JP6947269B1 - Coating agents for cyclic olefin resins, coating agent kits, cured products, and laminates - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating agent for a cyclic olefin resin, a coating agent kit, a cured product, and a laminate. The present disclosure provides a coating agent for a cyclic olefin resin, which comprises an active energy ray-curable resin compound containing an alkylene di (meth) acrylate and an oxime ester structure-containing photopolymerization initiator. [Selection diagram] None

Description

The present disclosure relates to coating agents for cyclic olefin resins, coating agent kits, cured products, and laminates.

Conventionally, a polarizing plate used in a liquid crystal display device is a polyvinyl alcohol film in which iodine or the like is adsorbed and a triacetyl cellulose film (TAC film) is bonded as a protective film on both sides of a polarizing element oriented by stretching or the like, and further, the surface thereof. A transparent photocurable resin composition is applied and cured to form a high-hardness film (hard coat layer), which is protected from scratches and the like. As a material for forming such a cured film, an active energy ray-curable resin composition using a polyfunctional (meth) acrylate or the like is known (Patent Document 1).

In recent years, due to the increase in size and quality of liquid crystal devices and the expansion of mobile applications, those that can withstand harsher usage environments (for example, high temperature and high humidity conditions) have been required, and it is clear that TAC films have limitations in terms of characteristics. Became. Under such circumstances, alternatives from TAC films to cyclic olefin resin-based films are expected to be promising. The cyclic olefin resin film is excellent in transparency, low birefringence, dimensional stability, etc., and has the performance required as an optical film. Further, it has a low moisture permeability, which is a major factor in replacing the TAC film in this respect. 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 film surface.

Conventionally, a primer layer is applied to a cyclic olefin resin-based film and electrical treatment (corona discharge treatment, atmospheric pressure plasma treatment) is performed to improve the adhesion between the base material and the hard coat layer (Patent Document). 2).

Japanese Unexamined Patent Publication No. 2009-286924 Japanese Unexamined Patent Publication No. 2014-189566

However, the above-mentioned method has a problem that a treatment step for improving the adhesion to the base material is required when producing the coating film, which leads to high cost. In addition, since the electrical treatment causes a change in the treated surface with time, there is also a restriction that the hard coat layer must be applied immediately after the treatment.

An object to be solved by the present invention is to provide a coating agent for a cyclic olefin resin, which has good adhesion between a cured product of the coating agent and the cyclic olefin resin.

As a result of diligent studies, the present inventors have found that a specific coating agent solves the above-mentioned problems.

The disclosure provides the following items:
(Item 1)
A coating agent for a cyclic olefin resin, which comprises an active energy ray-curable resin compound containing an alkylene di (meth) acrylate and an oxime ester structure-containing photopolymerization initiator.
(Item 2)
The coating agent for a cyclic olefin resin according to the above item, which comprises an ultraviolet absorber.
(Item 3)
The coating agent for a cyclic olefin resin according to any one of the above items, which contains only cycloalkylene di (meth) acrylate as an active energy ray-curable resin compound (item 4).
A coating agent kit comprising the coating agent for a cyclic olefin resin according to any one of the above items and a coating agent containing an oxime ester structure-free photopolymerization initiator.
(Item 5)
The coating agent for cyclic olefin resin according to any one of the above items, or the cured product of the coating agent kit according to item 4.
(Item 6)
A laminate containing the cured product according to the above item.

In the present disclosure, the above-mentioned one or more features may be provided in addition to the specified combinations.

By using the coating agent for cyclic olefin resin according to the present disclosure, it is possible to produce a laminate having excellent adhesion between the cured product layer of the coating agent and the cyclic olefin resin.

Throughout the present disclosure, the range of numerical values such as each physical property value and content can be set as appropriate (for example, by selecting from the upper and lower limit values described in each of the following items). Specifically, for the numerical value α, when A4, A3, A2, A1 (A4> A3> A2> A1) and the like are exemplified as the upper and lower limits of the numerical value α, the range of the numerical value α is A4 or less. Examples thereof include A3 or less, A2 or less, A1 or more, A2 or more, A3 or more, A1 to A2, A1 to A3, A1 to A4, A2 to A3, A2 to A4, and A3 to A4.

[Coating agent for cyclic olefin resin: Also called coating agent]
The present disclosure provides a coating agent for a cyclic olefin resin, which comprises an active energy ray-curable resin compound containing an alkylene di (meth) acrylate and an oxime ester structure-containing photopolymerization initiator.

In the present disclosure, "(meth) acrylic" means "at least one selected from the group consisting of acrylic and methacryl". Similarly, "(meth) acrylate" means "at least one selected from the group consisting of acrylates and methacrylates". Further, "(meth) acryloyl" means "at least one selected from the group consisting of acryloyl and methacryloyl".

<Active energy ray-curable resin compound: Also referred to as component (A)>
The active energy ray-curable resin compound may be used alone or in combination of two or more.

Examples of the active energy ray-curable resin compound include alkylene poly (meth) acrylate.

（式中、Ｒは水素原子又はメチル基である。）
を複数個有する化合物であって、当該化合物からオキシ（メタ）アクリロイル基を除いた部分が、炭素原子及び水素原子からなる飽和炭化水素基のみから構成される化合物を意味する。 In the present disclosure, the alkylene poly (meth) acrylate is an oxy (meth) acryloyl group.

