JP7036053B2 - Polymers, compositions, cured products and protective films - Google Patents
Polymers, compositions, cured products and protective films Download PDFInfo
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- JP7036053B2 JP7036053B2 JP2019014991A JP2019014991A JP7036053B2 JP 7036053 B2 JP7036053 B2 JP 7036053B2 JP 2019014991 A JP2019014991 A JP 2019014991A JP 2019014991 A JP2019014991 A JP 2019014991A JP 7036053 B2 JP7036053 B2 JP 7036053B2
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2433/12—Homopolymers or copolymers of methyl methacrylate
Description
本開示は、ポリマー、組成物、硬化物及び保護膜に関する。 The present disclosure relates to polymers, compositions, cured products and protective films.
従来、保護膜等の耐光性を向上させるため、樹脂組成物に低分子量の紫外線吸収剤を添加する手法が一般的に用いられてきた。 Conventionally, in order to improve the light resistance of a protective film or the like, a method of adding a low molecular weight ultraviolet absorber to a resin composition has been generally used.
しかし、低分子量の紫外線吸収剤は硬化性部位を有せずに塗膜内に溶解している状態であったことから、硬化膜では経時や熱雰囲気によりブリードするという問題を抱えていた。さらに、用途により、タック及びブリードがなく、硬度、耐擦傷性、耐光性がいずれも良好である保護膜を製造することも求められていた。 However, since the low molecular weight ultraviolet absorber was in a state of being dissolved in the coating film without having a curable portion, the cured film had a problem of bleeding due to aging and a hot atmosphere. Further, depending on the application, it has been required to produce a protective film having no tack and bleeding and having good hardness, scratch resistance, and light resistance.
そこで、本発明が解決しようとする課題は、紫外線吸収剤成分がブリードせず、タックフリーであり、かつ硬度、耐擦傷性、耐光性がいずれも良好である保護膜を製造するための物質及び手法を提供することとする。 Therefore, the problem to be solved by the present invention is a substance for producing a protective film in which the ultraviolet absorber component does not bleed, is tack-free, and has good hardness, scratch resistance, and light resistance. We will provide a method.
本発明者らは、鋭意検討した結果、特定の構成単位を有するポリマーにより、上記課題が解決されることを見出した。 As a result of diligent studies, the present inventors have found that a polymer having a specific structural unit solves the above-mentioned problems.
本開示により以下の項目が提供される。
（項目１）
構成単位１
を１０～５１質量％
構成単位２
を１～２０質量％
構成単位３
を４０～８０質量％
及び構成単位４
を０．１～２質量％含む、ポリマー。
（項目２）
色調がガードナーカラー１０以下である、上記項目に記載のポリマー。
（項目３）
上記項目のいずれか１項に記載のポリマーを含む、組成物。
（項目４）
上記項目に記載の組成物の硬化物。
（項目５）
上記項目に記載の硬化物を含む、保護膜。
The disclosure provides the following items:
(Item 1)
Configuration unit 1
10-51% by mass
Configuration unit 2
1 to 20% by mass
Configuration unit 3
40-80% by mass
And structural unit 4
A polymer containing 0.1 to 2% by mass.
(Item 2)
The polymer according to the above item, the color tone of which is Gardner color 10 or less.
(Item 3)
A composition comprising the polymer according to any one of the above items.
(Item 4)
A cured product of the composition according to the above item.
(Item 5)
A protective film containing the cured product according to the above item.
本開示において、上述した１又は複数の特徴は、明示された組み合わせに加え、さらに組み合わせて提供され得る。 In the present disclosure, the above-mentioned features may be provided in combination in addition to the specified combinations.
本発明のポリマーを用いることにより、紫外線吸収剤成分がブリードせず、タックフリーであり、かつ鉛筆硬度、耐擦傷性、耐光性がいずれも良好である保護膜を製造することができる。 By using the polymer of the present invention, it is possible to produce a protective film in which the ultraviolet absorber component does not bleed, is tack-free, and has good pencil hardness, scratch resistance, and light resistance.
本開示の全体にわたり、各物性値、含有量等の数値の範囲は、適宜（例えば下記の各項目に記載の上限及び下限の値から選択して）設定され得る。具体的には、数値αについて、数値αの上限及び下限としてＡ１、Ａ２、Ａ３、Ａ４（Ａ１＞Ａ２＞Ａ３＞Ａ４とする）等が例示される場合、数値αの範囲は、Ａ１以下、Ａ２以下、Ａ３以下、Ａ２以上、Ａ３以上、Ａ４以上、Ａ１～Ａ２、Ａ１～Ａ３、Ａ１～Ａ４、Ａ２～Ａ３、Ａ２～Ａ４、Ａ３～Ａ４等が例示される。 Throughout the present disclosure, the range of numerical values such as each physical property value and content can be appropriately set (for example, by selecting from the upper and lower limit values described in the following items). Specifically, for the numerical value α, when A1, A2, A3, A4 (A1> A2> A3> A4) and the like are exemplified as the upper limit and the lower limit of the numerical value α, the range of the numerical value α is A1 or less. Examples thereof include A2 or less, A3 or less, A2 or more, A3 or more, A4 or more, A1 to A2, A1 to A3, A1 to A4, A2 to A3, A2 to A4, A3 to A4 and the like.
［ポリマー］
本開示は、構成単位１
を１０～５１質量％
構成単位２
を１～２０質量％
構成単位３
を４０～８０質量％
及び構成単位４
を０．１～２質量％含む、ポリマーを提供する。
[polymer]
The present disclosure is based on structural unit 1.
10-51% by mass
Configuration unit 2
1 to 20% by mass
Configuration unit 3
40-80% by mass
And structural unit 4
Provided a polymer containing 0.1 to 2% by mass.
（構成単位１）
構成単位１は、モノマーとして、下記構造式
を有する紫外線吸収部位含有モノマーを用いた場合にポリマー鎖に含まれる構成単位である。上記紫外線吸収部位含有モノマーは２種以上を併用できる。
(Structure unit 1)
The structural unit 1 is a monomer having the following structural formula.
It is a structural unit contained in a polymer chain when a monomer containing an ultraviolet absorbing site having a above-mentioned substance is used. Two or more kinds of the above-mentioned ultraviolet absorption site-containing monomers can be used in combination.
アルキル基は、直鎖アルキル基、分岐アルキル基、シクロアルキル基等が例示される。 Examples of the alkyl group include a linear alkyl group, a branched alkyl group, a cycloalkyl group and the like.
直鎖アルキル基は、一般式：－ＣｎＨ２ｎ＋１（ｎは１以上の整数）で表される。直鎖アルキル基は、メチル基、エチル基、プロピル基、ｎ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基、ｎ－ノニル基、ｎ－デカメチル基等が例示される。 The linear alkyl group is represented by the general formula: -C n H 2n + 1 (n is an integer of 1 or more). The linear alkyl group includes a methyl group, an ethyl group, a propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decamethyl group and the like. Is exemplified.
分岐アルキル基は、直鎖アルキル基の１つ以上の水素原子がアルキル基によって置換された基である。分岐アルキル基は、ｉ－プロピル基、ｉ－ブチル基、ｓ－ブチル基、ｔ－－ブチル基、ｉ－ペンチル基、ネオペンチル基、ｔ－ペンチル基、ｉ－ヘキシル基等が例示される。 A branched alkyl group is a group in which one or more hydrogen atoms of a linear alkyl group are substituted with an alkyl group. Examples of the branched alkyl group include i-propyl group, i-butyl group, s-butyl group, t-butyl group, i-pentyl group, neopentyl group, t-pentyl group, i-hexyl group and the like.
シクロアルキル基は、環構造を有するアルキル基である。シクロアルキル基は、単環シクロアルキル基、架橋環シクロアルキル基、縮合環シクロアルキル基等が例示される。またシクロアルキル基は、１つ以上の水素原子が直鎖又は分岐アルキル基によって置換されていてもよい。 The cycloalkyl group is an alkyl group having a ring structure. Examples of the cycloalkyl group include a monocyclic cycloalkyl group, a crosslinked ring cycloalkyl group, and a condensed ring cycloalkyl group. Further, the cycloalkyl group may have one or more hydrogen atoms substituted with a linear or branched alkyl group.
本開示において、単環とは、炭素の共有結合により形成された内部に橋かけ構造を有しない環状構造を意味する。また、縮合環とは、２つ以上の単環が２つの原子を共有している（すなわち、それぞれの環の辺を互いに１つだけ共有（縮合）している）環状構造を意味する。架橋環とは、２つ以上の単環が３つ以上の原子を共有している環状構造を意味する。 In the present disclosure, a single ring means a cyclic structure formed by covalent bonds of carbon and having no bridging structure inside. Further, the fused ring means a cyclic structure in which two or more monocycles share two atoms (that is, only one side of each ring is shared (condensed) with each other). The crosslinked ring means a cyclic structure in which two or more monocycles share three or more atoms.
単環シクロアルキル基は、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロデシル基、３，５，５－トリメチルシクロヘキシル基等が例示される。 Examples of the monocyclic cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclodecyl group, a 3,5,5-trimethylcyclohexyl group and the like.
架橋環シクロアルキル基は、トリシクロデシル基、アダマンチル基、ノルボルニル基等が例示される。 Examples of the crosslinked ring cycloalkyl group include a tricyclodecyl group, an adamantyl group, a norbornyl group and the like.
縮合環シクロアルキル基は、ビシクロデシル基等が例示される。 Examples of the fused ring cycloalkyl group include a bicyclodecyl group and the like.
アルキレン基は、直鎖アルキレン基、分岐アルキレン基、シクロアルキレン基等が例示される。 Examples of the alkylene group include a linear alkylene group, a branched alkylene group, and a cycloalkylene group.
