JP2007100020A - Curable resin composition, over coat, and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable resin composition which can form an over coat having desired transparency, heat resistance, surface hardness, and adhesiveness, excellent in load withstanding property, even when heated, little in sublimate at the time of firing, and also excellent in the performance capability to eliminate the level difference of a color filter formed on an underlying substrate, and to provide an over coat formed by using the composition and a method for forming the over coat. <P>SOLUTION: The curable resin composition contains (A) a polymer containing at least two epoxy groups in a molecule thereof and obtained by the living radical polymerization, (B) a cationic polymerizable compound except a polymerizable unsaturated compound constituting the component A, wherein, the living radical polymerization for producing the polymer A is carryied out by using a specified thiocarbonylthio compound as a molecular weight controlling agent. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to 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 element (LCD), a charge coupled device (CCD), and a CMOS sensor. The present invention relates to a protective film formed from a composition and a method for forming the protective film.

In the process of manufacturing an optical device such as an LCD or CCD, the display element is subjected to an immersion treatment with a solvent, acid, alkali, or the like, and when the wiring electrode layer is formed by sputtering, the surface of the element is locally exposed to a high temperature. Therefore, in order to prevent the display element from being deteriorated or damaged by such treatment, a protective film having resistance to such treatment is provided on the surface of the display element.
Such a protective film is required to have high adhesion to the substrate or lower layer on which the protective film is to be formed, and further to the layer formed on the protective film. Further, the protective film itself is smooth and tough, has transparency, has high heat resistance and light resistance, does not cause deterioration such as coloring, yellowing, and whitening over a long period of time, water resistance, Performances such as excellent solvent resistance, acid resistance and alkali resistance are required. As a material for forming a protective film having these various performances, a thermosetting composition containing a polymer having a glycidyl group (see Patent Document 1: Japanese Patent Laid-Open No. 5-78453) is known. Yes.
In addition, when such a protective film is used for a color filter of an LCD, a CCD, or a CMOS sensor, it is also required that the step due to the color filter formed on the base substrate can be flattened.

In color liquid crystal display elements such as STN (Super Twisted Nematic) type or TFT (Thin Film Transistor) type color liquid crystal display elements, bead-like spacers are dispersed on the protective film in order to uniformly maintain the cell gap of the liquid crystal layer. After that, the panels are bonded together, and then the liquid crystal cell is sealed by thermo-compression of the sealing material, but the protective film in the part where the spacer exists is formed by the heat and pressure applied at that time. The phenomenon of depression is seen, and the problem is that the cell gap is distorted.
In particular, when manufacturing a color liquid crystal display element of STN method, the accuracy of bonding between the color filter and the counter substrate must be extremely strict, and the protective film has an extremely high level flattening performance and heat resistance. Pressure resistance is required.

In recent years, a method of forming 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 a strong alkali has been adopted. For this reason, the surface of the protective film is locally exposed to high temperatures during sputtering or subjected to various chemical treatments. Therefore, it is required to withstand these treatments, and to adhere to the wiring electrodes so that ITO does not peel off from the protective film during chemical treatment.
In the LCD panel, for the purpose of high luminance, a panel having a transparent electrode such as ITO and a TFT element laminated through a highly transparent interlayer insulating film and having a large opening area has been developed. Conventionally, the color filter and the TFT element are manufactured using different substrates, but when an interlayer insulating film is used, a method of forming a color filter on the TFT element has also been developed. Under such a technical background, it is desired to develop a protective film having high heat resistance and excellent performance (flattening ability) for flattening the steps of the color filter formed on the base substrate. .

Furthermore, with the recent increase in the size of panel substrates, unreacted monomers remaining in a trace amount are sublimated when a thermosetting composition is used to form a protective film, and are deposited in a baking furnace. This makes it difficult to control the baking conditions, and the deposited unreacted monomer and / or its heat-modified product adheres to the panel substrate and contaminates it, leading to display defects.
For forming a protective film for a color filter, it is convenient to use a curable resin composition having an advantage that a protective film having excellent surface hardness can be easily formed. A material that satisfies the above required performance, can form a protective film that can meet various requirements as described above, and has excellent storage stability as a composition has not yet been known.
JP-A-5-78453

  The present invention has been made on the basis of the circumstances as described above, and its tasks satisfy the required transparency, heat resistance, surface hardness, and adhesion, and are excellent in load resistance even under heating and fired. Curable resin composition capable of forming a protective film for optical devices, which has excellent performance for flattening the level difference of the color filter formed on the base substrate, and the protection formed from the composition. An object of the present invention is to provide a film and a method for forming the protective film.

According to the present invention, the above problem is firstly
(A) a polymer having two or more epoxy groups and obtained by living radical polymerization (hereinafter sometimes referred to as “(A) (A) polymer”), and (B) a cationic polymerizable compound (Excluding the polymerizable unsaturated compound constituting the component (A)), wherein the living radical polymerization for producing the polymer (A) is represented by the following formula (1) or A curable resin composition characterized by polymerization using a thiocarbonylthio compound represented by the formula (2) as a molecular weight control agent (hereinafter referred to as “one-component curable resin composition (α)”). Solved by.

(In Formula (1), Z ¹ is different from a hydrogen atom, a chlorine atom, a carboxyl group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a carbon atom. Monovalent heterocyclic group having 3 to 20 atoms in total with the term atom, -OR, -SR, -N (R) ₂ , -OC (= O) R, -C (= O) OR, -C (= O) N (R) ₂ , -P (= O) (OR) ₂ , -P (= O) (R) ₂ or a monovalent group having a polymer chain, wherein each R is mutually independent Or an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or 1 having 3 to 18 total atoms of carbon atoms and hetero atoms. A valent heterocyclic group, the above alkyl group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and a monovalent heterocyclic group having 3 to 20 atoms in total. Fine R may be each substituted, ^{R 1,} when the p = 1, an alkyl group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, 6 carbon atoms 20 monovalent aromatic hydrocarbon groups, monovalent heterocyclic groups having 3 to 20 total atoms of carbon atoms and hetero atoms, -OR, -SR, -N (R) ₂ or polymer chain Each R independently represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or carbon. 1 represents a monovalent heterocyclic group having 3 to 18 total atoms of atoms and hetero atoms, and when p ≧ 2, a p-valent group derived from an alkane having 1 to 20 carbon atoms, 6 to 20 carbon atoms A p-valent group derived from an aromatic hydrocarbon, a p-valent group derived from a heterocyclic compound having a total of 3 to 20 carbon atoms and hetero atoms, or A p-valent group having a polymer chain, the alkyl group having 1 to 20 carbon atoms, the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and the monovalent aromatic carbon group having 6 to 20 carbon atoms; A hydrogen group, a monovalent heterocyclic group having 3 to 20 atoms in total, R, a p-valent group derived from an alkane having 1 to 20 carbon atoms, and a p-value derived from an aromatic hydrocarbon having 6 to 20 carbon atoms And a p-valent group derived from a heterocyclic compound having 3 to 20 atoms in total may be substituted.)

(In Formula (2), Z ² is an m-valent group derived from an alkane having 1 to 20 carbon atoms, an m-valent group derived from an aromatic hydrocarbon having 6 to 20 carbon atoms, a carbon atom and an extraneous atom. M-valent group derived from a heterocyclic compound having 3 to 20 atoms in total or m-valent group having a polymer chain, m-valent group derived from an alkane having 1 to 20 carbon atoms, carbon number The m-valent group derived from an aromatic hydrocarbon having 6 to 20 and the m-valent group derived from a heterocyclic compound having 3 to 20 atoms in total may be substituted, and R ² may have 1 to 1 carbon atoms. 20 alkyl groups, monovalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms, monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms, and 3 to 20 total atoms of carbon atoms and hetero atoms A monovalent heterocyclic group, —OR, —SR, —N (R) ₂ or a monovalent group having a polymer chain, wherein each R is a phase Independently of each other, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or a total number of 3 atoms of carbon atoms and hetero atoms 18 represents a monovalent heterocyclic group, the above alkyl group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and a monovalent aromatic carbon group having 6 to 20 carbon atoms. A hydrogen group, a monovalent heterocyclic group having 3 to 20 atoms in total, and R may each be substituted.)
Here, the polymer (A) has a group represented by the following formula (i) or a group represented by the following formula (ii) at at least one terminal of each polymer chain constituting the polymer.

[In Formula (i), Z ¹ is the same as Formula (1), and in Formula (ii), Z ² and m are the same as in Formula (2). ]
According to the present invention, the above problem is secondly,
(A) component is (A1) (a) an epoxy group-containing polymerizable unsaturated compound, (b1) a polymerizable unsaturated carboxylic acid and / or a polymerizable unsaturated polyvalent carboxylic acid anhydride, and (b2) (a) This is preferably solved by the one-component curable resin composition (α) that is a copolymer with the component and a polymerizable unsaturated compound other than the component (b1).
According to the present invention, the above problem is thirdly,
The component (A) is a polymer containing (A2) two or more epoxy groups and at least one structure selected from the group consisting of an acetal structure, a ketal structure and a t-butoxycarbonyl structure in the molecule. A one-component curable resin composition (α),
Is preferably solved.
According to the present invention, the above problem is fourthly,
The component (A) is a copolymer of (A3) (a) an epoxy group-containing polymerizable unsaturated compound and (b5) a polymerizable unsaturated compound other than the component (a), and has a carboxyl group in the molecule. One-component curable resin composition (α), which is a copolymer having no group, carboxylic acid anhydride group, acetal structure, ketal structure and t-butoxycarbonyl structure,
Is preferably solved.
According to the present invention, fifthly, the above problem is
(A3) a copolymer of (a) an epoxy group-containing polymerizable unsaturated compound and a polymerizable unsaturated compound other than the component (b5) (a), wherein a carboxyl group or carboxylic anhydride group is present in the molecule. , A copolymer not having any of an acetal structure, a ketal structure and a t-butoxycarbonyl structure, (B) a cationic polymerizable compound (however, excluding a polymerizable unsaturated compound constituting the component (A3)), And (C) a curable resin composition containing a curing agent (hereinafter referred to as “one-component curable resin composition (α1)”),
Solved by.
According to the present invention, the above problem is sixth,
(1) the first component containing the component (A3) and (B) a cationic polymerizable compound (excluding the polymerizable unsaturated compound constituting the component (A3)); and (2) (C ) A two-component curable resin composition (β) comprising a combination with a second component containing a curing agent,
Is preferably solved.
As used herein, “two-component curable resin composition” means that the combination of the first component and the second component is handled as one article unit, but before being used for the final use, the first component and the second component. Means a composition in which the first component and the second component are mixed and used at the time of final use.
According to the present invention, the above problem is seventhly,
At least one selected from the group consisting of the component (A1) and the component (A2), (B) a cationically polymerizable compound (however, the polymerizable unsaturated compound constituting the component (A1) and the component (A2) (C) a curing agent, and (D) a curable resin composition containing a compound that generates an acid upon irradiation and / or heating (hereinafter referred to as “one-component type”). Curable resin composition (α2) ”),
Is preferably solved.
According to the present invention, the above problem is, eighthly,
The curable resin composition of the present invention, preferably each of the one-component curable resin composition (α), the one-component curable resin composition (α1), the one-component curable resin composition (α2) or A protective film formed from the two-component curable resin composition (β),
Solved by.
According to the present invention, the above problem is ninthly,
The curable resin composition of the present invention, preferably each of the one-component curable resin composition (α), the one-component curable resin composition (α1) or the two-component curable resin composition on a substrate. Forming a film using (β), and then heat-treating the protective film,
Achieved by:
According to the present invention, the above problem is tenth,
A method for forming a protective film, in which a film is formed on a substrate using the one-component curable resin composition (α2), and then subjected to radiation treatment and / or heat treatment,
Is preferably solved.

  According to the present invention, various properties conventionally required as a protective film, specifically, transparency, heat resistance, surface hardness, adhesion, and excellent load resistance even under heating and few sublimates, Moreover, the curable resin composition which can form the protective film for optical devices excellent in the performance which planarizes the level | step difference of the color filter formed on the base substrate can be obtained.

Hereinafter, the present invention will be described in detail.
Curable resin composition- (A) polymer-
The polymer (A) used in the present invention can be obtained by living radical polymerization of a monomer mixture containing an epoxy group-containing polymerizable unsaturated compound.
Next, (A) Living radical polymerization for producing a polymer will be described.
The polymerizable unsaturated compound can be produced by living radical polymerization, preferably together with another copolymerizable unsaturated compound, in a solvent in the presence of a radical polymerization initiator system that generates a living radical.