(In the formula, R is a hydrogen atom or a methyl group.)
This means a compound having a plurality of the above compounds, wherein the portion obtained by removing the oxy (meth) acryloyl group from the compound is composed of only a saturated hydrocarbon group composed of a carbon atom and a hydrogen atom.

In the present disclosure, the alkylene di (meth) acrylate is a compound having two oxy (meth) acryloyl groups, and the portion of the compound excluding the oxy (meth) acryloyl group is composed of only the alkylene group. Means.

（式中、Ｒ^ａ１は、水素原子又はメチル基であり、Ｒ^ａ２は、アルキレン基であり、Ｒ^ａ３は、水素原子又はメチル基である。）
で表される。 The alkylene di (meth) acrylate has the following structural formula.

(In the formula, Ra ¹ is a hydrogen atom or a methyl group, Ra ² is an alkylene group, and Ra ³ is a hydrogen atom or a methyl group.)
It is represented by.

Examples of the alkylene group include a linear alkylene group, a branched alkylene group, and a cycloalkylene group.

The linear alkylene group _{can be represented by the general formula of − (CH 2} ) _n − (n is an integer of 1 or more). The linear alkylene group includes a methylene group, an ethylene group, a propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, an n-nonylene group, an n-decamethylene group and the like. Is exemplified.

A branched alkylene group is a group in which at least one hydrogen atom of a linear alkylene group is substituted with an alkyl group and does not have a cyclic structure. Examples of the branched alkylene group include a diethylpentylene group, a trimethylbutylene group, a trimethylpentylene group, and a trimethylhexylene group.

Examples of the cycloalkylene group include a monocyclic cycloalkylene group, a crosslinked ring cycloalkylene group, and a condensed ring cycloalkylene group. Further, the cycloalkylene group may have one or more hydrogen atoms substituted with a linear or branched alkyl group.

The single ring is, for example, a cyclic structure formed by covalent bonds of carbon and having no bridging structure inside. Further, the condensed ring is, for example, a cyclic structure in which two or more monocycles share two atoms (that is, only one side of each ring is shared (condensed) with each other). The crosslinked ring is, for example, a cyclic structure in which two or more monocycles share three or more atoms.

Examples of the monocyclic cycloalkylene group include a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclodecylene group, a 3,5,5-trimethylcyclohexylene group and the like.

Examples of the crosslinked ring cycloalkylene group include a tricyclodecylene group, an adamantylene group, and a norbornene group.

Examples of the fused ring cycloalkylene group include a bicyclodecylene group.

The alkylene group also includes a group in which a linear alkylene group, a branched alkylene group, and a cycloalkylene group are combined. Examples of the combined group include a cycloalkylene alkylene group and an alkylene cycloalkylene alkylene group.

The cycloalkylene alkylene group is
^-R calkylene -R alkylene -
^{(Wherein, R Calkylene} represents a cycloalkylene ^{group, R Alkylene} represents an alkylene group)
It is a group represented by.

The alkylenecycloalkylene alkylene group is
^-R alkylene -R calkylene -R alkylene -
^{(Wherein, R Calkylene} represents a cycloalkylene ^{group, R Alkylene} represents an alkylene group)
It is a group represented by.

The linear alkylene di (meth) acrylate includes ethylene glycol di (meth) acrylate, 1,3-propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,5-pentanediol di (meth) acrylate. Meta) acrylate, 1,6-hexanediol di (meth) acrylate, 1,7-heptanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) Examples thereof include acrylates and 1,10-decanediol di (meth) acrylates.

The branched alkylene di (meth) acrylates are 1,2-propylene glycol di (meth) acrylate, 1,2-butanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, and 2-methyl-1. , 3-Propylene glycol di (meth) acrylate, 1,1-dimethyl-1,2-ethylene glycol di (meth) acrylate, 1,4-pentanediol di (meth) acrylate, 1,3-pentanediol di (meth) acrylate ) Acrylate, 1,2-pentanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, isononanediol diacrylate and the like are exemplified.

Cycloalkylene di (meth) acrylates include dimethylol-tricyclodecanedi (meth) acrylate, bis (4- (meth) acryloxicyclohexyl) methane, 2,2-bis (4- (meth) acryloxycyclohexyl) propane, 2,2-Bis (4- (meth) acryloxicyclohexyl) butane, 1,4-di (meth) acryloximethylcyclohexane, cyclohexane (meth) acrylate, hydrogenated bisphenol A di (meth) acrylate (2,2- Examples thereof include bis (4- (meth) acryloxycyclohexyl) propane) and hydrogenated bisphenol B di (meth) acrylate (2,2-bis (4- (meth) acryloxycyclohexyl) butane).

In one embodiment, the coating agent preferably contains only an alkylene di (meth) acrylate as an active energy ray-curable resin compound, and contains only a cycloalkylene di (meth) acrylate from the viewpoint of scratch resistance. It is more preferable, and from the viewpoint of adhesion, it is more preferable to contain only the acyclic alkylene di (meth) acrylate.

