TWI750452B - Polymer, composition, hardened product and protective film - Google Patents

Abstract

The present invention provides a polymer, a composition, a cured product and a protective film.

The present invention provides a polymer, a composition comprising the above-mentioned polymer, a cured product of the above-mentioned composition, and a protective film comprising the above-mentioned cured product, the polymer comprising a structural unit derived from a monomer containing an ultraviolet absorbing site, derived from ( Structural unit of alkyl meth)acrylate, structural unit obtained by reacting glycidyl (meth)acrylate and (meth)acrylic acid, and structural unit derived from glycidyl (meth)acrylate. In one embodiment, the Gardner chromaticity of the hue of the polymer is 10 or less.

Description

Polymers, Compositions, Cured Materials and Protective Films

The present invention relates to a polymer, a composition, a cured product and a protective film.

Conventionally, in order to improve the light resistance of a protective film etc., the method of adding a low molecular weight ultraviolet absorber to a resin composition is generally used.

However, the low-molecular-weight ultraviolet absorber does not have a sclerosing part and is in a state of being dissolved in the coating film, so there is a problem that it oozes out in the cured film over time or in a hot atmosphere. In addition, depending on the application, there is no stickiness or bleeding, and the production of a protective film having good hardness, scratch resistance, and light resistance is also being sought.

Therefore, the subject to be solved by the present invention is to provide a substance and a method for producing a protective film having excellent hardness, scratch resistance, and light resistance without bleeding or stickiness of the ultraviolet absorber component.

As a result of intensive research, the present inventors found that the above-mentioned problems can be solved by a polymer having a specific structural unit.

According to the present invention, the following items are provided.

(式中，R^1a為氫原子或甲基，R^1b為亞烷基，R^1c~R¹ⁱ各自獨立地為氫原子、烷基、鹵素原子、烷氧基、氰基或硝基。)；1~20質量%之結構單元2：

(式中，R^2a為氫原子或甲基，R^2b為烷基。)；40~80質量%之結構單元3：【化7】

(式中，R^3a~R^3b各自獨立地為氫原子或甲基。)；以及0.1~2質量%之結構單元4：

(式中，R^4a為氫原子或甲基。)。 (Item 1) A polymer characterized by comprising 10 to 51 mass % of the structural unit 1:

(In the formula, R ^1a is a hydrogen atom or a methyl group, R ^1b is an alkylene group, and R ^1c to R ¹ⁱ are each independently a hydrogen atom, an alkyl group, a halogen atom, an alkoxy group, a cyano group or a nitro group.); 1~20% by mass of structural unit 2:

(In the formula, R ^2a is a hydrogen atom or a methyl group, and R ^2b is an alkyl group.); 40-80% by mass of structural unit 3: [Chemical 7]

(In the formula, R ^3a to R ^3b are each independently a hydrogen atom or a methyl group.); and 0.1 to 2 mass % of structural unit 4:

(In the formula, R ^4a is a hydrogen atom or a methyl group.).

(Item 2) The polymer according to the above item, wherein the Gardner chromaticity of the hue is 10 or less.

(Item 3) A composition comprising the polymer according to any one of the above items.

(Item 4) A hardened product characterized by being a hardened product of the composition described in the above item.

(Item 5) A protective film comprising the cured product described in the above item.

In the present invention, one or more of the above-mentioned features may be based on an explicit combination On the basis of further combination to provide.

By using the polymer of the present invention, it is possible to manufacture a protective film having no bleed-out or stickiness of the ultraviolet absorber component, and good pencil hardness, scratch resistance, and light resistance.

In the whole of this invention, the range of numerical values, such as each physical property value and content, can be set suitably (for example, it can select from the upper limit and the lower limit value described in each item below). Specifically, regarding the numerical value α, when A1, A2, A3, A4 (A1>A2>A3>A4), etc. are exemplified as the upper and lower limits of the numerical value α, the range of the numerical value α can be exemplified as follows: A1 or less, Below A2, below A3, above A2, above A3, above A4, A1~A2, A1~A3, A1~A4, A2~A3, A2~A4, A3~A4, etc.

[polymer]

(式中，R^1a為氫原子或甲基，R^1b為亞烷基，R^1c~R¹ⁱ各自獨立地為氫原子或烷基。)；1~20質量%之結構單元2：

(式中，R^2a為氫原子或甲基，R^2b為烷基。)；40~80質量%之結構單元3：【化11】

(式中，R^3a~R^3b各自獨立地為氫原子或甲基。)；以及0.1~2質量%之結構單元4：

(式中，R^4a為氫原子或甲基。)。 The present invention provides a polymer comprising 10-51 mass % of the structural unit 1: [Chem. 9]

(In the formula, R ^1a is a hydrogen atom or a methyl group, R ^1b is an alkylene group, and R ^1c to R ¹ⁱ are each independently a hydrogen atom or an alkyl group.); 1 to 20% by mass of structural unit 2:

(In the formula, R ^2a is a hydrogen atom or a methyl group, and R ^2b is an alkyl group.); 40-80% by mass of structural unit 3: [Chemical 11]

(In the formula, R ^3a to R ^3b are each independently a hydrogen atom or a methyl group.); and 0.1 to 2 mass % of structural unit 4:

(In the formula, R ^4a is a hydrogen atom or a methyl group.).

