WO2019221135A1 - Curable resin composition - Google Patents

Abstract

Provided is a curable resin composition which contains monomer A and monomer B, and does not contain an alkyl (meth)acrylate having 10 or more carbon atoms, wherein monomer A is at least one compound represented by formula (1a) [in the formula, R1a represents a hydrogen atom or methyl, L1a represents –O-, -NH-, or the like, W1a represents a single bond or C1-20 alkylene, and R2 represents hydroxyl or the like], and monomer B is at least one compound represented by formula (1b) [in the formula, R1b represents a hydrogen atom or methyl, L1b represents –O-, -NH-, or the like, W1b represents a single bond or C1-20 alkylene, L2 represents a single bond or the like, W2 represents a single bond or the like, and R3 and R4 each independently represent a hydrogen atom, hydroxyl, or B(OH)2].

Description

Curable resin composition

The present invention contains a curable resin composition containing a (meth) acrylic acid derivative as a monomer component, an adhesive containing a polymer containing the monomer as a constituent unit, and a polymer containing the monomer as a constituent unit. It relates to a surface coating agent.

As a representative example of weight reduction of vehicles and airplanes, so-called multi-materials using a plurality of different materials are progressing. In multi-materialization, for example, by combining materials of different materials such as iron and aluminum alloy, metal and resin, metal and CFRP (Carbon Fiber Reinforced Plastics) (hereinafter referred to as bonding of different materials) Functions that are difficult to achieve with a single material can be added. In joining different types of materials, there are cases in which joining by welding may not be applicable, and therefore, bonding techniques capable of joining various types of materials are being studied.

Patent Document 1 discloses an adhesive monomer having a water-soluble main chain monomer, a crosslinking agent, a polymerization initiator, and a catechol group in a side chain as an adhesive hydrogel that binds firmly to the surface of various types of materials. And an adhesive hydrogel comprising the adhesive hydrogel and an adhesive comprising the adhesive hydrogel.

Also, surface coating agents that cover the surface of the substrate and protect the surface of the substrate, such as paint, are known. As the surface coating agent, a paint that is firmly bonded to the surface of various materials is known (for example, Patent Document 2).

International Publication No. 2016/190400 JP 2005-306971 A

An object of the present invention is to provide a curable resin composition, an adhesive, and a surface coating agent that are more firmly bonded to a wider variety of materials.

That is, in the present invention, for example, the following [1] to [12] are provided.

［式中、Ｒ^1aは、水素原子またはメチルを表し；
　Ｌ^1aは、－Ｏ－、－ＮＨ－、－ＮＲ⁵－、－ＮＨＣ（Ｏ）Ｏ－、または－ＮＨＣ（Ｏ）ＮＨ－を表し；
　Ｗ^1aは、単結合、またはＣ_1-20アルキレンを表し；
　Ｒ²は、メチル、ヒドロキシル、置換されていてもよいＣ_1-6アルコキシ、置換されていてもよいフェニル、置換されていてもよいフェノキシ、置換されていてもよい５員もしくは６員のヘテロアリール、置換されていてもよい３員～８員の飽和もしくは部分不飽和の炭化水素環基、または置換されていてもよい３員～８員の飽和もしくは部分不飽和のヘテロ環基を表し；
　Ｒ⁵は、置換されていてもよいＣ_1-8アルキルを表し；
　ここにおいて、Ｒ²がメチルのときは、Ｗ^1aが、単結合、またはＣ_1-8アルキレンであり；
　Ｒ²が、ヒドロキシル、置換されていてもよいＣ_1-6アルコキシ、または置換されていてもよいフェノキシのときは、Ｗ^1aがＣ_2-20アルキレンである］で表される１以上の化合物であり、
モノマーＢが、式（１ｂ）：

［式中、Ｒ^1bは、水素原子またはメチルを表し；
　Ｌ^1bは、－Ｏ－、－ＮＨ－、－ＮＨＣ（Ｏ）Ｏ－、または－ＮＨＣ（Ｏ）ＮＨ－を表し；
　Ｗ^1bは、単結合、またはＣ_1-20アルキレンを表し；
　Ｌ²は、単結合、－Ｏ－、－ＮＨ－、－ＮＨＣ（Ｏ）－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＨ－、－Ｃ（Ｏ）Ｏ－、－Ｃ（Ｏ）ＮＨ－、－ＯＣ（Ｏ）－、－ＯＣ（Ｏ）ＮＨ－、または－ＯＣ（Ｏ）Ｏ－を表し；
　Ｗ²は、単結合、またはＣ_1-2アルキレンを表し；
　Ｒ³およびＲ⁴は、それぞれ独立して、水素原子、ヒドロキシル、またＢ（ＯＨ）₂を表し；
　ここにおいて、Ｒ³およびＲ⁴がいずれも水素原子であることはない］で表される１以上の化合物である硬化性樹脂組成物。
〔２〕モノマーＡとモノマーＢを含有し、炭素数１０以上のアルキル－（メタ）アクリレートを含有しない硬化性樹脂組成物であって、
モノマーＡが、式（１ａ）：

［式中、Ｒ^1aは、水素原子またはメチルを表し；
　Ｌ^1aは、－Ｏ－、－ＮＨ－、－ＮＨＣ（Ｏ）Ｏ－、または－ＮＨＣ（Ｏ）ＮＨ－を表し；
　Ｗ^1aは、単結合、またはＣ_1-20アルキレンを表し；
　Ｒ²は、メチル、ヒドロキシル、置換されていてもよいＣ_1-6アルコキシ、置換されていてもよいフェニル、置換されていてもよい５員もしくは６員のヘテロアリール、置換されていてもよい３員～８員の飽和もしくは部分不飽和の炭化水素環基、または置換されていてもよい３員～８員の飽和もしくは部分不飽和のヘテロ環基を表し；
　ここにおいて、Ｒ²がメチルのときは、Ｗ^1aが、単結合、またはＣ_1-8アルキレンであり；
　Ｒ²が、ヒドロキシル、または置換されていてもよいＣ_1-6アルコキシのときは、Ｗ^1aがＣ_2-20アルキレンである］で表される１以上の化合物であり、
モノマーＢが、式（１ｂ）：

［式中、Ｒ^1bは、水素原子またはメチルを表し；
　Ｌ^1bは、－Ｏ－、－ＮＨ－、－ＮＨＣ（Ｏ）Ｏ－、または－ＮＨＣ（Ｏ）ＮＨ－を表し；
　Ｗ^1bは、単結合、またはＣ_1-20アルキレンを表し；
　Ｌ²は、単結合、－Ｏ－、－ＮＨ－、－ＮＨＣ（Ｏ）－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＨ－、－Ｃ（Ｏ）Ｏ－、－Ｃ（Ｏ）ＮＨ－、－ＯＣ（Ｏ）－、－ＯＣ（Ｏ）ＮＨ－、または－ＯＣ（Ｏ）Ｏ－を表し；
　Ｗ²は、単結合、またはＣ_1-2アルキレンを表し；
　Ｒ³およびＲ⁴は、それぞれ独立して、水素原子、ヒドロキシル、またＢ（ＯＨ）₂を表し；
　ここにおいて、Ｒ³およびＲ⁴がいずれも水素原子であることはなく；
　Ｌ²が単結合であり、Ｒ³およびＲ⁴がいずれもヒドロキシルのときは、式（１ａ）のＬ^1aが、－Ｏ－であり、Ｒ²が、ヒドロキシル、置換されていてもよいＣ_1-6アルコキシ、または置換されていてもよい３員～８員の飽和または部分不飽和のヘテロ環基であり；
　Ｌ²が、－Ｏ－、－ＮＨ－、－ＮＨＣ（Ｏ）－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＨ－、－ＯＣ（Ｏ）－、－ＯＣ（Ｏ）ＮＨ－、または－ＯＣ（Ｏ）Ｏ－ときは、Ｗ^1bがＣ_2-20アルキレンである］で表される１以上の化合物である、〔１〕記載の硬化性樹脂組成物。 [1] A curable resin composition containing monomer A and monomer B and not containing an alkyl- (meth) acrylate having 10 or more carbon atoms,
Monomer A is represented by the formula (1a):

[Wherein R ^1a represents a hydrogen atom or methyl;
L ^1a represents —O—, —NH—, —NR ⁵ —, —NHC (O) O—, or —NHC (O) NH—;
W ^1a represents a single bond or C _1-20 alkylene;
R ² is methyl, hydroxyl, optionally substituted C _1-6 alkoxy, optionally substituted phenyl, optionally substituted phenoxy, optionally substituted 5 or 6 membered heteroaryl. Represents an optionally substituted 3- to 8-membered saturated or partially unsaturated hydrocarbon ring group, or an optionally substituted 3- to 8-membered saturated or partially unsaturated heterocyclic group;
R ⁵ represents an optionally substituted C _1-8 alkyl;
Here, when R ² is methyl, W ^1a is a single bond or C _1-8 alkylene;
When R ² is hydroxyl, optionally substituted C _1-6 alkoxy, or optionally substituted phenoxy, W ^1a is C _2-20 alkylene]. Yes,
Monomer B is represented by formula (1b):

[Wherein R ^1b represents a hydrogen atom or methyl;
L ^1b represents —O—, —NH—, —NHC (O) O—, or —NHC (O) NH—;
W ^1b represents a single bond or C _1-20 alkylene;
L ² represents a single bond, —O—, —NH—, —NHC (O) —, —NHC (O) O—, —NHC (O) NH—, —C (O) O—, —C (O Represents NH—, —OC (O) —, —OC (O) NH—, or —OC (O) O—;
W ² represents a single bond or C _1-2 alkylene;
R ³ and R ⁴ each independently represents a hydrogen atom, hydroxyl, or B (OH) ₂ ;
Here, R ³ and R ⁴ are not hydrogen atoms.] A curable resin composition that is one or more compounds represented by:
[2] A curable resin composition containing monomer A and monomer B and not containing an alkyl- (meth) acrylate having 10 or more carbon atoms,
Monomer A is represented by the formula (1a):

[Wherein R ^1a represents a hydrogen atom or methyl;
L ^1a represents —O—, —NH—, —NHC (O) O—, or —NHC (O) NH—;
W ^1a represents a single bond or C _1-20 alkylene;
R ² is methyl, hydroxyl, optionally substituted C _1-6 alkoxy, optionally substituted phenyl, optionally substituted 5 or 6 membered heteroaryl, optionally substituted 3 Represents a membered to 8-membered saturated or partially unsaturated hydrocarbon ring group, or an optionally substituted 3 to 8 membered saturated or partially unsaturated heterocyclic group;
Here, when R ² is methyl, W ^1a is a single bond or C _1-8 alkylene;
When R ² is hydroxyl or optionally substituted C _1-6 alkoxy, W ^1a is C _2-20 alkylene],
Monomer B is represented by formula (1b):

[Wherein R ^1b represents a hydrogen atom or methyl;
L ^1b represents —O—, —NH—, —NHC (O) O—, or —NHC (O) NH—;
W ^1b represents a single bond or C _1-20 alkylene;
L ² represents a single bond, —O—, —NH—, —NHC (O) —, —NHC (O) O—, —NHC (O) NH—, —C (O) O—, —C (O Represents NH—, —OC (O) —, —OC (O) NH—, or —OC (O) O—;
W ² represents a single bond or C _1-2 alkylene;
R ³ and R ⁴ each independently represents a hydrogen atom, hydroxyl, or B (OH) ₂ ;
Where R ³ and R ⁴ are not both hydrogen atoms;
When L ² is a single bond, and R ³ and R ⁴ are both hydroxyl, L ^{1a in} formula (1a) is —O— and R ² is hydroxyl, optionally substituted C _{1 -6} alkoxy, or an optionally substituted 3- to 8-membered saturated or partially unsaturated heterocyclic group;
L ² is —O—, —NH—, —NHC (O) —, —NHC (O) O—, —NHC (O) NH—, —OC (O) —, —OC (O) NH—, Or, when —OC (O) O—, W ^1b is C _2-20 alkylene], the curable resin composition according to [1].

