KR101087309B1 - Curable resin composition, overcoats, and process for formation thereof - Google Patents

Abstract

The present invention satisfies the required transparency, heat resistance, surface hardness, and adhesiveness, and has excellent load resistance even under heating, less sublimation during firing, and flattening the step of the color filter formed on the support substrate. The curable resin composition which can form this excellent protective film for optical devices, the protective film formed from the said composition, and the formation method of this protective film are provided. Curable resin composition of this invention has (A) two or more epoxy groups, and ratio (Mw / Mn) of polystyrene conversion weight average molecular weight (Mw) and polystyrene conversion number average molecular weight (Mn) measured by gel permeation chromatography is 1.7. It contains a polymer which is the following, and a cationic polymerizable compound different from (B) (A) component, and is for protective film formation, It is characterized by the above-mentioned.

Curable resin composition, protective film

Description

Curable resin composition, protective film, and its formation method {CURABLE RESIN COMPOSITION, OVERCOATS, AND PROCESS FOR FORMATION THEREOF}

The present invention is a curable resin composition, in particular, a curable resin composition suitable as a material for forming a protective film used in an optical device such as a liquid crystal display device (LCD), a charge coupled device (CCD), a CMOS sensor, or the like, and the formation of a protective film and a protective film formed from the composition. It is about a method.

In the process of manufacturing an optical device such as an LCD or a CCD, the surface of the element is locally exposed to high temperatures when the display element is subjected to an immersion treatment with a solvent, an acid or an alkali, or when the wiring electrode layer is formed by sputtering. In order to prevent the display element from being degraded or damaged by such a process, a protective film resistant to such a process is provided on the surface of the display element.

Such a protective film is required to have a high adhesiveness with respect to the substrate or lower layer on which the protective film is to be formed, or the layer formed on the protective film. In addition, the protective film itself is smooth and strong, has transparency, has high heat resistance and light resistance, does not cause deterioration such as coloring, yellowing or whitening over a long period of time, excellent water resistance, solvent resistance, acid resistance and alkali resistance, etc. Performance is required. And as a material for forming the protective film which has these various performances, the thermosetting composition containing the polymer which has glycidyl group (refer Unexamined-Japanese-Patent No. 5-78453) is known.

In addition, when such a protective film is used for color filters of LCD, CCD or CMOS sensors, it is also required to be able to flatten the step by the color filter formed on the support substrate.

In color liquid crystal display elements, for example, STN (Super Twisted Nematic) or TFT (Thin Film Transister) type color liquid crystal display elements, in order to maintain the cell spacing of the liquid crystal layer uniformly, a bead-shaped spacer is dispersed on the protective film. Subsequently, the panel is bonded to each other, and the liquid crystal cell is then sealed by thermocompression bonding of the sealing material. However, a phenomenon occurs that the protective film in the portion where the spacer is present appears to dent due to the heat and pressure applied at this time. It is becoming.

In particular, when manufacturing the STN type color liquid crystal display element, the bonding accuracy between the color filter and the counter substrate must be very strictly performed, and a very high leveling flattening performance and a heat resistance voltage resistance performance are required for the protective film.

In recent years, a method of forming a film of a wiring electrode (ITO: indium tin oxide) by sputtering on a protective film of a color filter, and patterning ITO with a strong acid or strong alkali or the like has also been adopted. For this reason, the protective film is locally exposed to high temperatures during sputtering or subjected to numerous chemical treatments. Therefore, it is required to withstand these treatments, and adhesion with wiring electrodes is also required so that ITO does not peel off on the protective film during chemical treatment.

In the LCD panel, for the purpose of high brightness, a panel having a laminated structure in which a transparent electrode such as ITO and a TFT element are interposed through a highly transparent interlayer insulating film and a large opening area has been developed. Moreover, although the conventional color filter and TFT element have been manufactured using a separate board | substrate, the method of forming a color filter on a TFT element is also developed when using an interlayer insulation film. And under such a technical background, the development of the protective film which is high in heat resistance and excellent in the performance (flattening ability) of flattening the level difference of the color filter formed on the support substrate is desired.

In addition, with the recent increase in the size of panel substrates, when a thermosetting composition is used to form a protective film, unreacted monomers remaining in trace amounts are sublimated and deposited inside the kiln, contaminating the kiln, making it difficult to control the firing conditions or depositing. It has become a problem that the unreacted monomers and / or thermally modified substances thereof adhere to the panel substrates and contaminate them to generate display defects.

Although it is preferable to use curable resin composition which has the advantage of being able to easily form the protective film which is excellent in surface hardness, for formation of the protective film for color filters, it is various as mentioned above, satisfying the general required performance as a protective film, such as transparency. A material capable of forming a protective film that can meet the demand and excellent in storage stability as a composition is not known yet.

<Overview of invention>

The present invention has been made on the basis of the above circumstances, and the problem is to satisfy the required transparency, heat resistance, surface hardness, and adhesion, and to have excellent load resistance even under heating, and less sublimation during firing. The present invention also provides a curable resin composition capable of forming a protective film for an optical device with excellent performance of flattening a step of a color filter formed on a support substrate, a protective film formed of the composition, and a method of forming the protective film.

According to the present invention, the above object is first,

(A) A polymer having two or more epoxy groups and having a ratio (Mw / Mn) of polystyrene reduced weight average molecular weight (Mw) and polystyrene reduced number average molecular weight (Mn) measured by gel permeation chromatography (hereinafter referred to as "polymer ( A) ", and (B) curable resin composition which contains a cationically polymerizable compound different from (A) component (henceforth" one-component curable resin composition ((alpha)) "). Solved by

According to the present invention, the problem is second,

(A) component (A1) (a) epoxy group containing polymerizable unsaturated compound, (b1) polymerizable unsaturated carboxylic acid and / or polymerizable unsaturated polyhydric carboxylic anhydride, (b2) (a) component, and ( It is preferably solved by the one-component curable resin composition (α) which is a copolymer with a polymerizable unsaturated compound other than the component b1).

According to the present invention, the above object is the third,

A one-component curable resin composition wherein the component (A) is a polymer containing two or more epoxy groups in the molecule (A2) and at least one structure selected from the group consisting of acetal structures, ketal structures, and t-butoxycarbonyl structures ( It is preferably solved by α).

According to the present invention, the fourth problem is

(A) A component is a copolymer of (A3) (a) epoxy group containing polymeric unsaturated compound, and (b5) polymeric unsaturated compounds other than said (a) component, and is a carboxyl group, a carboxylic anhydride group, and acetal in a molecule | numerator It is preferably solved by the one-component curable resin composition (α) which is a copolymer having no structure, a ketal structure and a t-butoxycarbonyl structure.

According to the present invention, the problem is fifth,

It is achieved by curable resin composition whose (A) component is a (co) polymer obtained by living radical polymerization using a thiocarbonylthio compound as a control agent.

According to the present invention, the sixth problem,

(A3) A copolymer of (a) an epoxy group-containing polymerizable unsaturated compound and (b5) a polymerizable unsaturated compound other than the component (a), and contains a carboxyl group, a carboxylic anhydride group, an acetal structure, a ketal structure, and t in a molecule thereof. Curable resin composition containing the copolymer which has no -butoxycarbonyl structure, (B) (A3) component and another cationically polymerizable compound, and (C) hardening | curing agent (Hereinafter, "one-component curable resin composition ((alpha) 1 ) ").

According to the present invention, the problem is seventh,

(1) Two-component curable composition comprising a combination of a first component containing a cationically polymerizable compound different from the above-mentioned (A3) component and (B) (A3) component and (2) a curing agent-containing second component. It is preferably solved by the resin composition (β).

Although the combination of a 1st component and a 2nd component is handled as one article unit with "two-component type curable resin composition" here, it does not mix a 1st component and a 2nd component before providing it to an end use, and is used for an end use. It means the composition which mixes and uses a 1st component and a 2nd component at the time of providing.

According to the present invention, the problem is the eighth,

At least one selected from the group consisting of the above (A1) component and the above (A2) component, a cationic polymerizable compound different from the (B) (A1) component and the (A2) component, and (D) radiation and / or It is preferably solved by a curable resin composition (hereinafter referred to as "one-component curable resin composition (? 2)") containing a compound which generates an acid by heating.