(structural unit 1)

The structural unit 1 is a structural unit contained in a polymer chain when a monomer having an ultraviolet absorbing site having the following structural formula is used as a monomer.

【Chemical 13】

(wherein, R ^1a' is a hydrogen atom or a methyl group, R ^1b' is an alkylene group, and R ^1c' to R ^1i' are each independently a hydrogen atom, an alkyl group, a halogen atom, an alkoxy group, a cyano group or a nitro group base.)

The above-mentioned monomers containing an ultraviolet absorbing site may be used in combination of two or more.

Examples of the alkyl group include straight-chain alkyl groups, branched-chain alkyl groups, and cycloalkyl groups.

The straight-chain alkyl group is represented by the general formula: -C _n H _2n+1 (n is an integer of 1 or more). Examples of straight-chain alkyl groups include methyl, ethyl, propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl and the like.

The branched-chain alkyl group is a group obtained by substituting one or more hydrogen atoms of a straight-chain alkyl group with an alkyl group. Examples of branched alkyl groups include isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-amyl, isohexyl and the like.

A cycloalkyl group is an alkyl group having a ring structure. As a cycloalkyl system, a monocyclic cycloalkyl group, a cross-linked cyclic cycloalkyl group, a condensed ring cycloalkyl group, etc. can be illustrated, for example. In addition, one or more hydrogen atoms of the cycloalkyl group may be substituted with a straight-chain or branched-chain alkyl group.

In the present invention, the monocyclic ring refers to a cyclic structure which does not have a bridged structure inside formed by a covalent bond of carbon. In addition, the condensed ring refers to a cyclic structure in which two or more monocyclic rings share two atoms (that is, each ring shares (condenses) only one side with each other). Cross-linked ring refers to two or more A single ring has a cyclic structure with more than 3 atoms in total.

As a monocyclic cycloalkyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclodecyl group, a 3,5,5-trimethylcyclohexyl group, etc. can be illustrated, for example.

Examples of the cross-linked cyclocycloalkyl group include tricyclodecyl, adamantyl, norbornyl and the like.

Examples of the condensed cyclocycloalkyl system include bicyclodecyl and the like.

Examples of the alkylene group include a straight-chain alkylene group, a branched-chain alkylene group, a cycloalkylene group, and the like.

The straight-chain alkylene group is represented by the general formula: -(CH ₂ ) _n - (n is an integer of 1 or more). Examples of straight-chain alkylene groups include methylene, ethylene, propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, n-Decylidene, etc.

The branched-chain alkylene group is a group obtained by substituting one or more hydrogen atoms of a straight-chain alkylene group with an alkyl group. As a branched alkylene group, a diethylpentylene group, a trimethylbutylene group, a trimethylpentylene group, a trimethylhexylene group, etc. are illustrated, for example.

As a cycloalkylene group, a monocyclic cycloalkylene group, a cross-linked ring cycloalkylene group, a condensed ring cycloalkylene group, etc. are illustrated, for example. In addition, one or more hydrogen atoms of the cycloalkylene group may be substituted with a straight-chain or branched-chain alkyl group.

As a monocyclic cycloalkylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclodecylene group, a 3,5,5-trimethylcyclohexylene group, etc. can be illustrated, for example.

As a crosslinked cyclic cycloalkylene group, a tricyclodecylene group, an adamantylene group, a norbornylene group, etc. are illustrated, for example.

As a condensed ring cycloalkylene system, a bicyclodecylene group etc. are illustrated.

The alkoxy group is a group ^{represented by -OR alkyl} (R ^alkyl represents an alkyl group).

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom can be illustrated, for example.

The single system containing the above-mentioned ultraviolet absorption site can be exemplified, for example: 3-(2H-1,2,3-benzotriazol-2-yl)-4-hydroxyphenethyl=(meth)acrylate, 2- [2'-Hydroxy-5'-((meth)acryloyloxymethyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-((meth)acrylohydrin oxyethyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-3'-tert-butyl-5'-((meth)acryloyloxyethyl)phenyl]- 2H-benzotriazole, 2-[2'-hydroxy-5'-tert-butyl-3'-((meth)acryloyloxyethyl)phenyl]-2H-benzotriazole, 2- [2'-Hydroxy-5'-((meth)acryloyloxyethyl)phenyl]-5-chloro-2H-benzotriazole, 2-[2'-hydroxy-5'-((methyl (methyl)acryloyloxyethyl)phenyl]-5-methoxy-2H-benzotriazole, 2-[2'-hydroxy-5'-((meth)acryloyloxyethyl)benzene [methyl]-5-cyano-2H-benzotriazole, 2-[2'-hydroxy-5'-((meth)acryloyloxyethyl)phenyl]-tert-butyl-2H-benzo Triazole, 2-[2'-hydroxy-5'-((meth)acryloyloxyethyl)phenyl]-5-nitro-2H-benzotriazole, and the like.

The upper limit and the lower limit of the content of the structural unit 1 with respect to the total mass of the polymer can be, for example, 51, 50, 45, 40, 37, 30, 20, 15, 10 mass % and the like. In one embodiment, it is preferable to include 10-51 mass % of the structural unit 1 with respect to the total mass of the polymer.

