KR20070019605A - Resin Compositions, Process for Forming Protective Films of Color Filters, and Protective Films of Color Filters - Google Patents

Abstract

The present invention,

(A) (a1) a copolymer of a polymerizable unsaturated compound having an oxylanyl group or an oxetanyl group with (a2) a polymerizable unsaturated compound other than the above (a1), and

(B) Phosphoric acid ester having a structure represented by the following formula (1)

And a resin composition containing 0.01 to 50 parts by weight of component (B) with respect to 100 parts by weight of the component (A), which has a high flatness on the substrate even in a substrate having a low surface flatness. A cured film can be formed, and also transparency and surface hardness are high, and it can use suitably for forming the protective film for optical devices excellent in various tolerances, such as heat resistance, acid resistance, alkali resistance, and sputtering resistance.

<Formula 1>

Where

X is an integer from 0 to 2,

R ¹ represents a hydrogen atom or an organic group in which an atom adjacent to a phosphorus atom is carbon,

R ² represents an organic group wherein the atom adjacent to the oxygen atom is carbon.

Resin composition, color filter, protective film, oxylanyl group, oxetanyl group, polymerizable unsaturated compound, phosphoric acid ester

Description

Resin Compositions, Process for Forming Protective Films of Color Filters, and Protective Films of Color Filters}

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

[Patent Document 2] Japanese Unexamined Patent Publication No. 2001-91732

[Patent Document 3] Japanese Unexamined Patent Publication No. 4-218561

This invention relates to a resin composition, the method of forming the protective film for color filters with the said resin composition, and a color filter protective film. More specifically, a resin composition suitable as a material for forming a protective film used for a color filter for a liquid crystal display device (LCD) and a color filter for a charge coupled device (CCD), a method for forming a protective film using the resin composition, and the composition It relates to a protective film formed from.

Radiation devices such as LCDs and CCDs are immersed in a display element by a solvent, an acid or an alkaline solution, or the like during its manufacturing process, and when the wiring electrode layer is formed by sputtering, the surface of the element is locally exposed to high temperature. Therefore, in order to prevent an element from deteriorating or damaging by such a process, providing the protective film which consists of a thin film which is resistant to these processes is performed on the surface of an element.

Such a protective film has a high adhesiveness with respect to the base or lower layer on which the protective film is to be formed, and also a layer formed on the protective film, the film itself is smooth and strong, has transparency, high heat resistance and light resistance, The performance which does not cause deterioration, such as coloring, yellowing, whitening, etc. over the long term, and is excellent in water resistance, solvent resistance, acid resistance, and alkali resistance is calculated | required. As an example of the material for forming the protective film which satisfy | fills these various characteristics, the thermosetting composition containing the polymer which has glycidyl group is known (refer patent document 1 and patent document 2).

In addition, when using such a protective film as a protective film of the color filter of a color liquid crystal display device or a charge coupling element, it is generally required to be able to planarize the level | step difference by the color filter formed on the base substrate.

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

In particular, when manufacturing the STN type color liquid crystal display device, the bonding accuracy of the color filter and the opposing substrate must be very strictly performed, and the protection film required a very high leveling performance and heat resistance resistance performance.

In forming such a protective film, it is convenient to use a thermosetting composition having the advantage of forming a protective film having excellent hardness by a simple method, but the protective film resin composition for expressing various properties as described above forms a strong crosslinking. It has a problem that the shelf life of the composition itself is very short and the handling is very difficult because it has a crosslinking group or catalyst having good reactivity. That is, not only the application performance of the composition itself deteriorated with time, but also frequent maintenance, cleaning, etc. of the coating machine were required, and it was also complicated in operation.

A material which not only satisfies the general required performance as a protective film such as transparency and the like, but also can easily form a protective film that satisfies various performances as described above, and is excellent in storage stability as a composition is not yet known.

Moreover, although the thermosetting composition containing the latent carboxyl compound used for coating material, ink, an adhesive agent, and a molded article is disclosed by patent document 3, it does not disclose at all about the protective film of a color filter.

The present invention has been made on the basis of the above circumstances, and an object of the present invention is to form a cured film having high flatness on the substrate even in a substrate having a low surface flatness, and also have high transparency and surface hardness, heat resistance, A composition which is preferably used to form a protective film for an optical device that is excellent in various resistances such as acid resistance, alkali resistance, sputtering resistance, and also has excellent storage stability as a composition, a method of forming a protective film using the composition, and a protective film formed from the composition. Is to provide.

The present invention

(A) (a1) a copolymer of a polymerizable unsaturated compound having an oxylanyl group or an oxetanyl group with (a2) a polymerizable unsaturated compound other than the above (a1), and

(B) Phosphoric acid ester having a structure represented by the following formula (1)

And a component (B) in an amount of 0.01 to 50 parts by weight based on 100 parts by weight of the component (A).

Where

X is an integer from 0 to 2,

R ¹ represents a hydrogen atom or an organic group in which an atom adjacent to a phosphorus atom is carbon,

R ² represents an organic group wherein the atom adjacent to the oxygen atom is carbon.

Here, the component (B), the formula (1) of R ¹ is an alkyl group having 1 to 18 alkyl group, an aryl group, a benzyl group or a group having 1 to 8 carbon atoms at the terminal or side chain of the alkyl group having an alkoxy group having 1 to 4 carbon atoms, Or it is an acetate ester group, R <^2> is a C1-C18 alkyl group or an aryl group, or it is preferable that it is a benzyl group.

Moreover, trimethyl phosphate ester, and / or triethyl phosphate ester etc. are mentioned as a specific example of (B) component.

The resin composition of this invention may further contain 0.0001-20 weight part of (C) Lewis acid catalysts with respect to 100 weight part of (A) component.

Moreover, the resin composition of this invention may further contain (D) cationically polymerizable compound (except the said (A) component) for 3 to 200 weight part with respect to 100 weight part of (A) component.

The resin composition of this invention is useful for the protective film formation of a color filter.

Moreover, this invention relates to the formation method of the color filter protective film characterized by forming a coating film using the said resin composition, and then heat-processing.

Moreover, this invention relates to the color filter protective film formed from the said resin composition.

< To practice the invention  Best form for

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

(A) copolymer

The copolymer (A) of the present invention is derived from a polymerizable unit derived from a polymerizable unsaturated compound having (a1) an oxylalanyl group or an oxetanyl group and (a2) a polymerizable unsaturated compound other than the polymerized unit of (a1). It contains a polymerization unit.

In the (A) copolymer, the (a1) polymerizable unsaturated compound is not particularly limited as long as it has an oxiranyl group or an oxetanyl group and a polymerizable unsaturated group.

For example, examples of the oxylanyl group-containing polymerizable unsaturated compound include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, and α-n-butylacrylic acid. Glycidyl, acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6 , 7-epoxyheptyl, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether and the like.

In addition, examples of the oxetanyl group-containing polymerizable unsaturated compound include 3-methyl-3- (meth) acryloyloxymethyloxetane, 3-ethyl-3- (meth) acryloyloxymethyloxetane, and the like. Can be.

Of these, methacrylic acid glycidyl, methacrylic acid-6,7-epoxyheptyl, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, and the like are copolymerized. It is preferably used from the point of improving the reactivity, the heat resistance and surface hardness of the protective film or insulating film obtained.

The copolymer (A) further contains a polymer unit derived from a polymerizable unsaturated compound other than the component (a2) in addition to the component (a1). (a2) A polymerizable unsaturated compound is a (meth) acrylic-acid alkylester, (meth) acrylic-acid cyclic alkylester, (meth) acrylic-acid aryl ester, unsaturated dicarboxylic acid diester, bicyclo unsaturated compounds, maleimide compounding, for example. Logistics, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic anhydrides, acetal structures, unsaturated compounds having a ketal structure, and the like.