The upper and lower limits of the content of the active energy ray-curable resin compound in 100% by mass of the coating agent solid content are 99, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, Examples include 40, 35, 30, 25, 20, 15, 10, 5% by mass and the like. In one embodiment, the content is preferably 5 to 99% by mass.

<Oxime ester structure-containing photopolymerization initiator: also referred to as component (B)>
The oxime ester structure-containing photopolymerization initiator may be used alone or in combination of two or more.

（式中、Ｒ^ｏ１は、アリール基又はアルキル基であり、Ｒ^ｏ２はアルキル基であり、Ｒ^ｏ３は、アリール基である。）
で表される化合物が好ましく、下記構造式：

（式中、Ｒ^ｏ１は、アリール基又はアルキル基であり、Ｒ^ｏ２はアルキル基であり、Ｒ^ｏ３は、アリール基である。）
で表される化合物がより好ましい。 In one embodiment, the oxime ester structure-containing photopolymerization initiator has the following structural formula:

(In the formula, ^Ro1 is an aryl group or an alkyl group, ^Ro2 is an alkyl group, and ^Ro3 is an aryl group.)
The compound represented by is preferable, and the following structural formula:

(In the formula, ^Ro1 is an aryl group or an alkyl group, ^Ro2 is an alkyl group, and ^Ro3 is an aryl group.)
The compound represented by is more preferable.

Examples of the alkyl group include a linear alkyl group, a branched alkyl group, a cycloalkyl group and the like.

The linear alkyl group _{can be expressed by the general formula of −C n} H _{2n + 1} (n is an integer of 1 or more). The linear alkyl group includes methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group and n-decamethyl. Groups and the like are exemplified.

A branched alkyl group is a group in which at least one hydrogen atom of a linear alkyl group is substituted with an alkyl group and does not have a cyclic structure. Examples of the branched alkyl group include an i-propyl group, a diethylpentyl group, a trimethylbutyl group, a trimethylpentyl group, and a trimethylhexyl group.

Examples of the cycloalkyl group include a monocyclic cycloalkyl group, a crosslinked ring cycloalkyl group, and a condensed ring cycloalkyl group. Further, the cycloalkyl group may have one or more hydrogens substituted with a linear or branched alkyl group.

Examples of the monocyclic cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclodecyl group, a 3,5,5-trimethylcyclohexyl group and the like.

Examples of the crosslinked ring cycloalkyl group include a tricyclodecyl group, an adamantyl group, and a norbornyl group.

The alkyl group also includes a group in which a linear alkyl group, a branched alkyl group, and a cycloalkyl group are combined. Examples of the above-mentioned combined group include a cycloalkylalkyl group.

Cycloalkylalkyl groups
^R calkyl -R ^alkyl -
^{(Wherein, R Calkyl} represents a cycloalkyl ^{group, R alkyl} represents an alkyl group)
It is a group represented by.

Examples of the aryl group include a phenyl group, a naphthyl group, a fluorenyl group, a carbazoyl group and the like.

The aryl group may be substituted. Examples of the substituent of the aryl group include an alkyl group, a thioalkyl group, a thioaryl group, and a carbonylaryl group.

等が例示される。 Substituted aryl groups

Etc. are exemplified.

The oxime ester structure-containing photopolymerization initiator is 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (that is, 2-((benzoyloxy) imino) -1-. (4- (Phenylthio) phenyl) octane-1-one);
Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime) (ie 1-(((1- (9-ethyl-)- 6- (2-Methylbenzoyl) -9H-carbazole-3-yl) ethylidene) amino) oxy) ethane-1-one) and the like are exemplified.

Commercially available products of the oxime ester structure-containing photopolymerization initiator are Irgacure OXE 01, Irgacure OXE 02, Irgacure OXE 03, Irgacure OXE 04 (all manufactured by BASF Japan Ltd.), ADEKA KUTMER N-1919, and ADEKA ARCULS NCI-831. , ADEKA ARKULS NCI-930 (all manufactured by ADEKA CORPORATION) and the like are exemplified.

The upper and lower limits of the content of the oxime ester structure-containing photopolymerization initiator in the coating agent solid content of 100% by mass are 30, 25, 20, 15, 10, 5, 3, 1, 0.5, 0.2. , 0.1% by mass and the like. In one embodiment, the content is preferably 0.1 to 30% by mass.

Upper and lower limits of the mass ratio of the active energy ray-curable resin compound and the oxime ester structure-containing photopolymerization initiator in the above coating agent (mass of active energy ray-curable resin compound / mass of oxime ester structure-containing photopolymerization initiator) 990, 900, 750, 500, 250, 100, 75, 50, 25, 20, 19, 17, 15, 13, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, Examples include 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.17 and the like. In one embodiment, the mass ratio is preferably 0.17 to 990.

<UV absorber: also called component (C)>
In one embodiment, the coating agent comprises a UV absorber. The UV absorber may be used alone or in combination of two or more.

The ultraviolet absorber is a component that absorbs ultraviolet rays having high energy, converts them into harmless energy, and re-radiates them to bring about an ultraviolet blocking effect. UV absorbers include salicylate structure-containing UV absorbers, benzophenone structure-containing UV absorbers, benzotriazole structure-containing UV absorbers, substituted acrylonitrile structure-containing UV absorbers, triazine structure-containing UV absorbers, benzoate structure-containing UV absorbers, and polymers. Examples include type ultraviolet absorbers.