The upper limit and lower limit of the content of the structural unit 1 relative to 100 mol % of the total structural unit of the polymer can be exemplified by 37, 35, 30, 20, 10, 9, 7, 6 mol % and the like. In one embodiment, it is preferable to include 6-37 mol % of the structural unit 1 relative to 100 mol % of the total structural units of the polymer.

(structural unit 2)

The structural unit 2 is a structural unit contained in a polymer chain when an alkyl (meth)acrylate represented by the following structural formula is used as a monomer.

(In the formula, R ^2a' is a hydrogen atom or a methyl group, and R ^2b' is an alkyl group.)

Two or more types of alkyl (meth)acrylates may be used in combination.

In the present invention, "(meth)acrylic acid" means "at least one selected from the group consisting of acrylic acid and methacrylic acid". Likewise, "(meth)acrylate" means "at least one selected from the group consisting of acrylates and methacrylates". In addition, the "(meth)acryloyl group" means "at least one selected from the group consisting of an acryl group and a methacryloyl group".

(Meth)acrylic-acid alkylester type can be illustrated, for example: (meth)acrylic-acid linear alkylester, (meth)acrylic-acid branched-chain alkylester, (meth)acrylic-acid cyclic alkylester, etc. are mentioned.

(Meth)acrylic acid straight chain alkyl esters can be, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, (meth)acrylate n-amyl meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, and the like.

(Meth)acrylic acid branched alkyl esters are, for example: isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate , (meth) isooctyl acrylate, (meth) 2-ethylhexyl acrylate, etc.

Cyclic alkyl (meth)acrylic acid esters include, for example, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclopentyl (meth)acrylate. ester Wait.

The upper limit and the lower limit of the content of the structural unit 2 with respect to the total mass of the polymer are, for example, 20, 19, 15, 10, 5, 2, 1 mass %, and the like. In one embodiment, it is preferable to include 1-20 mass % of the structural unit 2 with respect to the total mass of the polymer.

The upper limit and the lower limit of the content of the structural unit 2 relative to 100 mol % of the total structural units of the polymer can be exemplified by 33, 30, 20, 10, 9, 5, 3, 2 mol %, and the like. In one embodiment, it is preferable to include 2-33 mol % of the structural unit 2 relative to 100 mol % of the total structural unit of the polymer.

(structural unit 3)

Regarding the structural unit 3, it is used as a monomer by the following structural formula

(In the formula, R ^3a' is a hydrogen atom or a methyl group.)

The structural unit contained in the polymer chain when the glycidyl (meth)acrylate represented is reacted with the (meth)acrylic acid represented by the following structural formula is the structural unit contained in the polymer chain.

【Chemical 16】

(In the formula, R ^3b' is a hydrogen atom or a methyl group.)

In addition, glycidyl acrylate and glycidyl methacrylate may be used in combination, and acrylic acid and methacrylic acid may be used in combination.

The upper limit and the lower limit of the content of the structural unit 3 with respect to the total mass of the polymer can be, for example, 80, 75, 70, 60, 50, 45, 40 mass % and the like. In one embodiment, it is preferable to include 40-80 mass % of the structural unit 3 with respect to the total mass of the polymer.

The upper limit of the content of the structural unit 3 relative to 100 mol % of the total structural units of the polymer can be, for example, 75, 70, 60, 50, 45, 44 mol % and the like. In one embodiment, it is preferable to include 44-75 mol % of the structural unit 3 relative to 100 mol % of the total structural unit of the polymer.

(structural unit 4)

The structural unit 4 is a structural unit contained in the polymer chain when glycidyl (meth)acrylate represented by the following structural formula is used as a monomer.

【Chemical 17】

(In the formula, R ^4a' is a hydrogen atom or a methyl group.)

Glycidyl acrylate and glycidyl methacrylate may be used in combination. Structural unit 4 is a structural unit in the process of generating structural unit 3 . The greater the amount of the structural unit 3, the higher the curability of the cured product of the polymer. Therefore, for example, in the case of using a polymer for the purpose of producing a coating film of high hardness, it is generally practiced not to generate the structural unit 4 . In other words, the inclusion of the structural unit 4 in the polymer has not been good in the past.

The upper limit and lower limit of the content of the structural unit 4 relative to the total mass of the polymer can be exemplified by: 0.6, 0.5, 0.4, 0.3, 0.2, 0.1 mass %, etc. In one embodiment, it is preferable to include 0.1-2 mass % of the structural unit 4 with respect to the total mass of the polymer.

The upper limit and lower limit of the content of the structural unit 4 relative to 100 mol % of the total structural unit of the polymer can be exemplified by 3.0, 2.9, 2.5, 2.0, 1.5, 1.0, 0.5, 0.2, 0.1 mol %, and the like. In one embodiment, it is preferable to include 0.1-3.0 mol % of the structural unit 4 relative to 100 mol % of the total structural unit of the polymer.