As a specific example of these (a2) polymerizable unsaturated compounds, As (meth) acrylic-acid alkylester, hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate , 4-hydroxybutyl (meth) acrylate, diethylene glycol mono (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, 2-methacryloxyethyl glycoside, 4-hydroxyphenyl (Meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (Meth) acrylate, n-lauryl (meth) acrylate, tridecyl (meth) acrylate, n-stearyl (meth) acrylate, t-butoxy (meth) acrylate, 1-dimethyl (iso) Propyl (meth) acrylate, 1-dimethyl (iso) butyl (meth) acrylate, 1 -Dimethyl (iso) octyl (meth) acrylate, 1-methyl-1-ethylethyl (meth) acrylate, 1-methyl-1-ethyl (iso) propyl (meth) acrylate, 1-methyl-1-ethyl (Iso) butyl (meth) acrylate, 1-methyl-1-ethyl (iso) octylacrylate, 1-diethyl (iso) propyl (meth) acrylate, 1-diethyl (iso) butyl (meth) acrylic Acrylate, 1-diethyl (iso) octyl (meth) acrylate, and the like;

As (meth) acrylic-acid cyclic alkylester, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yloxyethyl (meth) acrylate, isoboroyl (meth) acrylate, 1-methylcyclopropane (meth) acrylate, 1-methylcyclobutane (meth) Acrylate, 1-methylcyclopentyl (meth) acrylate, 1-methylcyclohexyl (meth) acrylate, 1-methylcycloheptane (meth) acrylate, 1-methylcyclooctane (meth) acrylate, 1-methyl Cyclononane (meth) acrylate, 1-ethylcyclodecane (meth) acrylate, 1-ethylcyclopropane (meth) acrylate, 1-ethylcyclobutane (meth) acrylate, 1-ethylcyclopentyl (meth) acrylic Rate, 1-ethylcyclohexyl (meth) acrylate, 1-ethylcycloheptane (meth) arc Rate, 1-ethylcyclooctane (meth) acrylate, 1-ethylcyclononane (meth) acrylate, 1-ethylcyclodecane (meth) acrylate, 1- (iso) propylcyclopropane (meth) acrylate, 1 -(Iso) propylcyclobutane (meth) acrylate, 1- (iso) propylcyclopentyl (meth) acrylate, 1- (iso) propylcyclohexyl (meth) acrylate, 1- (iso) propylcycloheptane ( Meth) acrylate, 1- (iso) propylcyclooctane (meth) acrylate, 1- (iso) propylcyclononane (meth) acrylate, 1- (iso) propylcyclodecane (meth) acrylate, 1- ( Iso) butylcyclopropane (meth) acrylate, 1- (iso) butylcyclobutane (meth) acrylate, 1- (iso) butylcyclopentyl (meth) acrylate, 1- (iso) butylcyclohexyl (meth) Acrylate, 1- (iso) butylcycloheptane (meth) acrylate, 1- (iso) butylcyclooctane ) Acrylate, 1- (iso) butylcyclononane (meth) acrylate, 1- (iso) butylcyclodecanyl (meth) acrylate, 1- (iso) pentylcyclopropanyl (meth) acrylate, 1 -(Iso) pentylcyclobutanyl (meth) acrylate, 1- (iso) pentylcyclopentyl (meth) acrylate, 1- (iso) pentylcyclohexyl (meth) acrylate, 1- (iso) pentylcyclohep Tanyl (meth) acrylate, 1- (iso) pentylcyclooctanyl (meth) acrylate, 1- (iso) pentylcyclononanyl (meth) acrylate, 1- (iso) pentylcyclodecanyl (meth) acrylic Rate,

1- (iso) hexylcyclopropanyl (meth) acrylate, 1- (iso) hexylcyclobutanyl (meth) acrylate, 1- (iso) hexylcyclohexyl (meth) acrylate, 1- ( Iso) hexylcycloheptanyl (meth) acrylate, 1- (iso) hexylcyclooctanyl (meth) acrylate, 1- (iso) hexylcyclononanyl (meth) acrylate, 1- (iso) Hexylcyclodecanyl (meth) acrylate,

1- (iso) heptylcyclopropanyl (meth) acrylate, 1- (iso) heptylcyclobutanyl (meth) acrylate, 1- (iso) heptylcycloheptyl (meth) acrylate, 1- (iso) heptyl Cycloheptyl (meth) acrylate, 1- (iso) heptylcycloheptanyl (meth) acrylate, 1- (iso) heptylcyclooctanyl (meth) acrylate, 1- (iso) heptylcyclononanyl (meth) Acrylate, 1- (iso) heptylcyclodecanyl (meth) acrylate,

1- (iso) octylcyclopropanyl (meth) acrylate, 1- (iso) octylcyclobutanyl (meth) acrylate, 1- (iso) octylcyclooctyl (meth) acrylate, 1- (iso) octyl Cyclooctyl (meth) acrylate, 1- (iso) octylcycloheptanyl (meth) acrylate, 1- (iso) octylcyclooctanyl (meth) acrylate, 1- (iso) octylcyclononanyl (meth) Acrylate, 1- (iso) octylcyclodecanyl (meth) acrylate,

2-ethyltricyclo [3.3.1.1 ^3,7 ] decan-2-yl- (meth) acrylate, 2-methyltricyclo [3.3.1.1 ^3,7 ] decan-2-yl- (meth) acrylate, 1-ethyltricyclo [3.3.1.1 ^3,7 ] decane-1-yl- (meth) acrylate, 1-ethyltricyclo [3.3.1.1 ^3,7 ] decane-1-yl- (meth) acrylate 3 Hydroxytricyclo [3.3.1.1 ^3,7 ] decane-1-yl- (meth) acrylate; and the like;

Here, the alkyl part of acrylic acid cyclic alkylester may be a lactone structure, a lactam structure, and an acetal structure. By way of example, 2-ethyl-γ-butyrolactone-2-yl- (meth) acrylate, 2-methyl-γ-butyrolactone-2-yl- (meth) acrylate, 2-ethyl-γ-part Tyrolactone-3-yl- (meth) acrylate, 2-methyl-γ-butyrolactone-3-yl- (meth) acrylate, 2-ethyl-γ-butyrolactone-4-yl- (meth) Acrylate, 2-methyl-γ-butyrolactone-4-yl- (meth) acrylate, 2-ethyl-δ-valerolactone-2-yl- (meth) acrylate, 2-ethyl-δ-valle Rolacton-2-yl- (meth) acrylate, 2-ethyl-δ-valerolactone-3-yl- (meth) acrylate, 2-ethyl-δ-valerolactone-3-yl- (meth) Acrylate, 2-ethyl-δ-valerolactone-4-yl- (meth) acrylate, 2-ethyl-δ-valerolactone-4-yl- (meth) acrylate, 2-ethyl-δ-valle Lactones such as rollactone-5-yl- (meth) acrylate and 2-ethyl-δ-valerolactone-5-yl- (meth) acrylate:

2-ethyl-γ-butyrolactam-2-yl- (meth) acrylate, 2-methyl-γ-butyrolactam-2-yl- (meth) acrylate, 2-ethyl-γ-butyrolactam- 3-yl- (meth) acrylate, 2-methyl-γ-butyrolactam-3-yl- (meth) acrylate, 2-ethyl-γ-butyrolactam-4-yl- (meth) acrylate , 2-methyl-γ-butyrolactam-4-yl- (meth) acrylate, 2-ethyl-δ-valerolactam-2-yl- (meth) acrylate, 2-ethyl-δ-valerolactam 2-yl- (meth) acrylate, 2-ethyl-δ-valerolactam-3-yl- (meth) acrylate, 2-ethyl-δ-valerolactam-3-yl- (meth) acrylate , 2-ethyl-δ-valerolactam-4-yl- (meth) acrylate, 2-ethyl-δ-valerolactam-4-yl- (meth) acrylate, 2-ethyl-δ-valerolactam Lactams such as -5-yl- (meth) acrylate, 2-ethyl-δ-valerolactam-5-yl- (meth) acrylate, and the like;