According to the present invention, the problem is the ninth,

Curable resin composition of this invention, Preferably it is formed with each said 1-component curable resin composition ((alpha)), 1-component curable resin composition ((alpha) 1), 1-component curable resin composition ((alpha) 2), or 2-component curable resin composition ((beta)). It is solved by a protective film.

According to this invention, the said subject is tenth,

On the curable resin composition of this invention, Preferably, a film is formed using each said 1-component curable resin composition ((alpha)), 1-component curable resin composition ((alpha) 1), or 2-component curable resin composition ((beta)), Subsequently, it heat-processes, and is achieved by the formation method of the protective film.

According to the present invention, the problem is the eleventh,

A film is formed on a board | substrate using 1-component curable resin composition ((alpha) 2), and then it solves suitably by the formation method of the protective film which irradiates a radiation and / or heat-processes.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

Curable Resin Composition

Polymer (A)

The polymer (A) used in the present invention can be advantageously obtained by living radical polymerization of a monomer mixture containing an epoxy group-containing polymerizable unsaturated compound.

As an initiator system of living radical polymerization, the initiator system comprised from the combination of the copper bromide and bromine containing ester compound proposed by TEMPO system, Matiasjaszewski etc. which were discovered, for example by Georges etc., An initiator system consisting of a combination of carbon tetrachloride and ruthenium (II) complexes proposed by Higashimura et al., Japanese Patent Publication No. 2000-515181, Japanese Patent Publication No. 2002-500251 and Japanese Patent Publication No. 2004 Combinations of thiocarbonylthio compounds and radical initiators described in -518773 are preferably used.

As a preferable living polymerization initiator system for obtaining the polymer (A) of the present invention, a system in which the growth terminal is not deactivated is appropriately selected depending on the monomer species used, but considering the polymerization efficiency or the like, the thiocarbonylthio compound is preferable. And a radical initiator. Here, as a thiocarbonylthio compound, dithio ester, dithiocarbonate, trithiocarbonate, xanthate, etc. are mentioned, for example.

As the specific example, the compound represented by a following formula is mentioned.

Among them, cumyldithiobenzoate, S-cyanomethyl-S-dodecyltrithiocarbonate, pyrazole-1-dithiocarboxylic acid phenyl-methyl ester, dithioesters used in Synthesis Example 6 below and The xanthate used by the following synthesis example 7 is mentioned.

Moreover, as a radical initiator, what is generally known as a radical polymerization initiator can be used, For example, 2,2'- azobisisobutyronitrile, 2,2'- azobis- (2, 4- dimethylvalle Azo compounds such as ronitrile) and 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile); Organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxy pivalate, 1,1'-bis- (t-butylperoxy) cyclohexane; Hydrogen peroxide; And redox initiators containing these peroxides and reducing agents.

These polymerization initiators can be used individually or in mixture of 2 or more types.

The amount of the thiocarbonylthio compound used is preferably 1 to 10,000 parts by weight, more preferably 10 to 1,000 parts by weight per 100 parts by weight of the polymerization initiator. The amount of the radical polymerization initiator used is preferably 0.01 to 100 parts by weight, more preferably 0.1 to 10 parts by weight, per 100 parts by weight of the monomer mixture containing the epoxy group-containing polymerizable unsaturated compound. Although there is no restriction | limiting in particular in the polymerization temperature at the time of the said living radical polymerization, Preferably it is 0 degreeC-100 degreeC, More preferably, it is 10-85 degreeC.

As a preferable polymer (A) in this invention, for example

(A1) (a) an epoxy group-containing polymerizable unsaturated compound (hereinafter referred to as "unsaturated compound (a)"), and (b1) polymerizable unsaturated carboxylic acid and / or polymerizable unsaturated polyhydric carboxylic anhydride (hereinafter, These are collectively referred to as " unsaturated compounds (b1) " and polymerizable unsaturated compounds other than (b2) unsaturated compounds (a) and unsaturated compounds (b1) (hereinafter referred to as " unsaturated compounds (b2) "). Copolymers (hereinafter referred to as "copolymer (A1)");

(A2) A polymer containing two or more epoxy groups in a molecule and at least one structure selected from the group consisting of acetal structures, ketal structures and t-butoxycarbonyl structures (hereinafter referred to as "polymer (A2)") ;

(A3) A copolymer of an unsaturated compound (a) and a polymerizable unsaturated compound (hereinafter referred to as "unsaturated compound (b5)") other than (b5) unsaturated compound (a), and contains a carboxyl group and a carboxylic acid in its molecule. The copolymer which does not have any of an anhydride group, an acetal structure, a ketal structure, and t-butoxycarbonyl structure (henceforth "copolymer (A3)") etc. are mentioned.

Moreover, as a polymer (A2), superposition | polymerization containing (A2-1) unsaturated compound (a) and (b3) at least 1 sort (s) of structure chosen from the group which consists of an acetal structure, a ketal structure, and t-butoxycarbonyl structure. Polymeric unsaturated compounds (hereinafter referred to as "unsaturated compounds (b3)") and (b4) unsaturated compounds (a) and unsaturated compounds (b3) other than unsaturated compounds (hereinafter referred to as "unsaturated compounds (b4)"). ) Is more preferred (hereinafter referred to as "copolymer (A2-1)").

In addition, the copolymer (A1) may further contain an acetal structure, ketal structure or t-butoxycarbonyl structure, and the polymer (A2) may further contain a carboxyl group or a carboxylic anhydride group.

In the copolymer (A1), the polymer (A2) and the copolymer (A3), as the unsaturated compound (a), for example, (meth) acrylic acid glycidyl, α-ethylacrylic acid glycidyl, α-n-propylacrylic acid Glycidyl, α-n-butyl acrylate Glycidyl, 3,4-epoxybutyl (meth) acrylate, 3,4-epoxybutyl (alpha) -ethyl acrylate, 6,7-epoxyheptyl (meth) acrylate, α-ethyl Acrylic acid 6,7-epoxyheptyl, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, and the like.

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 Cyl ether 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 the 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;

And unsaturated polyhydric carboxylic acid anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, cis-1,2,3,4-tetrahydrophthalic anhydride, and the like.

Among these unsaturated compounds (b1), as the unsaturated carboxylic acid, acrylic acid and methacrylic acid are particularly preferable, and as the unsaturated polyhydric carboxylic anhydride, maleic anhydride is particularly preferable. These preferable unsaturated compounds (b1) have high copolymerization reactivity and are effective for increasing 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.

Moreover, 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, sec-methacrylate (meth) acrylate (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 is called "dicyclopentanyl"), (meth) acrylic acid alicyclic ester such as 2-dicyclopentanyloxyethyl (meth) acrylic acid, 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;

Conjugated diene compounds such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and

Vinyl chloride, vinylidene chloride, vinyl acetate and the like.

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 high copolymerization reactivity and increase the heat resistance (except for 1,3-butadiene) and surface hardness (except for 1,3-butadiene) of the resulting protective film. It is effective for having.

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,

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

In these copolymers (A1),

Methacrylic acid glycidyl / methacrylic acid / methacrylic acid 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,

More preferred are methacrylic acid glycidyl / methacrylic acid / methacrylic acid dicyclopentanyl / styrene / 1,3-butadiene copolymer.

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 based on the total repeating units. The total content rate of the repeating units derived from the polymerizable unsaturated carboxylic acid and the polymerizable unsaturated polyhydric carboxylic anhydride is preferably 5 to 40% by weight, particularly preferably 10 to 30% by weight based on the total repeating units. . The content rate of the repeating unit derived from another polymerizable unsaturated compound is 10 to 70 weight% with respect to all the repeating units, Especially preferably, it is 20 to 50 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 a polymerizable unsaturated carboxylic acid and a polymerizable unsaturated polyhydric carboxylic anhydride is less than 5 weight%, there exists a tendency for the heat resistance, surface hardness, or chemical resistance of a protective film to fall, and 40 When it exceeds 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 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 fall. There is this.