Examples of the ultraviolet absorber containing a salicylate structure include phenyl salicylate, p-octylphenyl salicylate, and pt-butylphenyl salicylate.

Benzophenone structure-containing UV absorbers include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2 Examples thereof include −hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-octoxybenzophenone.

Benzotriazole structure-containing UV absorbers are 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert- Butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy) -3'-Isobutyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5'-propylphenyl) -5-chlorobenzotriazole, 2- (2' -Hydroxy-3', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- [2'-hydroxy-5'-(1, 1,3,3-Tetramethyl) phenyl] benzotriazole and the like are exemplified.

Examples of the substituted acrylonitrile structure-containing ultraviolet absorber include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate.

The triazine structure-containing ultraviolet absorbers are 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine and 2,4-diphenyl-6- (2-hydroxy-4-). Ethoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-propoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-) Butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-) Hydroxy-4-hexyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl -6- [2-hydroxy-4- (1-isooctyloxycarbonylethoxy)] -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-dodecyloxyphenyl) -1 , 3,5-Triazine, 2,4-diphenyl-6- (2-hydroxy-4-benzyloxyphenyl) -1,3,5-triazine and the like are exemplified.

Examples of the benzoate structure-containing ultraviolet absorber include resorcinol monobenzoate and 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate.

The polymer type UV absorber is 3- (2H-1,2,3-benzotriazole-
2-yl) -4-hydroxyphenetyl = (meth) acrylate, 2- [2'-hydroxy-5'-((meth) acryloyloxymethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy- 5'-((meth) acryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-t-butyl-5'-((meth) acryloyloxyethyl) phenyl] -2H- Benzotriazole, 2- [2'-hydroxy-5'-t-butyl-3'-((meth) acryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-((() Meta) acryloyloxyethyl) phenyl] -5-chloro-2H-benzotriazole, 2- [2'-hydroxy-5'-((meth) acryloyloxyethyl) phenyl] -5-methoxy-2H-benzotriazole, 2 -[2'-Hydroxy-5'-((meth) acryloyloxyethyl) phenyl] -5-cyano-2H-benzotriazole, 2- [2'-hydroxy-5'-((meth) acryloyloxyethyl) phenyl ] -T-Butyl-2H-benzotriazole, 2- [2'-hydroxy-5'-((meth) acryloyloxyethyl) phenyl] -5-nitro-2H-benzotriazole-derived structural unit, etc. Is exemplified.

The upper and lower limits of the content of the ultraviolet absorber in 100% by mass of the coating agent solid content are 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, and so on. 2, 1, 0% by mass and the like are exemplified. In one embodiment, the content is preferably 0 to 70% by mass.

The upper and lower limits of the mass ratio of the ultraviolet absorber and the active energy ray-curable resin compound (mass of the ultraviolet absorber / mass of the active energy ray-curable resin compound) in the above coating agent are 14, 13, 11, 10, and 1. 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0 and the like are exemplified. In one embodiment, the mass ratio is preferably 0 to 14.

The upper and lower limits of the mass ratio of the ultraviolet absorber and the oxime ester structure-containing photopolymerization initiator in the above coating agent (mass of the ultraviolet absorber / mass of the oxime ester structure-containing photopolymerization initiator) are 700, 500, 250, and so on. 100, 75, 50, 25, 20, 19, 17, 15, 13, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.9, 0.8, 0. 7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0 and the like are exemplified. In one embodiment, the mass ratio is preferably 0 to 700.

<Organic solvent: Also called component (D)>
In one embodiment, the coating agent may contain an organic solvent. The organic solvent may be used alone or in combination of two or more.

Organic solvents are ketone solvents such as methyl ethyl ketone, acetyl acetone, methyl isobutyl ketone and cyclohexanone; aromatic solvents such as toluene and xylene; alcohol solvents such as methanol, ethanol, n-propanol, isopropanol and butanol; ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, Glycol ether solvents such as triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and propylene glycol monomethyl ether acetate; ester solvents such as ethyl acetate, butyl acetate, methyl cellosolve acetate and cellosolve acetate; Examples thereof include petroleum-based solvents such as trade names (manufactured by Exxon); haloalkane solvents such as chloroform; and amide solvents such as dimethylformamide.

The upper and lower limits of the content of the organic solvent in 100% by mass of the coating agent are 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10 5, 0% by mass and the like are exemplified. In one embodiment, the content is preferably 0 to 90% by mass.

The organic solvent contained in the coating agent may contain an organic solvent used for producing the components (A) to (C).

<Additives>
The coating agent may contain an agent that does not correspond to any of the components (A) to (D) as an additive.

Examples of additives include photosensitizers, antioxidants, light stabilizers, leveling agents, pigments and the like.

In one embodiment, the content of the additive is exemplified by less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, 0 part by mass, etc. with respect to 100 parts by mass of the coating agent. .. Further, less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, 0 part by mass and the like are exemplified with respect to 100 parts by mass of any of the components (A) to (D).

