JP2020019827A - Undercoat agent and film - Google Patents

Abstract

To provide an undercoat agent and a film.SOLUTION: The present invention provides an undercoat agent containing a hydroxy group-containing (meth) acryl copolymer (A), a hydroxy group-containing poly (meth) acrylate (B), and polyisocyanate (C). According to one embodiment, it contains a photopolymerization initiator (D), and the hydroxy group-containing poly (meth) acrylate (B) is a hydroxy group-containing polymer poly (meth) acrylate, and a solid content mass ratio ((A)/(B)) of the hydroxy group-containing poly (meth) acryl copolymer (A) and the hydroxy group-containing poly (meth) acrylate (B) is 97/3-5/95.SELECTED DRAWING: None

Description

  The present disclosure relates to undercoat agents and films.

  As a method for producing a film, a method is known in which an undercoat agent is applied to the surface of a base and an undercoat layer is provided. Various undercoat agents have been developed according to the type of the base material.

  Patent Document 1 (Japanese Patent Application Laid-Open No. 2011-195835) discloses an undercoat agent containing a polyaziridine compound.

JP 2011-195835 A

  The undercoat agent described above is for producing an undercoat layer provided between the inorganic thin film and the substrate. In recent years, an undercoat agent for producing an undercoat layer provided between an active energy ray-curable resin and a substrate has been required.

  An object of the present invention is to provide an undercoat agent which is excellent in blocking resistance and excellent in interlayer adhesion between an active energy ray-curable resin and a substrate at an initial stage and after a wet heat resistance test.

  The present inventors have conducted intensive studies and as a result, the above-mentioned problems have been solved by including a hydroxyl group-containing (meth) acrylic copolymer, a hydroxyl group-containing poly (meth) acrylate, a polyisocyanate, and a photopolymerization initiator in an undercoat agent. I found that.

The following items are provided by the present disclosure.
(Item 1)
Hydroxyl-containing (meth) acrylic copolymer (A),
Hydroxyl-containing poly (meth) acrylate (B) and polyisocyanate (C)
And an undercoat agent.
(Item 2)
The undercoat agent according to the above item, comprising a photopolymerization initiator (D).
(Item 3)
The undercoat agent according to any one of the preceding items, wherein the hydroxyl group-containing poly (meth) acrylate (B) is a hydroxyl group-containing polymer poly (meth) acrylate.
(Item 4)
The solid content mass ratio ((A) / (B)) of the hydroxyl group-containing poly (meth) acrylic copolymer (A) and the hydroxyl group-containing poly (meth) acrylate (B) is 97/3 to 5/95. The undercoat agent according to any one of the above items.
(Item 5)
Any of the preceding items, wherein the ratio (NCO / OH) of the isocyanate group equivalent of the polyisocyanate (C) to the hydroxyl equivalent of the hydroxyl-containing poly (meth) acrylic polymer (A) is 0.05 to 2. The undercoat agent according to the above item.
(Item 6)
A film in which a cured undercoat agent layer containing a cured product of the undercoat agent according to any one of the above items is laminated on at least one surface of the film.
(Item 7)
The film according to the above item, wherein an active energy ray-curable resin cured material layer is laminated on the undercoat agent cured material layer.

  In this disclosure, one or more of the features described above may be provided in combination with the explicit combinations as well as further.

  The undercoat agent has excellent blocking resistance and excellent interlayer adhesion between the active energy ray-curable resin and the substrate at the initial stage and after the wet heat resistance test.

  Throughout the present disclosure, ranges of numerical values such as physical properties and contents can be set as appropriate (for example, by selecting from upper and lower limits described in the following items). Specifically, as for the numerical value α, the upper limit of the numerical value α is, for example, A1, A2, A3, and the like, and the lower limit of the numerical value α is, for example, B1, B2, B3, and the like. A2 or less, A3 or less, B1 or more, B2 or more, B3 or more, A1-B1, A1-B2, A1-B3, A2-B1, A2-B2, A2-B3, A3-B1, A3-B2, A3-B3 Etc. are exemplified.

[Undercoat agent]
The present disclosure provides an undercoating agent comprising a hydroxyl-containing (meth) acrylic copolymer (A), a hydroxyl-containing poly (meth) acrylate (B), and a polyisocyanate (C).

  In the present disclosure, “(meth) acryl” means “at least one selected from the group consisting of acryl 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”.

<Hydroxy group-containing (meth) acrylic copolymer (A): Also referred to as component (A)>
In the present disclosure, “hydroxyl-containing (meth) acrylic copolymer” is a copolymer containing a structural unit derived from a hydroxyl-free alkyl (meth) acrylate (a1) and a structural unit derived from a hydroxyl-containing alkyl (meth) acrylate (a2). It is. In the undercoat agent, two or more hydroxyl group-containing (meth) acrylic copolymers (A) may be used in combination.

(Hydroxyl-free alkyl (meth) acrylate (a1): Also referred to as component (a1))
The component (a1) has the following structural formula (a1)
(In the formula, R ^a1 is a hydrogen atom or a methyl group, and R ^a2 is a linear alkyl group, a branched alkyl group, or a cycloalkyl group.)
Is represented by As the component (a1), various known components can be used without particular limitation. As the component (a1), two or more types may be used in combination.

  Examples of the alkyl group include a linear alkyl group and a branched alkyl group.

Straight chain alkyl _{group, -C n H 2n + 1 (} n is an integer of 1 or more) represented by the general formula. Linear alkyl groups include methyl, ethyl, propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decamethyl and the like. Is exemplified.

  A branched alkyl group is a group in which at least one hydrogen of a linear alkyl group has been replaced by an alkyl group. Examples of the branched alkyl group include a diethylpentyl group, a trimethylbutyl group, a trimethylpentyl group, and a trimethylhexyl group.

  Examples of the cycloalkyl group include a monocyclic cycloalkyl group, a bridged ring cycloalkyl group, a condensed ring cycloalkyl group, and the like.

  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 bridged ring cycloalkyl group include a tricyclodecyl group, an adamantyl group, a norbornyl group, and the like.

  Examples of the fused ring cycloalkyl group include a bicyclodecyl group.

  Examples of the non-hydroxyl-containing alkyl (meth) acrylate (a1) include a non-hydroxyl-containing linear alkyl (meth) acrylate, a non-hydroxyl-containing branched alkyl (meth) acrylate, and a non-hydroxyl-containing cycloalkyl (meth) acrylate.

  Hydroxyl-free linear alkyl (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, and hexyl (meth) acrylate. , Heptyl (meth) acrylate, octyl (meth) acrylate, hexadecyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, icosyl (meth) acrylate, docosyl (meth) acrylate Is exemplified.

  Hydroxy group-free branched alkyl (meth) acrylates are isopropyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2- (meth) acrylate Ethylhexyl and the like are exemplified.

  Examples of the hydroxyl group-free cycloalkyl (meth) acrylate include cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, and the like.

  Among these, an alkyl (meth) acrylate having an alkyl group having about 1 to 20 carbon atoms is preferable because it contributes to the leveling property and the adhesion in the undercoat agent. In addition, by using the component (a1) having a different number of carbon atoms in the alkyl group, the physical properties such as the glass transition temperature of the component (A) can be adjusted.

  The upper limit of the content of the structural unit derived from the component (a1) in 100 mol% of all the structural units of the component (A) is exemplified by 98, 95, 90, 85, 80, 75, 70, 65 mol%, and the like. The lower limit is exemplified by 95, 90, 85, 80, 75, 70, 65, 62 mol%. In one embodiment, the range of the content of the structural unit derived from the component (a1) in 100 mol% of the total structural units of the component (A) is preferably about 62 to 98 mol%.