Tetrahydro-2H-pyran-2-yl ester etc. are mentioned as an acetal structure;

As (meth) acrylic-acid aryl ester, phenyl methacrylate, benzyl methacrylate, etc. are mentioned;

Examples of the unsaturated dicarboxylic acid diester include diethyl maleate, diethyl fumarate, diethyl itaconic acid, and the like;

As the bicyclo unsaturated compounds, bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene , 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2- N, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-dihydrate Roxybicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2'-hydroxyethyl) Bicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept -2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, and the like;

As maleimide compounds, phenylmaleimide, cyclohexyl maleimide, benzyl maleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl -6-maleimide caprolate, N-succinimidyl-3-maleimide propionate, N- (9-acridinyl) maleimide and the like;

As an unsaturated aromatic compound, styrene, (alpha) -methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxy styrene, etc. are mentioned;

1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc. are mentioned as a conjugated diene type compound;

As unsaturated monocarboxylic acid, acrylic acid, methacrylic acid, crotonic acid, etc. are mentioned;

Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid;

As an unsaturated dicarboxylic anhydride, each anhydride etc. of the said unsaturated dicarboxylic acid are mentioned;

Other unsaturated compounds include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, and the like.

Among them, styrene, tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate, p-methoxystyrene, 2-methylcyclohexyl acrylate, 1,3-butadiene, bicyclo [2.2.1 ] Hept-2-ene, N-cyclohexylmaleimide, methacrylic acid, 1-ethylcyclopentyl methacrylate, 2-methyl-2-propenoic acid, tetrahydro-2H-pyran-2-yl ester and the like copolymerized It is preferable at the point of reactivity, heat resistance, etc.

These may be used alone or in combination.

(A) The copolymer is a structural unit derived from the polymerizable unsaturated compound monomer, preferably (a1) 5 to 95% by weight, (a2) 95 to 5% by weight, more preferably (a1) 20 to 95% by weight %, (A2) 80 to 5% by weight, most preferably (a1) 30 to 90% by weight, (a2) 70 to 10% by weight [where (a1) + (a2) = 100% by weight] . Good flattening performance and heat resistance can be realized in the content in the above range.

As a preferred embodiment of the (A) copolymer,

Styrene / Glycidyl Glycidyl Copolymer, Styrene / Methacrylic Acid Tricyclo [5.2.1.0 ^2,6 ] Decan-8-yl / Glycidyl Glycidyl Copolymer, Styrene / N-cyclohexylmaleimide / Glyceryl methacrylate copolymer, styrene / N-phenylmaleimide / methacrylate glycidyl copolymer, N-cyclohexyl maleimide / methacrylate glycidyl copolymer, N-phenyl maleimide / methacryl Shanglycidyl copolymer, styrene / methacrylate tricyclo [5.2.1.0 ^2,6 ] decane-8-yl / methacrylic acid / methacrylic acid glycidyl copolymer, styrene / N-cyclohexylmaleimide / Methacrylic acid / methacrylic acid glycidyl copolymer, styrene / N-phenylmaleimide / methacrylic acid / methacrylic acid glycidyl copolymer,

Styrene / methacrylate tricyclo [5.2.1.0 ^2,6 ] decane-8-yl / 1-ethylcyclohexyl methacrylate / glycidyl methacrylate copolymer, styrene / N-cyclohexylmaleimide / 1- Ethylcyclohexyl methacrylate / glycidyl methacrylate copolymer, styrene / N-phenylmaleimide / 1-ethylcyclohexyl methacrylate / glycidyl methacrylate copolymer, styrene / methacrylate tricyclo [ 5.2.1.0 ^2,6 ] decane-8-yl / 1-ethylcyclopentylmethacrylate / glycidyl methacrylate copolymer, styrene / N-cyclohexylmaleimide / 1-ethylcyclopentylmethacrylate / meth Glycidyl methacrylate copolymer, styrene / N-phenylmaleimide / 1-ethylcyclopentyl methacrylate / glycidyl methacrylate copolymer, tricyclo styrene / methacrylate tricyclo [5.2.1.0 ^2,6 ] decane -8-yl / 1-methylcyclohexyl methacrylate / glycidyl methacrylate copolymer, styrene / N-cyclohexylmal Imide / 1-methylcyclohexyl methacrylate / glycidyl methacrylate copolymer, styrene / N-phenylmaleimide / 1-methylcyclohexyl methacrylate / glycidyl methacrylate copolymer, styrene / meta Krylic acid tricyclo [5.2.1.0 ^2,6 ] decane-8-yl / tetrahydro-2H-pyran-2-yl ester / methacrylic acid glycidyl copolymer, styrene / N-cyclohexylmaleimide / tetrahydro -2H-pyran-2-yl ester / methacrylate glycidyl copolymer, styrene / N-phenylmaleimide / tetrahydro-2H-pyran-2-yl ester / methacrylate glycidyl copolymer, etc. are mentioned. Can be.

The copolymer (A) preferably has a polystyrene reduced weight average molecular weight (hereinafter sometimes referred to as "Mw") measured by gel permeation chromatography (elution solvent: tetrahydrofuran), and more preferably 1,000 to 100,000. Preferably 2,000 to 50,000, particularly preferably 3,000 to 40,000. In this case, when Mw is less than 1,000, the coating property of a composition may become inadequate, or the heat resistance of the protective film formed may be inadequate, while when Mw exceeds 100,000, planarization performance may become inadequate.

Moreover, molecular weight distribution (Mw / Mn) of (A) copolymer becomes like this. Preferably it is 5.0 or less, More preferably, it is 3.0 or less.

Such (A) copolymer can synthesize | combine the said (a1) polymerizable unsaturated compound and (a2) other polymerizable unsaturated compound by a well-known method, for example, radical polymerization, in presence of a suitable solvent and a suitable polymerization initiator. have.

For example, the radical polymerization may include 5 to 95 parts by weight of (a1) polymerizable unsaturated compounds such as glycidyl glycidyl glycidyl and 95 to 5 parts by weight of (a2) other polymerizable unsaturated compounds such as styrene. [Where, (a1) + (a2) = 100 parts by weight), for example, is mixed with 100 to 400 parts by weight of a solvent such as ethyl cellosolve acetate and propylene glycol monomethyl ether acetate and azobisiso as a polymerization initiator. A radical polymerization initiator such as butyronitrile (AIBN) and 2,2'-azobis (2,4-dimethylvaleronitrile) is added in an amount of 0.5 to 15 parts by weight based on 100 parts by weight of the total amount of the monomer components, and then 70 to 100 ° C. It is obtained by polymerization for 3 to 10 hours.

(B) Phosphoric Acid Ester

Phosphoric acid ester (B) used in the present invention has a structure represented by the formula (1).

In the component (B), R ¹ in the formula (1) is preferably an alkyl group having 1 to 8 carbon atoms having an alkoxy group having 1 to 4 carbon atoms at the terminal or side chain of the alkyl group, aryl group, benzyl group or alkyl group having 1 to 18 carbon atoms. Or an acetate ester group, and R ² is preferably an alkyl group having 1 to 18 carbon atoms or an aryl group, benzyl group, or the like.

