KR20090053715A - Curable resin composition, protective film and method for forming the same - Google Patents

Abstract

The subject of this invention is providing the composition which is excellent in planarization performance, and shows a favorable external appearance also in various coating methods, the formation method of the protective film using this composition, and the protective film formed from the said composition.

The present invention relates to a curable resin composition containing a polymer having a repeating unit derived from a polymerizable unsaturated compound having an oxiranyl group or an oxetanyl group and a solvent represented by the following formula (1).

<Formula 1>

[In Formula 1, R ₁ is an alkyl group having 1 to 9 carbon atoms.]

Oxyranyl group, oxetanyl group, polymerizable unsaturated compound, polymer having a repeating unit, curable resin composition, polymerizable unsaturated carboxylic acid, polymerizable unsaturated polycarboxylic anhydride, carboxyl group, carboxylic anhydride group, carboxylic acid Acetal ester structure, ketal ester structure of carboxylic acid, 1-alkylcycloalkyl ester structure of carboxylic acid

Description

Curable resin composition, protective film, and protective film formation method {CURABLE RESIN COMPOSITION, PROTECTIVE FILM AND METHOD FOR FORMING THE SAME}

The present invention relates to a cured resin composition, a method for forming a protective film from the composition, and a protective film. More specifically, a composition suitable as a material for forming a protective film used for a color filter for a liquid crystal display device (LCD) and a color filter for a charge coupled device (CCD), a method for forming a protective film using the composition, and the composition It is about a protective film.

Radiation devices such as LCDs and CCDs are exposed to high temperatures locally when the display element is immersed in a display device by a solvent, an acid or an alkaline solution, or the like, and a wiring electrode layer is formed by sputtering. do. Therefore, in order to prevent an element from deteriorating or damaging by such a process, providing the protective film containing the thin film which is resistant to these processes is provided in the surface of an element. As a material for forming such a protective film, the thermosetting resin composition containing the polymer which has glycidyl group, for example is known (refer patent document 1 and patent document 2).

In addition, in a color liquid crystal display device, for example, a color liquid crystal display device of a super twisted nematic (STN) method or a thin film transistor (TFT) method, a bead-shaped spacer is formed on a protective film in order to maintain a uniform cell spacing of the liquid crystal layer. Bonding the panels after spreading is performed. Thereafter, the liquid crystal cell is sealed by thermocompression bonding of the sealing material, and a phenomenon in which the protective film in the portion where the beads are present is dented by heat and pressure applied at that time is a problem that the cell gap becomes uneven.

In particular, when manufacturing an STN type color liquid crystal display element, the precision of the bonding of a color filter and an opposing board | substrate must be performed very strictly, and a very high level | step difference planarization performance and heat-resistant withstand performance are calculated | required by a protective film.

In order to form such a protective film, the method of coating a resin liquid on board | substrates, such as a color filter, and forming it through a drying and hardening process is common. Conventionally, the spin type large size coating machine has been used for the coating of resin liquid, but the case using the slit type large size coating machine is increasing with the enlargement of a board | substrate. Also in any coating system, it is necessary for the external appearance to be favorable, without leaving a fog-like nonuniformity, the trace of the pin derived from a coating machine, etc. on the board | substrate after coating. In particular, in the spin method, a thick film portion called liquid regression is formed at the end of the substrate, and when the liquid regression is large, the glass area that can be used becomes small, which causes one decrease in yield.

For this reason, the development of the curable resin composition which was excellent in the planarization performance and showing the favorable external appearance also in various coating methods was strongly requested | required.

[Patent Document 1] Japanese Patent Application Laid-Open No. 5-78453

[Patent Document 2] Japanese Patent Application Laid-Open No. 2001-91732

This invention is made | formed based on the above circumstances, The objective is the composition which is excellent in planarization performance, and shows a favorable appearance also in various coating methods, the formation method of the protective film using this composition, and the protective film formed from the said composition. To provide.

Still other objects and advantages of the present invention will become apparent from the following description.

According to the present invention, the above object of the present invention, firstly, a polymer having a repeating unit derived from a polymerizable unsaturated compound having [A] an oxiranyl group or an oxetanyl group and a solvent represented by the following [B] It is achieved by the curable resin composition characterized by containing.

[In Formula 1, R ₁ is an alkyl group having 1 to 9 carbon atoms.]

The said objective of this invention is 2nd achieved by the protective film formed from the said curable resin composition.

The said object of this invention is 3rd achieved by the formation method of the protective film characterized by forming a film using the said curable resin composition, and then irradiating and / or heat-processing a radiation.

According to the present invention, any of the spin coating method or the slit coating method may be used to form a protective film having a good appearance and excellent planarization ability without generating various irregularities, and furthermore, using the curable resin composition and the resin composition. A method of forming a protective film and a protective film formed of the composition are provided.

Hereinafter, each component of the resin composition of this invention is demonstrated.

[A] polymer

[A] polymer of this invention is a polymer which has a repeating unit derived from the polymerizable unsaturated compound which has an oxiranyl group or an oxetanyl group.

[A] The polymer is not limited as long as the above conditions are satisfied, and any of an addition polymer, a polyaddition polymer, and a polycondensation polymer may be used.

As a preferable [A] polymer in this invention, for example,

[A1] (a) Oxyranyl group or oxetanyl group-containing polymerizable unsaturated compound (hereinafter referred to as "unsaturated compound (a)") and (b1) polymerizable unsaturated carboxylic acid and / or polymerizable unsaturated polyvalent carboxyl Acid anhydride (hereinafter, collectively referred to as "unsaturated compound (b1)") and other polymerizable unsaturated compounds different from the unsaturated compound (a) and the unsaturated compound (b1) (hereinafter referred to as "unsaturated compound (b2)") Copolymer (hereinafter referred to as "copolymer [A1]");

[A2] Two or more oxiranyl groups or oxetanyl groups in the molecule, acetal ester structure of carboxylic acid, ketal ester structure of carboxylic acid, 1-alkylcycloalkylester structure of carboxylic acid and t of carboxylic acid A polymer having at least one structure selected from the group consisting of -butyl ester structures (hereinafter referred to as "polymer [A2]");

[A3] A copolymer of an unsaturated compound (a) and another polymerizable unsaturated compound different from the unsaturated compound (a) (hereinafter referred to as an "unsaturated compound (b5)") in a molecule with a carboxyl group and a carboxylic acid Copolymer which has neither anhydride group, acetal ester structure of carboxylic acid, ketal ester structure of carboxylic acid, 1-alkylcycloalkylester structure of carboxylic acid, and t-butylester structure of carboxylic acid (Hereafter, "Copolymer [A3]", etc. are mentioned.

In addition, as a polymer [A2], [A2-1] unsaturated compound (a), (b3) the acetal ester structure of carboxylic acid, the ketal ester structure of carboxylic acid, and the 1-alkylcycloalkyl ester structure of carboxylic acid And a polymerizable unsaturated compound having one or more structures selected from the group consisting of t-butyl ester structures of carboxylic acids (hereinafter referred to as "unsaturated compound (b3)"), (b4) unsaturated compounds (a) and More preferred are copolymers (hereinafter referred to as "copolymer [A2-1]") of another polymerizable unsaturated compound (hereinafter referred to as "unsaturated compound (b4)") different from the unsaturated compound (b3).

In addition, the copolymer [A1] further has an acetal ester structure of carboxylic acid, a ketal ester structure of carboxylic acid, a 1-alkylcycloalkyl ester structure of carboxylic acid and a t-butylester structure of carboxylic acid. The polymer [A2] may further contain a carboxyl group or a carboxylic anhydride group.

In copolymer [A1], copolymer [A2-1], and copolymer [A3], as an unsaturated compound (a), for example, (meth) acrylic-acid glycidyl, (alpha)-ethylacrylic-acid glycidyl, (alpha)- Glycidyl n-propyl acrylate, Glycidyl α-butyl acrylate, 3,4-Epoxybutyl (meth) acrylate, 3,4-Epoxybutyl α-ethyl acrylate, 6,7-epoxyheptyl (meth) acrylate , α-ethylacrylic acid 6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3-methyl-3- (meth) acryloyl Oxymethyl oxetane, 3-ethyl-3- (meth) acryloyloxymethyl oxetane, etc. are mentioned.

Of these unsaturated compounds (a), (meth) acrylic acid glycidyl, (meth) acrylic acid 6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glyc Cydyl ether, 3-methyl-3- (meth) acryloyloxymethyloxetane, 3-ethyl-3- (meth) acryloyloxymethyloxetane, and the like are preferable. These preferable unsaturated compounds (a) have high copolymerization reactivity and are effective for raising the heat resistance and surface hardness of the protective film obtained.

The said unsaturated compound (a) can be used individually or in mixture of 2 or more types.

In the copolymer [A1], as an unsaturated compound (b1), for example

Unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, α-ethylacrylic acid, α-n-propylacrylic acid, α-n-butylacrylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid;

Unsaturated polyhydric carboxylic acid anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, cis-1,2,3,4-tetrahydrophthalic anhydride

Etc. can be mentioned.

Among these unsaturated compounds (b1), as unsaturated carboxylic acid, acrylic acid and methacrylic acid are especially preferable, and as unsaturated polyhydric carboxylic anhydride, maleic anhydride is especially preferable. These preferable unsaturated compounds (b1) have high copolymerization reactivity and are effective for raising the heat resistance and surface hardness of the protective film obtained.

The said unsaturated compound (b1) can be used individually or in mixture of 2 or more types.

In addition, in a copolymer [A1], as an unsaturated compound (b2), for example,

(Meth) acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, (meth) acrylate sec (Meth) acrylic acid alkyl esters such as -butyl and t-butyl (meth) acrylate;

Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo (meth) acrylate (5.2.1.0 ^2,6 ) decane-8-yl (hereinafter tricyclo [5.2 .1.0 ^2,6 ] Decan-8-yl ("dicyclopentanyl"), (meth) acrylic acid alicyclic esters such as 2-dicyclopentanyloxyethyl (meth) acrylate, and isoboroyl (meth) acrylate ;

(Meth) acrylic acid aryl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate;

Unsaturated dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconic acid;

N-phenylmaleimide, N-benzyl maleimide, N-cyclohexyl maleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl- Unsaturated dicarbonylimide derivatives such as 6-maleimide caproate, N-succinimidyl-3-maleimide propionate, N- (9-acridyl) maleimide;

Vinyl cyanide compounds such as (meth) acrylonitrile, α-chloroacrylonitrile and vinylidene cyanide;

Unsaturated amide compounds such as (meth) acrylamide and N, N-dimethyl (meth) acrylamide;

Aromatic vinyl compounds such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene and p-methoxystyrene;

Indene derivatives such as indene and 1-methylindene;

In addition to conjugated diene-based compounds such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene,

Vinyl chloride, vinylidene chloride, vinyl acetate

Etc. can be mentioned.

Of these unsaturated compounds (b2), methyl methacrylate, t-butyl methacrylate, cyclohexyl acrylate, dicyclopentanyl methacrylate, 2-methylcyclohexyl acrylate, N-phenylmaleimide, and N-cyclohexyl maleimide , Styrene, p-methoxystyrene, 1,3-butadiene and the like are preferable. These preferred unsaturated compounds (b2) have a high copolymerization reactivity, and also provide the heat resistance (except for 1,3-butadiene) and surface hardness (except for 1,3-butadiene) of the protective film obtained. It is effective to raise.

The said unsaturated compound (b2) can be used individually or in mixture of 2 or more types.