[3] L ^1a is -O- or -NR ⁵ - (wherein, R ⁵ represents hydroxyl or C _1-8 optionally C _1-8 alkyl optionally substituted by alkoxy) be; L ^1b is The curable resin composition according to [1], which is —NH—.

[4] R ² is
(1) hydroxyl,
(2) C _1-6 alkoxy optionally substituted with hydroxyl or C _1-6 alkoxy,
(3) 4 to 7-membered optionally substituted with 1 to 4 groups of the same or different types selected from the group consisting of a halogen atom, hydroxyl, C _1-6 alkyl, and C _1-6 alkoxy Oxygen-containing saturated heterocyclic group,
(4) phenyl optionally substituted by the same or different 1 to 4 groups selected from the group consisting of a halogen atom, C _1-6 alkyl, and C _1-6 alkoxy;
(5) phenoxy optionally substituted by 1 to 4 groups of the same or different types selected from the group consisting of halogen atoms, C _1-6 alkyl, and C _1-6 alkoxy, or
(6) The curable resin composition according to any one of [1] to [3], which is methyl.

[5] The curable resin composition according to any one of [1] to [4], wherein W ^1a and W ^1b are each independently a single bond or C _1-4 alkylene.

[6] The curable resin composition according to any one of [1] to [5], wherein L ² is a single bond, —O—, or —NHC (O) NH—.

[7] The curable resin composition according to any one of [1] to [6], wherein the monomer B includes a compound in which R ³ and / or R ⁴ is B (OH) ₂ .

[8] The curable resin composition according to any one of [1] to [7], wherein the monomer B includes a compound in which R ³ and / or R ⁴ is hydroxyl.

[9] The curable resin composition according to any one of [1] to [8], wherein the content of monomer B in the composition is 0.10 to 10.0% by mass.

[10] The curable resin composition according to any one of [1] to [9], further containing a crosslinkable monomer.

[11] The curable resin composition according to [10], wherein the crosslinkable monomer is a polyfunctional (meth) acrylate and / or a polyfunctional isocyanate.

［式中、Ｒ^1aは、水素原子またはメチルを表し；
　Ｌ^1aは、－Ｏ－、－ＮＨ－、－ＮＲ⁵－、－ＮＨＣ（Ｏ）Ｏ－、または－ＮＨＣ（Ｏ）ＮＨ－を表し；
　Ｗ^1aは、単結合、またはＣ_1-20アルキレンを表し；
　Ｒ²は、メチル、ヒドロキシル、置換されていてもよいＣ_1-6アルコキシ、置換されていてもよいフェニル、置換されていてもよいフェノキシ、置換されていてもよい５員もしくは６員のヘテロアリール、置換されていてもよい３員～８員の飽和もしくは部分不飽和の炭化水素環基、または置換されていてもよい３員～８員の飽和もしくは部分不飽和のヘテロ環基を表し；
　Ｒ⁵は、置換されていてもよいＣ_1-8アルキルを表し；
　ここにおいて、Ｒ²がメチルのときは、Ｗ^1aが、単結合、またはＣ_1-8アルキレンであり；
　Ｒ²が、ヒドロキシル、置換されていてもよいＣ_1-6アルコキシ、または置換されていてもよいフェノキシのときは、Ｗ^1aがＣ_2-20アルキレンである］で表される１以上の化合物であり、
モノマーＢが、式（１ｂ）：

［式中、Ｒ^1bは、水素原子またはメチルを表し；
　Ｌ^1bは、－Ｏ－、－ＮＨ－、－ＮＨＣ（Ｏ）Ｏ－、または－ＮＨＣ（Ｏ）ＮＨ－を表し；
　Ｗ^1bは、単結合、またはＣ_1-20アルキレンを表し；
　Ｌ²は、単結合、－Ｏ－、－ＮＨ－、－ＮＨＣ（Ｏ）－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＨ－、－Ｃ（Ｏ）Ｏ－、－Ｃ（Ｏ）ＮＨ－、－ＯＣ（Ｏ）－、－ＯＣ（Ｏ）ＮＨ－、または－ＯＣ（Ｏ）Ｏ－を表し；
　Ｗ²は、単結合、またはＣ_1-2アルキレンを表し；
　Ｒ³およびＲ⁴は、それぞれ独立して、水素原子、ヒドロキシル、またＢ（ＯＨ）₂を表し；
　ここにおいて、Ｒ³およびＲ⁴がいずれも水素原子であることはない］で表される１以上の化合物である粘接着剤。 [12] An adhesive containing a polymer containing monomer A and monomer B as constituent units (excluding a polymer containing alkyl- (meth) acrylate having 10 or more carbon atoms as constituent units),
Monomer A is represented by the formula (1a):

[Wherein R ^1a represents a hydrogen atom or methyl;
L ^1a represents —O—, —NH—, —NR ⁵ —, —NHC (O) O—, or —NHC (O) NH—;
W ^1a represents a single bond or C _1-20 alkylene;
R ² is methyl, hydroxyl, optionally substituted C _1-6 alkoxy, optionally substituted phenyl, optionally substituted phenoxy, optionally substituted 5 or 6 membered heteroaryl. Represents an optionally substituted 3- to 8-membered saturated or partially unsaturated hydrocarbon ring group, or an optionally substituted 3- to 8-membered saturated or partially unsaturated heterocyclic group;
R ⁵ represents an optionally substituted C _1-8 alkyl;
Here, when R ² is methyl, W ^1a is a single bond or C _1-8 alkylene;
When R ² is hydroxyl, optionally substituted C _1-6 alkoxy, or optionally substituted phenoxy, W ^1a is C _2-20 alkylene]. Yes,
Monomer B is represented by formula (1b):

[Wherein R ^1b represents a hydrogen atom or methyl;
L ^1b represents —O—, —NH—, —NHC (O) O—, or —NHC (O) NH—;
W ^1b represents a single bond or C _1-20 alkylene;
L ² represents a single bond, —O—, —NH—, —NHC (O) —, —NHC (O) O—, —NHC (O) NH—, —C (O) O—, —C (O Represents NH—, —OC (O) —, —OC (O) NH—, or —OC (O) O—;
W ² represents a single bond or C _1-2 alkylene;
R ³ and R ⁴ each independently represents a hydrogen atom, hydroxyl, or B (OH) ₂ ;
Here, neither R ³ nor R ⁴ is a hydrogen atom].

［式中、Ｒ^1aは、水素原子またはメチルを表し；
　Ｌ^1aは、－Ｏ－、－ＮＨ－、－ＮＨＣ（Ｏ）Ｏ－、または－ＮＨＣ（Ｏ）ＮＨ－を表し；
　Ｗ^1aは、単結合、またはＣ_1-20アルキレンを表し；
　Ｒ²は、メチル、ヒドロキシル、置換されていてもよいＣ_1-6アルコキシ、置換されていてもよいフェニル、置換されていてもよい５員もしくは６員のヘテロアリール、置換されていてもよい３員～８員の飽和もしくは部分不飽和の炭化水素環基、または置換されていてもよい３員～８員の飽和もしくは部分不飽和のヘテロ環基を表し；
　ここにおいて、Ｒ²がメチルのときは、Ｗ^1aが、単結合、またはＣ_1-8アルキレンであり；
　Ｒ²が、ヒドロキシル、または置換されていてもよいＣ_1-6アルコキシのときは、Ｗ^1aがＣ_2-20アルキレンである］で表される１以上の化合物であり、
モノマーＢが、式（１ｂ）：

［式中、Ｒ^1bは、水素原子またはメチルを表し；
　Ｌ^1bは、－Ｏ－、－ＮＨ－、－ＮＨＣ（Ｏ）Ｏ－、または－ＮＨＣ（Ｏ）ＮＨ－を表し；
　Ｗ^1bは、単結合、またはＣ_1-20アルキレンを表し；
　Ｌ²は、単結合、－Ｏ－、－ＮＨ－、－ＮＨＣ（Ｏ）－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＨ－、－Ｃ（Ｏ）Ｏ－、－Ｃ（Ｏ）ＮＨ－、－ＯＣ（Ｏ）－、－ＯＣ（Ｏ）ＮＨ－、または－ＯＣ（Ｏ）Ｏ－を表し；
　Ｗ²は、単結合、またはＣ_1-2アルキレンを表し；
　Ｒ³およびＲ⁴は、それぞれ独立して、水素原子、ヒドロキシル、またＢ（ＯＨ）₂を表し；
　ここにおいて、Ｒ³およびＲ⁴がいずれも水素原子であることはなく；
　Ｌ²が単結合であり、Ｒ³およびＲ⁴がいずれもヒドロキシルのときは、式（１ａ）のＬ^1aが、－Ｏ－であり、Ｒ²が、ヒドロキシル、置換されていてもよいＣ_1-6アルコキシ、または置換されていてもよい３員～８員の飽和または部分不飽和のヘテロ環基であり；
　Ｌ²が、－Ｏ－、－ＮＨ－、－ＮＨＣ（Ｏ）－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＨ－、－ＯＣ（Ｏ）－、－ＯＣ（Ｏ）ＮＨ－、または－ＯＣ（Ｏ）Ｏ－ときは、Ｗ^1bがＣ_2-20アルキレンである］で表される１以上の化合物である、〔１２〕記載の粘接着剤。 [13] An adhesive containing a polymer containing monomer A and monomer B as constituent units (excluding a polymer containing alkyl- (meth) acrylate having 10 or more carbon atoms as constituent units),
Monomer A is represented by the formula (1a):