  The upper limit of the content of the structural unit derived from the component (a1) in 100% by mass of all the structural units of the component (A) is exemplified by 98, 95, 90, 85, 80, 75, 70% by mass, and the like, and the lower limit is , 95, 90, 85, 80, 75, 70, 65% by mass and the like. In one embodiment, the range of the content of the structural unit derived from the component (a1) in 100% by weight of the total structural units of the component (A) is preferably about 65 to 98% by mass.

(Hydroxyl-containing alkyl (meth) acrylate (a2): Also referred to as component (a2))
The component (a2) has the following structural formula (a2)
(In the formula, ^Ra3 is a hydrogen atom or a methyl group, and ^Ra4 is a linear alkylene group, a branched alkylene group, or a cycloalkylene group.)
Is represented by As the component (a2), various known components can be used without particular limitation. As the component (a2), two or more types may be used in combination.

  Examples of the hydroxyl group-containing alkyl (meth) acrylate (a2) include a hydroxyl group-containing linear alkyl (meth) acrylate, a hydroxyl group-containing branched alkyl (meth) acrylate, and a hydroxyl group-containing cycloalkyl (meth) acrylate. From the viewpoint of the pot life of the undercoat agent and the like, those having about 1 to 4 carbon atoms in the hydroxyalkyl group are preferred.

  Examples of the hydroxyl group-containing linear alkyl (meth) acrylate include hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.

  Examples of the hydroxyl group-containing branched alkyl (meth) acrylate include 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxybutyl (meth) acrylate.

  Examples of the hydroxyl group-containing cycloalkyl (meth) acrylate include hydroxycyclohexyl (meth) acrylate and 4- (hydroxymethyl) cyclohexylmethyl (meth) acrylate.

  The upper limit of the content of the structural unit derived from the component (a2) relative to 100 mol% of all the structural units of the component (A) is 38, 35, 30, 25, 20, 15, 10, 5, 2.5 mol% or the like. And the lower limit is, for example, 35, 30, 25, 20, 15, 10, 5, 2.5, 1.5 mol%, or the like. In one embodiment, the range of the content of the constituent unit derived from the component (a2) in the total constituent unit of 100 mol% of the component (A) is preferably about 1.5 to 38 mol%.

  The upper limit of the content of the structural unit derived from the component (a2) occupying 100% by mass of all the structural units of the component (A) is, for example, 35, 30, 25, 20, 15, 10, 5, 2.5% by mass. The lower limit is, for example, 30, 25, 20, 15, 10, 5, 2.5, or 2% by mass. In one embodiment, the range of the content of the structural unit derived from the component (a2) in 100% by weight of the total structural units of the component (A) is preferably about 2 to 35% by mass.

The upper limit of the substance amount ratio ((a1) _mol / (a2) _mol ) of the constituent unit derived from the component (a1) and the constituent unit derived from the component (a2) in the component (A) is 57, 50, 40, 30. , 20, 10, 5, 2, etc., and the lower limit is 55, 50, 40, 30, 20, 10, 5, 2, 1.6, etc. In one embodiment, the substance ratio ((a1) _mol / (a2) _mol ) of the structural unit derived from the component (a1) to the structural unit derived from the component (a2) in the component (A) is 1.6. About 57 is preferable.

The upper limit of the mass ratio ((a1) _mass / (a2) _mass ) of the structural unit derived from the component (a1) to the structural unit derived from the component (a2) in the component (A) is 49, 40, 30, 20, or 10, 5, 2, etc. are exemplified, and the lower limit is, for example, 45, 40, 30, 20, 10, 5, 2, 1.8, etc. In one embodiment, the mass ratio ((a1) _mass / (a2) _mass ) of the structural unit derived from the component (a1) to the structural unit derived from the component (a2) in the component (A) is 1.8 to 1.8. About 49 is preferable.

(Monomer (a3) other than component (a1) and component (a2): Also referred to as component (a3))
When producing the component (A), a monomer (a3) that does not correspond to either the component (a1) or the component (a2) may be used. As the component (a3), two or more types may be used in combination. When the component (a3) is used in producing the component (A), the component (A) is incorporated into the polymer as a constituent unit derived from the component (a3).

The component (a3) includes (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, 3-carboxypropyl (meth) acrylate, 4-carboxybutyl (meth) acrylate, 3-butenoic acid, 4-pentenoic acid, Α, β-unsaturated carboxylic acids such as hexenoic acid, maleic acid, crotonic acid, maleic anhydride, fumaric acid and itaconic acid;
Epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate and β-methylglycidyl (meth) acrylate;
Styrenes such as styrene, α-methylstyrene and t-butylstyrene;
Α-olefins such as 2,4,4-trimethyl-1-pentene, 3-methyl-1-butene, 3-methyl-1-pentene, 1-hexene, vinylcyclohexane and 2-methylvinylcyclohexane;
Unsaturated alcohols such as (meth) allyl alcohol, 4-penten-1-ol, 1-methyl-3-buten-1-ol and 5-hexen-1-ol;
Aryl (meth) acrylates such as phenyl (meth) acrylate, benzyl (meth) acrylate and 4-methylbenzyl (meth) acrylate;
Dialkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate and salts thereof ;
Dialkylaminoalkyl (meth) acrylamides such as dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide and diethylaminopropyl (meth) acrylamide, and salts thereof;
N, N-dimethyl (meth) acrylamide, diacetone (meth) acrylamide, isopropyl (meth) acrylamide, 2- (meth) acrylamide-2-methylpropanesulfonic acid, 2- (meth) acrylamide-2-methylpropanecarboxylic acid And chain transfer monomers such as salts thereof;
Acrylonitrile such as (meth) acrylonitrile and methacrylonitrile;
Acrylamides such as (meth) acrylamide, N-methylol (meth) acrylamide;
Monofunctional monomers other than the above, such as vinylamine, aminoethyl (meth) acrylate, allyl mercaptan and glycidyl (meth) acrylate;
Bis (meth) acrylamides such as methylenebis (meth) acrylamide, ethylenebis (meth) acrylamide and hexamethylenebis (meth) acrylamide;
Di (meth) acrylic esters such as ethylene glycol di (meth) acrylic ester and diethylene glycol di (meth) acrylic ester; divinyl esters such as divinyl adipate and divinyl sebacate;
Other bifunctional monomers such as diallyldimethylammonium, diallylphthalate, diallylchlorendate and divinylbenzene;
Trifunctional monomers such as 1,3,5-triacryloylhexahydro-S-triazine, triallyl isocyanurate, triallylamine, triallyl trimellitate and N, N-diallylacrylamide;
Examples include tetrafunctional monomers such as tetramethylol methane tetraacrylate, tetraallyl pyromellitate and N, N, N ', N'-tetraallyl-1,4-diaminobutane.

  The upper limit of the content of the structural unit derived from the component (a3) relative to 100 mol% of all the structural units of the component (A) is, for example, 13, 10, 9, 5, 4, 1 mol%, and the like, and the lower limit is 12 , 10, 9, 5, 4, 1, 0 mol% and the like. In one embodiment, the range of the content of the structural unit derived from the component (a3) relative to 100 mol% of the total structural units of the component (A) is preferably about 0 to 13 mol%.

  The upper limit of the content of the structural unit derived from the component (a3) occupying 100% by mass of all the structural units of the component (A) is exemplified by 10, 9, 5, 4, 1 mol%, and the like, and the lower limit is 9, 5 4, 1, 0 mol% and the like. In one embodiment, the range of the content of the constituent unit derived from the component (a3) in 100% by mass of all the constituent units of the component (A) is preferably about 0 to 10% by mass.

The upper limit of the substance amount ratio ((a3) _mol / (a1) _mol ) of the structural unit derived from the component (a1) to the structural unit derived from the component (a3) in the component (A) is 0.22, 0.20. , 0.15, 0.10, 0.05, etc., and the lower limit is 0.20, 0.15, 0.10, 0.05, 0, etc. In one embodiment, the substance amount ratio ((a3) _mol / (a1) _mol ) of the structural unit derived from the component (a1) to the structural unit derived from the component (a3) in the component (A) is 0 to 0. .22 is preferable.