(other structural units)

The above-mentioned polymer may contain structural units other than the above-mentioned structural units 1 to 4 (also referred to as "other structural units"). As other structural units, for example, structural units derived from monomers other than the above-mentioned monomers (also referred to as "other monomers") can be exemplified. Examples of other monomer systems include (meth)acrylic acid, N,N-dialkyl(meth)acrylamide, N,N-dialkyl(meth)acrylic acid alkylamine, (meth)acrylic acid Hydroxy alkyl esters, vinyl monomers containing aromatic ring structures, etc.

The upper limit and lower limit of the content of other structural units with respect to the total mass of the polymer can be, for example, 10, 9, 7.5, 5, 2.5, 1, 0 mass % and the like. In one embodiment, it is preferable to include 0-10 mass % of other structural units relative to the total mass of the polymer.

The upper limit and lower limit of the content of other structural units relative to 100 mol % of the total structural units of the polymer can be exemplified by 10, 9, 7.5, 5, 2.5, 1, 0 mol % and the like. In one embodiment, relative to 100 mol % of all structural units of the polymer, it is preferable to include 0-10 mol % of other structural units.

(relative ratio between structural units contained in the polymer)

The upper and lower limits of the mass ratio of the structural unit 1 contained in the polymer to the structural unit 2 (the total mass of the structural unit 1 contained in the polymer/the total mass of the structural unit 2 contained in the polymer) can be exemplified as follows: 51 , 50, 40, 30, 20, 10, 5, 1, 0.5, etc. In one embodiment, the mass ratio of the structural unit 1 contained in the polymer to the structural unit 2 (the total mass of the structural unit 1 contained in the polymer/the total mass of the structural unit 2 contained in the polymer) is 0.5~51 better.

The upper and lower limits of the molar ratio of the structural unit 1 and the structural unit 2 contained in the polymer (the total amount of the structural unit 1 contained in the polymer/the total amount of the structural unit 2 contained in the polymer) For example: 19, 18, 15, 10, 9, 7.5, 5, 2.5, 1, 0.5, 0.2, 0.1, etc. In one embodiment, the molar ratio of the structural unit 1 contained in the polymer to the structural unit 2 (the total amount of the structural unit 1 contained in the polymer/the total amount of the structural unit 2 contained in the polymer) ) is preferably 0.1~19.

The upper and lower limits of the mass ratio of the structural unit 1 contained in the polymer to the structural unit 3 (the total mass of the structural unit 1 contained in the polymer/the total mass of the structural unit 3 contained in the polymer) can be exemplified as follows: 1.3 , 1.2, 1.0, 0.9, 0.5, 0.3, 0.2, 0.1, etc. In one embodiment, the mass ratio of the structural unit 1 contained in the polymer to the structural unit 3 (the total mass of the structural unit 1 contained in the polymer/the total mass of the structural unit 3 contained in the polymer) is 0.1~1.3 better.

The upper and lower limits of the molar ratio of the structural unit 1 and the structural unit 3 contained in the polymer (the total amount of the structural unit 1 contained in the polymer/the total amount of the structural unit 3 contained in the polymer) For example, 0.85, 0.80, 0.70, 0.60, 0.50, 0.40, 0.30, 0.20, 0.10, 0.08 and the like can be exemplified. In one embodiment, the molar ratio of the structural unit 1 contained in the polymer to the structural unit 3 (the total amount of the structural unit 1 contained in the polymer/the total amount of the structural unit 3 contained in the polymer) ) is preferably 0.08~0.85.

The upper and lower limits of the mass ratio of the structural unit 1 contained in the polymer to the structural unit 4 (the total mass of the structural unit 1 contained in the polymer/the total mass of the structural unit 4 contained in the polymer) can be exemplified as: 510 , 500, 400, 300, 200, 100, 50, 25, 10, 6, 5, etc. In one embodiment, the mass ratio of the structural unit 1 contained in the polymer to the structural unit 4 (the total mass of the structural unit 1 contained in the polymer/the total mass of the structural unit 4 contained in the polymer) is 5~510 better.

The molar ratio of structural unit 1 and structural unit 4 contained in the polymer (polymer The upper limit and lower limit of the total substance amount of the structural unit 1 contained in the polymer/the total substance amount of the structural unit 4 contained in the polymer) can be exemplified, for example: 370, 350, 300, 200, 100, 50, 25, 10 , 5, 3, 2, etc. In one embodiment, the molar ratio of the structural unit 1 and the structural unit 4 contained in the polymer (the total amount of the structural unit 1 contained in the polymer/the total amount of the structural unit 4 contained in the polymer) ) is preferably 2~370.

The upper limit and lower limit of the mass ratio of the structural unit 2 contained in the polymer to the structural unit 3 (the total mass of the structural unit 2 contained in the polymer/the total mass of the structural unit 3 contained in the polymer) can be exemplified, for example: 0.5 , 0.4, 0.3, 0.2, 0.1, 0.05, 0.02, 0.01, etc. In one embodiment, the mass ratio of the structural unit 2 contained in the polymer to the structural unit 3 (the total mass of the structural unit 2 contained in the polymer/the total mass of the structural unit 3 contained in the polymer) is 0.01~0.5 better.