When (B) component is trimethyl phosphate ester and / or triethyl phosphate ester, it is preferable at the point of the smoothness of a film surface, and a tact time.

As these (B) phosphate esters, when X = 0 in the said General formula (1), a trioctadecyl phosphate ester, a dioctadecyl phosphate ester, a monooctadecyl phosphate ester, a tri (iso) butyl phosphate ester, di (iso) Butyl phosphate ester, mono (iso) butyl phosphate ester, tri (iso) propyl phosphate ester, di (iso) propyl phosphate ester, mono (iso) propyl phosphate ester, triethyl phosphate ester, diethyl phosphate ester, monoethyl phosphate ester , Trimethyl phosphate ester, dimethyl phosphate ester, monomethyl phosphate ester, triphenyl phosphate ester, diphenyl phosphate ester, monophenyl phosphate ester, tribenzyl phosphate ester, dibenzyl phosphate ester, monobenzyl phosphate ester and the like.

In the above formula (1), when X = 1 and R ¹ is a hydrogen atom, specific examples of (B) phosphate ester include phosphonic acid dioctadecyl, phosphonic acid monooctadecyl, phosphonic acid di (iso) butyl, phosphonic acid Mono (iso) butyl, phosphonic acid di (iso) propyl, phosphonic acid mono (iso) propyl, phosphonic acid diethyl, phosphonic acid monoethyl, phosphonic acid dimethyl, phosphonic acid monomethyl, phosphonic acid diphenyl, phosphonic acid monophenyl Phosphonic acid dibenzyl, phosphonic acid monobenzyl and the like.

In the above formula (1), when X = 1 and R ¹ is a carbon adjacent to a phosphorus atom, specific examples of (B) phosphate ester include phosphonoacetic acid trimethyl, diethyl phthalimide methyl phosphate ester and trisacryl. Monooxyethyl phosphate, diacryloyloxyethyl phosphate, monoacryloyloxyethyl phosphate, and the like.

The addition amount of (B) component is 0.01-50 weight part with respect to 100 weight part of (A) component, Preferably it is 0.1-30 weight part, More preferably, it is 0.5-10 weight part. If it is less than 0.01 weight part, sufficient hardness will not be obtained, while if it exceeds 50 weight part, the tact time will become long.

(C) Lewis acid catalyst

Although the resin composition of this invention makes the said (A)-(B) component essential, it may also contain the (C) Lewis acid catalyst. (C) The Lewis acid catalyst serves to promote curing in the resin composition of the present invention.

Examples of the (C) Lewis acid catalyst used in the present invention include diethyl zinc, diphenyl zinc, zinc chloride, diisobutylphenyl aluminum, diethyl aluminum ethanethiolate, diethylphenyl aluminum, dimethyl aluminum methoxide, triphenyl aluminum, Tribenzyl aluminum, tri-t-butylaluminum, N-nitrosophenylhydroxylamine aluminum salt, diethyldichlorosilane, 1,1-dimethyl- 1 -cyclocyclopentane, tetraethylsilane, tetramethylsilane, triphenylchloro Silane, trimethylchlorosilane, chlorotribenzyl zirconium, zirconium chloride, triacetoxycyclopentadienyl zirconium, dichlorobis (cyclopentadienyl) zirconium, dibutyltin dilaurate, dibutyltin dioctylate, trimethylchlorotin (trimethylchlorostannane), trimethylmethoxystannane, chlorotribenzyl titanium, titanium chloride, chlorobis (cyclopentadienyl) titanium , Titanocene, trichloromethyltitanium, chlorotris (triphenylphosphine) nickel, tetrakis (triphenylphosphine) nickel, nickellocene, diethylchloroborane, diisopropylchloroborane, diphenylchloroborane, di Butyl chloroborane etc. are mentioned.

The amount of the (C) Lewis acid catalyst added is 0.0001 to 20 parts by weight, preferably 0.001 to 10 parts by weight, more preferably 0.005 to 5 parts by weight based on 100 parts by weight of the component (A). If it is less than 0.0001 part by weight, a sufficient promoting effect is not obtained. On the other hand, if it exceeds 20 parts by weight, it may precipitate or the film surface may be rough.

(D) cation Polymerizable  compound

Although the resin composition of this invention makes the said (A)-(B) component essential, it can also contain (D) cationically polymerizable compound [except the said (A) component]. (D) The cationically polymerizable compound plays a role of increasing the film hardness in the resin composition of the present invention.

The (D) cationically polymerizable compound used in the present invention is a compound having two or more oxylanyl groups or oxetanyl groups in the molecule (except the component (A) above). Examples of the compound having two or more oxylanyl groups or oxetanyl groups in the molecule include a compound having two or more epoxy groups in the molecule, or a compound having a 3,4-epoxycyclohexyl group.

Among these, examples of the compound having two or more epoxy groups in the molecule include 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, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, etc. Diglycidyl ethers of bisphenol compounds;

1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol digly Polyglycidyl ethers of polyhydric alcohols such as cyl ether;

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

Phenol novolac type epoxy resins;

Cresol novolac type epoxy resins;

Polyphenol type epoxy resins;

Diglycidyl esters of aliphatic long-chain dibasic acids;

Glycidyl esters of higher fatty acids;

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

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

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

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

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

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

As a cyclic aliphatic epoxy resin, CY-175, copper 177, copper 179, araldite CY-182, copper 192, 184 (above, Ciba Specialty Chemicals make), ERL-4234, 4299, 4221, 4206 (Above, UCC Corporation), Shodine 509 (Showa Denko Co., Ltd.), Epiclone 200, Copper 400 (above, Dai Nippon Ink Co., Ltd.), Epicoat 871, Copper 872 (above, Japan Epoxy) Resin (manufactured by Co., Ltd.), ED-5661, copper 5662 (above, manufactured by Seranise Coating Co., Ltd.), and the like;

As aliphatic polyglycidyl ether, epolite 100MF (made by Kyoesha Chemical Co., Ltd.), Epiol TMP (made by Nippon Yushi Corporation), etc. are mentioned.

Examples of the compound having two or more 3,4-epoxycyclohexyl groups in the molecule include 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, 2- (3,4-epoxy Cyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meth-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclo Hexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclo Pentadiene diepoxide, di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylenebis (3,4-epoxycyclohexanecarboxylate), lactone-modified 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexane carboxylate etc. are mentioned.

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

The amount of the (D) cationically polymerizable compound in the resin composition of the present invention is preferably 3 to 200 parts by weight, more preferably 5 to 100 parts by weight, particularly preferably 10 to 50 parts by weight, per 100 parts by weight of component (A). It is wealth. When the usage-amount of (D) cationically polymerizable compound is more than 200 weight part, the coating property of a composition may arise, and when it is less than 3 weight part, the hardness of the protective film obtained may be insufficient.

(E) Adhesion Aids

(E) Adhesion aid can be added to the resin composition of this invention in order to improve the adhesiveness of the protective film formed and a board | substrate.

As such (E) adhesion | attachment adjuvant, the functional silane coupling agent which has a reactive substituent can be used, for example. As said reactive substituent, a carboxyl group, methacryloyl group, an isocyanate group, an epoxy group, etc. are mentioned, for example.

Specific examples of the (E) adhesion aid include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane and γ -Glycidoxy propyl trimethoxysilane, (gamma)-glycidoxy propyl triethoxysilane, (beta)-(3, 4- epoxycyclohexyl) ethyl trimethoxysilane, etc. are mentioned.

Such (E) adhesion aid is preferably used in an amount of 30 parts by weight or less, more preferably 25 parts by weight or less, particularly preferably 5 to 20 parts by weight, per 100 parts by weight of the (A) copolymer. When the amount of (E) adhesion | attachment adjuvant exceeds 30 weight part, the heat resistance of the protective film obtained may become inadequate.