  In living radical polymerization, when using a compound having a functional group that may deactivate an active radical such as a carboxyl group as a polymerizable unsaturated compound, in order to prevent the growth terminal from being deactivated, (A) A polymer can also be obtained by polymerizing the functional group in the polymerizable unsaturated compound by protecting it by, for example, esterification and then deprotecting it.

  Various radical polymerization initiator systems for living radical polymerization of polymerizable unsaturated compounds have been proposed. For example, a TEMPO system proposed by Georges et al. (See, for example, Non-Patent Document 1), and proposed by Matyjazewski et al. A system composed of a combination of copper bromide and a bromine-containing ester compound (for example, see Non-Patent Document 2), a system composed of a combination of carbon tetrachloride and a ruthenium (II) complex proposed by Hamasaki et al. Non-patent document 3) or a system comprising a combination of a thiocarbonyl compound having a chain transfer constant greater than 0.1 and a radical initiator, as disclosed in Patent Document 2, Patent Document 3 and Patent Document 4. And so on.

M.K.Georges, R.P.N.Veregin, P.M.Kazmaier, G.K.Hamer, Macromolecules, 1993, Vol.26, p.2987 Matyjaszewski, K. Coca, S. Gaynor, G. wei, M. Woodworth, B.E. Macromolecules, 1997, Vol. 30, p. 7348 Hamasaki, S.Kamigaito, M.Sawamoto, M. Macromolecules, 2002, Vol.35, p.2934 Japanese Patent No. 3639859 (Japanese Patent Publication No. 2000-515181) Special Table 2002-2002 JP-T-2004-518773

As a suitable radical polymerization initiator system used for living radical polymerization, a system in which the active radical at the growth end is not deactivated is appropriately selected depending on the type of the polymerizable unsaturated compound used. In consideration of efficiency and metal-free system, a combination of a thiocarbonylthio compound that is a molecular weight control agent and a radical initiator is preferable.
The combination of the thiocarbonylthio compound and the radical initiator is described in detail in Patent Literature 2, Patent Literature 3, and Patent Literature 4 as well as the following patent literature.

Special table 2002-508409 gazette Japanese translation of PCT publication No. 2002-512653 Special table 2003-527458 gazette Patent 3634843 (Japanese Patent Publication No. 2003-536105) JP-T-2005-503452

  As described in Patent Documents 2 to 5, a random copolymer or block copolymer having a narrow molecular weight distribution is obtained by living radical polymerization of an unsaturated compound in the presence of a thiocarbonylthio compound and a radical initiator. Coalescence can be obtained. Moreover, since a functional group can be introduced into the obtained random copolymer and block copolymer, the copolymer is converted into an aqueous gel (see Patent Document 6), a photoresist (see Patent Document 7), and a surface activity. It has been clarified that it can also be used for applications such as an agent (see Patent Document 8).

  Preferred examples of the thiocarbonylthio compound in the present invention include compounds represented by the above formula (1) or (2).

In the above formula (1), examples of the alkyl group having 1 to 20 carbon atoms of Z ¹ include a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec -Butyl group, t-butyl group, n-pentyl group, 1,1-dimethylpropyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, 1,1-dimethyl-3,3- A dimethylbutyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group, n-octadecyl group, n-eicosyl group, etc. can be mentioned.
Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms of Z ¹ include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 9-anthracenyl group, a benzyl group, An α-methylbenzyl group, an α, α-dimethylbenzyl group, a phenethyl group, and the like can be given.

Examples of the monovalent heterocyclic group having 3 to 20 total atoms of the carbon atom and the hetero atom of Z ¹ include oxiranyl group, aziridinyl group, 2-furanyl group, 3-furanyl group, 2- Tetrahydrofuranyl group, 3-tetrahydrofuranyl group, 1-pyrrole group, 2-pyrrole group, 3-pyrrole group, 1-pyrrolidinyl group, 2-pyrrolidinyl group, 3-pyrrolidinyl group, 1-pyrazole group, 2-pyrazole group, 3-pyrazole group, 2-tetrahydropyranyl group, 3-tetrahydropyranyl group, 4-tetrahydropyranyl group, 2-thianyl group, 3-thianyl group, 4-thianyl group, 2-pyridinyl group, 3-pyridinyl group 4-pyridinyl group, 2-piperidinyl group, 3-piperidinyl group, 4-piperidinyl group, 2-morpholinyl group, 3-morpholinyl group, etc. be able to.

Z ¹ —OR, —SR, —N (R) ₂ , —OC (═O) R, —C (═O) OR, —C (═O) N (R) ₂ , —P (= O) (OR) ₂ and —P (═O) (R) ₂ , an alkyl group having 1 to 18 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or a carbon atom and a hetero atom. As the monovalent heterocyclic group having 3 to 18 atoms in total, for example, an alkyl group having 1 to 20 carbon atoms exemplified for Z ¹ , a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or Among the monovalent heterocyclic groups having 3 to 20 total atoms of carbon atoms and hetero atoms, there can be mentioned groups having 18 or less carbon atoms in total.

  Examples of the alkenyl group having 2 to 18 carbon atoms of the same R include, for example, a vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, and 1-pentenyl group. 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group and the like.

The above-mentioned alkyl group having 1 to 20 carbon atoms, monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, monovalent heterocyclic group having 3 to 20 total atoms of carbon atoms and hetero atoms, and R Examples of the substituent include, for example, hydroxyl group, carboxyl group, carboxylate group, sulfonate group, sulfonate group, isocyanate group, cyano group, vinyl group, epoxy group, silyl group, halogen atom, and Z ¹ . -OR, -SR, -N (R) ₂ , -OC (= O) R, -C (= O) OR, -C (= O) N (R) ₂ , -P (= O) (OR) ₂ or -P (= O) (R) ₂ ; an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms exemplified for R, or Same as monovalent heterocyclic group having 3 to 18 total atoms of carbon atom and hetero atom It can be appropriately selected from groups wherein the substituents can be present one or more types in substituted derivatives. However, it is preferable that the total number of carbon atoms or the total number of atoms in the substituted derivative does not exceed 20.

Examples of the monovalent group having a polymer chain of Z ¹ include α-olefins such as ethylene and propylene; aromatic vinyl compounds such as styrene and α-methylstyrene; vinyl fluoride, vinyl chloride, and chloride. Vinyl halides such as vinylidene; unsaturated alcohols such as vinyl alcohol and allyl alcohol; esters of unsaturated alcohols such as vinyl acetate and allyl acetate; unsaturated carboxylic acids such as (meth) acrylic acid and p-vinylbenzoic acid Acids: methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, t- (meth) acrylic acid (Meth) acrylic acid esters such as butyl, n-hexyl (meth) acrylate, and cyclohexyl (meth) acrylate (Meth) acrylamides, (meth) acrylamides such as N, N-dimethyl (meth) acramide; unsaturated nitriles such as (meth) acrylonitrile and vinylidene cyanide; conjugated dienes such as butadiene and isoprene In addition to a monovalent group having an addition polymerization polymer chain formed from one or more unsaturated compounds, polyoxyethylene whose terminal may be etherified, polyoxyethylene whose terminal may be etherified A monovalent group having a polyether such as propylene, a polyaddition polymer chain such as polyester, polyamide or polyimide, a polycondensation polymer chain, or the like can be given. In the monovalent group having these polymer chains, even when the polymer chain is directly bonded to the carbon atom of the thiocarbonyl group in the formula (1), for example, —CH ₂ —COO—, —C _{(CH 3) (CN) CH} 2 CH 2 -COO- may be bonded to the carbon atom of the thiocarbonyl group in the formula (1) via a connecting hands like.
In the above formula (1), a plurality of Z ¹ may be the same as or different from each other.

In Formula (1), when p = 1, R ¹ is an alkyl group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a monovalent group having 6 to 20 carbon atoms. A monovalent heterocyclic group, a monovalent heterocyclic group having 3 to 20 total atoms of carbon atoms and hetero atoms, -OR, -SR, -N (R) ₂ or a monovalent polymer chain Indicates a group.

The alkyl group having 1 to 20 carbon atoms, the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, the monovalent heterocyclic group having 3 to 20 atoms in total, -OR, -SR, -N (R As the monovalent group having ₂ or a polymer chain or a substituted derivative thereof, for example, the same groups as those exemplified for the respective corresponding groups of Z ¹ can be mentioned. In a monovalent group having a polymer chain of R ¹ (p = 1), even when the polymer chain is directly bonded to the sulfur atom in the formula (1), for example, —CH ₂ —COO—, -C (CH _{3) (CN)} may be through a linking hand, such _CH 2 CH 2 -COO- attached to the sulfur atom in the formula (1).

Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include a cyclopentyl group, a cyclohexyl group, a cyclopentenyl group, and a cyclohexenyl group.
Examples of the substituent for the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include, for example, an alkyl group having 1 to 20 carbon atoms in Z ^{1 and} a monovalent aromatic hydrocarbon having 6 to 20 carbon atoms. Group, a monovalent heterocyclic group having 3 to 20 total atoms of carbon atom and hetero atom, and a group similar to those exemplified for the substituent for R can be appropriately selected from these substituents. May be present in the substituted derivative one or more or one or more. However, it is preferable that the total number of carbon atoms or the total number of atoms in the substituted derivative does not exceed 20.

Further, when p ≧ 2, R ¹ is a p-valent group derived from an alkane having 1 to 20 carbon atoms, a p-valent group derived from an aromatic hydrocarbon having 6 to 20 carbon atoms, or a carbon atom different from R ^1. A p-valent group or a p-valent group having a polymer chain derived from a heterocyclic compound having 3 to 20 atoms in total with the atom is shown.

  Examples of the alkane having 1 to 20 carbon atoms include methane, ethane, propane, n-butane, i-butane, n-pentane, i-pentane, neopentane, n-hexane, n-heptane, n-octane, and n. -Nonane, n-decane, n-dodecane, n-tetradecane, n-hexadecane, n-octadecane, n-eicosane and the like can be mentioned.

  Examples of the aromatic hydrocarbon having 6 to 20 carbon atoms include benzene and 1,4-dimethylbenzene (for example, the carbon atom of each methyl group at the 1,4-position is a sulfur atom in the formula (1)). ), 1,2,4,5-tetramethylbenzene (for example, the carbon atom of each methyl group at the 1,2,4,5-position binds to the sulfur atom in formula (1).) 1,2,3,4,5,6-hexamethylbenzene (for example, the carbon atom of each methyl group at the 1,2,3,4,5,6-position binds to the sulfur atom in formula (1)) 1,4-di-i-propylbenzene (for example, the carbon atom at the 2-position of each i-propyl group at the 1,4-position is bonded to the sulfur atom in the formula (1)). Naphthalene, anthracene group and the like can be mentioned.

  Examples of the heterocyclic compound having 3 to 20 atoms in total include oxirane, aziridine, furan, tetrahydrofuran, pyrrole, pyrrolidine, pyrazole, tetrahydropyran, thiane, pyridine, piperidine and morpholine.

P-valent group derived from the alkane having 1 to 20 carbon atoms, p-valent group derived from an aromatic hydrocarbon having 6 to 20 carbon atoms, and p-valent group derived from a heterocyclic compound having 3 to 20 atoms in total. Examples of the substituent for the above group include, for example, an alkyl group having 1 to 20 carbon atoms of Z ^1, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and a total number of 3 atoms of carbon atoms and hetero atoms. -20 monovalent heterocyclic groups and the same groups as those exemplified for the substituent for R can be selected as appropriate, and these substituents are present in one or more or one or more kinds in the substituted derivative. be able to. However, it is preferable that the total number of carbon atoms or the total number of atoms in the substituted derivative does not exceed 20.

Examples of the polymer chain that gives the p-valent group of R ¹ include addition polymerization polymer chains, polyaddition polymer chains, and polycondensation systems exemplified for the monovalent group having the polymer chain of Z ^1. The thing similar to a polymer chain can be mentioned. In the p-valent group having the polymer chain of R ¹ , even when the polymer chain is directly bonded to the sulfur atom in the formula (1), for example, —CH ₂ —COO—, —C (CH ₃ ) ( _CN) via a coupling hand, such as CH ₂ CH 2 -COO- may be bonded to the sulfur atom in the formula (1).

Next, in the formula (2), examples of the alkane having 1 to 20 carbon atoms that gives an m-valent group of Z ² include, for example, alkanes having 1 to 20 carbon atoms that give a p-valent group of the above R ¹ The same compounds as those described above can be mentioned.