直鎖アルキレン基は、一般式：－（ＣＨ２）ｎ－（ｎは１以上の整数）で表される。直鎖アルキレン基は、メチレン基、エチレン基、プロピレン基、ｎ－ブチレン基、ｎ－ペンチレン基、ｎ－ヘキシレン基、ｎ－ヘプチレン基、ｎ－オクチレン基、ｎ－ノニレン基、ｎ－デカメチレン基等が例示される。 The linear alkylene group is represented by the general formula:-(CH 2 ) n- (n is an integer of 1 or more). The linear alkylene group includes a methylene group, an ethylene group, a propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, an n-nonylene group, an n-decamethylene group and the like. Is exemplified.
分岐アルキレン基は、直鎖アルキレン基の１つ以上の水素原子がアルキル基によって置換された基である。分岐アルキレン基は、ジエチルペンチレン基、トリメチルブチレン基、トリメチルペンチレン基、トリメチルヘキシレン基等が例示される。 A branched alkylene group is a group in which one or more hydrogen atoms of a linear alkylene group are substituted with an alkyl group. Examples of the branched alkylene group include a diethylpentylene group, a trimethylbutylene group, a trimethylpentylene group, and a trimethylhexylene group.
シクロアルキレン基は、単環シクロアルキレン基、架橋環シクロアルキレン基、縮合環シクロアルキレン基等が例示される。またシクロアルキレン基は、１つ以上の水素原子が直鎖又は分岐アルキル基によって置換されていてもよい。 Examples of the cycloalkylene group include a monocyclic cycloalkylene group, a crosslinked ring cycloalkylene group, and a condensed ring cycloalkylene group. Further, the cycloalkylene group may have one or more hydrogen atoms substituted with a linear or branched alkyl group.
単環シクロアルキレン基は、シクロペンチレン基、シクロヘキシレン基、シクロヘプチレン基、シクロデシレン基、３，５，５－トリメチルシクロヘキシレン基等が例示される。 Examples of the monocyclic cycloalkylene group include a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclodecylene group, a 3,5,5-trimethylcyclohexylene group and the like.
架橋環シクロアルキレン基は、トリシクロデシレン基、アダマンチレン基、ノルボルニレン基等が例示される。 Examples of the crosslinked ring cycloalkylene group include a tricyclodecylene group, an adamantylene group, a norbornene group and the like.
縮合環シクロアルキレン基は、ビシクロデシレン基等が例示される。
アルコキシ基は、－ＯＲａｌｋｙｌで表される基（Ｒａｌｋｙｌはアルキル基を表す）である。
ハロゲン原子は、フッ素原子、塩素原子、臭素原子、ヨウ素原子が例示される。
Examples of the fused ring cycloalkylene group include a bicyclodecylene group.
The alkoxy group is a group represented by -OR alcohol (R alcohol represents an alkyl group).
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
上記紫外線吸収部位含有モノマーは、３－（２Ｈ－１，２，３－ベンゾトリアゾール－２－イル）－４－ヒドロキシフェネチル＝（メタ）アクリレート、２－［２’－ヒドロキシ－５’－（（メタ）アクリロイルオキシメチル）フェニル］－２Ｈ－ベンゾトリアゾール、２－［２’－ヒドロキシ－５’－（（メタ）アクリロイルオキシエチル）フェニル］－２Ｈ－ベンゾトリアゾール、２－［２’－ヒドロキシ－３’－ｔ－ブチル－５’－（（メタ）アクリロイルオキシエチル）フェニル］－２Ｈ－ベンゾトリアゾール、２－［２’－ヒドロキシ－５’－ｔ－ブチル－３’－（（メタ）アクリロイルオキシエチル）フェニル］－２Ｈ－ベンゾトリアゾール、２－［２’－ヒドロキシ－５’－（（メタ）アクリロイルオキシエチル）フェニル］－５－クロロ－２Ｈ－ベンゾトリアゾール、２－［２’－ヒドロキシ－５’－（（メタ）アクリロイルオキシエチル）フェニル］－５－メトキシ－２Ｈ－ベンゾトリアゾール、２－［２’－ヒドロキシ－５’－（（メタ）アクリロイルオキシエチル）フェニル］－５－シアノ－２Ｈ－ベンゾトリアゾール、２－［２’－ヒドロキシ－５’－（（メタ）アクリロイルオキシエチル）フェニル］－ｔ－ブチル－２Ｈ－ベンゾトリアゾール、２－［２’－ヒドロキシ－５’－（（メタ）アクリロイルオキシエチル）フェニル］－５－ニトロ－２Ｈ－ベンゾトリアゾール等が例示される。 The above-mentioned monomer containing an ultraviolet absorbing site is 3- (2H-1,2,3-benzotriazole-2-yl) -4-hydroxyphenetyl = (meth) acrylate, 2- [2'-hydroxy-5'-(((). Meta) acryloyloxymethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-((meth) acryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-3 '-T-Butyl-5'-((meth) acryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-t-butyl-3'-((meth) acryloyloxyethyl)-((meth) acryloyloxyethyl) ) Phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-((meth) acryloyloxyethyl) phenyl] -5-chloro-2H-benzotriazole, 2- [2'-hydroxy-5' -((Meta) acryloyloxyethyl) phenyl] -5-methoxy-2H-benzotriazole, 2- [2'-hydroxy-5'-((meth) acryloyloxyethyl) phenyl] -5-cyano-2H-benzo Triazole, 2- [2'-hydroxy-5'-((meth) acryloyloxyethyl) phenyl] -t-butyl-2H-benzotriazole, 2- [2'-hydroxy-5'-((meth) acryloyloxy) Ethyl) phenyl] -5-nitro-2H-benzotriazole and the like are exemplified.
ポリマーの全質量に対する構成単位１の含有量の上限及び下限は、５１、５０、４５、４０、３７、３０、２０、１５、１０質量％等が例示される。１つの実施形態において、ポリマーの全質量に対して、構成単位１を１０～５１質量％含むことが好ましい。 The upper and lower limits of the content of the constituent unit 1 with respect to the total mass of the polymer are exemplified by 51, 50, 45, 40, 37, 30, 20, 15, 10% by mass and the like. In one embodiment, it is preferable to include the structural unit 1 in an amount of 10 to 51% by mass based on the total mass of the polymer.
ポリマーの全構成単位１００モル％に対する構成単位１の含有量の上限及び下限は、３７、３５、３０、２０、１０、９、７、６モル％等が例示される。１つの実施形態において、ポリマーの全構成単位１００モル％に対して、構成単位１を６～３７モル％含むことが好ましい。 The upper and lower limits of the content of the constituent unit 1 with respect to 100 mol% of all the constituent units of the polymer are exemplified by 37, 35, 30, 20, 10, 9, 7, 6 mol% and the like. In one embodiment, it is preferable to contain 6 to 37 mol% of the constituent unit 1 with respect to 100 mol% of the total constituent units of the polymer.
（構成単位２）
構成単位２は、モノマーとして、下記構造式で表わされる
（メタ）アクリル酸アルキルエステルを用いた場合にポリマー鎖に含まれる構成単位である。（メタ）アクリル酸アルキルエステルは２種以上を併用できる。
(Structure unit 2)
The structural unit 2 is represented by the following structural formula as a monomer.
(Meta) A structural unit contained in a polymer chain when an acrylic acid alkyl ester is used. Two or more kinds of (meth) acrylic acid alkyl esters can be used in combination.
本開示において「（メタ）アクリル」は「アクリル及びメタクリルからなる群より選択される少なくとも１つ」を意味する。同様に「（メタ）アクリレート」は「アクリレート及びメタクリレートからなる群より選択される少なくとも１つ」を意味する。また「（メタ）アクリロイル」は「アクリロイル及びメタクリロイルからなる群より選択される少なくとも１つ」を意味する。 In the present disclosure, "(meth) acrylic" means "at least one selected from the group consisting of acrylic and methacrylic". Similarly, "(meth) acrylate" means "at least one selected from the group consisting of acrylates and methacrylates". Further, "(meth) acryloyl" means "at least one selected from the group consisting of acryloyl and methacryloyl".
（メタ）アクリル酸アルキルエステルは、（メタ）アクリル酸直鎖アルキルエステル、（メタ）アクリル酸分岐アルキルエステル、（メタ）アクリル酸環状アルキルエステル等が例示される。 Examples of the (meth) acrylic acid alkyl ester include (meth) acrylic acid linear alkyl ester, (meth) acrylic acid branched alkyl ester, and (meth) acrylic acid cyclic alkyl ester.
（メタ）アクリル酸直鎖アルキルエステルは、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ－プロピル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸ｎ－ペンチル、（メタ）アクリル酸ｎ－へキシル、（メタ）アクリル酸ｎ－オクチル、（メタ）アクリル酸ラウリル、（メタ）アクリル酸ステアリル等が例示される。 The (meth) acrylic acid linear alkyl ester is methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, n-butyl (meth) acrylic acid, n-butyl (meth) acrylic acid. Examples thereof include pentyl, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate.
（メタ）アクリル酸分岐アルキルエステルは、（メタ）アクリル酸ｉ－プロピル、（メタ）アクリル酸ｉ－ブチル、（メタ）アクリル酸ｓ－ブチル、（メタ）アクリル酸ｔ－ブチル、（メタ）アクリル酸ｉ－オクチル、（メタ）アクリル酸２－エチルヘキシル等が例示される。 The (meth) acrylic acid branched alkyl ester is (meth) acrylic acid i-propyl, (meth) acrylic acid i-butyl, (meth) acrylic acid s-butyl, (meth) acrylic acid t-butyl, (meth) acrylic. Examples thereof include i-octyl acid, 2-ethylhexyl (meth) acrylate, and the like.