Subsequently, 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 structure or the ketal structure in the polymer (A2) can be introduced by bonding an acetal-forming functional group or a ketal-forming functional group as described below directly or by bonding to a carbon atom in the polymer (A2) via a bond such as a carbonyl group. Can be.

As a functional group (henceforth "acetal formation functional group") which can form an acetal structure, it is a, for example.

1-methoxyethoxy group, 1-ethoxyethoxy group, 1-n-propoxyethoxy group, 1-i-propoxyethoxy group, 1-n-butoxyethoxy group, 1-i- Butoxyethoxy group, 1-sec-butoxyethoxy group, 1-t-butoxyethoxy group, 1-cyclopentyloxyethoxy group, 1-cyclohexyloxyethoxy group, 1-norbornyloxy Ethoxy 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, (cyclo Hexyl) (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-tetrahydropyranyloxy group, etc. are mentioned.

Among these acetal-forming functional groups, 1-ethoxyethoxy group, 1-n-propoxyethoxy group, 1-cyclohexyloxyethoxy group, 2-tetrahydropyranyloxy group, 2-tetrahydropyranyloxy group, etc. This is preferred.

In addition, as a functional group (henceforth "a ketal formation functional group") which can form a ketal structure, it is a 1-methyl-1- methoxyethoxy group, 1-methyl-1-ethoxyethoxy group, for example. , 1-methyl-1-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-cyclohexyloxyethoxy 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-methoxy Ethoxy group, 1-cyclohexyl-1-ethoxyethoxy group, 1-cyclohexyl-1-n-propoxyethoxy group, 1-cyclohexyl-1-i-propoxyethoxy group, 1-cyclo Hexyl-1-cyclohexyloxyethoxy group, 1-cyclohex -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 ketal forming functional groups, 1-methyl-1-methoxyethoxy group, 1-methyl-1-cyclohexyloxyethoxy group, etc. are preferable.

Compared with the case where a copolymer (A1) is used, a polymer (A2) can obtain the 1-pack type curable resin composition ((alpha)) which is favorable in storage stability and excellent also in the planarization ability of the protective film obtained.

In the copolymer (A2-1), as the unsaturated compound (b3), for example, a norbornene-based compound having at least one structure selected from the group consisting of an acetal structure, a ketal structure and a t-butoxycarbonyl structure ( Hereinafter referred to as a "specific norbornene-based compound"; (Meth) acrylic acid ester compounds having an acetal structure and / or a ketal structure (hereinafter referred to as "specific (meth) acrylic acid ester compounds"); Or t-butyl (meth) acrylate.

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. are 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) 1-i-butoxyethyl acrylate, 1- (cyclopentyloxy) ethyl (meth) acrylate, 1- (cyclohexyloxy) ethyl (meth) acrylate, 1- (1,1-dimethylethoxy (meth) acrylate ) Ethyl, (meth) acrylic acid tetrahydro-2H-pyran-2-yl, etc. are mentioned.

Among these unsaturated compounds (b3), t-butyl (meth) acrylate is preferable as the specific (meth) acrylic acid ester compound, and in particular, methacrylic acid 1-ethoxyethyl, methacrylic acid 1-i-butoxyethyl, and meta Methacrylic acid 1- (cyclopentyloxy) ethyl, methacrylic acid 1- (cyclohexyloxy) ethyl, methacrylic acid 1- (1,1-dimethylethoxy) ethyl, methacrylic acid tetrahydro-2H-pyran- 2-yl, t-butyl methacrylate, and the like are more preferred. These preferable unsaturated compounds (b3) have high copolymerization reactivity, obtain a one-component curable resin composition (?) And a one-component curable resin composition (? 2) excellent in storage stability and planarization ability of the protective film, and at the same time, the heat resistance and surface hardness of the protective film obtained. Effective for raising

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

Moreover, as an unsaturated compound (b4), the thing similar to the compound illustrated about the said unsaturated compound (b1) and an unsaturated compound (b2) is mentioned, for example.

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 high copolymerization reactivity and increase the heat resistance (except for 1,3-butadiene) and surface hardness (except for 1,3-butadiene) of the resulting protective film. It is effective for having.

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 / methacrylate tetrahydro-2H-pyran-2-yl / methacrylate 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,

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

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 / methacrylic acid dicyclopentanyl / styrene copolymer,

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

Glycidyl methacrylate / t-butyl / N-cyclohexylmaleimide / styrene copolymer, and the like.

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 making the content rate of the repeating unit derived from an unsaturated compound (b3) into this range, the favorable heat resistance and surface hardness of a protective film can be implement | achieved.

In addition, although the content rate of the repeating unit derived from an unsaturated compound (b4) corresponds to the quantity which reduced the total content rate of the repeating unit derived from an unsaturated compound (a) and an unsaturated compound (b3) from 100 weight%, an unsaturated compound ( When using unsaturated carboxylic acids or unsaturated polyhydric carboxylic anhydrides as b4), 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, It is desirable not to exceed the value.

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

Of these unsaturated compounds (b5), 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 (b5) have high copolymerization reactivity and increase the heat resistance (except for 1,3-butadiene) and surface hardness (except for 1,3-butadiene) of the resulting protective film. It is effective for having.

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 and the like.

Among these copolymers (A3), More preferably, methacrylic acid glycidyl / styrene copolymer, methacrylic acid glycidyl / methacrylate dicyclopentanyl copolymer, methacrylic acid glycidyl / methacrylic acid Dicyclopentanyl / styrene copolymer, glycidyl methacrylate / N-cyclohexylmaleimide / styrene copolymer, and the like.

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%, there exists a tendency for the storage stability of a composition to fall. .

Copolymer (A1), copolymer (A2-1) and copolymer (A3) can be synthesized by living radical polymerization of each unsaturated compound in the presence of a suitable solvent and a polymerization initiator.

Examples of the solvent used for the polymerization include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol, propylene glycol monoalkyl ethers, propylene glycol alkyl ether acetates, propylene glycol alkyl ether propionates and aromatics. Hydrocarbons, ketones, esters and the like.

As these specific examples,

As the alcohol, for example, methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol and the like;

As ethers, for example tetrahydrofuran and the like:

As glycol ether, For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc .;

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

As diethylene glycol, For example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc .;

As propylene glycol monoalkyl ether, For example, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, etc .;

As propylene glycol alkyl ether propionate, For example, 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 acetate, For example, 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, For example, toluene, xylene, etc .;

As a ketone, For example, methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl- 2-pentanone, etc .;

Examples of the esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate and hydroxyacetic acid. Methyl, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxypropionate methyl, 3-hydroxypropionate, 3-hydroxypropionic acid propyl, 3-hydroxypropionic acid Butyl, 2-hydroxy-3-methyl butyrate, methyl methoxyacetate, ethyl methoxyacetate, methoxyacetic acid propyl, butyl acetate, ethoxyacetic acid, ethyl ethoxyacetate, ethoxyacetic acid propyl Butyl oxyacetate, methyl propoxy acetate, ethyl propoxy acetate, propyl propoxy acetate, butyl propoxy acetate, methyl butoxy acetate Ethyl butoxy acetate, propyl butoxy acetate, butyl butoxy acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate Ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, 3-methoxy methyl propionate, 3-methoxy ethylpropionate, 3-methoxy propylpropionate, 3-methoxy butyl propionate, 3-ethoxy propylpropionate, 3-ethoxy propylpropionate, 3-ethoxy propylpropionate, 3 Butyl ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, 3-butoxypropionic acid Butyl, can be given a 3-butoxy-propionic acid propyl, 3-butoxy-propionic acid butyl ester, etc., respectively.

Among these, ethylene glycol alkyl ether acetate, diethylene glycol, propylene glycol monoalkyl ether, and propylene glycol alkyl ether acetate are preferable, and among these, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol methyl ether, and propylene. Glycol methyl ether acetate is particularly preferred.

The said solvent can be used individually or in mixture of 2 or more types.

