Coating agent for cyclic olefin resin, hardened product, and laminate

Abstract

The present invention provides a coating agent for a cyclic olefin resin, a hardened product thereof, and a laminate, in which the adhesion between the hardened product of the coating agent and the cyclic olefin resin becomes good. The present disclosure provides a coating agent for a cyclic olefin resin, the coating agent for a cyclic olefin resin comprising: a poly(meth)acrylate having three or more (meth)acryloyl groups, a (meth)acryloyl group-containing silica particle, and an oxime ester structure-containing photopolymerization initiator.

Description

TECHNICAL FIELD

[0001] The present disclosure relates to a coating agent for a cyclic olefin resin, a hardened product, and a laminate. BACKGROUND

[0002] At present, a polarizing plate used in a liquid crystal display device is a polarizing sheet in which iodine or the like is adsorbed and extended to be oriented on both surfaces of a triacetyl cellulose film (TAC film) serving as a protective film. A transparent light-hardening type resin composition is applied to the surface of the TAC film, and is hardened to form a high-hardness coating film (hard coat layer) to protect it from damage and the like. As a material for forming such a hardened coating film, a reactive energy ray-hardening type resin composition using a multifunctional (meth) acrylate or the like is known (Patent Document 1).

[0003] In recent years, due to the large-scale or high-quality of liquid crystal devices and the expansion of mobile uses, it is required to be able to withstand more severe use environments (for example, high temperature, high humidity conditions, and the like). As a result, the TAC film has a very clear limitation in terms of characteristics. Among them, it is considered promising to replace the TAC film with a cyclic olefin resin-based film. The cyclic olefin resin-based film is excellent in transparency, low birefringence, dimensional stability, and the like, and has the necessary properties as an optical film. Furthermore, the cyclic olefin resin-based film has low moisture permeability, which is a major characteristic, and is a major reason for replacing the TAC film in this regard. However, the cyclic olefin resin-based film has a problem that it is difficult to form a hard coat layer having high adhesion on the surface of the film.

[0004] In the past, the adhesion of the substrate to the hard coat layer has been improved by performing a primer coating or an electrical treatment (corona discharge treatment, atmospheric pressure plasma treatment) on the cyclic olefin resin-based film.

[0005] [Related Art Documents]

[0006] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Laid-Open No. 2009-286924

[0008] [Patent Document 2] Japanese Patent Laid-Open No. 2014-189566 SUMMARY

[0009] [Problems to be Solved by the Invention]

[0010] However, in the method, a treatment process for improving adhesion to the substrate is required when producing the coated film, and there is a problem that it leads to high cost. In addition, since the electrical treatment causes a change in the treated surface over time, it is also limited that the hard coat layer must be applied promptly after the treatment. In addition, the surface free energy of the cyclic olefin resin is low. Therefore, there is a problem that the application of the coating agent is difficult.

[0011] The problem to be solved by the present application is to provide a coating agent for a cyclic olefin resin, in which the adhesion between the hardened product of the coating agent and the cyclic olefin resin becomes good.

[0012] [Means of solving the problem]

[0013] As a result of diligent studies by the present inventors, it has been found that the above problem can be solved by using a specific coating agent.

[0014] According to the present disclosure, the following items are provided.

[0015] (Item 1)

[0016] A coating agent for a cyclic olefin resin, the coating agent for a cyclic olefin resin comprising:

[0017] a poly(meth)acrylate having three or more (meth)acryloyl groups,

[0018] a (meth)acryloyl group-containing silica particle, and

[0019] a photopolymerization initiator containing an oxime ester structure.

[0020] (Item 2)

[0021] The coating agent for a cyclic olefin resin according to the item, further comprising no photopolymerization initiator containing an oxime ester structure.

[0022] (Item 3)

[0023] A hardened product of the coating agent for a cyclic olefin resin according to any one of the items.

[0024] (Item 4)

[0025] A laminate comprising the hardened product according to the item.

[0026] In the present disclosure, the one or more features can be further combined to provide, in addition to the explicit combinations.

[0027] [Effects of the invention]

[0028] By using the coating agent for a cyclic olefin resin of the present disclosure, a laminate in which the adhesion between the hardened product layer of the coating agent and the cyclic olefin resin is excellent can be manufactured. In addition, the coating agent for a cyclic olefin resin of the present disclosure is excellent in coatability for a cyclic olefin resin.

[0029] Specific Embodiments

[0030] In the entire present disclosure, the range of each physical property value, content, and the like can be suitably set (for example, selected from the values of the upper limit and the lower limit described in each item below). Specifically, with respect to the numerical value α, in the case where, for example, A3, A2, A1 (set as A3 > A2 > A1) and the like are exemplified as the upper limit and the lower limit of the numerical value α, the range of the numerical value α can be exemplified as A3 or less, A2 or less, less than A3, less than A2, A1 or more, A2 or more, greater than A1, greater than A2, A1 to A2 (A1 or more and A2 or less), A1 to A3, A2 to A3, A1 or more and less than A3, A1 or more and less than A2, A2 or more and less than A3, greater than A1 and less than A3, greater than A1 and less than A2, greater than A2 and less than A3, greater than A1 and A3 or less, greater than A1 and A2 or less, greater than A2 and A3 or less, and the like.

[0031] [Coating agent for cyclic olefin resin: also referred to as coating agent]

[0032] The present disclosure provides a coating agent for cyclic olefin resin, the coating agent for cyclic olefin resin comprising: a poly(meth)acrylate having three or more (meth)acryloyl groups, a (meth)acryloyl group-containing silica particle, and an oxime ester structure-containing photopolymerization initiator.

[0033] In the present disclosure, "(meth)acrylic acid" means "at least one selected from the group consisting of acrylic acid and methacrylic acid". Similarly, "(meth)acrylate" means "at least one selected from the group consisting of acrylate and methacrylate". In addition, "(meth)acryloyl group" means "at least one selected from the group consisting of acryloyl group and methacryloyl group".

[0034] [Poly(meth)acrylate having three or more (meth)acryloyl groups]

[0035] The poly(meth)acrylate having three or more (meth)acryloyl groups can be used alone or two or more.

[0036] The poly(meth)acrylate having three or more (meth)acryloyl groups can be exemplified by poly(meth)acrylic acid oxyalkylene ester, urethane poly(meth)acrylate, polymeric (meth)acrylate, and the like.

[0037] [Poly(meth)acrylic acid oxyalkylene ester having three or more (meth)acryloyl groups]

[0038] The poly(meth)acrylic acid oxyalkylene ester having three or more (meth)acryloyl groups can be exemplified by (poly) pentaerythritol poly(meth)acrylate, (poly)trimethylolpropane poly(meth)acrylate, (poly)glycerol poly(meth)acrylate, and the like.

[0039] In the present disclosure, poly(meth)allyloxyalkylene ester is a compound having a plurality of a meth)allyloxy group, and refers to a compound in which the moiety after removing the (meth)allyloxy group from the compound is constituted by only bonding oxygen atoms, carbon atoms, and hydrogen atoms using single bonds.

[0040] (poly)trimethylolpropane poly(meth)acrylate having three or more (meth)acryloyl groups

[0041] (poly)trimethylolpropane poly(meth)acrylate having three or more (meth)acryloyl groups is a compound represented by the following structural formula.

[0042] [Chemical Formula 1]

[0043]

[0044] (In the formula, m is an integer of 0 or more, R b1 ~R b6 are each independently a hydrogen atom or a (meth)acryloyl group, R b1 ~R b6 of which at least three are (meth)acryloyl groups. Further, R b3 and R b5 may be different groups for each structural unit.)