As a preferable specific example of copolymer [A1]

Glycidyl acrylate / acrylic acid / dicyclopentanyl / styrene copolymers,

Methacrylic acid glycidyl / methacrylic acid / methacrylic acid dicyclopentanyl / styrene copolymer,

Glycidyl methacrylate / methacrylic acid / methyl methacrylate / styrene copolymer,

Glycidyl methacrylate / methacrylic acid / cyclohexyl acrylate / p-methoxystyrene copolymer,

Glycidyl acrylate / acrylic acid / N-phenylmaleimide / styrene copolymer,

Methacrylic acid glycidyl / methacrylic acid / N-phenylmaleimide / styrene copolymer,

Methacrylic acid glycidyl / methacrylic acid / N-cyclohexylmaleimide / styrene copolymer,

Methacrylic acid glycidyl / methacrylic acid / methacrylic acid dicyclopentanyl / 1,3-butadiene copolymer,

Methacrylic acid 6,7-epoxyheptyl / methacrylic acid / methacrylic acid dicyclopentanyl / styrene copolymer,

Methacrylic acid glycidyl / methacrylic acid / methacrylic acid dicyclopentanyl / styrene / 1,3-butadiene copolymer,

Methacrylic acid 6,7-epoxyheptyl / acrylic acid / maleic anhydride / styrene copolymer,

Methacrylic acid 6,7-epoxyheptyl / acrylic acid / maleic anhydride / methacrylic acid t-butyl copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / acrylic acid / acrylic acid dicyclopentanyl / styrene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid / methacrylic acid dicyclopentanyl / styrene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid / methyl methacrylate / styrene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid / cyclohexyl acrylate / p-methoxystyrene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / acrylic acid / N-phenylmaleimide / styrene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid / N-phenylmaleimide / styrene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid / N-cyclohexylmaleimide / styrene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid / methacrylic dicyclopentanyl / 1,3-butadiene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid / methacrylic acid dicyclopentanyl / styrene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid / methacrylate dicyclopentanyl / styrene / 1,3-butadiene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / acrylic acid / maleic anhydride / styrene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / acrylic acid / maleic anhydride / methacrylic acid t-butyl copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / acrylic acid / acrylic acid dicyclopentanyl / styrene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid / methacrylic dicyclopentanyl / styrene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid / methyl methacrylate / styrene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid / cyclohexyl acrylate / p-methoxystyrene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / acrylic acid / N-phenylmaleimide / styrene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid / N-phenylmaleimide / styrene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid / N-cyclohexylmaleimide / styrene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid / methacrylic acid dicyclopentanyl / 1,3-butadiene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid / methacrylic dicyclopentanyl / styrene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid / methacrylate dicyclopentanyl / styrene / 1,3-butadiene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / acrylic acid / maleic anhydride / styrene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / acrylic acid / maleic anhydride / methacrylic acid t-butyl copolymer

Etc. can be mentioned.

Among these copolymers [A1], more preferably

Methacrylate glycidyl / methacrylic acid / methacrylate dicyclopentanyl / styrene copolymer,

Methacrylic acid glycidyl / methacrylic acid / N-phenylmaleimide / styrene copolymer,

Methacrylic acid glycidyl / methacrylic acid / N-cyclohexylmaleimide / styrene copolymer,

Methacrylic acid glycidyl / methacrylic acid / methacrylic acid dicyclopentanyl / 1,3-butadiene copolymer,

Methacrylic acid glycidyl / methacrylic acid / methacrylic acid dicyclopentanyl / styrene / 1,3-butadiene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid / N-phenylmaleimide / styrene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid / N-cyclohexylmaleimide / styrene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid / N-phenylmaleimide / styrene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid / N-cyclohexylmaleimide / styrene copolymer

And so on.

 In the copolymer [A1], the content of the repeating unit derived from the unsaturated compound (a) is preferably 10 to 70% by weight, particularly preferably 20 to 60% by weight. (b1) The total content of repeating units derived from polymerizable unsaturated carboxylic acid and polymerizable unsaturated polyhydric carboxylic anhydride is preferably 5 to 40% by weight, particularly preferably 10 to 30% by weight. (b2) The content rate of the repeating unit derived from another polymerizable unsaturated compound becomes like this. Preferably it is 10 to 70 weight%, Especially preferably, it is 20 to 50 weight%.

Here, the repeating unit derived from the repeating unit + unsaturated compound (b1) derived from an unsaturated compound (a), and the repeating unit derived from an unsaturated compound (b2) = 100 weight%.

When the content rate of the repeating unit derived from an unsaturated compound (a) is less than 10 weight%, there exists a tendency for the heat resistance and surface hardness of a protective film to fall, and when it exceeds 70 weight%, there exists a tendency for the storage stability of a composition to fall. . Moreover, when the total content rate of the repeating unit derived from (b1) polymerizable unsaturated carboxylic acid and polymerizable unsaturated polyhydric carboxylic anhydride is less than 5 weight%, there exists a tendency for the heat resistance, surface hardness, and chemical-resistance of a protective film to fall. On the other hand, when it exceeds 40 weight%, there exists a tendency for the storage stability of a composition to fall. Moreover, when the content rate of the repeating unit derived from (b2) another polymerizable unsaturated compound is less than 10 weight%, there exists a tendency for the storage stability of a composition to fall, and when it exceeds 70 weight%, the heat resistance and surface hardness of a protective film will be It tends to be lowered.

Next, the polymer (A2) is selected from the group consisting of an acetal ester structure of carboxylic acid, a ketal ester structure of carboxylic acid, a 1-alkylcycloalkyl ester structure of carboxylic acid and a t-butylester structure of carboxylic acid. It has one or more types of structures. The polymer (A2) is not particularly limited as long as the above requirements are satisfied, and any of an addition polymer, a polyaddition polymer, a polycondensation polymer, and the like may be used.

The acetal ester structure of carboxylic acid is a structure represented by following formula (2).

[Formula 2, R ₂ and R ₃ are independently from each other an alkyl group having 1 to 20 carbon atoms, an alicyclic group having 3 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, R ₂ and R ₃ are bonded to each other ring May be formed, and (*) represents a residue which removed the carboxyl group from the carboxylic acid.]

As a group which couple | bonds with a carboxyl group and forms the acetal ester structure of carboxylic acid, it is a 1-methoxyethoxy group, 1-ethoxyethoxy group, 1-n-propoxyethoxy group, 1-i-, for example. Propoxyethoxy group, 1-n-butoxyethoxy group, 1-i-butoxyethoxy group, 1-sec-butoxyethoxy group, 1-t-butoxyethoxy group, 1-cyclopentyl Oxyethoxy group, 1-cyclohexyloxyethoxy group, 1-norbornyloxyethoxy group, 1-bornyloxyethoxy group, 1-phenoxyethoxy group, 1- (1-naphthyloxy) Ethoxy group, 1-benzyloxyethoxy group, 1-phenethyloxyethoxy group,

(Cyclohexyl) (methoxy) methoxy group, (cyclohexyl) (ethoxy) methoxy group, (cyclohexyl) (n-propoxy) methoxy group, (cyclohexyl) (i-propoxy) methoxy group, ( Cyclohexyl) (cyclohexyloxy) methoxy group, (cyclohexyl) (phenoxy) methoxy group, (cyclohexyl) (benzyloxy) methoxy group, (phenyl) (methoxy) methoxy group, (phenyl) (ethoxy ) Methoxy group, (phenyl) (n-propoxy) methoxy group, (phenyl) (i-propoxy) methoxy group, (phenyl) (cyclohexyloxy) methoxy group, (phenyl) (phenoxy) methoxy group, (Phenyl) (benzyloxy) methoxy group, (benzyl) (methoxy) methoxy group, (benzyl) (ethoxy) methoxy group, (benzyl) (n-propoxy) methoxy group, (benzyl) (i-propoxy ) Methoxy group, (benzyl) (cyclohexyloxy) methoxy group, (benzyl) (phenoxy) methoxy group, (benzyl) (benzyloxy) methoxy group, 2-tetrahydrofuranyloxy group, 2-tetrahydropyranyl jade Season, etc. can be mentioned.

Among these, 1-ethoxyethoxy group, 1-n-propoxyethoxy group, 1-cyclohexyloxyethoxy group, 2-tetrahydrofuranyloxy group, 2-tetrahydropyranyloxy group, etc. are preferable.

The ketal ester structure of carboxylic acid is a structure represented by following formula (3).

[In Formula 3, R <_3> -R <_5> represents a C1-C20 alkyl group, a C3-C20 alicyclic group, or a C6-C20 aromatic hydrocarbon group independently of each other, (*) represents a carboxyl group from a carboxylic acid. Indicates residues removed]

As a group which couple | bonds with a carboxyl group and forms the ketal ester structure of carboxylic acid, it is a 1-methyl-1- methoxyethoxy group, 1-methyl-1- ethoxyethoxy group, 1-methyl-1-, for example. n-propoxyethoxy group, 1-methyl-1-i-propoxyethoxy group, 1-methyl-1-n-butoxyethoxy group, 1-methyl-1-i-butoxyethoxy group, 1-methyl-1-sec-butoxyethoxy group, 1-methyl-1-t-butoxyethoxy group, 1-methyl-1-cyclopentyloxyethoxy group, 1-methyl-1-cyclohexyloxy Ethoxy group, 1-methyl-1-norbornyloxyethoxy group, 1-methyl-1-bornyloxyethoxy group, 1-methyl-1-phenoxyethoxy group, 1-methyl-1- ( 1-naphthyloxy) ethoxy group, 1-methyl-1-benzyloxyethoxy group, 1-methyl-1-phenethyloxyethoxy group, 1-cyclohexyl-1-methoxyethoxy group, 1-cyclo Hexyl-1-ethoxyethoxy group, 1-cyclohexyl-1-n-propoxyethoxy group, 1-cyclohexyl-1-i-propoxyethoxy group, 1-cyclohexyl-1-cyclohexyloxy Ethoxy group, 1-cyclohexyl -1-phenoxyethoxy group, 1-cyclohexyl-1-benzyloxyethoxy group, 1-phenyl-1-methoxyethoxy group, 1-phenyl-1-ethoxyethoxy group, 1-phenyl- 1-n-propoxyethoxy group, 1-phenyl-1-i-propoxyethoxy group, 1-phenyl-1-cyclohexyloxyethoxy group, 1-phenyl-1-phenoxyethoxy group, 1 -Phenyl-1-benzyloxyethoxy group, 1-benzyl-1-methoxyethoxy group, 1-benzyl-1-ethoxyethoxy group, 1-benzyl-1-n-propoxyethoxy group, 1 -Benzyl-1-i-propoxyethoxy group, 1-benzyl-1-cyclohexyloxyethoxy group, 1-benzyl-1-phenoxyethoxy group, 1-benzyl-1-benzyloxyethoxy group, 1-methoxycyclopentyloxy group, 1-methoxycyclohexyloxy group, 2- (2-methyltetrahydrofuranyl) oxy group, 2- (2-methyltetrahydropyranyl) oxy group, etc. are mentioned. .

Among these, 1-methyl-1-methoxyethoxy group, 1-methyl-1-cyclohexyloxyethoxy group, etc. are preferable.

As a group which forms the 1-alkylcycloalkylester structure of carboxylic acid, it is a 1-methylcyclopropyl group, 1-methylcyclobutyl group, 1-methylcyclopentyl group, 1-methylcyclohexyl group, 1-, for example. Methylcycloheptyl group, 1-methylcyclooctyl group, 1-methylcyclononyl group, 1-methylcyclodecyl group, 1-ethylcyclopropyl group, 1-ethylcyclobutyl group, 1-ethylcyclopentyl group, 1-ethyl Cyclohexyl group, 1-ethylcycloheptyl group, 1-ethylcyclooctyl group, 1-ethylcyclononyl group, 1-ethylcyclodecyl group, 1- (iso) propylcyclopropyl group, 1- (iso) propylcyclobutyl Group, 1- (iso) propylcyclopentyl group, 1- (iso) propylcyclohexyl group, 1- (iso) propylcycloheptyl group, 1- (iso) propylcyclooctyl group, 1- (iso) propylcyclono Neyl group, 1- (iso) propylcyclodecyl group, 1- (iso) butylcyclopropyl group, 1- (iso) butylcyclobutyl group, 1- (iso) butylcyclopentyl group, 1- (iso) moiety Cyclohexyl group, 1- (iso) butylcycloheptyl group, 1- (iso) butylcyclooctyl group, 1- (iso) butylcyclononyl group, 1- (iso) butylcyclodecyl group, 1- (iso) pentyl Cyclopropyl group, 1- (iso) pentylcyclobutyl group, 1- (iso) pentylcyclopentyl group, 1- (iso) pentylcyclohexyl group, 1- (iso) pentylcycloheptyl group, 1- (iso) pentyl Cyclooctyl group, 1- (iso) pentylcyclononyl group, 1- (iso) pentylcyclodecyl group, 1- (iso) hexylcyclopropyl group, 1- (iso) hexylcyclobutyl group, 1- (iso ) Hexylcyclopentyl group, 1- (iso) hexylcyclohexyl group, 1- (iso) hexylcycloheptyl group, 1- (iso) hexylcyclooctyl group, 1- (iso) hexylcyclononyl group , 1- (iso) hexylcyclodecyl group, 1- (iso) heptylcyclopropyl group, 1- (iso) heptylcyclobutyl group, 1- (iso) heptylcyclopentyl group, 1- (iso) heptylcyclohexyl Real group, 1- (iso) heptylcycloheptyl group, 1- (iso) heptylcyclooctyl group, 1- (iso) heptylcyclononyl , 1- (iso) heptylcyclodecyl group, 1- (iso) octylcyclopropyl group, 1- (iso) octylcyclobutyl group, 1- (iso) octylcyclopentyl group, 1- (iso) octylcyclohexyl group , 1- (iso) octylcycloheptyl group, 1- (iso) octylcyclooctyl group, 1- (iso) octylcyclononyl group, 1- (iso) octylcyclodecyl group, and the like.

Compared with the case where a copolymer [A1] is used for a polymer [A2], the one-part curable resin composition ((alpha)) mentioned later which is excellent in storage stability and excellent also in the planarization ability of the protective film obtained can be obtained.