The polymer (A) used in the present invention is a ratio of the polystyrene reduced weight average molecular weight (hereinafter referred to as "Mw") and the polystyrene reduced number average molecular weight (hereinafter referred to as "Mn") measured by gel permeation chromatography ( Mw / Mn) is 1.7 or less, Preferably it is 1.5 or less. When Mw / Mn exceeds 1.7, heat resistance may be inferior. In addition, Mw is preferably 2x10 ³ to 1x10 ⁵ , and more preferably 5x10 ³ to 5x10 ⁴ . When Mw is less than 2x10 <^3> , the applicability | paintability of a composition may become inadequate or the heat resistance of the protective film formed may become inadequate. On the other hand, when Mw exceeds 1 * 10 < ⁵ >, planarization performance may become inadequate. Moreover, Mn becomes like this. Preferably it is 1.2 * 10 <^3> -1 * 10 <^5> , More preferably, it is 2.9 * 10 <^3> -5 * 10 <^4> .

In addition, the residual monomer amount measured by the gel permeation chromatography of the polymer (A) used in the present invention is preferably less than 5.0%, more preferably less than 3.0%, particularly preferably less than 2.0%. By using the copolymer of such residual monomer content, the coating film in which the sublimation at the time of baking is reduced can be obtained.

In the present invention, the polymer (A) may be used alone or in combination of two or more thereof, and in the one-component curable resin composition (α2), one or more of the group of the copolymer (A1) and the polymer (A2) may be used. have.

-(B) cationically polymerizable compound-

(B) component in this invention contains a polymer (A) and other cationically polymerizable compound.

Although it does not specifically limit as a cationically polymerizable compound as long as it can superpose | polymerize under acidic conditions, For example, 1 or more types chosen from the group which consists of an oxetane ring skeleton, a 3, 4- epoxycyclohexane skeleton, and an epoxy group are contained in a molecule | numerator. The compound which has group which can react with the epoxy group in a polymer (A), such as a compound which has two or more, is mentioned.

As a specific example of a cationically polymerizable compound, the following are mentioned.

As a compound which has two or more oxetane ring skeleton in a molecule | numerator, for example

3,7-bis (3-oxetanyl) -5-oxanonane, 3,3 '-[1,3- (2-methylenyl) propanediylbis (oxymethylene)] bis (3-ethyloxetane) , 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, 1,2-bis [(3-ethyl-3-oxetanyl) methoxymethyl] ethane, 1,3 -Bis [(3-ethyl-3-oxetanyl) methoxymethyl] propane,

Ethylene glycol bis [(3-ethyl-3-oxetanyl) methyl] ether, dicyclopentenyl bis [(3-ethyl-3-oxetanyl) methyl] ether, triethylene glycol bis [(3-ethyl- 3-oxetanyl) methyl] ether, tetraethyleneglycolbis [(3-ethyl-3-oxetanyl) methyl] ether, tricyclodecanediyl dimethylenebis [(3-ethyl-3-oxetanyl) methyl ] Ether, trimethylolpropanetris [(3-ethyl-3-oxetanyl) methyl] ether, 1,4-bis [(3-ethyl-3-oxetanyl) methoxy] butane, 1,6-bis [(3-ethyl-3-oxetanyl) methoxy] hexane, pentaerythritol tris [(3-ethyl-3-oxetanyl) methyl] ether, pentaerythritol tetrakis [(3-ethyl-3- Oxetanyl) methyl] ether, polyethylene glycol bis [(3-ethyl-3-oxetanyl) methyl] ether, dipentaerythritol hexakis [(3-ethyl-3-oxetanyl) methyl] ether, di Pentaerythritol pentakis [(3-ethyl-3-oxetanyl) methyl] ether, dipentaerythritol tetrakis [(3-e 3-oxetanyl) methyl] ether,

Reaction product of dipentaerythritol hexakis [(3-ethyl-3-oxetanyl) methyl] ether with caprolactone, dipentaerythritol pentakis [(3-ethyl-3-oxetanyl) methyl] ether Reaction product of with caprolactone, ditrimethylolpropanetetrakis ((3-ethyl-3-oxetanyl) methyl] ether, bisphenol A bis [(3-ethyl-3-oxetanyl) methyl] ether and ethylene Reaction product with oxide, bisphenol A bis [(3-ethyl-3-oxetanyl) methyl] ether with propylene oxide product, hydrogenated bisphenol A bis [(3-ethyl-3-oxetanyl Reaction product of methyl) ether with ethylene oxide, hydrogenated bisphenol A bis [(3-ethyl-3-oxetanyl) methyl] reaction product of propylene oxide, bisphenol F bis [(3-ethyl And reaction products of -3-oxetanyl) methyl] ether with ethylene oxide.

As a compound which has 2 or more of 3, 4- epoxycyclohexane frame | skeleton in a molecule | numerator, for example

3,4-Epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta- Dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol bis (3,4-epoxycyclohexylmethyl) ether, ethylene Bis (3,4-epoxycyclohexanecarboxylate), lactone-modified 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, and the like.

As a compound which has two or more epoxy groups in a molecule | numerator, for example

Bisphenol A diglycidyl ether, Bisphenol F diglycidyl ether, Bisphenol S diglycidyl ether, Hydrogenated bisphenol A diglycidyl ether, Hydrogenated bisphenol F diglycidyl ether, Hydrogenated bisphenol AD diglyl Diglycidyl ethers of bisphenol compounds such as cydyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl F, and brominated bisphenol S diglycidyl ether;

1,4-butanediol diglycidyl ether, 1,6-hexanediol 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 the reaction of aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin with one or two or more alkylene oxides;

Epoxy resins such as phenol novolac type epoxy resins, cresol novolac type epoxy resins, polyphenol type epoxy resins, and cyclic aliphatic epoxy resins;

Diglycidyl esters of aliphatic long chain dibasic acids;

Polyglycidyl esters of higher polyvalent 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 a molecule | numerator, for example

As polyglycidyl ether of polyhydric alcohol, Epolight 100MF (made by Kyoesha Chemical Co., Ltd.), Epiol TMP (made by Nippon Yushi Co., Ltd.);

Examples of the bisphenol A epoxy resin include Epicoat 828, Copper 1001, Copper 1002, Copper 1003, Copper 1004, Copper 1007, Copper 1009, Copper 1010 (above, manufactured by Yuka Shell Epoxy Co., Ltd.), and the like;

As bisphenol F-type epoxy resin, Epicoat 807 (made by Yuka Shell Epoxy Co., Ltd.) etc .;

As a phenol novolak-type epoxy resin, Epicoat 152, Copper 154, Copper 157S65 (above, manufactured by Yucca Shell Epoxy), DPPN201, Copper 202 (above, manufactured by Nippon Kayaku Co., Ltd.), etc .;

As a cresol novolak-type epoxy resin, DOCN102, 103S, 104S, 1020, 1025, 1027 (above, Nippon Kayaku Co., Ltd.), Epicoat 180S75 (Yukaka Shell Epoxy Co., Ltd.), etc .;

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

As cyclic aliphatic epoxy resin, CY-175, copper 177, copper 179, Araldite CY-182, copper 192, copper 184 (above, Ciba Specialty Chemicals Corporation make), DRL-4221, Copper 4206, copper 4234, copper 4299 (above, manufactured by UCC Corporation), Shodine 509 (manufactured by Showa Denko Co., Ltd.), epiclon 200, copper 400 (or more, Dainippon Ink Co., Ltd.) Epicoat 871, copper 872 (above, manufactured by Yuka Shell Epoxy Co., Ltd.), DD-5661, copper 5662 (above, manufactured by Celanese Co., Ltd.), and the like.

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

In this invention, a cationically polymerizable compound can be used individually or in mixture of 2 or more types.

(C) Curing agent-

The hardening | curing agent in 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 such a hardening | curing agent, the copolymer of polyhydric carboxylic acid, polyhydric carboxylic anhydride, unsaturated polyhydric carboxylic anhydride, and another olefinic unsaturated compound (except the copolymer which has 2 or more epoxy groups) is mentioned, for example. (Hereinafter, referred to as "carboxylic acid anhydride group-containing copolymer") and the like.

As said polyhydric carboxylic acid, For example, aliphatic polyhydric carboxylic acid, 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-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid and cyclopentanetetracarboxylic acid; Phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, and aromatic polyhydric carboxylic acids such as 1,2,5,8-naphthalenetetracarboxylic acid.