[0045] Further, the "may be different groups for each structural unit" means, for example, in the above structural formula, when m is 2,

[0046] [Chemical Formula 2]

[0047]

[0048] R b3A and R b3B may be different groups, R b5A and R b5B may be different groups (the same applies hereinafter).

[0049] The (poly)trimethylolpropane poly(meth)acrylate having three or more (meth)acryloyl groups can be exemplified by trimethylolpropane tri(meth)acrylate, trimethylolpropane tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol tri(meth)acrylate, tripentaerythritol tetra(meth)acrylate, tripentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, and the like.

[0050] (poly)trimethylolpropane poly(meth)acrylate having three or more (meth)acryloyl groups

[0051] The (poly)trimethylolpropane poly(meth)acrylate having three or more (meth)acryloyl groups is a compound represented by the following structural formula.

[0052] [Chemical Formula 3]

[0053]

[0054] (In the formula, p is an integer of 0 or more, R b7 ~R b10 is a hydrogen atom or a (meth)acryloyl group, R b7 ~R b10 of which at least three are (meth)acryloyl groups. Further, R b9 may be different for each structural unit.)

[0055] The (poly)trimethylolpropane poly(meth)acrylate can exemplify trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, and the like.

[0056] (poly)glycerol poly(meth)acrylate having three or more (meth)acryloyl groups

[0057] The (poly)glycerol poly(meth)acrylate having three or more (meth)acryloyl groups is a compound represented by the following structural formula.

[0058] [Chemical Formula 4]

[0059]

[0060] (In the formula, q is an integer of 0 or more, R b11 ~R b13 is a hydrogen atom or a (meth)acryloyl group, R b11 ~R b13 of which at least three are (meth)acryloyl groups. Further, R b12 may be different for each structural unit.)

[0061] The (poly)glycerol poly(meth)acrylate having three or more (meth)acryloyl groups can exemplify glycerol tri(meth)acrylate, diglycerol tri(meth)acrylate, diglycerol tetra(meth)acrylate, and the like.

[0062] The poly(meth)acrylic acid oxyalkylene ester can be modified with an alkylene oxide or an epoxy group.

[0063] Oxyalkylene poly(alkylene oxide-modified (meth)acrylate) is a compound in which the oxy (meth) acryloyl group of the poly (meth) acrylate is substituted with an oxyalkylene group

[0064] [Chemical Formula 5]

[0065]

[0066] (In the formula, q is an integer of 1 to 16, R 1 '~R 2 'are each independently a hydrogen atom or an alkyl group, R 1 'can be different groups for each unit.)

[0067] a compound thus obtained.

[0068] Oxyalkylene poly(alkylene oxide-modified (meth)acrylate) is a compound in which the oxy (meth) acryloyl group of the poly (meth) acrylate is substituted with an oxyalkylene group

[0069] [Chemical Formula 6]

[0070]

[0071] (In the formula, R 3' are each independently a hydrogen atom or an alkyl group)

[0072] a compound thus obtained.

[0073] <urethane poly(meth)acrylate having three or more (meth)acryloyl groups>

[0074] The urethane poly(meth)acrylate can exemplify a group of reactants including a hydroxyl group-containing poly(meth)acrylate having three or more (meth)acryloyl groups and a polyisocyanate, and the like.

[0075] The hydroxyl group-containing poly(meth)acrylate having three or more (meth)acryloyl groups, which is a raw material of the urethane poly(meth)acrylate, can exemplify the substance, and the like.

[0076] The polyisocyanate can exemplify a compound described later, and the like.

[0077] (polymer poly(meth)acrylate)

[0078] In the present disclosure, the so-called "polymer poly(meth)acrylate" refers to a polymer having two or more (meth)acryloyl groups.

[0079] The polymer poly(meth)acrylate can be manufactured by a publicly known method. The manufacturing method of the polymer poly(meth)acrylate exemplifies a method of reacting an epoxy group-containing (meth)acrylic copolymer with an α, β-unsaturated carboxylic acid, and the like.

[0080] The upper limit and lower limit of the content of the structural unit derived from the (meth)acrylate having an epoxy group in 100 mol% of the total structural units of the (meth)acrylate polymer having an epoxy group can be exemplified by 100 mol%, 95 mol%, 90 mol%, 85 mol%, 80 mol%, 75 mol%, 70 mol%, 65 mol%, 60 mol%, 55 mol%, 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 7 mol%, and the like. In one embodiment, the content is preferably 7 mol% to 100 mol%.

[0081] The upper limit and lower limit of the content of the structural unit derived from the (meth)acrylate having an epoxy group in 100 mass% of the total structural units of the (meth)acrylate polymer having an epoxy group can be exemplified by 100 mass%, 95 mass%, 90 mass%, 85 mass%, 80 mass%, 75 mass%, 70 mass%, 65 mass%, 62 mass%, 60 mass%, 55 mass%, 50 mass%, 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 20 mass%, 15 mass%, 10 mass%, and the like. In one embodiment, the content is preferably 10 mass% to 100 mass%.

[0082] The upper limit and lower limit of the content of the structural unit derived from the alkyl (meth)acrylate not having a hydroxyl group in 100 mol% of the total structural units of the (meth)acrylate polymer having an epoxy group can be exemplified by 93 mol%, 90 mol%, 85 mol%, 80 mol%, 75 mol%, 70 mol%, 65 mol%, 60 mol%, 55 mol%, 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, 5 mol%, 0 mol%, and the like. In one embodiment, the content is preferably 0 mol% to 93 mol%.

[0083] The upper limit and lower limit of the content of the structural unit derived from the alkyl (meth)acrylate not having a hydroxyl group in 100 mass% of the total structural units of the (meth)acrylate polymer having an epoxy group can be exemplified by 90 mass%, 85 mass%, 80 mass%, 75 mass%, 70 mass%, 65 mass%, 60 mass%, 55 mass%, 50 mass%, 45 mass%, 40 mass%, 38 mass%, 35 mass%, 30 mass%, 25 mass%, 20 mass%, 15 mass%, 10 mass%, 5 mass%, 0 mass%, and the like. In one embodiment, the content is preferably 0 mass% to 90 mass%.

[0084] The upper limit and the lower limit of the amount of α,β-unsaturated carboxylic acid reacted per 100 mol% of the structural unit derived from the epoxy group-containing (meth)acrylate can be exemplified by 100 mol%, 95 mol%, 90 mol%, 85 mol%, 80 mol%, 75 mol%, 70 mol%, 65 mol%, 60 mol%, 55 mol%, 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 20 mol%, 15 mol%, 10 mol%, and the like. In one embodiment, the amount is preferably 10 mol% to 100 mol%.

[0085] The upper limit and the lower limit of the amount of α,β-unsaturated carboxylic acid reacted per 100 mass% of the structural unit derived from the epoxy group-containing (meth)acrylate can be exemplified by 50 mass%, 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 20 mass%, 15 mass%, 10 mass%, 5 mass%, and the like. In one embodiment, the amount is preferably 5 mass% to 50 mass%.

[0086] The epoxy group-containing (meth)acrylic polymer can be produced using a publicly known radical polymerization method.

[0087] In one embodiment, the active energy ray-curable resin compound contained in the coating agent not containing an oxime is preferably a poly(oxyalkylene) (meth)acrylate.

[0088] The upper limit and the lower limit of the content of the poly(meth)acrylate having three or more (meth)acryloyl groups in 100 mass% of the nonvolatile component of the coating agent can be exemplified by 90 mass%, 89 mass%, 85 mass%, 80 mass%, 75 mass%, 74 mass%, 71 mass%, 70 mass%, 69 mass%, 67 mass%, 65 mass%, 63 mass%, 61 mass%, 60 mass%, 59 mass%, 55 mass%, 50 mass%, 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 20 mass%, 15 mass%, 10 mass%, and the like. In one embodiment, the content is preferably 10 mass% to 90 mass%, more preferably 25 mass% to 90 mass%.