The upper and lower limits of the molar ratio of the structural unit 2 and the structural unit 3 contained in the polymer (the total amount of the structural unit 2 contained in the polymer/the total amount of the structural unit 3 contained in the polymer) For example, 0.75, 0.70, 0.50, 0.25, 0.10, 0.05, 0.02 and the like can be exemplified. In one embodiment, the molar ratio between the structural unit 2 and the structural unit 3 (the amount of the substance in the structural unit 2/the amount of the substance in the structural unit 3) is preferably 0.02 to 0.75.

The upper and lower limits of the mass ratio of the structural unit 2 contained in the polymer to the structural unit 4 (the total mass of the structural unit 2 contained in the polymer/the total mass of the structural unit 4 contained in the polymer) can be exemplified as: 200 , 175, 150, 125, 100, 75, 50, 25, 5, 1, 0.5, etc. In one embodiment, the mass ratio of the structural unit 2 contained in the polymer to the structural unit 4 (the total mass of the structural unit 2 contained in the polymer/the total mass of the structural unit 4 contained in the polymer) is 0.5~200 better.

The upper and lower limits of the molar ratio of the structural unit 2 and the structural unit 4 contained in the polymer (the total amount of the structural unit 2 contained in the polymer/the total amount of the structural unit 4 contained in the polymer) For example: 330, 300, 200, 100, 50, 25, 10, 5, 1, 0.6, etc. In one embodiment, the molar ratio of the structural unit 2 contained in the polymer to the structural unit 4 (the total amount of the structural unit 2 contained in the polymer/the total amount of the structural unit 4 contained in the polymer) ) is preferably 0.6~330.

The upper and lower limits of the mass ratio of the structural unit 3 contained in the polymer to the structural unit 4 (the total mass of the structural unit 3 contained in the polymer/the total mass of the structural unit 4 contained in the polymer) can be exemplified as: 800 , 700, 500, 250, 100, 75, 50, 25, 20, etc. In one embodiment, the mass ratio of the structural unit 3 contained in the polymer to the structural unit 4 (the total mass of the structural unit 3 contained in the polymer/the total mass of the structural unit 4 contained in the polymer) is 20~800 better.

The upper and lower limits of the molar ratio of the structural unit 3 and the structural unit 4 contained in the polymer (the total amount of the structural unit 3 contained in the polymer/the total amount of the structural unit 4 contained in the polymer) For example: 750, 700, 500, 250, 100, 50, 20, 15, 14, etc. In one embodiment, the molar ratio of the structural unit 3 contained in the polymer to the structural unit 4 (the total amount of the structural unit 3 contained in the polymer/the total amount of the structural unit 4 contained in the polymer) ) is preferably 14~750.

The upper and lower limits of the mass ratio of the other structural units contained in the polymer to the structural unit 1 (the total mass of the other structural units contained in the polymer/the total mass of the structural unit 1 contained in the polymer) can be exemplified as follows: 1 , 0.9, 0.7, 0.5, 0.3, 0.1, 0, etc. In one embodiment, the mass ratio of other structural units contained in the polymer to structural unit 1 (contained in the polymer The total mass of other structural units/the total mass of structural units 1 contained in the polymer) is preferably 0 to 1.

The upper and lower limits of the molar ratio of the other structural units contained in the polymer to the structural unit 1 (the total amount of the other structural units contained in the polymer/the total amount of the structural unit 1 contained in the polymer) For example, 2, 1.9, 1.5, 1, 0.9, 0.5, 0.1, 0, etc. can be exemplified. In one embodiment, the molar ratio of the other structural units contained in the polymer to the structural unit 1 (the total amount of the other structural units contained in the polymer/the total amount of the structural unit 1 contained in the polymer) ) is preferably 0~2.

The upper and lower limits of the mass ratio of the other structural units contained in the polymer to the structural unit 2 (the total mass of the other structural units contained in the polymer/the total mass of the structural unit 2 contained in the polymer) can be exemplified as: 10 , 9, 7.5, 5, 2.5, 1, 0, etc. In one embodiment, the mass ratio of the other structural units contained in the polymer to the structural unit 2 (the total mass of the other structural units contained in the polymer/the total mass of the structural units 2 contained in the polymer) is 0 to 10 better.

The upper and lower limits of the molar ratio of the other structural units contained in the polymer to the structural unit 2 (the total amount of other structural units contained in the polymer/the total amount of the structural unit 2 contained in the polymer) For example: 5, 4, 3, 2, 1, 0, etc. In one embodiment, the molar ratio of the other structural units contained in the polymer to the structural unit 2 (the total amount of the other structural units contained in the polymer/the total amount of the structural unit 2 contained in the polymer) ) is preferably 0~5.

The mass ratio of other structural units contained in the polymer to structural unit 3 (total mass of other structural units contained in the polymer/total mass of structural units contained in the polymer 3 The upper limit and lower limit of the amount) can be exemplified by 0.25, 0.20, 0.15, 0.10, 0.05, 0 and the like. In one embodiment, the mass ratio of the other structural units contained in the polymer to the structural unit 3 (the total mass of the other structural units contained in the polymer/the total mass of the structural unit 3 contained in the polymer) is 0~0.25 better.