Among these polyhydric carboxylic acids, aromatic polyhydric carboxylic acids are preferable from the viewpoints of the reactivity of the curable resin composition, the heat resistance of the protective film formed, and the like.

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

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 is obtained.

In the carboxylic anhydride group-containing copolymer, examples of the unsaturated polyhydric 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.

Moreover, as another olefinic unsaturated compound, For example, styrene, p-methylstyrene, p-methoxy styrene, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylic acid, (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, a maleic anhydride / styrene copolymer, a citraconic anhydride / methacrylic acid dicyclopentanyl copolymer, etc. are mentioned.

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

Mw 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.

The said hardening | curing agent can be used individually or in mixture of 2 or more types.

Moreover, in this invention, the two-component curable resin composition ((beta)) is combined with the 1st component containing the 1-component curable resin composition ((alpha)) whose (A) component is a copolymer (A3), and the 2nd component containing a hardening | curing agent. You can do

(D) acid generator-

Among the compounds which generate an acid by radiation irradiation and / or heating in a one-pack type curable resin composition (α2) (hereinafter referred to as an "acid generator"), those which generate an acid by radiation irradiation are referred to as "radiation acid." "Generator", which generates acid by heating, is referred to as "thermal acid generator".

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

As the thermal acid generator, for example, sulfonium salts (excluding the triarylsulfonium salts), benzothiazonium salts, ammonium salts and phosphonium salts (except the diarylphosphonium salts) These etc. are mentioned, A sulfonium salt and a benzothiazonium salt are preferable in these.

Among the radiation-sensitive acid generators, examples of the diaryl iodonium salt include diphenyl iodonium tetrafluoroborate, diphenyl iodonium hexafluorophosphonate, and diphenyl iodonium hexafluoro ar. Senate, 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- Methoxyphenylphenyl iodonium trifluoroacetate, 4-methoxyphenylphenyl iodonium p-toluenesulfonate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis (4-t- Butylphenyl) iodonium hexafluoroarsenate, Bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium trifluoroacetate, bis (4-t-butylphenyl) iodonium p- Toluenesulfonate, and the like.

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

Moreover, as said triaryl sulfonium salt, a triphenyl sulfonium tetrafluoro borate, a triphenyl sulfonium hexafluoro phosphonate, a triphenyl sulfonium hexafluoro arsenate, and a triphenyl sulfonium trifluoro, for example Romethanesulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium p-toluenesulfonate, 4-methoxyphenyldiphenylsulfoniumtetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluoro Phosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium p-toluenesulfonate, 4-phenylthiophenyldiphenyltetrafluoroborate, 4-phenylthiophenyldiphenylhexafluorophosphonate, 4-phenylthiophenyldiphenylhexa May be mentioned are the Senate, such as 4-thiophenyl-diphenyl-trifluoromethane sulfonate, 4-thiophenyl-diphenyl-trifluoroacetate, 4-thiophenyl-diphenyl-p- toluenesulfonate in Luo.

Among these triarylsulfonium salts, triphenylsulfonium trifluoromethanesulfonate 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. product); CI-2481, CI-2624, CI-2639, CI-2064 (above, the Nippon 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 (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 by UVI-6970, UVI-6974, UVI-6990, Adeka Optomer SP-170, Adeka Optomer SP-171, CD-1012, MPI-103, etc. has a high surface hardness. It is preferable at the point.

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

Subsequently, as the sulfonium salt in the 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-nitrobenzyl-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.

Moreover, as said benzothiazonium salt, 3-benzyl benzothiazonium hexafluoro antimonate, 3-benzyl benzothiazonium hexafluoro phosphate, 3-benzyl benzothiazonium tetrafluoro borate, 3- (4-methoxybenzyl) benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimo Benzyl benzothiazonium salts such as nate; and the like. 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 Optomer CP-66, Adeka Optomer 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 (above, Sanshin Kagaku 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.

Embodiment of the 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 (A) (preferably at least one of the group of the copolymer (A1), the copolymer (A2) and the copolymer (A3)) and (B) a cationically polymerizable compound, optionally The one-component curable resin composition (α) further containing an optional additive component described later, wherein the amount of the cationically polymerizable compound used is 3 to 100 parts by weight, more preferably 5 to 50 parts by weight, based on 100 parts by weight of the polymer (A). .

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

(II) A copolymer (A3), (B) a cationically polymerizable compound, and (C) hardening | curing agent are further contained, Optionally, it contains the optional additional component mentioned later, and (C) cationic polymerization with respect to 100 weight part of polymers The amount of the compound is 3 to 100 parts by weight, more preferably 5 to 50 parts by weight, and the amount of the curing agent is 20 to 60 parts by weight, more preferably 20 to 50 parts by weight (one-component curable resin composition (α1). )).

In this one-component curable resin composition (α1), by using the amount of the curing agent in the above range, good curing characteristics are exhibited and various characteristics of the protective film are not impaired.

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

(III) It consists of a combination of the 1st component containing (1) copolymer (A3), (B) cationically polymerizable compound, etc., and (2) the 2nd component containing a hardening | curing agent, and a 1st component and / Or the second component optionally further contains the optional additive component described below, and the amount of the cationic polymerizable compound is 3 to 100 parts by weight, more preferably 5 to 50 parts by weight based on 100 parts by weight of the polymer (A). The amount of the curing agent is 20 to 60 parts by weight, more preferably 20 to 50 parts by weight of the two-component curable resin composition (β).

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

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

When manufacturing the one-component curable resin composition (α1) of (II) and the two-component curable resin composition (β) of (III), the curing agent is usually used as a solution dissolved in a suitable solvent. The concentration of the curing agent in the solution is preferably 5 to 50% by weight, more preferably 10 to 40% by weight. As a solvent used here, the solvent similar to what was illustrated as a solvent used for the synthesis | combination of a copolymer (A1), a copolymer (A2-1), and a copolymer (A3) can be used.

(IV) one or more of the group of the copolymer (A1) and the polymer (A2) (preferably copolymer (A2-1)), (B) a cationically polymerizable compound and (D) an acid generator, Optionally, it further contains optional additive components described later, and the amount of the cationically polymerizable compound is 3 to 100 parts by weight, more preferably 5 to 5 parts by weight based on 100 parts by weight of the total of the copolymer (A1) and the polymer (A2). 1 part type curable resin composition ((alpha) 2) which is 50 weight part and the usage-amount of an acid generator is 20 weight part or less, More preferably, it is 0.05-20 weight part, Especially preferably, it is 0.1-10 weight part.

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.

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 transparency, heat resistance, and surface for which a protective film formed from them is required. It satisfies hardness and adhesion, and also has excellent load resistance even under heating, and has excellent performance of flattening the step of the color filter formed on the support substrate.

Optional Additives

The curable resin composition of this invention can mix | blend optional additive components other than the said components, for example surfactant, an adhesion | attachment adjuvant, etc. in the range which does not impair the effect of this invention as needed.

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. Can be.

As said polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, etc. are mentioned, for example, As said polyoxyethylene aryl ether, for example, Polyoxyethylene 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 commercial items of surfactant, For example, BM-1000 and BM-1100 (above, BM CHIMID company make); Mega Pack F142D, Mega Pack F172, Mega Pack F173, Mega Pack F183 (above, manufactured by Dainippon Ink Chemical Industries, Ltd.); FLUORAD FC-135, FLOWRAD FC-170C, FLOWRAD FC-430, FLOWRAD FC-431 (above, Sumitomo 3M Co., Ltd. product); Suplon (SURFLON) S-112, Suplon S-113, Suplon S-131, Supron S-141, Supron S-145, Supron S-382, Suplon SC-101, Suplon SC-102 And Suplon SC-103, Suplon SC-104, Suplon SC-105, and Suplon SC-106 (above, manufactured by Asahi Glass Co., Ltd.).

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

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

The compounding quantity of 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, there exists a tendency for a coating film to become easy to be rough.

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.

Specific examples of the adhesion aid include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, and γ -Glycidoxy propyl 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.

Preparation of Curable Resin Composition

The resin composition of this invention is manufactured by dissolving or disperse | distributing each said component preferably in a suitable solvent preferably. As a solvent used, what melt | dissolves or disperse | distributes each component of a composition and does not react with each component is used preferably.