（メタ）アクリル酸環状アルキルエステルは、（メタ）アクリル酸シクロペンチル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸イソボルニル、（メタ）アクリル酸ジシクロペンタニル等が例示される。 Examples of the (meth) acrylic acid cyclic alkyl ester include (meth) acrylic acid cyclopentyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid isobornyl, and (meth) acrylic acid dicyclopentanyl.
ポリマーの全質量に対する構成単位２の含有量の上限及び下限は、２０、１９、１５、１０、５、２、１質量％等が例示される。１つの実施形態において、ポリマーの全質量に対して、構成単位２を１～２０質量％含むことが好ましい。 The upper and lower limits of the content of the constituent unit 2 with respect to the total mass of the polymer are exemplified by 20, 19, 15, 10, 5, 2, 1% by mass and the like. In one embodiment, it is preferable to contain 1 to 20% by mass of the constituent unit 2 with respect to the total mass of the polymer.
ポリマーの全構成単位１００モル％に対する構成単位２の含有量の上限及び下限は、３３、３０、２０、１０、９、５、３、２モル％等が例示される。１つの実施形態において、ポリマーの全構成単位１００モル％に対して、構成単位２を２～３３モル％含むことが好ましい。 The upper and lower limits of the content of the constituent unit 2 with respect to 100 mol% of all the constituent units of the polymer are exemplified by 33, 30, 20, 10, 9, 5, 3, 2 mol% and the like. In one embodiment, it is preferable to contain 2 to 33 mol% of the constituent unit 2 with respect to 100 mol% of the total constituent units of the polymer.
（構成単位３）
構成単位３は、モノマーとして、下記構造式で表わされる
（メタ）アクリル酸グリシジルを用いた場合にポリマー鎖に含まれる構成単位と、下記構造式で表わされる
（メタ）アクリル酸とが反応した場合にポリマー鎖に含まれる構成単位である。なお、アクリル酸グリシジルとメタクリル酸グリシジルは併用可能であるし、アクリル酸とメタクリル酸も併用可能である。
(Structure unit 3)
The structural unit 3 is represented by the following structural formula as a monomer.
When glycidyl (meth) acrylate is used, it is represented by the structural unit contained in the polymer chain and the following structural formula.
(Meta) A structural unit contained in a polymer chain when it reacts with acrylic acid. In addition, glycidyl acrylate and methacrylic acid can be used in combination, and acrylic acid and methacrylic acid can also be used in combination.
ポリマーの全質量に対する構成単位３の含有量の上限及び下限は、８０、７５、７０、６０、５０、４５、４０質量％等が例示される。１つの実施形態において、ポリマーの全質量に対して、構成単位３を４０～８０質量％含むことが好ましい。 The upper and lower limits of the content of the constituent unit 3 with respect to the total mass of the polymer are exemplified by 80, 75, 70, 60, 50, 45, 40% by mass and the like. In one embodiment, it is preferable to contain 40 to 80% by mass of the structural unit 3 with respect to the total mass of the polymer.
ポリマーの全構成単位１００モル％に対する構成単位３の含有量の上限は、７５、７０、６０、５０、４５、４４モル％等が例示される。１つの実施形態において、ポリマーの全構成単位１００モル％に対して、構成単位３を４４～７５モル％含むことが好ましい。 The upper limit of the content of the constituent unit 3 with respect to 100 mol% of all the constituent units of the polymer is exemplified by 75, 70, 60, 50, 45, 44 mol% and the like. In one embodiment, it is preferable to contain 44 to 75 mol% of the constituent unit 3 with respect to 100 mol% of the total constituent units of the polymer.
（構成単位４）
構成単位４は、モノマーとして、下記構造式で表わされる
（メタ）アクリル酸グリシジルを用いた場合にポリマー鎖に含まれる構成単位である。アクリル酸グリシジルとメタクリル酸グリシジルは併用できる。構成単位４は、構成単位３が生成される途中の構成単位である。構成単位３の量が多い程、ポリマーの硬化物の硬化性が高くなる。そのため、例えば高硬度の塗膜を製造する用途でポリマーを用いる場合には構成単位４が生じないようにすることが通常行われていた。言い換えると、従来、ポリマーに構成単位４を含むことは好まれなかった。
(Structure unit 4)
The structural unit 4 is represented by the following structural formula as a monomer.
(Meta) A structural unit contained in a polymer chain when glycidyl acrylate is used. Glycidyl acrylate and glycidyl methacrylate can be used in combination. The structural unit 4 is a structural unit in the process of being generated. The larger the amount of the structural unit 3, the higher the curability of the cured product of the polymer. Therefore, for example, when a polymer is used in an application for producing a high-hardness coating film, it is usually practiced to prevent the constituent unit 4 from being generated. In other words, conventionally, it was not preferred to include the constituent unit 4 in the polymer.
ポリマーの全質量に対する構成単位４の含有量の上限及び下限は、２．０、１．９、１．８、１．７、１．６、１．５、１．４、１．３、１．２、１．１、１．０、０．９、０．８、０．７、０．６、０．５、０．４、０．３、０．２、０．１質量％等が例示される。１つの実施形態において、ポリマーの全質量に対して、構成単位４が０．１～２質量％含まれることが好ましい。 The upper and lower limits of the content of building blocks 4 relative to the total mass of the polymer are 2.0, 1.9, 1.8, 1.7, 1.6, 1.5, 1.4, 1.3, 1 .2, 1.1, 1.0, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1% by mass, etc. Illustrated. In one embodiment, it is preferable that the structural unit 4 is contained in an amount of 0.1 to 2% by mass based on the total mass of the polymer.
ポリマーの全構成単位１００モル％に対する構成単位４の含有量の上限及び下限は、３．０、２．９、２．５、２．０、１．５、１．０、０．５、０．２、０．１モル％等が例示される。１つの実施形態において、ポリマーの全構成単位１００モル％に対して、構成単位４を０．１～３．０モル％含むことが好ましい。 The upper and lower limits of the content of constituent unit 4 with respect to 100 mol% of all constituent units of the polymer are 3.0, 2.9, 2.5, 2.0, 1.5, 1.0, 0.5, 0. .2, 0.1 mol% and the like are exemplified. In one embodiment, it is preferable to contain 0.1 to 3.0 mol% of the constituent unit 4 with respect to 100 mol% of all the constituent units of the polymer.
（その他の構成単位）
上記ポリマーには、上記構成単位１～４以外の構成単位（「その他の構成単位」ともいう）を含んでいてもよい。その他の構成単位は、上述したモノマー以外のモノマー（「その他のモノマー」ともいう）に由来する構成単位等が例示される。その他のモノマーは、（メタ）アクリル酸、Ｎ，Ｎ－ジアルキル（メタ）アクリルアミド、Ｎ，Ｎ－ジアルキル（メタ）アクリル酸アルキルアミン、（メタ）アクリル酸ヒドロキシアルキル、芳香環構造含有ビニルモノマー等が例示される。
(Other building blocks)
The polymer may contain structural units other than the structural units 1 to 4 (also referred to as "other structural units"). Examples of other structural units include structural units derived from monomers other than the above-mentioned monomers (also referred to as “other monomers”). Other monomers include (meth) acrylic acid, N, N-dialkyl (meth) acrylamide, N, N-dialkyl (meth) acrylic acid alkylamine, (meth) acrylic acid hydroxyalkyl, aromatic ring structure-containing vinyl monomer, and the like. Illustrated.
ポリマーの全質量に対するその他の構成単位の含有量の上限及び下限は、１０、９、７．５、５、２．５、１、０質量％等が例示される。１つの実施形態において、ポリマーの全質量に対して、その他の構成単位を０～１０質量％を含むことが好ましい。 The upper and lower limits of the content of other structural units with respect to the total mass of the polymer are exemplified by 10, 9, 7.5, 5, 2.5, 1, 0% by mass and the like. In one embodiment, it is preferable to include 0 to 10% by mass of other structural units with respect to the total mass of the polymer.
ポリマーの全構成単位１００モル％に対するその他の構成単位の含有量の上限及び下限は、１０、９、７．５、５、２．５、１、０モル％等が例示される。１つの実施形態において、ポリマーの全構成単位１００モル％に対して、その他の構成単位を０～１０モル％含むことが好ましい。 The upper and lower limits of the content of other constituent units with respect to 100 mol% of all constituent units of the polymer are exemplified by 10, 9, 7.5, 5, 2.5, 1, 0 mol% and the like. In one embodiment, it is preferable to contain 0 to 10 mol% of the other structural units with respect to 100 mol% of the total structural units of the polymer.
（ポリマーに含まれる構成単位間の相対比）
ポリマーに含まれる構成単位１と構成単位２との質量比（ポリマーに含まれる構成単位１の合計質量／ポリマーに含まれる構成単位２の合計質量）の上限及び下限は、５１、５０、４０、３０、２０、１０、５、１、０．５等が例示される。１つの実施形態において、ポリマーに含まれる構成単位１と構成単位２との質量比（ポリマーに含まれる構成単位１の合計質量／ポリマーに含まれる構成単位２の合計質量））は０．５～５１が好ましい。
(Relative ratio between structural units contained in polymer)
The upper and lower limits of the mass ratio between the structural unit 1 contained in the polymer and the structural unit 2 (total mass of the structural unit 1 contained in the polymer / total mass of the structural unit 2 contained in the polymer) are 51, 50, 40, and 30, 20, 10, 5, 1, 0.5 and the like are exemplified. In one embodiment, the mass ratio of the structural unit 1 contained in the polymer to the structural unit 2 (total mass of the structural unit 1 contained in the polymer / total mass of the structural unit 2 contained in the polymer) is 0.5 to. 51 is preferable.