In addition, examples of the aromatic hydrocarbon having 6 to 20 carbon atoms that give an m-valent group of Z ² include, for example, compounds exemplified for the aromatic hydrocarbon having 6 to 20 carbon atoms that give a p-valent group of R ¹ above. The same thing can be mentioned.

In addition, examples of the heterocyclic compound having a total of 3 to 20 carbon atoms and a hetero atom of a carbon atom that gives an m-valent group of Z ² include, for example, the carbon atom and the hetero ring that give a p-valent group of R ¹ above. The thing similar to the compound illustrated about the heterocyclic compound of 3-20 total atoms with an atom can be mentioned.

Derived from an m-valent group derived from an alkane having 1 to 20 carbon atoms of Z ² , an m-valent group derived from an aromatic hydrocarbon having 6 to 20 carbon atoms, and a heterocyclic compound having 3 to 20 atoms in total Examples of the substituent for the m-valent group include, for example, an alkyl group having 1 to 20 carbon atoms of Z ^1, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and a total atom of carbon atoms and hetero atoms. The monovalent heterocyclic group of 3 to 20 and the same groups as those exemplified for the substituent for R can be selected as appropriate, and these substituents are one or more or one or more in the substituted derivatives. Can exist. However, it is preferable that the total number of carbon atoms or the total number of atoms in the substituted derivative does not exceed 20.

Examples of the polymer chain that gives an m-valent group of Z ² include, for example, an addition polymerization polymer chain, a polyaddition polymer chain, a heavy chain exemplified for the monovalent group having a polymer chain of Z ¹ above. The thing similar to a condensation type polymer chain can be mentioned. In the m-valent group having a polymer chain of Z ² , even when the polymer chain is directly bonded to the carbon atom of the thiocarbonyl group in the formula (2), for example, —CH ₂ —COO—, — _{C (CH 3) (CN)} CH 2 CH 2 -COO- may be bonded to the carbon atom of the thiocarbonyl group in the formula (2) via a connecting hands like.

In the formula (2), a C 1-20 alkyl group of R ² , a C 6-20 monovalent aromatic hydrocarbon group, a monovalent C 3-20 monovalent carbon atom and a hetero atom. As the monovalent group having a heterocyclic group, —OR, —SR, —N (R) ₂ and a polymer chain, or a substituted derivative thereof, for example, groups exemplified for the corresponding groups of Z ¹ above The same thing can be mentioned. In the monovalent group having the polymer chain of R ² , even when the polymer chain is directly bonded to the sulfur atom in the formula (2), for example, —CH ₂ —COO—, —C (CH ₃ ) ( _CN) via a coupling hand, such as CH ₂ CH 2 -COO- may be bonded to the sulfur atom in the formula (2).

In addition, examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms of R ² and substituted derivatives thereof include, for example, monovalent fats having 3 to 20 carbon atoms of the above R ¹ (p = 1). The thing similar to the group illustrated about the cyclic hydrocarbon group and its substituted derivative can be mentioned.
In the formula (2), a plurality of R ² may be the same as or different from each other.

In Formula (2), when the connecting part between Z ² and —C (═S) —S—R ² is an aliphatic carbon atom, the aliphatic carbon atom in Z ² is —C (═S ) When bonded to —S—R ² and the linking moiety is an aromatic carbon atom, the aromatic carbon atom in Z ² is bonded to —C (═S) —S—R ^2, and When the moiety is a sulfur atom, the sulfur atom in —SR representing Z ² is bonded to —C (═S) —S—R ² .

  Specific examples of particularly preferred thiocarbonylthio compounds in the present invention include compounds represented by the following formulas (3) to (22).

These thiocarbonylthio compounds can be used alone or in admixture of two or more.
In the present invention, at the time of living radical polymerization, other molecular weight control agents such as α-methylstyrene dimer and t-dodecyl mercaptan can be used in combination with the thiocarbonylthio compound.

The radical initiator used in the living radical polymerization is not particularly limited, and those generally known as radical polymerization initiators can be used, for example, 2,2′-azobisisobutyrate. Azo compounds such as rhonitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, 1 , 1'-bis (t-butylperoxy) cyclohexane, organic peroxides such as t-butylperoxypivalate; hydrogen peroxide; redox initiators composed of these peroxides and reducing agents. it can.
These radical initiators can be used alone or in admixture of two or more.

The solvent used in the living radical polymerization is not particularly limited as long as the active radical is not deactivated.
Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether;
Ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, dipropylene glycol methyl ether acetate, dipropylene glycol ethyl ether acetate, etc. Poly) alkylene glycol alkyl ether acetates;
(Poly) alkylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl ethyl ether, dipropylene glycol diethyl ether;
Other ethers such as tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;
Ketoalcohols such as diacetone alcohol (ie 4-hydroxy-4-methylpentan-2-one), 4-hydroxy-4-methylhexane-2-one;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
Ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropion Ethyl acetate, ethyl ethoxyacetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-acetate Butyl, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate , Methyl acetoacetate, ethyl acetoacetate, 2-oxobutanoic acid Other esters such as Le;
Aromatic hydrocarbons such as toluene and xylene;
Examples thereof include amides such as N-methylpyrrolidone, N, N-dimethylformamide, and N, N-dimethylacetamide.

Of these solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether from the viewpoints of solubility and coating properties of each component when used as a curable resin composition. Acetate, dipropylene glycol methyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropion Ethyl acetate, 3-methyl-3-methoxybutylpropionate, n-butyl acetate, i-butyl acetate, Acid n- pentyl acetate, i- pentyl, n- butyl propionate, ethyl butyrate, i- propyl butyrate n- butyl, ethyl pyruvate are preferred.
The said solvent can be used individually or in mixture of 2 or more types.

In the living radical polymerization, the amount of the thiocarbonylthio compound used is usually 0.1 to 50 parts by weight, preferably 0.2 to 16 parts by weight, based on 100 parts by weight of the total unsaturated compounds. The usage-amount of an initiator is 0.1-50 weight part normally with respect to 100 weight part of all the unsaturated compounds, Preferably it is 0.1-20 weight part.
The polymerization temperature is usually 0 to 150 ° C., preferably 50 to 120 ° C., and the polymerization time is usually 10 minutes to 20 hours, preferably 30 minutes to 6 hours.

As the preferred (A) polymer in the present invention, for example,
(A1) (a) Epoxy group-containing polymerizable unsaturated compound (hereinafter referred to as “unsaturated compound (a)”) and (b1) polymerizable unsaturated carboxylic acid and / or polymerizable unsaturated polyvalent carboxylic acid anhydride (Hereinafter collectively referred to as “unsaturated compound (b1)”) and (b2) polymerizable unsaturated compound other than unsaturated compound (a) and unsaturated compound (b1) (hereinafter referred to as “unsaturated compound”). (B2) ") and a copolymer (hereinafter referred to as" copolymer (A1) ");
(A2) A polymer containing two or more epoxy groups in the molecule and 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 “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), A copolymer having no carboxyl group, carboxylic anhydride group, acetal structure, ketal structure or t-butoxycarbonyl structure in the molecule (hereinafter referred to as “copolymer (A3)”).
And so on.

The polymer (A2) contains (A2-1) an unsaturated compound (a) and (b3) at least one structure selected from the group consisting of an acetal structure, a ketal structure and a t-butoxycarbonyl structure. Polymerizable unsaturated compound (hereinafter referred to as “unsaturated compound (b3)”) and (b4) a polymerizable unsaturated compound other than unsaturated compound (a) and unsaturated compound (b3) (hereinafter referred to as “unsaturated compound”). A copolymer with a saturated compound (b4) ”(hereinafter referred to as“ copolymer (A2-1) ”) is more preferable.
The copolymer (A1) can further contain an acetal structure, a ketal structure or a t-butoxycarbonyl structure, and the polymer (A2) can further contain a carboxyl group or a carboxylic anhydride group. it can.

In copolymer (A1), polymer (A2) and copolymer (A3), examples of unsaturated compound (a) include glycidyl (meth) acrylate, glycidyl α-ethyl acrylate, α-n- Glycidyl propyl acrylate, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl (meth) acrylate, 3,4-epoxybutyl α-ethyl acrylate, 6,7-epoxyheptyl (meth) acrylate, Examples include α-ethyl acrylate 6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and the like.
Among these unsaturated compounds (a), glycidyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether Etc. are preferable. These preferable unsaturated compounds (a) have high copolymerization reactivity, and are effective in increasing the heat resistance and surface hardness of the resulting protective film.
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, itaconic acid acid;
Mention may be made of maleic anhydride, itaconic anhydride, citraconic anhydride, and unsaturated polycarboxylic anhydrides such as cis-1,2,3,4-tetrahydrophthalic anhydride.
Of these unsaturated compounds (b1), acrylic acid and methacrylic acid are particularly preferable as the unsaturated carboxylic acid, and maleic anhydride is particularly preferable as the unsaturated polyvalent carboxylic acid anhydride. These preferable unsaturated compounds (b1) have high copolymerization reactivity and are effective in 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 (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl;
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, (Meth) acrylic acid alkyl ester such as (meth) acrylic acid sec-butyl, (meth) acrylic acid t-butyl;
(Meth) acrylic acid cyclopentyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid 2-methylcyclohexyl, (meth) acrylic acid tricyclo [5.2.1.0 ^2.6 ] decan-8-yl (hereinafter, Tricyclo [5.2.1.0 ^2.6 ] decan-8-yl is referred to as “dicyclopentanyl”), 2-dicyclopentanyloxyethyl (meth) acrylate, and isobornyl (meth) acrylate. Such (meth) acrylic acid alicyclic ester;
(Meth) acrylic acid aryl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate;
Unsaturated dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
N-phenylmaleimide, N-benzylmaleimide, N-cyclohexylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Unsaturated dicarbonylimide derivatives such as maleimide propionate, N- (9-acridyl) maleimide;
Vinyl cyanide compounds such as (meth) acrylonitrile, α-chloroacrylonitrile, 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, p-methoxystyrene;
Indene, indene derivatives such as 1-methylindene;
In addition to conjugated diene compounds such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene,
Examples include vinyl chloride, vinylidene chloride, and vinyl acetate.

Among these unsaturated compounds (b2), methyl methacrylate, t-butyl methacrylate, cyclohexyl acrylate, dicyclopentanyl methacrylate, 2-methylcyclohexyl acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, styrene , P-methoxystyrene, 1,3-butadiene and the like are preferable. These preferable unsaturated compounds (b2) have high copolymerization reactivity, and the heat resistance of the protective film obtained (except for the case of 1,3-butadiene) and surface hardness (however, 1,3- It is effective to enhance the case of butadiene.
The said unsaturated compound (b2) can be used individually or in mixture of 2 or more types.

As preferable specific examples of the copolymer (A1),
Glycidyl acrylate / acrylic acid / dicyclopentanyl acrylate / styrene copolymer,
Glycidyl methacrylate / methacrylic acid / dicyclopentanyl methacrylate / 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,
Glycidyl methacrylate / methacrylic acid / N-phenylmaleimide / styrene copolymer,
Glycidyl methacrylate / methacrylic acid / N-cyclohexylmaleimide / styrene copolymer,
Glycidyl methacrylate / methacrylic acid / dicyclopentanyl methacrylate / 1,3-butadiene copolymer,
6,7-epoxyheptyl methacrylate / methacrylic acid / dicyclopentanyl methacrylate / styrene copolymer,
Glycidyl methacrylate / methacrylic acid / dicyclopentanyl methacrylate / styrene / 1,3-butadiene copolymer,
6,7-epoxyheptyl methacrylate / acrylic acid / maleic anhydride / styrene copolymer,
Mention may be made of 6,7-epoxyheptyl methacrylate / acrylic acid / maleic anhydride / t-butyl methacrylate copolymer.