The upper limit of the mass ratio ((a3) _mass / (a1) _mass ) of the structural unit derived from the component (a1) to the structural unit derived from the component (a3) in the component (A) is 0.19, 0.15, 0.10, 0.05, etc. are exemplified, and the lower limit is 0.15, 0.10, 0.05, 0, etc. In one embodiment, the mass ratio ((a3) _mass / (a1) _mass ) of the structural unit derived from the component (a1) to the structural unit derived from the component (a3) in the component (A) is 0 to 0.1. About 19 is preferable.

The upper limit of the substance amount ratio ((a3) _mol / (a2) _mol ) of the constituent unit derived from the component (a2) to the constituent unit derived from the component (a3) in the component (A) is 8.0 or 7.0. , 6.0, 5.0, 4.0, 3.0, 2.0, 1.0, 0.5, etc., and the lower limit is 7.5, 7.0, 6.0, 5.0. 0, 4.0, 3.0, 2.0, 1.0, 0.5, 0 and the like. In one embodiment, the substance ratio ((a3) _mol / (a2) _mol ) of the structural unit derived from the component (a2) to the structural unit derived from the component (a3) in the component (A) is 0 to 8; 0.0 is preferable.

The upper limit of the mass ratio ((a3) _mass / (a2) _mass ) of the structural unit derived from the component (a2) and the structural unit derived from the component (a3) in the component (A) is 5.0, 4.0, 3.0, 2.0, 1.0, 0.5, etc. are exemplified, and the lower limit is 4.5, 4.0, 3.0, 2.0, 1.0, 0.5, 0, etc. Is exemplified. In one embodiment, the mass ratio ((a3) _mass / (a2) _mass ) of the constituent unit derived from the component (a2) to the constituent unit derived from the component (a3) in the component (A) is from 0 to 5. About 0 is preferable.

  The component (A) can be produced by various known methods. The method for producing the component (A) is as follows: the component (a1) and the component (a2), and if necessary, the component (a3) are prepared in the absence of a solvent or in an organic solvent in the presence of a polymerization initiator at 80 to 180 ° C. For example, a method of causing a copolymerization reaction for about 1 to 10 hours is exemplified. Examples of the organic solvent and the polymerization initiator used for producing the component (A) include those described below.

  The upper limit of the glass transition temperature of the component (A) is, for example, 100, 90, 80, 70, 60, 50, 40, 35 ° C., and the lower limit is 95, 90, 80, 70, 60, 50, 40, 40. 35, 30, and 20 ° C. are exemplified. In one embodiment, the glass transition temperature of the component (A) is preferably about 20 to 100 ° C, more preferably about 30 to 80 ° C. The glass transition temperature is measured using a commercially available measuring instrument (for example, product name “DSC8230B”, manufactured by Rigaku Corporation).

  The upper limit of the hydroxyl equivalent of the component (A) is, for example, 2.7, 2.5, 2.0, 1.8, 1.5, 1.0, 0.5, 0.25 meq / g and the like, and the lower limit. Is 2.5, 2.0, 1.8, 1.5, 1.0, 0.5, 0.25, 0.17 meq / g and the like. In one embodiment, the hydroxyl equivalent of the component (A) is preferably about 0.17 to 2.7 meq / g, more preferably about 0.5 to 1.8 meq / g. In the present disclosure, the hydroxyl equivalent is the amount of the hydroxyl group present in 1 g of solid.

  The upper limit of the hydroxyl value (solid base) of the component (A) is exemplified by 150, 140, 130, 120, 110, 100, 90, 80, 70, 60, 50, 40, 30, 20, 15 mg KOH / g, and the like. The lower limit is exemplified by 140, 130, 120, 110, 100, 90, 80, 70, 60, 50, 40, 30, 20, 15, 10 mg KOH / g and the like. In one embodiment, the hydroxyl value (solid content of the main component) of the component (A) is preferably about 10 to 150 mgKOH / g, more preferably about 30 to 100 mgKOH / g.

  In the present disclosure, the hydroxyl value is measured, for example, by a method based on JIS K1557-1.

  The upper limit of the acid value of the component (A) is, for example, 0.4, 0.3, 0.2, 0.18, 0.1, 0.09, 0.05 meq / g, and the like. 35, 0.3, 0.2, 0.18, 0.1, 0.09, 0.05, 0.04 meq / g and the like. In one embodiment, the acid value of the component (A) is preferably about 0.04 to 0.4 meq / g, and more preferably about 0.09 to 0.18 meq / g, particularly in consideration of curability. The acid value is measured by a method according to JIS K0070.

  The upper limit of the weight average molecular weight (Mw) of the component (A) is, for example, 100,000, 90,000, 80,000, 70,000, 60,000, 50,000, 40,000, 30,000, 20,000, 10,000, 5000, 4000, and the like, and the lower limit is 90,000, 80,000. 70,000, 60,000, 50,000, 40,000, 30,000, 20,000, 10,000, 5000, 4000, 3000 and the like. In one embodiment, the weight average molecular weight (Mw) of the component (A) is preferably about 3,000 to 100,000, and more preferably 10,000 to 80,000, from the viewpoints of blocking resistance, initial adhesion, and wet heat resistance of the undercoat agent. The degree is more preferred.

  The upper limit of the number average molecular weight (Mn) of the component (A) is, for example, 100,000, 90,000, 80,000, 70,000, 60,000, 50,000, 40,000, 30,000, 20,000, 10,000, 5,000, 4000, and the like, and the lower limit is 90,000, 80,000. 70,000, 60,000, 50,000, 40,000, 30,000, 20,000, 10,000, 5000, 4000, 3000 and the like. In one embodiment, the number average molecular weight (Mn) of the component (A) is preferably about 3,000 to 100,000, and more preferably 10,000 to 80,000, from the viewpoints of blocking resistance, initial adhesion, and wet heat resistance of the undercoat agent. The degree is more preferred.

  The weight average molecular weight and the number average molecular weight are measured using a commercially available gel permeation chromatography device (for example, product name “HLC-8220GPC”, manufactured by Tosoh Corporation).

  The upper limit of the molecular weight distribution (Mw / Mn) of the component (A) is, for example, 10, 7.5, 5, 2.5, 2, or the like, and the lower limit is 9.5, 7.5, 5, 2.5. In one embodiment, for example, 2, 1.5, etc., the molecular weight distribution (Mw / Mn) of the component (A) is preferably about 1.5 to 10.

  The upper limit of the content of the component (A) in the undercoat agent is, for example, 88, 85, 80, 70, 60, 50, 40, 30, 20, 10, 5% by mass or the like, and the lower limit is 85, 80. , 70, 60, 50, 40, 30, 20, 10, 5, 3% by mass and the like. In one embodiment, the content of the component (A) in the undercoat agent is preferably about 3 to 88% by mass.

<Hydroxyl-containing poly (meth) acrylate (B): Also referred to as component (B)>
In the present disclosure, “hydroxyl group-containing poly (meth) acrylate” means a compound having one or more hydroxyl groups and two or more (meth) acryloyl groups. In the undercoat agent, the poly (meth) acrylate (B) may be used alone, or two or more kinds may be used in combination.

  Examples of the hydroxyl group-containing poly (meth) acrylate include a hydroxyl group-containing polymer poly (meth) acrylate and a hydroxyl group-containing oligomer poly (meth) acrylate.

(Hydroxyl-containing polymer poly (meth) acrylate)
In the present disclosure, “hydroxyl group-containing polymer poly (meth) acrylate” means a polymer having one or more hydroxyl groups and two or more (meth) acryloyl groups.