ポリマーに含まれる構成単位１と構成単位２とのモル比（ポリマーに含まれる構成単位１の合計物質量／ポリマーに含まれる構成単位２の合計物質量）の上限及び下限は、１９、１８、１５、１０、９、７．５、５、２．５、１、０．５、０．２、０．１等が例示される。１つの実施形態において、ポリマーに含まれる構成単位１と構成単位２とのモル比（ポリマーに含まれる構成単位１の合計物質量／ポリマーに含まれる構成単位２の合計物質量）は０．１～１９が好ましい。 The upper and lower limits of the molar ratio of the constituent unit 1 contained in the polymer to the constituent unit 2 (the total amount of substance of the constituent unit 1 contained in the polymer / the total amount of substance of the constituent unit 2 contained in the polymer) are 19, 18, Examples include 15, 10, 9, 7.5, 5, 2.5, 1, 0.5, 0.2, 0.1 and the like. In one embodiment, the molar ratio of constituent unit 1 to constituent unit 2 contained in the polymer (total amount of substance of constituent unit 1 contained in the polymer / total amount of substance of constituent unit 2 contained in the polymer) is 0.1. ~ 19 is preferable.
ポリマーに含まれる構成単位１と構成単位３との質量比（ポリマーに含まれる構成単位１の合計質量／ポリマーに含まれる構成単位３の合計質量）の上限及び下限は、１．３、１．２、１．０、０．９、０．５、０．３、０．２、０．１等が例示される。１つの実施形態において、ポリマーに含まれる構成単位１と構成単位３との質量比（ポリマーに含まれる構成単位１の合計質量／ポリマーに含まれる構成単位３の合計質量）は０．１～１．３が好ましい。 The upper and lower limits of the mass ratio between the structural unit 1 contained in the polymer and the structural unit 3 (total mass of the structural unit 1 contained in the polymer / total mass of the structural unit 3 contained in the polymer) are 1.3, 1. 2, 1.0, 0.9, 0.5, 0.3, 0.2, 0.1 and the like are exemplified. In one embodiment, the mass ratio of the structural unit 1 contained in the polymer to the structural unit 3 (total mass of the structural unit 1 contained in the polymer / total mass of the structural unit 3 contained in the polymer) is 0.1 to 1. .3 is preferable.
ポリマーに含まれる構成単位１と構成単位３とのモル比（ポリマーに含まれる構成単位１の合計物質量／ポリマーに含まれる構成単位３の合計物質量）の上限及び下限は、０．８５、０．８０、０．７０、０．６０、０．５０、０．４０、０．３０、０．２０、０．１０、０．０８等が例示される。１つの実施形態において、ポリマーに含まれる構成単位１と構成単位３とのモル比（ポリマーに含まれる構成単位１の合計物質量／ポリマーに含まれる構成単位３の合計物質量）は０．０８～０．８５が好ましい。 The upper and lower limits of the molar ratio of the constituent unit 1 contained in the polymer to the constituent unit 3 (the total amount of substance of the constituent unit 1 contained in the polymer / the total amount of substance of the constituent unit 3 contained in the polymer) are 0.85. Examples thereof include 0.80, 0.70, 0.60, 0.50, 0.40, 0.30, 0.20, 0.10, 0.08 and the like. In one embodiment, the molar ratio of constituent unit 1 to constituent unit 3 contained in the polymer (total amount of substance of constituent unit 1 contained in the polymer / total amount of substance of constituent unit 3 contained in the polymer) is 0.08. ~ 0.85 is preferable.
ポリマーに含まれる構成単位１と構成単位４との質量比（ポリマーに含まれる構成単位１の合計質量／ポリマーに含まれる構成単位４の合計質量）の上限及び下限は、５１０、５００、４００、３００、２００、１００、５０、２５、１０、６、５等が例示される。１つの実施形態において、ポリマーに含まれる構成単位１と構成単位４との質量比（ポリマーに含まれる構成単位１の合計質量／ポリマーに含まれる構成単位４の合計質量）は５～５１０が好ましい。 The upper and lower limits of the mass ratio between the structural unit 1 contained in the polymer and the structural unit 4 (total mass of the structural unit 1 contained in the polymer / total mass of the structural unit 4 contained in the polymer) are 510, 500, 400, 300, 200, 100, 50, 25, 10, 6, 5, etc. are exemplified. In one embodiment, the mass ratio of the structural unit 1 contained in the polymer to the structural unit 4 (total mass of the structural unit 1 contained in the polymer / total mass of the structural unit 4 contained in the polymer) is preferably 5 to 510. ..
ポリマーに含まれる構成単位１と構成単位４とのモル比（ポリマーに含まれる構成単位１の合計物質量／ポリマーに含まれる構成単位４の合計物質量）の上限及び下限は、３７０、３５０、３００、２００、１００、５０、２５、１０、５、３、２等が例示される。１つの実施形態において、ポリマーに含まれる構成単位１と構成単位４とのモル比（ポリマーに含まれる構成単位１の合計物質量／ポリマーに含まれる構成単位４の合計物質量）は２～３７０が好ましい。 The upper and lower limits of the molar ratio of the constituent unit 1 contained in the polymer to the constituent unit 4 (the total amount of substance of the constituent unit 1 contained in the polymer / the total amount of substance of the constituent unit 4 contained in the polymer) are 370, 350, 300, 200, 100, 50, 25, 10, 5, 3, 2, etc. are exemplified. In one embodiment, the molar ratio of constituent unit 1 to constituent unit 4 contained in the polymer (total amount of substance of constituent unit 1 contained in the polymer / total amount of substance of constituent unit 4 contained in the polymer) is 2 to 370. Is preferable.
ポリマーに含まれる構成単位２と構成単位３との質量比（ポリマーに含まれる構成単位２の合計質量／ポリマーに含まれる構成単位３の合計質量）の上限及び下限は、０．５、０．４、０．３、０．２、０．１、０．０５、０．０２、０．０１等が例示される。１つの実施形態において、ポリマーに含まれる構成単位２と構成単位３との質量比（ポリマーに含まれる構成単位２の合計質量／ポリマーに含まれる構成単位３の合計質量）は０．０１～０．５が好ましい。 The upper and lower limits of the mass ratio between the structural unit 2 contained in the polymer and the structural unit 3 (total mass of the structural unit 2 contained in the polymer / total mass of the structural unit 3 contained in the polymer) are 0.5, 0. 4, 0.3, 0.2, 0.1, 0.05, 0.02, 0.01 and the like are exemplified. In one embodiment, the mass ratio of the structural unit 2 contained in the polymer to the structural unit 3 (total mass of the structural unit 2 contained in the polymer / total mass of the structural unit 3 contained in the polymer) is 0.01 to 0. .5 is preferable.
ポリマーに含まれる構成単位２と構成単位３とのモル比（ポリマーに含まれる構成単位２の合計物質量／ポリマーに含まれる構成単位３の合計物質量）の上限及び下限は、０．７５、０．７０、０．５０、０．２５、０．１０、０．０５、０．０２等が例示される。１つの実施形態において、構成単位２と構成単位３とのモル比（構成単位２の物質量／構成単位３の物質量）は０．０２～０．７５が好ましい。 The upper and lower limits of the molar ratio of the constituent unit 2 contained in the polymer to the constituent unit 3 (the total amount of substance of the constituent unit 2 contained in the polymer / the total amount of substance of the constituent unit 3 contained in the polymer) are 0.75. 0.70, 0.50, 0.25, 0.10, 0.05, 0.02 and the like are exemplified. In one embodiment, the molar ratio of the constituent unit 2 to the constituent unit 3 (the amount of substance of the constituent unit 2 / the amount of substance of the constituent unit 3) is preferably 0.02 to 0.75.
ポリマーに含まれる構成単位２と構成単位４との質量比（ポリマーに含まれる構成単位２の合計質量／ポリマーに含まれる構成単位４の合計質量）の上限及び下限は、２００、１７５、１５０、１２５、１００、７５、５０、２５、５、１、０．５等が例示される。１つの実施形態において、ポリマーに含まれる構成単位２と構成単位４との質量比（ポリマーに含まれる構成単位２の合計質量／ポリマーに含まれる構成単位４の合計質量）は０．５～２００が好ましい。 The upper and lower limits of the mass ratio between the structural unit 2 contained in the polymer and the structural unit 4 (total mass of the structural unit 2 contained in the polymer / total mass of the structural unit 4 contained in the polymer) are 200, 175, 150, Examples thereof include 125, 100, 75, 50, 25, 5, 1, 0.5 and the like. In one embodiment, the mass ratio of the structural unit 2 contained in the polymer to the structural unit 4 (total mass of the structural unit 2 contained in the polymer / total mass of the structural unit 4 contained in the polymer) is 0.5 to 200. Is preferable.
ポリマーに含まれる構成単位２と構成単位４とのモル比（ポリマーに含まれる構成単位２の合計物質量／ポリマーに含まれる構成単位４の合計物質量）の上限及び下限は、３３０、３００、２００、１００、５０、２５、１０、５、１、０．６等が例示される。１つの実施形態において、ポリマーに含まれる構成単位２と構成単位４とのモル比（ポリマーに含まれる構成単位２の合計物質量／ポリマーに含まれる構成単位４の合計物質量）は０．６～３３０が好ましい。 The upper and lower limits of the molar ratio of the constituent unit 2 contained in the polymer to the constituent unit 4 (the total amount of substance of the constituent unit 2 contained in the polymer / the total amount of substance of the constituent unit 4 contained in the polymer) are 330, 300, Examples thereof include 200, 100, 50, 25, 10, 5, 1, 0.6 and the like. In one embodiment, the molar ratio of constituent unit 2 to constituent unit 4 contained in the polymer (total amount of substance of constituent unit 2 contained in the polymer / total amount of substance of constituent unit 4 contained in the polymer) is 0.6. ~ 330 is preferable.