Of these copolymers (A1), more preferably,
Glycidyl methacrylate / methacrylic acid / dicyclopentanyl methacrylate / styrene copolymer,
Glycidyl methacrylate / methacrylic acid / N-phenylmaleimide / styrene copolymer,
Glycidyl methacrylate / methacrylic acid / N-cyclohexylmaleimide / styrene copolymer,
Glycidyl methacrylate / methacrylic acid / dicyclopentanyl methacrylate / 1,3-butadiene copolymer,
Examples thereof include glycidyl methacrylate / methacrylic acid / dicyclopentanyl methacrylate / 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 all the repeating units. (B1) The total content of repeating units derived from the polymerizable unsaturated carboxylic acid and polymerizable unsaturated polyvalent carboxylic acid anhydride is preferably 5 to 40% by weight, particularly preferably 10%, based on all repeating units. ~ 30% by weight. (B2) The content of repeating units derived from other polymerizable unsaturated compounds is preferably 10 to 70% by weight, particularly preferably 20 to 50% by weight, based on all repeating units.
If the content of the repeating unit derived from the unsaturated compound (a) is less than 10% by weight, the heat resistance and surface hardness of the protective film tend to decrease, whereas if it exceeds 70% by weight, the storage stability of the composition is increased. Tends to decrease. In addition, when the total content of the repeating units derived from (b1) polymerizable unsaturated carboxylic acid and polymerizable unsaturated polyvalent carboxylic acid anhydride is less than 5% by weight, the heat resistance, surface hardness and chemical resistance of the protective film On the other hand, if it exceeds 40% by weight, the storage stability of the composition tends to decrease. In addition, when the content of the repeating unit derived from (b2) another polymerizable unsaturated compound is less than 10% by weight, the storage stability of the composition tends to be lowered, whereas when it exceeds 70% by weight, the protective film There is a tendency for the heat resistance and surface hardness of the steel to decrease.

Next, 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 ketal structure in the polymer (A2) is obtained by combining the carbon in the polymer (A2) with an acetal-forming functional group or ketal-forming functional group as described below directly or through a bond such as a carbonyl group. It can be introduced by bonding to an atom.

Examples of the functional group capable of forming an acetal structure (hereinafter referred to as “acetal-forming functional group”) include:
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 Group, 1-t-butoxyethoxy group, 1-cyclopentyloxyethoxy group, 1-cyclohexyloxyethoxy group, 1-norbornyloxyethoxy group, 1-bornyloxyethoxy group, 1-phenoxyethoxy group, 1- ( 1-naphthyloxy) ethoxy group, 1-benzyloxyethoxy group, 1-phenethyloxyethoxy group,
(Cyclohexyl) (methoxy) methoxy group, (cyclohexyl) (ethoxy) methoxy group, (cyclohexyl) (n-propoxy) methoxy group, (cyclohexyl) (i-propoxy) methoxy group, (cyclohexyl) (cyclohexyloxy) methoxy group, (Cyclohexyl) (phenoxy) methoxy group, (cyclohexyl) (benzyloxy) methoxy group, (phenyl) (methoxy) methoxy group, (phenyl) (ethoxy) methoxy group, (phenyl) (n-propoxy) methoxy group, (phenyl) ) (I-propoxy) methoxy group, (phenyl) (cyclohexyloxy) methoxy group, (phenyl) (phenoxy) methoxy group, (phenyl) (benzyloxy) methoxy group, (benzyl) (methoxy) methoxy group, (benzyl) (Etoki ) Methoxy group, (benzyl) (n-propoxy) methoxy group, (benzyl) (i-propoxy) methoxy group, (benzyl) (cyclohexyloxy) methoxy group, (benzyl) (phenoxy) methoxy group, (benzyl) (benzyl) Oxy) methoxy group, 2-tetrahydrofuranyloxy group, 2-tetrahydropyranyloxy group and the like.
Of these acetal-forming functional groups, 1-ethoxyethoxy group, 1-n-propoxyethoxy group, 1-cyclohexyloxyethoxy group, 2-tetrahydropyranyloxy group, 2-tetrahydropyranyloxy group and the like are preferable.

Examples of the functional group capable of forming a ketal structure (hereinafter referred to as “ketal-forming functional group”) include, for example, 1-methyl-1-methoxyethoxy group, 1-methyl-1-ethoxyethoxy group, 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- ( -Naphthyloxy) ethoxy group, 1-methyl-1-benzyloxyethoxy group, 1-methyl-1-phenethyloxyethoxy group, 1-cyclohexyl-1-methoxyethoxy group, 1-cyclohexyl-1-ethoxyethoxy group, 1 -Cyclohexyl-1-n-propoxyethoxy group, 1-cyclohexyl-1-i-propoxyethoxy group, 1-cyclohexyl-1-cyclohexyloxyethoxy group, 1-cyclohexyl-1-phenoxyethoxy group, 1-cyclohexyl-1- Benzyloxyethoxy group, 1-phenyl-1-methoxyethoxy group, 1-phenyl-1-ethoxyethoxy group, 1-phenyl-1-n-propoxyethoxy group, 1-phenyl-1-i-propoxyethoxy group, 1 -Phenyl-1-cyclohexyloxyethoxy Group, 1-phenyl-1-phenoxyethoxy group, 1-phenyl-1-benzyloxyethoxy group, 1-benzyl-1-methoxyethoxy group, 1-benzyl-1-ethoxyethoxy group, 1-benzyl-1-n -Propoxyethoxy group, 1-benzyl-1-i-propoxyethoxy group, 1-benzyl-1-cyclohexyloxyethoxy group, 1-benzyl-1-phenoxyethoxy group, 1-benzyl-1-benzyloxyethoxy group, 1 -Methoxycyclopentyloxy group, 1-methoxycyclohexyloxy group, 2- (2-methyltetrahydrofuranyl) oxy group, 2- (2-methyltetrahydropyranyl) oxy group and the like can be mentioned.
Of these ketal-forming functional groups, 1-methyl-1-methoxyethoxy group, 1-methyl-1-cyclohexyloxyethoxy group and the like are preferable.

  The polymer (A2) is a one-component curable resin composition (α) that has excellent storage stability and excellent flattening ability of the resulting protective film compared to the case of using the copolymer (A1). ).

  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 “an unsaturated compound (b3)”) A (meth) acrylic acid ester compound having an acetal structure and / or a ketal structure (hereinafter referred to as a “specific (meth) acrylic acid ester compound”), or (meth) acrylic acid. Examples thereof include t-butyl.

As a specific example of the specific norbornene 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,
Examples include 2,3-di (t-butoxycarbonyl) -5-norbornene.

Specific examples of the specific (meth) acrylate compound include 1-ethoxyethyl (meth) acrylate, 1-n-propoxyethyl (meth) acrylate, 1-n-butoxyethyl (meth) acrylate, (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, and the like.
Of these unsaturated compounds (b3), specific (meth) acrylic acid ester compounds and t-butyl (meth) acrylate are preferred, and in particular, 1-ethoxyethyl methacrylate, 1-i-butoxyethyl methacrylate, methacryl 1- (cyclopentyloxy) ethyl acid, 1- (cyclohexyloxy) ethyl methacrylate, 1- (1,1-dimethylethoxy) ethyl methacrylate, tetrahydro-2H-pyran-2-yl methacrylate, t-butyl methacrylate Etc. are particularly preferred. These preferable unsaturated compounds (b3) have a high copolymerization reactivity and are excellent in storage stability and flattening ability of the protective film. One-component curable resin composition (α) and one-component curable resin It is effective for providing the composition (α2) and enhancing the heat resistance and surface hardness of the protective film obtained.
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 unsaturated compound (b2) can be mentioned, for example.
Of these unsaturated compounds (b4), methyl methacrylate, cyclohexyl acrylate, dicyclopentanyl methacrylate, 2-methylcyclohexyl acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, styrene, p-methoxystyrene, 1,3-butadiene is preferred. These preferred unsaturated compounds (b4) have high copolymerization reactivity, and the heat resistance of the protective film obtained (except for the case of 1,3-butadiene) and surface hardness (however, 1,3- It is effective to enhance the case of butadiene.
The said unsaturated compound (b4) can be used individually or in mixture of 2 or more types.

As a preferable specific example of the copolymer (A2-1),
Glycidyl methacrylate / tetrahydro-2H-pyran-2-yl acrylate / dicyclopentanyl methacrylate / styrene copolymer,
Glycidyl methacrylate / tetrahydro-2H-pyran-2-yl methacrylate / dicyclopentanyl methacrylate / styrene copolymer,
Glycidyl methacrylate / tetrahydro-2H-pyran-2-yl acrylate / N-phenylmaleimide / styrene copolymer,
Glycidyl methacrylate / tetrahydro-2H-pyran-2-yl methacrylate / N-phenylmaleimide / styrene copolymer,
Glycidyl methacrylate / tetrahydro-2H-pyran-2-yl acrylate / N-cyclohexylmaleimide / styrene copolymer,
Glycidyl methacrylate / tetrahydro-2H-pyran-2-yl methacrylate / N-cyclohexylmaleimide / styrene copolymer,
Glycidyl methacrylate / 1- (cyclohexyloxy) ethyl acrylate / dicyclopentanyl methacrylate / styrene copolymer,
Glycidyl methacrylate / 1- (cyclohexyloxy) ethyl methacrylate / dicyclopentanyl methacrylate / styrene copolymer,
Glycidyl methacrylate / 1- (cyclohexyloxy) ethyl acrylate / N-cyclohexylmaleimide / styrene copolymer,
Glycidyl methacrylate / l- (cyclohexyloxy) ethyl methacrylate / N-cyclohexylmaleimide / styrene copolymer,
Glycidyl methacrylate / 2,3-di (tetrahydropyran-2-yloxycarbonyl) -5-norbornene / dicyclopentanyl methacrylate / styrene copolymer,
Glycidyl methacrylate / 2,3-di (tetrahydropyran-2-yloxycarbonyl) -5-norbornene / N-cyclohexylmaleimide / styrene copolymer,
Glycidyl methacrylate / tetrahydro-2H-pyran-2-yl acrylate / dicyclopentanyl methacrylate / 1,3-butadiene copolymer,
Glycidyl methacrylate / tetrahydro-2H-pyran-2-yl methacrylate / dicyclopentanyl methacrylate / 1,3-butadiene copolymer,
Glycidyl methacrylate / tetrahydro-2H-pyran-2-yl acrylate / methyl methacrylate / styrene copolymer,
Glycidyl methacrylate / tetrahydro-2H-pyran-2-yl methacrylate / methyl methacrylate / styrene copolymer,
Glycidyl methacrylate / tetrahydro-2H-pyran-2-yl acrylate / cyclohexyl acrylate / p-methoxystyrene copolymer,
Glycidyl methacrylate / tetrahydro-2H-pyran-2-yl methacrylate / cyclohexyl acrylate / p-methoxystyrene copolymer,
Glycidyl acrylate / t-butyl methacrylate / N-phenylmaleimide / styrene copolymer,
Glycidyl methacrylate / t-butyl methacrylate / N-cyclohexylmaleimide / styrene copolymer,
6,7-epoxyheptyl methacrylate / tetrahydro-2H-pyran-2-yl acrylate / t-butyl methacrylate / maleic anhydride copolymer,
6,7-epoxyheptyl methacrylate / tetrahydro-2H-pyran-2-yl methacrylate / t-butyl methacrylate / maleic anhydride copolymer,
6,7-epoxyheptyl methacrylate / t-butyl methacrylate / dicyclopentanyl methacrylate / styrene copolymer,
6,7-epoxyheptyl methacrylate / t-butyl methacrylate / maleic anhydride / styrene copolymer,
Glycidyl methacrylate / acrylic acid 1- (cyclohexyloxy) ethyl / dicyclopentanyl methacrylate / styrene / 1,3-butadiene copolymer,
Examples thereof include glycidyl methacrylate / 1- (cyclohexyloxy) ethyl methacrylate / dicyclopentanyl methacrylate / styrene / 1,3-butadiene copolymer.

Of these copolymers (A2-1), more preferably,
Glycidyl methacrylate / tetrahydro-2H-pyran-2-yl acrylate / dicyclopentanyl methacrylate / styrene copolymer,
Glycidyl methacrylate / tetrahydro-2H-pyran-2-yl methacrylate / dicyclopentanyl methacrylate / styrene copolymer,
Glycidyl methacrylate / tetrahydro-2H-pyran-2-yl acrylate / N-phenylmaleimide / styrene copolymer,
Glycidyl methacrylate / tetrahydro-2H-pyran-2-yl methacrylate / N-phenylmaleimide / styrene copolymer,
Glycidyl methacrylate / tetrahydro-2H-pyran-2-yl acrylate / N-cyclohexylmaleimide / styrene copolymer,
Glycidyl methacrylate / tetrahydro-2H-pyran-2-yl methacrylate / N-cyclohexylmaleimide / styrene copolymer,
Glycidyl methacrylate / 1- (cyclohexyloxy) ethyl acrylate / N-cyclohexylmaleimide / styrene copolymer,
Glycidyl methacrylate / l- (cyclohexyloxy) ethyl methacrylate / N-cyclohexylmaleimide / styrene copolymer,
Glycidyl methacrylate / 2,3-di (tetrahydropyran-2-yloxycarbonyl) -5-norbornene / dicyclopentanyl methacrylate / styrene copolymer,
Glycidyl methacrylate / 2,3-di (tetrahydropyran-2-yloxycarbonyl) -5-norbornene / N-cyclohexylmaleimide / styrene copolymer,
And glycidyl methacrylate / t-butyl methacrylate / N-cyclohexylmaleimide / styrene copolymer.