 In the copolymer [A2-1], as an unsaturated compound (b3), it has 1 or more types of structures chosen from the group which consists of an acetal structure, a ketal structure, a cyclic cycloalkane structure, and t-butoxycarbonyl structure, for example. Norbornene-based compounds (hereinafter referred to as "specific norbornene-based compounds"); (Meth) acrylic acid ester compound having an acetal structure and / or a ketal structure and / or a cyclic cycloalkane structure (hereinafter referred to as a "specific (meth) acrylic acid ester compound") or (meth) acrylic acid t-butyl

Etc. can be mentioned.

As a specific example of a specific norbornene-type compound

2,3-di (1-methoxyethoxycarbonyl) -5-norbornene,

2,3-di (1-t-butoxyethoxycarbonyl) -5-norbornene,

2,3-di (1-benzyloxyethoxycarbonyl) -5-norbornene,

2,3-di (1-methyl-1-methoxyethoxycarbonyl) -5-norbornene,

2,3-di (1-methyl-1-i-butoxyethoxycarbonyl) -5-norbornene,

2,3-di ((cyclohexyl) (ethoxy) methoxycarbonyl) -5-norbornene,

2,3-di ((benzyl) (ethoxy) methoxycarbonyl) -5-norbornene,

2,3-di (tetrahydrofuran-2-yloxycarbonyl) -5-norbornene,

2,3-di (tetrahydropyran-2-yloxycarbonyl) -5-norbornene,

2,3-di (t-butoxycarbonyl) -5-norbornene

Etc. can be mentioned.

As a specific example of a specific (meth) acrylic acid ester compound, (meth) acrylic acid 1-ethoxyethyl, (meth) acrylic acid 1-n-propoxyethyl, (meth) acrylic acid 1-n-butoxyethyl, (meth) acrylic acid 1- i-butoxyethyl, (meth) acrylic acid 1- (cyclopentyloxy) ethyl, (meth) acrylic acid 1- (cyclohexyloxy) ethyl, (meth) acrylic acid 1- (1,1-dimethylethoxy) ethyl, (Meth) acrylic acid tetrahydro-2H-pyran-2-yl, 1-ethylcyclopentyl (meth) acrylate, 1-ethylcyclohexyl (meth) acrylate, 1- (iso) propylcyclopentyl (meth) acrylate And 1- (iso) propylcyclohexyl (meth) acrylate, 1- (iso) butylcyclopentyl (meth) acrylate, 1- (iso) butylcyclohexyl (meth) acrylate, and the like.

Among these unsaturated compounds (b3), specific (meth) acrylic acid ester compounds and t-butyl (meth) acrylate are preferable, and in particular, methacrylic acid 1-ethoxyethyl, methacrylic acid 1-i-butoxyethyl and methacryl Acid 1- (cyclopentyloxy) ethyl, methacrylic acid 1- (cyclohexyloxy) ethyl, methacrylic acid 1- (1,1-dimethylethoxy) ethyl, methacrylic acid tetrahydro-2H-pyran-2 -Yl, 1-ethylcyclopentyl (meth) acrylate, 1-ethylcyclohexyl (meth) acrylate, t-butyl methacrylate and the like are particularly preferred. These preferable unsaturated compounds (b3) have a high copolymerization reactivity and are excellent in the planarization ability of a protective film, acquire the below-mentioned one-component curable resin composition ((alpha)) and one-component curable resin composition ((alpha) 2), and at the same time, heat resistance and surface of the protective film obtained Effective for increasing hardness.

The said unsaturated compound (b3) can be used individually or in mixture of 2 or more types.

In the copolymer [A2-1], examples of the unsaturated compound (b4) include the same compounds as those exemplified for the unsaturated compound (b1) and the unsaturated compound (b2).

Of these unsaturated compounds (b4), methyl methacrylate, cyclohexyl acrylate, dicyclopentanyl methacrylate, 2-methylcyclohexyl acrylate, N-phenylmaleimide, N-cyclohexyl maleimide, styrene, p-methoxy Styrene, 1,3-butadiene and the like are preferred. These preferred unsaturated compounds (b4) have a high copolymerization reactivity, and also exhibit the heat resistance (except for 1,3-butadiene) and surface hardness (except for 1,3-butadiene) of the protective film obtained. It is effective to raise.

The said unsaturated compound (b4) can be used individually or in mixture of 2 or more types.

As a preferable specific example of copolymer [A2-1]

Glycidyl methacrylate / tetrahydro-2H-pyran-2-yl / methacrylate dicyclopentanyl / styrene copolymer,

Methacrylate glycidyl / methacrylate tetrahydro-2H-pyran-2-yl / methacrylate dicyclopentanyl / styrene copolymer,

Glycidyl methacrylate / tetrahydro-2H-pyran-2-yl / N-phenylmaleimide / styrene copolymer,

Glycidyl methacrylate / methacrylic acid tetrahydro-2H-pyran-2-yl / N-phenylmaleimide / styrene copolymer,

Glycidyl methacrylate / tetrahydro-2H-pyran-2-yl / N-cyclohexylmaleimide / styrene copolymer,

Glycidyl methacrylate / methacrylic acid tetrahydro-2H-pyran-2-yl / N-cyclohexylmaleimide / styrene copolymer,

Glycidyl methacrylate / acrylic acid 1- (cyclohexyloxy) ethyl / methacrylic acid dicyclopentanyl / styrene copolymer,

Glycidyl methacrylate / methacrylic acid 1- (cyclohexyloxy) ethyl / methacrylic acid dicyclopentanyl / styrene copolymer,

Glycidyl methacrylate / acrylic acid 1- (cyclohexyloxy) ethyl / N-cyclohexylmaleimide / styrene copolymer,

Methacrylic acid glycidyl / methacrylic acid 1- (cyclohexyloxy) ethyl / N-cyclohexylmaleimide / styrene copolymer,

Glycidyl methacrylate / 2,3-di (tetrahydropyran-2-yloxycarbonyl) -5-norbornene / methacrylic acid dicyclopentanyl / styrene copolymer,

Glycidyl methacrylate / 2,3-di (tetrahydropyran-2-yloxycarbonyl) -5-norbornene / N-cyclohexylmaleimide / styrene copolymer,

Glycidyl methacrylate / tetrahydro-2H-pyran-2-yl / methacrylate dicyclopentanyl / 1,3-butadiene copolymer,

Glycidyl methacrylate / methacrylic acid tetrahydro-2H-pyran-2-yl / methacrylate dicyclopentanyl / 1,3-butadiene copolymer,

Glycidyl methacrylate / tetrahydro-2H-pyran-2-yl / methyl methacrylate / styrene copolymer,

Glycidyl methacrylate / methacrylate tetrahydro-2H-pyran-2-yl / methyl methacrylate / styrene copolymer,

Glycidyl methacrylate / tetrahydro-2H-pyran-2-yl / cyclohexyl acrylate / p-methoxystyrene copolymer,

Glycidyl methacrylate / methacrylic acid tetrahydro-2H-pyran-2-yl / cyclohexyl acrylate / p-methoxystyrene copolymer,

Glycidyl acrylate / methacrylic acid t-butyl / N-phenylmaleimide / styrene copolymer,

Glycidyl methacrylate / methacrylic acid t-butyl / N-cyclohexylmaleimide / styrene copolymer,

Methacrylic acid 6,7-epoxyheptyl / acrylic acid tetrahydro-2H-pyran-2-yl / methacrylate t-butyl / maleic anhydride copolymer,

Methacrylic acid 6,7-epoxyheptyl / methacrylic acid tetrahydro-2H-pyran-2-yl / methacrylic acid t-butyl / maleic anhydride copolymer,

Methacrylic acid 6,7-epoxyheptyl / methacrylic acid t-butyl / methacrylate dicyclopentanyl / styrene copolymer,

Methacrylic acid 6,7-epoxyheptyl / methacrylic acid t-butyl / maleic anhydride / styrene copolymer,

Glycidyl methacrylate / acrylic acid 1- (cyclohexyloxy) ethyl / methacrylate dicyclopentanyl / styrene / 1,3-butadiene copolymer,

Glycidyl methacrylate / methacrylic acid 1- (cyclohexyloxy) ethyl / methacrylate dicyclopentanyl / styrene / 1,3-butadiene copolymer,

Glycidyl methacrylate / 1-ethylcyclopentylacrylate / N-phenylmaleimide / styrene copolymer,

Glycidyl methacrylate / 1-ethylcyclohexyl acrylate / N-phenylmaleimide / styrene copolymer,

Glycidyl methacrylate / 1-ethylcyclopentylacrylate / N-phenylmaleimide / styrene / methacrylic acid copolymer,

Glycidyl methacrylate / 1-ethylcyclopentylacrylate / dicyclopentanyl / styrene methacrylate,

Glycidyl methacrylate / 1-ethylcyclohexyl acrylate / dicyclopentanyl / styrene methacrylate,

3-methyl-3- (meth) acryloyloxymethyloxetane / tetrahydro-2H-pyran-2-yl / methacrylate dicyclopentanyl / styrene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / methacrylate tetrahydro-2H-pyran-2-yl / methacrylate dicyclopentanyl / styrene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / acrylic acid tetrahydro-2H-pyran-2-yl / N-phenylmaleimide / styrene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid tetrahydro-2H-pyran-2-yl / N-phenylmaleimide / styrene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / acrylic acid tetrahydro-2H-pyran-2-yl / N-cyclohexylmaleimide / styrene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid tetrahydro-2H-pyran-2-yl / N-cyclohexylmaleimide / styrene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / acrylic acid 1- (cyclohexyloxy) ethyl / methacrylate dicyclopentanyl / styrene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / methacrylate 1- (cyclohexyloxy) ethyl / methacrylate dicyclopentanyl / styrene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / acrylic acid 1- (cyclohexyloxy) ethyl / N-cyclohexylmaleimide / styrene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid 1- (cyclohexyloxy) ethyl / N-cyclohexylmaleimide / styrene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / 2,3-di (tetrahydropyran-2-yloxycarbonyl) -5-norbornene / methacrylic acid dicyclopentanyl / styrene copolymer ,

3-methyl-3- (meth) acryloyloxymethyloxetane / 2,3-di (tetrahydropyran-2-yloxy carbonyl) -5-norbornene / N-cyclohexylmaleimide / styrene copolymer ,

3-methyl-3- (meth) acryloyloxymethyloxetane / tetrahydro-2H-pyran-2-yl / dicyclopentanyl / 1,3-butadiene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / methacrylate tetrahydro-2H-pyran-2-yl / methacrylate dicyclopentanyl / 1,3-butadiene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / acrylic acid tetrahydro-2H-pyran-2-yl / methyl methacrylate / styrene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / methacrylate tetrahydro-2H-pyran-2-yl / methyl methacrylate / styrene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / tetrahydro-2H-pyran-2-yl / cyclohexyl acrylate / p-methoxystyrene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / methacrylate tetrahydro-2H-pyran-2-yl / cyclohexyl acrylate / p-methoxystyrene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid t-butyl / N-phenylmaleimide / styrene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid t-butyl / N-cyclohexylmaleimide / styrene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / acrylic acid tetrahydro-2H-pyran-2-yl / methacrylate t-butyl / maleic anhydride copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / methacrylate tetrahydro-2H-pyran-2-yl / methacrylate t-butyl / maleic anhydride copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / methacrylate t-butyl / methacrylate dicyclopentanyl / styrene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid t-butyl / maleic anhydride / styrene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / acrylic acid 1- (cyclohexyloxy) ethyl / methacrylate dicyclopentanyl / styrene / 1,3-butadiene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / methacrylate 1- (cyclohexyloxy) ethyl / methacrylate dicyclopentanyl / styrene / 1,3-butadiene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / 1-ethylcyclopentylacrylate / N-phenylmaleimide / styrene copolymer,

Glycidyl methacrylate / 1-ethylcyclohexyl acrylate / N-phenylmaleimide / styrene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / 1-ethylcyclopentylacrylate / N-phenylmaleimide / styrene / methacrylic acid copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / 1-ethylcyclopentylacrylate / methacrylic acid dicyclopentanyl / styrene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane-ethylcyclohexyl acrylate / methacryl dicyclopentanyl / styrene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / acrylic acid tetrahydro-2H-pyran-2-yl / methacrylate dicyclopentanyl / styrene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / methacrylate tetrahydro-2H-pyran-2-yl / methacrylate dicyclopentanyl / styrene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / acrylic acid tetrahydro-2H-pyran-2-yl / N-phenylmaleimide / styrene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid tetrahydro-2H-pyran-2-yl / N-phenylmaleimide / styrene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / acrylic acid tetrahydro-2H-pyran-2-yl / N-cyclohexylmaleimide / styrene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid tetrahydro-2H-pyran-2-yl / N-cyclohexylmaleimide / styrene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / acrylic acid 1- (cyclohexyloxy) ethyl / methacrylate dicyclopentanyl / styrene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / methacrylate 1- (cyclohexyloxy) ethyl / methacrylate dicyclopentanyl / styrene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / acrylic acid 1- (cyclohexyloxy) ethyl / N-cyclohexylmaleimide / styrene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid 1- (cyclohexyloxy) ethyl / N-cyclohexylmaleimide / styrene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / 2,3-di (tetrahydropyran-2-yloxylcarbonyl) -5-norbornene / methacrylic acid dicyclopentanyl / styrene aerial coalescence,