ポリマーに含まれる構成単位３と構成単位４との質量比（ポリマーに含まれる構成単位３の合計質量／ポリマーに含まれる構成単位４の合計質量）の上限及び下限は、８００、７００、５００、２５０、１００、７５、５０、２５、２０等が例示される。１つの実施形態において、ポリマーに含まれる構成単位３と構成単位４との質量比（ポリマーに含まれる構成単位３の合計質量／ポリマーに含まれる構成単位４の合計質量）は２０～８００が好ましい。 The upper and lower limits of the mass ratio between the structural unit 3 contained in the polymer and the structural unit 4 (total mass of the structural unit 3 contained in the polymer / total mass of the structural unit 4 contained in the polymer) are 800, 700, 500, Examples include 250, 100, 75, 50, 25, 20 and the like. In one embodiment, the mass ratio of the structural unit 3 contained in the polymer to the structural unit 4 (total mass of the structural unit 3 contained in the polymer / total mass of the structural unit 4 contained in the polymer) is preferably 20 to 800. ..
ポリマーに含まれる構成単位３と構成単位４とのモル比（ポリマーに含まれる構成単位３の合計物質量／ポリマーに含まれる構成単位４の合計物質量）の上限及び下限は、７５０、７００、５００、２５０、１００、５０、２０、１５、１４等が例示される。１つの実施形態において、ポリマーに含まれる構成単位３と構成単位４とのモル比（ポリマーに含まれる構成単位３の合計物質量／ポリマーに含まれる構成単位４の合計物質量）は１４～７５０が好ましい。 The upper and lower limits of the molar ratio of the constituent unit 3 contained in the polymer to the constituent unit 4 (the total amount of substance of the constituent unit 3 contained in the polymer / the total amount of substance of the constituent unit 4 contained in the polymer) are 750, 700, Examples thereof include 500, 250, 100, 50, 20, 15, 14 and the like. In one embodiment, the molar ratio of constituent unit 3 to constituent unit 4 contained in the polymer (total amount of substance of constituent unit 3 contained in the polymer / total amount of substance of constituent unit 4 contained in the polymer) is 14 to 750. Is preferable.
ポリマーに含まれるその他の構成単位と構成単位１との質量比（ポリマーに含まれるその他の構成単位の合計質量／ポリマーに含まれる構成単位１の合計質量）の上限及び下限は、１、０．９、０．７、０．５、０．３、０．１、０等が例示される。１つの実施形態において、ポリマーに含まれるその他の構成単位と構成単位１との質量比（ポリマーに含まれるその他の構成単位の合計質量／ポリマーに含まれる構成単位１の合計質量）は０～１が好ましい。 The upper and lower limits of the mass ratio of the other structural units contained in the polymer to the structural unit 1 (total mass of other structural units contained in the polymer / total mass of the structural unit 1 contained in the polymer) are 1, 0. 9, 0.7, 0.5, 0.3, 0.1, 0 and the like are exemplified. In one embodiment, the mass ratio of the other building blocks contained in the polymer to the building blocks 1 (total mass of the other building blocks contained in the polymer / total mass of building blocks 1 contained in the polymer) is 0 to 1. Is preferable.
ポリマーに含まれるその他の構成単位と構成単位１とのモル比（ポリマーに含まれるその他の構成単位の合計物質量／ポリマーに含まれる構成単位１の合計物質量）の上限及び下限は、２、１．９、１．５、１、０．９、０．５、０．１、０等が例示される。１つの実施形態において、ポリマーに含まれるその他の構成単位と構成単位１とのモル比（ポリマーに含まれるその他の構成単位の合計物質量／ポリマーに含まれる構成単位１の合計物質量）は０～２が好ましい。 The upper and lower limits of the molar ratio of the other constituent units contained in the polymer to the constituent unit 1 (total amount of substance of the other constituent units contained in the polymer / total amount of substance of the constituent unit 1 contained in the polymer) are 2. Examples include 1.9, 1.5, 1, 0.9, 0.5, 0.1, 0 and the like. In one embodiment, the molar ratio of the other structural units contained in the polymer to the constituent unit 1 (total amount of substance of the other constituent units contained in the polymer / total amount of substance of the constituent unit 1 contained in the polymer) is 0. ~ 2 is preferable.
ポリマーに含まれるその他の構成単位と構成単位２との質量比（ポリマーに含まれるその他の構成単位の合計質量／ポリマーに含まれる構成単位２の合計質量）の上限及び下限は、１０、９、７．５、５、２．５、１、０等が例示される。１つの実施形態において、ポリマーに含まれるその他の構成単位と構成単位２との質量比（ポリマーに含まれるその他の構成単位の合計質量／ポリマーに含まれる構成単位２の合計質量）は０～１０が好ましい。 The upper and lower limits of the mass ratio of the other constituent units contained in the polymer to the constituent unit 2 (total mass of other constituent units contained in the polymer / total mass of the constituent unit 2 contained in the polymer) are 10, 9, 7.5, 5, 2.5, 1, 0 and the like are exemplified. In one embodiment, the mass ratio of the other building blocks contained in the polymer to the building blocks 2 (total mass of the other building blocks contained in the polymer / total mass of building blocks 2 contained in the polymer) is 0-10. Is preferable.
ポリマーに含まれるその他の構成単位と構成単位２とのモル比（ポリマーに含まれるその他の構成単位の合計物質量／ポリマーに含まれる構成単位２の合計物質量）の上限及び下限は、５、４、３、２、１、０等が例示される。１つの実施形態において、ポリマーに含まれるその他の構成単位と構成単位２とのモル比（ポリマーに含まれるその他の構成単位の合計物質量／ポリマーに含まれる構成単位２の合計物質量）は０～５が好ましい。 The upper and lower limits of the molar ratio of the other constituent units contained in the polymer to the constituent unit 2 (total amount of substance of the other constituent units contained in the polymer / total amount of substance of the constituent unit 2 contained in the polymer) are 5, 4, 3, 2, 1, 0 and the like are exemplified. In one embodiment, the molar ratio of the other building blocks contained in the polymer to the building blocks 2 (total amount of substance of the other building blocks contained in the polymer / total amount of substance of building blocks 2 contained in the polymer) is 0. ~ 5 is preferable.
ポリマーに含まれるその他の構成単位と構成単位３との質量比（ポリマーに含まれるその他の構成単位の合計質量／ポリマーに含まれる構成単位３の合計質量）の上限及び下限は、０．２５、０．２０、０．１５、０．１０、０．０５、０等が例示される。１つの実施形態において、ポリマーに含まれるその他の構成単位と構成単位３との質量比（ポリマーに含まれるその他の構成単位の合計質量／ポリマーに含まれる構成単位３の合計質量）は０～０．２５が好ましい。 The upper and lower limits of the mass ratio of the other structural units contained in the polymer to the structural unit 3 (total mass of other structural units contained in the polymer / total mass of the structural unit 3 contained in the polymer) are 0.25. 0.20, 0.15, 0.10, 0.05, 0 and the like are exemplified. In one embodiment, the mass ratio of the other building blocks contained in the polymer to the building blocks 3 (total mass of the other building blocks contained in the polymer / total mass of building blocks 3 contained in the polymer) is 0 to 0. .25 is preferred.
ポリマーに含まれるその他の構成単位と構成単位３とのモル比（ポリマーに含まれるその他の構成単位の合計物質量／ポリマーに含まれる構成単位３の合計物質量）の上限及び下限は、０．２５、０．２０、０．１０、０．０５、０等が例示される。１つの実施形態において、ポリマーに含まれるその他の構成単位と構成単位３とのモル比（ポリマーに含まれるその他の構成単位の合計物質量／ポリマーに含まれる構成単位３の合計物質量）は０～０．２５が好ましい。 The upper and lower limits of the molar ratio of the other constituent units contained in the polymer to the constituent unit 3 (total amount of substance of other constituent units contained in the polymer / total amount of substance of the constituent unit 3 contained in the polymer) are 0. 25, 0.20, 0.10, 0.05, 0 and the like are exemplified. In one embodiment, the molar ratio of the other building blocks contained in the polymer to the building blocks 3 (total amount of substance of the other building blocks contained in the polymer / total amount of substance of building blocks 3 contained in the polymer) is 0. ~ 0.25 is preferable.
ポリマーに含まれるその他の構成単位と構成単位４との質量比（ポリマーに含まれるその他の構成単位の合計質量／ポリマーに含まれる構成単位４の合計質量）の上限及び下限は、１００、９０、７５、５０、２５、１０、５、１、０等が例示される。１つの実施形態において、ポリマーに含まれるその他の構成単位と構成単位４との質量比（ポリマーに含まれるその他の構成単位の合計質量／ポリマーに含まれる構成単位４の合計質量）は０～１００が好ましい。 The upper and lower limits of the mass ratio of the 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 the structural unit 4 contained in the polymer) are 100, 90, Examples include 75, 50, 25, 10, 5, 1, 0 and the like. In one embodiment, the mass ratio of the other building blocks contained in the polymer to the building blocks 4 (total mass of the other building blocks contained in the polymer / total mass of building blocks 4 contained in the polymer) is 0-100. Is preferable.