(F) surfactant

In order to improve the application | coating performance of the resin composition of this invention, surfactant (F) can be added to the resin composition of this invention.

As such (F) surfactant, a fluorochemical surfactant, silicone type surfactant, nonionic surfactant, other surfactant, etc. are mentioned, for example.

As said fluorine-type surfactant, BM CHIMIE make brand names: BM-1000, BM-1100, Dainippon Ink & Chemicals Co., Ltd. make brand names: Megapack F142D, copper F172, copper F173, copper F183, Sumitomo 3M Co., Ltd. brand name: Florade FC-135, copper FC-170C, copper FC-430, copper FC-431, neos Co., Ltd. brand name: Pentant 250, copper 251, copper 222F, FTX- 218, Asahi Glass Co., Ltd. product name: Saffron S-112, S-113, S-131, S-141, S-145, S-382, S-101, S- Commercial items, such as 102, SC-103, SC-104, SC-105, and SC-106, are mentioned.

As said silicone type surfactant, Toray Dow Corning Silicone Co., Ltd. brand name: SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190, for example. Commercial products, such as the Shin-Etsu Chemical Co., Ltd. brand name: KP341, Shin-Kaida Kasei Co., Ltd. brand name: F-top EF301, copper EF303, and EF352.

As said nonionic surfactant, polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene dialkyl ester, etc. are mentioned, for example.

As said polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, etc. are mentioned, for example, As polyoxyethylene aryl ether, For example, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, etc. are mentioned, As polyoxyethylene dialkyl esters, polyoxyethylene dilaurate, polyoxyethylene distearate, etc. are mentioned, for example. have.

As said other surfactant, Kyoeisha Chemical Co., Ltd. brand name: (meth) acrylic-acid copolymer polyflow N0.57, copper N0.90, etc. are mentioned.

The addition amount of these (F) surfactant is used in 100 weight part of (A) component, Preferably it is 5 weight part or less, More preferably, it is 2 weight part or less, Especially preferably, it is used in 0.001 to 1.0 weight part. When the amount of (F) surfactant exceeds 5 weight part, the film roughness of a coating film may become easy to generate | occur | produce in a coating process.

(G) thermosensitive acid Generator

A thermosensitive acid generator can be added to the resin composition of this invention in order to increase a film strength. (G) Examples of the thermal acid generator include sulfonium salts, benzothiazonium salts, ammonium salts, phosphonium salts, and the like. Among these, sulfonium salts and benzothiazonium salts are preferably used.

Specific examples of the sulfonium salts include 4-acetophenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, and dimethyl-4- (benzyloxycarbonyloxy) phenylsulphur. Phosphorus hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro- Alkylsulfonium salts such as 4-acetoxyphenylsulfonium hexafluoroantimonate;

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

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

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

Among them, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate , Dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylsulfonium hexafluoroantimonate and the like are preferably used.

Examples of the benzothiazonium salts include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, and 3- (p-methoxybenzyl). Benzyl benzothiazo such as benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate And other salts may be mentioned.

Among these, 3-benzyl benzothiazonium hexafluoro antimonate etc. are used preferably.

(G) As a commercial item of the acid generator preferably used as a thermal acid generator, Asahi Denka Kogyo Co., Ltd. brand name: Adeka Opton CP-66, CP-77, etc. are mentioned.

In addition, as a benzyl sulfonium salt, Sanshin Kagaku Kogyo Co., Ltd. brand name: SI-60, SI-80, SI-100, SI-110, SI-145, SI-150, SI-80L, SI-100L, SI- 110L etc. are mentioned.

Among these, SI-80, SI-100, and SI-110 are preferable because the protective film obtained has high surface hardness.

The amount of the (G) thermal acid generator to be used is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, and particularly preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the component (A). When it exceeds 20 weight part, it may precipitate or the film surface may become rough.

Preparation of Resin Compositions and Solvents

The resin composition of this invention is manufactured by dissolving or disperse | distributing each said component uniformly in a suitable solvent preferably. As a solvent used, it is preferable to use what does not react with each component, even if each component of a composition is melt | dissolved or disperse | distributed.

Such solvents include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol monoalkyl ethers, diethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol alkyl ether acetates, Propylene glycol alkyl ether propionate, aromatic hydrocarbons, ketones, esters, etc. are mentioned.

Specific examples of the alcohols include methanol, ethanol, benzyl alcohol, and the like;

Tetrahydrofuran etc. are mentioned as ethers;

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc. are mentioned as glycol ethers;

Examples of ethylene glycol alkyl ether acetates include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, and the like;

Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, etc. are mentioned as diethylene glycol monoalkyl ether;

Diethylene glycol dialkyl ethers include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether and the like;

Propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, etc. are mentioned as propylene glycol monoalkyl ether;

Examples of propylene glycol alkyl ether acetates include propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, and the like;

Propylene glycol alkyl ether propionates include propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate and the like;

Toluene, xylene, etc. are mentioned as aromatic hydrocarbons;

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

Examples of the esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate and hydroxide. Ethyl hydroxy acetate, butyl hydroxy acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, 3-hydroxypropionate, butyl 3-hydroxypropionate, 2 Methyl hydroxy-3-methyl butyrate, methyl methoxy acetate, ethyl methoxy acetate, methoxy acetate propyl, butyl butyl acetate, ethoxy acetate, ethoxy acetate, ethoxy acetate, ethoxy acetate Methyl propoxy acetate, ethyl propoxy acetate, propyl propoxy acetate, butyl propoxy acetate, methyl butoxy acetate, butoxide Ethyl acetate, propyl butoxy acetate, butyl butoxy acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2- Ethyl ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, 3-meth Methyl oxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, 3-ethoxy Butyl propionate, 3-propoxy methyl propionate, 3-propoxy propionate, 3-propoxy propionate, 3-butyl propoxypropionate, 3-butoxy methyl propionate, 3-butoxy propionate, 3- Propyl butoxy propionate, butyl 3-butoxy propionate, and the like.

Among these, alcohols, diethylene glycols, propylene glycol alkyl acetates, ethylene glycol alkyl ether acetates and diethylene glycol dialkyl ethers are preferable, and benzyl alcohol, diethylene glycol ethyl methyl ether and propylene glycol methyl ether are particularly preferred. Acetate, propylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether are preferable.

The amount of the solvent used is preferably in the range of 1 to 50% by weight, more preferably 5 to 40% by weight, of the total solid content (the amount of the solvent excluding the total amount of the composition including the solvent) in the composition of the present invention. to be.

Moreover, a high boiling point solvent can be used together with the said solvent. As a high boiling point solvent which can be used together here, for example, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N- Methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate And diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and the like.

The usage-amount when using a high boiling point solvent together is preferably 90 weight% or less with respect to the total amount of solvent, More preferably, it is 80 weight% or less.

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

Formation of color filter protective film

Now, the method of forming the protective film of a color filter using the resin composition of this invention is demonstrated.

That is, the resin composition solution of this invention can be apply | coated to the board | substrate surface, a solvent is removed by prefiring, a coating film is formed, and heat processing is performed, and the protective film of the target color filter can be formed.

As what can be used as said board | substrate, board | substrates, such as glass, quartz, a silicone, resin, can be used, for example. Examples of the resin include polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, polyimide, resins such as ring-opening polymers of cyclic olefins and hydrogenated substances thereof.

As the coating method, for example, a spraying method, a roll coating method, a rotary 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 employed. It is preferable to use.