3-ethyl-3- (meth) acryloyloxymethyloxetane / 2,3-di (tetrahydropyran-2-yloxycarbonyl) -5-norbornene / N-cyclohexylmaleimide / styrene copolymer ,

3-ethyl-3- (meth) acryloyloxymethyloxetane / tetrahydro-2H-pyran-2-yl / dicyclopentanyl / 1,3-butadiene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / methacrylate tetrahydro-2H-pyran-2-yl / methacrylate dicyclopentanyl / 1,3-butadiene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / acrylic acid tetrahydro-2H-pyran-2-yl / methyl methacrylate / styrene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / methacrylate tetrahydro-2H-pyran-2-yl / methyl methacrylate / styrene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / tetrahydro-2H-pyran-2-yl / cyclohexyl acrylate / p-methoxystyrene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / methacrylate tetrahydro-2H-pyran-2-yl / cyclohexyl acrylate / p-methoxystyrene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid t-butyl / N-phenylmaleimide / styrene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid t-butyl / N-cyclohexylmaleimide / styrene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / acrylic acid tetrahydro-2H-pyran-2-yl / methacrylate t-butyl / maleic anhydride copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid tetrahydro-2H-pyran-2-yl / methacrylic acid t-butyl / maleic anhydride copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / methacrylate t-butyl / methacrylate dicyclopentanyl / styrene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / t-butyl methacrylate / maleic anhydride / styrene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / acrylic acid 1- (cyclohexyloxy) ethyl / methacrylate dicyclopentanyl / styrene / 1,3-butadiene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / methacrylate 1- (cyclohexyloxy) ethyl / methacrylate dicyclopentanyl / styrene / 1,3-butadiene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / 1-ethylcyclopentylacrylate / N-phenylmaleimide / styrene copolymer,

Glycidyl methacrylate / 1-ethylcyclohexyl acrylate / N-phenylmaleimide / styrene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / 1-ethylcyclopentylacrylate / N-phenylmaleimide / styrene / methacrylic acid copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / 1-ethylcyclopentylacrylate / methacrylic acid dicyclopentanyl / styrene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / 1-ethylcyclohexylacrylate / methacryl dicyclopentanyl / styrene copolymer

Etc. can be mentioned.

Among these copolymers [A2-1], more preferably

Glycidyl methacrylate / tetrahydro-2H-pyran-2-yl / methacrylate dicyclopentanyl / styrene copolymer,

Methacrylate glycidyl / methacrylate tetrahydro-2H-pyran-2-yl / methacrylate dicyclopentanyl / styrene copolymer,

Glycidyl methacrylate / tetrahydro-2H-pyran-2-yl / N-phenylmaleimide / styrene copolymer,

Glycidyl methacrylate / methacrylic acid tetrahydro-2H-pyran-2-yl / N-phenylmaleimide / styrene copolymer,

Glycidyl methacrylate / tetrahydro-2H-pyran-2-yl / N-cyclohexylmaleimide / styrene copolymer,

Glycidyl methacrylate / methacrylic acid tetrahydro-2H-pyran-2-yl / N-cyclohexylmaleimide / styrene copolymer,

Glycidyl methacrylate / acrylic acid 1- (cyclohexyloxy) ethyl / N-cyclohexylmaleimide / styrene copolymer,

Methacrylic acid glycidyl / methacrylic acid 1- (cyclohexyloxy) ethyl / N-cyclohexylmaleimide / styrene copolymer,

Glycidyl methacrylate / 2,3-di (tetrahydropyran-2-yloxycarbonyl) -5-norbornene / methacryl dicyclopentanyl / styrene copolymer,

Glycidyl methacrylate / 2,3-di (tetrahydropyran-2-yloxycarbonyl) -5-norbornene / N-cyclohexylmaleimide / styrene copolymer,

Glycidyl methacrylate / methacrylic acid t-butyl / N-cyclohexylmaleimide / styrene copolymer,

Glycidyl methacrylate / 1-ethylcyclopentylacrylate / N-phenylmaleimide / styrene copolymer,

Glycidyl methacrylate / 1-ethylcyclohexyl acrylate / N-phenylmaleimide / styrene copolymer,

Glycidyl methacrylate / 1-ethylcyclopentylacrylate / N-phenylmaleimide / styrene / methacrylic acid copolymer,

Glycidyl methacrylate / 1-ethylcyclopentylmethacrylate / N-phenylmaleimide / styrene copolymer,

Glycidyl methacrylate / 1-ethylcyclohexyl methacrylate / N-phenylmaleimide / styrene copolymer,

Glycidyl methacrylate / 1-ethylcyclopentyl methacrylate / N-phenylmaleimide / styrene / methacrylic acid copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / methacrylate tetrahydro-2H-pyran-2-yl / methacrylate dicyclopentanyl / styrene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid tetrahydro-2H-pyran-2-yl / N-phenylmaleimide / styrene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid tetrahydro-2H-pyran-2-yl / N-cyclohexylmaleimide / styrene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / acrylic acid 1- (cyclohexyloxy) ethyl / N-cyclohexylmaleimide / styrene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid 1- (cyclohexyloxy) ethyl / N-cyclohexylmaleimide / styrene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid t-butyl / N-cyclohexylmaleimide / styrene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / 1-ethylcyclopentyl methacrylate / N-phenylmaleimide / styrene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / 1-ethylcyclohexyl methacrylate / N-phenylmaleimide / styrene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / methacrylate tetrahydro-2H-pyran-2-yl / methacrylate dicyclopentanyl / styrene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid tetrahydro-2H-pyran-2-yl / N-phenylmaleimide / styrene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid tetrahydro-2H-pyran-2-yl / N-cyclohexylmaleimide / styrene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / acrylic acid 1- (cyclohexyloxy) ethyl / N-cyclohexylmaleimide / styrene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid 1- (cyclohexyloxy) ethyl / N-cyclohexylmaleimide / styrene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid t-butyl / N-cyclohexylmaleimide / styrene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / 1-ethylcyclopentyl methacrylate / N-phenylmaleimide / styrene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / 1-ethylcyclohexyl methacrylate / N-phenylmaleimide / styrene copolymer

And so on.

In the copolymer [A2-1], the content rate of the repeating unit derived from the unsaturated compound (a) is preferably 10 to 70% by weight, particularly preferably 20 to 60% by weight based on the total repeating units. When the content rate of the repeating unit derived from an unsaturated compound (a) is less than 10 weight%, there exists a tendency for the heat resistance and surface hardness of a protective film to fall, and when it exceeds 70 weight%, there exists a tendency for the storage stability of a composition to fall. .

Moreover, the content rate of the repeating unit derived from an unsaturated compound (b3) becomes like this. Preferably it is 5 to 60 weight%, Especially preferably, it is 10 to 50 weight%. By carrying out the content rate of the repeating unit derived from an unsaturated compound (b3) in this range, the favorable heat resistance and surface hardness of a protective film can be implement | achieved.

In addition, the content rate of the repeating unit derived from an unsaturated compound (b4) becomes the amount which subtracted the total content rate of the repeating unit derived from an unsaturated compound (a) and an unsaturated compound (b3) from 100 weight%, As an unsaturated compound (b4) When using an unsaturated carboxylic acid or unsaturated polyhydric carboxylic anhydride, when the total content rate of the repeating unit derived from these exceeds 40 weight%, there exists a possibility that the storage stability of a composition may be impaired, and it does not exceed this value. It is preferable not to.

Next, in a copolymer [A3], the same thing as the compound illustrated about the said unsaturated compound (b2) is mentioned as an unsaturated compound (b5), for example.

Of these unsaturated compounds (b5), methyl methacrylate, cyclohexyl acrylate, dicyclopentanyl methacrylate, 2-methylcyclohexyl acrylate, N-phenylmaleimide, N-cyclohexyl maleimide, styrene, p-methoxy Styrene, 1,3-butadiene and the like are preferred. These preferred unsaturated compounds (b5) have a high copolymerization reactivity, and also have a difference in the heat resistance (except for 1,3-butadiene) and surface hardness (except for 1,3-butadiene) of the protective film obtained. It is effective to raise.

The said unsaturated compound (b5) can be used individually or in mixture of 2 or more types.

As a preferable specific example of copolymer [A3]

Acrylic acid glycidyl / styrene copolymer,

Methacrylate glycidyl / styrene copolymer,

Glycidyl acrylate / methacrylic acid dicyclopentanyl copolymer,

Methacrylate glycidyl / methacrylate dicyclopentanyl copolymer,

Methacrylic acid 6,7-epoxyheptyl / styrene copolymer,

Methacrylate glycidyl / methacrylate dicyclopentanyl / styrene copolymer,

Methacrylate glycidyl / N-phenylmaleimide / styrene copolymer,

Glycidyl methacrylate / N-cyclohexylmaleimide / styrene copolymer,

Methacrylic acid 6,7-epoxyheptyl / methacrylic acid dicyclopentanyl copolymer,

Methacrylic acid 6,7-epoxyheptyl / N-cyclohexylmaleimide / styrene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / styrene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid dicyclopentanyl copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid dicyclopentanyl / styrene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / N-phenylmaleimide / styrene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / N-cyclohexylmaleimide / styrene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / styrene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid dicyclopentanyl copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid dicyclopentanyl / styrene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / N-phenylmaleimide / styrene copolymer,

3-ethyl-3- (meth) acryloyloxymethyloxetane / N-cyclohexylmaleimide / styrene copolymer

Etc. can be mentioned.

Among these copolymers [A3], More preferably, methacrylic acid glycidyl / styrene copolymer, methacrylic acid glycidyl / methacrylate dicyclopentanyl copolymer, and methacrylic acid glycidyl / methacrylate Clofentanil / styrene copolymer, methacrylic acid glycidyl / N-cyclohexylmaleimide / styrene copolymer, 3-methyl-3- (meth) acryloyloxymethyloxetane / styrene copolymer, 3-ethyl-3 -(Meth) acryloyloxymethyloxetane / styrene copolymer.

 In the copolymer [A3], the content rate of the repeating unit derived from the unsaturated compound (a) is preferably 1 to 90% by weight, particularly preferably 40 to 90% by weight based on the total repeating units. When the content rate of the repeating unit derived from an unsaturated compound (a) is less than 1 weight%, there exists a tendency for the heat resistance and surface hardness of a protective film to fall, and when it exceeds 90 weight%, the heat resistance and the storage stability of a composition fall. There is this.

In addition, in copolymer [A3], the content rate of the repeating unit derived from an unsaturated compound (b5) becomes the quantity which reduced the content rate of the repeating unit derived from an unsaturated compound (a) from 100 weight%.

The above-mentioned [A] polymer preferably has a polystyrene reduced number average molecular weight (hereinafter sometimes referred to as "Mn") measured by gel permeation chromatography (elution solvent tetrahydrofuran), more preferably 1,000 to 100,000, more preferably 2,000 To 50,000, particularly preferably 3,000 to 40,000. When Mn is less than 1,000, the coating property of a composition may become inadequate, or the heat resistance of the protective film formed may be inadequate, while when Mn exceeds 100,000, planarization performance may become inadequate.

In addition, the molecular weight distribution (Mw / Mn) of the polymer [A] is preferably 5.0 or less, and more preferably 3.0 or less.

Such a polymer [A] is the said polymerizable unsaturated compound (a1), an unsaturated compound (b1), and an unsaturated compound (b2) in a copolymer [A1], In a copolymer [A2-1], an unsaturated compound (a), For the unsaturated compound (b3) and the unsaturated compound (b4), in the copolymer [A3], the unsaturated compound (a) and the unsaturated compound (b5) are respectively known methods in the presence of a suitable solvent and a suitable polymerization initiator, for example. It can synthesize | combine by radical polymerization.

For example, [A] polymer of this invention mixes 100 weight part of said monomer components with 100-400 weight part of polymerization solvents, such as diethylene glycol methyl ethyl ether and propylene glycol methyl ether acetate, and azobis as a polymerization initiator. 0.5-15 weight part of radical polymerization initiators, such as isobutyronitrile (AIBN) and 2,2'- azobis (2, 4- dimethylvaleronitrile), are added with respect to 100 weight part of total amounts of a monomer component, for example. It is obtained by polymerizing at 70 to 100 ° C for 3 to 10 hours.