  The hydroxyl group-containing polymer poly (meth) acrylate can be produced using a known technique. Examples of the method for producing the polymer poly (meth) acrylate include a method of reacting an epoxy group-containing (meth) acrylic copolymer with an α, β-unsaturated carboxylic acid. Examples of the epoxy group-containing (meth) acrylate and α, β-unsaturated carboxylic acid include those described above.

  The epoxy group-containing (meth) acrylic copolymer can be produced using a known technique. The epoxy group-containing (meth) acrylic copolymer is produced by using an epoxy group-containing (meth) acrylate instead of the hydroxyl group-containing alkyl (meth) acrylate (a2) in the production of the hydroxyl group-containing (meth) acrylic copolymer (A). Can be manufactured.

(Hydroxyl-containing oligomer poly (meth) acrylate)
Examples of the hydroxyl group-containing oligomer poly (meth) acrylate include hydroxyl group-containing (poly) pentaerythritol poly (meth) acrylate, hydroxyl group-containing (poly) trimethylolpropane poly (meth) acrylate, and hydroxyl group-containing glycerin di (meth) acrylate. .

(Hydroxy group-containing (poly) pentaerythritol poly (meth) acrylate)
Hydroxyl-containing (poly) pentaerythritol poly (meth) acrylate has the structural formula (1)
(In the formula, m is an integer of 0 or more, R ^{b1 to} R ^b6 are each independently a hydrogen atom or a (meth) acryloyl group, and at least two of R ^{b1 to} R ^b6 are a (meth) acryloyl group And at least one of R ^{b1 to} R ^b6 is a hydrogen atom. The groups of R ^b3 and R ^b5 may be different for each structural unit.)
Is a compound represented by

  In the present disclosure, “(poly) pentaerythritol poly (meth) acrylate” means “at least one selected from the group consisting of pentaerythritol poly (meth) acrylate and polypentaerythritol poly (meth) acrylate”.

Further, “a group may be different for each structural unit” means, for example, that when m is 2 in the structural formula (1),
R ^b3A and R ^b3B may be different groups, which means that R ^b5A and R ^b5B may be different groups (the same applies hereinafter).

  Examples of the hydroxyl group-containing pentaerythritol poly (meth) acrylate include pentaerythritol di (meth) acrylate and pentaerythritol tri (meth) acrylate.

  Hydroxyl-containing polypentaerythritol poly (meth) acrylate includes dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripenta Erythritol di (meth) acrylate, tripentaerythritol tri (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) Acrylate and the like are exemplified.

(Hydroxy group-containing (poly) trimethylolpropane poly (meth) acrylate)
(Poly) trimethylolpropane poly (meth) acrylate has the structural formula (2)
(In the formula, p is an integer of 0 or more; R ^{b7 to} R ^b10 are a hydrogen atom or a (meth) acryloyl group; and at least two of R ^{b7 to} R ^b10 are a (meth) acryloyl group; ^At least one of ^{b7 to Rb10} is a hydrogen atom. Note that ^Rb9 may have a different group for each structural unit.)
Is a compound represented by

  In the present disclosure, “(poly) trimethylolpropane poly (meth) acrylate” refers to “at least one selected from the group consisting of trimethylolpropane poly (meth) acrylate and polytrimethylolpropane poly (meth) acrylate”. means.

  Examples of the hydroxyl group-containing trimethylolpropane poly (meth) acrylate include trimethylolpropane di (meth) acrylate.

  Examples of the hydroxyl group-containing polytrimethylol poly (meth) acrylate include ditrimethylol di (meth) acrylate and ditrimethylol tri (meth) acrylate.

(Hydroxy group-containing glycerin di (meth) acrylate)
Hydroxy group-containing glycerin (meth) acrylate has the structural formula (3)
(In the formula, two of R ^{b11 to} R ^b13 are (meth) acryloyl groups, and one of R ^{b1 to} R ^b3 is a hydrogen atom.)
Is a compound represented by

  Examples of the hydroxyl group-containing glycerin (meth) acrylate include 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate and 1-hydroxy-2- (meth) acryloyloxypropyl (meth) acrylate.

  The upper limit of the content of the component (B) in the undercoat agent is, for example, 85, 80, 70, 60, 50, 40, 30, 20, 10, 5% by mass or the like, and the lower limit is 80, 70, 60. , 50, 40, 30, 20, 10, 5, 2% by mass and the like. In one embodiment, the content of the component (B) in the undercoat agent is preferably about 2 to 85% by mass.

  The upper limit of the solid content mass ratio ((A) / (B)) of the hydroxyl group-containing poly (meth) acryl copolymer (A) and the hydroxyl group-containing glycerin di (meth) acrylate poly (meth) acrylate (B) is 97/3. , 95/5, 90/10, 80/20, 70/30, 60/40, 50/50, 40/60, 30/70, 20/80, 10/90, and the like. 5, 90/10, 80/20, 70/30, 60/40, 50/50, 40/60, 30/70, 20/80, 10/90, 5/95 and the like. In one embodiment, the solid content mass ratio ((A) / (B)) of the hydroxyl group-containing poly (meth) acrylic copolymer (A) and the hydroxyl group-containing glycerin di (meth) acrylate poly (meth) acrylate (B) is , 97/3 to 5/95.

  The upper limit of the acrylic equivalent of the hydroxyl group-containing poly (meth) acrylate is, for example, 360, 358, 350, 300, 290, 250, 225, 215 g / eq, and the lower limit is 358, 350, 300, 290, 250, 225. , 215, 214 g / eq and the like. In one embodiment, the (meth) acrylic equivalent of the hydroxyl group-containing poly (meth) acrylate is preferably about 214 to 360 g / eq, more preferably about 214 to 290 g / eq.

  In the present disclosure, the (meth) acrylic equivalent means a calculated value (g / eq) of the mass of an active energy ray-curable resin containing 1 mol of a (meth) acryloyl group.

  The upper limit of the hydroxyl value of the hydroxyl group-containing poly (meth) acrylate is, for example, 300, 290, 270, 250, 225, 200, 175, 150, 130, 110 g / eq, and the lower limit is 290, 270, 250, 225. , 200, 175, 150, 130, 110, 100 g / eq, and the like. In one embodiment, the hydroxyl value of the hydroxyl group-containing poly (meth) acrylate is preferably about 100 to 300 g / eq, and more preferably about 130 to 270 g / eq.

<Polyisocyanate (C): Also referred to as component (C)>
In the present disclosure, “polyisocyanate” is a compound having two or more isocyanate groups (—N ＝ C ＝ O). Examples of the polyisocyanate include linear aliphatic polyisocyanate, branched aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, and biuret, isocyanurate, allophanate, and adduct thereof. In the above undercoat agent, two or more polyisocyanates (C) may be used in combination.

Examples of the linear aliphatic group include a linear alkylene group. Linear alkylene group is represented by formula _:-( CH ₂₎ n - (n is represented by an integer of 1 or more). Linear alkylene groups include methylene, ethylene, propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, n-decamethylene and the like. Is exemplified.

  Examples of the linear aliphatic polyisocyanate include methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, and the like. You.

  Examples of the branched aliphatic group include a branched alkylene group. A branched alkylene group is a group in which at least one hydrogen atom of a straight-chain alkylene group has been replaced by an alkyl group. Examples of the branched alkylene group include a diethylpentylene group, a trimethylbutylene group, a trimethylpentylene group, and a trimethylhexylene group (trimethylhexamethylene group).

  Examples of the branched aliphatic polyisocyanate include diethyl pentylene diisocyanate, trimethyl butylene diisocyanate, trimethyl pentylene diisocyanate, and trimethyl hexamethylene diisocyanate.

  Examples of the alicyclic group include a cycloalkylene group. Examples of the cycloalkylene group include a monocyclic cycloalkylene group, a cross-linked cycloalkylene group, and a condensed-ring cycloalkylene group. Further, in the cycloalkylene group, one or more hydrogen atoms may be substituted by a linear or branched alkyl group.