As such a solvent, the thing similar to what was illustrated as a solvent which can be used in order to manufacture the said copolymer (A1), a copolymer (A2), and a copolymer (A3) is mentioned.

Among these solvents, for example, alcohols, glycol ethers, ethylene glycol alkyl ether acetates, esters, and diethylene glycol are preferably used in view of solubility of each component, reactivity with each component, ease of coating film formation, and the like. Among them, for example, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethylmethyl Ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl methoxy propionate and ethyl ethoxypropionate can be particularly preferably used.

Moreover, in order to improve the in-plane uniformity of a film thickness, the high boiling point solvent can also be used together with the said solvent. As a high boiling point solvent which can be used together, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methyl, for example Pyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, Diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and the like. Among these, N-methylpyrrolidone, γ-butyrolactone, and N, N-dimethylacetamide are preferable.

When using a high boiling point solvent together as a solvent of the radiation sensitive resin composition of this invention, the usage-amount is 50 weight% or less with respect to solvent whole quantity, More preferably, it is 40 weight% or less, More preferably, it is 30 weight It can be made% or less. When the usage-amount of a high boiling point solvent exceeds this usage-amount, the film thickness uniformity, a sensitivity, and a residual film ratio of a coating film may fall.

As the usage-amount of a solvent, content of the total solid (amount except the amount of a solvent from the total amount of the composition containing a solvent) in the composition of this invention becomes like this. Preferably it is 1-50 weight%, More preferably, it is 5-40 weight It is the range which becomes%.

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

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 (D) one-component curable resin composition (α2) using a thermal acid generator as an acid generator, a composition solution is applied onto a substrate. The desired protective film can be formed by heat-processing, after forming a film by prebaking and removing a solvent.

Further, the two-component curable resin composition (β) is prepared by mixing the first component and the second component at the time of its use, and preparing the composition solution, and preferably applying the composition solution onto the substrate within 24 hours after the production, After forming a film by prebaking and removing a solvent, a desired protective film can be formed by heat processing.

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, and a ring-opening polymer 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. Application can preferably be 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 70-90 degreeC.

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

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

In addition, in the case of the one-component curable resin composition (α2) using the radiation-sensitive acid generator as the acid generator (D), the film is formed by applying the composition solution onto a substrate, prebaking to remove the solvent, and then radiation. The desired protective film can be formed by performing an irradiation process (exposure process) and heat-processing 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 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>.

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

The film thickness of the protective film formed in this way becomes like this. Preferably it is 0.1-8 micrometers, More preferably, it is 0.1-6 micrometers, More preferably, it is 0.1-4 micrometers. 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 from the top of a color filter.

The protective film of the present invention satisfies the required transparency, heat resistance, surface hardness, adhesion, and the like, and is excellent in load resistance even under heating, and the generation of sublimation during firing is reduced, and the color filter formed on the support substrate It is excellent in the performance of flattening the step difference, and is particularly preferable as a protective film for an optical device.

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

<Measurement of Molecular Weight of Copolymer by Gel Permeation Chromatography>

Apparatus: GPC-101 (manufactured by Showa Denko Co., Ltd.)

Column: GPC-KF-801, GPC-KF-802, GPC-KF-803, and GPC-KF-804

Mobile phase: Tetrahydrofuran comprising 0.5% by weight phosphoric acid.

Synthesis of Copolymer (A)

Synthesis Example 1

1 part by weight of azoisobutyronitrile, 4 parts by weight of cumyldithiobenzoate, and 50 parts by weight of diethylene glycol ethylmethyl ether were charged into a flask equipped with a cooling tube and a stirrer. Subsequently, after adding 80 parts by weight of glycidyl methacrylate and 20 parts by weight of styrene to replace the nitrogen, the temperature of the reaction solution was raised to 60 ° C. with gentle stirring, and the temperature was maintained for 24 hours, followed by azoisobuty. 3 parts by weight of ronitrile was added, stirring was further performed at 60 ° C. for 4 hours, and 200 parts by weight of diethylene glycol ethylmethyl ether was added to obtain a solution of copolymer (A-1). The polystyrene reduced weight average molecular weight (Mw) of the copolymer (A-1) was 1.3, and the molecular weight distribution (Mw / Mn) was 1.3 and the residual monomer was 1.7 wt%. Solid content concentration of the polymer solution was 29.7 weight%.

Synthesis Example 2

1 part by weight of azoisobutyronitrile, 4 parts by weight of cumyldithiobenzoate, and 50 parts by weight of diethylene glycol ethylmethyl ether were charged into a flask equipped with a cooling tube and a stirrer. Subsequently, 50 parts by weight of glycidyl methacrylate, 20 parts by weight of tricyclodecanyl methacrylate, and 30 parts by weight of methacrylic acid were added to replace the nitrogen, and the temperature of the reaction solution was raised to 60 ° C. with gentle stirring. After maintaining this temperature for 24 hours, 3 parts by weight of azoisobutyronitrile was added and stirred at 60 ° C. for 4 hours, and 200 parts by weight of diethylene glycol ethylmethyl ether was added to give a copolymer (A-2 Polymer solution was obtained. As for the polystyrene reduced weight average molecular weight (Mw) of the copolymer (A-2), 11,000 and molecular weight distribution (Mw / Mn) were 1.4 and the residual monomer was 1.3 weight%. Solid content concentration of the polymer solution was 29.0 weight%.

&Lt; Synthesis Example 3 &

1 part by weight of 2,2'-azobis (2,4-dimethylvaleronitrile), 4 parts by weight of cumyldithiobenzoate, and 50 parts by weight of diethylene glycol ethylmethyl ether were injected into a flask equipped with a cooling tube and a stirrer. It was. Subsequently, 30 parts by weight of styrene, 20 parts by weight of tetrahydropyranyl methacrylate, and 50 parts by weight of glycidyl methacrylate were added to replace the nitrogen, followed by gentle stirring to raise the temperature of the reaction solution to 60 ° C. After maintaining for 24 hours, 3 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) was added, stirring was further performed at 60 ° C for 4 hours, and diethylene glycol ethylmethyl ether 200 The weight part was added and the polymer solution containing copolymer (A-3) was obtained. As for the polystyrene reduced weight average molecular weight (Mw) of copolymer (A-3), 12,000 and molecular weight distribution (Mw / Mn) were 1.4 and the residual monomer was 1.8 weight%. Solid content concentration of the polymer solution was 29.8 weight%.

&Lt; Synthesis Example 4 &

In Synthesis Example 1, a solution of Copolymer (A-4) was obtained according to Synthesis Example 1 except that S-cyanomethyl-S-dodecyltrithiocarbonate was used instead of cumyldithiobenzoate. As for the polystyrene reduced weight average molecular weight (Mw) of the copolymer (A-4), 8,000 and molecular weight distribution (Mw / Mn) were 1.2, and the residual monomer was 1.5 weight%. Solid content concentration of the polymer solution was 30.1 weight%.

&Lt; Synthesis Example 5 &

In the synthesis example 2, the polymer solution containing copolymer (A-5) was obtained according to the synthesis example 2 except having used pyrazole-1-dithiocarboxylic acid phenyl-methyl ester instead of cumyldithiobenzoate. . Polystyrene conversion weight average molecular weight (Mw) of the copolymer (A-5) was 1.3, and molecular weight distribution (Mw / Mn) was 1.3 and the residual monomer was 1.4 weight%. Solid content concentration of the polymer solution was 29.2 weight%.

&Lt; Synthesis Example 6 &

In the synthesis example 1, the polymer solution containing copolymer (A-6) was obtained according to the synthesis example 1 except having used the dithioester of the following formula instead of cumyldithiobenzoate. The polystyrene reduced weight average molecular weight (Mw) of the copolymer (A-6) was 12,000, the molecular weight distribution (Mw / Mn) was 1.3, and the residual monomer was 1.4 wt%. Solid content concentration of the polymer solution was 29.2 weight%.

Synthesis Example 7

In the synthesis example 2, the polymer solution containing copolymer (A-7) was obtained according to the synthesis example 2 except having used xanthate of the following formula instead of cumyldithiobenzoate. As for the polystyrene reduced weight average molecular weight (Mw) of copolymer (A-7), 10,500, molecular weight distribution (Mw / Mn) were 1.2, and the residual monomer was 1.3 weight%. Solid content concentration of the polymer solution was 29.5 weight%.