(B) solvent

Curable resin composition of this invention is characterized by containing the solvent represented by the said General formula (1). R ₁ in Formula 1 is an alkyl group having 1 to 9 carbon atoms. This alkyl group may be linear, branched or cyclic.

Examples of the compound represented by the formula (1) include propylene glycol dimethyl ether, propylene glycol methyl ethyl ether, propylene glycol methyl propyl ether, propylene glycol methyl isopropyl ether, propylene glycol methyl butyl ether, propylene glycol methyl isobutyl ether, and propylene glycol. Methyl pentyl ether, propylene glycol methyl cyclopentyl ether, propylene glycol methyl hexyl ether, propylene glycol methyl cyclohexyl ether, propylene glycol methyl heptyl ether, propylene glycol methyl octyl ether, etc. are mentioned.

Among them, propylene glycol methyl propyl ether, propylene glycol methyl butyl ether, propylene glycol methyl pentyl ether, propylene glycol methyl isopropyl ether, and propylene glycol methyl isobutyl ether are preferably used.

The content of the solvent represented by the formula (1) is preferably 10% by weight or more, more preferably 15% by weight or more, and even more preferably 20% by weight or more with respect to the total amount of the solvent.

If the solvent represented by General formula (1) is less than 10 weight% among all the solvents, favorable coatability will not be obtained.

As a solvent other than the solvent represented by General formula (1), what melt | dissolves or disperse | distributes each component of a composition and does not react with each component is used preferably.

Examples of such other solvents include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol monoalkyl ethers, diethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol alkyl ether acetates, and propylene glycol alkyl ether pros. Cypionate, aromatic hydrocarbon, ketone, ester, etc. are mentioned.

As an example of these other solvent, For example, as alcohol, methanol, ethanol, benzyl alcohol, etc .;

As ether, tetrahydrofuran and the like;

As glycol ether, Ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, etc .;

As ethylene glycol alkyl ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, etc .;

As diethylene glycol monoalkyl ether, Diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, etc .;

As diethylene glycol dialkyl ether, Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc .;

As propylene glycol monoalkyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, etc .;

As propylene glycol alkyl ether acetates, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, etc .;

As propylene glycol alkyl ether propionate, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate, etc .;

As an aromatic hydrocarbon, toluene, xylene, etc .;

Examples of the ketone include methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl isoamyl ketone, and the like;

As the ester, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, hydroxide Ethyl hydroxyacetic acid, butyl hydroxyacetic acid, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxypropionate methyl, 3-hydroxypropionate ethyl, 3-hydroxypropionic acid propyl, 3-hydroxypropionate butyl, 2 -Methyl hydroxy-3-methylbutanoic acid, methyl methoxyacetate, ethyl methoxyacetic acid, methoxyacetic acid propyl, butyl acetate, ethoxyacetic acid methyl, ethoxyacetic acid ethyl, ethoxyacetic acid propyl, ethoxyacetic acid butyl Methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetic acid, butyl propoxyacetic acid, butoxy Methyl butyrate, ethyl butoxyacetate, butoxyacetic acid propyl, butyl butoxyacetic acid, 2-methoxypropionate methyl, 2-methoxypropionate ethyl, 2-methoxypropionic acid propyl, 2-methoxypropionic acid butyl, 2-e Methyl oxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, 2-butoxy Butyl propionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-ethoxypropionic acid Propyl, 3-Ethoxy Propionate, 3-Propoxy Propionate, 3-Propyl Propionate, 3-Propoxy Propionate, 3-Propoxy Propionate, 3-Butoxyprop Propionic acid methyl, 3-butoxy-ethyl, 3-butoxy propyl propionate, and 3-butoxy-propionic acid butyl, respectively.

Among them, alcohols, diethylene glycol dialkyl ethers, propylene glycol alkyl acetates, ethylene glycol alkyl ether acetates, diethylene glycol dialkyl ethers are preferable, and benzyl alcohol, diethylene glycol ethyl methyl ether, propylene glycol methyl ether acetate, Propylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate and diethylene glycol diethyl ether are preferable.

[B] As the usage-amount of a solvent (when using another solvent together, the said other solvent is included), content of the total solid (the amount remove | excluding the quantity of a solvent from the total amount of the composition containing a solvent) in the composition of this invention is preferable. Preferably it is the range of 1 to 50 weight%, More preferably, it is 5 to 40 weight%.

The said (B) solvent (including other solvent) can use a high boiling point solvent together with the said solvent. Here, as a high boiling point solvent which can be used together, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N- Methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, acetic acid benzyl, ethyl benzoate, oxalic acid di Ethyl, diethyl maleate, 7-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and the like.

As a usage-amount when using a high boiling point solvent together, Preferably it is 70 weight% or less with respect to the total solvent amount, More preferably, it is 60 weight% or less.

[C] hardener

According to the present invention, the curable resin composition wherein the component [A] is a copolymer [A3] further contains a curing agent [C], and the one-component curable resin composition (α) and (1) the component [A] are copolymers. The two-component curable resin composition (β) comprising a combination of a first component and a second component, wherein the curable resin composition as [A3] is used as the first component, and the second component (C) is the second component. Is provided. Curing agent [C] in these 1-component curable resin composition ((alpha) 1) and 2-component curable resin composition ((beta)) contains the compound which has 1 or more types of functional groups which can react with the epoxy group in copolymer [A3].

As a [C] hardening | curing agent, it is a copolymer of polyhydric carboxylic acid, polyhydric carboxylic anhydride, the said unsaturated polyhydric carboxylic anhydride, and another olefinic unsaturated compound (henceforth a "carboxylic anhydride group containing copolymer"). And the like).

As said polyhydric carboxylic acid, For example, aliphatic polyhydric carboxylic acids, such as succinic acid, glutaric acid, adipic acid, 1,2,3,4-butane tetracarboxylic acid, maleic acid, itaconic acid; Alicyclic polyhydric carboxylic acids such as hexahydrophthalic acid, 1,2-cyclohexane dicarboxylic acid, 1,2,4-cyclohexane tricarboxylic acid and cyclopentanetetracarboxylic acid; And aromatic polyhydric carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid and 1,2,5,8-naphthalenetetracarboxylic acid.

Among these polyhydric carboxylic acids, aromatic polyhydric carboxylic acids are preferred in view of the reactivity of the curable resin composition, the heat resistance of the protective film formed, and the like.

As said polyhydric carboxylic anhydride, itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarbanic acid, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, anhydride, for example Aliphatic dicarboxylic acid anhydrides such as himic acid; Alicyclic polyhydric carboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride and cyclopentane tetracarboxylic dianhydride; Aromatic polyhydric carboxylic acid anhydrides such as phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, and benzophenonetetracarboxylic anhydride; Ester group-containing acid anhydrides such as ethylene glycol bis anhydrous trimellitate and glycerin tris anhydrous trimellitate.

Among these polyhydric carboxylic anhydrides, aromatic polyhydric carboxylic anhydrides are preferred, and trimellitic anhydride is particularly preferable in that a protective film having high heat resistance can be obtained.

In the carboxylic anhydride group-containing copolymer, examples of the unsaturated polyvalent carboxylic anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, cis-1,2,3,4-tetrahydrophthalic anhydride, and the like. Can be mentioned. These unsaturated polyhydric carboxylic anhydrides can be used individually or in mixture of 2 or more types.

As other olefinically unsaturated compounds, for example, styrene, p-methylstyrene, p-methoxystyrene, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and (meth) acrylic acid i -Propyl, n-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, etc. Can be mentioned. These other olefinically unsaturated compounds can be used individually or in mixture of 2 or more types.

As a preferable specific example of a carboxylic acid anhydride group containing copolymer, maleic anhydride / styrene copolymer, a citraconic acid anhydride / dicyclopentanyl copolymer, etc. are mentioned.

The copolymerization ratio of the unsaturated polyvalent carboxylic anhydride in the carboxylic acid anhydride group-containing copolymer is preferably 1 to 80% by weight, more preferably 10 to 60% by weight. By using the copolymer of such a copolymerization ratio, the protective film excellent in the planarization ability can be obtained.

The number average molecular weight (Mn) of the carboxylic acid anhydride group-containing copolymer is preferably 500 to 50,000, more preferably 500 to 10,000. By using the copolymer of such a molecular weight range, the protective film excellent in the planarization ability can be obtained.

Said [C] hardener can be used individually or in mixture of 2 or more types.

[C] The amount of the curing agent used is preferably 1 to 100 parts by weight, more preferably 3 to 50 parts by weight based on 100 parts by weight of the copolymer [A3]. If it is less than 1 weight part, sufficient crosslinking density of a cured film may not be obtained and the various tolerances of this protective film may fall. On the other hand, when it exceeds 100 weight part, unreacted component [C] remains in the formed protective film, As a result, the property of the said protective film may become unstable, or the adhesiveness of a board | substrate and a protective film may fall.

[D] polyfunctional compounds

As the [D] polyfunctional compound used in the present invention, a cationically polymerizable compound and / or a polyfunctional (meth) acryl compound is used.

A cationically polymerizable compound is a compound (except the said [A1] component, [A2] component, and [A3] component) which has two or more oxiranyl group or oxetanyl group in a molecule | numerator. As a compound which has 2 or more oxiranyl group or an oxetanyl group in the said molecule, the compound which has 2 or more epoxy groups in a molecule | numerator, or the compound which has a 3, 4- epoxycyclohexyl group is mentioned, for example.

As a compound which has two or more epoxy groups in the said molecule, For example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogen Of bisphenol compounds such as added bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, and brominated bisphenol S diglycidyl ether Diglycidyl ether;

1,4-butanediol diglycidyl ether, 1,6-hexane diol diglycidyl ether, glycerin triglycidyl ether, trimethylol propane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol digly Polyglycidyl ethers of polyhydric alcohols such as cydyl ether;

Polyglycidyl ethers of polyether polyols obtained by adding one or two or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin;

Phenol novolac type epoxy resins;

Cresol novolac type epoxy resins;

Polyphenol type epoxy resins;

Diglycidyl esters of aliphatic long chain dibasic acids;

Glycidyl esters of higher fatty acids;

Epoxidized soybean oil, epoxidized linseed oil, etc. are mentioned.

As a commercial item of the compound which has two or more epoxy groups in the said molecule | numerator, it is a bisphenol-A epoxy resin, for example, Epicoat 1001, copper 1002, copper 1003, copper 1004, copper 1007, copper 1009, copper 1010, copper 828 (or more) Japan Epoxy Resin Co., Ltd.);

As bisphenol F type epoxy resin, Epicoat 807 (made by Japan Epoxy Resin Co., Ltd.) etc .;

As a phenol novolak-type epoxy resin, Epicoat 152, Copper 154, Copper 157S65 (above, Japan Epoxy Resin Co., Ltd. product), EPPN201, Copper 202 (above, Nippon Kayaku Co., Ltd. product) etc .;

As a cresol novolak-type epoxy resin, EOCN102, 103S, 104S, 1020, 1025, 1027 (above, Nippon Kayaku Co., Ltd.), Epicoat 180S75 (made by Japan Epoxy Resin Co., Ltd.), etc .;

As a polyphenol type epoxy resin, Epicoat 1032H60, XY-4000 (above, Japan Epoxy Resin Co., Ltd. product) etc. are mentioned;

As the cyclic aliphatic epoxy resin, CY-175, copper 177, copper 179, araldite CY-182, copper 192, 184 (above, manufactured by Ciba Specialty Chemicals Co., Ltd.), ERL-4234, 4299, 4221, 4206 ( UCC Co., Ltd.), Shodyne 509 (Showa Denko Co., Ltd.), Epiclone 200, Copper 400 (above, Dainippon Ink Co., Ltd.), Epicoat 871, Copper 872 (above, Japan epoxy resin (Manufactured by Co., Ltd.), ED-5661, 5662 (7 or more, manufactured by Celanese Coating Co., Ltd.), etc .;

Examples of the aliphatic polyglycidyl ethers include epolite 100MF (manufactured by Kyoesha Chemical Co., Ltd.), epiol TMP (manufactured by Nippon Yushi Co., Ltd.), and the like.

Examples of the compound having two or more 3,4-epoxycyclohexyl groups in the molecule include 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate and 2- (3,4 -Epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methyl Cyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dish Clopentadiene diepoxide, di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylenebis (3,4-epoxycyclohexanecarboxylate), lactone modified 3,4-epoxycyclohexylmethyl-3 ' And 4'-epoxycyclohexane carboxylate.

Among these cationic polymerizable compounds, phenol novolak type epoxy resins and polyphenol type epoxy resins are preferable.

