to any one of <1> to <4>, wherein the polymer free of a hydrophilic functional group has an acid value of 1 mg KOH/g or less. < 6> The light-curing composition according to any one of <1> to <5>, additionally containing a colorant.< 7> A co A photopolymerizable composition according to any one of <1> to <6>, wherein an amount of the monofunctional monomer having a viscosity of 5 mPa.s or less at 25°C is from 5 parts by mass to 30 parts by mass with to 1 part by mass of an amount of glycerol dimethacrylate.< 8> A light-curing paint, containing: the light-curing composition according to any one of <1> to <7>. < 9> The light-curing ink according to <8>, wherein the light-curing ink is for use in inkjet printing.< 10> A composition container, containing: a container; and the photopolymerizable inkjet composition according to any one of <1> to <7>, housed in the container.< 11> A method for forming a cured product or image, comprising: applying the photopolymerizable composition according to any one of <1> to <7>, or the light-curing ink according to <8> or <9>; radiating the light-curing composition, or the light-curing ink applied to the base material with active energy rays to cure the light-curing composition, or the light-curing ink.< 12> The method according to <11>, wherein the image or product is cured before of cure has an average thickness of 5 μm to 20 μm.< 13> The method according to <11> or <12>, wherein the irradiation is to irradiate the light curing composition, or the light curing ink applied to the base material with rays of active energy a radiation dose of which is 1,000 mJ/cm2 to 2,000 mJ/cm2 to cure the light-curing composition, or the light-curing paint.< 14> The method according to any one of <11> to <13>, wherein the base material is paper, plastic, metal, ceramic, glass, a material composed of any of the above materials, or any combination of the above materials. <15> A cured product or image forming device, containing: an application unit configured to apply the light-cured composition according to any one of <1> to <7>, or the light-cured ink according to <8> or <9> for a base material; and a curing unit configured to irradiate the photopolymerizable composition, or the photopolymerizable ink applied to the base material with active energy rays to cure the photopolymerizable composition, or the photopolymerizable ink.< 16> The cured product or image forming device accordingly with <15>, where a pre-cure image or a cured product composed of the light-curing composition, the light-curing ink, or the light-curing inkjet ink has an average thickness of 5 µm to 20 µm.< 17> A cured product or image, which is obtained by a method comprising: applying the light-curing composition according to any one of <1> to <7>, or the light-curing ink according to <8> or <9> to a base material; cure the light-curing composition, or the light-curing ink.Reference Signal List200: ink cartridge241: ink pouch242: ink inlet243: ink out244: cartridge casing
    权利要求:
    Claims (17)
    [0001]
    1. A polymerizable composition characterized by comprising: a monofunctional monomer having a viscosity of 5 mPa.s or less at 25°C; one or more polyfunctional monomers including glycerol dimethacrylate; and a polymer free of a hydrophilic functional group having an acid value of 1 mg KOH/g or less, where a mass ratio (A/B) of an amount (A) of the polymer free of a hydrophilic functional group to an amount (B) of the polyfunctional monomers is greater than 0.80 but 3 or less.
    [0002]
    2. Photopolymerizable composition characterized by comprising: a monofunctional monomer having a viscosity of 5 mPa.s or less at 25°C; one or more polyfunctional monomers including glycerol dimethacrylate; and a polymer free of a hydrophilic functional group, in which a mass ratio (A/B) of an amount (A) of the polymer free of a hydrophilic functional group to an amount (B) of the polyfunctional monomers is greater than 0.80 but 3 or less.
    [0003]
    3. Light curing composition according to claim 2, characterized in that the mass ratio (A/B) is from 1.3 to 2.
    [0004]
    4. Light curing composition according to claim 2 or 3, characterized in that the polyfunctional monomers additionally comprise tricyclodecane dimethanol dimethacrylate.
    [0005]
    5. Light curing composition, according to any one of claims 2 to 4, characterized in that the polymer free of a hydrophilic functional group has a weight average molecular weight from 4,400 to 450,000.
    [0006]
    6. Photopolymerizable composition according to any one of claims 2 to 5, characterized in that it additionally comprises a colorant.