The coating agent can be produced by dispersing and mixing the components (A) to (B), and if necessary, the components (C) to (D) and additives by various known means. The order of addition of each component is not particularly limited. Further, as the dispersion / mixing means, various known devices (emulsification disperser, ultrasonic disperser, etc.) can be used.

The coating agent can be used as a coating agent for a cyclic olefin resin that has not been subjected to an easy-adhesion treatment.

[Coating agent kit]
The present disclosure provides a coating agent kit containing the above-mentioned coating agent for cyclic olefin resin and a coating agent containing an oxime ester structure-free photopolymerization initiator.

<Coating agent containing an oxime ester structure-free photopolymerization initiator: Also referred to as an oxime-free coating agent>
The oxime ester structure-free photopolymerization initiator may be contained alone or in combination of two or more.

Examples of the oxime ester structure-free photopolymerization initiator include α-hydroxyalkylphenone, unsubstituted or substituted alkylphenone, unsubstituted or substituted benzyl, unsubstituted or substituted benzophenone, acylphosphine oxide, oxime ester, substituted thioxanthone and the like. ..

α-Hydroxyalkylphenone is 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-4'-(2-hydroxyethoxy) -2-methylpropiophenone (1- [4] -(2-Hydroxyethoxyl) -phenyl] -2-hydroxy-methylpropanol)), 2-hydroxy-1- (4- (4- (2-hydroxy-2-methylpropionyl) benzyl) phenyl) -2- Methylpropan-1-one) and the like are exemplified.

The unsubstituted or substituted alkylphenone is benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin ethyl ether, acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-phenyl-2. -(P-Toluenesulfonyloxy) acetophenone, benzoin, 2-benzyl-2- (dimethylamino) -4'-morpholinobtyrophenone, 2-methyl-4'-(methylthio) -2-morpholinopropiophenone, 2-iso Examples thereof include nitrosopropiophenone and 2,2-dimethoxy-1,2-diphenylethane-1-one.

Examples of the unsubstituted or substituted benzyl include unsubstituted or substituted benzyls such as benzyl and p-anisyl.

The unsubstituted or substituted benzophenone is benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-dichlorobenzophenone, 1,4-dibenzoylbenzene, 2- Examples thereof include benzoyl benzoic acid, 4-benzoyl benzoic acid, and methyl 2-benzoyl benzoate.

Examples of the acylphosphine oxide include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.

Examples of the substituted thioxanthone include 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone and the like.

Oxime-free coating agent The upper and lower limits of the content of the oxime ester structure-free photopolymerization initiator in 100% by mass of solid content are 30, 28, 25, 23, 20, 17, 15, 13, 10, 9, 7 5, 2, 1, 0.5% by mass and the like are exemplified. In one embodiment, the content is preferably 0.5 to 30% by mass.

In one embodiment, the oxime-free coating agent comprises an active energy ray-curable resin compound. The active energy ray-curable resin compound may be contained alone or in combination of two or more. Examples of the active energy ray-curable resin compound include those described above, such as alkylene poly (meth) acrylate having three or more (meth) acryloyl groups, oxyalkylene poly (meth) acrylate, and polymer poly (meth) acrylate.

<alkylene poly (meth) acrylate having 3 or more (meth) acryloyl groups>
The alkylene poly (meth) acrylate having three or more (meth) acryloyl groups includes pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin tri (meth) acrylate and the like. Is exemplified.

<Oxyalkylene poly (meth) acrylate>
Examples of the oxyalkylene poly (meth) acrylate include polypentaerythritol poly (meth) acrylate, polytrimethylolpropane poly (meth) acrylate, and polyglycerin poly (meth) acrylate.

In the present disclosure, the oxyalkylene poly (meth) acrylate is a compound having a plurality of oxy (meth) acryloyl groups, and the portion obtained by removing the oxy (meth) acryloyl group from the compound is an oxygen atom, a carbon atom and a hydrogen atom. It means a compound composed of only atoms bonded by a single bond.

（式中、ｍは１以上の整数であり、Ｒ^ｂ１〜Ｒ^ｂ６は、それぞれ独立に水素原子、又は（メタ）アクリロイル基であり、かつＲ^ｂ１〜Ｒ^ｂ６の少なくとも２つが（メタ）アクリロイル基である。なお、Ｒ^ｂ３及びＲ^ｂ５は、各構成単位ごとに基が異なっていてもよい。）
により示される化合物である。 (Polypentaerythritol poly (meth) acrylate)
Polypentaerythritol poly (meth) acrylate has the following structural formula

(In the formula, m is an integer of 1 or more, R ^{b1 to} R ^b6 are independently hydrogen atoms or (meth) acryloyl groups, and ^{at least two of R b1 to} R ^b6 are (meth) acryloyl groups. In addition, R ^b3 and R ^b5 may have different groups for each structural unit.)
It is a compound indicated by.

Ｒ^ｂ３ＡとＲ^ｂ３Ｂとは異なる基であってよく、Ｒ^ｂ５ＡとＲ^ｂ５Ｂとは異なる基であってよいことを意味する（以下同様）。 Further, "the group may be different for each structural unit" means, for example, when m is 2 in the above structural formula.