On the other hand, as a polyfunctional (meth) acrylate compound, for example

Ethylene glycol di (meth) acrylate, 1,6-hexane diol di (meth) acrylate, 1,9-nonanediol (meth) acrylate, polypropylene glycol di (meth) acrylate, tetraethylene glycol di (meth ) Acrylate, bisphenoxyethanol fluorene diacrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythrate Lithol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, triacryloyloxypentaerythritol succinic acid {alias: 3-acryloyloxy-2 , 2-bisacryloyloxymethyl-propyl) ester}, diacryloyloxy pentaerythritol succinic acid {alias: 3-acryloyloxy-2-acryloyloxymethyl-propyl) ester}, pentaacrylo Iloxydefentae Litritol succinic acid {alias: [3- (3-acryloyloxy-2,2-bis-acryloyloxymethyl-propyl) -2,2-bis-acryloyloxymethyl-propyl] ester}}, tetra Acryloyloxydipentaerythritol succinic acid {alias: [3- (3-acryloyloxy-2,2-bis-acryloyloxymethyl-propyl) -2-acryloyloxymethyl-propyl] ester} Can be mentioned.

As its commercial item, for example, Aronix M-210, M-240, M-6200, M-309, M-400, M-402, M-405, M-450, M -7100, East M-8030, East M-8060 (manufactured by Toa Kosei Kogyo Co., Ltd.), KAYARAD HDDA, East HX-220, East R-604, East TMPTA, East DPHA, East DPCA-20, East DPCA-30 , East DPCA-60, East DPCA-120 (manufactured by Nippon Kayaku Co., Ltd.), Biscot 260, East 312, East 335 HP, East 295, East 300, East 360, East GPT, East 3PA, East 400 (O Osaka Yuki Kogyo Co., Ltd.) etc. are mentioned.

These are used alone or in combination.

The usage-amount of the [D] polyfunctional compound in the resin composition of this invention is per 100 weight part of total amounts of the [A] polymer, Preferably it is 3-200 weight part, More preferably, it is 5-100 weight part, Especially 10- 50 parts by weight. [D] When the usage-amount of a polyfunctional compound is more than 200 weight part, a problem may arise in the coating property of a composition, and when it is less than 3 weight part, the hardness of the protective film obtained may be insufficient.

[E] acid generator

Irradiation of radiation among the compounds (hereinafter, referred to as "[E] acid generator") which generate | occur | produce an acid by irradiation of [E] radiation and / or heating in a one-component curable resin composition ((alpha) 2) mentioned later. The generation of acid by means of a "radiation acid generator" is called the "radiation acid generator" which generates acid by heating.

As a radiation sensitive acid generator, a diaryl iodonium salt, a triaryl sulfonium salt, a diaryl phosphonium salt, etc. are mentioned, for example, These can all be used preferably.

As the thermal acid generator, for example, sulfonium salts (except the triarylsulfonium salts), benzothiazonium salts, ammonium salts, and phosphonium salts (except the diarylphosphonium salts), etc. The sulfonium salt and the benzothiazonium salt are preferable among these.

Among the radiation-sensitive acid generators, examples of the diaryl iodonium salt include diphenyl iodonium tetrafluoroborate, diphenyl iodonium hexafluorophosphonate, and diphenyl iodonium hexafluoro arse. Nitrate, diphenyl iodonium trifluoromethanesulfonate, diphenyl iodonium trifluoroacetate, diphenyl iodonium p-toluenesulfonate, 4-methoxyphenylphenyl iodonium tetrafluoroborate, 4 -Methoxyphenylphenyl iodonium hexafluorophosphonate, 4-methoxyphenylphenyl iodonium hexafluoroarsenate, 4-methoxyphenylphenyl iodonium trifluoromethanesulfonate, 4-methoxy Methoxyphenylphenyl iodonium trifluoroacetate, 4-methoxyphenylphenyl iodonium p-toluenesulfonate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis (4-t-butyl Phenyl) iodonium hexafluoroarsenei , Bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium trifluoroacetate, bis (4-t-butylphenyl) iodonium p-toluenesulfonate etc. are mentioned.

Among these diaryl iodonium salts, diphenyl iodonium hexafluorophosphonate is particularly preferable.

As the triarylsulfonium salt, for example, triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, and triphenylsulfonium trifluoro Methanesulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium p-toluenesulfonate, 4-methoxyphenyldiphenylsulfoniumtetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluoroforce Fonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfoniumtrifluoroacetate, 4 -Methoxyphenyldiphenylsulfonium p-toluenesulfonate, 4-phenylthiophenyldiphenyltetrafluoroborate, 4-phenylthiophenyldiphenylhexafluorophosphonate, 4-phenylthiophenyldiphenylhexane Fluoroarsenate, 4-phenylthiophenyldiphenyltrifluoromethanesulfonate, 4-phenylthiophenyldiphenyltrifluoroacetate, 4-phenylthiophenyldiphenyl p-toluenesulfonate, and the like. .

Among these triarylsulfonium salts, triphenylsulfonium trifluoro? Tantansulfonate is particularly preferable.

Moreover, as said diaryl phosphonium salt, (1-6- (eta)-cumene) ((eta) -cyclopentadienyl) iron hexafluoro phosphonate etc. are mentioned, for example.

In the commercial item of a radiation sensitive acid generator, as a diaryliodonium salt, it is UVI-6950, UVI-6970, UVI-6974, UVI-6990 (above, Union Carbide company make), for example; MPI-103, BBI-103 (above, Midori Kagaku Co., Ltd.), etc. are mentioned.

As the triarylsulfonium salt, for example, Adeka Optomer SP-150, Adeka Optomer SP-151, Adeka Optomer SP-170, Adeka Optomer SP-171 (above, Asahi Denka Kogyo Co., Ltd.) ) Produce); CI-2481, CI-2624, CI-2639, CI-2064 (above, Nihon Soda Co., Ltd. product); DTS-102, DTS-103, NAT-103, NDS-103, TPS-103, MDS-103 (above, manufactured by Midori Kagaku Co., Ltd.); CD-1010, CD-1011, CD-1012 (above, the Satomer company), etc. are mentioned.

Examples of the diaryl phosphonium salt include Irgacure-261 (manufactured by Ciba Specialty Chemicals Co., Ltd.); PCI-061T, PCI-062T, PCI-020T, PCI-022T (above, Nippon Kayaku Co., Ltd.), etc. are mentioned.

Among these commercial items, the protective film obtained has UVI-6970, UVI-6974, UVI-6990, Adeka Optomer SP-170, Adeka Optomer SP-171, CD-1012, MPI-103, and the like. It is preferable at the point.

The radiation sensitive acid generators may be used alone or in combination of two or more thereof.

Next, as a sulfonium salt in a thermal acid generator, for example,

4-acetophenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbonyloxy) phenylsulfonium hexafluoroantimonate, Dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro-4-acetoxyphenylsulfonium hexa Alkylsulfonium salts such as fluoroantimonate;

Benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, benzyl- 4-methoxyphenylmethylsulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium Benzylsulfonium salts such as hexafluoroarsenate and 4-methoxybenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate;

Dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, dibenzyl-4-acetoxyphenylsulfonium hexafluoroantimonate, di Benzyl-4-methoxyphenylsulfonium hexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5 dibenzylsulfonium salts such as -t-butylphenylsulfonium hexafluoroantimonate and benzyl-4-methoxybenzyl-4-hydroxyphenylsulfonium hexafluorophosphate;

4-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-nitro benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-chlorobenzyl-4-hydroxyphenyl Methylsulfonium hexafluorophosphate, 4-nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoro Substituted benzyl sulfonium salts, such as an antimonate and 2-chlorobenzyl-3- chloro-4- hydroxyphenyl methyl sulfonium hexafluoro antimonate, etc. are mentioned.

Of these sulfonium salts, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroanti Monate, dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-acetoxyphenylsulfonium hexafluoroantimonate, etc. are preferable.

As the benzothiazonium salt, for example, 3-benzylbenzothiazonium hexafluororumonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, 3- ( 4-methoxybenzyl) benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate Benzyl benzothiazonium salt, such as these, etc. are mentioned. Among these benzothiazonium salts, 3-benzylbenzothiazonium hexafluoroantimonate is particularly preferable.

As a commercially available product of a thermal acid generator, as an alkyl sulfonium salt, Adeka Opton CP-66, Adeka Opton CP-77 (above, Asahi Denka Kogyo Co., Ltd. product) etc. are mentioned, for example.

As the benzylsulfonium salt, for example, SI-60, SI-80, SI-100, SI-110, SI-145, SI-150, SI-80L, SI-100L, SI-110L KK Kogyo Co., Ltd.) etc. are mentioned.

Among these commercial items, SI-80, SI-100, SI-110, etc. are preferable at the point which the protective film obtained has high surface hardness.

The said thermal acid generator can be used individually or in mixture of 2 or more types.

The amount of the acid generator [E] used in the resin composition of the present invention is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, particularly 1 to 1, per 100 parts by weight of the total amount of the polymer [A]. 5 parts by weight. If the amount of the acid generator (E) is more than 20 parts by weight, heat coloring resistance may deteriorate. On the other hand, when it is less than 0.1 weight part, hardening does not fully advance and hardness may become inadequate.

Embodiment of curable resin composition

If the preferable embodiment of each curable resin composition of this invention is shown more concretely, the thing of following (I)-(IV) is mentioned.

(I) [A] polymer (preferably one or more types of group consisting of copolymer [A1], polymer [A2] and copolymer [A3]), and (D) polyfunctional compound. One-component type curable further containing the following optional additional components, wherein the amount of the cationically polymerizable compound is preferably 3 to 100 parts by weight, more preferably 5 to 50 parts by weight based on 100 parts by weight of the polymer (A). Resin composition (α).

In this one-component curable resin composition (α), a protective film having sufficient surface hardness can be obtained by setting the amount of the polyfunctional compound to be in the above range. This one-component curable resin composition (α) is particularly excellent in long-term storage stability.

(II) Copolymer [A3], [C] hardening | curing agent, and [D] polyfunctional compound are contained, Optionally, it further contains the following optional additives, and with respect to 100 weight part of copolymers [A3] , [D] The amount of the polyfunctional compound is preferably 3 to 100 parts by weight, more preferably 5 to 50 parts by weight, and the amount of the [C] curing agent is preferably 20 to 60 parts by weight, more preferably. Preferably it is 20-50 weight part (referred to as 1-component curable resin composition ((alpha) 1)).

In this one-component curable resin composition (α1), by using the amount of the [C] curing agent in the above range, it exhibits good curing characteristics and does not impair various characteristics of the protective film.

In addition, this one-component curable resin composition (? 1) is preferably provided for use within 24 hours after production.

(III) A 1st component containing the combination of (1) copolymer [A3], the 1st component containing [D] polyfunctional compound, etc., and (2) the 2nd component containing [C] hardening | curing agent, And / or the second component optionally further contains the following optional additive components, and the amount of the [D] polyfunctional compound to 100 parts by weight of the copolymer [A3] is preferably 3 to 100 weight. Part, More preferably, it is 5-50 weight part, and the usage-amount of [C] hardening | curing agent becomes like this. Preferably it is 20-60 weight part, More preferably, it is 20-50 weight part, Two-component curable resin composition ((beta)).

In this two-component curable resin composition (β), by using the amount of the [C] curing agent in the above range, good curing characteristics are exhibited and various characteristics of the protective film are not impaired.

In addition, this two-component curable resin composition (β) is preferably provided for use within 24 hours after mixing of the first component and the second component.

In addition, when manufacturing the 1-component curable resin composition ((alpha) 1) and the 2-component curable resin composition ((beta)) of (III), [C] hardening | curing agent is normally used as the solution melt | dissolved in a suitable solvent. The concentration of the [C] curing agent in the solution is preferably 5 to 50% by weight, more preferably 10 to 40% by weight.

(IV) [A] a polymer (preferably at least 1 type of group which consists of a copolymer [A1], a polymer [A2], and a copolymer [A3]), a [D] polyfunctional compound, and (E) acid generation The agent, and optionally further contains the following optional additives, and the amount of the [D] polyfunctional compound is preferably 3 to 100 parts by weight, based on 100 parts by weight of the total of [A] polymer, It is more preferably 5 to 50 parts by weight, and the amount of the [E] acid generator is preferably 20 parts by weight or less, more preferably 0.05 to 20 parts by weight, particularly preferably 0.1 to 10 parts by weight. Curable Resin Composition (α2).

In this one-component curable resin composition (? 2), by using an acid generator in the above range, good curing characteristics are exhibited and various characteristics of the protective film are not impaired.

Preparation of Curable Resin Composition of the Present Invention

The resin composition of this invention is manufactured by melt | dissolving or disperse | distributing each said component uniformly in the solvent containing the [B] solvent.

The composition prepared as described above may be used for use after filtration and separation using a Millipore filter having a pore size of preferably 0.2 to 3.0 μm, more preferably about 0.2 to 0.5 μm, and the like.