[0089] In the present disclosure, the "nonvolatile component" means the total mass of components other than the organic solvent and water. In one embodiment, the "nonvolatile component of the object A" means the total mass of the components remaining when 1 g of the object A is heated at 130°C until the mass becomes constant.

[0090] < (Meth)acryloyl group-containing silica particle>

[0091] The (meth)acryloyl group-containing silica particle can be used alone or two or more kinds thereof can be used.

[0092] The (meth)acryloyl group-containing silica particle is a reaction product of a silica particle and a (meth)acryloyl group-containing compound.

[0093] The silica particle

[0094] The silica particle can be used alone or two or more kinds can be used.

[0095] The upper limit and the lower limit of the particle diameter of the silica particle can be exemplified by 100 nm, 95 nm, 90 nm, 85 nm, 80 nm, 75 nm, 70 nm, 65 nm, 60 nm, 55 nm, 50 nm, 45 nm, 40 nm, 35 nm, 30 nm, 25 nm, 20 nm, 15 nm, 10 nm, 5 nm, and the like. In one embodiment, the particle diameter of the silica particle is preferably 5 nm to 100 nm.

[0096] The shape of the silica particle can be exemplified by a spherical shape, a hollow shape, a solid shape, a porous shape, a rod shape, a plate shape, a fiber shape, an amorphous shape, and the like. In one embodiment, the shape of the silica particle is preferably a spherical shape. In addition, in one embodiment, the silica particle is preferably a solid silica particle.

[0097] In one embodiment, the silica particle is preferably in the form of a powder or a solvent-dispersed sol.

[0098] In the case where the silica particle is a solvent-dispersed sol, the dispersion solvent is preferably an organic solvent from the viewpoint of compatibility with other components and dispersibility.

[0099] The organic solvent can be used alone or two or more kinds can be used.

[0100] The organic solvent can be exemplified by a ketone solvent, an aromatic solvent, an alcohol solvent, a glycol solvent, a glycol ether solvent, an ester solvent, a petroleum-based solvent, a halogenated alkane solvent, an amide solvent, and the like.

[0101] The ketone solvent can be exemplified by methyl ethyl ketone, acetylacetone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and the like.

[0102] The aromatic solvent can be exemplified by toluene, xylene, and the like.

[0103] The alcohol solvent can be exemplified by methanol, ethanol, n-propanol, isopropanol, butanol, and the like.

[0104] The glycol solvent can be exemplified by ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polyethylene glycol, polypropylene glycol, and the like.

[0105] The glycol ether solvent can be exemplified by ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-i-propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-i-butyl ether, and the like.

[0106] The ester solvent can be exemplified by ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, and the like.

[0107] The petroleum solvent can be exemplified by aromatic hydrocarbon oil (SOLVESSO) #100 (manufactured by Exxon), aromatic hydrocarbon oil (SOLVESSO) #150 (manufactured by Exxon), and the like.

[0108] The halogenated alkane solvent can be exemplified by chloroform, and the like.

[0109] The amide solvent can be exemplified by dimethylformamide, and the like.

[0110] The commercially available product of the silica particle (colloidal silica) can be exemplified by the trade name: methanol silica sol, IPA-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL, MEK-ST-L, MIBK-T-L, and the like, manufactured by Nippon Shokubai Co., Ltd.

[0111] The commercially available product of the silica particle (powdered silica) can be exemplified by the trade name: AEROSIL 130, AEROSIL 300, AEROSIL 380, AEROSIL TT600, AEROSIL OX50, manufactured by Nippon AEROSIL Co., Ltd.; SHIELDEX H31, H32, H51, H52, H121, H122, manufactured by Asahi Glass Co., Ltd.; E220A, E220, manufactured by Nippon Silica Industrial Co., Ltd.; SYLYSIA 470, manufactured by Fuji Silysia Chemical Co., Ltd.; SG flack, manufactured by Nippon Sheet Glass Co., Ltd., and the like.

[0112] (The (Meth)acryloyl Group-Containing Compound)

[0113] The (meth)acryloyl group-containing compound can be used alone or two or more kinds thereof.

[0114] In one embodiment, the (meth)acryloyl group-containing compound contains a group represented by formula U.

[0115] <Formula U>

[0116] [Chemical Formula 7]

[0117]

[0118] (In the formula, X is NH, O, or S, and Y is O or S).

[0119] Specific groups represented by the above group [-X-C(=Y)-NH-] are [-0-C(=0)-NH-], [-0-C(=S)-NH-], [-S-C(=0)-NH-], [-NH-C(=0)-NH-], [-NH-C(=S)-NH-], and [-S-C(=S)-NH-]. These groups can be used alone or in combination of two or more. In one embodiment, from the viewpoint of heat stability, the (meth)acryl group-containing silica particle has [-0-C(=0)-NH-] and [-0-C(=S)-NH-] and / or [-S-C(=0)-NH-] is preferable.

[0120] It is considered that the above group [-X-C(=Y)-NH-] generates a moderate cohesive force through hydrogen bonding between molecules, and imparts excellent mechanical strength, adhesion to a substrate, heat resistance, and the like when a cured product is formed. Furthermore, the above is merely one statement, and the present application is not intended to be bound by the above statement.

[0121] The above (meth)acryl group-containing compound is preferably a silanol group-containing compound (also referred to as a silanol group-containing compound) or a compound that generates a silanol group by hydrolysis (also referred to as a silanol group-generating compound).

[0122] The silanol group-generating compound can be exemplified by a compound having an alkoxy group, an aryloxy group, an acetoxy group, an amino group, a halogen group, or the like on a silicon atom, and the like. In one embodiment, the silanol group-generating compound is preferably a compound containing an alkoxy group or an aryloxy group.

[0123] The silanol group or the silanol group-generating site of the silanol group-generating compound is a structural unit that is bonded to the silica particle through a condensation reaction or a condensation reaction that occurs after hydrolysis.

[0124] In one embodiment, the (meth)acryl group-containing compound is preferably a compound represented by Formula S.

[0125] <Formula S>

[0126] [Chemical Formula 8]

[0127]

[0128] (In the formula, R s1, R s2 are each independently a hydrogen atom, an alkyl group, or an aryl group, R s3 is an alkylene group or an arylene group, R s4 is a divalent organic group, R s5 is a (s" + 1)-valent organic group, Z is a (meth)acryloyl group, s' is 1, 2, or 3, and s" is an integer of 1 to 20

[0129] The alkyl group can exemplify a straight-chain alkyl group, a branched-chain alkyl group, a cyclic alkyl group, and the like.

[0130] The straight-chain alkyl group is represented by the general formula of -C n H 2n+1 (n is an integer of 1 or more). The straight-chain alkyl group can exemplify a methyl group, an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl group, a n-hexyl group, a n-heptyl group, a n-octyl group, a n-nonyl group, a n-decyl group, a undecyl group, a dodecyl group (lauryl group), a tridecyl group, a tetradecyl group (myristyl group), a pentadecyl group, a hexadecyl group (palmityl group), a heptadecyl group, a octadecyl group (stearyl group), a nonadecyl group, an eicosyl group, a heneicosyl group, a docosyl group, and the like.

[0131] The branched-chain alkyl group is a straight-chain alkyl group in which at least one hydrogen atom is substituted with an alkyl group. The branched-chain alkyl group can exemplify an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a diethylpentyl group, a trimethylbutyl group, a trimethylpentyl group, a trimethylhexyl group, a 2-ethylhexyl group, and the like.

[0132] The cyclic alkyl group can exemplify a monocyclic cyclic alkyl group, a cross-linked cyclic alkyl group, a fused cyclic alkyl group, and the like.