    [0007]
    7. Light curing composition according to any one of claims 2 to 6, characterized in that an amount of the monofunctional monomer having a viscosity of 5 mPa.s or less at 25°C is 5 parts by mass to 30 parts in mass with respect to 1 part by mass of an amount of glycerol dimethacrylate.
    [0008]
    8. Photopolymerizable paint characterized in that it comprises: the polymerizable composition as defined in claim 1, or the photopolymerizable composition as defined in any one of claims 2 to 7.
    [0009]
    9. Light-curing ink according to claim 8, characterized in that the light-curing ink is for use in inkjet printing.
    [0010]
    10. Composition container characterized by comprising: a container; and the polymerizable composition as defined in claim 1, or the photopolymerizable composition as defined in any one of claims 2 to 7, housed in the container.
    [0011]
    A method for forming an image or a cured product comprising: applying the polymerizable composition as defined in claim 1, the photopolymerizable composition as defined in any one of claims 2 to 7, or the photopolymerizable paint as defined in claim 8 or 9 , on a base material; radiating the polymerizable composition, the photopolymerizable composition, or the photopolymerizable ink applied to the base material with active energy rays to cure the polymerizable composition, the photopolymerizable composition, or the photopolymerizable ink.
    [0012]
    12. Method according to claim 11, characterized in that the cured product or the image before curing has an average thickness of 5 μm to 20 μm.
    [0013]
    13. Method according to claim 11 or 12, characterized in that the irradiation is irradiation of the polymerizable composition, light-curing composition, or light-curing ink applied to the base material with active energy rays whose radiation dose is 1,000 mJ/cm2 to 2000 mJ/cm2 to cure the polymerizable composition, the light-curing composition, or the light-curing ink.
    [0014]
    14. Method according to any one of claims 11 to 13, characterized in that the base material is paper, plastic, metal, ceramic, glass, a material composed of any of the above materials, or any combination of the materials above.
    [0015]
    A cured product or image forming device characterized in that it comprises: an application unit configured to apply the polymerizable composition as defined in claim 1, the light-curing composition as defined in any one of claims 2 to 7, or the light-curing ink as defined in claim 8 or 9 for a base material; and a curing unit configured to irradiate the polymerizable composition, light-curing composition, or light-curing ink applied to the base material with active energy rays to cure the polymerizable composition, light-curing composition, or light-curing ink.
    [0016]
    16. A cured product or image forming device according to claim 15, characterized in that an image before curing or a cured product composed of the polymerizable composition, light-curing composition, or light-curing ink has an average thickness of 5 µm to 20 µm.
    [0017]
    A cured product or image characterized in that it is obtained by a method comprising: applying the polymerizable composition as defined in claim 1, or the light-curing composition as defined in any one of claims 2 to 7, or the light-curing paint as defined in claim 8 or 9 on a base material; curing the polymerizable composition, the light-curing composition, or the light-curing ink.
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    同族专利:
    公开号 | 公开日
    CA2950700A1|2015-12-10|
    EP3152240A4|2017-06-14|
    RU2682964C2|2019-03-25|
    CN106414513B|2018-11-30|
    RU2016147692A3|2018-07-09|
    US20170073445A1|2017-03-16|
    EP3152240A1|2017-04-12|
    JP2016011416A|2016-01-21|
    WO2015186340A1|2015-12-10|
    JP6519320B2|2019-05-29|
    EP3152240B1|2020-04-01|
    BR112016028322A2|2017-08-22|
    CA2950700C|2018-08-21|
    RU2016147692A|2018-07-09|
    US10829575B2|2020-11-10|
    CN106414513A|2017-02-15|
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    法律状态:
    2020-03-31| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-06-08| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-07-27| B09X| Republication of the decision to grant [chapter 9.1.3 patent gazette]|
    2021-08-03| 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 01/06/2015, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2014117770|2014-06-06|
    JP2014-117770|2014-06-06|
    PCT/JP2015/002764|WO2015186340A1|2014-06-06|2015-06-01|Photopolymerizable composition, photopolymerizable ink, composition container, image or cured product forming method, image or cured product forming device, and image or cured product|
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