The upper and lower limits of the molar ratio of the other structural units contained in the polymer to the structural unit 3 (the total amount of the other structural units contained in the polymer/the total amount of the structural unit 3 contained in the polymer) For example, 0.25, 0.20, 0.10, 0.05, 0, etc. can be exemplified. In one embodiment, the molar ratio of the other structural units contained in the polymer to the structural unit 3 (the total amount of the other structural units contained in the polymer/the total amount of the structural unit 3 contained in the polymer) ) is preferably 0~0.25.

The upper and lower limits of the mass ratio of other structural units contained in the polymer to the structural unit 4 (total mass of other structural units contained in the polymer/total mass of structural units 4 contained in the polymer) can be exemplified as: 100 , 90, 75, 50, 25, 10, 5, 1, 0, etc. In one embodiment, the mass ratio of the other structural units contained in the polymer to the structural unit 4 (the total mass of the other structural units contained in the polymer/the total mass of the structural units 4 contained in the polymer) is 0 to 100 better.

The upper and lower limits of the molar ratio of other structural units contained in the polymer to the structural unit 4 (the total amount of the other structural units contained in the polymer/the total amount of the structural unit 4 contained in the polymer) For example: 100, 90, 75, 50, 25, 10, 5, 1, 0, etc. In one embodiment, the molar ratio of the other structural units contained in the polymer to the structural unit 4 (the total amount of the other structural units contained in the polymer/the total amount of the structural unit 4 contained in the polymer) ) is preferably 0~100.

(Physical properties of polymers, etc.)

In one embodiment, the Gardner chromaticity of the hue of the polymer is 10 or less (for example, 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, 0 or less). ) is better. The Gardner color system can be measured according to JIS K5400.

The upper and lower limits of the weight-average molecular weight (Mw) of the above-mentioned polymers can be exemplified, for example: Wait. In one embodiment, the weight-average molecular weight (Mw) of the above-mentioned polymer is preferably 10,000-100,000.

The upper limit and lower limit of the number-average molecular weight (Mn) of the above-mentioned polymer can be, for example, 8000, 7900, 7500, 7000, 6500, 6100, 6000 and the like. In one embodiment, the number-average molecular weight (Mn) of the above-mentioned polymer is preferably 6000-8000.

The weight-average molecular weight and the number-average molecular weight are obtained, for example, in terms of polystyrene values measured by gel permeation chromatography (GPC) in an appropriate solvent.

The upper limit and lower limit of the molecular weight distribution (Mw/Mn) of the polymer can be, for example, 4.0, 3.9, 3.5, 3.0, 2.5, 2.1, 2.0, and the like. In one embodiment, the molecular weight distribution (Mw/Mn) of the polymer is preferably 2.0 to 4.0.

Examples of the upper and lower limits of the acid value of the polymer include 6.0, 5.9, 5.0, 4.0, 3.0, 2.0, 1.0, 0.5, 0.3, 0.2 mgKOH/g, and the like. In one embodiment, the acid value of the polymer is preferably 0.2-6.0 mgKOH/g. The acid value was calculated|required by the method based on Japanese Industrial Standard JIS K 0070.

The upper limit and the lower limit of the epoxy equivalent of the polymer can be exemplified, for example: 7500, 7100g/eq, etc. In one embodiment, the epoxy equivalent of the polymer is preferably 7100-140,000 g/eq.

In addition, the epoxy equivalent of a polymer is measured by the following method, for example. Accurately weigh 15 g of the sample into a 250 mL stoppered flask, add 25 mL of 0.2N hydrochloric acid dioxane solution, mix thoroughly to dissolve it, and leave it at room temperature for 15 minutes, add 25 mL of neutral butyl cellosolve solvent, and add 0.1 The N KOH ethanol solution was titrated, and the value calculated by the formula (1) was taken as the epoxy equivalent g/eq.

Formula (1) epoxy equivalent (g/eq)=10000W/f(B-(A-C))

W represents the number of grams of the weighed sample, f represents the factor of the 0.1N KOH ethanol solution, B represents the titration (mL) of the 0.1N KOH ethanol solution required for the blank test, and A represents the 0.1N required for the titration of the sample The titration (mL) of the KOH ethanol solution, C represents the titration (mL) of the 0.1N KOH ethanol solution required for the acid value titration of 15 g of the sample.

In one embodiment, regarding the color difference of the polymer, h ^{calculated from L*, a*, b* using h=tan -1} (b*/a*) is 115 or less (for example, 110 or less, 100 or less, 90 or less, 80 or less, 70 or less, 60 or less, 50 or less, 40 or less, 30 or less, 20 or less, 10 or less) are preferred. The color difference of a polymer is calculated|required by the transmission method etc. of a color difference meter (trade name: ZE 6000, made by Nippon Denshoku Kogyo Co., Ltd.).

The method for producing the above-mentioned polymer can be exemplified by a method including a step of polymerizing a monomer containing an ultraviolet absorbing site, an alkyl (meth)acrylate, glycidyl (meth)acrylate, and other monomers. step (1); step (2) of reacting the polymer obtained by step (1) with (meth)acrylic acid.

[composition]

The present invention provides a composition comprising the above-mentioned polymer. The above-mentioned composition can be suitably used for coating purposes. In one embodiment, the above-mentioned composition can be used as an active energy ray-curable resin composition.