In the copolymer (A2-1), 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 all the repeating units. is there. If the content of the repeating unit derived from the unsaturated compound (a) is less than 10% by weight, the heat resistance and surface hardness of the protective film tend to decrease, whereas if it exceeds 70% by weight, the storage stability of the composition is increased. Tends to decrease.
The content of the repeating unit derived from the unsaturated compound (b3) is preferably 5 to 60% by weight, particularly preferably 10 to 50% by weight. By setting the content of the repeating unit derived from the unsaturated compound (b3) within this range, good heat resistance and surface hardness of the protective film can be realized.
Further, the content of the repeating unit derived from the unsaturated compound (b4) is an amount obtained by subtracting the total content of the repeating unit derived from the unsaturated compound (a) and the unsaturated compound (b3) from 100% by weight. However, when unsaturated carboxylic acids or unsaturated polyvalent carboxylic acid anhydrides are used as the unsaturated compound (b4), if the total content of repeating units derived from these exceeds 40% by weight, the composition is preserved. Since stability may be impaired, it is preferable not to exceed this value.

Next, in the copolymer (A3), examples of the unsaturated compound (b5) include the same compounds as those exemplified for the unsaturated compound (b2).
Among these unsaturated compounds (b5), methyl methacrylate, t-butyl methacrylate, cyclohexyl acrylate, dicyclopentanyl methacrylate, 2-methylcyclohexyl acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, styrene , P-methoxystyrene, 1,3-butadiene and the like are preferable. These preferable unsaturated compounds (b5) have high copolymerization reactivity, and the heat resistance (excluding the case of 1,3-butadiene) and surface hardness (however, 1,3-butadiene is obtained). This is effective in enhancing the case of butadiene.
The said unsaturated compound (b5) can be used individually or in mixture of 2 or more types.

As a preferable specific example of the copolymer (A3),
Glycidyl acrylate / styrene copolymer,
Glycidyl methacrylate / styrene copolymer,
Glycidyl acrylate / dicyclopentanyl methacrylate copolymer,
Glycidyl methacrylate / dicyclopentanyl methacrylate copolymer,
Methacrylic acid 6,7-epoxyheptyl / styrene copolymer,
Glycidyl methacrylate / dicyclopentanyl methacrylate / styrene copolymer,
Glycidyl methacrylate / N-phenylmaleimide / styrene copolymer,
Glycidyl methacrylate / N-cyclohexylmaleimide / styrene copolymer, 6,7-epoxyheptyl methacrylate / dicyclopentanyl methacrylate copolymer,
Mention may be made of 6,7-epoxyheptyl methacrylate / N-cyclohexylmaleimide / styrene copolymer.

  Of these copolymers (A3), more preferably, glycidyl methacrylate / styrene copolymer, glycidyl methacrylate / dicyclopentanyl methacrylate copolymer, glycidyl methacrylate / dicyclopentanyl methacrylate / styrene. Copolymers, glycidyl methacrylate / N-cyclohexylmaleimide / styrene copolymers, and the like.

In the copolymer (A3), the content 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 all repeating units.
If the content of the repeating unit derived from the unsaturated compound (a) is less than 1% by weight, the heat resistance and surface hardness of the protective film tend to decrease, whereas if it exceeds 90% by weight, the storage stability of the composition is increased. Tends to decrease.

  The polymer (A) used in the curable resin composition of the present invention can be obtained by living radical polymerization of an unsaturated compound as described above. At that time, the above formula (1) or the above formula ( The thiocarbonylthio compound represented by 2) is used as a molecular weight control agent. For this reason, the polymer (A) is a group represented by the above formula (i) derived from the compound of the above formula (1) at at least one end of the polymer chain, or the above formula derived from the above formula (2). It has a group represented by the formula (ii).

The polymer (A) used in the present invention is a ratio of polystyrene-equivalent weight average molecular weight (hereinafter referred to as “Mw”) and polystyrene-equivalent number average molecular weight (hereinafter referred to as “Mn”) measured by gel permeation chromatography ( Mw / Mn) is 1.7 or less, preferably 1.5 or less. When Mw / Mn exceeds 1.7, heat resistance may be inferior. Further, Mw is preferably 2 × 10 ³ to 1 × 10 ⁵ , more preferably 5 × 10 ^{3 to} 5 × 10 ⁴ . When Mw is less than 2 × 10 ³ , the coating property of the composition may be insufficient, or the heat resistance of the protective film to be formed may be insufficient. On the other hand, if Mw exceeds 1 × 10 ⁵ , the planarization performance may be insufficient. Further, Mn is preferably 1.2 × 10 ³ to 1 × 10 ⁵ , and more preferably 2.9 × 10 ^{3 to} 5 × 10 ⁴ .

Further, the residual monomer amount measured by gel permeation chromatography of the (A) polymer used in the present invention is preferably less than 5.0%, more preferably less than 3.0%, and particularly preferably 2.0%. Is less than. By using a copolymer having such a residual monomer content, a coating film in which sublimates during firing are reduced can be obtained.
In the present invention, the (A) polymer can be used alone or in admixture of two or more. In the one-component curable resin composition (α2), the copolymer (A1) and the polymer can be used. At least one member of the group (A2) can be used.

-(B) Cationic polymerizable compound-
(B) component in this invention consists of a cationically polymerizable compound different from the unsaturated compound which comprises (A) polymer.
The cationic polymerizable compound is not particularly limited as long as it can be polymerized under acidic conditions. For example, at least one selected from the group consisting of an oxetane ring skeleton, a 3,4-epoxycyclohexane skeleton, and an epoxy group. Examples thereof include a compound having a group that can undergo an addition reaction with an epoxy group in the polymer (A), such as a compound having two or more species in the molecule.

Specific examples of the cationically polymerizable compound include the following.
As a compound having two or more oxetane ring skeletons in the molecule, 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, tetraethylene glycol bis ((3-ethyl-3-oxetanyl) methyl) ether, tricyclodecanediyldimethylene bis ((3-ethyl-3-oxetanyl) methyl) ether, trimethylolpropane tris ((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) me 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, dipentaerythritol pentakis ((3-ethyl-3-oxetanyl) methyl) ether, dipentaerythritol tetrakis ((3-ethyl-3-oxetanyl) methyl) ether,
Reaction product of dipentaerythritol hexakis ((3-ethyl-3-oxetanyl) methyl) ether and caprolactone, reaction product of dipentaerythritol pentakis ((3-ethyl-3-oxetanyl) methyl) ether and caprolactone Product, ditrimethylolpropanetetrakis ((3-ethyl-3-oxetanyl) methyl) ether, reaction product of bisphenol A bis ((3-ethyl-3-oxetanyl) methyl) ether and ethylene oxide, bisphenol A bis (( Reaction product of 3-ethyl-3-oxetanyl) methyl) ether and propylene oxide, reaction product of hydrogenated bisphenol A bis ((3-ethyl-3-oxetanyl) methyl) ether and ethylene oxide, hydrogenated bisphenol A bis (( - ethyl-3-oxetanyl) methyl) reaction products of ether and propylene oxide, and the like bisphenol F bis ((3-ethyl-3-oxetanyl) methyl) reaction products of ether and ethylene oxide.

As a compound having two or more 3,4-epoxycyclohexane skeletons in the molecule, 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′-methylcyclohexanecarboxy Rate, methylene bis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol bis (3,4-epoxycyclohexylmethyl) ether, ethylene bis (3,4-epoxycyclohexanecarboxylate), lactone modified 3,4 -D Carboxymethyl epoxycyclohexylmethyl-3 ', and the like 4'-epoxycyclohexane carboxylate.

As a compound having two or more epoxy groups in the molecule, 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 diglycidyl ether, brominated bisphenol A diglycidyl ether, Diglycidyl ethers of bisphenol compounds such as brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether;
Polyhydric alcohols such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether Glycidyl ether;
A polyglycidyl ether of a polyether polyol obtained by reaction of an aliphatic polyhydric alcohol such as ethylene glycol, propylene glycol, or glycerin with one or more alkylene oxides;
Epoxy resins such as phenol novolac type epoxy resins, cresol novolak type epoxy resins, polyphenol type epoxy resins, cyclic aliphatic epoxy resins; diglycidyl esters of aliphatic long-chain dibasic acids;
Polyglycidyl esters of higher polyhydric fatty acids;
Examples include epoxidized soybean oil and epoxidized linseed oil.

As a commercial product of a compound having two or more epoxy groups in the molecule, for example,
As polyglycidyl ether of a polyhydric alcohol, Epolite 100MF (manufactured by Kyoeisha Chemical Co., Ltd.), Epiol TMP (manufactured by NOF Corporation);
As bisphenol A type epoxy resin, Epicoat 828, 1001, 1002, 1003, 1004, 1007, 1009, 1010 (above, manufactured by Yuka Shell Epoxy Co., Ltd.) and the like;
As bisphenol F type epoxy resin, Epicoat 807 (manufactured by Yuka Shell Epoxy Co., Ltd.) and the like;
Examples of the phenol novolac type epoxy resin include Epicoat 152, 154, and 157S65 (manufactured by Yuka Shell Epoxy Co., Ltd.), DPPN201, 202 (manufactured by Nippon Kayaku Co., Ltd.), and the like;
Examples of cresol novolac type epoxy resins include DOCN102, 103S, 104S, 1020, 1025, 1027 (above, manufactured by Nippon Kayaku Co., Ltd.), Epicoat 180S75 (manufactured by Yuka Shell Epoxy Co., Ltd.), etc .;
As polyphenol type epoxy resin, Epicoat 1032H60, XY-4000 (above, manufactured by Yuka Shell Epoxy Co., Ltd.) and the like;
Cyclic aliphatic epoxy resins include CY-175, 177, 179, Araldite CY-182, 192, 184 (above, manufactured by Ciba Specialty Chemicals), DRL-4221, 4206, 4234, 4299 (above, manufactured by UC Corporation), Shodyne 509 (made by Showa Denko KK), Epicron 200, 400 (above, manufactured by Dainippon Ink Co., Ltd.), Epicoat 871, 872 (Above, manufactured by Yuka Shell Epoxy Co., Ltd.), DD-5661, 5562 (above, manufactured by Celanese Coating Co., Ltd.), etc.
Can be mentioned.

Of these (B) cationically polymerizable compounds, phenol novolac type epoxy resins, polyphenol type epoxy resins and the like are preferable.
In the present invention, the (B) cationically polymerizable compound can be used alone or in admixture of two or more.

-(C) Curing agent-
The curing agent in the one-component curable resin composition (α1) and the two-component curable resin composition (β) is a compound having at least one functional group capable of reacting with an epoxy group in the copolymer (A3). Consists of.
Examples of such a curing agent include polyvalent carboxylic acids, polyvalent carboxylic acid anhydrides, copolymers of unsaturated polyvalent carboxylic acid anhydrides and other olefinic unsaturated compounds (however, two or more (Excluding copolymers having an epoxy group) (hereinafter referred to as “carboxylic anhydride group-containing copolymer”).

Examples of the polycarboxylic acid include aliphatic polycarboxylic acids such as succinic acid, glutaric acid, adipic acid, 1,2,3,4-butanetetracarboxylic acid, maleic acid, and itaconic acid; hexahydrophthalic acid , 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cycloaliphatic polycarboxylic acid such as cyclopentanetetracarboxylic acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid And aromatic polycarboxylic acids such as 1,2,5,8-naphthalenetetracarboxylic acid.
Of these polyvalent carboxylic acids, aromatic polyvalent carboxylic acids are preferred from the viewpoint of the reactivity of the curable resin composition, the heat resistance of the protective film to be formed, and the like.