[0133] In the present disclosure, the monocyclic ring refers to a ring structure in which there is no bridging structure inside the ring formed by covalent bonds of carbon. In addition, the fused ring refers to a ring structure in which two or more monocyclic rings share two atoms (i.e., share only one side of each ring (fused) with each other). The cross-linked ring refers to a ring structure in which two or more monocyclic rings share three or more atoms.

[0134] The monocyclic cyclic alkyl group can exemplify a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclodecyl group, a 3,5,5-trimethylcyclohexyl group, and the like.

[0135] The cross-linked cyclic alkyl group can exemplify a tricyclodecyl group, an adamantyl group, a norbornyl group, and the like.

[0136] The fused cyclic alkyl group can exemplify a bis-cyclodecyl group, and the like.

[0137] The aryl group can exemplify a monocyclic aryl group, a fused aryl group, and the like. In addition, in the aryl group, one or more hydrogen atoms can be substituted with a straight-chain alkyl group or a branched-chain alkyl group.

[0138] The monocyclic aryl group can exemplify a phenyl group, a tolyl group, a 2,4,6-trimethylphenyl group (mesityl group), and the like.

[0139] The condensed ring aryl group can be exemplified by a naphthyl group, etc.

[0140] In formula S, R s1 O) s’ R s2 3-s’ The group represented by Si- can be exemplified by a trimethoxysilyl group, a triethoxysilyl group, a triphenoxysilyl group, a methyldimethoxysilyl group, a dimethylmethoxysilyl group, etc. Among these, a trimethoxysilyl group or a triethoxysilyl group is preferable.

[0141] The alkylene group can be exemplified by a linear alkylene group, a branched alkylene group, a cycloalkylene group, etc.

[0142] The linear alkylene group is represented by a general formula of -(CH2) n -(n is an integer of 1 or more). The linear alkylene group can be exemplified by a methylene group, an ethylene group, a n-propylene group, a n-butylene group, a n-pentylene group, a n-hexylene group, a n-heptylene group, a n-octylene group, a n-nonylene group, a n-decylene group, etc.

[0143] The branched alkylene group is a linear alkylene group in which at least one hydrogen atom is substituted with an alkyl group. The branched alkylene group can be exemplified by a diethylpentylene group, a trimethylbutylene group, a trimethylpentylene group, a trimethylhexylene group (trimethylhexamethylene group), etc.

[0144] The cycloalkylene group can be exemplified by a monocycloalkylene group, a crosslinked cycloalkylene group, a condensed cycloalkylene group, etc. Also, in the cycloalkylene group, one or more hydrogen atoms can be substituted with a linear alkyl group or a branched alkyl group.

[0145] The monocycloalkylene group can be exemplified by a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclodecylene group, a 3,5,5-trimethylcyclohexylene group, etc.

[0146] The crosslinked cycloalkylene group can be exemplified by a tricyclodecylene group, an adamantylene group, a norbornylene group, etc.

[0147] The condensed cycloalkylene group can be exemplified by a bicyclodecylene group, etc.

[0148] The arylene group can be exemplified by a monocyclic arylene group, a condensed arylene group, etc. Also, in the arylene group, one or more hydrogen atoms can be substituted with a linear alkyl group or a branched alkyl group.

[0149] The monocyclic arylene group can be exemplified by a phenylene group, a tolylene group, etc.

[0150] The condensed aryl group can be exemplified by a naphthylene group, etc.

[0151] In formula S, R s4 is a divalent organic group.

[0152] R s4The molecular weight of the compound is preferably 14 to 10,000, more preferably 76 to 500.

[0153] R s4 Examples include alkylene groups, arylene groups, and the like. s4 The compound can contain elements other than carbon and hydrogen atoms, and can contain a polyether bond, a polyester bond, a polyamide bond, a polycarbonate bond, and can also contain a group represented by formula U.

[0154] In formula S, R s5 is an organic group having a valence of (s" + 1), and is preferably selected from a saturated hydrocarbon group, an unsaturated hydrocarbon group, a linear, branched, or cyclic group.

[0155] R s5 Examples include

[0156] [Chemical Formula 9]

[0157]

[0158] (S"'is an integer of 0 to 2)

[0159] and the like.

[0160] In formula S, S" is an integer of 1 to 20, preferably 1 to 10, and more preferably 1 to 5.

[0161] The synthesis method of the (meth)acryl group-containing compound represented by formula S can be exemplified by the method described in Japanese Patent Application Laid-Open No. 9-100111, and the like. That is, as the synthesis method of the (meth)acryl group-containing compound, the following methods can be exemplified: (A) an addition reaction of a mercaptoalkoxysilane with a polyisocyanate and a (meth)acrylate containing an active hydrogen group, (B) a reaction of a compound having an alkoxysilyl group and an isocyanate group with a (meth)acrylate containing an active hydrogen group, (C) an addition reaction of a compound having a (meth)acryl group and an isocyanate group with a mercaptoalkoxysilane or an aminosilane, and the like.

[0162] In one embodiment, the method for synthesizing the (meth)acryloyl group-containing compound represented by formula S is preferably the method described above as (A). In more detail, the following methods, etc. can be exemplified: (A1) a method including the following steps: a step of reacting a mercaptoalkoxysilane with a polyisocyanate to form an intermediate containing an alkoxysilyl group, a [-S-C(=O)NH-] group, and an isocyanate group; and a step of reacting the intermediate with a (poly)(meth)acrylate containing a hydroxyl group to form a [-O-C(=O)NH-] bond, (A2) a method including the following steps: a step of reacting a polyisocyanate with a (poly)(meth)acrylate containing a hydroxyl group to form an intermediate containing a (meth)acryloyl group, a [-O-C(=O)NH-] group, and an isocyanate group; and a step of reacting a mercaptoalkoxysilane with the intermediate to form a [-S-C(=O)-NH-] bond,

[0163] (A1) is preferable from the viewpoint that the polymerizable unsaturated group is not reduced by the Michael addition reaction.

[0164] The mercaptoalkoxysilane can be used alone or two or more kinds thereof can be used.

[0165] The mercaptoalkoxysilane can be exemplified by mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, mercaptopropylmethyldiethoxysilane, mercaptopropyldimethoxymethylsilane, mercaptopropylmethoxydimethylsilane, mercaptopropyltriphenyloxysilane, mercaptopropyltributyloxysilane, and the like.

[0166] In one embodiment, the mercaptoalkoxysilane is preferably mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane.

[0167] Commercially available products of the mercaptoalkoxysilane can be exemplified by SH6062 manufactured by DuPont Toray Specialty Materials K.K., and the like. In addition, an addition product between an amino-substituted alkoxysilane and an epoxy-substituted mercaptan, an addition product between an epoxy silane and an α,ω-dimercapto compound can also be used.

[0168] The polyisocyanate can be used alone or two or more kinds thereof can be used.

[0169] In the present disclosure, the "polyisocyanate" refers to a compound having two or more isocyanate groups (-N=C=O).

[0170] The polyisocyanate can be exemplified by a linear aliphatic polyisocyanate, a branched aliphatic polyisocyanate, an alicyclic polyisocyanate, an aromatic polyisocyanate, and a biuret body, an isocyanurate body, a uretonimine body, an adduct body, and the like thereof.

[0171] Straight-chain aliphatic polyisocyanates can include methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, and the like.

[0172] Branched aliphatic polyisocyanates can include diethyl pentylene diisocyanate, trimethyl butylene diisocyanate, trimethyl pentylene diisocyanate, trimethyl hexamethylene diisocyanate, and the like.