These one-component curable resin compositions (α), one-component curable resin compositions (α1), one-component curable resin compositions (α2), and two-component curable resin compositions (β) have a protective film formed therefrom even in various coating methods. It exhibits good coating properties, satisfies required transparency, heat resistance, surface hardness, and adhesion, and is excellent in load resistance even under heating, and excellent in flattening the level difference of the color filter formed on the base substrate.

Optional additive ingredients

To the curable resin composition of the present invention, any optional components other than those described above, for example, surfactants, adhesion aids, curing accelerators, and the like can be blended in a range that does not impair the effects of the present invention as necessary.

The surfactant is added to improve the applicability of the composition.

As such surfactant, Preferably, fluorine-type surfactant, silicone type surfactant, nonionic surfactant, such as polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene dialkyl ester, etc. are mentioned, for example.

As said polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, etc. are mentioned, for example, As said polyoxyethylene aryl ether, it is polyoxy, for example. Ethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, and the like. As said polyoxyethylene dialkyl ester, polyoxyethylene dilaurate, polyoxyethylene distearate, etc. are mentioned, for example.

As a fluorine-type surfactant among the commercial items of surfactant, For example, BM-1000 and BM-1100 (above, BM CHIMID company make); Megapack F142D, Megapack F172, Megapack F173, Megapack F183, Megapack R08-MH (above, manufactured by Dainippon Ink Chemical Industries, Ltd.); Fluoride FC-135, Fluoride FC-170C, Fluoride FC-430, Fluoride FC-431 (above, Sumitomo 3M Co., Ltd. product); Footgent 250, copper 251, copper 222F, FTX-218 (above, Neos Co., Ltd.), Suplon S-112, Suplon S-113, Suplon S-131, Suplon S-141, Suplon S-145, Suplon S-382, Suplon SC-101, Suplon SC-102, Suplon SC-103, Suplon SC-104, Suplon SC-105, Suplon SC-106 (above, Asahi Glass Co., Ltd.) etc. are mentioned.

As the silicone surfactant, for example, SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (above, manufactured by Toray Dow Corning Silicon Co., Ltd.); KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); F-top DF301, f-top DF303, f-top DF352 (above, manufactured by Shin-Akita Kasei Co., Ltd.), and the like.

Moreover, as another commercial item of surfactant, polyflow No. 57 which is a (meth) acrylic-acid type copolymer, polyflow No. 90 (above, Kyoesha Chemical Co., Ltd. product), etc. are mentioned.

The blending amount of the surfactant is preferably 5 parts by weight or less, and more preferably 2 parts by weight or less, based on 100 parts by weight of the polymer [A]. When the compounding quantity of surfactant exceeds 5 weight part, it exists in the tendency for the film roughness of a coating film to occur easily.

In addition, the said adhesion | attachment adjuvant is added in order to improve adhesiveness with the protective film formed, a board | substrate, etc ..

As such an adhesion | attachment adjuvant, the silane coupling agent which has reactive groups, such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group, an epoxy group, is preferable, for example.

As a specific example of an adhesion | attachment adjuvant, for example, trimethoxy silyl benzoic acid, (gamma) -methacryloxypropyl trimethoxysilane, vinyl triacetoxy silane, vinyl trimethoxysilane, 7-isocyanate propyl triethoxysilane, (gamma) -glycid Doxypropyl trimethoxysilane, (beta)-(3, 4- epoxycyclohexyl) ethyl trimethoxysilane, etc. are mentioned.

The compounding quantity of an adhesion | attachment adjuvant becomes like this. Preferably it is 30 weight part or less, More preferably, it is 25 weight part or less with respect to 100 weight part of (A) polymers. When the compounding quantity of an adhesion | attachment adjuvant exceeds 30 weight part, there exists a possibility that the heat resistance of the protective film obtained may become inadequate.

As a curing accelerator, for example, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 2,4-diamino-6- [2'-methyl Imidazolyl- (1 ')]-ethyl-S-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1')]-ethyl-S-triazine, 2 , 4-Diamino-6- [2'-ethyl-4'-methylimidazolyl undecylimidazolyl- (1 ')]-ethyl-S-triazine, 2-phenyl-4,5-dihydrate Oxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenylimidazole isocyanuric acid adduct, 2,4-diamino-6- [2'-methyl Imidazolyl- (1 ')]-ethyl-S-triazine isocyanuric acid addition product etc. are mentioned.

As addition amount of a hardening accelerator, it is preferable to add 0.0001-10 weight part with respect to 100 weight part of [A] polymers. It is more preferable to add 0.001 to 1 part by weight in terms of heat resistance and storage stability.

How to form a protective film

Next, the method of forming the protective film of this invention using each curable resin composition of this invention is demonstrated.

In the case of the one-component curable resin composition (α), the one-component curable resin composition (α1) and the (E) one-component curable resin composition (α2) using a thermal acid generator as the acid generator, the composition solution is applied onto a substrate. After forming a film by prebaking and removing a solvent, the target protective film can be formed by heat processing.

In addition, the two-component curable resin composition (β), in the use thereof, after mixing the first component and the second component to prepare a composition solution, preferably applying the composition solution on the substrate within 24 hours after production The target protective film can be formed by heat-processing after forming a film by prebaking and removing a solvent.

As a board | substrate which forms a protective film, what consists of glass, quartz, silicone, a transparent resin, etc. can be used, for example.

Examples of the transparent resin include polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, polyimide, ring-opening polymers of cyclic olefins, hydrogenated substances thereof and the like.

As the coating method, for example, a spraying method, a roll coating method, a rotary coating method, a bar coating method, an inkjet method, or the like can be adopted. Particularly, a spin coater, a slit and spin coater, a spinless coater, and a slit die coater The applied coating is preferably used.

Although the conditions of the said prebaking differ according to the kind, compounding ratio, etc. of each component, Preferably it is about 1 to 15 minutes at 70-140 degreeC.

The heat treatment after film formation can be performed by a suitable heating apparatus, such as a hotplate and oven.

As for the processing temperature at the time of heat processing, about 150-250 degreeC is preferable, and also as for processing time, about 5 to 30 minutes when using a hotplate as a heating apparatus, about 30 to 90 minutes are preferable when using an oven.

In addition, in the case of the resin composition using the radiation sensitive acid generator (E) as an acid generator, after forming a film by apply | coating a composition solution on a board | substrate, and prebaking and removing a solvent, the radiation irradiation process (exposure process) The target protective film can be formed by performing a heat treatment after that as needed.

In this case, the same thing as the above can be used as a board | substrate, and the formation method of a coating film can be performed similarly to the above.

As the radiation used for the exposure treatment, for example, visible rays, ultraviolet rays, far ultraviolet rays, electron beams, X-rays and the like can be employed, but ultraviolet rays containing light having a wavelength of 190 to 450 nm are preferable.

Exposure amount becomes like this. Preferably it is 100-20,000 J / m <2>, More preferably, it is 150-10,000 J / m <2>.

150-250 degreeC is preferable for the processing temperature at the time of the heat processing after an exposure process, and the processing time is about 30 to 90 minutes when using an oven for about 5 to 30 minutes when using a hotplate as a heating apparatus. Degree is preferred.

The film thickness of the protective film thus formed is preferably 0.1 to 8 µm, more preferably 0.1 to 6 µm, and still more preferably 0.1 to 4 µm. However, when a protective film is formed on the board | substrate which has the level | step difference of a color filter, the said film thickness means the thickness in the uppermost part of a color filter.

The protective film of the present invention exhibits good coating properties in various coating methods, satisfies required transparency, heat resistance, surface hardness, adhesiveness, and the like, and has excellent load resistance even under heating, and reduces generation of sublimation during firing. It is excellent in the performance of flattening the level difference of the color filter formed on the base substrate, and is particularly preferable as a protective film for an optical device.

Although a synthesis example and an Example are described to the following and this invention is demonstrated to it further more concretely, this invention is not limited to a following example.

Preparation of (co) polymer

Synthesis Example 1

5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol methylethyl ether were added to a flask equipped with a cooling tube and a stirrer. Subsequently, 40 parts by weight of glycidyl methacrylate, 10 parts by weight of styrene, 30 parts by weight of methacrylic acid, and 20 parts by weight of cyclohexylmaleimide were added thereto, followed by nitrogen substitution, followed by slow stirring. The solution temperature was raised to 70 ° C, and the temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-1). Solid content concentration of the obtained polymer solution was 33.1 weight%. The number average molecular weight of the obtained polymer was 7,000 (number average molecular weight is polystyrene conversion molecular weight measured using GPC (gel permeation chromatography) HLC-8020 (made by Tosoh Corporation)). Moreover, molecular weight distribution (Mw / Mn) was 2.

Synthesis Example 2

5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol methylethyl ether were added to a flask equipped with a cooling tube and a stirrer. Subsequently, 40 parts by weight of glycidyl methacrylate, 10 parts by weight of styrene, 30 parts by weight of tetrahydro-2H-pyran-2-yl methacrylate and 20 parts by weight of dicyclopentanyl methacrylate were added, followed by nitrogen substitution. Agitation was started. The solution temperature was raised to 70 ° C, and the temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (A-2). Solid content concentration of the obtained polymer solution was 33.0 weight%. The number average molecular weight of the obtained polymer was 6,000. In addition, the molecular weight distribution (Mw / Mn) was 2.0.

Synthesis Example 3

5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol methylethyl ether were added to a flask equipped with a cooling tube and a stirrer. Subsequently, 40 parts by weight of glycidyl methacrylate, 10 parts by weight of styrene, 30 parts by weight of t-butyl methacrylate and 20 parts by weight of dicyclopentanyl methacrylate were added thereto, followed by nitrogen substitution, followed by slow stirring. The solution temperature was raised to 70 ° C., and the temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (A-3). Solid content concentration of the obtained polymer solution was 32.8 weight%. The number average molecular weight of the obtained polymer was 6,500. In addition, the molecular weight distribution (Mw / Mn) was 2.0.

Synthesis Example 4

5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol methylethyl ether were added to a flask equipped with a cooling tube and a stirrer. Subsequently, 40 parts by weight of glycidyl methacrylate, 10 parts by weight of styrene, 30 parts by weight of 1-ethylcyclopentyl methacrylate and 20 parts by weight of cyclohexylmaleimide were added thereto, followed by nitrogen substitution, followed by slow stirring. The solution temperature was raised to 70 ° C. and maintained at this temperature for 5 hours to obtain a polymer solution containing a copolymer (A-4). Solid content concentration of the obtained polymer solution was 33.3 weight%. The number average molecular weight of the obtained polymer was 6,500. In addition, the molecular weight distribution (Mw / Mn) was 2.0.

Synthesis Example 5

5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol methylethyl ether were added to a flask equipped with a cooling tube and a stirrer. Subsequently, 40 parts by weight of glycidyl methacrylate, 10 parts by weight of styrene, 30 parts by weight of 1-ethylcyclopentyl methacrylate, 5 parts by weight of methacrylic acid and 15 parts by weight of cyclohexylmaleimide were added, followed by nitrogen substitution. Agitation was started. The solution temperature was raised to 70 ° C, and this temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (A-5). Solid content concentration of the obtained polymer solution was 33.5 weight%. The number average molecular weight of the obtained polymer was 6,000. In addition, the molecular weight distribution (Mw / Mn) was 2.0.

Synthesis Example 6

5 parts by weight of 2,2'-azobis-isobutyronitrile and 200 parts by weight of diethylene glycol methylethyl ether were added to a flask equipped with a cooling tube and a stirrer. Subsequently, 70 parts by weight of glycidyl methacrylate and 30 parts by weight of styrene were added, nitrogen was substituted, and stirring was slowly started. The solution temperature was raised to 70 ° C., and the temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (A-6). Solid content concentration of the obtained polymer solution was 33.1 weight%. The number average molecular weight of the obtained polymer was 5,000. In addition, the molecular weight distribution (Mw / Mn) was 2.0.

Synthesis Example 7

5 parts by weight of 2,2'-azobis-isobutyronitrile and 200 parts by weight of diethylene glycol methylethyl ether were added to a flask equipped with a cooling tube and a stirrer. Subsequently, 50 parts by weight of glycidyl methacrylate and 50 parts by weight of styrene were added, nitrogen was substituted, and stirring was started slowly. The solution temperature was raised to 70 ° C, and the temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (A-7). Solid content concentration of the obtained polymer solution was 32.6 weight%. The number average molecular weight of the obtained polymer was 5,500. In addition, the molecular weight distribution (Mw / Mn) was 2.0.

Synthesis Example 8

5 parts by weight of 2,2'-azobis-isobutyronitrile and 200 parts by weight of diethylene glycol methylethyl ether were added to a flask equipped with a cooling tube and a stirrer. Subsequently, 80 parts by weight of glycidyl methacrylate and 20 parts by weight of styrene were added thereto, and after nitrogen replacement, stirring was started slowly. The solution temperature was raised to 70 ° C., and the temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (A-8). Solid content concentration of the obtained polymer solution was 33.0 weight%. The number average molecular weight of the obtained polymer was 5,500. In addition, the molecular weight distribution (Mw / Mn) was 2.0.