The upper limit and lower limit of the content of the above-mentioned polymer with respect to the total mass of the composition include, for example, 100, 90, 80, 70, 60, 50, 40, 30, 20, 15, 10 mass % and the like. In one embodiment, it is preferable to include 10-100 mass % of the above-mentioned polymer with respect to the total mass of the composition.

In one embodiment, a photopolymerization initiator is included in the composition. A photopolymerization initiator may use 2 or more types together. Examples of photopolymerization initiators include: 1-hydroxy-cyclohexyl-phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-cyclohexyl phenyl ketone , 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1- Propan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2,4,6-trimethylbenzyl- Diphenyl-phosphine oxide, 4-methylbenzophenone, etc.

In addition, the photoinitiator is used in the case of UV curing, and is not essential in the case of electron beam curing.

The upper limit and lower limit of the content of the photopolymerization initiator with respect to the total mass of the composition include, for example, 10, 9, 7.5, 5, 2.5, 1, 0.5, 0 mass %, and the like. In one embodiment, the photopolymerization initiator is contained in an amount of about 0 to 10 mass % with respect to the total mass of the composition.

The upper limit and the lower limit of the content of the photopolymerization initiator with respect to the total mass of the polymer are, for example, 10, 9, 7.5, 5, 2.5, 1, 0.5, 0 mass %, and the like. In one embodiment, the photopolymerization initiator contains about 0 to 10 mass % with respect to the total mass of the polymer.

In one embodiment, a diluting solvent is included in the composition. Two or more types of dilution solvents may be used in combination. Examples of the dilution solvent system include methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, diacetone alcohol, acetone acetone, toluene, xylene, n-hexane, cyclohexane, methylcyclohexane, n-heptane, isopropyl ether, methyl cellosolve, ethyl cellosolve, 1,4-dioxane, propylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, etc.

The upper limit and lower limit of the content of the dilution solvent with respect to the total mass of the composition include, for example, 80, 70, 60, 50, 40, 30, 20, 10, 5, 1, 0 mass % and the like. In one embodiment, from the viewpoint of the viscosity suitable for coating, the dilution solvent system can be, for example, about 0 to 80% by mass relative to the total mass of the composition.

The upper limit and the lower limit of the content of the diluting solvent with respect to the total mass of the polymer are, for example, 80, 70, 60, 50, 40, 30, 20, 10, 5, 1, 0 mass %, and the like. In one embodiment, the dilution solvent system contains about 0-80 mass % with respect to the total mass of the polymer.

(additive)

The above-mentioned composition may contain reagents other than the above-mentioned polymer, photopolymerization initiator, and diluting solvent as additives. Examples of additives include hardening aids, antioxidants, ultraviolet absorbers, light stabilizers, defoaming agents, surface conditioners, antifouling agents, inorganic fillers, silane coupling agents, colloidal silica, pigments, antistatic agents agent, metal oxide microparticle dispersion, etc. In one embodiment, relative to 100 parts by mass of the composition, the content of the additive can be exemplified as follows: 0.1 to 20 parts by mass, less than 10 parts by mass, less than 1 part by mass, less than 5 parts by mass, less than 0.1 part by mass, less than 0.01 part by mass parts by mass, 0 parts by mass, etc., in another embodiment, with respect to 100 parts by mass of the above-mentioned polymer, the content of the additive can be exemplified as: 0.1 to 20 parts by mass, less than 10 parts by mass, Less than 5 parts by mass, less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, 0 part by mass, and the like.

[hardened product]

The present invention provides a cured product of the above composition. The above-mentioned cured product can be obtained by a method including a step of irradiating the above-mentioned composition with active energy rays such as ultraviolet rays, electron beams, and radiation.

As an ultraviolet light source, a xenon lamp, a high pressure mercury lamp, a metal halide, an LED lamp etc. can be illustrated, for example. The amount of ultraviolet rays can be appropriately adjusted according to the thickness of the cured product. In addition, the amount of light, the configuration of the light source, the conveying speed, etc. can be adjusted as required. For example, in the case of using a high-pressure mercury lamp, compared with a lamp with a lamp output power of about 80-160W/cm, the output power is about 5-50m/cm It is better to harden at a conveying speed of minutes. On the other hand, in the case of electron beams, it is preferable to perform curing at a conveying speed of about 5 to 50 m/min using an electron beam accelerator having an accelerating voltage of about 10 to 300 kV.

[protective film]

The present invention provides a protective film comprising the above cured product. The said protective film is manufactured by the method etc. which consist of the process of coating on a base material, the process of irradiating active energy rays, hardening, and laminating|stacking. In addition, the step of irradiating active energy rays can be performed during and/or after drying of the coating material.

Examples of the base material include: polyethylene terephthalate (PET), polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triethyl ether Acetyl cellulose resin, ABS resin, AS resin, norbornene-based resin, etc.

Examples of coating methods include bar coater coating, wire bar coating, and air knife coating. Cloth, gravure coating, reverse gravure coating, offset printing, flexographic printing, screen printing method, etc.

The said protective film system can be used for a barrier film, a polarizing plate, a film for decoration, a film for packaging, etc., for example.