[0173] Alicyclic polyisocyanates can include monocyclic alicyclic polyisocyanates, cross-linked cyclic alicyclic polyisocyanates, fused ring alicyclic polyisocyanates, and the like.

[0174] Monocyclic alicyclic polyisocyanates can include hydrogenated xylene diisocyanate, isophorone diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, cycloheptylene diisocyanate, cyclodecylene diisocyanate, 3,5,5-trimethylcyclohexylene diisocyanate, dicyclohexylmethane diisocyanate, and the like.

[0175] Cross-linked cyclic alicyclic polyisocyanates can include tricyclodecylene diisocyanate, adamantane diisocyanate, norbornene diisocyanate, and the like.

[0176] Fused ring alicyclic polyisocyanates can include bicyclodecylene diisocyanate, and the like.

[0177] Aromatic polyisocyanates can include monocyclic aromatic polyisocyanates, fused ring aromatic polyisocyanates, and the like.

[0178] Monocyclic aromatic polyisocyanates can include dialkyl diphenylmethane diisocyanates such as 4,4'-diphenyl dimethylmethane diisocyanate, tetraalkyl diphenylmethane diisocyanates such as 4,4'-diphenyl tetramethylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, toluene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate, and the like.

[0179] Fused ring aromatic polyisocyanates can include 1,5-naphthalene diisocyanate, and the like.

[0180] The hydroxyl group-containing (poly)(meth)acrylate can be used alone or two or more kinds can be used in combination.

[0181] The hydroxyl group-containing (poly)(meth)acrylate can include a hydroxyl group-containing (meth)acrylate, a hydroxyl group-containing poly(meth)acrylate, and the like.

[0182] The hydroxyl group-containing (meth)acrylate can be exemplified by 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, and the like.

[0183] In one embodiment, the hydroxyl group-containing poly(meth)acrylate is preferably trimethylolpropane di(meth)acrylate, trimethyloloethane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate.

[0184] In one embodiment, the hydroxyl group-containing poly(meth)acrylate is preferably trimethylolpropane di(meth)acrylate, trimethyloloethane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate.

[0185] In one embodiment, the (meth)acryloyl group-containing compound does not include a group represented by Formula U.

[0186] <Formula U>

[0187] [Chemical Formula 10]

[0188]

[0189] (In the formula, X is NH, O, or S, and Y is O or S).

[0190] The (meth)acryloyl group-containing compound not including a group represented by Formula U can be exemplified by a compound represented by Formula U1, and the like.

[0191] <Formula U1>

[0192] [Chemical Formula 11]

[0193] (Z u -O-R u1 ) u -Si-((OR u2 ) 4-u

[0194] (In the formula, Z u is a (meth)acryloyl group, R u1 is an alkylene group or an arylene group, R u2 is an alkyl group or an aryl group, and u is an integer of 1 to 3).

[0195] Examples of the compound represented by formula U1 include tris(meth)acryloxyethyl monomethoxysilane, di(meth)acryloxyethyl dimethoxysilane, (meth)acryloxyethyl trimethoxysilane, tris(meth)acryloxypropyl monomethoxysilane, di(meth)acryloxypropyl dimethoxysilane, (meth)acryloxypropyl trimethoxysilane, tris(meth)acryloxypropyl monoethoxysilane, di(meth)acryloxypropyl diethoxysilane, (meth)acryloxypropyl triethoxysilane, tris(meth)acryloxypropyl monophenoxysilane, di(meth)acryloxypropyl diphenoxysilane, and (meth)acryloxypropyl triphenoxysilane.

[0196] Examples of the method for producing the (meth)acryl group-containing silica particle include a method including a step of hydrolyzing an alkoxysilane to obtain an alkoxysilane hydrolyzate, and a step of mixing the alkoxysilane hydrolyzate with a powder silica particle or a solvent-dispersed sol of the silica particle and performing heating and stirring. Examples of the method for producing the (meth)acryl group-containing silica particle also include a method in which hydrolysis of the alkoxysilane is performed in the presence of the silica particle. In one embodiment, the method for producing the (meth)acryl group-containing silica particle is preferably the method in which hydrolysis of the alkoxysilane is performed in the presence of the silica particle.

[0197] The temperature during production of the (meth)acryl group-containing silica particle is preferably from 0°C to 150°C, and more preferably from 20°C to 100°C. The reaction time is preferably from 5 minutes to 24 hours.

[0198] During production of the (meth)acryl group-containing silica particle, an organic solvent that is uniformly miscible with water can be added in order to allow the reaction to proceed smoothly and uniformly. The amount of the organic solvent to be added is not particularly limited as long as the purpose of allowing the reaction to proceed smoothly and uniformly is achieved.

[0199] During production of the (meth)acryl group-containing silica particle, an acid, a salt, or a base can be added as a catalyst in order to promote the reaction.

[0200] During production of the (meth)acryl group-containing silica particle, a dehydrating agent can be added in order to promote the reaction.

[0201] Examples of the dehydrating agent include inorganic dehydrating agents such as zeolite, anhydrous silica, and anhydrous alumina; and organic dehydrating agents such as methyl orthoformate, ethyl orthoformate, tetraethoxymethane, and tetrabutoxymethane. In one embodiment, the dehydrating agent is preferably an organic dehydrating agent, and more preferably an ortho ester such as methyl orthoformate or ethyl orthoformate.

[0202] The amount of alkoxysilane bonded to the (meth)acryloyl group-containing silica particle can be obtained by thermogravimetric analysis from 110°C to 800°C in air as a constant value of the mass reduction % when the dry powder is completely combusted in air.

[0203] The upper limit and the lower limit of the particle diameter of the (meth)acryloyl group-containing silica particle can be exemplified by 150 nm, 145 nm, 140 nm, 135 nm, 130 nm, 125 nm, 120 nm, 115 nm, 110 nm, 105 nm, 100 nm, 95 nm, 90 nm, 85 nm, 80 nm, 75 nm, 70 nm, 65 nm, 60 nm, 55 nm, 50 nm, 45 nm, 40 nm, 35 nm, 30 nm, 25 nm, 20 nm, 15 nm, 10 nm, 5 nm, and the like. In one embodiment, the particle diameter of the (meth)acryloyl group-containing silica particle is preferably 5 nm to 150 nm.

[0204] In the present disclosure, the measurement of the particle diameter is performed by the particle size distribution measurement by the dynamic light scattering method using a commercially available measuring instrument (product name "DYNAMIC LIGHT SCATTERING NANOPARTICLE SIZE ANALYZER LB-550", HORIBA, Ltd.) according to JIS Z8828:2013.

[0205] In one embodiment, the (meth)acryloyl group-containing silica particle contains a group represented by Formula U.

[0206] <Formula U>

[0207] [Chemical Formula 12]

[0208]

[0209] (In the formula, X is NH, O, or S, and Y is O or S).

[0210] In one embodiment, the (meth)acryloyl group-containing silica particle does not contain a group represented by Formula U.

[0211] <Formula U>

[0212] [Chemical Formula 13]

[0213]

[0214] (In the formula, X is NH, O, or S, and Y is O or S).

[0215] The upper limit and the lower limit of the content of the (meth)acryloyl-containing silica particles in 100 mass% of the nonvolatile component of the coating agent can be exemplified by 70 mass%, 69 mass%, 67 mass%, 65 mass%, 60 mass%, 55 mass%, 50 mass%, 45 mass%, 40 mass%, 35 mass%, 30 mass%, 29 mass%, 27 mass%, 26 mass%, 25 mass%, 24 mass%, 22 mass%, 20 mass%, 15 mass%, 10 mass%, 5 mass%, and the like. In one embodiment, the content is preferably 5 mass% to 70 mass%.

[0216] [Light polymerization initiator containing oxime ester structure]

[0217] The light polymerization initiator containing oxime ester structure can be used alone or two or more kinds thereof.