[Wherein R ^1a represents a hydrogen atom or methyl;
L ^1a represents —O—, —NH—, —NHC (O) O—, or —NHC (O) NH—;
W ^1a represents a single bond or C _1-20 alkylene;
R ² is methyl, hydroxyl, optionally substituted C _1-6 alkoxy, optionally substituted phenyl, optionally substituted 5 or 6 membered heteroaryl, optionally substituted 3 Represents a membered to 8-membered saturated or partially unsaturated hydrocarbon ring group, or an optionally substituted 3 to 8 membered saturated or partially unsaturated heterocyclic group;
Here, when R ² is methyl, W ^1a is a single bond or C _1-8 alkylene;
When R ² is hydroxyl or optionally substituted C _1-6 alkoxy, W ^1a is C _2-20 alkylene],
Monomer B is represented by formula (1b):

[Wherein R ^1b represents a hydrogen atom or methyl;
L ^1b represents —O—, —NH—, —NHC (O) O—, or —NHC (O) NH—;
W ^1b represents a single bond or C _1-20 alkylene;
L ² represents a single bond, —O—, —NH—, —NHC (O) —, —NHC (O) O—, —NHC (O) NH—, —C (O) O—, —C (O Represents NH—, —OC (O) —, —OC (O) NH—, or —OC (O) O—;
W ² represents a single bond or C _1-2 alkylene;
R ³ and R ⁴ each independently represents a hydrogen atom, hydroxyl, or B (OH) ₂ ;
Where R ³ and R ⁴ are not both hydrogen atoms;
When L ² is a single bond, and R ³ and R ⁴ are both hydroxyl, L ^{1a in} formula (1a) is —O— and R ² is hydroxyl, optionally substituted C _{1 -6} alkoxy, or an optionally substituted 3- to 8-membered saturated or partially unsaturated heterocyclic group;
L ² is —O—, —NH—, —NHC (O) —, —NHC (O) O—, —NHC (O) NH—, —OC (O) —, —OC (O) NH—, Or, when —OC (O) O—, W ^1b is C _2-20 alkylene], the adhesive according to [12].

[14] The adhesive according to [12] or [13], wherein the polymer further contains a crosslinkable monomer as a constituent unit.

［式中、Ｒ^1aは、水素原子またはメチルを表し；
　Ｌ^1aは、－Ｏ－、－ＮＨ－、－ＮＲ⁵－、－ＮＨＣ（Ｏ）Ｏ－、または－ＮＨＣ（Ｏ）ＮＨ－を表し；
　Ｗ^1aは、単結合、またはＣ_1-20アルキレンを表し；
　Ｒ²は、メチル、ヒドロキシル、置換されていてもよいＣ_1-6アルコキシ、置換されていてもよいフェニル、置換されていてもよいフェノキシ、置換されていてもよい５員もしくは６員のヘテロアリール、置換されていてもよい３員～８員の飽和もしくは部分不飽和の炭化水素環基、または置換されていてもよい３員～８員の飽和もしくは部分不飽和のヘテロ環基を表し；
　Ｒ⁵は、置換されていてもよいＣ_1-8アルキルを表し；
　ここにおいて、Ｒ²がメチルのときは、Ｗ^1aが、単結合、またはＣ_1-8アルキレンであり；
　Ｒ²が、ヒドロキシル、置換されていてもよいＣ_1-6アルコキシ、または置換されていてもよいフェノキシのときは、Ｗ^1aがＣ_2-20アルキレンである］で表される１以上の化合物であり、
モノマーＢが、式（１ｂ）：

［式中、Ｒ^1bは、水素原子またはメチルを表し；
　Ｌ^1bは、－Ｏ－、－ＮＨ－、－ＮＨＣ（Ｏ）Ｏ－、または－ＮＨＣ（Ｏ）ＮＨ－を表し；
　Ｗ^1bは、単結合、またはＣ_1-20アルキレンを表し；
　Ｌ²は、単結合、－Ｏ－、－ＮＨ－、－ＮＨＣ（Ｏ）－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＨ－、－Ｃ（Ｏ）Ｏ－、－Ｃ（Ｏ）ＮＨ－、－ＯＣ（Ｏ）－、－ＯＣ（Ｏ）ＮＨ－、または－ＯＣ（Ｏ）Ｏ－を表し；
　Ｗ²は、単結合、またはＣ_1-2アルキレンを表し；
　Ｒ³およびＲ⁴は、それぞれ独立して、水素原子、ヒドロキシル、またＢ（ＯＨ）₂を表し；
　ここにおいて、Ｒ³およびＲ⁴がいずれも水素原子であることはない］で表される１以上の化合物である表面コート剤。
〔１６〕モノマーＡおよびモノマーＢを構成単位として含むポリマー（ただし、炭素数１０以上のアルキル－（メタ）アクリレートを構成単位として含むポリマーを除く）を含有する表面コート剤であって、
モノマーＡが、式（１ａ）：

［式中、Ｒ^1aは、水素原子またはメチルを表し；
　Ｌ^1aは、－Ｏ－、－ＮＨ－、－ＮＨＣ（Ｏ）Ｏ－、または－ＮＨＣ（Ｏ）ＮＨ－を表し；
　Ｗ^1aは、単結合、またはＣ_1-20アルキレンを表し；
　Ｒ²は、メチル、ヒドロキシル、置換されていてもよいＣ_1-6アルコキシ、置換されていてもよいフェニル、置換されていてもよい５員もしくは６員のヘテロアリール、置換されていてもよい３員～８員の飽和もしくは部分不飽和の炭化水素環基、または置換されていてもよい３員～８員の飽和もしくは部分不飽和のヘテロ環基を表し；
　ここにおいて、Ｒ²がメチルのときは、Ｗ^1aが、単結合、またはＣ_1-8アルキレンであり；
　Ｒ²が、ヒドロキシル、または置換されていてもよいＣ_1-6アルコキシのときは、Ｗ^1aがＣ_2-20アルキレンである］で表される１以上の化合物であり、
モノマーＢが、式（１ｂ）：

［式中、Ｒ^1bは、水素原子またはメチルを表し；
　Ｌ^1bは、－Ｏ－、－ＮＨ－、－ＮＨＣ（Ｏ）Ｏ－、または－ＮＨＣ（Ｏ）ＮＨ－を表し；
　Ｗ^1bは、単結合、またはＣ_1-20アルキレンを表し；
　Ｌ²は、単結合、－Ｏ－、－ＮＨ－、－ＮＨＣ（Ｏ）－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＨ－、－Ｃ（Ｏ）Ｏ－、－Ｃ（Ｏ）ＮＨ－、－ＯＣ（Ｏ）－、－ＯＣ（Ｏ）ＮＨ－、または－ＯＣ（Ｏ）Ｏ－を表し；
　Ｗ²は、単結合、またはＣ_1-2アルキレンを表し；
　Ｒ³およびＲ⁴は、それぞれ独立して、水素原子、ヒドロキシル、またＢ（ＯＨ）₂を表し；
　ここにおいて、Ｒ³およびＲ⁴がいずれも水素原子であることはなく；
　Ｌ²が単結合であり、Ｒ³およびＲ⁴がいずれもヒドロキシルのときは、式（１ａ）のＬ^1aが、－Ｏ－であり、Ｒ²が、ヒドロキシル、置換されていてもよいＣ_1-6アルコキシ、または置換されていてもよい３員～８員の飽和または部分不飽和のヘテロ環基であり；
　Ｌ²が、－Ｏ－、－ＮＨ－、－ＮＨＣ（Ｏ）－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＨ－、－ＯＣ（Ｏ）－、－ＯＣ（Ｏ）ＮＨ－、または－ＯＣ（Ｏ）Ｏ－ときは、Ｗ^1bがＣ_2-20アルキレンである］で表される１以上の化合物である、〔１５〕記載の表面コート剤。 [15] A surface coating agent containing a monomer A, a monomer B, and a polymer containing a crosslinkable monomer as a constituent unit (excluding a polymer containing an alkyl- (meth) acrylate having 10 or more carbon atoms as a constituent unit) There,
Monomer A is represented by the formula (1a):

[Wherein R ^1a represents a hydrogen atom or methyl;
L ^1a represents —O—, —NH—, —NR ⁵ —, —NHC (O) O—, or —NHC (O) NH—;
W ^1a represents a single bond or C _1-20 alkylene;
R ² is methyl, hydroxyl, optionally substituted C _1-6 alkoxy, optionally substituted phenyl, optionally substituted phenoxy, optionally substituted 5 or 6 membered heteroaryl. Represents an optionally substituted 3- to 8-membered saturated or partially unsaturated hydrocarbon ring group, or an optionally substituted 3- to 8-membered saturated or partially unsaturated heterocyclic group;
R ⁵ represents an optionally substituted C _1-8 alkyl;
Here, when R ² is methyl, W ^1a is a single bond or C _1-8 alkylene;
When R ² is hydroxyl, optionally substituted C _1-6 alkoxy, or optionally substituted phenoxy, W ^1a is C _2-20 alkylene]. Yes,
Monomer B is represented by formula (1b):

[Wherein R ^1b represents a hydrogen atom or methyl;
L ^1b represents —O—, —NH—, —NHC (O) O—, or —NHC (O) NH—;
W ^1b represents a single bond or C _1-20 alkylene;
L ² represents a single bond, —O—, —NH—, —NHC (O) —, —NHC (O) O—, —NHC (O) NH—, —C (O) O—, —C (O Represents NH—, —OC (O) —, —OC (O) NH—, or —OC (O) O—;
W ² represents a single bond or C _1-2 alkylene;
R ³ and R ⁴ each independently represents a hydrogen atom, hydroxyl, or B (OH) ₂ ;
Here, R ³ and R ⁴ are not hydrogen atoms.] A surface coating agent that is one or more compounds represented by:
[16] A surface coating agent containing a polymer containing monomer A and monomer B as constituent units (excluding a polymer containing alkyl- (meth) acrylate having 10 or more carbon atoms as constituent units),
Monomer A is represented by the formula (1a):