ポリマーに含まれるその他の構成単位と構成単位４とのモル比（ポリマーに含まれるその他の構成単位の合計物質量／ポリマーに含まれる構成単位４の合計物質量）の上限及び下限は、１００、９０、７５、５０、２５、１０、５、１、０等が例示される。１つの実施形態において、ポリマーに含まれるその他の構成単位と構成単位４とのモル比（ポリマーに含まれるその他の構成単位の合計物質量／ポリマーに含まれる構成単位４の合計物質量）は０～１００が好ましい。 The upper and lower limits of the molar ratio of the other constituent units contained in the polymer to the constituent unit 4 (total amount of substance of the other constituent units contained in the polymer / total amount of substance of the constituent unit 4 contained in the polymer) are 100, Examples thereof include 90, 75, 50, 25, 10, 5, 1, 0 and the like. In one embodiment, the molar ratio of the other building blocks contained in the polymer to the building blocks 4 (total amount of substance of the other building blocks contained in the polymer / total amount of substance of building blocks 4 contained in the polymer) is 0. ~ 100 is preferable.
（ポリマーの物性等）
１つの実施形態において、上記ポリマーの色調は、ガードナーカラー１０以下（例えば、９以下、８以下、７以下、６以下、５以下、４以下、３以下、２以下、１以下、０）が好ましい。ガードナーカラーは、ＪＩＳ Ｋ５４００に準拠して測定され得る。
(Physical characteristics of polymer, etc.)
In one embodiment, the color tone of the polymer is preferably Gardner color 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). .. Gardner color can be measured according to JIS K5400.
上記ポリマーの重量平均分子量（Ｍｗ）の上限及び下限は、１０００００、９００００、８００００、７００００、６００００、５００００、４００００、３００００、２１０００、２００００、１９０００、１８０００、１７０００、１５０００、１１０００、１００００等が例示される。１つの実施形態において、上記ポリマーの重量平均分子量（Ｍｗ）は、１００００～１０００００が好ましい。 Examples of the upper and lower limits of the weight average molecular weight (Mw) of the polymer are 100,000, 90000, 80000, 70000, 60000, 50000, 40,000, 30000, 21000, 20000, 19000, 18000, 17000, 15000, 11000, 10000 and the like. To. In one embodiment, the weight average molecular weight (Mw) of the polymer is preferably 10,000 to 100,000.
上記ポリマーの数平均分子量（Ｍｎ）の上限及び下限は、８０００、７９００、７５００、７０００、６５００、６１００、６０００等が例示される。１つの実施形態において、上記ポリマーの数平均分子量（Ｍｎ）は、６０００～８０００が好ましい。 Examples of the upper limit and the lower limit of the number average molecular weight (Mn) of the polymer are 8000, 7900, 7500, 7000, 6500, 6100, 6000 and the like. In one embodiment, the number average molecular weight (Mn) of the polymer is preferably 6000 to 8000.
重量平均分子量及び数平均分子量は、例えばゲルパーミエーションクロマトグラフィー（ＧＰＣ）により適切な溶媒下で測定したポリスチレン換算値として求められる。 The weight average molecular weight and the number average molecular weight are determined as polystyrene-equivalent values measured under an appropriate solvent by, for example, gel permeation chromatography (GPC).
ポリマーの分子量分布（Ｍｗ／Ｍｎ）の上限及び下限は、４．０、３．９、３．５、３．０、２．５、２．１、２．０等が例示される。１つの実施形態において、ポリマーの分子量分布（Ｍｗ／Ｍｎ）は、２．０～４．０が好ましい。 Examples of the upper and lower limits of the molecular weight distribution (Mw / Mn) of the polymer are 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.
ポリマーの酸価の上限及び下限は、６．０、５．９、５．０、４．０、３．０、２．０、１．０、０．５、０．３、０．２ｍｇＫＯＨ／ｇ等が例示される。１つの実施形態において、ポリマーの酸価は、０．２～６．０ｍｇＫＯＨ／ｇが好ましい。酸価は、日本工業規格 ＪＩＳ Ｋ ００７０に準ずる方法により求められる。 The upper and lower limits of the acid value of the polymer are 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 are exemplified. In one embodiment, the acid value of the polymer is preferably 0.2-6.0 mgKOH / g. The acid value is determined by a method according to the Japanese Industrial Standards JIS K 0070.
ポリマーのエポキシ当量の上限及び下限は、１４００００、１２５０００、１０００００、９００００、７５０００、５００００、２５０００、１００００、９０００、８０００、７５００、７１００ｇ／ｅｑ等が例示される。１つの実施形態において、ポリマーのエポキシ当量は、７１００～１４０，０００ｇ／ｅｑが好ましい。 Examples of the upper and lower limits of the epoxy equivalent of the polymer are 140000, 125000, 100,000, 90000, 75000, 50000, 25000, 10000, 9000, 8000, 7500, 7100 g / eq and the like. In one embodiment, the epoxy equivalent of the polymer is preferably 7100-140,000 g / eq.
なお、ポリマーのエポキシ当量は、例えば下記の方法により測定される。試料１５ｇを２５０ｍＬ密栓付フラスコに精評し、０．２Ｎ塩酸ジオキサン溶液を２５ｍＬ加え、十分に混合して溶解させ、室温で１５分間放置後、中性ブチセロ溶媒を２５ｍＬ加え、０．１Ｎ ＫＯＨエタノール溶液で滴定し、式（１）より算出される値をエポキシ当量 ｇ／ｅｑとする。
式（１）
エポキシ当量（ｇ／ｅｑ）＝１００００Ｗ／ｆ（Ｂ－（Ａ－Ｃ））
Ｗは秤量した試料のｇ数、ｆは０．１Ｎ ＫＯＨエタノール溶液のファクター、Ｂはブランクテストに要した０．１Ｎ ＫＯＨエタノール溶液の滴定量（ｍＬ）、Ａは試料の滴定に要した０．１Ｎ ＫＯＨエタノール溶液の滴定量（ｍＬ）、Ｃは試料１５ｇの酸価滴定に要した０．１Ｎ ＫＯＨエタノール溶液の滴定量（ｍＬ）を示す。
The epoxy equivalent of the polymer is measured by, for example, the following method. Carefully evaluate 15 g of the sample in a 250 mL flask with a tight stopper, add 25 mL of 0.2N dioxane hydrochloride solution, mix well to dissolve, leave at room temperature for 15 minutes, add 25 mL of neutral buticello solvent, and add 0.1 N KOH ethanol. Titrate with a solution and use the value calculated from the formula (1) as the epoxy equivalent g / eq.
Equation (1)
Epoxy equivalent (g / eq) = 10000 W / f (B- (AC))
W is the g number of the weighed sample, f is the factor of the 0.1N KOH ethanol solution, B is the titration amount (mL) of the 0.1N KOH ethanol solution required for the blank test, and A is the titration of the sample. Titration of 1N KOH ethanol solution (mL), C indicates titration of 0.1N KOH ethanol solution required for acid value titration of 15 g of sample (mL).
１つの実施形態において、ポリマーの色差は、Ｌ＊、ａ＊、ｂ＊よりｈ＝ｔａｎ－１（ｂ＊／ａ＊）にて算出されるｈが１１５以下（例えば、１１０以下、１００以下、９０以下、８０以下、７０以下、６０以下、５０以下、４０以下、３０以下、２０以下、１０以下）が好ましい。ポリマーの色差は色差計（商品名：ＺＥ ６０００ 日本電色工業（株）製）の透過法等により求められる。 In one embodiment, the color difference of the polymer is such that h calculated by h = tan -1 (b * / a *) from L *, a *, b * 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 preferable. The color difference of the polymer is obtained by a transmission method or the like of a color difference meter (trade name: ZE 6000 manufactured by Nippon Denshoku Kogyo Co., Ltd.).
上記ポリマーを製造する方法は、紫外線吸収部位含有モノマー、（メタ）アクリル酸アルキルエステル、及び（メタ）アクリル酸グリシジル並びにその他のモノマーを重合させる工程（１）、工程（１）により得られたポリマーと（メタ）アクリル酸を反応させる工程（２）を含む方法等が例示される。 The method for producing the above polymer is a polymer obtained by the steps (1) and (1) of polymerizing a monomer containing an ultraviolet absorbing site, a (meth) acrylic acid alkyl ester, and (meth) glycidyl acrylate and other monomers. An example includes a method including the step (2) of reacting with (meth) acrylic acid.
[組成物]
本開示は、上記ポリマーを含む、組成物を提供する。上記組成物は、コーティング用途において好適に用いられ得る。１つの実施形態において、上記組成物は活性エネルギー線硬化性樹脂組成物として用いられ得る。
[Composition]
The present disclosure provides a composition comprising the above polymer. The above composition can be suitably used in coating applications. In one embodiment, the composition can be used as an active energy ray-curable resin composition.
組成物の全質量に対する上記ポリマーの含有量の上限及び下限は、１００、９０、８０、７０、６０、５０、４０、３０、２０、１５、１０質量％等が例示される。１つの実施形態において、組成物の全質量に対して、上記ポリマーを１０～１００質量％含むことが好ましい。 The upper and lower limits of the content of the polymer with respect to the total mass of the composition are exemplified by 100, 90, 80, 70, 60, 50, 40, 30, 20, 15, 10% by mass and the like. In one embodiment, the polymer is preferably contained in an amount of 10 to 100% by mass based on the total mass of the composition.
１つの実施形態において、上記組成物には、光重合開始剤が含まれる。光重合開始剤は２種以上を併用してもよい。光重合開始剤は、１－ヒドロキシ－シクロヘキシル－フェニルケトン、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン、１－シクロヘキシルフェニルケトン、２－ヒドロキシ－２－メチル－１－フェニル－プロパン－１－オン、１－［４－（２－ヒドロキシエトキシ）－フェニル］－２－ヒドロキシ－２－メチル－１－プロパン－１－オン、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルホリノプロパン－１－オン、２，４，６－トリメチルベンゾイル－ジフェニル－ホスフィンオキサイド、４－メチルベンゾフェノン等が例示される。 In one embodiment, the composition comprises a photopolymerization initiator. Two or more kinds of photopolymerization initiators may be used in combination. The photopolymerization initiators are 1-hydroxy-cyclohexyl-phenylketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-cyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenyl-. Propane-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-methyl-1- [4- (methylthio) phenyl ] -2-Molholinopropane-1-one, 2,4,6-trimethylbenzoyl-diphenyl-phosphinoxide, 4-methylbenzophenone and the like are exemplified.