Synthesis Example 9

5 parts by weight of 2,2'-azobis-isobutyronitrile and 200 parts by weight of diethylene glycol methylethyl ether were added to a flask equipped with a cooling tube and a stirrer. Subsequently, 50 parts by weight of 6,7-epoxyheptyl methacrylic acid and 50 parts by weight of styrene were added, nitrogen was substituted, and stirring was started slowly. The solution temperature was raised to 70 ° C., and the temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (A-9). Solid content concentration of the obtained polymer solution was 33.0 weight%. The number average molecular weight of the obtained polymer was 6,000. In addition, the molecular weight distribution (Mw / Mn) was 2.0.

Synthesis Example 10

5 parts by weight of 2,2'-azobis-isobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate were charged into a flask equipped with a cooling tube and a stirrer. Subsequently, 50 parts by weight of glycidyl methacrylate and 50 parts by weight of styrene were added, nitrogen was substituted, and stirring was started slowly. The solution temperature was raised to 70 ° C, and this temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (A-10). Solid content concentration of the obtained polymer solution was 33.0 weight%. The number average molecular weight of the obtained polymer was 5,500. In addition, the molecular weight distribution (Mw / Mn) was 2.0.

Preparation and Evaluation of Resin Compositions

Example 1 (evaluation of one-component curable resin composition (α))

Solution containing the copolymer (A-1) obtained by the said synthesis example 1 (amount corresponded to 100 weight part (solid content) of copolymer (A-1)), and (D-1) novolak-type epoxy resin (Japan epoxy Resin Co., Ltd. brand name: Epicoat 152) 40.0 parts by weight, (F) γ-glycidoxypropyltrimethoxysilane 20.0 parts by weight, FTX-218 (manufactured by Neos Co., Ltd.) as a surfactant 0.2 parts by weight was added and propylene glycol methyl butyl ether (B-1) and diethylene glycol ethyl methyl ether (B-3) were added at a weight ratio of 5 to 5 so that the solid content concentration was 15% by weight. A resin composition was prepared by filtration with a Millipore filter having a pore size of 0.5 μm.

Evaluation of the shield

(1) Evaluation of appearance

The composition was coated on a Cr substrate using a slit and spin coater and a slit coater to have a (dry) cured film thickness of 1.0 μm, vacuum dried at 100 Pa, and prebaked at 80 ° C. for 2 minutes to form a coating film. Then, the appearance was observed under a sodium lamp. Fog irregularities occurring throughout were evaluated as fog unevenness and nonuniformity derived from proxy pins in the preliminary baking as pin unevenness. (Circle) and the case where it sees a little, (triangle | delta) and the case where it looks reliably were made into the case where almost no nonuniformity was seen. In addition, when coating with a slit and spin coater, the part from which the film thickness of the board | substrate edge part was made into liquid return was measured, and the distance from the board | substrate edge to the location where liquid return did not generate | occur | produced was measured. The measurement was performed by n = 5, and made the average into liquid regression.

(2) evaluation of flatness

On a SiO ₂ deep glass substrate, a pigment-based color resist (brand names "JCR RED 689", "JCR GREEN 706", "CR 8200B", above, JSR Corporation make) is apply | coated with a spinner, and it is 90 on a hotplate. It prebaked at 150 degreeC and formed the coating film. Then, i-line conversion of ghi line (wavelength 436 nm, 405 nm, 365 nm intensity ratio = 2.7: 2.5: 4.8) using the exposure machine Canon PLA 501F (made by Canon Co., Ltd.) via a predetermined | prescribed pattern mask. Irradiated at an exposure dose of 2,000 J / m 2, developed using 0.05 wt% aqueous potassium hydroxide solution, washed with ultrapure water for 60 seconds, and further heated at 230 ° C. for 30 minutes in an oven, red, green, and Three colors of blue stripe-like color filters (stripe width 100 mu m) were formed.

It was 1.0 micrometer when the unevenness | corrugation of the surface of the board | substrate with which this color filter was formed was measured by the surface roughness meter "(alpha) -step" (brand name: Tenkor Corporation make). However, it measured by measurement length 2,000 micrometers, the measurement range 2,000 micrometers angle, and the measurement number n = 5. That is, the measurement direction is made into two directions of the stripe line short axis direction in the red, green, and blue directions and the stripe line major axis direction of the same colors of red, red, green, green, blue, and blue, and n = 5 for each direction. It measured (the n-number of the sum is 10).

After applying the composition for forming a protective film with a spinner thereon, the film is prebaked at 90 ° C. for 5 minutes on a hot plate to form a coating film, and further heated at 230 ° C. for 60 minutes in an oven. A protective film having a film thickness of 2.0 mu m was formed. However, the film thickness here means the thickness in the uppermost surface of the color filter formed on the board | substrate.

About the board | substrate which has a protective film on the color filter formed as mentioned above, the unevenness | corrugation of the surface of a protective film was measured by the contact type film thickness measuring apparatus (alpha) -step (made by Tencol Japan Co., Ltd.). However, it measured by the measurement length 2,000 micrometers, the measurement range 2,000 micrometers angle, and the measurement number n = 5. That is, the measurement direction is made into two directions of the stripe line short axis direction in the red, green, and blue directions and the stripe line major axis direction of the same colors of red, red, green, green, blue, and blue, and n = 5 for each direction. It was measured (n number of total is 10). The average value of ten times of the highest and lowest difference (nm) for each measurement is shown in Table 1 below. When this value is 300 nm or less, it can be said that planarization property is favorable.

Examples 2 to 11 and Comparative Example 1

The resin composition was manufactured like Example 1 except having set the kind and quantity of each component of a composition as Table 1, and using the solvent of Table 1 and adjusting to the solid content concentration of Table 1.

Using the resin composition for protective film formation manufactured as mentioned above, the protective film was formed like Example 1 and evaluated. The results are shown in Table 1.

Example 12 (Evaluation of Two-Liquid Curable Resin Composition (β))

A solution containing the copolymer (A-6) obtained in Synthesis Example 6 as the component (A) (amount equivalent to 100 parts by weight of the copolymer (A-6)), and a novolak-type epoxy as the component (D-1). 40.0 parts by weight of resin (Japan Epoxy Resin Co., Ltd. product name: Epicoat 152), (F) 20.0 parts by weight of γ-glycidoxypropyltrimethoxysilane as an adhesion aid, and FTX- as a (G-1) surfactant. 0.2 parts by weight of 218 (manufactured by Neos) is added, 1 part by weight of 1-benzyl-2-methylimidazole is mixed as a (H-1) curing accelerator, and (B-1) propylene glycol methyl butyl as a solvent. After adding 1,080 parts by weight of ether, it was filtered through a Millipore filter with a pore size of 0.5 mu m to prepare a solution of the first component.

Next, to the solution of the first component, a second component obtained by dissolving 40 parts by weight of trimellitic anhydride as 520 parts by weight of (B-3) diethylene glycol methylethyl ether as the component (C-1) was added to the solution of the composition. Was prepared.

The protective film was formed and evaluated similarly to Example 1 using the resin composition for protective film formation manufactured as mentioned above. The results are shown in Table 2 below.

Examples 13-15

The resin composition was produced like Example 12 except having adjusted the kind and quantity of each component of a composition as Table 2, and using the solvent of Table 2 to the solid content concentration of Table 2. Using the resin composition for protective film formation manufactured as mentioned above, the protective film was formed like Example 1 and evaluated. The results are shown in Table 2.

Examples 16-22 and Comparative Examples 2-3 (evaluation of 1-component curable resin composition ((alpha) 1))

The resin composition was manufactured like Example 1 except having adjusted the kind and quantity of each component of a composition to the solid content concentration of Table 2 using the solvent of Table 2 as described in Table 2.

Using the resin composition for protective film formation manufactured as mentioned above, the protective film was formed like Example 1 and evaluated. The results are shown in Table 2.

In addition, in Tables 1-2, [B] solvent, [C] hardening | curing agent, [D] polyfunctional monomer, [E] thermosensitive acid generator, [F] adhesion | attachment adjuvant, [G] surfactant, [H] The abbreviation of a hardening accelerator shows the following, respectively.

B-1: propylene glycol methyl butyl ether

B-2: propylene glycol methyl propyl ether

B-3: diethylene glycol methyl ethyl ether

B-4: Propylene Glycol Monomethyl Ether Acetate

C-1: trimellitic anhydride

D-1: Novolak-type epoxy resin (Japan Epoxy Resin Co., Ltd. product brand name: Epicoat 152)

D-2: dipentaerythritol hexaacrylate

D-3: A mixture of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentaacrylate and monoester compound with succinic acid (Toa Kosei Co., Ltd. product name: TO-1382)

D-4: Bisphenol A novolak-type epoxy resin (Japan Epoxy Resin Co., Ltd. product brand name: Epicoat 157S65)

E-1: benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate

F-1: γ-glycidoxypropyltrimethoxysilane

G-1: Fluorine-type surfactant (Neo Co., Ltd. brand name: FTX-218)

G-2: Silicone type surfactant (Toray Dow Corning Silicone Co., Ltd. brand name: SH-28PA)

G-3: fluorine-based surfactant (Dai Nippon Ink Co., Ltd. product name: Megapack R08-MH)

H-1: 1-benzyl-2-methylimidazole

H-2: 2-phenyl-4-methylimidazole-5-hydroxymethylimidazole

H-3: 2-phenyl-1-benzylimidazole

H-4: 2-phenyl-4-methylimidazole

Claims (12)

[A] A curable resin composition comprising a polymer having a repeating unit derived from a polymerizable unsaturated compound having an oxiranyl group or an oxetanyl group, and a solvent represented by the following [B] formula (1). <Formula 1>

[In Formula 1, R ₁ is an alkyl group having 1 to 9 carbon atoms.] 2. The component (A) according to claim 1, wherein the component (A) comprises (A) a polymerizable unsaturated compound having an oxiranyl group or an oxetanyl group, and (b1) a polymerizable unsaturated carboxylic acid and a polymerizable unsaturated polycarboxylic anhydride. Curable resin composition which is a copolymer of 1 or more types chosen from the group which consists of, and another polymerizable unsaturated compound different from (b) component and (b1) component. 2. The component (A) according to claim 1, wherein the component (A) is two or more oxiranyl groups or oxetanyl groups in the molecule (A2), an acetal ester structure of carboxylic acid, a ketal ester structure of carboxylic acid, and one of carboxylic acid. Curable resin composition which is a polymer which has 1 or more types of structure chosen from the group which consists of an alkylcycloalkyl ester structure and the t-butylester structure of carboxylic acid. The polymerizable unsaturated compound which [A2] component [A2-1] has [a2] an oxiranyl group or an oxetanyl group, (b3) Acetal ester structure of carboxylic acid, Ketal of carboxylic acid A polymerizable unsaturated compound having at least one structure selected from the group consisting of an ester structure, a 1-alkylcycloalkylester structure of a carboxylic acid and a t-butylester structure of a carboxylic acid, and (b4) the component (a) And (b3) a curable resin composition which is a copolymer of another polymerizable unsaturated compound different from the component. The copolymer of the polymerizable unsaturated compound in which [A] component has [A3] (a) oxiranyl group or oxetanyl group, and (b5) another polymerizable unsaturated compound different from the said (a) component. As a molecule, a carboxyl group, a carboxylic anhydride group, an acetal ester structure of a carboxylic acid, a ketal ester structure of a carboxylic acid, a 1-alkylcycloalkylester structure of a carboxylic acid and a t-butylester structure of a carboxylic acid Curable resin composition which is a copolymer which does not have all. Curable resin composition of Claim 5 which further contains a [C] hardening | curing agent. The two-component curable resin composition according to claim 6, comprising a combination of (1) a first component comprising the curable resin composition according to claim 5 and (2) a second component containing the [C] curing agent. The polyfunctional compound according to any one of claims 1 to 7, wherein the polyfunctional compound is a cationic polymerizable compound (except for the [A1] component, the [A2] component and the [A3] component) and the polyfunctional compound. Curable resin composition containing 1 or more types chosen from the group which consists of a (meth) acryl compound. (E) Curable resin composition as described in any one of Claims 1-8 which further contains the compound which generate | occur | produces an acid by irradiation of radiation and / or heating. The solvent represented by the formula (1) is propylene glycol methyl propyl ether, propylene glycol methyl butyl ether, propylene glycol methyl pentyl ether, propylene glycol methyl isopropyl ether and propylene glycol methyl according to any one of claims 1 to 9. Curable resin composition which is 1 or more types chosen from the group which consists of isobutyl ether. The protective film formed from the curable resin composition in any one of Claims 1-10. The film is formed using the curable resin composition in any one of Claims 1-10, and then the irradiation process of radiation and / or heat processing are carried out, The formation method of the protective film characterized by the above-mentioned.