[Wherein R ^1a represents a hydrogen atom or methyl;
L ^1a represents —O—, —NH—, —NHC (O) O—, or —NHC (O) NH—;
W ^1a represents a single bond or C _1-20 alkylene;
R ² is methyl, hydroxyl, optionally substituted C _1-6 alkoxy, optionally substituted phenyl, optionally substituted 5 or 6 membered heteroaryl, optionally substituted 3 Represents a membered to 8-membered saturated or partially unsaturated hydrocarbon ring group, or an optionally substituted 3 to 8 membered saturated or partially unsaturated heterocyclic group;
Here, when R ² is methyl, W ^1a is a single bond or C _1-8 alkylene;
When R ² is hydroxyl or optionally substituted C _1-6 alkoxy, W ^1a is C _2-20 alkylene],
Monomer B is represented by formula (1b):

[Wherein R ^1b represents a hydrogen atom or methyl;
L ^1b represents —O—, —NH—, —NHC (O) O—, or —NHC (O) NH—;
W ^1b represents a single bond or C _1-20 alkylene;
L ² represents a single bond, —O—, —NH—, —NHC (O) —, —NHC (O) O—, —NHC (O) NH—, —C (O) O—, —C (O Represents NH—, —OC (O) —, —OC (O) NH—, or —OC (O) O—;
W ² represents a single bond or C _1-2 alkylene;
R ³ and R ⁴ each independently represents a hydrogen atom, hydroxyl, or B (OH) ₂ ;
Where R ³ and R ⁴ are not both hydrogen atoms;
When L ² is a single bond, and R ³ and R ⁴ are both hydroxyl, L ^{1a in} formula (1a) is —O— and R ² is hydroxyl, optionally substituted C _{1 -6} alkoxy, or an optionally substituted 3- to 8-membered saturated or partially unsaturated heterocyclic group;
L ² is —O—, —NH—, —NHC (O) —, —NHC (O) O—, —NHC (O) NH—, —OC (O) —, —OC (O) NH—, Or, when —OC (O) O—, W ^1b is C _2-20 alkylene], the surface coating agent according to [15].

[17] The surface coating agent according to [15] or [16], wherein the polymer further contains a crosslinkable monomer as a structural unit.

According to the present invention, it is possible to provide a curable resin composition, an adhesive, and a surface coating agent that are more firmly bonded to a wider variety of materials.

In the present specification, the number of carbons in the definition of “substituent” may be expressed as “C _1-6 ”, for example. Specifically, the expression “C _1-6 alkyl” is synonymous with an alkyl group having 1 to 6 carbon atoms.

Specific examples of “halogen atom” include fluorine atom, chlorine atom, bromine atom or iodine atom.

“C _1-6 alkyl” means a straight or branched saturated hydrocarbon group having 1 to 6 carbon atoms. Preferred is “C _1-4 alkyl”. Specific examples of “C _1-6 alkyl” include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, 1-ethylpropyl, hexyl, isohexyl, Examples include heptyl, octyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl and the like.

“C _1-20 alkylene” means a linear or branched divalent saturated hydrocarbon group having 1 to 20 carbon atoms. “C _1-8 alkylene” is preferable, “C _1-6 alkylene” is more preferable, and “C _1-4 alkylene” is still more preferable. Specific examples of “C _1-20 alkylene” include, for example, methylene, ethylene, trimethylene, tetramethylene, hexamethylene, octamethylene, 1-methylmethylene, 1-ethylmethylene, 1-propylmethylene, 1-methylethylene, Examples include 2-methylethylene and 1-ethylethylene.

The “C _1-6 alkyl” part of “C _1-6 alkoxy” has the same _{meaning as} the above “C _1-6 alkyl”. Preferred is “C _1-4 alkoxy”. Specific examples of “C _1-6 alkoxy” include, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy and the like.

Examples of the “5-membered or 6-membered heteroaryl” include a 5-membered or 6-membered monocyclic aromatic heterocyclic group, etc., and the group is selected from a nitrogen atom, a sulfur atom and an oxygen atom. 1 or more (for example, 1 to 4) of the same or different heteroatoms. Specific examples include pyridyl, pyrimidyl, pyrazyl, pyridazyl, triazyl, imidazolyl, pyrazolyl, triazoyl, tetrazoyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl and the like.

Examples of the “3- to 8-membered saturated or partially unsaturated hydrocarbon group” include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopentenyl, cyclohexenyl, cyclohexadienyl, and the like. .

As the “3- to 8-membered saturated or partially unsaturated heterocyclic group”, for example, a 3- to 8-membered group having 1 to 3 of the same or different atoms selected from a nitrogen atom, an oxygen atom and a sulfur atom And monocyclic saturated or partially unsaturated heterocyclic groups. The nitrogen atom, oxygen atom and sulfur atom are all atoms constituting a ring. Preferred is a 4- to 6-membered saturated or partially unsaturated heterocyclic group, and more preferred is a 4- to 6-membered saturated or partially unsaturated saturated heterocyclic group containing 1 to 2 oxygen atoms. . Specifically, oxiranyl, oxetanyl, tetrahydrofuryl, dihydrofuryl, pyranyl, dihydropyranyl, tetrahydropyranyl, dioxanyl, dioxolanyl, oxazolidinyl, oxepanyl, oxecanyl, aziridinyl, azetidinyl, pyrrolidinyl, piperidinyl, piperazinyl, azepanyl, azepanyl, azepanyl, azepanyl, azepanyl, azepanyl, azepanyl And thiomorpholinyl. The bond of the group may be any of a carbon atom and a nitrogen atom constituting the ring.

The “3- to 8-membered oxygen-containing saturated heterocyclic group” includes, for example, 1 to 2 oxygen atoms, and optionally 1 to 2 of the same or different atoms selected from nitrogen and sulfur atoms. Examples thereof include 3- to 8-membered monocyclic saturated heterocyclic groups. The oxygen atom, nitrogen atom and sulfur atom are all atoms constituting a ring. Specific examples include oxiranyl, oxetanyl, tetrahydrofuryl, tetrahydropyranyl, dioxanyl, dioxolanyl, oxazolidinyl, oxepanyl, oxecanyl, morpholinyl, and the like; oxetanyl, tetrahydrofuryl, tetrahydropyranyl, dioxanyl, and dioxolanyl are preferred; oxetanyl and Tetrahydrofuryl is more preferred.

Examples of the substituent in “optionally substituted C _1-8 alkyl” and “optionally substituted C _1-6 alkoxy” include hydroxyl, halogen atom, C _1-6 alkoxy and the like.

“Optionally substituted phenyl” “optionally substituted phenoxy”, “optionally substituted 5 or 6 membered heteroaryl”, “optionally substituted 3 to 8 membered saturation” Examples of the substituent in “or partially unsaturated hydrocarbon ring group” and “optionally substituted 3- to 8-membered saturated or partially unsaturated heterocyclic group” include, for example, hydroxyl, amino, halogen atom, C _1-6 alkyl, C _1-6 alkoxy and the like can be mentioned.

In this specification, when a numerical range is indicated using “to”, the numerical values at both ends shall be included.

<Monomer component>
The curable resin composition which concerns on one Embodiment of this invention is a composition couple | bonded with a base material by hardening | curing. A curable resin composition according to an embodiment of the present invention contains a first monomer (monomer A) and a second monomer (monomer B), and contains an alkyl- (meth) acrylate having 10 or more carbon atoms. It is characterized by not.

［式中、Ｒ^1aは、水素原子またはメチルを表し；Ｌ^1aは、－Ｏ－、－ＮＨ－、－ＮＲ⁵－、－ＮＨＣ（Ｏ）Ｏ－、または－ＮＨＣ（Ｏ）ＮＨ－を表し；Ｗ^1aは、単結合、またはＣ_1-20アルキレンを表し；Ｒ²は、メチル、ヒドロキシル、置換されていてもよいＣ_1-6アルコキシ、置換されていてもよいフェニル、置換されていてもよいフェノキシ、置換されていてもよい５員もしくは６員のヘテロアリール、置換されていてもよい３員～８員の飽和もしくは部分不飽和の炭化水素環基、または置換されていてもよい３員～８員の飽和もしくは部分不飽和のヘテロ環基を表し；Ｒ⁵は、置換されていてもよいＣ_1-8アルキルを表し；ここにおいて、Ｒ²がメチルのときは、Ｗ^1aが、単結合、またはＣ_1-8アルキレンであり；Ｒ²が、ヒドロキシル、置換されていてもよいＣ_1-6アルコキシ、または置換されていてもよいフェノキシのときは、Ｗ^1aがＣ_2-20アルキレンである］で表される１以上の化合物を含有する。 (Monomer A)
The curable resin composition which concerns on one Embodiment of this invention is a following formula (1a) as a 1st monomer (monomer A):

[Wherein R ^1a represents a hydrogen atom or methyl; L ^1a represents —O—, —NH—, —NR ⁵ —, —NHC (O) O—, or —NHC (O) NH—. W ^1a represents a single bond or C _1-20 alkylene; R ² represents methyl, hydroxyl, optionally substituted C _1-6 alkoxy, optionally substituted phenyl, optionally substituted; Good phenoxy, optionally substituted 5 or 6 membered heteroaryl, optionally substituted 3 to 8 membered saturated or partially unsaturated hydrocarbon ring group, or optionally substituted 3 member Represents a ˜8-membered saturated or partially unsaturated heterocyclic group; R ⁵ represents an optionally substituted C _1-8 alkyl; here, when R ² is methyl, W ^1a is A bond, or C _1-8 alkylene; R ² is hydroxyl, substituted In the case of C _1-6 alkoxy which may be substituted, or phenoxy which may be substituted, one or more compounds represented by W ^1a is C _2-20 alkylene are contained.

The preferred L ^1a, -O- or -NR ⁵ - (wherein, R ⁵ is hydroxyl or C _1-8 represent an C _1-8 alkyl optionally substituted with alkoxy); and more preferably -O-. Compounds of formula (1a) L ^1a is -O- may or monomers A in an embodiment the curable resin composition according to the L ^1a which may contain is not -O- compounds of formula (1a), below This is preferable because of good compatibility with other monomers.

W ^1a is preferably a single bond or C _1-8 alkylene; more preferably a single bond or C _1-4 alkylene. Further, as another embodiment of W ^1a , C _1-8 alkylene, C _1-6 alkylene, C _2-6 alkylene, C _1-4 alkylene, C _2-4 alkylene and the like can be mentioned.