Examples of the polyvalent carboxylic acid anhydride include itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarbanilic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and hymic anhydride. Aliphatic dicarboxylic anhydrides such as acids; Alicyclic polycarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride and cyclopentanetetracarboxylic dianhydrides; phthalic anhydride , Aromatic polycarboxylic acid anhydrides such as pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride; ester group-containing acid anhydrides such as ethylene glycol bistrimellitic anhydride and glycerin tris anhydrous trimellitate Can do.
Of these polyvalent carboxylic acid anhydrides, aromatic polyvalent carboxylic acid anhydrides are preferable, and trimellitic anhydride is particularly preferable because a protective film having high heat resistance can be obtained.

  In the carboxylic acid anhydride group-containing copolymer, examples of the unsaturated polycarboxylic acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, cis-1,2,3,4-tetrahydrophthalic anhydride. Things can be mentioned. These unsaturated polyvalent carboxylic acid anhydrides can be used alone or in admixture of two or more.

  Examples of other olefinically unsaturated compounds include styrene, p-methylstyrene, p-methoxystyrene, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, ( I-propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, N-phenylmaleimide , N-cyclohexylmaleimide and the like. These other olefinically unsaturated compounds can be used alone or in admixture of two or more.

Preferable specific examples of the carboxylic acid anhydride group-containing copolymer include maleic anhydride / styrene copolymer, citraconic anhydride / dicyclopentanyl methacrylate copolymer, and the like.
The copolymerization ratio of the unsaturated polyvalent carboxylic acid anhydride in the carboxylic acid anhydride group-containing copolymer is preferably 1 to 80% by weight, more preferably 10 to 60% by weight. By using a copolymer having such a copolymerization ratio, a protective film having excellent planarization ability can be obtained.
The Mw of the carboxylic acid anhydride group-containing copolymer is preferably 500 to 50,000, more preferably 500 to 10,000. By using a copolymer having such a molecular weight range, a protective film having excellent planarization ability can be obtained.
The said hardening | curing agent can be used individually or in mixture of 2 or more types.

  Furthermore, in the present invention, the first component comprising the one-component curable resin composition (α) in which the component (A) is a copolymer (A3), and the second component containing a curing agent (C) To form a two-component curable resin composition (β).

-(D) Acid generator-
Among the compounds (D) in the one-component curable resin composition (α2) that generate an acid upon irradiation and / or heating (hereinafter referred to as “acid generator”), an acid is generated upon irradiation with radiation. This is called a “radiation-sensitive acid generator”, and one that generates an acid upon heating is called a “thermal acid generator”.

Examples of the radiation-sensitive acid generator include diaryliodonium salts, triarylsulfonium salts, diarylphosphonium salts, and the like, and any of these can be preferably used.
Examples of the thermal acid generator include sulfonium salts (excluding the above triarylsulfonium salts), benzothiazonium salts, ammonium salts, phosphonium salts (excluding the above diarylphosphonium salts), and the like. Of these, sulfonium salts and benzothiazonium salts are preferred.

Among the radiation-sensitive acid generators, examples of the diaryl iodonium salt include diphenyl iodonium tetrafluoroborate, diphenyl iodonium hexafluorophosphonate, diphenyl iodonium hexafluoroarsenate, diphenyl iodonium trifluoromethanesulfonate, diphenyl iodonium trifluoroacetate, and diphenyl iodonium. p-toluenesulfonate, 4-methoxyphenylphenyliodonium tetrafluoroborate, 4-methoxyphenylphenyliodonium hexafluorophosphonate, 4-methoxyphenylphenyliodonium hexafluoroarsenate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenyl Phenylyo Donium trifluoroacetate, 4-methoxyphenylphenyl iodonium p-toluenesulfonate, bis (4-tert-butylphenyl) iodonium tetrafluoroborate, bis (4-tert-butylphenyl) iodonium hexafluoroarsenate, bis (4- Examples thereof include t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium trifluoroacetate, and bis (4-t-butylphenyl) iodonium p-toluenesulfonate.
Of these diaryl iodonium salts, diphenyl iodonium hexafluorophosphonate is particularly preferable.

Examples of the triarylsulfonium salt include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, and triphenyl. Sulfonium p-toluenesulfonate, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxy Phenyldiphe Rusulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium p-toluenesulfonate, 4-phenylthiophenyldiphenyltetrafluoroborate, 4-phenylthiophenyldiphenylhexafluorophosphonate, 4-phenylthiophenyldiphenylhexafluoroarsenate, 4- Examples thereof include phenylthiophenyl diphenyl trifluoromethane sulfonate, 4-phenyl thiophenyl diphenyl trifluoroacetate, and 4-phenyl thiophenyl diphenyl p-toluene sulfonate.
Of these triarylsulfonium salts, triphenylsulfonium trifluoromethanesulfonate is particularly preferable.

  Examples of the diarylphosphonium salt include (1-6-η-cumene) (η-cyclopentadienyl) iron hexafluorophosphonate.

  Among the commercially available products of radiation-sensitive acid generators, examples of diaryliodonium salts include UVI-6950, UVI-6970, UVI-6974, UVI-6990 (above Union Carbide); MPI-103, BBI-103. (Midori Chemical Co., Ltd.).

  Examples of the triarylsulfonium salt include, for example, Adekaoptomer SP-150, Adekaoptomer SP-151, Adekaoptomer SP-170, Adekaoptomer SP-171 (manufactured by Asahi Denka Kogyo Co., Ltd.); CI-2481, CI-2624, CI-2639, CI-2064 (Nippon Soda Co., Ltd.); DTS-102, DTS-103, NAT-103, NDS-103, TPS-103, MDS-103 ( As mentioned above, Midori Chemical Co., Ltd.); CD-1010, CD-1011, CD-1012 (above, manufactured by Sartomer) and the like can be mentioned.

Examples of the diarylphosphonium salt include Irgacure 261 (manufactured by Ciba Specialty Chemicals); PCI-061T, PCI-062T, PCI-020T, and PCI-022T (above, Nippon Kayaku Co., Ltd.). Can be mentioned.
Among these commercially available products, UVI-6970, UVI-6974, UVI-6990, Adekaoptomer SP-170, Adekaoptomer SP-171, CD-1012, MPI-103, etc. have a high protective film surface. It is preferable at the point which has hardness.
The above radiation-sensitive acid generators can be used alone or in admixture of two or more.

Next, among the thermal acid generators, as the sulfonium salt, for example,
4-acetophenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbonyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexamonate Alkylsulfonium salts such as fluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro-4-acetoxyphenylsulfonium hexafluoroantimonate;
Benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, benzyl-4-methoxyphenylmethylsulfonium hexafluoroantimonate, Such as benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, etc. Benzylsulfonium salt;
Dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, dibenzyl-4-acetoxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-methoxyphenylsulfonium hexafluoroantimonate, dibenzyl-3 -Chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5-t-butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl-4-hydroxyphenylsulfonium hexafluorophosphate Dibenzylsulfonium salts such as;
4-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-nitro Benzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 2-chlorobenzyl-3-chloro-4-hydroxyphenylmethylsulfonium Examples thereof include substituted benzylsulfonium salts such as hexafluoroantimonate.

  Among these sulfonium salts, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium Hexafluoroantimonate, dibenzyl-4-acetoxyphenylsulfonium hexafluoroantimonate and the like are preferable.

  Examples of the benzothiazonium salt include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, 3- ( Benzylbenzothia such as 4-methoxybenzyl) benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate Zonium salts can be mentioned. Of these benzothiazonium salts, 3-benzylbenzothiazonium hexafluoroantimonate is particularly preferable.

Among the commercially available products of thermal acid generators, examples of the alkylsulfonium salt include ADEKA OPTON CP-66, ADEKA OPTON CP-77 (manufactured by Asahi Denka Kogyo Co., Ltd.), and the like.
Examples of the benzylsulfonium salt include SI-60, SI-80, SI-100, SI-110, SI-145, SI-150, SI-80L, SI-100L, SI-110L (above, Sanshin). Chemical Industry Co., Ltd.).
Among these commercially available products, SI-80, SI-100, SI-110 and the like are preferable in that the obtained protective film has high surface hardness.
The said heat-sensitive acid generator can be used individually or in mixture of 2 or more types.

-Embodiment of curable resin composition-
More specifically, preferred embodiments of each curable resin composition of the present invention include the following (I) to (IV).

(I) containing (A) a polymer (preferably at least one of the group of copolymer (A1), copolymer (A2) and copolymer (A3)), and (B) a cationic polymerizable compound. In some cases, an optional additive component described below is further contained, and the amount of the cationic polymerizable compound used is 3 to 100 parts by weight, more preferably 5 to 50 parts by weight with respect to 100 parts by weight of the polymer (A). One-component curable resin composition (α).
In this one-component curable resin composition (α), a protective film having a sufficient surface hardness can be obtained by setting the amount of the cationic polymerizable compound used 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 cationic polymerizable compound, and (C) a curing agent, and optionally further containing optional addition components described below, (A) 100 parts by weight of the polymer The amount of the cationic polymerizable compound used is 3 to 100 parts by weight, more preferably 5 to 50 parts by weight, and the amount of the curing agent used is 20 to 60 parts by weight, more preferably 20 to 50 parts by weight. (Referred to as one-component curable resin composition (α1)).
In this one-component curable resin composition (α1), when the amount of the curing agent used is within the above range, the curing property is exhibited and various properties of the protective film are not impaired.
The one-component curable resin composition (α1) is preferably used within 24 hours after preparation.

(III) A combination of (1) a copolymer (A3), (B) a first component containing a cationic polymerizable compound, and (2) (C) a second component containing a curing agent. In some cases, the first component and / or the second component further contains the following optional additional components, and the amount of the (B) cationic polymerizable compound used is 3 to 100 parts by weight of the polymer (A). Two-part curable resin composition (100 parts by weight, more preferably 5 to 50 parts by weight, and (C) the curing agent is used in an amount of 20 to 60 parts by weight, more preferably 20 to 50 parts by weight. β).
In the two-component curable resin composition (β), when the amount of the (C) curing agent used is within the above range, good curing characteristics are exhibited and various characteristics of the protective film are not impaired.
The two-component curable resin composition (β) is preferably used within 24 hours after mixing the first component and the second component.

  When preparing the two-component curable resin composition (α1) of (II) and the two-component curable resin composition (β) of (III), the curing agent is usually a solution dissolved in an appropriate solvent. used. 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) at least one of the group of copolymer (A1) and polymer (A2) (preferably copolymer (A2-1)), (B) a cationic polymerizable compound, and (D) an acid generator And optionally further containing the optional addition components described below. The amount of the (B) cationically polymerizable compound used is 3 with respect to 100 parts by weight of the total of the copolymer (A1) and the polymer (A2). To 100 parts by weight, more preferably 5 to 50 parts by weight, and the amount of (D) acid generator used is 20 parts by weight or less, more preferably 0.05 to 20 parts by weight, particularly preferably 0.1 to 0.1 parts by weight. 1 part type curable resin composition ((alpha) 2) which is 10 weight part.
In this one-component curable resin composition (α2), 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 composition (α), one-component curable resin composition (α1), one-component curable resin composition (α2) and two-component curable resin composition (β) are The protective film formed from them satisfies the required transparency, heat resistance, surface hardness, and adhesion, and also has excellent load resistance even under heating, and the level difference of the color filter formed on the base substrate is flat. Excellent performance.

-Optional components-
In each curable resin composition of the present invention, optional additional components other than those described above, for example, surfactants, adhesion assistants, and the like can be blended as necessary, as long as the effects of the present invention are not impaired. .
The surfactant is added to improve the coating property of the composition.
As such a surfactant, preferably, for example, a fluorosurfactant, a silicone surfactant, and a nonionic surfactant such as polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene dialkyl ester, etc. An agent etc. can be mentioned.

  Examples of the polyoxyethylene alkyl ether include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether. Examples of the polyoxyethylene aryl ether include polyoxyethylene n -Octylphenyl ether, polyoxyethylene n-nonylphenyl ether, etc. can be mentioned. Examples of the polyoxyethylene dialkyl ester include polyoxyethylene dilaurate and polyoxyethylene distearate.

  Among the commercially available surfactants, examples of the fluorosurfactant include BM-1000 and BM-1100 (manufactured by BM CHIMID); MegaFuck F142D, MegaFuck F172, MegaFuck F173, and MegaFuck F183. (Above, Dainippon Ink & Chemicals, Inc.); Fluorad FC-135, Fluorad FC-170C, Fluorad FC-430, Fluorard FC-431 (above, manufactured by Sumitomo 3M); Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, Surflon S-145, Surflon S-382, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-106 (above, And the like can be mentioned glass Co., Ltd.).