As the conditions for preliminary firing, although it depends on the kind of each component, a mixing ratio, etc., the conditions of about 1 to 15 minutes can be employ | adopted normally at 70-90 degreeC. As thickness of a coating film, Preferably, it is 0.15-8.5 micrometers, More preferably, it is 0.15-6.5 micrometers, More preferably, it is 0.15-4.5 micrometers. In addition, the thickness of the coating film here should be understood as thickness after solvent removal.

The heat treatment after coating film formation can be performed with a suitable heating apparatus, such as a hotplate and a clean oven. The treatment temperature is preferably about 150 to 250 ° C, and the heating time may be a treatment time for 5 to 30 minutes in the case of using a hot plate, and 30 to 90 minutes in the case of using an oven.

In addition, when a radiation sensitive acid generator is used for a resin composition, after apply | coating the said radiation sensitive resin composition to the surface of a board | substrate, removing a solvent by prefiring, and making it into a coating film, it carries out irradiation treatment (exposure treatment), The target protective film can be formed by performing heat processing.

As used herein, a radiation sensitive acid generator that generates an acid by irradiation of radiation can promote the reaction through the action of an acid generated by exposure. Examples of such acid generators include (1) onium salts, (2) halogen-containing compounds, (3) diazoketone compounds, (4) sulfone compounds, and (5) sulfonic acid compounds. The following are mentioned as an example of these acid generators.

(1) As onium salt, an iodonium salt, a sulfonium salt, a phosphonium salt, a diazonium salt, a pyridinium salt, etc. are mentioned, for example. Specific examples of preferred onium salts include diphenyl iodonium triflate, diphenyl iodonium pyrenesulfonate, diphenyl iodonium dodecylbenzenesulfonate, bis (4-t-butylphenyl) iodonium triflate and bis ( 4-t-butylphenyl) iodonium dodecylbenzenesulfonate, bis (4-t-butylphenyl) iodonium naphthalenesulfonate, bis (4-t-butylphenyl) iodonium hexafluoroantimonate , Triphenylsulfonium triflate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium naphthalenesulfonate, (hydroxyphenyl) benzenemethylsulfonium toluenesulfonate, 1- (naphthylacetomethyl) thiola Triflate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium triflate, dicyclohexyl (2-oxocyclohexyl) sulfonium triflate, dimethyl (2-oxocyclohexyl) sulfonium triflate, dimethyl (4 Hydroxynaphthyl) sulfonium tree Latex, dimethyl (4-hydroxynaphthyl) sulfonium tosylate, dimethyl (4-hydroxynaphthyl) sulfonium dodecylbenzenesulfonate, dimethyl (4-hydroxynaphthyl) sulfonium naphthalenesulfonate, diphenyl Iodonium hexafluoroantimonate, triphenylsulfonium camphorsulfonate, (4-hydroxyphenyl) benzylmethylsulfonium toluenesulfonate, and the like.

(2) Examples of the halogen-containing compound include a haloalkyl group-containing hydrocarbon compound, a haloalkyl group-containing heterocyclic compound, and the like. Specific examples of preferred halogen-containing compounds include phenyl-bis (trichloromethyl) -s-triazine, methoxyphenyl-bis (trichloromethyl) -s-triazine, naphthyl-bis (trichloromethyl) -s- (Trichloromethyl) -s-triazine derivatives such as triazine, or 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane.

(3) As an example of a diazo ketone compound, a 1, 3- diketo-2- diazo compound, a diazo benzoquinone compound, a diazonaphthoquinone compound, etc. are mentioned. Specific examples of preferred diazoketones include 1,2-naphthoquinonediazide-4-sulfonylchloride, 1,2-naphthoquinonediazide-5-sulfonylchloride, 2,3,4,4'-tetrahydro 1,2-naphthoquinone diazide-4-sulfonic acid ester or 1,2-naphthoquinone diazide-5-sulfonic acid ester of benzophenone, 1 of 1,1,1-tris (4-hydroxyphenyl) ethane And 2-naphthoquinone diazide-4-sulfonic acid ester or 1,2-naphthoquinone diazide-5-sulfonic acid ester.

(4) As an example of a sulfone compound, (beta) -keto sulfone, (beta) -sulfonyl sulfone, the (alpha)-diazo compound of these compounds, etc. are mentioned. As a specific example of a preferable sulfone compound, 4-trisfenacyl sulfone, mesityl penacyl sulfone, bis (phenylsulfonyl) methane, etc. are mentioned.

(5) Examples of the sulfonic acid compound include alkyl sulfonic acid esters, alkyl sulfonic acid imides, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, imino sulfonates, and the like. Specific examples of preferred sulfonic acid compounds include benzointosylate, tristriplate of pyrogallol, nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, trifluoro methane sulfonylbicyclo [2.2.1] hept-5- Ene-2,3-dicarbodiimide, N-hydroxysuccinimide triflate, 1,8-naphthalenedicarboxylic acid imide triflate, and the like.

Among these acid generators, in particular, diphenyl iodonium triflate, bis (4-t-butylphenyl) iodonium triflate, triphenylsulfonium triflate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium tri Plate, Dicyclohexyl (2-oxocyclohexyl) sulfonium triflate, Dimethyl (2-oxocyclohexyl) sulfonium triflate, 1- (naphthylacetomethyl) thiolanium triflate, 4-hydroxynaphthyl Dimethylsulfonium triflate, dimethyl (4-hydroxynaphthyl) sulfonium triflate, trifluoromethanesulfonylbicyclo [2.2.1] hept-5-ene-2,3-dicarbodiimide, N-hydride Roxysuccinimide triflate, 1,8-naphthalenedicarboxylic acid imide triflate, etc. are preferable.

In the present invention, the acid generators may be used alone or in combination of two or more thereof.

The use amount of the acid generator is usually 0.1 to 10 parts by weight, preferably 0.5 to 7 parts by weight based on 100 parts by weight of the (A) copolymer. In this case, when the usage-amount of an acid generator is less than 0.1 weight part, sufficient reaction promoting effect will not be acquired, and when it exceeds 10 weight part, transparency may fall.

Examples of the radiation that can be used during the irradiation treatment of the radiation include visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, and the like, but ultraviolet light containing light having a wavelength of 190 to 450 nm is preferable.

The exposure dose is usually 100 to 20,000 J / m ² , preferably 150 to 10,000 J / m ² .

 After radiation irradiation, heat processing is further performed. 150-250 degreeC of heating temperature at this time is preferable, and a suitable apparatus, such as a hotplate and a clean oven, can be used as a heating apparatus, for example. The heating time may employ a treatment time of 5 to 30 minutes for hot plate use and 15 to 90 minutes for oven use.

Shield of color filter

The protective film thus formed has a film thickness of preferably 0.1 to 8 mu m, more preferably 0.1 to 6 mu m, still more preferably 0.1 to 4 mu m. In addition, when the protective film of the present invention is formed on a substrate having a step of the color filter, the above film thickness should be understood as the thickness at the top of the color filter.

As apparent from the following examples, the protective film of the present invention satisfies adhesion, surface hardness, transparency, heat resistance, light resistance, solvent resistance, and the like, and does not dent under load applied with heat. It is preferable as a protective film for optical devices which is excellent in the performance of flattening the level difference of the color filter formed in the film filter.

In particular, since the protective film of the present invention may be exposed to heating exceeding 250 ° C. in the panel manufacturing process, it is ensured that the film has sufficient dimensional stability at 270 ° C. even if it has sufficient heat resistance.

Thermosensitive dry film

A thermosensitive dry film is obtained by laminating | stacking the heat-sensitive layer which consists of said thermosensitive resin composition of this invention on a base film, Preferably a flexible base film.

The thermosensitive dry film can be formed by laminating a thermosensitive layer by applying the thermosensitive resin composition on the base film as a liquid composition, and then drying it.