R ² is preferably
(1) hydroxyl,
(2) C _1-6 alkoxy optionally substituted with hydroxyl or C _1-6 alkoxy,
(3) 4 to 7-membered optionally substituted with 1 to 4 groups of the same or different types selected from the group consisting of a halogen atom, hydroxyl, C _1-6 alkyl, and C _1-6 alkoxy Oxygen-containing saturated heterocyclic groups (eg, oxetanyl, tetrahydrofuryl, tetrahydropyranyl, dioxanyl, dioxolanyl, oxazolidinyl, oxepanyl, morpholinyl, etc.),
(4) phenyl optionally substituted by the same or different 1 to 4 groups selected from the group consisting of a halogen atom, C _1-6 alkyl, and C _1-6 alkoxy;
(5) phenoxy optionally substituted by 1 to 4 groups of the same or different types selected from the group consisting of halogen atoms, C _1-6 alkyl, and C _1-6 alkoxy, or
(6) methyl; more preferably
(1) hydroxyl,
(2) hydroxyl or C _1-6 alkoxy optionally substituted C _1-6 alkoxy or (3) a halogen atom, is selected hydroxyl, from C _1-6 alkyl, and the group consisting of C _1-6 alkoxy A 4- to 7-membered oxygen-containing saturated heterocyclic group which may be substituted with the same or different 1 to 4 groups; more preferably hydroxyl or 1 to 4 C _1-6 alkyl A 4- to 6-membered oxygen-containing saturated heterocyclic group which may be substituted with

From the viewpoint of adhesiveness, it is preferable that the monomer A contains a compound in which R ² is hydroxyl (monomer A1); the monomer A1 and a monomer A other than the monomer A1 (that is, R ² is methyl, substituted) C _1-6 alkoxy, optionally substituted phenyl, optionally substituted phenoxy, optionally substituted 5 or 6 membered heteroaryl, optionally substituted 3 to 8 membered A saturated or partially unsaturated hydrocarbon ring group, or an optionally substituted 3- to 8-membered saturated or partially unsaturated heterocyclic group (hereinafter sometimes referred to as “monomer A2”) ) In combination (that is, composed of monomer A1 and monomer A2).

As another embodiment of the monomer A, L ^1a in the formula (1a) is —O—, W ^1a is C _2-20 alkylene, R ² is hydroxyl, and optionally substituted C _1-6 Alkoxy or optionally substituted phenoxy, L ^1a is —O—, W ^1a is a single bond or C _1-20 alkylene, and R ² is an optionally substituted 3-membered or a heterocyclic group, saturated or partially unsaturated 1-8 membered, L ^1a is -NR ⁵ - (wherein, R ⁵ is optionally C _1-8 optionally substituted by hydroxyl or C _1-8 alkoxy an alkyl), W ^1a is a single bond, or a C _1-8 alkylene, R ² is hydroxyl, may include a C _1-8 alkoxy or one or more compounds is methyl, preferably; L ^1a There is -O-, W ^1a is a C _2-20 alkylene, R ² is hydroxyl, Whether the conversion is C _1-6 alkoxy optionally or may phenoxy optionally substituted,, L ^1a is -O-, W ^1a is a single bond, or C _1-20 alkylene, R ² More preferably includes one or more compounds which are optionally substituted 3- to 8-membered saturated or partially unsaturated heterocyclic groups; L ^1a is —O—, and W ^1a is C ₂ More preferably, it includes one or more compounds that are _-20 alkylene, R ² is hydroxyl; L ^1a is —O—, W ^1a is C _2-20 alkylene, and R ² is hydroxyl 1 It is particularly preferred to comprise the above compound and one or more compounds wherein L ^1a is —O—, W ^1a is a single bond or C _1-8 alkylene, and R ² is methyl.

When the monomer A1 and the monomer A2 are used in combination, the mass ratio of the content of the monomer A1 to the content of the monomer A2 [monomer A1 / monomer A2] is preferably 0.01 to 100, more preferably 0.02 to 10, 0.03-1.0 is more preferable, and 0.04-0.5 is particularly preferable.

The content of monomer A with respect to the total amount of monomers is not particularly limited, and the remainder excluding monomer B, crosslinkable monomer, and other monomers described later can be used as the content, but 75% by mass or more is preferable. 80 mass% or more is more preferable, 90 mass% or more is further more preferable, and 93 mass% or more is especially preferable. By setting the content of monomer A to 75% by mass or more, 80% by mass or more, 90% by mass or more, and 93% by mass or more, the characteristics of monomer A can be exhibited. The upper limit of the content of monomer A with respect to the total amount of monomers is preferably 99.9% by mass or less, more preferably 99% by mass or less, still more preferably 98% by mass or less, and particularly preferably 97% by mass or less. An example of the characteristics of the monomer A is flexibility.

［式中、Ｒ^1bは、水素原子またはメチルを表し；Ｌ^1bは、－Ｏ－、－ＮＨ－、－ＮＨＣ（Ｏ）Ｏ－、または－ＮＨＣ（Ｏ）ＮＨ－を表し；Ｗ^1bは、単結合、またはＣ_1-20アルキレンを表し；Ｌ²は、単結合、－Ｏ－、－ＮＨ－、－ＮＨＣ（Ｏ）－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＨ－、－Ｃ（Ｏ）Ｏ－、－Ｃ（Ｏ）ＮＨ－、－ＯＣ（Ｏ）－、－ＯＣ（Ｏ）ＮＨ－、または－ＯＣ（Ｏ）Ｏ－を表し；Ｗ²は、単結合、またはＣ_1-2アルキレンを表し；Ｒ³およびＲ⁴は、それぞれ独立して、水素原子、ヒドロキシル、またＢ（ＯＨ）₂を表し；ここにおいて、Ｒ³およびＲ⁴がいずれも水素原子であることはなく；Ｌ²が単結合であり、Ｒ³およびＲ⁴がいずれもヒドロキシルのときは、式（１ａ）のＬ^1aが、－Ｏ－であり、Ｒ²が、ヒドロキシル、置換されていてもよいＣ_1-6アルコキシ、または置換されていてもよい３員～８員の飽和または部分不飽和のヘテロ環基であり；Ｌ²が、－Ｏ－、－ＮＨ－、－ＮＨＣ（Ｏ）－、－ＮＨＣ（Ｏ）Ｏ－、－ＮＨＣ（Ｏ）ＮＨ－、－ＯＣ（Ｏ）－、－ＯＣ（Ｏ）ＮＨ－、または－ＯＣ（Ｏ）Ｏ－ときは、Ｗ^1bがＣ_2-20アルキレンである］で表される１以上の化合物を含有する。 (Monomer B)
The curable resin composition according to an embodiment of the present invention is represented by the formula (1b) as the second monomer (monomer B):

[Wherein, R ^1b represents a hydrogen atom or methyl; L ^1b represents —O—, —NH—, —NHC (O) O—, or —NHC (O) NH—; W ^1b represents Represents a single bond, or C _1-20 alkylene; L ² represents a single bond, —O—, —NH—, —NHC (O) —, —NHC (O) O—, —NHC (O) NH—, Represents —C (O) O—, —C (O) NH—, —OC (O) —, —OC (O) NH—, or —OC (O) O—; W ² represents a single bond, or C _1-2 alkylene is represented; R ³ and R ⁴ each independently represent a hydrogen atom, hydroxyl, or B (OH) ₂ ; where R ³ and R ⁴ are both hydrogen atoms When L ² is a single bond and R ³ and R ⁴ are both hydroxyl, L ^{1a in} formula (1a) is —O— and R ² is hydroxy , Optionally substituted C _1-6 alkoxy, or optionally substituted 3- to 8-membered saturated or partially unsaturated heterocyclic group; L ² represents —O—, —NH—. , —NHC (O) —, —NHC (O) O—, —NHC (O) NH—, —OC (O) —, —OC (O) NH—, or —OC (O) O— W ^1b is C _2-20 alkylene].

As described above, the monomer B has hydroxyl or B (OH) ₂ in the benzene ring. The curable resin composition which is an embodiment of the present invention and the adhesive and surface coating agent described below are more robust against more types of materials by orienting these groups on the adhesive surface. This is considered to be one factor that can be combined.

L ^1b is preferably —O— or —NH—; more preferably —NH—. A compound of the formula (1b) in which L ^1b is —NH— is preferable because it becomes an adhesive or a surface coating agent that is difficult to hydrolyze after the curable resin composition is cured.

W ^1b is preferably a single bond or C _1-8 alkylene; more preferably a single bond or C _1-4 alkylene; and still more preferably a single bond or C _1-2 alkylene. When R ³ and R ⁴ are both hydroxyl, W ^1b is preferably ethylene, and when R ³ or R ⁴ is B (OH) ₂ , W ^1b is preferably a single bond.

L ² is preferably a single bond, —O—, —NHC (O) O—, or —NHC (O) NH—; more preferably a single bond.

W ² is preferably a single bond.

R ³ and R ⁴ are preferably both hydroxyl. In another embodiment, R ³ is B (OH) ₂ and R ⁴ is a hydrogen atom, or R ³ is a hydrogen atom and R ⁴ is B (OH) _2. From the viewpoint of improving the property.

One embodiment of monomer B includes compounds wherein R ³ and / or R ⁴ is B (OH) ₂ . Another embodiment includes compounds in which R ³ and / or R ⁴ are hydroxyl. Among them, a compound (monomer B1) in which R ³ is B (OH) ₂ , R ⁴ is a hydrogen atom, R ³ is a hydrogen atom, and R ⁴ is B (OH) ₂ , and R ^A preferred embodiment is a compound (monomer B2) in which ³ and R ⁴ are both hydroxyl.

Monomer B1 and monomer B2 can be used in an appropriate amount depending on the adhesiveness between the materials, and only one of monomer B1 and monomer B2 may be used. B2 may be used in combination. When the monomer B1 and the monomer B2 are used in combination, the mass ratio of the content of the monomer B1 to the content of the monomer B2 [monomer B1 / monomer B2] is, for example, 0.01 to 100, 0.05 to 20, The range is from 1 to 10, 0.2 to 5.0, 0.4 to 2.5, 0.5 to 2.0, and 0.7 to 1.4.

The monomer B preferably includes the monomer B1, more preferably includes the monomer B1 and the monomer B2, and further preferably includes only the monomer B1 and the monomer B2.

When the monomer B consists only of the monomer B2, the monomer A is substituted with L ^1a in formula (1a) is —O—, W ^1a is C _2-20 alkylene, and R ² is hydroxyl, substituted. _Optionally substituted C _1-6 alkoxy, or optionally substituted phenoxy, L ^1a is —O—, W ^1a is a single bond, or C _1-20 alkylene, and R ² is substituted. An optionally substituted 3- to 8-membered saturated or partially unsaturated heterocyclic group, or L ^1a is —NR ⁵ — (wherein R ⁵ is substituted with hydroxyl or C _1-8 alkoxy; and is also represent an C _1-8 alkyl), W ^1a is a single bond, or a C _1-8 alkylene, R ² is hydroxyl, C _1-8 alkoxy or one or more compounds is methyl, Preferably, L ^1a is —O— and W ^1a is C _2-20 alkylene. R ² is hydroxyl, optionally substituted C _1-6 alkoxy, or optionally substituted phenoxy, L ^1a is —O—, W ^1a is a single bond, or C 1 More preferably, it comprises one or more compounds that are _1-20 alkylene and R ² is an optionally substituted 3- to 8-membered saturated or partially unsaturated heterocyclic group; L ^1a is —O More preferably, it includes one or more compounds in which W ^1a is C _2-20 alkylene and R ² is hydroxyl; L ^1a is —O—, and W ^1a is C _2-20 alkylene. And one or more compounds wherein R ² is hydroxyl, and one or more compounds wherein L ^1a is —O—, W ^1a is a single bond or C _1-8 alkylene, and R ² is methyl. It is particularly preferred that

Monomer A and monomer B are synthesized by a method combining a known compound and a known synthesis method. Moreover, you may use a commercial item as the monomer A and the monomer B.