Comparative 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, followed by 50 parts by weight of styrene and methacryl. 50 parts by weight of acid glycidyl was substituted with nitrogen, followed by gentle stirring to raise the temperature of the reaction solution to 70 ° C., and maintaining the temperature to polymerize for 5 hours, thereby polymer comprising copolymer (a-1) A solution was obtained. The polystyrene reduced weight average molecular weight (Mw) of the copolymer (a-1) was 2.4, and the residual monomer was 7.1 weight% for 20,000, molecular weight distribution (Mw / Mn). Solid content concentration of the polymer solution was 32.9 weight%.

In the following Examples and Comparative Examples, "parts" means "parts by weight".

<Example 1> (Evaluation of two-component curable resin composition (β))

Solution containing the copolymer (A-1) obtained by the synthesis example 1 as (A) component (amount corresponded to 100 parts of copolymers (A-1)), and a bisphenol A novolak-type epoxy resin as (B) component 10 parts of "Epicoat 157S65" (trade name, manufactured by Yuka Shell Epoxy Co., Ltd.), 15 parts of γ-glycidoxypropyltrimethoxysilane as an adhesion aid, and SH-28PA (Toray Dow Corning Silicone ( Note) Manufacture) 0.1 part was mixed, and propylene glycol monomethyl ether acetate was added so that the solid content concentration was 20% by weight, followed by filtration with a Millipore filter having a pore size of 0.5 µm to prepare a solution of the first component.

Subsequently, the 2nd component which melt | dissolved 35 parts of trimellitic anhydride as 65 parts of diethylene glycol methylethyl ether was added to the solution of this 1st component as (C) component, and the composition solution was prepared.

About the obtained composition solution, the protective film was formed and evaluated on the board | substrate by the following method. The evaluation results are shown in Table 1.

Formation of protective film

The composition solution was applied onto the SiO ₂ deep glass substrate using a spinner, then prebaked at 80 ° C. on a hot plate for 5 minutes to form a coating film, and further heated at 230 ° C. in an oven for 60 minutes, and onto the substrate. A protective film with a thickness of 2.0 mu m was formed.

Evaluation of protective film

Evaluation of Transparency:

About the board | substrate with which the protective film was formed, the transmittance | permeability (%) in the wavelength range 400-800 nm is measured using the spectrophotometer 150-20 type Double Beam (made by Hitachi Seisakusho Co., Ltd.). It evaluated by the minimum value. When this value is 95% or more, transparency of a protective film can be said to be favorable.

Evaluation of heat resistant dimensional stability:

About the board | substrate with a protective film, it heated at 250 degreeC in oven for 1 hour, the film thickness before and behind heating was measured, and it evaluated by the value computed by following formula (1). When this value is 95% or more, it can be said that heat-resistant dimensional stability is favorable.

Heat-resistant dimensional stability (%) = (film thickness after heating) x 100 / (film thickness before heating)

Evaluation of heat discoloration resistance:

The substrate on which the protective film was formed was heated at 250 ° C. for 1 hour in an oven, the transmittance was measured in the wavelength range of 400 to 800 nm before and after heating, and then the value calculated by the following equation (2) using the minimum value. Evaluated by. When this value is 5% or less, heat discoloration resistance can be said to be favorable.

Heat discoloration resistance (%) = (minimum value of transmittance before heating)-(minimum value of transmittance after heating)

Evaluation of Surface Hardness:

The board | substrate with which the protective film was formed was evaluated by performing the 8.4.1 pencil scratch test of JISK-5400-1990. When this value is 4H or harder, the surface hardness can be said to be good.

Evaluation of Dynamic Microhardness:

With respect to the substrate on which the protective film was formed, the load was 0.1 gf and the speed was 0.0145 by Shimazu Dynamic Microhardness Tester DUH-201 (manufactured by Shimadzu Corporation), and by indentation test of a ridge angle 115 ° triangular indenter (Herkovitch type). The temperature was set to 23 ° C. and 140 ° C. under conditions of gf / sec and a holding time of 5 seconds.

Evaluation of adhesion:

After performing, pressure cooker test (at a temperature of 120 ℃, humidity of 100%, measured 24 hours) with respect to a substrate in which a protective film, by 8.5.3 adherent checkerboard grid tape method of JIS K-5400-1990, SiO ₂ glass deep Adhesion to the substrate (in Table 1, denoted as "SiO ₂ ") was evaluated.

In addition, a protective film having a film thickness of 2.0 μm was formed in the same manner as above except that a Cr substrate was used instead of the SiO ₂ deep glass substrate, and the adhesion to the Cr substrate (in Table 1, denoted as “Cr”) was evaluated.

The numerical value of Table 1 is the number of remaining checkerboard ticks among 100 checkerboard ticks.

Evaluation of planarization power:

Pigment-based color resists (trade names "JCR RED 689", "JCR GREEN 706" or "CR 8200B"; above, manufactured by JSR Corporation) were coated with a spinner on a SiO ₂ deep glass substrate, and 90 ° C on a hot plate. Prebaked for 150 seconds at to form a coating film. Subsequently, a predetermined pattern mask was interposed using Canon PLA501F (manufactured by Canon Corporation), which is an exposure machine, and g / h / i rays (wavelength ratios of 436 nm, 405 nm, and 365 nm = 2.7). : 2.5: 4.8) in an i-line conversion at an exposure dose of 2,000 J / m 2, then developed using 0.05% potassium hydroxide aqueous solution, washed with ultrapure water for 60 seconds, and further heated at 230 ° C. in an oven for 30 minutes. As a result, a stripe-like color filter (stripe width of 100 µm) of three colors of red, green, and blue was formed.

Subsequently, the surface unevenness | corrugation of the board | substrate which formed this color filter was made into the measurement length 2,000 micrometers, the measurement range 2,000 micrometers ² , and the measurement score n = 5 using the surface roughness alpha-step (manufactured by Tencol Japan Co., Ltd.), and the measurement direction Is set as two directions of the stripe line short axis direction of red, green, and blue direction and the stripe line major axis direction of the same color of red, red, green, green, blue, and blue, and n = 5 (n number of totals) for each direction It was 1.0 micrometer when measured by = 10).

Furthermore, after apply | coating the composition solution manufactured similarly to the above using the spinner on the board | substrate with which the color filter was formed in the same manner to the above, prebaking for 5 minutes at 80 degreeC on a hotplate, and forming a coating film further, By heat-processing for 60 minutes at 230 degreeC in oven, the protective film whose film thickness from the upper surface of a color filter was 2.0 micrometers was formed on the color filter.

Subsequently, about the board | substrate which has a protective film on this color filter, the unevenness | corrugation of the protective film surface was made into a measurement length of 2,000 micrometers, measurement range 2,000 micrometer <^2> , using contact type film thickness measuring apparatus (alpha) -step (manufactured by Tencol Japan Co., Ltd.). The measurement score is n = 5, and the measurement direction is two directions of the stripe line short axis direction of red, green, and blue direction, and the stripe line major axis direction of the same color of red, red, green, green, blue, and blue, and each direction Was measured by n = 5 (n number of total was 10), the height difference (nm) of the highest part and the lowest part was measured 10 times for each measurement, and the average value was evaluated. When this value is 300 nm or less, the planarization performance can be said to be good.

Sublimation rating:

The composition solution was applied on a silicon substrate using a spinner, and then prebaked at 90 ° C. for 2 minutes on a hot plate to form a coating film having a film thickness of 3.0 μm. This silicon substrate was heated at 220 degreeC in the clean oven for 1 hour, and the cured film was obtained. Cooling bare silicon wafers were attached at an interval of 1 cm on the obtained cured film, and heated at 230 ° C. on a hot plate for 1 hour. After continuously processing 20 sheets of the silicon substrate in which the cured film was formed separately without replacing the cooling bare silicon wafer, the presence or absence of a sublimation adhered to the bare silicon was visually verified. The sublimation evaluation can be said to be good when the sublimation is not confirmed. The evaluation results are shown in Table 1.