As a base film of a thermosensitive dry film, synthetic resin films, such as a polyethylene terephthalate (PET) film, polyethylene, a polypropylene, polycarbonate, polyvinyl chloride, can be used, for example.

The thickness of the base film is suitably in the range of 15 to 125 mu m.

Although the coating method at the time of laminating | stacking a heat-sensitive layer on a base film is not specifically limited, For example, the appropriate method, such as an applicator coating method, the bar coating method, the roll coating method, the curtain flow coating method, can be employ | adopted.

As for the film thickness of the obtained thermal layer, about 1-30 micrometers is preferable.

In addition, a thermosensitive dry film can also be preserve | saved by further laminating | stacking a cover film on the heat sensitive layer at the time of nonuse.

This cover film is for stably protecting the heat-sensitive layer when not in use, and is removed during use. Therefore, the cover film needs to have a suitable release property so that it may not peel at the time of non-use, but may peel easily at the time of use. As a cover film which satisfies these conditions, the film which apply | coated or baked the silicone type release agent to the surface of synthetic resin films, such as PET film, a polypropylene film, a polyethylene film, and polyvinyl chloride, can be used, for example. .

The thickness of the cover film is usually about 25 m.

In the case of the dry film method, in the case where the cover film is laminated, the heat-sensitive dry film is peeled off so that the heat-sensitive layer is on the substrate side, such as an atmospheric pressure hot roll press method, a vacuum hot roll press method, or a vacuum hot press press method. By crimping | bonding with a board | substrate, applying a suitable heat and pressure with a crimping method, a thermosensitive ray layer is transferred to a board | substrate surface, and the film of a thermosensitive resin composition is formed on a board | substrate.

Thus, the thermosensitive dry film obtained is useful for the use of the protective film for optical devices, such as a protective film for color filters.

< Example >

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

Preparation of Copolymer

Synthesis Example  One

5 parts by weight of 2,2'-azobis-isobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate were introduced into a flask equipped with a cooling tube and a stirrer. Subsequently, 50 parts by weight of glycidyl methacrylate and 50 parts by weight of styrene were introduced to replace the nitrogen, and then stirring was gradually started. The solution temperature was raised to 70 ° C. and maintained at this temperature for 5 hours to obtain a polymer solution containing the copolymer (A-1). Solid content concentration of the obtained polymer solution was 32.9 weight%.

Synthesis Example  2

5 parts by weight of 2,2'-azobis-isobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate were introduced into a flask equipped with a cooling tube and a stirrer. Subsequently, 50 parts by weight of (3-ethyl-3-oxyethananyl) methyl methacrylate and 50 parts by weight of styrene were introduced to replace nitrogen, and then stirring was gradually started. The solution temperature was raised to 70 ° C. and maintained at this temperature for 5 hours to obtain a polymer solution containing the copolymer (A-2). Solid content concentration of the obtained polymer solution was 33.2 weight%.

Synthesis Example  3

5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were introduced into a flask equipped with a cooling tube and a stirrer. Subsequently, 40 parts by weight of glycidyl methacrylate, 40 parts by weight of methacrylic acid, 10 parts by weight of styrene and 10 parts by weight of methacrylic acid tricyclo [5.2.1.0 ^2,6 ] decane-8-yl were introduced and nitrogen-substituted. After that slowly stirring was started. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-3). Solid content concentration of the obtained polymer solution was 33.2 weight%.

Synthesis Example  4

5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were introduced into a flask equipped with a cooling tube and a stirrer. Subsequently, 40 parts by weight of glycidyl methacrylate, 40 parts by weight of 1-ethylcyclohexyl methacrylate, 10 parts by weight of styrene, and 10 parts by weight of N-cyclohexylmaleimide were introduced, and then nitrogen was slowly stirred. The solution temperature was raised to 70 ° C. and maintained at this temperature for 5 hours to obtain a polymer solution containing the copolymer (A-4). Solid content concentration of the obtained polymer solution was 33.2 weight%.

Synthesis Example  5

5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were introduced into a flask equipped with a cooling tube and a stirrer. Then, 40 parts by weight of glycidyl methacrylate, 20 parts by weight of styrene, 20 parts by weight of N-cyclohexyl maleimide, 20 parts by weight of 2-methyl-2-propene acid tetrahydro-2H-pyran-2-yl ester After the introduction and nitrogen replacement, stirring was gradually started. The solution temperature was raised to 70 ° C. and maintained at this temperature for 5 hours to obtain a polymer solution containing the copolymer (A-5). Solid content concentration of the obtained polymer solution was 29.9 weight%.

Preparation and Evaluation of Resin Compositions

Example  One

A solution containing the copolymer (A-1) obtained in Synthesis Example 1 (an amount corresponding to 100 parts by weight (solid content) of the copolymer (A-1)) and 5.0 parts by weight of (B) tri-n-octadecyl phosphate ester 0.1 parts by weight of (C) N-nitrosolphenylhydroxylamine Al salt, (D) 10.0 parts by weight of bisphenol A novolac-type epoxy resin, (E) 5.0 parts by weight of γ-glycidoxypropyltrimethoxysilane, (F) 0.1 weight part of SH-28PA (made by Toray Dow Corning Silicon Co., Ltd.) as surfactant, and propylene glycol monomethyl ether acetate are added so that solid content concentration may be 20 weight%, and then 0.5 micrometer of pore diameters It filtered with the Millipore filter of and prepared the resin composition.

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

Evaluation of the shield

(1) evaluation of transparency

About the board | substrate with a protective film formed as mentioned above, the transmittance | permeability of 400-800 nm was measured using the spectrophotometer (150-20 type double beam (made by Hitachi Seisakusho Co., Ltd.)). Table 1 shows the minimum values of transmittance between 400 and 800 nm. When this value is 95% or more, it can be said that transparency of a protective film is favorable.

(2) Evaluation of heat resistance dimensional stability

About the board | substrate which has the protective film formed as mentioned above, it heated on 250 degreeC in conditions of 1 hour in oven, and measured the film thickness before and behind heating. Table 1 shows the heat-resistant dimensional stability calculated according to the following formula. When this value is 95% or more, it can be said that heat-resistant dimensional stability is favorable.

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

(3) heat resistant Fading  evaluation

About the board | substrate with a protective film formed as mentioned above, it heated at 250 degreeC in oven for 1 hour, and the transparency before and behind heating was measured similarly to said (1). Table 1 shows the heat discoloration resistance calculated according to the following formula. It can be said that heat discoloration resistance is favorable that this value is 5% or less.

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

(4) measurement of surface hardness

About the board | substrate with a protective film formed as mentioned above, the surface hardness of the protective film was measured through the 8.4.1 pencil scraping test of JISK-5400-1990. This value is shown in Table 1. If this value is 4H or harder, it can be said that surface hardness is favorable.

(5) dynamic  Measurement of micro hardness

The substrate having the protective film formed as described above was subjected to the indentation test of a ridge angle 115 ° triangular indenter (Herkovitch type) using Shimadzu Dynamic Microhardness Tester DUH-201 (manufactured by Shimadzu Corporation). The dynamic microhardness of the protective film was measured under measurement conditions of a load of 0.1 gf, a speed of 0.0145 gf / sec, a holding time of 5 seconds, a temperature of 23 ° C, and 140 ° C. The results are shown in Table 1.

(6) Evaluation of adhesiveness

After the pressure vessel test (120 degreeC, 100% of humidity, 4 hours) was performed with respect to the board | substrate which has the protective film formed as mentioned above, the protective film was made through the 8.5.3 adhesive checkerboard eye tape method of JISK-5400-1990. The adhesion (adhesion to SiO ₂ ) was evaluated. Table 1 shows the number of checkerboard eyes remaining among the checkerboard eyes.