【Example】

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to these examples. In addition, in each example, part and % are based on mass unless otherwise specified.

<Example 1>

3-(2H-1,2,3-benzotriazol-2-yl)-4-hydroxybenzene was added to a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet and a dropping funnel Ethyl = 11 parts of methacrylate (hereinafter referred to as UVA), 49.8 parts of glycidyl methacrylate (hereinafter referred to as GMA), 15 parts of methyl methacrylate (hereinafter referred to as MMA), azobis as a polymerization initiator 3 parts of isobutyronitrile (hereinafter referred to as AIBN) and 100 parts of butyl acetate were stirred, and the temperature was raised to 100° C. under a nitrogen stream to react for 10 hours. Next, 24.2 parts of acrylic acid (hereinafter referred to as AA), 0.1 part of 4-methoxyphenol (hereinafter referred to as MQ), and 0.3 part of triphenylphosphine as a reaction catalyst were added and reacted at 100°C for 8 hours to obtain a polymer.

Moreover, the weight average molecular weight (polystyrene conversion value based on GPC) was 4,600. The weight average molecular weight is shown by gel permeation chromatography (manufactured by Tosoh Corporation, trade name "HLC-8220"), and three columns: manufactured by Tosoh Corporation, trade name "TSKgel superHZM-M" Values determined by series connection.

To the obtained polymer, 5 parts of photopolymerization initiator 1-hydroxycyclohexyl phenyl ketone (trade name "Irgacure 184" BASF, hereinafter referred to as Irg184) was added to prepare a coating liquid, which was applied to a thickness of after one side of the easy-bonding process 188μm polyethylene terephthalate film (trade name "A4100" manufactured by Toyobo Co., Ltd.) of easily adhering surface, dried for 1 minute 80 deg.] C, irradiated with 600mJ / cm ² of ultraviolet light to obtain a cured film with a film thickness of 5 μm.

<Examples 2 to 6, and Comparative Examples 1 to 3>

Cured films were produced in the same manner with the polymerizable monomers and ratios shown in the following tables. The values of monomers, solvents, polymerization initiators, polymerization inhibitors, reaction catalysts, and structural units in the table are values based on mass. In addition, in Comparative Example 2, in the step of imparting acrylic acid, the viscosity increased rapidly and gelation occurred.

EA: Ethyl Acrylate

SMA: Stearyl Methacrylate

IBXA: Isobornyl Acrylate

DCP-A: Dicyclopentyl methacrylate

AA: Acrylic

Reaction catalyst: triphenylphosphine

Hardener A: Biuret-modified triisocyanate of 1,6-hexanediisocyanate

Hardener B: Cymel 300 (Mitsui Cytec)

UV curing conditions: 1 high pressure mercury lamp 600mJ/cm ² (at 360nm ^-1 )

About the cured film produced using the hard coating agent of each Example and a comparative example, it tested according to the following items and evaluation methods.

(sticky evaluation)

By touching the surface of the coating film with a finger, the evaluation was performed as follows.

None = Resin component does not adhere to fingers. Does not feel sticky.

With = resin component adheres to the finger. Feel sticky.

(Evaluation of pencil hardness)

Evaluation was performed according to the test method of JIS-K-5600.

(Evaluation of scratch resistance)

^{On the surface of the cured film, a load of 100 g/cm 2 was} applied to steel wool (#0000), and the back-and-forth friction was performed 10 times, and it was judged by the presence or absence of damage.

(Evaluation of seepage)

The coated product was allowed to stand for 24 hours in a constant temperature and humidity machine at 80°C and 90%, and the change in the surface of the coating film was visually confirmed. Evaluation was performed according to the following criteria.

None = no change in appearance before and after the test

Yes = Appearance changes before and after the test

(Evaluation of light fastness)

After irradiating with a metal halide light source (80 mW/cm ² ) for 12 hours, it was evaluated by the degree of change in the yellowness index (hereinafter, YI) of the cured film. The YI value before the test was subtracted from the YI value after the test, and the difference obtained was taken as ΔYI. When 2 or less was evaluated as good light resistance, it was described as ○, and when it was greater than 2, it was evaluated as insufficient light resistance and described. is ×.

Claims (5)

A polymer, characterized in that it comprises 10 to 51 mass % of the structural unit 1:

In the formula, R ^1a is a hydrogen atom or a methyl group, R ^1b is an ethylene group, and R ^1c to R ¹ⁱ are hydrogen atoms; 1 to 20 mass % of the structural unit 2:

In the formula, R ^2a is a hydrogen atom or a methyl group, and R ^2b is a methyl group; 40-80% by mass of structural unit 3: [Chemical 3]

In the formula, R ^3a to R ^3b are each independently a hydrogen atom or a methyl group; and 0.1 to 2 mass % of the structural unit 4:

In the formula, R ^4a is a hydrogen atom or a methyl group. The polymer according to claim 1, wherein the Gardner chromaticity of the hue is 10 or less. A composition characterized by comprising the polymer described in claim 1 or 2 of the claimed scope. A hardened product characterized in that it is a hardened product of the composition described in claim 3. A protective film comprising the cured product described in claim 4 of the scope of application.