It ^means that R b3A and R ^b3B may be different groups, and R ^b5A and R ^b5B may be different groups (the same shall apply hereinafter).

Polypentaerythritol poly (meth) acrylate is dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa. (Meta) acrylate, tripentaerythritol di (meth) acrylate, tripentaerythritol tri (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, Examples thereof include trypentaerythritol hepta (meth) acrylate and tripentaerythritol octa (meth) acrylate.

（式中、ｐは１以上の整数であり、Ｒ^ｂ７〜Ｒ^ｂ１０は水素原子、又は（メタ）アクリロイル基であり、かつＲ^ｂ７〜Ｒ^ｂ１０の少なくとも２つが（メタ）アクリロイル基である。なお、Ｒ^ｂ９は、各構成単位ごとに基が異なっていてもよい。）
により示される化合物である。 (Polytrimethylolpropane poly (meth) acrylate)
Polytrimethylolpropane poly (meth) acrylate has the following structural formula.

(In the formula, p is an integer of 1 or more, R ^{b7 to} R ^b10 are hydrogen atoms or (meth) acryloyl groups, and ^{at least two of R b7 to} R ^b10 are (meth) acryloyl groups. , R ^b9 may have different groups for each structural unit.)
It is a compound indicated by.

Examples of the polytrimethylolpoly (meth) acrylate include ditrimethyloldi (meth) acrylate and ditrimethylolstyrene (meth) acrylate.

（式中、ｑは１以上の整数であり、Ｒ^ｂ１１〜Ｒ^ｂ１３は、それぞれ独立に水素原子、又は（メタ）アクリロイル基であり、かつＲ^ｂ１１〜Ｒ^ｂ１３の少なくとも２つが（メタ）アクリロイル基である。なお、Ｒ^ｂ１２は、各構成単位ごとに基が異なっていてもよい。）
により示される化合物である。 (Polyglycerin poly (meth) acrylate)
Polyglycerin poly (meth) acrylate has the following structural formula

(In the formula, q is an integer of 1 or more, R ^{b11 to} R ^b13 are independently hydrogen atoms or (meth) acryloyl groups, and ^{at least two of R b11 to} R ^b13 are (meth) acryloyl groups. In addition, R ^b12 may have a different group for each structural unit.)
It is a compound indicated by.

Examples of the polyglycerin poly (meth) acrylate include diglycerin di (meth) acrylate, diglycerin tri (meth) acrylate, and diglycerin tetra (meth) acrylate.

The oxyalkylene poly (meth) acrylate may be alkylene oxide-modified or epoxy-modified.

（式中、ｑは１〜１６の整数であり、Ｒ^１’〜Ｒ^２’はそれぞれ独立に水素原子又はアルキル基であり、Ｒ^１’は各単位ごとに基が異なっていてもよい。）
に置換された化合物である。 The oxyalkylene poly (alkylene oxide-modified (meth) acrylate) contains the oxy (meth) acryloyl group of the above-mentioned oxyalkylene poly (meth) acrylate.

(Wherein, q is 1 to 16 integer, R 1 ^{'~R 2'} are each independently a hydrogen atom or an alkyl group, R 1 ^'may be different groups for each unit.)
It is a compound substituted with.

（式中、Ｒ^{３ ’}はそれぞれ独立に水素原子又はアルキル基である。）
に置換された化合物である。 The oxyalkylene poly (epoxy-modified (meth) acrylate) has the oxy (meth) acryloyl group of the above-mentioned oxyalkylene poly (meth) acrylate.

(Wherein, R ^{3 'is} independently a hydrogen atom or an alkyl group.)
It is a compound substituted with.

<Polymer poly (meth) acrylate>
In the present disclosure, "polymer poly (meth) acrylate" means a polymer having two or more (meth) acryloyl groups.

Polymer poly (meth) acrylates can be produced using known techniques. Examples of the method for producing the polymer poly (meth) acrylate include a method of reacting an epoxy group-containing (meth) acrylic polymer with an α, β-unsaturated carboxylic acid.

The upper and lower limits of the content of the epoxy group-containing (meth) acrylate-derived structural unit in 100 mol% of the total structural unit of the epoxy group-containing (meth) acrylic polymer are 100, 95, 90, 85, 80, 75, 70. , 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 7 mol% and the like. In one embodiment, the content is preferably 7-100 mol%.

The upper and lower limits of the content of the epoxy group-containing (meth) acrylate-derived structural unit in 100% by mass of the total structural unit of the epoxy group-containing (meth) acrylic polymer are 100, 95, 90, 85, 80, 75, 70. , 65, 62, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10% by mass and the like. In one embodiment, the content is preferably 10 to 100% by mass.

The upper and lower limits of the content of the hydroxyl group-free alkyl (meth) acrylate-derived structural unit in 100 mol% of the total structural unit of the epoxy group-containing (meth) acrylic polymer are 93, 90, 85, 80, 75, 70, Examples thereof include 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 0 mol% and the like. In one embodiment, the content is preferably 0 to 93 mol%.