<Examples 2-4> (Evaluation of 2-component curable resin composition ((beta)))

Except having used each component shown in Table 1, it carried out similarly to Example 1, the solution of the 1st component and the solution of the 2nd component were manufactured, and the composition solution was produced.

About each obtained composition solution, it carried out similarly to Example 1, formed the protective film on the board | substrate, and evaluated. The evaluation results are shown in Table 1.

Comparative Example 1

Except having used each component shown in Table 1, it carried out similarly to Example 1, and prepared the composition solution.

About each obtained composition solution, it carried out similarly to Example 1, formed the protective film on the board | substrate, and evaluated. The evaluation results are shown in Table 2 below.

<Example 5> (Evaluation of 1-component curable resin composition ((alpha)))

A solution containing the copolymer (A-1) obtained in Synthesis Example 1 as the component (A) (amount corresponding to 100 parts of the copolymer (A-1)), and a bisphenol A novolac-type epoxy as the component (B) 10 parts of resin (brand name: Epicoat 157S65, Yuka Shell Epoxy Co., Ltd. product), (D) component as a benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoro antimonate, and an adhesion | attachment adjuvant 15 parts of? -glycidoxypropyltrimethoxysilane and 0.1 part of SH-28PA (manufactured by Toray Dow Corning Silicone Co., Ltd.) as surfactants are further mixed, and the propylene glycol monomethyl is further added so that the solid content concentration is 20%. After addition of ether acetate, the composition solution was prepared by filtration with a Millipore filter having a pore size of 0.5 mu m. The appearance of this composition solution was colorless and transparent.

About the obtained composition solution, the protective film was formed on the board | substrate by the following method, and it evaluated like Example 1. The evaluation results are shown in Table 2.

Formation of protective film

The composition solution was applied onto a SiO ₂ deep glass substrate using a spinner, and then prebaked at 80 ° C. on a hot plate for 5 minutes to form a coating film, and further heated at 230 ° C. in an oven for 60 minutes to form a coating on the substrate. A protective film with a thickness of 2.0 mu m was formed on the substrate.

A protective film was formed on the substrate on which the color filter was formed in the same manner as in Example 1 in the same manner as above.

<Examples 6-12> (Evaluation of 1-component curable resin composition ((alpha)))

Except having used each component shown in Table 2, it carried out similarly to Example 5, and manufactured the composition solution.

About each obtained composition solution, it carried out similarly to Example 5, formed a protective film on the board | substrate, and evaluated similarly to Example 1. The evaluation results are shown in Table 2.

(B) component, (C) component, (D) component, and a solvent in Table 1, 2 are as follows, respectively.

B-1: Bisphenol A novolak-type epoxy resin (brand name: Epicoat 157S65, Yuka Shell Epoxy Co., Ltd. product)

B-2: Bisphenol A type epoxy resin (brand name: Epicoat 828, Yuka Shell Epoxy Co., Ltd. product)

C-1: trimellitic anhydride

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

S-1: Propylene Glycol Monomethyl Ether Acetate

S-2: diethylene glycol dimethyl ether

According to the present invention, it satisfies various characteristics conventionally required as a protective film, specifically, transparency, heat resistance, surface hardness, and adhesion, and also has excellent load resistance under heating, low sublimation, and on a supporting substrate. Curable resin composition which can form the protective film for optical devices which is excellent in the performance of flattening the level difference of the formed color filter can be obtained.

Claims (12)

(A) a polymer having two or more epoxy groups and a ratio (Mw / Mn) of polystyrene reduced weight average molecular weight (Mw) and polystyrene reduced number average molecular weight (Mn) measured by gel permeation chromatography to 1.7 or less; and (B) A cationically polymerizable compound different from the component (A) Wherein (A) component contains (A1) (a) epoxy group-containing polymerizable unsaturated compound, (b1) polymerizable unsaturated carboxylic acid, polymerizable unsaturated polyhydric carboxylic anhydride, or both, (b2 ) Methyl methacrylate, t-butyl methacrylate, cyclohexyl acrylate, dicyclopentanyl methacrylate, 2-methylcyclohexyl acrylate, N-phenylmaleimide, N-cyclohexyl maleimide, styrene, p-methoxy A copolymer with one or more polymerizable unsaturated compounds selected from the group consisting of styrene and 1,3-butadiene, Curable resin composition for forming a protective film. (A) a polymer having two or more epoxy groups and a ratio (Mw / Mn) of polystyrene reduced weight average molecular weight (Mw) and polystyrene reduced number average molecular weight (Mn) measured by gel permeation chromatography to 1.7 or less; and (B) A cationically polymerizable compound different from the component (A) Wherein the component (A) is a polymer containing two or more epoxy groups in the molecule (A2) and at least one structure selected from the group consisting of an acetal structure, a ketal structure and a t-butoxycarbonyl structure, Curable resin composition for forming a protective film. The component (A2) according to claim 2, wherein the component (A2) is selected from the group consisting of (A2-1) (a) an epoxy group-containing polymerizable unsaturated compound and (b3) an acetal structure, a ketal structure and a t-butoxycarbonyl structure. (B4) Methyl methacrylate, cyclohexyl acrylate, dicyclopentanyl methacrylate, 2-methylcyclohexyl acrylate, N-phenylmaleimide, N-cyclohexyl maleimide Curable resin composition which is a copolymer with 1 or more types of polymerizable unsaturated compounds chosen from the group which consists of styrene, p-methoxy styrene, and 1, 3- butadiene. The curable resin composition according to any one of claims 1 to 3, wherein the component (A) is a (co) polymer obtained by living radical polymerization using a thiocarbonylthio compound as a control agent. (A) a polymer having two or more epoxy groups and a ratio (Mw / Mn) of polystyrene reduced weight average molecular weight (Mw) and polystyrene reduced number average molecular weight (Mn) measured by gel permeation chromatography to 1.7 or less; and (B) A cationically polymerizable compound different from the component (A) Wherein (A) component is (A3) (a) epoxy group-containing polymerizable unsaturated compound, (b5) methyl methacrylate, t-butyl methacrylate, cyclohexyl acrylate, dicyclopentanyl methacrylate, Copolymer with at least one polymerizable unsaturated compound selected from the group consisting of 2-methylcyclohexyl, N-phenylmaleimide, N-cyclohexylmaleimide, styrene, p-methoxystyrene and 1,3-butadiene Is a copolymer having no carboxyl group, carboxylic anhydride group, acetal structure, ketal structure and t-butoxycarbonyl structure in the molecule, Curable resin composition for forming a protective film. (C) Curable resin composition of Claim 5 which further contains a hardening | curing agent. (1) A two-component curable resin composition comprising a combination of a first component containing the curable resin composition according to claim 5 and a second component containing a curing agent (2). (A1) (a) an epoxy group containing polymerizable unsaturated compound, (b1) a polymerizable unsaturated carboxylic acid, a polymerizable unsaturated polyhydric carboxylic anhydride, or both, (b2) methyl methacrylate and methacrylic acid t Group consisting of -butyl, cyclohexyl acrylate, dicyclopentanyl methacrylate, 2-methylcyclohexyl acrylate, N-phenylmaleimide, N-cyclohexyl maleimide, styrene, p-methoxystyrene and 1,3-butadiene At least one structure selected from the group consisting of at least two epoxy groups and an acetal structure, a ketal structure and a t-butoxycarbonyl structure in a copolymer with at least one polymerizable unsaturated compound selected from Containing polymer At least one selected from the group consisting of (B) a cationically polymerizable compound different from the (A1) component and the (A2) component, and (D) a compound that generates an acid by irradiation with radiation, heating, or both Curable resin composition containing the. The protective film formed from the curable resin composition of any one of Claims 1-3, 5, 6, and 8, or the two-component curable resin composition of Claim 7. The film is formed on the board | substrate using the curable resin composition of any one of Claims 1-3, 5 and 6 or the two-component curable resin composition of Claim 7, and then heat-processed A method of forming a protective film, characterized in that. A film is formed on the board | substrate using the curable resin composition of Claim 8, and then processed by irradiation of radiation, heating, or both, The formation method of the protective film characterized by the above-mentioned. delete