Examples of the silicone surfactant include SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (above, Toray Dow Corning Silicone Co., Ltd. KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); F-top DF301, F-top DF303, F-top DF352 (above, manufactured by Shin-Akita Kasei Co., Ltd.) and the like.
Furthermore, other commercially available surfactants include polyflow No. 1 which is a (meth) acrylic acid copolymer. 57 and polyflow no. 90 (manufactured by Kyoeisha Chemical Co., Ltd.).

  The compounding amount of the surfactant is preferably 5 parts by weight or less, more preferably 2 parts by weight or less, with respect to 100 parts by weight of the polymer (A). When the compounding amount of the surfactant exceeds 5 parts by weight, the coating film tends to be rough.

The adhesion assistant is added to improve the adhesion between the protective film to be formed and the substrate.
As such an adhesion assistant, for example, a silane coupling agent having a reactive group such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group, or an epoxy group is preferable.
Specific examples of the adhesion assistant include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxy. Examples include silane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
The compounding amount of the adhesion assistant is preferably 30 parts by weight or less, more preferably 25 parts by weight or less with respect to 100 parts by weight of the polymer (A). When the compounding amount of the adhesion aid exceeds 30 parts by weight, the heat resistance of the protective film obtained may be insufficient.

Preparation of Curable Resin Composition The resin composition of the present invention is prepared by uniformly dissolving or dispersing the above components, preferably in a suitable solvent. As the solvent to be used, a solvent in which each component of the composition is dissolved or dispersed and does not react with each component is preferably used.
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) can be mentioned.

  Of these solvents, alcohols, glycol ethers, ethylene glycol alkyl ether acetates, esters and diethylene glycol are preferably used from the viewpoints of solubility of each component, reactivity with each component, and ease of film formation. It is done. Among these, 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 ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether Propylene glycol monomethyl ether acetate, methyl methoxypropionate, and ethyl ethoxypropionate can be particularly preferably used.

  Furthermore, in order to improve the in-plane uniformity of the film thickness together with the above solvent, a high boiling point solvent can be used in combination. Examples of the high boiling point solvent that can be used in combination include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and benzylethyl 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 Examples include cellosolve acetate. Of these, N-methylpyrrolidone, γ-butyrolactone, and N, N-dimethylacetamide are preferable.

When a high boiling point solvent is used in combination as a solvent for the thermosetting resin composition of the present invention, the amount used is preferably 50% by weight or less, more preferably 40% by weight or less, and still more preferably based on the total amount of the solvent. It can be 30 wt% or less. If the amount of the high-boiling solvent used exceeds this amount, the coating film thickness uniformity, sensitivity, and residual film rate may be reduced.
As a usage-amount of a solvent, content of the total solid in the composition of this invention (The quantity remove | excluding the quantity of the solvent from the total amount of the composition containing a solvent) becomes like this. Preferably it is 1-50 weight%, More preferably The range is 5 to 40% by weight.
The composition prepared as described above can be used after being filtered using a Millipore filter having a pore size of 0.2 to 3.0 μm, preferably about 0.2 to 0.5 μm. .

Method of forming the protective film Next, a method of forming a protective film of the present invention will be described with reference to the curable resin composition of the present invention.
1-component curable resin composition (α), 1-component curable resin composition (α1) and (D) 1-component curable resin composition (α2) using a thermal acid generator as an acid generator. In this case, the target protective film can be formed by applying the composition solution onto the substrate, prebaking to remove the solvent, and forming a film, followed by heat treatment.
In addition, the two-component curable resin composition (β) is prepared by mixing the first component and the second component to prepare a composition solution, and preferably within 24 hours after the preparation. The target protective film can be formed by applying a solution on a substrate, prebaking to form a film by removing the solvent, and then performing heat treatment.

As the substrate on which the protective film is formed, for example, a substrate made of glass, quartz, silicon, transparent resin, or the like can be used.
Examples of the transparent resin include polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide, a ring-opening polymer of a cyclic olefin, and a hydrogenated product thereof.

As a coating method, for example, an appropriate method such as a spray method, a roll coating method, a spin coating method, a bar coating method, an ink jet method or the like can be adopted, and in particular, coating using a spin coater, a spinless coater, or a slit die coater. Can be suitably used.
The pre-baking conditions vary depending on the types and blending ratios of the components, but are preferably about 70 to 90 ° C. for about 1 to 15 minutes.
The heat treatment after the coating is formed can be performed by an appropriate heating device such as a hot plate or an oven.
The treatment temperature during the heat treatment is preferably about 150 to 250 ° C., and the treatment time is preferably about 5 to 30 minutes when a hot plate is used as a heating device, and about 30 to 90 minutes when an oven is used.

In the case of the one-component curable resin composition (α2) using a radiation-sensitive acid generator as the acid generator (D), the composition solution is applied on a substrate and pre-baked to remove the solvent. After the formation of the coating film, the target protective film can be formed by performing a radiation irradiation process (exposure process) and then performing a heat treatment as necessary.
In this case, the same substrate as described above can be used, and the method for forming a coating film can be performed in the same manner as described above.

As the radiation used for the exposure treatment, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be adopted, and ultraviolet light including light having a wavelength of 190 to 450 nm is preferable.
Exposure is preferably 100~20,000J / ^{m 2,} more preferably a 150~10,000J / ^{m 2.}

The processing temperature during the heat treatment after the exposure processing is preferably about 150 to 250 ° C., and the processing time is about 5 to 30 minutes when using a hot plate as a heating device, and about 30 to 90 minutes when using an oven. Is preferred.
The thickness of the protective film thus formed is preferably 0.1 to 8 μm, more preferably 0.1 to 6 μm, and still more preferably 0.1 to 4 μm. However, when the protective film is formed on a substrate having a color filter level difference, the film thickness means the thickness from the top of the color filter.

  The protective film of the present invention satisfies the required transparency, heat resistance, surface hardness, adhesion, etc., has excellent load resistance even under heating, reduces the generation of sublimates during firing, and is on the base substrate. It is excellent in the performance of flattening the level difference of the color filter formed on, and is particularly suitable as a protective film for optical devices.

Hereinafter, the present invention will be described more specifically with reference to synthesis examples and examples. However, the present invention is not limited to the following examples.
<Measurement of molecular weight of copolymer by gel permeation chromatography>
Apparatus: GPC-101 (made by Showa Denko KK)
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 are combined Mobile phase: Tetrahydrofuran containing 0.5% by weight of phosphoric acid.

(A) Polymer Synthesis Synthesis Examples 1 to 10
In a flask equipped with a condenser and a stirrer, 2 parts by weight of 2,2′-azobisisobutyronitrile and the compounds represented by the above formulas (3) to (12) as molecular weight control agents are shown in Table 1. The amount shown and 200 parts by weight of diethylene glycol dimethyl ether were charged. Subsequently, 80 parts by weight of glycidyl methacrylate and 20 parts by weight of styrene were charged and the atmosphere was purged with nitrogen. The polymerization was continued for 6 hours. Thereafter, the temperature of the reaction solution was raised to 100 ° C., 1 part by weight of 2,2′-azobisisobutyronitrile was added, and polymerization was further continued for 1 hour, whereby the polymers (A− Each solution of 1) to polymer (A-10) was obtained. The solid content, Mw, and Mw / Mn values of the obtained polymers were measured and found to be as shown in Table 1.

Synthesis Examples 11-20
In the same manner as in Synthesis Example 1, in a flask equipped with a condenser and a stirrer, 2 parts by weight of 2,2′-azobisisobutyronitrile and each of the above formulas (13) to (22) as molecular weight control agents were used. After the amount of the compound shown in Table 1 and 200 parts by weight of diethylene glycol dimethyl ether were charged, 50 parts by weight of glycidyl methacrylate, 20 parts by weight of tricyclodecanyl methacrylate and 30 parts by weight of methacrylic acid were charged, and nitrogen substitution was performed. While stirring, the temperature of the reaction solution was raised to 70 ° C., and this temperature was maintained for polymerization for 6 hours. Thereafter, the temperature of the reaction solution was raised to 100 ° C., 1 part by weight of 2,2′-azobisisobutyronitrile was added, and polymerization was further continued for 1 hour, whereby the polymers (A− 11) to each solution of polymer (A-20) were obtained. The solid content, Mw, and Mw / Mn values of the obtained polymers were measured and found to be as shown in Table 1.

Comparative Synthesis Example 1
A flask equipped with a condenser and a stirrer was charged with 7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol methyl ethyl ether, followed by 50 parts by weight of styrene and 50 parts by weight of glycidyl methacrylate. After the part was purged with nitrogen and gently stirred, the temperature of the reaction solution was raised to 70 ° C., and this temperature was maintained and polymerization was carried out for 5 hours to obtain a polymer containing the copolymer (a-1). A coalesced solution was obtained. The copolymer (a-1) had a polystyrene equivalent weight average molecular weight (Mw) of 14,000 and a molecular weight distribution (Mw / Mn) of 1.8. The solid content concentration of the polymer solution was 30.0% by weight.

Comparative Synthesis Example 2
A flask equipped with a condenser and a stirrer was charged with 6 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol methyl ethyl ether, followed by 50 parts by weight of glycidyl methacrylate and tricyclodeca After adding 20 parts by weight of nyl methacrylate and 30 parts by weight of methacrylic acid and substituting with nitrogen, the mixture was stirred gently to raise the temperature of the reaction solution to 70 ° C. and polymerized for 5 hours while maintaining this temperature. A polymer solution containing the coalescence (a-2) was obtained. The copolymer (a-2) had a polystyrene equivalent weight average molecular weight (Mw) of 15,000 and a molecular weight distribution (Mw / Mn) of 2.4. The solid content concentration of the polymer solution was 30.5% by weight.
In the following Examples and Comparative Examples, “part” means “part by weight”.

Example 1 (Evaluation of two-component curable resin composition (β))
(A) A solution containing the copolymer (A-1) obtained in Synthesis Example 1 as the component (an amount corresponding to 100 parts of the copolymer (A-1)) and a bisphenol A novolac type epoxy as the (B) component 10 parts of resin “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 as a surfactant) -After mixing 0.1 part of Silicone Co., Ltd. and further adding propylene glycol monomethyl ether acetate so that the solid content concentration is 20% by weight, it is filtered through a Millipore filter with a pore size of 0.5 μm. A one-component solution was prepared.
Next, a second component prepared by dissolving 35 parts of trimellitic anhydride in 65 parts of diethylene glycol methyl ethyl ether as component (C) was added to the first component solution to prepare a composition solution.
The obtained composition solution was evaluated by forming a protective film on the substrate in the following manner. The evaluation results are shown in Table 2.

-Formation of protective film-
The composition solution was applied onto a SiO ₂ dip glass substrate using a spinner, and then pre-baked on a hot plate at 80 ° C. for 5 minutes to form a coating film, and further in an oven at 230 ° C. for 60 minutes. A heat treatment was performed to form a protective film having a thickness of 2.0 μm on the substrate.

-Evaluation of protective film-
Evaluation of transparency:
About the board | substrate in which the protective film was formed, the transmittance | permeability (%) in wavelength range 400-800 nm was measured using the spectrophotometer 150-20 type double beam (made by Hitachi, Ltd.), and it evaluated by the minimum value. . When this value is 95% or more, it can be said that the transparency of the protective film is good.

Evaluation of heat-resistant dimensional stability:
About the board | substrate with which the protective film was formed, it heated at 250 degreeC in oven for 1 hour, measured the film thickness before and behind a heating, and evaluated it by the value computed by the following formula. When this value is 95% or more, it can be said that the heat-resistant dimensional stability is good.
Heat-resistant dimensional stability (%) = (film thickness after heating) × 100 / (film thickness before heating)

Evaluation of heat discoloration:
About the board | substrate which formed the protective film, it heated at 250 degreeC in oven for 1 hour, measured the transmittance | permeability in the wavelength range 400-800 nm before and behind a heating, and evaluated it by the value computed by the following formula using the minimum value. . When this value is 5% or less, the heat discoloration is good.
Heat discoloration (%) = (minimum value of transmittance before heating)-(minimum value of transmittance after heating)

Evaluation of surface hardness:
The substrate on which the protective film was formed was evaluated by conducting a 8.4.1 pencil scratch test of JIS K-5400-1990. When this value is 4H or higher, the surface hardness is good.