The upper and lower limits of the content of the hydroxyl group-free alkyl (meth) acrylate-derived structural unit in 100% by mass of the total structural unit of the epoxy group-containing (meth) acrylic polymer are 90, 85, 80, 75, 70, 65, Examples thereof include 60, 55, 50, 45, 40, 38, 35, 30, 25, 20, 15, 10, 5, 0% by mass and the like. In one embodiment, the content is preferably 0 to 90% by mass.

The upper and lower limits of the amount of α, β-unsaturated carboxylic acid to react with 100 mol% of the constituent unit derived from the epoxy group-containing (meth) acrylate are 100, 95, 90, 85, 80, 75, 70, 65, Examples include 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10 mol% and the like. In one embodiment, the amount is preferably 10 to 100 mol%.

The upper and lower limits of the amount of α, β-unsaturated carboxylic acid to be reacted with respect to 100% by mass of the constituent unit derived from the epoxy group-containing (meth) acrylate are 50, 45, 40, 35, 30, 25, 20, 15, and so on. Examples include 10, 5% by mass and the like. In one embodiment, the amount is preferably 5 to 50% by mass.

Epoxy group-containing (meth) acrylic polymers can be produced using known radical polymerization methods.

In one embodiment, the active energy ray-curable resin compound contained in the oxime-free coating agent is preferably an oxyalkylene poly (meth) acrylate.

The upper and lower limits of the content of the active energy ray-curable resin compound in 100% by mass of the oxime-free coating agent solid content are 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45. , 40, 35, 30, 25, 20, 15, 10, 5, 1, 0% by mass and the like. In one embodiment, the content is preferably 0 to 100% by mass.

In one embodiment, the oxime-free coating agent comprises a UV absorber. The UV absorber may be contained alone or in combination of two or more. Examples of the ultraviolet absorber include those described above.

The upper and lower limits of the content of the ultraviolet absorber in 100% by mass of the oxime-free coating agent solid content are 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15 10, 5, 1, 0% by mass and the like are exemplified. In one embodiment, the content is preferably 0 to 80% by mass.

In one embodiment, the oxime-free coating may include an organic solvent. The organic solvent may be used alone or in combination of two or more. Examples of the organic solvent include those described above.

The upper and lower limits of the content of the organic solvent in 100% by mass of the oxime-free coating agent are 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, Examples include 15, 10, 5, 1, 0% by mass and the like. In one embodiment, the content is preferably 0 to 90% by mass.

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

Examples of the curing conditions are those described below.

[Laminate]
The present disclosure provides a laminate containing the cured product.

In one embodiment, a coating agent for a cyclic olefin resin or a cured product layer made of a cured product of the coating agent kit is laminated on at least one surface of a cyclic olefin resin base material. In one embodiment, the cyclic olefin resin coating agent cured product layer composed of the cured product of the cyclic olefin resin coating agent is laminated on at least one surface of the cyclic olefin resin base material to form the cyclic olefin resin coating agent cured product layer. An oxime-free coating agent cured product layer composed of a cured product of an oxime-free coating agent is laminated.

The thickness of the cyclic olefin resin base material is not particularly limited, but is preferably about 10 to 2000 μm. The thickness of the cured product layer is not particularly limited, but is preferably about 0.1 to 5 μm.

In one embodiment, the cyclic olefin resin base material is a cyclic olefin resin base material that has not been subjected to an easy adhesion treatment.

The laminate is produced by various known methods. In one embodiment, the method for producing a laminate is a step of applying an undercoating agent to at least one surface of a base material (coating step), or by irradiating an active energy ray with an active energy ray-curable resin cured product. It includes a step of forming a layer (active energy ray curing step).

(Coating process)
Examples of coating methods include bar coater coating, wire bar coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, flow coating coating, offset printing, flexographic printing, screen printing method, etc. Will be done.

The amount of coating is not particularly limited. The amount of coating is preferably about 0.1 to 30 g / m ² after drying, and more preferably about 1 to ²⁰ g / m 2.

(Active energy ray curing process)
Examples of the active energy ray used for the active energy ray curing reaction include ultraviolet rays and electron beams. Examples of the ultraviolet light source include a xenon lamp, a high-pressure mercury lamp, an ultraviolet irradiation device having a metal halide lamp, and the like. The amount of light, the arrangement of the light source, the transport speed, and the like can be adjusted as needed. When a high-pressure mercury lamp is used, it is preferable to cure one lamp having a light amount of about 80 to 160 W / cm at a transport speed of about 2 to 50 m / min. On the other hand, in the case of an electron beam, it is preferable to cure it with an electron beam accelerator having an acceleration voltage of about 10 to 300 kV at a transport speed of about 5 to 50 m / min.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. However, the above description of the preferred embodiment and the following examples are provided only for the purpose of illustration, and are not provided for the purpose of limiting the present invention. Therefore, the scope of the present invention is not limited to the embodiments or examples specifically described in the present specification, but is limited only by the claims. Further, in each Example and Comparative Example, unless otherwise specified, numerical values such as parts and% are based on mass.