In addition, as evaluation of the adhesion to Cr, a protective film having a thickness of 2.0 μm was formed in the same manner as above except that a Cr substrate was used instead of a SiO ₂ dip glass substrate, and the same evaluation was made using the checkerboard eye tape method. . The results are shown in Table 1.

(7) Flattened  evaluation

Pigment-based color resists (trade names "JCR RED 689", "JCR GREEN 706", "CR 8200B", above, manufactured by JSR Co., Ltd.) were coated on a SiO ₂ dip glass substrate with a spinner, and then heated to 90 ° C on a hot plate. Presintering was performed for 150 seconds to form a coating film. Subsequently, i-line conversion of the ghi line (wavelength 436 nm, 405 nm, 365 nm intensity ratio = 2.7: 2.5: 4.8) using an exposure machine Canon PLA501F (manufactured by Canon Corporation) through a predetermined pattern mask Irradiated with an exposure dose of 2,000 J / m ² , developed using 0.05% aqueous potassium hydroxide solution, rinsed with ultrapure water for 60 seconds, and then heated in an oven at 230 ° C. for 30 minutes to give a red, green and blue color. A tricolor striped color filter (stripe width 100 mu m) was formed.

It was 1.0 micrometer when the unevenness | corrugation of the surface of the board | substrate with which this color filter was formed was measured by the surface roughness meter "(alpha) -step" (brand name: Tencol Corporation make). At this time, it measured with the measurement length 2,000 micrometers, the measurement range 2,000 micrometers (horizontal), and the measurement score n = 5. That is, the measurement direction is measured in two directions of the stripe line short axis direction in the red, green, and blue directions, and in the long axis direction of the same color stripe line of red, red, green, green, blue, and blue, and the measurement is performed at n = 5 for each direction. (N-number of total is 10).

After coating the protective film-forming composition with a spinner thereon, a pre-baked film was formed at 90 ° C. for 5 minutes on a hot plate to form a coating film. A protective film having a thickness of 2.0 mu m was formed. That is, the film thickness here means the thickness in the uppermost surface of the color filter formed on the substrate.

The surface unevenness | corrugation of the protective film was measured with the contact film thickness measuring apparatus (alpha) -step (made by Tencol Japan Co., Ltd.) with respect to the board | substrate which has a protective film on the color filter formed as mentioned above. At this time, it measured as 2,000 micrometers of measurement lengths, 2,000 micrometers of measurement range (vertical), and the measurement score n = 5. That is, the measurement direction is measured in two directions of the stripe line short axis direction in the red, green, and blue directions, and in the long axis direction of the same color stripe line of red, red, green, green, blue, and blue, and the measurement is performed at n = 5 for each direction. (N-number of total is 10). Table 1 shows ten average values of the height difference (nm) of the highest part and the lowest part of each measurement. If this value is 300 nm or less, it can be said that planarization property is favorable.

(8) Evaluation of storage stability

The viscosity of the resin composition for protective film formation manufactured in Example 1 was measured with the Tokyo Keiki Co., Ltd. ELD type viscometer. The solution viscosity at 25 ° C. was then measured daily with the composition still at 25 ° C. The number of days required to thicken 5% based on the viscosity immediately after manufacture was calculated | required, and this day is shown in Table 1. It can be said that storage stability is favorable that this day is 20 days or more.

Example  2 to 17 and Comparative example  1 to 2

The type and amount of each component of the composition were as described in Tables 1 and 2, and the same as in Example 1 except that the solids concentrations shown in Tables 1 and 2 were adjusted using the solvents shown in Tables 1 and 2. A resin composition was prepared.

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

Example  18 to 20

The resin composition was produced like Example 1 except having set the kind and quantity of each component of a composition as Table 2, and using the solvent of Table 2 and adjusting to the solid content concentration of Table 2.

A protective film was formed and evaluated in the same manner as in Example 1 except that the slit die coater was applied instead of the spin coater. The results are shown in Table 2.

In addition, in Table 1 and Table 2, abbreviation of (A) component, (C) Lewis acid metal catalyst, (D) cationically polymerizable compound, (E) adhesion adjuvant, (F) surfactant, and (S) solvent is The following is shown respectively.

(A) Ingredient:

ST = styrene

GMA = glycidyl methacrylate

O-MA = (3-ethyl-3-oxyethananyl) methylmethacrylate

CHMI = N-cyclohexylmaleimide

MA = methacrylic acid

M-THP = 1-ethylcyclohexyl methacrylate

ECPMA = 2-methyl-2-propene tetrahydro-2H-pyran-2-ylester

C-1: zinc chloride

C-2: N-nitrosophenylhydroxyamine Al salt

D-1: Bisphenol A novolak-type epoxy resin (Japan Epoxy Resin Co., Ltd. make brand name: Epicoat 157S65)

E-1: γ-glycidoxypropyltrimethoxysilane

F-1: Silicone type surfactant (Toray Dow Corning Silicone Co., Ltd. make brand name: SH-28PA)

S-1: Propylene Glycol Monomethyl Ether Acetate

Industrial Applicability

The resin composition of the present invention can form a cured film having high flatness on the substrate even on a substrate having a low surface flatness, high transparency and high surface hardness, and various kinds of heat resistance, acid resistance, alkali resistance, sputtering resistance and the like. It is excellent in resistance and is useful as a protective film for optical devices, such as a color filter for liquid crystal display elements (LCD), and a color filter for charge-coupled elements (CCD).

According to the present invention, even in a substrate having a low surface flatness, a cured film having a high flatness can be formed on the substrate, and transparency and surface hardness are high, and various resistances such as heat resistance, acid resistance, alkali resistance, sputtering resistance, and the like can be obtained. A resin composition which is preferably used for forming this excellent protective film for an optical device and is excellent in storage stability as a composition, a method for forming a protective film using the resin composition, and a protective film formed from the composition is provided.

Claims (8)

(A) (a1) a copolymer of a polymerizable unsaturated compound having an oxylanyl group or an oxetanyl group with (a2) a polymerizable unsaturated compound other than the above (a1), and (B) Phosphoric acid ester having a structure represented by the following formula (1) And 0.01 to 50 parts by weight of component (B), based on 100 parts by weight of the component (A). <Formula 1>

Where X is an integer from 0 to 2, R ¹ represents a hydrogen atom or an organic group in which an atom adjacent to a phosphorus atom is carbon, R ² represents an organic group wherein the atom adjacent to the oxygen atom is carbon. According to claim 1, (B) component of 1 to 8 carbon atoms is R ¹ in the formula (I) having an alkoxy of 1 to 4 carbon atoms group at the terminal or the side chain of an alkyl group, an aryl group, a benzyl group or an alkyl group having 1 to 18 carbon atoms The resin composition which is an alkyl group or an acetate ester group, R <^2> is a C1-C18 alkyl group or an aryl group, or a benzyl group. The resin composition of Claim 1 whose (B) component is trimethyl phosphate ester and / or triethyl phosphate ester. The resin composition of any one of Claims 1-3 which further contains 0.0001-20 weight part of (C) Lewis acid catalysts with respect to 100 weight part of (A) component. The method according to any one of claims 1 to 4, further comprising 3 to 200 parts by weight of the (D) cationically polymerizable compound (except the component (A)) based on 100 parts by weight of the component (A). Resin composition. The resin composition of any one of Claims 1-5 for forming the protective film of a color filter. It heat-processes after forming a coating film using the resin composition of Claim 6 on a board | substrate, The formation method of the color filter protective film characterized by the above-mentioned. The color filter protective film formed from the resin composition of Claim 6.