[0218] In one embodiment, the light polymerization initiator containing oxime ester structure is preferably the following structural formula:

[0219] [Chemical 14]

[0220]

[0221] (In the formula, R o1 is an aryl group or an alkyl group, R o2 is an alkyl group, and R o3 is an aryl group.)

[0222] The compound represented is more preferably the following structural formula:

[0223] [Chemical 15]

[0224]

[0225] (In the formula, R o1 is an aryl group or an alkyl group, R o2 is an alkyl group, and R o3 is an aryl group.)

[0226] The compound represented.

[0227] The aryl group in the structural formula can also be substituted. The substituent of the aryl group can be exemplified by an alkyl group, a thioalkyl group, a thioaryl group, a carbonylaryl group, and the like.

[0228] The substituted aryl group can be exemplified by

[0229] [Chemical 16]

[0230]

[0231] and the like.

[0232] A photopolymerization initiator containing an oxime ester structure can be exemplified by 1,2-octanedione, 1-[4-(phenylthio)-, 2-(o-benzoyl oxime)] (i.e., 2-((benzoyloxy)imino)-1-(4-(phenylthio)phenyl)octan-1-one);

[0233] A photopolymerization initiator containing an oxime ester structure can be exemplified by 1,2-octanedione, 1-[4-(phenylthio)-, 2-(o-benzoyl oxime)] (i.e., 2-((benzoyloxy)imino)-1-(4-(phenylthio)phenyl)octan-1-one);

[0234] Commercially available products of a photopolymerization initiator containing an oxime ester structure can be exemplified by Irgacure OXE 01, Irgacure OXE 02, Irgacure OXE 03, Irgacure OXE 04 (all of which are manufactured by JAPAN BASF Co., Ltd.), Adeka Optomer N-1919, Adeka Arkls NCI-831, Adeka Arkls NCI-930 (all of which are manufactured by ADEKA Co., Ltd.), Omnirad 1312, Omnirad 1314, Omnirad 1316 (all of which are manufactured by IGM Resins Co., Ltd.), TR-PBG-305, TR-PBG-3057, TR-PBG-304, TR-PBG-314 (all of which are manufactured by Changzhou Qiangli Electronics New Material Co., Ltd.), and the like.

[0235] An upper limit and a lower limit of the content of a photopolymerization initiator containing an oxime ester structure in 100% by mass of nonvolatile components of the coating agent can be exemplified by 10% by mass, 9% by mass, 8% by mass, 7% by mass, 6% by mass, 5% by mass, 4% by mass, 3.5% by mass, 3.4% by mass, 3.2% by mass, 3.1% by mass, 3% by mass, 2.9% by mass, 2.7% by mass, 2.5% by mass, 2.4% by mass, 2% by mass, 1% by mass, 0.9% by mass, 0.7% by mass, 0.6% by mass, 0.5% by mass, 0.4% by mass, 0.2% by mass, 0.1% by mass, and the like. In one embodiment, the content is preferably 0.1% by mass to 10% by mass, more preferably 1% by mass to 5% by mass.

[0236] <Photopolymerization initiator not containing an oxime ester structure>

[0237] In one embodiment, the coating agent can include a photopolymerization initiator not containing an oxime ester structure. A photopolymerization initiator not containing an oxime ester structure can be used alone or two or more kinds thereof.

[0238] The photopolymerization initiator not containing the hydroxyl ester structure can be exemplified by α-hydroxyphenyl alkyl ketone, unsubstituted or substituted phenyl alkyl ketone, unsubstituted or substituted benzyl, unsubstituted or substituted benzophenone, acyl phosphine oxide, hydroxyl ester, substituted thioxanthone, and the like.

[0239] The α-hydroxyphenyl alkyl ketone can be exemplified by 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone (1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-methylpropanone), 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropanoyl)benzyl)phenyl)-2-methylpropan-1-one, and the like.

[0240] The unsubstituted or substituted phenyl alkyl ketone can be exemplified by methyl benzoate, isopropyl benzoate, isobutyl benzoate, ethyl benzoate, acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-phenyl-2-(p-toluenesulfonyloxy)acetophenone, benzoin, 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone, 2-methyl-4'-(methylthio)-2-morpholinopropiophenone, 2-isopropylidene-5-methylcyclohexane-1,3-dione, 2,2-dimethoxy-1,2-diphenylethane-1-one, and the like.

[0241] The unsubstituted or substituted benzyl can be exemplified by benzyl, p-anisyl, and the like unsubstituted or substituted benzyl, and the like.

[0242] The unsubstituted or substituted benzophenone can be exemplified by benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-dichlorobenzophenone, 1,4-benzoylbenzene, 2-benzoylbenzoic acid, 4-benzoylbenzoic acid, methyl 2-benzoylbenzoate, and the like.

[0243] The acyl phosphine oxide can be exemplified by 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenyl phosphine oxide, and the like.

[0244] The substituted thioxanthone can be exemplified by 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, and the like.

[0245] The upper limit and the lower limit of the content of the oxime ester structure not containing the photopolymerization initiator in 100 mass% of the nonvolatile component of the coating agent can be exemplified by 10 mass%, 9 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%, 4 mass%, 3.5 mass%, 3.4 mass%, 3.2 mass%, 3.1 mass%, 3 mass%, 2.9 mass%, 2.7 mass%, 2.5 mass%, 2.4 mass%, 2.2 mass%, 2 mass%, 1.9 mass%, 1.7. mass%, 1.5 mass%, 1.3 mass%, 1.1 mass%, 1 mass%, 0.9 mass%, 0.7 mass%, 0.6 mass%, 0.5 mass%, 0.4 mass%, 0.2 mass%, 0.1 mass%, 0 mass%, and the like. In one embodiment, the content is preferably 0 mass% to 10 mass%, more preferably 0 mass% to 3 mass%.

[0246] <Polymethacrylate having two or less (meth)acryloyl groups>

[0247] In one embodiment, the coating agent can include a polymethacrylate having two or less (meth)acryloyl groups. The polymethacrylate having two or less (meth)acryloyl groups can be used alone or two or more.

[0248] The polymethacrylate having two or less (meth)acryloyl groups can be exemplified by an alkylene di(meth)acrylate, an oxyalkylene di(meth)acrylate, and the like.

[0249] In the present disclosure, the alkylene di(meth)acrylate is a compound having two oxymethyl)acryloyl groups, and refers to a compound in which the portion after removing the oxymethyl)acryloyl groups from the compound consists of only an alkylene group.

[0250] The alkylene di(meth)acrylate has the following structural formula

[0251] [Chemical Formula 17]

[0252]

[0253] (In the formula, R a1 is a hydrogen atom or a methyl group, R a2 is an alkylene group, and R a3 is a hydrogen atom or a methyl group.)

[0254] is represented.

[0255] The straight-chain alkylene di(meth)acrylate can be exemplified by ethylene glycol di(meth)acrylate, 1,3-propanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and the like.

[0256] The branched alkylene di(meth)acrylate can be exemplified by 1,2-propanediol di(meth)acrylate, 1,2-butanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 2-methyl-1,3-propanediol di(meth)acrylate, 1,1-dimethyl-1,2-ethanediol di(meth)acrylate, 1,4-pentanediol di(meth)acrylate, 1,3-pentanediol di(meth)acrylate, 1,2-pentanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, isononyl glycol diacrylate, and the like.