  In the present disclosure, the term “single ring” means a cyclic structure having no cross-linked structure formed by a covalent bond of carbon. In addition, the condensed ring means a cyclic structure in which two or more monocycles share two atoms (that is, only one side of each ring is shared (fused) with each other). A bridged ring means 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 cross-linked cycloalkylene group include a tricyclodecylene group, an adamantylene group, and a norbornylene group.

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

  Examples of the alicyclic polyisocyanate include a monocyclic alicyclic polyisocyanate, a crosslinked alicyclic polyisocyanate, a condensed alicyclic polyisocyanate, and the like.

  Monocyclic alicyclic polyisocyanates include hydrogenated xylene diisocyanate, isophorone diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, cycloheptylene diisocyanate, cyclodecylene diisocyanate, 3,5,5-trimethylcyclohexylene diisocyanate, and dicyclohexyl methane. Examples thereof include diisocyanate.

  Examples of the cross-linked alicyclic polyisocyanate include tricyclodecylene diisocyanate, adamantane diisocyanate, norbornene diisocyanate, and the like.

  Examples of the condensed ring alicyclic polyisocyanate include bicyclodecylene diisocyanate.

  Examples of the aromatic group include a monocyclic aromatic group and a condensed ring aromatic group. Further, in the aromatic group, one or more hydrogen atoms may be substituted by a linear or branched alkyl group.

  Examples of the monocyclic aromatic group include a phenyl group (phenylene group), a tolyl group (tolylene group), and a mesityl group (mesitylene group). Examples of the condensed ring aromatic group include a naphthyl group (naphthylene group) and the like.

  Examples of the aromatic polyisocyanate include a monocyclic aromatic polyisocyanate and a condensed ring aromatic polyisocyanate.

  Monocyclic aromatic polyisocyanates include dialkyldiphenylmethane diisocyanate such as 4,4'-diphenyldimethylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate such as 4,4'-diphenyltetramethylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, Examples thereof include 4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and m-tetramethyl xylylene diisocyanate. You.

  Examples of the condensed ring aromatic polyisocyanate include 1,5-naphthylene diisocyanate.

The biuret of polyisocyanate is
The following structural formula:
[In the formula, n ^b is an integer of 1 or more, R ^{bA to} R ^bE are each independently an alkylene group or an arylene group, and R ^{bα to} R ^bβ are each independently an isocyanate group or
(N ^b1 is an integer of 0 or more; R ^{b1 to} R ^b5 are each independently an alkylene group or an arylene group; R ^b ′ to R ^b ″ are each independently a isocyanate group or R ^{bα to} R ^{b bβ} own a group ^{.R b4 ~R b5, R b '} ' is may be different groups in each constitutional unit.). R ^{bD to} R ^bE and R ^bβ may have different groups for each structural unit. And the like.

The biuret body of polyisocyanate is Duranate 24A-100, Duranate 22A-75P, Duranate 21S-75E (manufactured by Asahi Kasei Corporation), Desmodur N3200A (biuret body of hexamethylene diisocyanate) (manufactured by Sumitomo Bayer Urethane Co., Ltd.) ) Are exemplified.

Isocyanurate form of polyisocyanate,
The following structural formula:
Wherein, ^{n i} is an integer of 0 or ^more, R iA ^{to R iE} are each independently an alkylene group or an arylene group, in each of ^{R i.alpha} to R ^i.beta independently, an isocyanate group or
^{(N i1} is an integer of 0 or ^more, R i1 ^{to R i5} is independently an alkylene group or an arylene group, the ^{R i '~R i'} 'are each independently, an isocyanate group, or ^{R i.alpha} to R ^iβ own a group .R ^{i5, R} i ^'' is may be different groups in each constitutional unit.). R ^{iD to} R ^iE and R ^iβ may have different groups for each structural unit. And the like.

The isocyanurate form of polyisocyanate is Duranate TPA-100, Duranate TKA-100, Duranate MFA-75B, Duranate MHG-80B (from Asahi Kasei Corporation), Coronate HXR (isocyanurate form from hexamethylene diisocyanate) (from Tosoh Corporation) Co., Ltd.), Takenate D-127N (isocyanurate of hydrogenated xylene diisocyanate) (manufactured by Mitsui Chemicals, Inc.), VESTANAT T1890 / 100 (isocyanurate of isophorone diisocyanate (manufactured by Evonik Japan Co., Ltd.) ) Are exemplified.

Allophanate form of polyisocyanate,
The following structural formula:
Wherein, ^{n a} is an integer of 0 or ^{more, R aA} is an alkyl group or an aryl ^group, in each of R aB ^{to R aG} independently an alkylene group or an arylene ^{group, R} aα ^~R aγ Are each independently an isocyanate group or
(N ^a1 is an integer of 0 or more; R ^{a1 to} R ^a6 are each independently an alkylene group or an arylene group; R ^a ′ to R ^a ′ ″ are each independently an isocyanate group or R ^aα to R ^a1 is a group of R ^aγ itself, and R ^{a1 to} R ^a4 and R ^a ′ to R ^a ′ ″ may be different for each structural unit.). R ^{aB to} R ^aE and R ^{aα to} R ^aγ may have different groups for each structural unit. And the like.

Examples of commercially available products of the allophanate derivative of polyisocyanate include Takenate D-178N (manufactured by Mitsui Chemicals, Inc.).

The adduct of polyisocyanate is
The following structural formula:
[In the formula, n ^ad is an integer of 0 or more, R ^{adA to} R ^adE are each independently an alkylene group or an arylene group, and R ^{ad1 to} R ^ad2 are each independently
(In the formula, n ^{ad ′} is an integer of 0 or more, R ^{ad ′ to} R ^{ad ″} are each independently an alkylene group or an arylene group, and R ^{ad ′ ″} is the same as R ^{ad1 to} R ^ad2 itself. R ^{ad ′ to} R ^{ad ′ ″} may be different for each structural unit.)
R ^{adD to} R ^adE and R ^ad2 may have different groups for each structural unit. ]
An adduct of trimethylolpropane and a polyisocyanate represented by
The following structural formula
[In the formula, n ^ad1 is an integer of 0 or more, R ^{adα to} R ^adε are each independently an alkylene group or an arylene group, and R ^{adA to} R ^adB are each independently
( ^Where n ^{ad1 ′} is an integer of 0 or more, R ^{adδ ′ to} R ^{adε ′} are each independently an alkylene group or an arylene group, and R ^{adB ′} is a group of R ^{adA to} R ^adB itself. , R ^{adδ ′ to} R ^{adε ′} and R ^{adB ′} may have different groups for each structural unit.)
R ^{adδ to} R ^adε may have different groups for each structural unit. ]
And an adduct of glycerin and polyisocyanate, and the like.

Examples of the adduct of polyisocyanate include Duranate P301-75E (all manufactured by Asahi Kasei Corporation), Takenate D110N and Takenate D160N (all manufactured by Mitsui Chemicals, Inc.), Coronate L (all manufactured by Tosoh Corporation), and the like. .

  The upper limit of the content of the component (C) in the undercoat agent is, for example, 40, 30, 20, 15% by mass, and the like, and the lower limit is, for example, 35, 30, 20, 10% by mass and the like. In one embodiment, the content of the component (C) in the undercoat agent is preferably about 10 to 40% by mass.

  The upper limit of the solid content mass ratio ((A) / (C)) of the hydroxyl group-containing poly (meth) acryl copolymer (A) and polyisocyanate (C) is 1.6, 1.5, 1.25, and 1. 0, 0.75, 0.5, 0.4, etc. are exemplified, and the lower limit is 1.5, 1.25, 1.0, 0.75, 0.5, 0.4, 0.35, etc. Is exemplified. In one embodiment, the solid content mass ratio ((A) / (C)) of the hydroxyl group-containing poly (meth) acryl copolymer (A) and the polyisocyanate (C) is preferably about 0.35 to 1.6. .