Evaluation of dynamic microhardness:
Using a Shimadzu dynamic microhardness meter DUH-201 (manufactured by Shimadzu Corp.), a substrate having a protective film formed thereon was subjected to a ridge angle 115 ° triangular indenter (Helkovic type) indentation test with a load of 0.1 gf and a speed of 0.0145 gf. The temperature was evaluated as 23 ° C. and 140 ° C. under the conditions of / sec and holding time of 5 seconds.

Evaluation of adhesion:
The substrate on which the protective film was formed was subjected to a pressure cooker test (temperature 120 ° C., humidity 100%, measurement 24 hours), and then was subjected to SiO 5.3 by the JIS K-5400-1990 8.5.3 adhesive cross-cut tape method. Adhesion to a _2- dip glass substrate (in Table 2, expressed as “SiO ₂ ”) was evaluated.
Further, a protective film having a thickness of 2.0 μm was formed in the same manner as described above except that a Cr substrate was used instead of the SiO ₂ dip glass substrate, and adhesion to the Cr substrate (in Table 2, “Cr” (Notation) was evaluated.
The numerical values in Table 1 are the number of grids remaining in 100 grids.

Evaluation of flattening ability:
A pigment-based color resist (trade name “JCR RED 689”, “JCR GREEN 706” or “CR 8200B”; manufactured by JSR Co., Ltd.) is applied to the SiO ₂ dip glass substrate by a spinner, and is applied on a hot plate. Pre-baking was performed at 90 ° C. for 150 seconds to form a coating film. Thereafter, using an exposure machine Canon PLA501F (manufactured by Canon Inc.), the intensity ratio of g / h / i line (wavelengths of 436 nm, 405 nm and 365 nm = 2.7: 2.5: 4) through a predetermined pattern mask. .8) is exposed at an exposure dose of 2,000 J / m ^{2 in} terms of i-line, developed with 0.05% aqueous potassium hydroxide, washed with ultrapure water for 60 seconds, and further exposed to an oven. The film was heat-treated at 230 ° C. for 30 minutes to form red, green and blue stripe color filters (stripe width 100 μm).
Next, the surface roughness of the substrate on which this color filter was formed was measured using a surface roughness meter α-step (manufactured by Tencor Japan Co., Ltd.), measuring length 2,000 μm, measuring range 2,000 μm square, measuring point n = 5 and the measurement direction is two directions of the stripe line minor axis direction of red, green and blue directions and the stripe axis major axis direction of red, red, green, green, blue and blue, and n = 5 for each direction. When measured by (total n number = 10), it was 1.0 μm.
In addition, a composition solution prepared in the same manner as described above was applied on a substrate on which a color filter was formed in the same manner as described above using a spinner, and then pre-baked at 80 ° C. for 5 minutes on a hot plate. And a heat treatment at 230 ° C. for 60 minutes in an oven to form a protective film having a thickness of 2.0 μm from the upper surface of the color filter on the color filter.
Next, for the substrate having a protective film on this color filter, the unevenness of the surface of the protective film was measured using a contact-type film thickness measuring device α-step (manufactured by Tencor Japan Co., Ltd.), measuring length 2,000 μm, measuring range 2,000 μm square, number of measurement points n = 5, the measurement direction is 2 in the stripe axis major axis direction of red, green, blue direction and stripe line major axis direction of red / red, green / green, blue / blue. The direction was measured with n = 5 (total number of n is 10) in each direction, and the height difference (nm) between the highest part and the lowest part in each measurement was measured 10 times, and the average value was evaluated. When this value is 300 nm or less, it can be said that the planarization ability is good.

Sublimation rating:
The composition solution was applied onto a silicon substrate using a spinner and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. This silicon substrate was heated in a clean oven at 220 ° C. for 1 hour to obtain a cured film. A bare silicon wafer for cooling was mounted at an interval of 1 cm above the obtained cured film, and a heating process was performed at 230 ° C. for 1 hour on a hot plate. Without replacing the bare silicon wafer for cooling, 20 silicon substrates on which the cured film was separately formed were processed in succession, and then the presence or absence of sublimated material adhering to the bare silicon was verified visually. When the sublimate is not confirmed, the sublimate evaluation is good. The evaluation results are shown in Table 2.

Examples 2 to 10, Comparative Example 1
A two-component curable resin composition was prepared and evaluated in the same manner as in Example 1 except that the formulation was as shown in Table 2. The results are shown in Table 2.

Example 11 (Evaluation of one-component curable resin composition (α))
As the component (A), a solution containing the polymer (A) obtained in Synthesis Example 1 (an amount corresponding to 100 parts of the copolymer (A-11)), and a bisphenol A novolac type epoxy resin as the component (B). (Product name: Epicoat 157S65, manufactured by Yuka Shell Epoxy Co., Ltd.) 10 parts, (D) component benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate 1 part, and adhesion aid γ-gly 15 parts of Sidoxypropyltrimethoxysilane and 0.1 part of SH-28PA (manufactured by Toray Dow Corning Silicone Co., Ltd.) as a surfactant are mixed, and propylene glycol is added so that the solid content concentration becomes 20%. After adding monomethyl ether acetate, filter through a Millipore filter with a pore size of 0.5 μm to prepare a composition solution. It was. The appearance of this composition solution was colorless and transparent.
About the obtained composition solution, the protective film was formed on the board | substrate in the following way, and it evaluated similarly to Example 1. FIG. The evaluation results are shown in Table 3.

-Formation of protective film-
The composition solution was applied onto a SiO ₂ dip glass substrate using a spinner, then pre-baked on a hot plate at 80 ° C. for 5 minutes to form a coating film, and further in an oven at 230 ° C. at 60 ° C. A protective film having a thickness of 2.0 μm was formed on the substrate by heat treatment for a minute.
Further, a protective film was formed in the same manner as described above on the substrate on which the color filter was formed in the same manner as described in Example 1. The evaluation results are shown in Table 3.

Examples 12 to 20, Comparative Example 2
A one-component curable resin composition was prepared and evaluated in the same manner as in Example 11 except that the formulation was as shown in Table 3. The results are shown in Table 3.

The components (B), (C), (D) and solvents in Tables 2 and 3 are as follows.
B-1: Bisphenol A novolak type epoxy resin (trade name: Epicoat 157S65, manufactured by Yuka Shell Epoxy Co., Ltd.)
B-2: Bisphenol A type epoxy resin (trade name: Epicoat 828, manufactured by Yuka Shell Epoxy Co., Ltd.)
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

Claims (12)

(A) A polymer containing two or more epoxy groups in the molecule and obtained by living radical polymerization, and (B) a cationic polymerizable compound (however, the polymerizable unsaturated compound constituting the component (A) A living radical polymerization for producing the polymer (A) using a thiocarbonylthio compound represented by the following formula (1) or formula (2) as a molecular weight control agent: A curable resin composition, which is a polymerization used.

(In Formula (1), Z ¹ is different from a hydrogen atom, a chlorine atom, a carboxyl group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a carbon atom. Monovalent heterocyclic group having 3 to 20 atoms in total with the term atom, -OR, -SR, -N (R) ₂ , -OC (= O) R, -C (= O) OR, -C (= O) N (R) ₂ , -P (= O) (OR) ₂ , -P (= O) (R) ₂ or a monovalent group having a polymer chain, wherein each R is mutually independent Or an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or 1 having 3 to 18 total atoms of carbon atoms and hetero atoms. A valent heterocyclic group, the above alkyl group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and a monovalent heterocyclic group having 3 to 20 atoms in total. Fine R may be each substituted, ^{R 1,} when the p = 1, an alkyl group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, 6 carbon atoms 20 monovalent aromatic hydrocarbon groups, monovalent heterocyclic groups having 3 to 20 total atoms of carbon atoms and hetero atoms, -OR, -SR, -N (R) ₂ or polymer chain Each R independently represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or carbon. 1 represents a monovalent heterocyclic group having 3 to 18 total atoms of atoms and hetero atoms, and when p ≧ 2, a p-valent group derived from an alkane having 1 to 20 carbon atoms, 6 to 20 carbon atoms A p-valent group derived from an aromatic hydrocarbon, a p-valent group derived from a heterocyclic compound having a total of 3 to 20 carbon atoms and hetero atoms, or A p-valent group having a polymer chain, the alkyl group having 1 to 20 carbon atoms, the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and the monovalent aromatic carbon group having 6 to 20 carbon atoms; A hydrogen group, a monovalent heterocyclic group having 3 to 20 atoms in total, R, a p-valent group derived from an alkane having 1 to 20 carbon atoms, and a p-value derived from an aromatic hydrocarbon having 6 to 20 carbon atoms And a p-valent group derived from a heterocyclic compound having 3 to 20 atoms in total may be substituted.)

(In Formula (2), Z ² is an m-valent group derived from an alkane having 1 to 20 carbon atoms, an m-valent group derived from an aromatic hydrocarbon having 6 to 20 carbon atoms, a carbon atom and an extraneous atom. M-valent group derived from a heterocyclic compound having 3 to 20 atoms in total or m-valent group having a polymer chain, m-valent group derived from an alkane having 1 to 20 carbon atoms, carbon number The m-valent group derived from an aromatic hydrocarbon having 6 to 20 and the m-valent group derived from a heterocyclic compound having 3 to 20 atoms in total may be substituted, and R ² may have 1 to 1 carbon atoms. 20 alkyl groups, monovalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms, monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms, and 3 to 20 total atoms of carbon atoms and hetero atoms A monovalent heterocyclic group, —OR, —SR, —N (R) ₂ or a monovalent group having a polymer chain, wherein each R is a phase Independently of each other, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or a total number of 3 atoms of carbon atoms and hetero atoms 18 represents a monovalent heterocyclic group, the above alkyl group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and a monovalent aromatic carbon group having 6 to 20 carbon atoms. A hydrogen group, a monovalent heterocyclic group having 3 to 20 atoms in total, and R may each be substituted.) The polymer (A) has a group represented by the following formula (i) or a group represented by the following formula (ii) at at least one terminal of each polymer chain constituting the polymer. Curable resin composition.

(In formula (i), Z ¹ is the same as in formula (1), and in formula (ii), Z ² and m are the same as in formula (2).)   The component (A) obtained by living radical polymerization comprises (A1) (a) an epoxy group-containing polymerizable unsaturated compound and (b1) a polymerizable unsaturated carboxylic acid and / or polymerizable unsaturated polyvalent carboxylic acid anhydride. The curable resin composition according to claim 1 or 2, which is a copolymer of (b2) a polymerizable unsaturated compound other than the components (a) and (b1).   The component (A) obtained by living radical polymerization comprises (A2) two or more epoxy groups in the molecule and at least one structure selected from the group of an acetal structure, a ketal structure and a t-butoxycarbonyl structure. The curable resin composition according to claim 1, which is a polymer to be contained.   The component (A2) contains (A2-1) (a) an epoxy group-containing polymerizable unsaturated compound and (b3) at least one structure selected from the group of an acetal structure, a ketal structure, and a t-butoxycarbonyl structure. The curable resin composition according to claim 4, which is a copolymer of a polymerizable unsaturated compound to be polymerized and (b4) a polymerizable unsaturated compound other than the component (a) and the component (b3).   The component (A) is a copolymer of (A3) (a) an epoxy group-containing polymerizable unsaturated compound and (b5) a polymerizable unsaturated compound other than the component (a), and has a carboxyl group in the molecule. The curable resin composition according to claim 1 or 2, which is a copolymer having no group, carboxylic anhydride group, acetal structure, ketal structure and t-butoxycarbonyl structure.   Furthermore, the curable resin composition of Claim 6 containing the (C) hardening | curing agent.   (1) A two-component curable resin composition comprising a combination of a first component comprising the curable resin composition according to claim 6 and a second component containing (2) (C) a curing agent.   At least one selected from the group consisting of the component (A1) according to claim 3 and the component (A2) according to claim 4, (B) a cationic polymerizable compound (however, the polymerizability constituting the component (A1)) Except for unsaturated compounds and polymerizable unsaturated compounds constituting component (A2)), (C) a curing agent, and (D) a curable resin containing a compound that generates an acid upon irradiation and / or heating of radiation. Composition.   A protective film formed from the curable resin composition according to claim 1, the two-component curable resin composition according to claim 8, or the curable resin composition according to claim 9.   A film is formed on the substrate using the curable resin composition according to any one of claims 1 to 7 or the two-component curable resin composition according to claim 8, and then heat-treated. Forming a protective film. A method for forming a protective film, comprising: forming a film on a substrate using the curable resin composition according to claim 9, and then performing radiation treatment and / or heat treatment.