[0257] The cycloalkylene di(meth)acrylate can be exemplified by dimethylol-tricyclodecane di(meth)acrylate, bis(4-(meth)acryloyloxycyclohexyl)methane, 2,2-bis(4-(meth)acryloyloxycyclohexyl)propane, 2,2-bis(4-(meth)acryloyloxycyclohexyl)butane, 1,4-bis(meth)acryloyloxymethylcyclohexane, cyclohexane (meth)acrylate, hydrogenated bisphenol A di(meth)acrylate (2,2-bis(4-(meth)acryloyloxycyclohexyl)propane), hydrogenated bisphenol B di(meth)acrylate (2,2-bis(4-(meth)acryloyloxycyclohexyl)butane).

[0258] The oxyalkylene di(meth)acrylate can be exemplified by dipentaerythritol di(meth)acrylate, tripentaerythritol di(meth)acrylate, ditrimethylolpropane di(meth)acrylate, diglycerol di(meth)acrylate, and the like.

[0259] The upper limit and the lower limit of the content of the poly(meth)acrylate having two or less (meth)acryloyl groups in 100% by mass of the nonvolatile component of the coating agent can be exemplified by 50% by mass, 45% by mass, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 20% by mass, 15% by mass, 10% by mass, 5% by mass, 4% by mass, 2% by mass, 1% by mass, 0% by mass, and the like. In one embodiment, the content is preferably 0% by mass to 50% by mass, and more preferably 0% by mass to 35% by mass.

[0260] <Organic Solvent>

[0261] In one embodiment, the coating agent can include an organic solvent. The organic solvent can be used alone or two or more kinds can be used.

[0262] The organic solvent can be exemplified by the aforementioned substances, etc.

[0263] The upper limit and the lower limit of the organic solvent in 100 mass% of the nonvolatile component of the coating agent can be exemplified by 90 mass%, 85 mass%, 80 mass%, 75 mass%, 70 mass%, 65 mass%, 60 mass%, 55 mass%, 50 mass%, 45 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, 20 mass%, 15 mass%, 10 mass%, 5 mass%, 4 mass%, 2 mass%, 1 mass%, 0 mass%, etc. In one embodiment, the content is preferably 0 mass% to 90 mass%, more preferably 0 mass% to 70 mass%.

[0264] <additives>

[0265] An additive that does not coincide with any of the poly(meth)acrylate having three or more (meth)acryloyl groups, the (meth)acryloyl group-containing silica particle, the photopolymerization initiator having the oxime ester structure, the photopolymerization initiator not having the oxime ester structure, the poly(meth)acrylate having two or less (meth)acryloyl groups, and the organic solvent can be contained in the coating agent.

[0266] The additive can be exemplified by a photosensitizer, an antioxidant, a light stabilizer, a leveling agent, a pigment, etc.

[0267] In one embodiment, the content of the additive can be exemplified by less than 1 mass%, less than 0.1 mass%, less than 0.01 mass%, 0 mass%, etc., with respect to 100 mass% of the coating agent. In addition, with respect to 100 mass% of any of the poly(meth)acrylate having three or more (meth)acryloyl groups, the (meth)acryloyl group-containing silica particle, the photopolymerization initiator having the oxime ester structure, the photopolymerization initiator not having the oxime ester structure, the poly(meth)acrylate having two or less (meth)acryloyl groups, and the organic solvent, the content can be exemplified by less than 1 mass%, less than 0.1 mass%, less than 0.01 mass%, 0 mass%, etc.

[0268] The coating agent can be produced by dispersing and mixing the poly(meth)acrylate having three or more (meth)acryloyl groups, the (meth)acryloyl group-containing silica particles, the oxime ester structure-containing photopolymerization initiator, and, as necessary, the oxime ester structure-free photopolymerization initiator, the poly(meth)acrylate having two or less (meth)acryloyl groups, the organic solvent component, and the additive, using various publicly known devices (emulsion dispersing machines, ultrasonic dispersing devices, etc.). The order of addition of the respective components is not particularly limited. The dispersing and mixing device can use various publicly known devices (emulsion dispersing machines, ultrasonic dispersing devices, etc.).

[0269] The upper limit and the lower limit of the mass ratio of the poly(meth)acrylate having three or more (meth)acryloyl groups to the (meth)acryloyl group-containing silica particles (mass of the poly(meth)acrylate having three or more (meth)acryloyl groups / mass of the (meth)acryloyl group-containing silica particles) in the coating agent can be exemplified by 18, 17, 15, 14, 12, 10, 9, 7, 5, 4, 2, 1, 0.9, 0.7, 0.5, 0.3, 0.2, 0.14, etc. In one embodiment, the mass ratio is preferably 0.14 to 18.

[0270] The upper limit and the lower limit of the mass ratio of the poly(meth)acrylate having three or more (meth)acryloyl groups to the oxime ester structure-containing photopolymerization initiator (mass of the poly(meth)acrylate having three or more (meth)acryloyl groups / mass of the oxime ester structure-containing photopolymerization initiator) in the coating agent can be exemplified by 900, 700, 500, 250, 100, 90, 75, 50, 25, 20, 19, 15, 14, 12, 10, 9, 7, 5, 4, 2, 1, etc. In one embodiment, the mass ratio is preferably 1 to 900.

[0271] The upper limit and the lower limit of the mass ratio of the (meth)acryloyl group-containing silica particles to the oxime ester structure-containing photopolymerization initiator (mass of the (meth)acryloyl group-containing silica particles / mass of the oxime ester structure-containing photopolymerization initiator) in the coating agent can be exemplified by 700, 500, 250, 100, 90, 75, 50, 25, 20, 19, 15, 14, 12, 10, 9, 7, 5, 4, 2, 1, 0.9, 0.7, 0.5, etc. In one embodiment, the mass ratio is preferably 0.5 to 700.

[0272] The coating agent can be used as a coating agent for a cyclic olefin resin which has not been subjected to an easy-adhesion treatment, and can be directly applied to a cyclic olefin resin which has not been subjected to an easy-adhesion treatment. The coating agent for a cyclic olefin resin is used.

[0273] [Hardened product]

[0274] The present disclosure provides a hardened product of the coating agent for the cyclic olefin resin or the coating agent kit.

[0275] The hardening conditions can be exemplified by the conditions described later.

[0276] [Layered product]

[0277] The present disclosure provides a layered product containing the hardened product.

[0278] The thickness of the cyclic olefin resin substrate is not particularly limited, and is preferably around 10 to 2000 μm. In addition, the thickness of the hardened product layer is not particularly limited, and is preferably around 0.1 μm to 5 μm.

[0279] In one embodiment, the cyclic olefin resin substrate is a cyclic olefin resin substrate that has not been subjected to an easy adhesion treatment.

[0280] The layered product is manufactured by various publicly known methods. In one embodiment, the method for manufacturing the layered product includes a step of applying the coating agent to at least one side of the substrate (application step), and a step of forming a layer of the active energy ray hardenable resin hardened product by irradiation of an active energy ray (active energy ray hardening step).

[0281] (Application step)

[0282] The application method can be exemplified by bar coater application, wire bar application, Mayer bar application, air knife application, gravure application, reverse gravure application, offset printing, flexographic printing, screen printing method, and the like.

[0283] The application amount is not particularly limited. The application amount is preferably an amount in which the mass after drying becomes 0.1 g / m 2 ~ 30 g / m 2 , more preferably an amount in which it becomes 1 g / m 2 ~ 20 g / m 2 .

[0284] (Active energy ray irradiation step)

[0285] The active energy ray used in the active energy ray irradiation step can be exemplified by ultraviolet rays or electron beams, and the like.

[0286] The light source of the ultraviolet rays can be exemplified by ultraviolet irradiation devices having a xenon lamp, a high-pressure mercury lamp, a metal halide lamp, and the like. Furthermore, the light amount or light source arrangement, conveyance speed, and the like can be adjusted as needed.