  The upper limit of the NCO content (NCO%) of the polyisocyanate (C) is exemplified by 30, 25, 20, 15 and the like, and the lower limit is exemplified by 25, 20, 15, 10 and the like. In one embodiment, the NCO content (NCO%) of the polyisocyanate (C) is preferably from 10 to 30.

  The upper limit of the isocyanate group equivalent of the polyisocyanate (C) is exemplified by 10, 9, 8, 7, 6, 5, 4, 3, 2 meq / g and the like, and the lower limit is 9, 8, 7, 6, 5, 4, 3, 2, 1 meq / g and the like are exemplified. In one embodiment, the isocyanate group equivalent of the polyisocyanate (C) is preferably about 1 to 10 meq / g. In the present disclosure, the isocyanate group equivalent means a substance amount of the isocyanate group present in 1 g of the solid.

  The upper limit of the ratio (NCO / OH) between the isocyanate group equivalent of the polyisocyanate (C) and the hydroxyl equivalent of the hydroxyl group-containing poly (meth) acrylic copolymer (A) is 2, 1.75, 1.5, 1.25, 1, 0.75, 0.5, 0.25, 0.1, etc. are exemplified, and the lower limit is 1.75, 1.5, 1.25, 1, 0.75, 0.5, 0.25 , 0.1, 0.05 and the like. In one embodiment, the ratio (NCO / OH) of the isocyanate group equivalent of the polyisocyanate (C) to the hydroxyl group equivalent of the hydroxyl group-containing poly (meth) acrylic copolymer (A) is preferably about 0.05 to 2.

The upper limit of the consumed OH group amount is, for example, 150, 125, 100, 75, 50, 25 mg KOH / g, and the lower limit is, for example, 125, 100, 75, 50, 25, 10 mg KOH / g. In one embodiment, the amount of consumed OH groups is preferably from 10 to 150 mgKOH / g. In the present disclosure, the consumed OH group amount is an index indicating how much NCO that consumes the OH group in the main agent is added. The amount of consumed OH groups is calculated by the following formula: OH consumed amount = isocyanate group equivalent × 56.1.
Is calculated by

<Photopolymerization initiator (D): Also referred to as component (D)>
Examples of the photopolymerization initiator include a photoradical polymerization initiator, a photocationic polymerization initiator, and a photoanionic polymerization initiator. In the undercoat agent, two or more photopolymerization initiators may be used in combination.

  Examples of the photoradical polymerization initiator include α-hydroxyalkylphenone, unsubstituted or substituted alkylphenone, unsubstituted or substituted benzyl, unsubstituted or substituted benzophenone, acylphosphine oxide, oxime ester, and substituted thioxanthone.

  α-Hydroxyalkylphenone is 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-4 ′-(2-hydroxyethoxy) -2-methylpropiophenone (1- [4 -(2-hydroxyethoxyl) -phenyl] -2-hydroxy-methylpropanone)), 2-hydroxy-1- (4- (4- (2-hydroxy-2-methylpropionyl) benzyl) phenyl) -2- Methylpropan-1-one) and the like.

  Unsubstituted or substituted alkylphenones include benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin ethyl ether, acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 2-phenyl-2. -(P-toluenesulfonyloxy) acetophenone, benzoin, 2-benzyl-2- (dimethylamino) -4'-morpholinobtyrophenone, 2-methyl-4 '-(methylthio) -2-morpholinopropiophenone, 2-iso Nitrosopropiophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one and the like are exemplified.

  Unsubstituted or substituted benzyl is exemplified by unsubstituted or substituted benzyl such as benzyl and p-anisyl.

  Unsubstituted or substituted benzophenones include benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-dichlorobenzophenone, 1,4-dibenzoylbenzene, Benzoylbenzoic acid, 4-benzoylbenzoic acid, methyl 2-benzoylbenzoate and the like are exemplified.

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

  The oxime esters are 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H. -Carbazol-3-yl]-, 1- (O-acetyloxime) and the like.

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

  Other photoradical polymerization initiators include lithium phenyl (2,4,6-trimethylbenzoyl) phosphinate, 2-ethylanthraquinone, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5. '-Tetraphenyl-1,2'-biimidazole, 2- (1,3-benzodioxol-5-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, phenylgly Oxylic acid methyl ester and the like are exemplified.

  Examples of the cationic photopolymerization initiator include an iodonium salt polymerization initiator, a sulfonium salt polymerization initiator, and a diazonium salt polymerization initiator.

  The iodonium salt polymerization initiator is bis (4-tert-butylphenyl) iodonium hexafluorophosphate, bis (4-fluorophenyl) iodonium trifluoromethanesulfonate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroarsenate, diphenyl Iodonium trifluoromethanesulfonic acid, 4-isopropyl-4′-methyldiphenyliodonium tetrakis (pentafluorophenyl) borate, (2-methylphenyl) (2,4,6-trimethylphenyl) iodonium trifluoromethanesulfonate, (3-methyl Phenyl) (2,4,6-trimethylphenyl) iodonium trifluoromethanesulfonate, (4-methylphenyl) (2,4,6-triphenyl) (Tylphenyl) iodonium trifluoromethanesulfonate, (4-nitrophenyl) (phenyl) iodonium trifluoromethanesulfonate, phenyl [4- (trimethylsilyl) thiophen-3-yl] iodonium trifluoromethanesulfonate, [3- (trifluoromethyl) Phenyl] (2,4,6-trimethylphenyl) iodonium trifluoromethanesulfonate and [4- (trifluoromethyl) phenyl] (2,4,6-trimethylphenyl) iodonium trifluoromethanesulfonate are exemplified.

  Sulfonium salt polymerization initiator is cyclopropyldiphenylsulfonium tetrafluoroborate, dimethylphenacylsulfonium tetrafluoroborate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium bromide, tri-p-tolylsulfonium hexafluorophosphate, tri- Examples thereof include p-tolylsulfonium trifluoromethanesulfonate.

  Examples of the diazonium salt polymerization initiator include 4-nitrobenzenediazonium tetrafluoroborate.

  Other than the above, the cationic photopolymerization initiator is 2- (3,4-dimethoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (furan-2-yl) ) Vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (5-methylfuran-2-yl) vinyl] -4,6-bis (trichloromethyl)- 1,3,5-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyryl) -4,6-bis ( Examples thereof include substituted 4,6-bis (trichloromethyl) -1,3,5-triazines such as (trichloromethyl) -1,3,5-triazine.

  Examples of the photoanionic polymerization initiator include cyclohexylcarbamate, 2- (9-oxoxanthen-2-yl) propionate, and the like.

  Examples of the cyclohexylcarbamate include 1,2-bis (4-methoxyphenyl) -2-oxoethyl cyclohexylcarbamate and 2-nitrobenzyl cyclohexylcarbamate.

  2- (9-oxoxanthen-2-yl) propionate is 2- (9-oxoxanthen-2-yl) propionic acid 1,5,7-triazabicyclo [4.4.0] deca-5. -Ene, 1,5-diazabicyclo [4.3.0] non-5-ene, 2- (9-oxoxanthen-2-yl) propionic acid 1,2- (9-oxoxanthen-2-yl) propionic acid , 8-diazabicyclo [5.4.0] undec-7-ene and the like.

  Examples of the photoanionic polymerization initiator other than the above include acetophenone O-benzoyl oxime, nifedipine and the like.

  When the photopolymerization initiator (D) is contained in the undercoat agent, the upper limit of the content of the component (D) in the undercoat agent is 10, 9, 8, 7, 6, 5, 4, 3, 2 mass. %, Etc., and the lower limit is exemplified by 9, 8, 7, 6, 5, 4, 3, 2, 1, 1% by mass and the like. In one embodiment, when the photopolymerization initiator (D) is contained in the undercoat agent, the content of the component (D) in the undercoat agent is preferably about 1 to 10% by mass.