The content of the monomer B with respect to the total amount of monomers is preferably 0.10 to 10.0% by mass, more preferably 0.15 to 5.0% by mass, further preferably 0.20 to 3.0% by mass, 0.35 to 2.0 mass% is particularly preferable. By setting the content of monomer B to 0.10% by mass or more, 0.15% by mass or more, 0.20% by mass or more, and 0.35% by mass or more with respect to the total amount of monomers, It can be set as the curable resin composition, adhesive agent, and surface coating agent which couple | bond more firmly. Further, the content of the monomer B with respect to the total amount of the monomers is 10.0% by mass or less, 5.0% by mass or less, 3.0% by mass or less, and 2.0% by mass or less, so that various types of monomers can be used. It can be set as the curable resin composition, adhesive agent, and surface coating agent which couple | bond firmly to a material.

(Crosslinkable monomer)
You may mix | blend a crosslinkable monomer with the curable resin composition which concerns on one Embodiment of this invention within the range which does not inhibit the objective of this invention. The crosslinkable monomer is a monomer having at least two polymerizable functional groups. Examples of the crosslinkable monomer include polyfunctional (meth) acrylamides having two or more (preferably two) (meth) acryloyl groups such as methylene bisacrylamide and methylene bismethacrylamide; ethylene di (meth) acrylate, ethylene glycol di (Meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) ) Acrylate, 1,9-nonanediol di (meth) acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol 2 or more (preferably 2 or 3) of (meth) acryloyl groups such as di (meth) acrylate, tetraethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate and pentaerythritol tri (meth) acrylate ) Polyfunctional (meth) acrylates; hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane-4,4′-diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, lysine triisocyanate, methylidyne triphenylene triisocyanate Polyfunctional isocyanate having 2 or more (preferably 2 or 3) isocyanate groups such as 2 or more carbon-carbon double bonds such as diallylamine and triallylamine (preferably Is a polyfunctional amine having 2 or 3 carbon atoms; a polyfunctional monomer such as an aromatic compound having 2 or more (preferably 2 or 3) carbon-carbon double bonds such as divinylbenzene and diallylbenzene. . These crosslinkable monomers may be used alone or in combination of two or more.

The content of the crosslinkable monomer with respect to the total amount of monomers is preferably 0.10 to 20% by mass, more preferably 0.50 to 15% by mass, and further preferably 1.0 to 10% by mass. Curing that more firmly binds to various types of materials by setting the content of the crosslinkable monomer to the total amount of the monomers to be 0.10% by mass or more, 0.50% by mass or more, and 1.0% by mass or more. Resin composition, adhesive, and surface coating agent. Further, by setting the content of monomer B to 20% by mass or less, 15% by mass or less, and 10% by mass or less with respect to the total amount of monomers, a curable resin composition that can be firmly bonded to a wider variety of materials, Adhesives and surface coating agents can be used.

(Other monomers)
In the curable resin composition according to one embodiment of the present invention, other monomers other than the monomer A, the monomer B, and the crosslinkable monomer described above may be blended within a range that does not impair the object of the present invention. . Examples of other monomers include, but are not limited to, acrylate resins and methacrylate resins not included in the above formula (1). However, it does not contain an alkyl- (meth) acrylate having 10 or more carbon atoms. In the present specification, the term “alkyl- (meth) acrylate having 10 or more carbon atoms” refers to an alkyl ester of (meth) acrylic acid, wherein the alkyl group constituting the alkyl ester moiety is a straight chain having 10 or more carbon atoms. It means alkyl- (meth) acrylate which is a linear or branched alkyl group. That is, the carbon which comprises a (meth) acrylic acid part is not contained in the said carbon number.

The content of other monomers with respect to the total amount of monomers is not particularly limited, and monomer A
The remainder excluding the monomer B and the crosslinkable monomer can be the content.

The above-described monomer components (monomer A, monomer A1, monomer A2, monomer B, monomer B1, monomer B2, crosslinkable monomer, and other monomers) may be used alone or in combination of two or more. Also good.

The curable resin composition according to one embodiment of the present invention, in addition to the above-described monomer components (monomer A, monomer B, crosslinkable monomer, and other monomers), as long as the object of the present invention is not impaired. You may contain the additive generally added to a solvent, an adhesive, or an adhesive agent. Examples of the additive include a silane coupling agent, a crosslinking agent, a polymerization initiator, an ultraviolet absorber, a tackifier, an adhesion promoter, an anti-aging agent, a plasticizer, a softener, a dye, a pigment, and a filler. Etc. Especially, it is preferable to contain the polymerization initiator of a postscript.

<Adhesive and production method thereof>
The adhesive according to an embodiment of the present invention binds to both one base material and the other base material, and prevents one base material from moving relative to the other base material. The material to do. Preventing the movement of the other substrate relative to one substrate does not only mean that one substrate does not move completely when viewed from the other substrate, but one substrate is the other. It also includes fixing to allow movement within a certain range with respect to the substrate. In other words, the adhesive according to an embodiment of the present invention does not need to be completely cured. The certain range may be determined according to the place where both base materials are arranged, the purpose of use, and the like. In other words, the adhesive may be a pressure-sensitive adhesive having adhesiveness that is difficult to peel off, or an adhesive having a softness similar to the pressure-sensitive adhesive. The adhesive is sometimes used instead of a joining method such as fastening with bolts or welding from the viewpoint of weight reduction or simplification of work in joining where strength is not required. Moreover, the adhesive agent which has softness is used suitably for the use as which vibration resistance etc. are calculated | required.

The adhesive according to the present embodiment contains a polymer (copolymer) containing monomer A and monomer B as constituent units, and preferably further contains a crosslinkable monomer as constituent units. Further, if necessary, a solvent, a silane coupling agent, a crosslinking agent, a polymerization initiator, an ultraviolet absorber, a tackifier, an adhesion promoter, an anti-aging agent, a plasticizer, a softener, a dye, a pigment, and It may contain additives that are commonly added to pressure sensitive adhesives or adhesives, such as fillers.

The adhesive according to an embodiment of the present invention has strong adhesiveness to various types of materials. Examples of the material of the base material that can be bonded by the adhesive according to an embodiment of the present invention include inorganic materials such as glass, hydroxyapatite, titanium oxide, zinc oxide, iron oxide, and indium tin oxide (ITO). Metal materials such as aluminum (Al), copper (Cu), iron (Fe), gold (Pt), silver (Ag), zinc (Zn), tin (Sn), titanium (Ti) and alloys thereof; polyethylene Terephthalate (PET), polypropylene (PP), polyethylene (PE), acrylonitrile butadiene styrene copolymer resin (ABS), polytetrafluoroethylene (PTFE), polyimide (PI), fiber reinforced plastic (FRP), molybdenum-aluminum-molybdenum And organic materials such as a laminated structure (MAM). Moreover, since the adhesive according to the present embodiment has good adhesiveness to various base materials, it is suitable as an adhesive that joins different base materials. Of course, you may use the adhesive agent which concerns on one Embodiment of this invention in order to join the base materials of the same material.

Furthermore, the adhesive according to one embodiment of the present invention is also intended to be used for the purpose of bonding a surface coating agent such as paint, such as a so-called undercoat paint, intermediate coat paint, primer, and the substrate.

The shape of the substrates fixed by the adhesive according to an embodiment of the present invention is not particularly limited. As an example of the shape of the substrate, one and the other shapes may be any one selected from a plate shape, a sheet shape, a rod shape, and the like.

The polymer contained in the adhesive can be obtained by polymerizing monomer A, monomer B, and a crosslinkable monomer. Although it does not specifically limit as a polymerization method, For example, a block polymerization method, a solution polymerization method, an emulsion polymerization method, a suspension polymerization method etc. are mentioned. In particular, from the viewpoints of manufacturability and handleability, the bulk polymerization method and the solution polymerization method are preferable, and the bulk polymerization method is more preferable.

As the solvent for polymerizing the monomer component by the solution polymerization method, a non-aqueous organic solvent is preferable from the viewpoints of manufacturability and handleability. Non-aqueous organic solvents include, for example, hydrocarbon organic solvents such as hexane, heptane, octane, isooctane, decane and liquid paraffin; ether organic solvents such as dimethyl ether, diethyl ether and tetrahydrofuran; ketone organic solvents such as acetone and methyl ethyl ketone Solvent; ester organic solvents such as methyl acetate, ethyl acetate, butyl acetate; chloride organic solvents such as methylene chloride, chloroform, carbon tetrachloride; dimethylformamide, diethylformamide, dimethyl sulfoxide, dioxane and the like. These organic solvents may be used alone or in combination of two or more. The amount of the solvent is usually about 100 to 1000 parts by mass per 100 parts by mass of the monomer component, but is not limited to this range.

When the monomer component is polymerized, a polymerization initiator can be used. Examples of the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator. Of these, a photopolymerization initiator is preferable from the viewpoint of leaving no heat history in the adhesive.

Examples of the photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,1. '-Biimidazole, 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (p-methoxyphenylvinyl) -1,3,5 -Triazine, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphate, 4,4'-di-tert-butyldiphenyliodonium tetrafluoroborate, 4-diethylaminophenylbenzenediazonium hexafluorophosphate, benzoin, 2-hydroxy-2-methyl -1-phenylpropane-2 ON, benzophenone, thioxanthone, 2,4,6-trimethylbenzoyldiphenylacylphosphine oxide (TPO), triphenylbutyl borate tetraethylammonium, diphenyl-4-phenylthiophenylsulfonium hexafluorophosphate, 2,2-dimethoxy-1,2 -Diphenylethane-1-one, phenylglyoxylic acid methyl ester, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, bis (2,4,6-trimethyl) Benzoyl) -phenylphosphine oxide, 1,2-octanedione, 1- [4- (phenylthio) -2- (o-benzoyloxime)], bis (η5-2,4-cyclopentadien-1-yl) bis [2,6-difluoro Photoradical polymerization initiators such as -3- (1H-pyrrol-1-yl) phenyltitanium]; 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2,4-bis (trichloro Methyl) -6- (p-methoxyphenylvinyl) -1,3,5-triazine, diphenyliodonium tetrafluoroborate, 4,4′-di-tert-butyldiphenyliodonium tetrafluoroborate, 4-diethylaminophenylbenzenediazonium hexa Examples include photocation ring-opening polymerization initiators such as fluorophosphate and diphenyl-4-phenylthiophenylsulfonium hexafluorophosphate. These photopolymerization initiators may be used alone or in combination of two or more.