[0287] In the case of using a high-pressure mercury lamp, it is preferable to harden at a conveyance speed of around 2 m / minute to 50 m / minute with respect to one lamp having a light amount of around 80 W / cm to 160 W / cm.

[0288] In the case of an electron beam, it is preferable to harden under conditions of a transport speed of 5 m / min to 50 m / min or so by means of an electron beam acceleration device having an acceleration voltage of 10 kV to 300 kV or so.

[0289] [Examples]

[0290] Hereinafter, the present application will be specifically described by way of examples and comparative examples. However, the description in the preferred embodiments and the following examples are provided for the purpose of illustration only and are not provided for the purpose of limiting the present application. Therefore, the scope of the present application is not limited to the embodiments specifically described in the present specification nor to the examples, but is only limited by the claims. In addition, in each of the examples and comparative examples, the values of parts, %, and the like are on a mass basis, unless otherwise specifically mentioned.

[0291] Example 1

[0292] In a reaction vessel including a stirrer, a thermometer, a dropping funnel, a cooling tube, and an air inlet, Aronix M-305 (manufactured by Toagosei Co., Ltd.) was mixed at 70 parts by mass on a non-volatile basis, PGM-AC-2140Y (manufactured by Nissan Chemical Industries, Ltd.) was mixed at 27 parts by mass on a non-volatile basis, and Irgacure OXE01 (manufactured by JAPAN BASF Co., Ltd.) was mixed at 3 parts by mass on a non-volatile basis, and a coating agent for a cyclic olefin resin was obtained by adjusting the non-volatile content to 30% in methyl ethyl ketone. Using a bar coater, the prepared coating agent for a cyclic olefin resin was coated on Zeonor Film ZF-16 (manufactured by ZEON Co., Ltd.) having a thickness of 100 μm so that the film thickness after drying became 1 μm, and dried at 80°C for 60 seconds in a commercially available warm air drier. Then, a laminate was obtained by irradiating 300 mJ / cm2of ultraviolet rays using a metal halide lamp under a nitrogen atmosphere. 2

[0293] Examples other than Example 1 were changed as shown in the following table, unless otherwise specifically mentioned, and were processed in the same manner as in Example 1.

[0294] [Table 1]

[0295]

[0296] [Table 2]

[0297]

[0298] [Explanation of Abbreviations]

[0299] ​Aronix M-305: Pentaerythritol tri- and tetraacrylate (manufactured by Toagosei Co., Ltd.)

[0300] Aronix M-400: Dipentaerythritol penta- and hexaacrylate (manufactured by Toagosei Co., Ltd.)

[0301] Biscoat #802: Mixture of tri-, mono- and di-pentaerythritol polyacrylate, and poly-pentaerythritol polyacrylate (all having three or more acryloyl groups) (manufactured by Osaka Organic Chemical Industry Ltd.)

[0302] Aronix M-408: Dimethylolpropane tetraacrylate (manufactured by Toagosei Co., Ltd.)

[0303] Denacol Acrylate DA-314: Acrylic acid adduct of glycerol polyglycidyl ether (having three or more acryloyl groups) (manufactured by Nagase Corporation)

[0304] Miramer PU610: Aliphatic urethane hexaacrylate (manufactured by Miwon Specialty Chemical Co., Ltd.)

[0305] Aronix M-7100: Polyester polyacrylate (having three or more acryloyl groups) (manufactured by Toagosei Co., Ltd.)

[0306] HDDA: 1,6-hexanediol diacrylate (manufactured by DAICEL ALLNEX Co., Ltd.)

[0307] Light Acrylate 3EG-A: Triethylene glycol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.)

[0308] Biscoat #540: Diacrylate, which is a reaction product of acrylic acid and 2- (chloromethyl)oxirane · 4,4'-(isopropylidene) bisphenol polymer (manufactured by Osaka Organic Chemical Industry Ltd.) (manufactured by Osaka Organic Chemical Industry Ltd.)

[0309] PGM-AC-2140Y: [3- (Methacryloyloxy) propyl] trimethoxysilane surface-modified special grade (particle diameter 10 nm to 15 nm) of propylene glycol monomethyl ether dispersed silica sol (manufactured by Nissan Chemical Industries, Ltd.)

[0310] MEK-AC-2140Z: [3- (Methacryloyloxy) propyl] trimethoxysilane surface-modified special grade (particle diameter 10 nm to 15 nm) of methyl ethyl ketone dispersed silica sol (manufactured by Nissan Chemical Industries, Ltd.)

[0311] PGM-AC-4130Y: [3-(methacryloyloxy)propyl]trimethoxysilane surface-modified special grade (particle diameter 40 nm to 50 nm) of propylene glycol monomethyl ether dispersed silica sol (manufactured by Nissan Chemical (Co.))

[0312] Irgacure OXE 01: 1,2-octanedione, 1-[4-(phenylthio)-, 2-(o-benzoyl oxime)] (i.e., 2-((benzoyloxy)imino)-1-(4-(phenylthio)phenyl)octan-1-one) (manufactured by Japan BASF (Co.))

[0313] Irgacure OXE 04: photopolymerization initiator containing oxime ester structure (manufactured by Japan BASF (Co.))

[0314] OMNIRAD 1316: photopolymerization initiator containing oxime ester structure (manufactured by IGM Resins (Co.))

[0315] TR-PBG-305: 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(o-benzoyl oxime) (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.)

[0316] OMNIRAD 184: 1-hydroxycyclohexyl-phenyl ketone (manufactured by IGM Resins (Co.))

[0317] OMNIRAD 127: 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropanoyl)benzyl)phenyl)-2-methylpropan-1-one (manufactured by IGM Resins (Co.))

[0318] OMNIRAD 754: mixture of oxyphenyl acetic acid 2-[2-oxo-2-phenyl-acetyloxy-ethoxy] ethyl ester and oxyphenyl acetic acid 2-[2-hydroxy-ethoxy] ethyl ester (manufactured by IGM Resins (Co.))

[0319] OMNIRAD 907: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (manufactured by IGM Resins (Co.))

[0320] Speedcure TPO: 2,4,6-trimethylbenzoyl diphenyl phosphine oxide (manufactured by LAMBSON Co.)

[0321] Esacure One: difunctional alpha hydroxy ketone (manufactured by IGM Resins (Co.))

[0322] <Substrate adhesion>

[0323] For the obtained laminates, adhesiveness was evaluated by a 100-square lattice peeling test in accordance with Japanese Industrial Standards (JIS) K5600-5-4. The result was expressed as (the number of squares remaining in the peeling test / 100).

[0324] <Coatability>

[0325] For the obtained laminates, visual evaluation was performed.

[0326] O: After the coating agent was applied to the laminate, the coating agent was not repelled on the surface of the laminate, and the area on the film to which the coating agent was applied was 100% covered with the coating agent.

[0327] X: After the coating agent was applied to the laminate, the coating agent was repelled on the surface of the laminate, and the area on the film to which the coating agent was applied was 100% not covered with the coating agent.

Claims

1. A coating agent for a cyclic olefin resin, the coating agent for a cyclic olefin resin consisting of: a poly(meth)acrylate having three or more (meth)acryloyl groups, (meth)acryloyl group-containing silica particles, a photopolymerization initiator containing an hydroxam ester structure, a photopolymerization initiator not containing an hydroxam ester structure, and an organic solvent, the content of the photopolymerization initiator not containing an hydroxam ester structure in the nonvolatile component of the coating agent is 0 mass% or more in 100 mass%, the content of the organic solvent in the nonvolatile component of the coating agent is 0 mass% or more in 100 mass%.

2. A hardened product, which is a hardened product of the coating agent for a cyclic olefin resin described in claim 1.

3. A laminate comprising the hardened product described in claim 2. ​ ​ ​ ​ ​

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