  When the photopolymerization initiator (D) is contained in the undercoat agent, the solid content mass ratio of the hydroxyl group-containing poly (meth) acryl copolymer (A) and the photopolymerization initiator (D) ((A) / (D)) Are, for example, 1, 0.75, 0.5, 0.25, 0.05, etc., and the lower limit is 0.9, 0.75, 0.5, 0.25, 0.05, 0, etc. .01 and the like. In one embodiment, when the photopolymerization initiator (D) is included in the undercoat agent, the solid content mass ratio of the hydroxyl-containing poly (meth) acrylic copolymer (A) to the photopolymerization initiator (D) ((A ) / (D)) is preferably about 0.01 to 1.

<Organic solvent (E): Also referred to as component (E)>
The undercoat agent may contain an organic solvent. The organic solvent may be contained alone or in combination of two or more. Organic solvents are ketone solvents such as methyl ethyl ketone, acetylacetone, 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; Solvesso # 100 and Solvesso # 150 ( Exxon . Haloalkanes solvent such as chloroform; Ltd.) petroleum solvents such as amide solvent such as dimethylformamide and the like. Among these, ketone solvents are preferred from the viewpoint of the pot life of the undercoat agent of the present invention, and acetylacetone is preferred among ketone solvents.

  When the organic solvent (E) is contained in the undercoat agent, the upper limit of the content of the organic solvent in the undercoat agent is, for example, 90, 80, 70, 60, 55% by mass or the like, and the lower limit is 85, 80. , 70, 60, 55, 50% by mass, and the like. In one embodiment, when the organic solvent (E) is contained in the undercoat agent, the content of the organic solvent in the undercoat agent is preferably about 90 to 50% by mass. The organic solvent contained in the undercoat agent includes the organic solvent used in producing the component (A) and / or the organic solvent contained in the component (B) and / or the component (C). May be.

<Curing catalyst (F): Also referred to as component (F)>
The curing catalyst may be an organic typical metal catalyst such as an organic tin catalyst such as dibutyltin dilaurate or dioctyltin dilaurate, or an organic bismuth catalyst such as bismuth octylate;
Organic metal catalysts such as organic titanium catalysts such as titanium ethyl acetoacetate, organic zirconium catalysts such as zirconium tetraacetylacetonate, organic fiber metal catalysts such as organic iron catalysts such as iron acetylacetonate;
Examples thereof include organic amine catalysts such as diazabicyclooctane, dimethylcyclohexylamine, tetramethylpropylenediamine, ethylmorpholine, dimethylethanolamine, triethylamine, and triethylenediamine. Two or more curing catalysts may be used in combination.

  When the curing catalyst (F) is contained in the undercoat agent, the upper limit of the content of the curing catalyst in the undercoat agent is 1, 0.9, 0.75, 0.5, 0.25, 0.1, 0.09, 0.05, 0.02% by mass, etc. are exemplified, and the lower limit is 0.9, 0.75, 0.5, 0.25, 0.1, 0.09, 0.05, 0. 0.02, 0.01% by mass and the like. In one embodiment, when the curing catalyst (F) is contained in the undercoat agent, the content of the curing catalyst in the undercoat agent is preferably about 0.01 to 1% by mass.

<Additives>
The undercoat agent may contain an agent other than the components (A) to (F) as an additive. Examples of the additive include a polymerization inhibitor, an antioxidant, a light stabilizer, an antifoaming agent, a surface conditioner, a pigment, an antistatic agent, a metal oxide fine particle dispersion, and an organic fine particle dispersion. In one embodiment, the content of the additive is about 0.1 to 10% by mass of the undercoat agent, about 10 parts by mass, about 5 parts by mass, about 1 part by mass, less than 0.1 parts by mass. , Less than 0.01 parts by mass, about 0 parts by mass, and the like.

  The undercoat agent is obtained by mixing the components (A) to (C) and, if necessary, the component (D), the component (E), the component (F), and / or additives by various known means. Is obtained by In one embodiment, the undercoat agent is prepared by mixing the components (A) and (B), and if necessary, the component (D) and / or the component (E) to produce a main agent mixture, A method comprising the steps of: mixing a component (C) and, if necessary, a component (E) to produce a curing agent solution; and mixing a base compounding solution and a curing agent solution and the component (F) to produce an undercoat agent. It is manufactured by

[the film]
The present disclosure provides a film in which a cured undercoat agent layer containing a cured product of the above undercoat agent is laminated on at least one surface of the film.

  Various known substrates are employed. Substrates are polycarbonate film, acrylic film (polymethyl methacrylate film, etc.), polystyrene film, polyester film, polyolefin film, epoxy resin film, melamine resin film, triacetyl cellulose film, ABS film, AS film, norbornene resin film, cyclic Olefin films and polyvinyl alcohol films are exemplified. Further, a vapor-deposited layer of a metal oxide or the like, an easy-adhesion layer, a hard coat layer, or the like may be provided on the surface. Although the thickness of the substrate is not particularly limited, it is preferably about 50 to 200 μm. The thickness of the undercoat layer is not particularly limited, but is preferably about 0.1 to 5 μm.

  The film is manufactured by various known methods. In one embodiment, the method for producing a film includes a step of applying an undercoat agent to at least one surface of a substrate (coating step), and a step of heat-curing to form a cured undercoat agent layer (thermosetting step) )including. In one embodiment, in the above-mentioned film, an active energy ray-curable resin cured material layer is laminated on an undercoat agent cured material layer. In this case, a step of applying the active energy ray-curable resin to the cured undercoat agent layer (coating step), a step of drying as necessary (drying step), and irradiation of the active energy ray to activate the active energy ray-curable resin. The method further includes a step of forming an energy ray-curable resin cured material layer (active energy ray curing step).

(Coating process)
Examples of the coating method include bar coater coating, wire bar coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, and screen printing.

The coating amount is not particularly limited. Coating weight, the weight after drying preferably from about 0.1 to 30 g / ^{m 2,} about from 1 to 20 g / ^{m 2} is more preferable.

(Heat curing process)
The drying method is exemplified by drying with a circulating air dryer or the like. Drying conditions include, for example, standing at 120 ° C. for 30 seconds.

  When manufacturing a film, an aging treatment is performed after drying as necessary. As an example, aging treatment at 40 ° C. for 72 hours is exemplified.

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

  Active energy ray-curable resins include radical-curable resins such as (meth) acrylic ester, urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, and polyacryl (meth) acrylate (for example, Arakawa Chemical) "Beamset Series" manufactured by Kogyo Co., Ltd.), resins that cure epoxides, oxetanes, vinyl ethers, and the like with cations or anions, and resins that cure by an ene-thiol reaction between alkenes and thiols. These may be used in combination.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. The present invention is not limited to the following examples. In the following, "parts" and "%" mean parts by mass and% by mass, respectively, unless otherwise specified.

(Example 1)
Acrylic resin A (manufactured by Arakawa Chemical Co., Ltd .: copolymer of methyl methacrylate, butyl acrylate, 2-hydroxyethyl acrylate. Weight average molecular weight: 50,000, glass transition temperature: 70 ° C., hydroxyl value: 80 gKOH / g, nonvolatile content 35%, solvent methyl ethyl ketone (hereinafter also referred to as MEK): 160 g, polyacrylate A (manufactured by Arakawa Chemical Co., Ltd .: polyglycidyl methacrylate / acrylic acid adduct, Mw 10,000, nonvolatile content 60%, solvent MEK / methyl isobutyl ketone ( (Hereinafter also referred to as MIBK)): 31.2 g, acetylacetone: 6.6 g, Omnirad 2959: 1.8 g, MEK: 12.7 g, MIBK: 6.4 g, and agitated for 15 minutes to prepare a main agent mixed liquid. did.
Further, 40 g of Duranate 24A100 (manufactured by Asahi Kasei Corporation): biuret of hexamethylene diisocyanate, solid content = 100% by mass, NCO% = 23.5%) and 60 g of MEK were mixed and stirred, and the curing agent solution was stirred. Created.
Furthermore, 25 g of Neostan U810 (manufactured by Nitto Kasei Corporation: dioctyltin dilaurate) and 75 g of ethyl acetate were mixed and stirred to prepare a curing catalyst solution.
10.0 g of the main component compounding solution, 2.3 g of the curing agent solution, 0.008 g of the curing catalyst solution, and 9.8 g of MEK were mixed to obtain a coating liquid (solid content: 20%).