なお、光重合開始剤は、紫外線硬化を行なう場合に使用されるが、電子線硬化をする場合には、必ずしも必要ではない。 Although the photopolymerization initiator is used for ultraviolet curing, it is not always necessary for electron beam curing.
組成物の全質量に対する光重合開始剤の含有量の上限及び下限は、１０、９、７．５、５、２．５、１、０．５、０質量％等が例示される。１つの実施形態において、光重合開始剤は組成物の全質量に対し、０～１０質量％程度含まれる。 The upper and lower limits of the content of the photopolymerization initiator with respect to the total mass of the composition are exemplified by 10, 9, 7.5, 5, 2.5, 1, 0.5, 0% by mass and the like. In one embodiment, the photopolymerization initiator is contained in an amount of about 0 to 10% by mass based on the total mass of the composition.
ポリマーの全質量に対する光重合開始剤の含有量の上限及び下限は、１０、９、７．５、５、２．５、１、０．５、０質量％等が例示される。１つの実施形態において、上記ポリマーの全質量に対し光重合開始剤は、０～１０質量％程度含まれる。 The upper and lower limits of the content of the photopolymerization initiator with respect to the total mass of the polymer are exemplified by 10, 9, 7.5, 5, 2.5, 1, 0.5, 0% by mass and the like. In one embodiment, the photopolymerization initiator is contained in an amount of about 0 to 10% by mass based on the total mass of the polymer.
１つの実施形態において、上記組成物には希釈溶媒が含まれる。希釈溶媒は２種以上を併用してもよい。希釈溶媒は、メチルエチルケトン、メチルイソブチルケトン、酢酸メチル、酢酸エチル、酢酸ブチル、エタノール、ｎ－プロピルアルコール、イソプロピルアルコール、ｎ－ブタノール、イソブチルアルコール、ｔ－ブチルアルコール、ジアセトンアルコール、アセチルアセトン、トルエン、キシレン、ｎ－ヘキサン、シクロヘキサン、メチルシクロヘキサン、ｎ－ヘプタン、イソプロピルエーテル、メチルセロソルブ、エチルセロソルブ、１，４－ジオキサン、プロピレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート等が例示される。 In one embodiment, the composition comprises a diluent solvent. Two or more kinds of diluting solvents may be used in combination. Diluting solvents are methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, isobutyl alcohol, t-butyl alcohol, diacetone alcohol, acetylacetone, 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 and the like. Alcohol.
組成物の全質量に対する希釈溶媒の含有量の上限及び下限は、８０、７０、６０、５０、４０、３０、２０、１０、５、１、０質量％等が例示される。１つの実施形態において、組成物の全質量に対し、希釈溶媒は、塗工時に適する粘度の観点から、０～８０質量％程度等が例示される。 The upper and lower limits of the content of the diluting solvent with respect to the total mass of the composition are exemplified by 80, 70, 60, 50, 40, 30, 20, 10, 5, 1, 0% by mass and the like. In one embodiment, the diluting solvent is exemplified by about 0 to 80% by mass with respect to the total mass of the composition from the viewpoint of the viscosity suitable for coating.
ポリマーの全質量に対する希釈溶媒の含有量の上限及び下限は、８０、７０、６０、５０、４０、３０、２０、１０、５、１、０質量％等が例示される。１つの実施形態において、ポリマーの全質量に対し、希釈溶媒は、０～８０質量％程度含まれる。 The upper and lower limits of the content of the diluting solvent with respect to the total mass of the polymer are exemplified by 80, 70, 60, 50, 40, 30, 20, 10, 5, 1, 0% by mass and the like. In one embodiment, the diluent solvent is contained in an amount of about 0 to 80% by mass based on the total mass of the polymer.
（添加剤）
上記組成物には、上記ポリマー、光重合開始剤、希釈溶媒以外の剤を添加剤として含み得る。添加剤は、硬化助剤、酸化防止剤、紫外線吸収剤、光安定剤、消泡剤、表面調整剤、防汚染剤、無機フィラー、シランカップリング剤、コロイダルシリカ、顔料、帯電防止剤、金属酸化物微粒子分散体等が例示される。１つの実施形態において、添加剤の含有量は、組成物１００質量部に対して、０．１～２０質量部、１０質量部未満、１質量部未満、５質量部未満、０．１質量部未満、０．０１質量部未満、０質量部等が例示され、別の実施形態において、上記ポリマー１００質量部に対して、０．１～２０質量部、１０質量部未満、５質量部未満、１質量部未満、０．１質量部未満、０．０１質量部未満、０質量部等が例示される。
(Additive)
The composition may contain an agent other than the polymer, the photopolymerization initiator, and the diluting solvent as an additive. Additives include curing aids, antioxidants, UV absorbers, light stabilizers, defoamers, surface modifiers, antifouling agents, inorganic fillers, silane coupling agents, colloidal silica, pigments, antistatic agents, metals. Examples thereof include oxide fine particle dispersions. In one embodiment, the content of the additive is 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, 0.1 parts by mass with respect to 100 parts by mass of the composition. Less than, less than 0.01 parts by mass, 0 parts by mass, etc. are exemplified, and in another embodiment, 0.1 to 20 parts by mass, less than 10 parts by mass, less than 5 parts by mass, with respect to 100 parts by mass of the polymer. Examples thereof include 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.
[硬化物]
本開示は、上記組成物の硬化物を提供する。上記硬化物は、上記組成物に、紫外線、電子線、放射線等の活性エネルギー線を照射する工程を含む方法により得られる。
[Cursed product]
The present disclosure provides a cured product of the above composition. The cured product is obtained by a method including a step of irradiating the composition with active energy rays such as ultraviolet rays, electron beams, and radiation.
紫外線光源は、キセノンランプ、高圧水銀灯、メタルハライド、ＬＥＤランプ等が例示される。紫外線量は硬化物の厚さに応じて適宜調整され得る。なお、光量や光源配置、搬送速度等は必要に応じて調整でき、例えば高圧水銀灯を使用する場合には、８０～１６０Ｗ／ｃｍ程度のランプ出力を有するランプ１灯に対して搬送速度５～５０ｍ／分程度で硬化させるのが好ましい。一方、電子線の場合には、１０～３００ｋＶ程度の加速電圧を有する電子線加速装置にて、搬送速度５～５０ｍ／分程度で硬化させることが好ましい。 Examples of the ultraviolet light source include a xenon lamp, a high-pressure mercury lamp, a metal halide, and an LED lamp. The amount of ultraviolet rays can be appropriately adjusted according to the thickness of the cured product. The amount of light, the arrangement of the light source, the transport speed, etc. can be adjusted as needed. For example, when a high-pressure mercury lamp is used, the transport speed is 5 to 50 m for one lamp having a lamp output of about 80 to 160 W / cm. It is preferable to cure at about / minute. On the other hand, in the case of an electron beam, it is preferable to cure it at a transport speed of about 5 to 50 m / min with an electron beam accelerator having an acceleration voltage of about 10 to 300 kV.
[保護膜]
本開示は、上記硬化物を含む、保護膜を提供する。上記保護膜は、基材に塗布する工程、活性エネルギー線を照射して硬化させて積層させる工程を含む方法等により製造される。また活性エネルギー線を照射する工程は、塗布物の乾燥中及び／又は乾燥後に行われ得る。
[Protective film]
The present disclosure provides a protective film containing the cured product. The protective film is manufactured by a method including a step of applying it to a base material, a step of irradiating it with active energy rays to cure it, and laminating it. Further, the step of irradiating the active energy ray may be performed during and / or after the drying of the coating material.
基材は、ポリエチレンテレフタレート（ＰＥＴ）、ポリカーボネート、ポリメチルメタクリレート、ポリスチレン、ポリエステル、ポリオレフィン、エポキシ樹脂、メラミン樹脂、トリアセチルセルロース樹脂、ＡＢＳ樹脂、ＡＳ樹脂、ノルボルネン系樹脂等が例示される。 Examples of the base material include polyethylene terephthalate (PET), polycarbonate, polymethylmethacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene-based resin and the like.
塗布方法は、バーコーター塗工、メイヤーバー塗工、エアナイフ塗工、グラビア塗工、リバースグラビア塗工、オフセット印刷、フレキソ印刷、スクリーン印刷法等が例示される。 Examples of the coating method include bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, screen printing method and the like.
上記保護膜は、例えば、バリアフィルム、偏光板、加飾用フィルム、包装用フィルム等に用いられ得る。 The protective film can be used, for example, as a barrier film, a polarizing plate, a decorative film, a packaging film, or the like.
以下に、実施例及び比較例をあげて本発明を具体的に説明するが、本発明はこれらの例に限定されるものではない。なお、各例中、部及び％は特記しない限りすべて質量基準である。 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 each example, parts and% are all based on mass unless otherwise specified.