Examples of the thermal polymerization initiator include dimethyl-2,2′-azobis (2-methylpropionate), 2,2′-azobisisobutyronitrile (AIBN), dimethyl 2,2′-azobisisobutyrate, Examples thereof include azo polymerization initiators such as azobisdimethylvaleronitrile; peroxide polymerization initiators such as benzoyl peroxide, potassium persulfate, and ammonium persulfate. These thermal polymerization initiators may be used alone or in combination of two or more.

The addition amount of the polymerization initiator is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and further preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the monomer component.

The order of blending each monomer when polymerizing each monomer to produce an adhesive is not particularly limited. As an example, after the monomer A, the monomer B, and the crosslinkable monomer are blended, the respective monomers are polymerized to produce an adhesive. As another example, after blending monomer A and monomer B, both monomers are polymerized to produce a first polymer, and then the first polymer and a crosslinkable monomer are blended so that the first polymer is crosslinked. You may manufacture the 2nd polymer (adhesive) bridge | crosslinked with the adhesive monomer.

<Surface coating agent>
The surface coating agent which concerns on one Embodiment of this invention says the material which couple | bonds with a base material and hardens | cures and protects the surface of a base material. An example of the surface coating agent is a paint. In addition to the above-described materials, the base material includes an undercoat paint, an intermediate paint, a primer, and the like.

The surface coating agent which concerns on one Embodiment of this invention contains the polymer (copolymer) which contains the monomer A and the monomer B as a structural unit similarly to the adhesive agent which concerns on one Embodiment of this invention mentioned above. It is preferable that a crosslinkable monomer is further included as a structural unit. In other words, the curable resin composition according to one embodiment of the present invention is a cured product cured on the surface of the substrate, and the surface of the cured product on the substrate side is bonded to the substrate, and the other surface ( Typically, this is an aspect in which the opposing surface of the substrate is exposed. Therefore, the basic configuration and the manufacturing method are the same as those of the adhesive according to the embodiment of the invention described above, and the description is omitted.

As described above, the adhesive and the surface coating agent according to one embodiment of the present invention exhibit at least one of adhesion, tackiness, and adhesiveness for various types of materials, It is thought that it binds to the substrate more firmly. In general, adhesion, tackiness, and adhesiveness can be evaluated for each performance by a test method as described in the examples described later, depending on the use and purpose of the adhesive. . Therefore, all the performances are performances for evaluating the bonding strength of the adhesive and the surface coating agent according to the embodiment of the present invention to the base material.

Adhesion (adhesion strength) refers to the adhesive force between the substrate and the adhesive / cured surface coating agent (paint) interface, and is generally an intermolecular force or ionic bond. Hydrogen bonds are involved in the magnitude of the adhesion between the substrate and the adhesive. Moreover, the anchor effect of the unevenness | corrugation of a base material and adhesive agent contributes to an adhesive improvement. Therefore, for example, peeling between the paint and the substrate can be suppressed by improving the adhesion.

Adhesiveness (adhesive strength) indicates, for example, the force to peel off two substrates pasted with an adhesive, the adhesiveness between the substrate and the adhesive, and the adhesive It is a force that combines the viscoelasticity and toughness of the agent itself. In general, the viscoelasticity and toughness of the resin, which is an adhesive, involve intermolecular forces, ionic bonds, and hydrogen bonds as well as the adhesion, as well as the molecular weight and three-dimensional structure of the resin. As an example, when the adhesive is suppressed, and the adhesive is excellent in viscoelasticity and toughness, a peelable adhesive tape or the like can be produced. Moreover, when the adhesiveness, viscoelasticity, and toughness of the adhesive are improved, for example, a pressure-sensitive adhesive tape that can guarantee a relatively long-term bonding can be produced.

Adhesiveness (adhesive strength) is, for example, interfacial peeling (adhesiveness) between an adhesive and a substrate and an adhesive in two substrates joined by an adhesive. It is a force that combines the forces (toughness) required to cause resin destruction. Generally, when measuring adhesiveness, a joint between two base materials collapse | disintegrates because an adhesive agent fractures | ruptures or a coupling | bonding with a base material and an adhesive agent cut | disconnects. The difference between adhesiveness and adhesiveness is generally that adhesiveness is an index of easy adhesion and easy peeling, and adhesiveness is an index of the strength of joining two substrates. The adhesive capable of strong bonding can be used as an adhesive in fields requiring strength, such as the construction field and automobile field where durability and heat resistance are required. Moreover, the adhesive which has viscoelasticity can be used for the base material and interior material, joining etc. in the construction field or the automotive field.

The reason why the adhesive according to an embodiment of the present invention is firmly bonded to more types of substrates is not necessarily clear, but is considered as follows. When one base material is bonded to the other base material with an adhesive, the adhesive is interposed between the base materials, and typically, the adhesive is between the base materials. A cured product is formed. Similarly, the surface coating agent can be said to be a cured product obtained by bonding a cured product after curing to the substrate. Depending on the installation location and application of the substrate, these cured products may be directly or indirectly subjected to stress such as vibration or impact, resulting in the destruction of the cured product or the surface of the substrate and the surface of the cured product. The bond may be broken. That is, there is a possibility that the adhesive between the substrates (so-called relative positional relationship between the substrates) cannot be maintained in the adhesive, and the surface coating agent and the substrate cannot be maintained in the surface coating agent. Since the adhesive and the surface coating agent according to the embodiment of the present invention are excellent in at least one of adhesion, tackiness, and adhesiveness, even when a stress is directly or indirectly applied to the cured product, It is considered that the bonding with can be maintained.

Moreover, the monomer B which comprises the adhesive agent and surface coating agent which concern on one Embodiment of this invention has hydroxyl or B (OH) ₂ . With these groups oriented on the surface side of the base material, the adhesive and the surface coating agent according to one embodiment of the present invention can be more firmly bonded to a wider variety of materials. It is thought that it has become.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the examples. In addition, the compound names shown in the following examples and comparative examples do not necessarily follow the IUPAC nomenclature.

In the present embodiment, the following abbreviations may be used.
BA: butyl acrylate 4-HBA: 4-hydroxybutyl acrylate HEA: 2-hydroxyethyl acrylate THFA: tetrahydrofurfuryl acrylate EA: ethyl acrylate INAA: isononyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
EHA: 2-ethylhexyl acrylate 2-MTA: 2-methoxyethyl acrylate OXE-10: 3-ethyl-3-oxetanyl methyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
BZA: benzyl acrylate PHEA: phenoxyethyl acrylate DMAA: dimethylacrylamide DEAA: diethylacrylamide DA: N- (3,4-dihydroxyphenethyl) acrylamide 4-MAPB: 4- (methacrylamide) phenylboronic acid TMP3A: trimethylolpropane triacrylate TDI: Toluene diisocyanate PET: Polyethylene terephthalate PP: Polypropylene PE: Polyethylene ABS: Acrylonitrile butadiene styrene copolymer resin FRP: Fiber reinforced plastic Cu: Copper Al: Aluminum ITO: Indium tin oxide MAM: Molybdenum-aluminum-molybdenum

<Adhesion test>
≪Preparation of test piece≫
After preparing each formulation in which monomer A, monomer B, and crosslinkable monomer were blended in the proportions shown in Table 1, 2,4,6-trimethylbenzoyldiphenylacylphosphine oxide (TPO) was added to each blend as a polymerization initiator. ) Is added in an amount of 10% by mass based on the total amount of monomers contained in each formulation, mixed well, and each curable resin composition according to each Example and Comparative Example shown in Table 1 (hereinafter also referred to as monomer solution) ) Was prepared. In addition, the blending ratio of each monomer in each Example and Comparative Example in Table 1 is% by mass (the same applies to Table 2, Table 3, and Table 4 described later), and the crosslinkable monomer is included in some Examples. There is nothing. Next, each prepared monomer solution was charged with a bar coater No. 10 was applied on a test plate formed of each material described in Table 1. Next, using a UV exposure machine, UV of an exposure amount of 3000 mJ / cm ² was irradiated to completely cure the coating film to prepare each test piece, which was allowed to stand at room temperature for 24 hours.

≪Test method≫
The adhesion test was carried out in accordance with JIS K 5600-5-6: 1999 “Paint General Test Method—Part 5: Mechanical Properties of Coating Film—Section 6: Adhesion (Cross Cut Method)”. About said test piece, the coating film was cross-cut (25 squares) in the shape of a grid of 2x2 mm using the cutter knife. Subsequently, a cellophane tape having a width of 24 mm made of Nichiban was attached to the mass, and the cellophane tape was pressed by the hand of the examiner for 2 minutes. After that, when the cellophane tape is peeled off at an angle of 45 ° with respect to the substrate within 0.5 seconds and when it is peeled off in 2 seconds, the number of cells remaining on the substrate is counted and averaged. evaluated.

[Evaluation criteria]
0: The cut line is completely smooth and there is no peeling in the eyes of any lattice.
1: Small peeling at the intersection of cuts.
Less than 5% is affected by the cross cut.
2: The coating film is peeled along the edge of the cut and / or at the intersection.
5-15% of crosscuts are affected.
3: The coating film is partially or completely peeled along the edge of the cut, and / or various parts of the eye are partially or completely peeled off.
The percentage affected by the crosscut is 15-35%.
4: The coating film is partially or completely peeled along the edge of the cut, and / or some eyes are partially or completely peeled off.
Less than 35% of the cross-cut parts are affected.
5: Exfoliation large enough not to be classified by 4 above.

≪Result≫
The results are shown in Table 1. In addition, it shows that adhesiveness with a base | substrate is so favorable that a numerical value is small. When Examples 1 to 9 are compared with Comparative Example 1, it can be seen that inclusion of monomer B increases the types of base materials that exhibit adhesion. Comparing Examples 4 to 6 with Comparative Example 1, it can be seen that when monomer A is HEA, the addition of monomer B greatly improves the adhesion to glass. Further, comparing Examples 1 to 3 and 7 to 9 with Comparative Example 1, when monomer A is 4-HBA, when monomer B is added, the addition of plastic material such as PET and ABS, and Al and ITO It can be seen that the adhesion is improved and the adhesion to glass is greatly improved.