(Examples 2 to 13, Comparative Examples 1 to 5)
The undercoat agents of Examples 2 to 13 and Comparative Examples 1 to 5 were produced in the same manner as in Example 1 except that the component compositions were changed as shown in the following table.

(Film production)
(1) Formation of cured layer of undercoat agent The undercoat agent according to Examples 1 to 13 and Comparative Examples 1 to 5 on a single-sided corona-treated PET (E5100, manufactured by Toyobo Co., Ltd.) had a thickness of 1 μm after drying. Coating was performed so that the coating was dried at 120 ° C. for 30 seconds, and then aging was performed for 40 × 72 hours.
(2) Formation of cured layer of active energy ray-curable resin On the cured layer of undercoat agent, an active energy ray-curable resin is applied so as to have a film thickness of 5 to 6 μm after drying, and 80 ° C. × After drying for 30 seconds, UV curing was performed at 300 mJ / cm ² . As the active energy ray-curable resin, a polyfunctional acrylic ester-based (dipentaerythritol polyacrylate) BS700 (manufactured by Arakawa Chemical Co., Ltd.) and a urethane acrylate-based BS577 (manufactured by Arakawa Chemical Co., Ltd.) were evaluated. Carried out. In each case, Irgacure 184 was added as a photopolymerization initiator in an amount of 5% based on the solid content of the active energy ray-curable resin.

(Evaluation of blocking resistance)
The film produced above was allowed to stand at 40 ° C. for 72 hours under a load of 5 kg / cm ² . Thereafter, the coated film and the uncoated film were peeled off, and the evaluation of blocking resistance was performed. Specifically, those in which peeling of the coating film was observed during peeling were rated as x, and those in which the coating film did not peel and had no resistance were rated as と し た.

(Evaluation of adhesion to active energy ray-curable resin)
The UV adhesion at the initial stage and after 85% × 360 hours at 85 ° C. (after resistance to moist heat) was evaluated by a cellophane tape cross-cut peel test specified in JIS K5400. The evaluation items are as shown below.
5: No peeling was observed.
4: Less than 5% peeling between the active energy ray-curable resin layer and the anchor layer is observed.
3: Exfoliation of 5% or more and less than 20% is observed between the active energy ray-curable resin layer and the anchor layer.
2: A separation of 20% or more and less than 50% is observed between the active energy ray-curable resin layer and the anchor layer.
1: 50% to 100% peeling between the active energy ray-curable resin layer and the anchor layer is observed.

<Hydroxy group-containing (meth) acrylic copolymer (A)>
A1: Acrylic resin A1 (manufactured by Arakawa Chemical Co., Ltd .: copolymer of methyl methacrylate, butyl acrylate, 2-hydroxyethyl acrylate. Weight average molecular weight: 50,000, glass transition temperature: 70 ° C., hydroxyl value: 80 gKOH / g)
A2: Acrylic resin A2 (manufactured by Arakawa Chemical Co., Ltd .: copolymer of methyl methacrylate, butyl acrylate, 2-hydroxyethyl acrylate, styrene. Weight average molecular weight: 45000, glass transition temperature: 70 ° C., hydroxyl value: 35 g KOH / g.
A3: Acrylic resin A3 (manufactured by Arakawa Chemical Co., Ltd .: copolymer of methyl methacrylate, butyl acrylate, 2-hydroxyethyl acrylate. Weight average molecular weight: 50,000, glass transition temperature: 35 ° C., hydroxyl value: 35 gKOH / g.

<Poly (meth) acrylate (B)>
B1: Polymer acrylate (manufactured by Arakawa Chemical Co., Ltd .: polyglycidyl methacrylate / acrylic acid adduct, Mw 10,000)
B2: Polymer acrylate (manufactured by Arakawa Chemical Co., Ltd .: polyglycidyl methacrylate / acrylic acid adduct, Mw 30000)
B3: Pentaerythritol triacrylate (Viscort 300, manufactured by Osaka Organic Chemical Industry Co., Ltd.)

<Polyisocyanate (C)>
HDI biuret: (Duranate 24A100 (manufactured by Asahi Kasei Corporation): biuret of hexamethylene diisocyanate, solid content = 100% by mass, NCO% = 23.5%)
HDI Nurate: (Coronate HX (manufactured by Tosoh Corp.): Nurate of hexamethylene diisocyanate, solid content = 100% by mass, NCO% = 20.5 to 22.0%)

<Photopolymerization initiator (D)>
2959: Omnirad 2959 (1- [4- (2-hydroxyethoxyl) -phenyl] -2-hydroxy-methylpropanone manufactured by IgM resins)
127: Omnirad 127 (2-hydroxy-1- (4- (4- (2-hydroxy-2-methylpropionyl) benzyl) phenyl) -2-methylpropan-1-one, manufactured by IgM resins)

<Comparative example>
Polyester A: Arakawa Chemical Co., Ltd .: Polycondensate composed of terephthalic acid, isophthalic acid, azelaic acid, ethylene glycol, 1,6-hexanediol, neopentyl glycol, and trimethylolpropane. Number average molecular weight: 10,000, glass transition temperature: 40 ° C., hydroxyl value: 20 g KOH / g, nonvolatile content 50%, solvent MEK, MIBK
Polyester B: Arakawa Chemical Co., Ltd .: Polycondensate composed of terephthalic acid, isophthalic acid, azelaic acid, ethylene glycol, 1,6-hexanediol, neopentyl glycol, trimethylolpropane, and trimellitic anhydride. Number average molecular weight: 20,000, glass transition temperature: 40 ° C., acid value: 30 g KOH / g, nonvolatile content 60%, solvent MEK, MIBK
Polybasic acid-modified acrylic oligomer: Aronix M510 (manufactured by Toagosei Co., Ltd.)
Aziridine: trimethylolpropane tris- (β-aziridinylpropionate)

Claims (7)

Hydroxyl-containing (meth) acrylic copolymer (A),
Hydroxyl-containing poly (meth) acrylate (B) and polyisocyanate (C)
And an undercoat agent. The undercoat agent according to claim 1, comprising a photopolymerization initiator (D). The undercoat agent according to claim 1 or 2, wherein the hydroxyl group-containing poly (meth) acrylate (B) is a hydroxyl group-containing polymer poly (meth) acrylate. The solid content mass ratio ((A) / (B)) of the hydroxyl group-containing poly (meth) acryl copolymer (A) and the hydroxyl group-containing poly (meth) acrylate (B) is 97/3 to 5/95. The undercoat agent according to any one of claims 1 to 3. The ratio (NCO / OH) of the isocyanate group equivalent of the polyisocyanate (C) to the hydroxyl group equivalent of the hydroxyl group-containing poly (meth) acrylic polymer (A) is 0.05 to 2, according to claim 1 to 4. An undercoat agent according to any one of the preceding claims. A film, wherein a cured product of an undercoat agent containing the cured product of the undercoat agent according to any one of claims 1 to 5 is laminated on at least one surface of the film. The film according to claim 6, wherein an active energy ray-curable resin cured material layer is laminated on the undercoat agent cured material layer.