＜実施例１＞
撹拌機、温度計、還流冷却機、窒素流入口及び滴下ロートを取り付けた四つ口フラスコに、３－（２Ｈ－１，２，３－ベンゾトリアゾール－２－イル）－４－ヒドロキシフェネチル＝メタクリレート（以下、ＵＶＡ）１１部、グリシジルメタクリレート（以下、ＧＭＡ）４９．８部、メチルメタクリレート（以下、ＭＭＡ）１５部、重合開始剤としてアゾビスイソブチロニトリル（以下、ＡＩＢＮ）３部、酢酸ブチル １００部を仕込んで撹拌し、窒素気流下で１００℃まで昇温させ１０時間反応させた。その後、アクリル酸（以下、ＡＡ） ２４．２部、４－メトキシフェノール（以下、ＭＱ）０．１部、反応触媒としてトリフェニルホスフィン ０．３部を仕込み、１００℃８時間反応させることで、ポリマーを得た。
なお、重量平均分子量（ＧＰＣによるポリスチレン換算値）は４，６００であった。重量平均分子量は、ゲルパーメーションクロマトグラフィー（東ソー（株）製、商品名「ＨＬＣ－８２２０」、カラム：東ソー（株）製、商品名「ＴＳＫｇｅｌ ｓｕｐｅｒＨＺＭ-Ｍ」を３本直列に連結して測定した値を示す。
得られたポリマーに、光重合開始剤 １－ヒドロキシシクロヘキシルフェニルケトン（商品名「イルガキュア１８４」ＢＡＳＦ、以下、Ｉｒｇ１８４）５部加えて、塗液を作成し、厚さ１８８μｍの片面易接着処理ポリエチレンテレフタレートフィルム（商品名「Ａ４１００」東洋紡績株式会社）の易接着面にバーコーターで塗布し、８０℃１分間乾燥させた後、紫外線光を６００ｍＪ/ｃｍ２照射し、膜厚５μｍの硬化膜を得た。
<Example 1>
3- (2H-1,2,3-benzotriazol-2-yl) -4-hydroxyphenethyl = methacrylate in a four-necked flask equipped with a stirrer, thermometer, reflux cooler, nitrogen inlet and dropping funnel. (Hereinafter UVA) 11 parts, glycidyl methacrylate (hereinafter GMA) 49.8 parts, methyl methacrylate (hereinafter MMA) 15 parts, azobisisobutyronitrile (hereinafter AIBN) 3 parts as a polymerization initiator, butyl acetate 100 parts were charged, stirred, heated to 100 ° C. under a nitrogen stream, and reacted for 10 hours. Then, 24.2 parts of acrylic acid (hereinafter, AA), 0.1 part of 4-methoxyphenol (hereinafter, MQ), and 0.3 part of triphenylphosphine as a reaction catalyst were charged and reacted at 100 ° C. for 8 hours. Obtained a polymer.
The weight average molecular weight (polystyrene conversion value by GPC) was 4,600. The weight average molecular weight is measured by connecting three gel permeation chromatography (manufactured by Tosoh Corporation, trade name "HLC-8220", column: manufactured by Tosoh Co., Ltd., trade name "TSKgel superHZM-M" in series. Indicates the value.
To the obtained polymer, 5 parts of the photopolymerization initiator 1-hydroxycyclohexylphenylketone (trade name "Irgacure 184" BASF, hereinafter, Irg184) was added to prepare a coating liquid, and a one-sided easy-adhesion-treated polyethylene terephthalate having a thickness of 188 μm was prepared. The film (trade name "A4100" Toyo Spinning Co., Ltd.) is coated on the easy-adhesive surface with a bar coater, dried at 80 ° C. for 1 minute, and then irradiated with ultraviolet light at 600 mJ / cm 2 to obtain a cured film with a thickness of 5 μm. rice field.
＜実施例２～６、及び比較例１～３＞
下記表に示す重合性モノマー、及び比率にて、同様に硬化膜を作成した。表中のモノマー、溶媒、重合開始剤、重合禁止剤、反応触媒、構成単位についての数値は質量基準のものである。なお、比較例２では、アクリル酸を付与する工程で増粘が激しく、ゲル化してしまった。
<Examples 2 to 6 and Comparative Examples 1 to 3>
A cured film was similarly prepared with the polymerizable monomers and ratios shown in the table below. Numerical values for the monomer, solvent, polymerization initiator, polymerization inhibitor, reaction catalyst, and structural unit in the table are based on mass. In Comparative Example 2, the thickening was severe in the step of applying acrylic acid, and gelation occurred.
ＳＭＡ：ステアリルメタアクリレート
ＩＢＸＡ：イソボルニルアクリレート
ＤＣＰ－Ａ：ジシクロペンタニルメタクリレート
ＡＡ：アクリル酸
反応触媒：トリフェニルホスフィン
硬化剤Ａ：１，６－ヘキサンジイソシアネートのビウレット変性トリイソシアネート
硬化剤Ｂ：サイメル３００（三井サイテック社）
ＵＶ硬化条件：１ 高圧水銀灯 ６００ｍＪ／ｃｍ２（３６０ｎｍ－１時）
UV curing conditions: 1 High-pressure mercury lamp 600 mJ / cm 2 (360 nm -1 o'clock)
各実施例及び比較例のハードコート剤を用い作成された硬化膜は、以下の項目、評価方法にて、試験を行った。 The cured films prepared using the hardcoat agents of each Example and Comparative Example were tested according to the following items and evaluation methods.
（タックの評価）
塗膜表面を指触により、以下のように評価した。
なし＝樹脂成分が指に付着しない。タックを感じない
有り＝樹脂成分が指に付着する。タックを感じる
(Evaluation of tack)
The surface of the coating film was evaluated by touch as follows.
None = Resin component does not adhere to fingers. No tack is felt = Resin component adheres to the finger. Feel the tack
（鉛筆硬度の評価）
ＪＩＳ－Ｋ－５６００の試験方法に則り評価した。
(Evaluation of pencil hardness)
The evaluation was made according to the test method of JIS-K-5600.
（耐擦傷性の評価）
硬化膜表面にスチールウール（＃００００）に１００ｇ／ｃｍ２荷重を掛けて、１０往復ラビングを行い、傷の有無にて判断を行った。
(Evaluation of scratch resistance)
A load of 100 g / cm 2 was applied to the surface of the cured film on steel wool (# 0000), and 10 reciprocating rubbing was performed to make a judgment based on the presence or absence of scratches.
（ブリードの評価）
塗工品を８０℃９０％の恒温恒湿機に２４時間静置し、塗膜表面の変化を目視で確認。以下の基準で評価した。
なし＝試験前後で外観変化無し
有り＝試験前後で外観変化有り
(Evaluation of bleed)
The coated product was allowed to stand in a constant temperature and humidity chamber at 80 ° C. and 90% for 24 hours, and changes in the coating film surface were visually confirmed. It was evaluated according to the following criteria.
None = No change in appearance before and after the test Yes = There is a change in appearance before and after the test
（耐光性の評価）
メタルハライド光源にて照射（８０ｍＷ／ｃｍ２）を１２時間行った後、硬化膜のイエローインデックス（以下、ＹＩ）の変化度合により評価。試験後のＹＩ値から、試験前のＹＩ値を差し引いた数値をΔＹＩとし、２以下を耐光性良好として○、２より大きい場合を耐光性不十分として×と記載した。
(Evaluation of light resistance)
After irradiating with a metal halide light source (80 mW / cm 2 ) for 12 hours, it is evaluated by the degree of change in the yellow index (hereinafter, YI) of the cured film. The value obtained by subtracting the YI value before the test from the YI value after the test was described as ΔYI, and when it was 2 or less, it was described as good light resistance, and when it was larger than 2, it was described as x as insufficient light resistance.
Claims (5)
を１０～５１質量％
構成単位２
を１～２０質量％
構成単位３
を４０～８０質量％
及び構成単位４
を０．１～２質量％含む、ポリマー。 Configuration unit 1
10-51% by mass
Configuration unit 2
1 to 20% by mass
Configuration unit 3
40-80% by mass
And structural unit 4
A polymer containing 0.1 to 2% by mass.
A protective film containing the cured product according to claim 4.
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| KR100365967B1 (en) * | 1998-10-05 | 2002-12-26 | 니폰 쇼쿠바이 컴파니 리미티드 | Ultraviolet-absorbing laminated resinous material |
| EP1598373A4 (en) * | 2003-02-19 | 2010-03-03 | Kansai Paint Co Ltd | Process for producing aqueous resin dispersion |
| CA2523569A1 (en) * | 2003-05-06 | 2004-11-18 | Ciba Specialty Chemicals Holding Inc. | Photo-cured and stabilized coatings |
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| KR20140129378A (en) * | 2008-12-22 | 2014-11-06 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | Microstructured optical films comprising polymerizable ultraviolet absorber |
| KR101666479B1 (en) * | 2013-08-27 | 2016-10-14 | 서울대학교산학협력단 | Benzotriazole based (meth)acrylate copolymer and adhesive composition comprising same |
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|---|---|---|---|---|
| JP2000128940A (en) | 1998-10-23 | 2000-05-09 | Nippon Shokubai Co Ltd | Polymerizable polymer and its production |
| JP2004143344A (en) | 2002-10-25 | 2004-05-20 | Toagosei Co Ltd | Crosslinkable resin composition having ultraviolet light-absorbing ability |
| JP2007238823A (en) | 2006-03-09 | 2007-09-20 | Chugoku Marine Paints Ltd | Photocurable (meth)acrylic resin copolymerized with reactive ultraviolet ray absorbent, photocurable resin composition containing the resin and its weather-resistant coating film |
| JP2008274209A (en) | 2007-05-04 | 2008-11-13 | Chang Chun Plastic Co Ltd | Uv-curable resin, method for producing the same and composition containing the resin |
| JP2015124254A (en) | 2013-12-26 | 2015-07-06 | Dic株式会社 | Photo-curable polymer, photo-curable resin composition, cured product thereof, and cured coating-film |
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| CN110117338A (en) | 2019-08-13 |
| CN110117338B (en) | 2022-03-29 |
| JP2019137844A (en) | 2019-08-22 |
| TW201936674A (en) | 2019-09-16 |
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