Example 1
In a reaction vessel equipped with a stirrer, thermometer, dropping funnel, cooling tube and air inlet, 95 parts by mass of HDDA (manufactured by Daicel Ornex Co., Ltd.) as solid content, Irgacure OXE01 (manufactured by BASF Japan Ltd.) 5 parts by mass of the solid content was mixed, and the solid content was adjusted to 20% with methyl ethyl ketone to obtain a resin composition. The produced resin composition was applied to a 100 μm-thick Zeonoa film ZF-16 (manufactured by Nippon Zeon Corporation) using a bar coater so that the film thickness after drying was 1 μm, and the temperature was 80 ° C. for 60 seconds. It was dried in a commercially available warm air dryer. Then, a laminate was obtained by irradiating with an ultraviolet ray of ^{300 mJ / cm 2} using a metal halide lamp in a nitrogen atmosphere.

Unless otherwise specified, Examples and Comparative Examples were carried out in the same manner as in Example 1 except that they were changed as shown in the table below.

Example 5
In a reaction vessel equipped with a stirrer, thermometer, dropping funnel, cooling tube and air inlet, 55 parts by mass of Viscote # 300 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) as a solid content, photopolymerization initiator OMNIRAD 184 (IGM) Mix 5 parts by mass of Regins (manufactured by Regins Co., Ltd.) and 40 parts by mass of the ultraviolet absorber TINUVIN477 (manufactured by BASF Japan Ltd.) as a solid content, and adjust the solid content to 30% with methyl ethyl ketone. Obtained a resin composition. The produced resin composition was applied onto the laminate produced in Example 2 using a bar coater so that the film thickness after drying was 3 μm, and the temperature was 80 ° C. for 60 seconds in a commercially available warm air dryer. It was dried. Then, a laminate was obtained by irradiating with an ultraviolet ray of ^{300 mJ / cm 2} using a metal halide lamp in a nitrogen atmosphere.

<Explanation of abbreviations>
HDDA: 1,6-Hexanediol diacrylate (manufactured by Daicel Ornex Co., Ltd.)
Light Acrylate MPD-A: 3-Methyl-1,5-pentanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.)
Light Acrylate A-DCP: Tricyclodecanedimethanol Diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.)
Viscoat # 300: Mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate Mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)

Irgacure OXE01: 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (ie 2-((benzoyloxy) imino) -1-(4- (phenylthio) phenyl) ) Octane-1-on) (manufactured by BASF Japan Ltd.)
Irgacure OXE02: Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime) (ie 1-(((1- (9) 1- (9) -Ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl) etylidene) amino) oxy) ethane-1-one) (manufactured by BASF Japan Ltd.)
Irgacure OXE03: Oxime ester structure-containing photopolymerization initiator (manufactured by BASF Japan Ltd.)
Irgacure OXE04: Oxime ester structure-containing photopolymerization initiator (manufactured by BASF Japan Ltd.)

OMNIRAD 184: 1-Hydroxycyclohexyl-phenylketone (manufactured by IGM Regins Co., Ltd.)
Speedcure TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by LAMBSON)
OMNIRAD 819: Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (manufactured by IGM Regins Co., Ltd.)
OMNIRAD 754: A mixture of 2- [2-oxo-2-phenyl-acetoxy-ethoxy] ethyl ester of oxyphenylacetic acid and 2- [2-hydroxy-ethoxy] ethyl ester of oxyphenylacetic acid (manufactured by IGM Regins Co., Ltd.)
OMNIRAD 907: 2-Methyl-1- [4- (Methylthio) Phenyl] -2-morpholinopropane-1-one (manufactured by IGM Regins Co., Ltd.)
OMNIRAD 127: 2-Hydroxy-1- (4- (4- (2-hydroxy-2-methylpropionyl) benzyl) phenyl) -2-methylpropan-1-one (manufactured by IGM Regins Co., Ltd.)
Esacure One: Bifunctional alpha hydroxyketone (manufactured by IGM Regins Co., Ltd.)

TINUVIN 477: UV absorber (hydroxyphenyltriazine) (manufactured by BASF Japan Ltd.)

<Evaluation of substrate adhesion>
The adhesion of the laminate obtained above was evaluated by a 100-square grid peeling test according to JIS K5600-5-4. The display of the result is (the number of squares remaining in the peeling test / 100).

Claims (6)

The active energy ray curable resin compound containing alkylene (meth) acrylate, and the oxime ester structure-containing photopolymerization initiator seen including,
The content of the organic solvent in 100% by mass of the coating agent is 10 to 90% by mass.
A coating agent for a cyclic olefin resin that has not been subjected to an easy-adhesion treatment, which is directly applied to a cyclic olefin resin that has not been subjected to an easy-adhesion treatment. A coating agent for a cyclic olefin resin that contains an ultraviolet absorber and has not undergone the easy-adhesion treatment according to claim 1. A coating agent for a cyclic olefin resin that does not have undergone the easy-adhesion treatment according to claim 1 or 2, which contains only cycloalkylene di (meth) acrylate as an active energy ray-curable resin compound. A coating agent kit comprising a coating agent for a cyclic olefin resin which has not been subjected to the easy-adhesion treatment according to any one of claims 1 to 3 and a coating agent containing an oxime ester structure-free photopolymerization initiator. The coating agent for a cyclic olefin resin that has not been subjected to the easy-adhesion treatment according to any one of claims 1 to 3, or the cured product of the coating agent kit according to claim 4. A laminate containing the cured product according to claim 5.