<Adhesion test>
≪Sample preparation≫
After preparing each formulation in which monomer A and monomer B were blended in the proportions shown in Table 2, each formulation was blended with 2,4,6-trimethylbenzoyldiphenylacylphosphine oxide (TPO) as a polymerization initiator. A monomer solution according to each Example and Comparative Example shown in Table 2 was prepared by adding 10% by mass to the total amount of monomers contained in the blend and mixing well. Next, the prepared monomer solution was charged with a bar coater No. 10 was applied on a test plate formed of each material described in Table 2. Next, a PET film or PP film cut to 300 mm × 24 mm is placed on the coating film and pressure-bonded, and the coating film is completely cured by irradiating UV with an exposure amount of 3000 mJ / cm ² using a UV exposure machine. Each sample was prepared and allowed to stand at room temperature for 24 hours.

≪Test method≫
The adhesion test was performed in accordance with the “180 ° peel adhesion test method” described in the 17th revised Japanese Pharmacopoeia 6.12. In each of the above samples, the end of the film was gripped and turned back to 180 ° and peeled off from the test plate by 25 mm. Then, the test plate was fixed to the lower chuck of the tensile tester, and the film was fixed to the upper chuck. Measurement was started by moving the tensile tester at a peeling speed of 300 mm / second in an environment of room temperature and humidity of 45%, and the 50% length of the adhesive strength measurement value peeled off from the test plate was averaged to peel off. The force was measured.

≪Result≫
The results are shown in Table 2. The combination of materials in the evaluation of adhesiveness in Table 2 indicates “film material / test plate material”. The peel adhesive strengths of Examples 10 to 12 are indicated by an index, with the peel adhesive strength of Comparative Example 2 as the peel adhesive strength of Examples 13 to 15 and the peel adhesive strength of Comparative Example 3 as 100, respectively. In addition, adhesiveness shows that adhesive force is so high that a numerical value is large. When Examples 10 to 12 and Comparative Example 2 are compared, by using THFA as monomer A and using 4-MAPB and DA as monomer B, test plates (PP, Cu, Al, The adhesive strength to ITO, MAM, Al) is improved, and there is almost no influence on the adhesive strength to glass. Thereby, it turns out that the curable resin composition which concerns on one Embodiment of this invention can be used for joining of a various kind of material.

<Adhesion test>
≪Preparation of test piece≫
A mixture was prepared by mixing monomer A and monomer B in the proportions shown in Table 3, and 2,2′-azobisisobutyronitrile (AIBN) as a polymerization initiator was added to each mixture in the total amount of monomers. 1 mass% was added with respect to it, and it stirred at 85 degreeC for 5 hours. Thereafter, toluene diisocyanate (a mixture of 2,4-tolylene diisocyanate / 2,6-tolylene diisocyanate = 80: 20) manufactured by Tosoh Corporation was added as a crosslinkable monomer to each mixture. Thereafter, each mixture was applied to one of two test plates (length: 25 mm × width: 10 mm) of the combination (PP-Al) shown in Table 3 on the entire surface from one end side in the length direction to a position of 12 mm. did. The other test plate is placed so that one end in the length direction of the other test plate protrudes in the length direction from one end side of the one test plate and the other end is positioned at 12 mm of one end of the one test plate. By placing, the other test plate was brought into contact with each mixture. Both test plates were brought into contact so that one test plate would not protrude from the width direction of the other test plate. Then, what hardened each mixture by exposing both test boards in a warm air circulation type thermostat at 80 degreeC for 3 hours was used as the test piece. In addition, two test pieces having the combinations of materials shown in Table 4 were similarly prepared using a part of each mixture.

≪Test method≫
In accordance with JIS K 6850: 1999 “Testing method for tensile shear bond strength of adhesive-rigid adherend”, one test plate constituting the test piece is pulled in the longitudinal direction, and the other test piece is attached to one of the test pieces. The test plate was pulled in the direction opposite to the direction in which it was pulled, and the adhesive force between the materials was measured. The tensile speed was set to 5.0 mm / second for all the test pieces.

≪Result≫
The results are shown in Tables 3-5. The adhesive strength was indicated as an index for each test piece, with the adhesive strength for each test piece of Comparative Example 4 being 100. It shows that adhesive force is so high that a numerical value is large. From Table 3, it can be seen that by using BA (monomer A2) and 4-HBA (monomer A1) as the monomer A, including the monomer B and including the crosslinkable monomer, the adhesiveness of PP-Al is improved. Table 4 also shows that it can be used for bonding various types of materials. Furthermore, it can be seen from Table 5 that as the monomer A2, an acrylate ester having an ether or cyclic structure in the ester moiety, N, N-dialkylacrylamide, or the like can be used.

According to the present invention, it is possible to provide a curable resin composition, an adhesive, and a surface coating agent that are more firmly bonded to a wider variety of materials.

Claims (11)

A curable resin composition containing monomer A and monomer B and containing no alkyl- (meth) acrylate having 10 or more carbon atoms,
Monomer A is represented by the formula (1a):

[Wherein R ^1a represents a hydrogen atom or methyl;
L ^1a represents —O—, —NH—, —NR ⁵ —, —NHC (O) O—, or —NHC (O) NH—;
W ^1a represents a single bond or C _1-20 alkylene;
R ² is methyl, hydroxyl, optionally substituted C _1-6 alkoxy, optionally substituted phenyl, optionally substituted phenoxy, optionally substituted 5 or 6 membered heteroaryl. Represents an optionally substituted 3- to 8-membered saturated or partially unsaturated hydrocarbon ring group, or an optionally substituted 3- to 8-membered saturated or partially unsaturated heterocyclic group;
R ⁵ represents an optionally substituted C _1-8 alkyl;
Here, when R ² is methyl, W ^1a is a single bond or C _1-8 alkylene;
When R ² is hydroxyl, optionally substituted C _1-6 alkoxy, or optionally substituted phenoxy, W ^1a is C _2-20 alkylene]. Yes,
Monomer B is represented by formula (1b):

[Wherein R ^1b represents a hydrogen atom or methyl;
L ^1b represents —O—, —NH—, —NHC (O) O—, or —NHC (O) NH—;
W ^1b represents a single bond or C _1-20 alkylene;
L ² represents a single bond, —O—, —NH—, —NHC (O) —, —NHC (O) O—, —NHC (O) NH—, —C (O) O—, —C (O Represents NH—, —OC (O) —, —OC (O) NH—, or —OC (O) O—;
W ² represents a single bond or C _1-2 alkylene;
R ³ and R ⁴ each independently represents a hydrogen atom, hydroxyl, or B (OH) ₂ ;
Here, R ³ and R ⁴ are not hydrogen atoms.] A curable resin composition that is one or more compounds represented by: L ^1a is -O- or -NR ⁵ - (wherein, R ⁵ represents hydroxyl or C _1-8 optionally C _1-8 alkyl optionally substituted by alkoxy) be; L ^1b is -NH- The curable resin composition according to claim 1, wherein R ² is
(1) hydroxyl,
(2) C _1-6 alkoxy optionally substituted with hydroxyl or C _1-6 alkoxy,
(3) 4 to 7-membered optionally substituted with 1 to 4 groups of the same or different types selected from the group consisting of a halogen atom, hydroxyl, C _1-6 alkyl, and C _1-6 alkoxy Oxygen-containing saturated heterocyclic group,
(4) phenyl optionally substituted by the same or different 1 to 4 groups selected from the group consisting of a halogen atom, C _1-6 alkyl, and C _1-6 alkoxy;
(5) phenoxy optionally substituted by 1 to 4 groups of the same or different types selected from the group consisting of halogen atoms, C _1-6 alkyl, and C _1-6 alkoxy, or
(6) The curable resin composition according to claim 1 or 2, which is methyl. The curable resin composition according to any one of claims 1 to 3, wherein W ^1a and W ^1b are each independently a single bond or C _1-4 alkylene. The curable resin composition according to any one of claims 1 to 4, wherein L ² is a single bond, -O-, or -NHC (O) NH-. The curable resin composition according to any one of claims 1 to 5, wherein the monomer B includes a compound in which R ³ and / or R ⁴ is B (OH) ₂ . The curable resin composition according to any one of claims 1 to 5, wherein the monomer B comprises a compound in which R ³ and / or R ⁴ is hydroxyl. The curable resin composition according to any one of claims 1 to 7, wherein the content of the monomer B in the composition is 0.10 to 10.0% by mass. The curable resin composition according to any one of claims 1 to 8, further comprising a crosslinkable monomer. The curable resin composition according to claim 9, wherein the crosslinkable monomer is a polyfunctional (meth) acrylate and / or a polyfunctional isocyanate. An adhesive or a surface coating agent containing a polymer containing monomer A and monomer B as constituent units (excluding a polymer containing alkyl- (meth) acrylate having 10 or more carbon atoms as constituent units),
Monomer A is represented by the formula (1a):

[Wherein R ^1a represents a hydrogen atom or methyl;
L ^1a represents —O—, —NH—, —NR ⁵ —, —NHC (O) O—, or —NHC (O) NH—;
W ^1a represents a single bond or C _1-20 alkylene;
R ² is methyl, hydroxyl, optionally substituted C _1-6 alkoxy, optionally substituted phenyl, optionally substituted phenoxy, optionally substituted 5 or 6 membered heteroaryl. Represents an optionally substituted 3- to 8-membered saturated or partially unsaturated hydrocarbon ring group, or an optionally substituted 3- to 8-membered saturated or partially unsaturated heterocyclic group;
R ⁵ represents an optionally substituted C _1-8 alkyl;
Here, when R ² is methyl, W ^1a is a single bond or C _1-8 alkylene;
When R ² is hydroxyl or optionally substituted C _1-6 alkoxy, W ^1a is C _2-20 alkylene],
Monomer B is represented by formula (1b):

[Wherein R ^1b represents a hydrogen atom or methyl;
L ^1b represents —O—, —NH—, —NHC (O) O—, or —NHC (O) NH—;
W ^1b represents a single bond or C _1-20 alkylene;
L ² represents a single bond, —O—, —NH—, —NHC (O) —, —NHC (O) O—, —NHC (O) NH—, —C (O) O—, —C (O Represents NH—, —OC (O) —, —OC (O) NH—, or —OC (O) O—;
W ² represents a single bond or C _1-2 alkylene;
R ³ and R ⁴ each independently represents a hydrogen atom, hydroxyl, or B (OH) ₂ ;
Here, R ³ and R ⁴ are not hydrogen atoms.] An adhesive or surface coating agent that is one or more compounds represented by the formula: