KR100826081B1 - Resin composition, process for forming protective films of color filters and protective films of color filters - Google Patents

Abstract

The present invention can form a cured film having high flatness on the substrate even with a substrate having a low surface flatness, high transparency and high surface hardness, and excellent light resistance such as heat resistance, acid resistance, alkali resistance and sputter resistance. It is used suitably for forming the protective film for devices, and also provides the composition excellent in the storage stability as a composition.

The present invention relates to a copolymer of a polymerizable unsaturated compound having an [A] (a1) oxylanyl group or an oxetanyl group with (a2) a polymerizable unsaturated compound other than the above (a1), and [B] (b1) an acid anhydride group A polymer containing a polymerizable unsaturated compound having and / or (b2) an acid anhydride formed from a polyhydric carboxylic anhydride, and [C] a compound having a basic skeleton structure represented by the following formula (1) and / or represented by the following formula (2): The resin composition containing the hardening accelerator formed from the compound which has a basic skeleton structure is provided.

<Formula 1>

<Formula 2>

Resin composition, protective film of color filter, curing accelerator

Description

Resin composition, formation method of protective film of color filter and protective film of color filter {RESIN COMPOSITION, 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 Patent Application Laid-Open No. 2001-91732

[Patent Document 3] Japanese Patent Application Laid-Open No. 4-218561

This invention relates to the resin composition, the formation method of the protective film of a color filter using this resin composition, and the protective film of a color filter. More specifically, the resin composition which is very suitable as a material for forming the protective film used for the color filter for liquid crystal display elements (LCD) and the color filter for charge coupling elements (CCD), the formation method of the protective film using this resin composition, and this It relates to a protective film formed of the composition.

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 temperatures. Therefore, in order to prevent the element from deteriorating or being damaged by such a process, a protective film made of a thin film resistant to such a process is provided on the surface of the element.

Such a protective film has high adhesion to the substrate or lower layer on which the protective film is to be formed, and a layer further formed on the protective film, the film itself is smooth and strong, has transparency, has high heat resistance and light resistance, and is colored over a long period of time. Performance such as not causing deterioration such as yellowing, yellowing, and whitening, and having excellent water resistance, solvent resistance, acid resistance, and alkali resistance are required. As a material for forming the protective film which satisfies such various characteristics, the thermosetting composition containing the polymer which has glycidyl group, for example is known. (See Patent Document 1 and Patent Document 2)

Moreover, 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 single yarn 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 transister (TFT) method, a bead-shaped spacer is dispersed on a protective film in order to maintain a uniform cell gap of the liquid crystal layer. It is done to attach panels after coating. Then, the liquid crystal cell is sealed by thermocompression bonding the sealing material. At this time, a phenomenon in which the protective film in the portion where beads are present occurs due to heat and pressure applied is a problem that the cell gap is disturbed.

In particular, when manufacturing the STN type color liquid crystal display device, the color filter and the opposing substrate must be very precisely bonded to each other, and the protective film is required to have a very high level of single yarn flattening and heat-resistant resistance. .

In recent years, a wiring electrode (indium tin oxide: ITO or indium zinc oxide: IZO) is formed on the protective film of the color filter by sputtering, and a method of patterning ITO or IZO with strong acid or strong alkali is also employed. Since the protective film of a color filter is sputtered, the surface is locally exposed to high temperature or many chemical treatments are performed. Therefore, the adhesiveness with the wiring electrode which withstands this process and prevents ITO or IZO from peeling off on a protective film at the time of chemical processing is calculated | required.

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 a protective film resin composition for expressing various properties as described above. Silver has a problem that the shelf life of the composition itself is very short because it has a highly reactive crosslinking group or catalyst which forms a solid crosslinking, which is very difficult to treat. That is, not only the coating performance itself of the composition deteriorated with time, but also frequent maintenance, cleaning, etc. of the coating machine were required, and it was complicated in operation.

The material which satisfies the general required performance as a protective film, such as transparency, and which can easily form the protective film which satisfy | fills the various said performances, and is excellent in the storage stability as a composition is still unknown.

Patent Document 3 discloses a thermosetting composition which is used for paints, inks, adhesives, and molded articles and contains latent carboxyl compounds, but nothing is disclosed about the protective film of the color filter.

The present invention is formed on the basis of the above circumstances, and its object is to form a cured film having high flatness on the substrate even with a substrate having a low surface flatness, and also has high transparency and surface hardness, heat resistance, acid resistance and alkali resistance. It is very suitably used to form a protective film for an optical device excellent in various resistances such as sputter resistance, and also excellent in storage stability as a composition, a method of forming a protective film using the composition, and a protective film formed by the composition. Is in.

The present invention relates to a copolymer of a polymerizable unsaturated compound having an [A] (a1) oxylanyl group or an oxetanyl group with (a2) a polymerizable unsaturated compound other than the above (a1), and [B] (b1) an acid anhydride group (B2) an acid anhydride formed from a polymer containing a polymerizable unsaturated compound and / or (b2) a polyhydric carboxylic anhydride and a compound having a basic skeleton structure represented by the following Chemical Formula 1 (hereinafter referred to as [Compound (1)]): And / or a curing accelerator formed from a compound having a basic skeleton structure represented by Chemical Formula 2 (hereinafter also referred to as [compound (2)]).

Here, as said [C] hardening accelerator, the compound represented by following formula (3) (henceforth [compound (3)]) and / or the compound represented by following formula (4) (henceforth [compound (4)]) desirable.

R ₁ or R ₂ in Formula 3 or 4 represents a hydrogen atom, an alkyl group of 1 to 8 carbon atoms, an alkyl group of 1 to 8 carbon atoms having a C 1 to 4 alkoxy group, a phenyl group, a benzyl group, or a hydroxymethyl group, and Or R ₄ and R ₂ in (4) may be combined to be a phenyl ring and a cycloalkane ring having 4 to 8 carbon atoms, and R ₃ of Formula 3 may be a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy having 1 to 4 carbon atoms. An alkyl group having 1 to 8 carbon atoms, a phenyl group, a benzyl group or a cyanoethyl group having a group, and R ₄ in Formula 4 represents an alkyl group having 1 to 18 carbon atoms, an alkyl group having 1 to 18 carbon atoms or a phenyl group having an alkoxy group having 1 to 4 carbon atoms. Indicates.

The resin composition of this invention can further contain a [D] cationically polymerizable compound (except the said [A] copolymer).

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

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

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

Best Mode for Carrying Out the Invention

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

[A] copolymer

[A] copolymer of this invention is a polymerized unit derived from the polymerizable unsaturated compound which has (a1) an oxylalanyl group or an oxetanyl group, and (a2) a synthetic unsaturated compound among other than the polymerization unit of said (a1). It is formed by containing the polymerized unit derived.

In the copolymer (A), the (a1) polymerizable unsaturated compound is not particularly limited as long as it has an oxylanyl group or an oxetanyl group and a polymerizable unsaturated group, but examples thereof include, for example, acrylic acid. Glycidyl, Glycidyl methacrylate, Glycidyl α-ethyl acrylate, Glycidyl α-propyl acrylate, Glycidyl α-butyl acrylate, Glycidyl acrylate, 3,4-Epoxybutyl acrylate, Methacrylic Acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether, a l-vinyl benzyl glycidyl ether, etc. are mentioned.

As the oxetanyl group-containing polymerizable unsaturated compound, for example, 3-methyl-3- (meth) acryloyloxymethyloxetane, 3-ethyl-3- (meth) acryloyloxymethyloxetane, etc. Can be mentioned.

Among these, methacrylic acid glycidyl, methacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether, l-vinyl benzyl glycidyl ether, and the like, It is preferably used in view of increasing the copolymerization reactivity and the heat resistance and surface hardness of the resulting protective film or insulating film.

The copolymer (A) contains, in addition to (a1), (a2) polymerized units derived from other polymerizable unsaturated compounds other than the above (a1). (a2) As another polymerizable unsaturated compound, (meth) acrylic-acid alkylester, (meth) acrylic-acid cyclic alkylester, (meth) acrylic-acid aryl ester, unsaturated dicarboxylic acid diester, bicyclo unsaturated compound logistics, and Malay Mid compounds, an unsaturated aromatic compound, conjugated diene type compound, unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, unsaturated dicarboxylic acid anhydride, an acetal structure, an unsaturated compound which has a ketal structure, etc. are mentioned.

As a specific example of these, for example, as (meth) acrylic-acid alkylester, hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxy Oxybutyl (meth) acrylate, diethylene glycol mono (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, 2-methacryloxyethylglycoside, 4-hydroxyphenyl (meth) acrylic Acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylic Acrylate, n-lauryl (meth) acrylate, tridecyl (meth) acrylate, n-stearyl (meth) acrylate, tet-butoxy (meth) acrylate, 1-dimethyl (iso) propyl (meth) Acrylate, 1-dimethyl (iso) moiety Methyl (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) 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, isobornyl (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- Methylcyclononane (meth) acrylate, 1-ethylcyclodecane (meth) acrylate, 1-ethylcyclopropane (meth) acrylate, 1-ethylcyclobutane (meth) acrylate, 1-ethylcyclopentyl (meth) Acrylate, 1-ethylcyclohexyl (meth) acrylate, 1-ethylcycloheptane (Meth) acrylate, 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) butylcyclo Hexyl (meth) acrylate, 1- (iso) butylcycloheptane (meth) acrylate, 1- ( Small) butylcyclooctane (meth) 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) pentylcycloheptanyl (meth) acrylate, 1- (iso) pentylcyclooctanyl (meth) acrylate, 1- (iso) pentylcyclononanyl (meth) acrylate, 1- (iso) pentyl Cyclodecanyl (meth) acrylate, 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- ( Small) hexylcyclononanyl (meth) acrylate, 1- (iso) hexylcyclodecanyl (meth) acrylate, 1- (iso) heptylcyclopropanyl (meth) acrylate, 1- (iso) heptyl Cyclobutanyl (meth) acrylate, 1- (iso) heptylcycloheptyl (meth) acrylate, 1- (iso) heptylcycloheptyl (meth) acrylate, 1- (iso) heptylcycloheptanyl (meth) acrylic Late, 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) octylcyclooctyl ( Metha) 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 ] decan-1-yl- (meth) Acrylate, 1-ethyltricyclo [3.3.1.1 ^3,7 ] decan-1-yl- (meth) acrylate, 3-hydroxytricyclo [3.3.1.1 ^3,7 ] decan-1-yl- (meth ) Acrylates and the like;

In addition, the alkyl part of an acrylic acid cyclic alkylester may be a lactone structure, a lactam structure, and an acetal structure. Examples include 2-ethyl-γ-butyrolactone-2-yl- (meth) acrylate, 2-methyl-γ-butyrolactone-2-yl- (meth) acrylate, 2-ethyl-γ-butyrol Lactone-3-yl- (meth) acrylate, 2-methyl-γ-butyrolactone-3-yl- (meth) acrylate, 2-ethyl-γ-butyrolactone-4-yl- (meth) acrylic Late, 2-methyl-γ-butyrolactone-4-yl- (meth) acrylate, 2-ethyl-δ-valerolactone-2-yl- (meth) acrylate, 2-ethyl-δ-valero Lactone-2-yl- (meth) acrylate, 2-ethyl-δ-valerolactone-3-yl- (meth) acrylate, 2-ethyl-δ-valerolactone-3-yl- (meth) acrylic Late, # 2-ethyl-δ-valerolactone-4-yl- (meth) acrylate, 2-ethyl-δ-valerolactone-4-yl- (meth) acrylate, 2-ethyl-δ-valero Lactones such as lactone-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. as an acetal structure;

As (meth) acrylic-acid aryl ester, Phenyl methacrylate, benzyl methacrylate, etc .;

Examples of the unsaturated dicarboxylic acid diester include diethyl maleate, diethyl fumarate, diethyl itaconate 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- N, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2 -Ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di Hydroxybicyclo [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 butylate, N-succinimi Di--6-maleimide caproate, N-succinimidyl-3-maleimide propionate, N- (9-acridinyl) maleimide and the like;

As an unsaturated aromatic compound, Styrene, (alpha) -methylstyrene, m-methylstyrene, X-methylstyrene, vinyltoluene, X-methoxystyrene, etc .;

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

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

As unsaturated dicarboxylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, etc .;

As unsaturated dicarboxylic anhydride, each anhydride of the said unsaturated dicarboxylic acid;

Examples of 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-yl methacrylate, l-methoxystyrene, 2-methylcyclohexyl acrylate, 1,3-butadiene, bicyclo [2.2.1 ] Hept-2-ene, N-cyclohexylmaleimide, methacrylic acid, 1-ethylcyclopentyl methacrylate, 2-methyl-2-propene acid tetrahydro-2H-pyran-2-yl ester and the like are copolymerizable. It is preferable at the point of heat resistance.

These can be used individually or in combination with each other.

The copolymer (A) has a structural unit derived from the polymerizable unsaturated compound monomer in terms of monomers, preferably (a1) 5 to 95% by weight and (a2) 95 to 5% by weight, more preferably (a1). ) 20 to 95% by weight and (a2) 80 to 5% by weight, most preferably (a1) 30 to 90% by weight and (a2) 70 to 10% by weight [where (a1) + (a2) = 100% by weight %]. It is possible to realize good planarization performance and heat resistance in the content in this range.

As a preferable example of the [A] copolymer, For example, a styrene / methacrylate glycidyl copolymer, a styrene / methacrylate tricyclo [5.2.1.0 ^2,6 ] decane-8-yl / glycidyl methacrylate Copolymer, Styrene / N-cyclohexyl maleimide / Glycylate methacrylate, Styrene / N-phenylmaleimide / Glycidyl methacrylate copolymer, N-cyclohexyl maleimide / Glymethacrylate Dyl Copolymer, N-Phenylmaleimide / Glycrylate Glycidyl Copolymer, Styrene / Methacrylic Acid Tricyclo [5.2.1.0 ^2,6 ] Decan-8-yl / Methacrylic Acid / Glycrylate Methacrylic Acid Copolymer, styrene / N-cyclohexylmaleimide / methacrylic acid / methacrylate glycidyl copolymer, styrene / N-phenylmaleimide / methacrylic acid / methacrylate glycidyl copolymer, styrene / methacryl acid tricyclo [5.2.1.0 ^2,6] decane-8-yl / 1-ethyl cyclohexyl methacrylate / glycidyl methacrylate copolymer, Scotland Ethylene / N-cyclohexyl maleimide / 1-ethylcyclohexyl methacrylate / glycidyl methacrylate copolymer, styrene / N-phenylmaleimide / 1-ethylcyclohexyl methacrylate / glymethacrylate Dyl Copolymer, Styrene / Methacrylate Tricyclo [5.2.1.0 ^2,6 ] decane-8-yl / 1-ethylcyclopentyl methacrylate / Glycidyl Glycidyl Copolymer, Styrene / N-cyclohexylmalee Mid / 1-ethylcyclopentylmethacrylate / glycidyl methacrylate copolymer, styrene / N-phenylmaleimide / 1-ethylcyclopentylmethacrylate / glycidyl copolymer, styrene / methacryl Santricyclo [5.2.1.0 ^2,6 ] decane-8-yl / 1-methylcyclohexyl methacrylate / glycidyl methacrylate copolymer, styrene / N-cyclohexylmaleimide / 1-methylcyclohexyl meta Acrylate / methacrylate glycidyl copolymer, styrene / N-phenylmaleimide / 1-methylcyclohexylmethac Relate / Glycidyl Glycidyl Copolymer, Styrene / Methacrylic Acid Tricyclo [5.2.1.0 ^2,6 ] decane-8-yl / tetrahydro-2H-pyran-2-ylester / glymethacrylate Dill Copolymer, Styrene / N-cyclohexylmaleimide / tetrahydro-2H-pyran-2-ylester / glycidyl methacrylate copolymer, Styrene / N-phenylmaleimide / tetrahydro-2H-pyran-2 -Monoester / methacrylate glycidyl copolymer, etc. are mentioned.

The copolymer (A) has a polystyrene reduced weight average molecular weight (hereinafter referred to as [Mw]) measured by gel permeation chromatography (elution solvent: tetrahydrofuran), preferably 1,000 to 100,000, more 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 become inadequate, On the other hand, when Mw exceeds 100,000, planarization performance may become inadequate.

And 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] copolymers may be used to synthesize the (a1) polymerizable unsaturated compounds and (a2) other polymerizable unsaturated compounds by known methods such as radical polymerization in the presence of a suitable solvent and a suitable polymerization initiator. Can be. For example, the radical polymerization may include 5 to 95 parts by weight of (a1) polymerizable unsaturated compounds such as glycidyl methacrylate and 95 to 5 parts by weight of (a2) other polymerizable unsaturated compounds such as styrene. a1) + (a2) = 100 parts by weight] of azobisisobutyronitrile (AIBN) as a polymerization initiator, for example, by mixing 100 to 400 parts by weight of a solvent such as ethyl cellosolve acetate and propylene glycol monomethyl ether acetate. ) And 0.5 to 15 parts by weight of a radical polymerization initiator such as 2,2'-azobis (2,4-dimethylvaleronitrile) based on 100 parts by weight of the total amount of the monomer components, and 3 to 10 at 70 to 100 ° C. It can obtain by time-polymerizing.

[B] acid anhydrides

In the resin composition of this invention, in order to improve surface hardness, heat resistance, acid resistance, and alkali resistance, it is a polymer containing the polymerizable unsaturated compound which has [B] (b1) acid anhydride group, and / or (b2) polyhydric carboxylic anhydride. The acid anhydride formed is added.

The polymer containing the polymerizable unsaturated compound which has an acid anhydride group here (b1) is a copolymer of the polymerizable unsaturated compound which has an acid anhydride group, and an olefinic unsaturated compound.

As a polymerizable unsaturated compound which has an acid anhydride group used for synthesize | combining the polymer containing the polymerizable unsaturated compound which has the said acid anhydride group, it is for example, itaconic anhydride, a citraconic anhydride, a maleic anhydride, and a cis 1 And at least one selected from the group consisting of, 2,3,4-tetrahydrophthalic anhydride.

Moreover, as an olefinic unsaturated compound used in order to synthesize | combine the copolymer of the polymerizable unsaturated compound which has an acid anhydride group, and an olefinic unsaturated compound, for example, styrene, X-methylstyrene, X-methoxy styrene, and methyl methacrylate at least one selected from the group consisting of: -butyl methacrylate, tricyclo methacrylate [5.2.1.0 ^2,6 ] decane-8-yl, 2-methylcyclohexyl acrylate, phenylmaleimide and cyclohexyl Can be mentioned.

The copolymerization ratio of the polymerizable unsaturated compound having an acid anhydride group in 100 parts by weight of the copolymer of the polymerizable unsaturated compound having an acid anhydride group and the olefinically unsaturated compound is preferably 1 to 80 parts by weight, more preferably 10 to 60 parts by weight. By using such a copolymer, a protective film excellent in planarization property can be obtained.

Preferred examples of the copolymer of a polymerizable unsaturated compound having an acid anhydride group and an olefinically unsaturated compound include maleic anhydride / styrene copolymer and citraconic anhydride / methacrylic acid tricyclo [5.2.1.0 ^2,6 ] decane-8- One copolymer etc. are mentioned.

And the polystyrene reduced weight average molecular weight of the copolymer of the polymerizable unsaturated compound and olefinic unsaturated compound which has the said acid anhydride group becomes like this. Preferably it is 500-50,000, More preferably, it is 500-10,000. By using the copolymer of such a molecular weight range, the protective film excellent in planarization property can be obtained.

On the other hand, as said (b2) polyhydric carboxylic anhydride, for example, itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarvanic anhydride, maleic anhydride, hexahydrophthalic anhydride, Aliphatic dicarboxylic acid anhydrides such as methyltetrahydrophthalic anhydride and hydrobic acid anhydride; Alicyclic polyvalent carboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride and cyclopentane tetracarboxylic dianhydride; Aromatic polyhydric carboxylic anhydrides such as phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, and benzophenonetetracarboxylic anhydride; Acid anhydrides containing ester groups, such as ethylene glycol bis anhydride trimellitate and glycerol tris anhydride trimellitate, are mentioned. Among these, aromatic polyhydric carboxylic anhydride, particularly trimellitic anhydride, is preferable in that a cured film having high heat resistance is obtained.

The compounding quantity of the above-mentioned [B] acid anhydride becomes like this. Preferably it is 1-200 weight part with respect to 100 weight part of [A] copolymer, More preferably, it is 10-100 weight part. If it is less than 1 weight part, heat resistance may deteriorate. On the other hand, when it exceeds 200 weight part, adhesiveness with a board | substrate may fall.

[C] hardening accelerator

[C] The curing accelerator is a compound having a basic skeleton structure represented by the formula (1) or a compound having a basic skeleton structure represented by the formula (2), and by containing such a compound, the desired properties of the present invention (heat resistance and ITO sputtering) ) Can be obtained.

[C] The curing accelerator has any chemical structure as long as it is a compound [compound (1)] having a basic skeleton structure represented by the formula (1) or a compound [compound (2)] having a basic skeleton structure represented by the formula (2). You may also For example, the imidazole ring of compound (1) or compound (2) may be substituted by arbitrary substituents. As compound (1), Preferably, the said compound (3) is mentioned. Moreover, as compound (2), the said compound (4) is mentioned preferably.

The above-mentioned [C] hardening accelerator [Compound (1)-(2) or Compound (3)-(4)] may be used individually by 1 type, or may use two or more together.

 As a specific example of the [C] hardening accelerator, it is a compound represented by General formula (3), Comprising: 1-methyl- 2-phenylimidazole, 1-ethyl- 2-phenylimidazole, 2-phenylimidazole, 2-phenyl- 4-methylimidazole, 2-phenyl-4-ethylimidazole, 2,4-diphenylimidazole, 2,4,5-triphenylimidazole, 1-benzyl-2-phenylimidazole , 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenyl Imidazole isocyanuric acid adducts and the like;

In the compound represented by the formula (3), R ₁ and R ₂ are cyclized compounds, 2-phenyl-1 (H) -benzoimidazole, 2-phenyl-4,5,6,7-tetrahydro-1 (H) -benzoimidazole, 2-phenyl-1,4,5,6-tetrahydrocyclopentamidazole, 2-phenyl 1,4,5,6,7,8-hexahydrocyclohepta-imidazole, and the like. ;

As the compound represented by the formula (4), 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-S-triazine, 2,4-diamino-6- [2 '-Undecylimidazolyl- (1')]-ethyl-S-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl undecylimidazolyl- ( 1 ')]-ethyl-S-triazine, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethyl imidazole, 2-phenylimidazole Isocyanuric acid adducts, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-S-triazineisocyanuric acid adduct;

In the compound represented by the formula (4), R ₁ and R ₃ is a cyclic compound, 6- [2- (2-methyl-4,5,6,7-tetrahydrobenzoimidazol-1-yl)- Ethyl]-[1,3,5] triazine-2,4-diamine, 6- [2- (2-phenyl-benzoimidazol-1-yl) -ethyl]-[1,3,5] triazine -2,4-diamine etc. are mentioned.

Among these [C] hardening accelerators, 1-benzyl-2-phenylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2-phenyl are improved in the hardness of the protective film obtained. Preference is given to -1 (H) -benzoimidazole.

As addition amount of a hardening accelerator (C), it is preferable to add 0.0001-10 weight part with respect to 100 weight part of [A] copolymers. It is more preferable to add 0.001-1 weight part from a viewpoint of heat resistance and storage stability. The heat resistance of the resin composition obtained will deteriorate that it is less than 0.0001 weight part, and when it exceeds 10 weight part, storage stability will worsen significantly.

[D] cationically polymerizable compound

[D] cationically polymerizable compound may be further added to the resin composition of the present invention in order to increase the hardness of the protective film obtained and to improve heat resistance and alkali resistance.

[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 for the above-mentioned [A] copolymer). As a compound which has 2 or more oxylanyl group or an oxetanyl group in the said molecule, the compound which has 2 or more epoxy groups in a molecule | numerator, or the compound which has a 3, 4- epoxycyclohexyl group is mentioned, for example.

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, and hydrogenated bisphenol. Diglycidyl of bisphenol compounds, such as F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, and brominated bisphenol S diglycidyl ether Ethers;

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

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

Phenol novolac type epoxy resins;

Cresol novolac type epoxy resins;

Polyphenol type epoxy resins;

Diglycidyl esters of aliphatic long chain dibasic acids;

Glycidyl esters of higher fatty acids;

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

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

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

As a phenol novolak-type epoxy resin, EPIKOTE 152, copper 154, copper 157S65 (above, Japan epoxy resin Co., Ltd.), EPPN 201, copper 202 (above, Nippon Kayaku Co., Ltd. product) etc .;

As a cresol novolak-type epoxy resin, EOCN102, 103S, 104S, 1020, 1025, 1027 (above, Nippon Kayaku Co., Ltd. product), EPIKOTE180S75 (made by Japan epoxy resin Co., Ltd.), etc .;

Examples of the polyphenol type epoxy resin include JEPIKOTE 1032H60, XY-4000 (above, manufactured by Japan Epoxy Resin Co., Ltd.), and the like;

As the cyclic aliphatic epoxy resin, CY-175, copper 177, copper 179, Araldite CY-182, copper 192, 184 (above, manufactured by Ciba Specialty Chemicals, Inc.), ERL-4234, 4299, 4221 , 4206 (above, made by CC.), Shodyne 509 (made by Fire Extinguishing Co., Ltd.), EPICLON 200, East 400 (made by Japan Nippon Inks Co., Ltd.), EPIKOTE 871, copper 872 (above, Japan epoxy resin) Co., Ltd.), ED-5661, copper 5562 (above, Celanese coating Co., Ltd.), etc .;

Examples of the aliphatic polyglycidyl ethers include EPOLIGHT 100MF (manufactured by Kyoeisha Chemical Co., Ltd.), EPIOL TMP (manufactured by Nippon Yushi Co., Ltd.), and the like.

Examples of the compound having two or more 3,4-epoxycyclohexyl groups in the molecule include 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate and 2- (3,4 -Epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipinate, bis (3,4-epoxy-6- Methylcyclohexylmethyl) adipinate, 3,4-epoxy-6-methylcyclohexyl-3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane) , Dicyclopentadiene 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] cationically polymerizable compounds, a phenol novolak-type epoxy resin and a polyphenol-type epoxy resin 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 per 100 parts by weight of the [A] copolymer. Is 10 to 50 parts by weight. When the usage-amount of a (D) cationically polymerizable compound is more than 200 weight part, a problem may arise in the coating property of a composition, and when it is less than 3 weight part, the hardness of the protective film obtained may become insufficient.

[E] Adhesion Preparation

[E] adhesion aid may be added to the resin composition of the present invention in order to improve the adhesion between the protective film to be formed and the substrate.

As this [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, for example, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, (gamma) -glycidoxypropyl trimethoxysilane, (gamma)-glycidoxy propyl triethoxysilane, (beta)-(3, 4- epoxycyclohexyl) ethyl trimethoxysilane, etc. are mentioned.

These [E] adhesion aids are preferably used in an amount of 30 parts by weight or less, more preferably 25 parts by weight or less per 100 parts by weight of the [A] copolymer. When the amount of the adhesive assistant exceeds 30 parts by weight, the heat resistance of the protective film obtained may be insufficient.

[F] surfactants

[F] surfactant may be added to the resin composition of the present invention in order to improve coating performance. As such [F] surfactant, a fluorine type surfactant, a silicone type surfactant, an anionic surfactant, and other surfactant are mentioned, for example.

As said fluorine-type surfactant, BM CHIMIE company make (brand name) BM-1000, BM-1100, Nippon Ink Chemical Co., Ltd. brand name: MEGAFACE F142D, copper F172, copper F173, copper F183, Sumitomo 3M Product name: Fluorad FC-135, copper FC-170C, copper FC-430, copper FC-431, neos Co., Ltd. Product name: Ftergent 250, copper 251, copper 222F, FTX-218, Asahi Glass Co., Ltd. Product name: Surflon S112, S-113, S-131, S-141, S-145, S-382, S-101, SSC-102, SSC-103, SSC-104, Commercial items, such as SC-105 and SC-106, are mentioned.

As said silicone type surfactant, Dow Corning Toray Co., Ltd. product name: SH-28PA, SH-190, SH-193, S-6032, SF-8428, DC-57, DC-190, for example. , PAINTAD 19, FＺ-2101, East 77, East 2118, L-7001, L-7002, BYK-Kemi Japan Co., Ltd., Bxxxｋ-300, East 306, East 310, East 335, East 341, East 344, 370, Shin-Etsu Chemical Co., Ltd. product name: JP341, Shin-Kagawa Seisai Co., Ltd. brand name: EFTOP EF301, EF303, EF352 etc. are commercially available products.

As said anionic 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, it is poly, for example, Oxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, etc. are mentioned, As polyoxyethylene dialkyl ester, polyoxyethylene dilaurate, polyoxyethylene distearate, etc. are mentioned, for example.

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

The amount of such [F] surfactant added is preferably 5 parts by weight or less, more preferably 2 parts by weight or less per 100 parts by weight of the [A] copolymer. When the amount of the surfactant exceeds 5 parts by weight, the coating film may be easily roughened in the coating step.

[G] Multifunctional Acrylate Monomers

The polyfunctional acrylate monomer can be added to the resin composition of this invention for the purpose of expressing the film peeling characteristic of a protective film.

As a polyfunctional acrylate monomer, a trifunctional or more than trifunctional acrylate monomer is preferable so that the hardness of a protective film may not be impaired.

For example, triacryloyloxy pentaerythritol succinic acid {alias: 3-acryloyloxy-2,2-bisacryloyloxymethyl-propyl) ester}, diacryloyloxy pentaerythritol succinic acid {alias : 3-acryloyloxy-2-acryloyloxymethyl-propyl) ester}, pentaacryloyloxy dipentaerythritol succinic acid {alias: [3- (3-acryloyloxy-2,2-bis- Acryloyloxymethyl-propyl) -2,2-bisacryloyloxymethyl-propyl] ester}, tetraacryloyloxy dipentaerythritol succinic acid {alias: [3- (3-acryloyloxy-2 , 2-bisacryloyloxymethyl-propyl) -2-acryloyloxymethyl-propyl] ester}, triacryloyloxyethyl isocyanuric acid {alias: tris (acryloxyethyl) isocyanurate}, Dipentaerythritol hexaacrylate (DPHA), pentaerythritol triacrylate, trimethylolpropanetriacrylate , And the like tree acryloyloxy ethyl phosphate trimethylol propane EO added triacrylate, pentaerythritol tetraacrylate.

Above all, for the purpose of improving the hardness, pentaacryloyloxy pentaerythritol succinic acid {alias: [3- (3-acryloyloxy-2,2-bis-acryloyloxymethyl-propyl) -2,2 -Bisacryloyloxymethyl-propyl] ester, abbreviated: PADPS}, dipentaerythritol hexaacrylate (DPHA), triacryloyloxy ethyl isocyanuric acid {alias: tris (acryloxyethyl) isocyanurate } Is preferred, and pentaacryloyloxy dipentaerythritol succinic acid {alias: [3- (3-acryloyloxy-2,2-bisacryloyloxymethyl-propyl) -2,2-bisacrylo Iloxymethyl-propyl] ester and abbreviation: PADPS} are more preferable.

The amount of the [G] polyfunctional acrylate monomer added is preferably 150 parts by weight or less, more preferably 120 parts by weight or less based on 100 parts by weight of the [A] copolymer. When it exceeds 150 weight part, since adhesiveness with a board | substrate falls, it is unpreferable.

[H] thermosensitive acid generators

[H] The thermosensitive acid generator may be added to the resin composition of the present invention in order to increase the curing speed. Examples of the thermosensitive acid generator include sulfonium salts, benzothiazonium salts, ammonium salts, and phosphonium salts. Among them, sulfonium salts and benzothiazonium salts are preferably used.

The amount of the [H] thermosensitive acid generator added is preferably 30 parts by weight or less, even more preferably 20 parts by weight or less based on 100 parts by weight of the [A] copolymer. When it exceeds 30 weight part, hardness will fall significantly.

Preparation of Resin Composition

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

As such a solvent, 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 propionates, aromatic hydrocarbons, ketones, esters and the like can be given.

 As specific examples thereof, for example, alcohols include methanol, ethanol, benzyl alcohol and the like;

As ethers, tetrahydrofuran etc .;

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

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

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

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

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

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

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

As aromatic hydrocarbons, toluene, xylene, etc .;

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 and methyl hydroxyacetate, Ethyl hydroxy acetate, butyl hydroxy acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, 3-hydroxypropyl propionate, butyl 3-hydroxypropionate, 2-hydroxy-3-methyl butyrate, methyl methoxyacetate, ethyl methoxyacetate, methoxyacetic acid propyl, butyl acetate, ethoxyacetic acid methyl, ethoxyacetate, ethoxyacetic acid propyl, ethoxyacetic acid Butyl, methyl propoxy acetate, ethyl propoxy acetate, propyl propoxy acetate, butyl propoxyacetate, part Methyl acetate, ethyl butoxy acetate, propyl butoxy acetate, butyl butoxy acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, 2- Methyl ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, 2-part Butyl oxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-ethoxy Propionate Propyl, 3-Ethoxy Propionate, 3-Propoxy Propionate, 3-Propoxy Propionate, 3-Propoxy Propionate, 3-Propyl Propionate, 3-Butoxy Propionate, 3-part Ethyl oxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate, 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 are particularly preferred. Ether acetate, propylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate and diethylene glycol diethyl ether are preferable.

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

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-methylacetoamide, N, N-dimethylacetoamide, N-methylpi Ralidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isoform, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, maleic acid di Ethyl, (gamma) -butyrolactone, ethylene carbonate, a propylene carbonate, a phenyl cellosolve acetate, etc. are mentioned.

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 resin composition prepared as described above may be provided for use after filtration using a millimeter pore filter or the like having a pore size of 0.2 to 3.0 μm, preferably about 0.2 to 0.5 μm.

Protective film formation of color filter

Next, the method to form the protective film of a color filter using the resin composition of this invention is demonstrated.

The resin composition solution of this invention is apply | coated to the surface of a board | substrate, prebaked, a solvent is removed, a coating film is formed, and heat-processing can form the protective film of a desired color filter.

As the substrate that can be used, for example, a substrate such as glass, quartz, silicon, resin, or the like can be used. As resin, resin, such as a ring-opening polymer of polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, polyimide, and cyclic olefin, and its hydrogenated substance, is mentioned, for example.

 As the coating method, for example, a spraying method, a roll coating method, a spin coating method, a bar coating method, an ink jet method, or the like may be adopted. Particularly, a spin coater, a spinless coater, and a slit die coater may be used. Used coating can be used suitably.

Although it changes also with the kind of each component, a compounding ratio, etc. as conditions of the said prebaking, the conditions of about 1 to 15 minutes can be employ | adopted normally at 70-90 degreeC. The thickness of the coating film is preferably 0.15 to 8.5 µm, more preferably 0.15 to 6.5 µm, still more preferably 0.15 to 4.5 µm. And the thickness of the coating film here should be understood as the 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. As processing temperature, about 150-250 degreeC is preferable, The heating time can employ | adopt the processing time for 5 to 30 minutes when using a hotplate, and 30 to 90 minutes when using an oven.

 In the case where a radiation sensitive acid generator is used in the resin composition, the resin composition is applied to the surface of the substrate, the solvent is removed through a prebaking to form a coating film, and then subjected to irradiation treatment (exposure treatment) to form a desired protective film. Can be formed. As needed, you may further heat-process after exposure process.

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

Exposure as is usually from 100 to 20,000 J / m ^2, preferably from 150 to 10,000J / m ^2.

You may further heat-process again after irradiation. As heating temperature at this time, about 150-250 degreeC is preferable, As a heating apparatus, a suitable apparatus, such as a hotplate and a clean oven, can be used, for example. The heating time can employ | adopt the processing time of 5 to 30 minutes, when using a hotplate, and 30 to 90 minutes, when using an oven.

Shield of color filter

The protective film thus formed has a film thickness of preferably 0.1 to 8 m, more preferably 0.1 to 6 m, still more preferably 0.1 to 4 m. And when the protective film of this invention is formed on the board | substrate which has the single yarn of a color filter, the thickness of the said film should be understood as the thickness from the top of a color filter.

As is 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 is not damaged by a load in the state of applying heat, and also a base substrate. It is very suitable as a protective film for optical devices which is excellent in the ability to flatten the single yarn of the color filter formed above.

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. to have sufficient heat resistance even in such a case.

<Example>

Synthesis Examples and Examples are shown below to illustrate the present invention more specifically, but the present invention is not limited to the following Examples.

Preparation of Copolymer

Synthesis Example 1

5 parts by weight of 2,2'-azobis-isobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate were placed in a flask equipped with a cooling tube and a stirrer. Subsequently, 70 parts by weight of glycidyl methacrylate (GMA) and 30 parts by weight of styrene (ST) were added thereto, followed by nitrogen substitution, followed by gentle stirring. 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 33.1 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 placed in a flask equipped with a cooling tube and a stirrer. Subsequently, 80 parts by weight of (3-ethyl-3-oxyethananyl) methyl methacrylate (O-MA) and 20 parts by weight of styrene (ST) were added thereto, followed by nitrogen substitution, followed by gentle stirring. The solution temperature was raised to 70 ° C. and maintained at this temperature for 5 hours to obtain a polymer solution containing a copolymer (A-2). Solid content concentration of the obtained polymer solution was 32.9 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 placed in a flask equipped with a cooling tube and a stirrer. Subsequently, 60 parts by weight of glycidyl methacrylate (GMA), 20 parts by weight of styrene (ST) and 20 parts by weight of N-cyclohexylmaleimide (CHMI) were added thereto, followed by nitrogen substitution, followed by gentle stirring. The solution temperature was raised to 70 ° C. and maintained at this temperature for 5 hours to obtain a polymer solution containing a copolymer (A-3). Solid content concentration of the obtained polymer solution was 32.8 weight%.

Synthesis Example 4

In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were placed. Subsequently, 60 parts by weight of glycidyl methacrylate (GMA), 20 parts by weight of styrene (ST) and 20 parts by weight of tricyclo methacrylate [5.2.1.0 ^2,6 ] decane-8-yl (DCM) were added and nitrogen-substituted. Then gentle stirring began. The temperature of the solution was raised to 70 ° C. and maintained at this temperature for 5 hours to obtain a polymer solution containing a copolymer (A-4). Solid content concentration of the obtained polymer solution was 33.1 weight%.

Synthesis Example 5

In a flask equipped with a cooling tube and a stirrer, 2 parts by weight of 2,2'-azobis-isobutyronitrile and 200 parts by weight of methyl 3-methoxypropionate were added. Subsequently, 80 parts by weight of glycidyl methacrylate and 20 parts by weight of styrene were added thereto, followed by nitrogen substitution, followed by gentle stirring. The temperature of the solution was raised to 70 ° C. and maintained at this temperature for 5 hours to obtain a polymer solution containing a copolymer (A-5). Solid content concentration of the obtained polymer solution was 33.2 weight%.

Synthesis Example 6

In a flask equipped with a cooling tube and a stirrer, 3 parts by weight of 2,2'-azobis-isobutyronitrile and 200 parts by weight of cyclohexyl acetate were placed. Subsequently, 80 parts by weight of glycidyl methacrylate and 20 parts by weight of styrene were added thereto, followed by nitrogen substitution, followed by gentle stirring. The temperature of the solution was raised to 70 ° C. and maintained at this temperature for 5 hours to obtain a polymer solution containing a copolymer (A-6). Solid content concentration of the obtained polymer solution was 32.6 weight%.

Synthesis Example 7

In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were placed. Subsequently, 40 parts by weight of glycidyl methacrylate, 20 parts by weight of styrene, 20 parts by weight of N-cyclohexylmaleimide and 20 parts by weight of methacrylic acid were added thereto, followed by nitrogen substitution, followed by gentle stirring. The temperature of the solution was raised to 70 ° C. and maintained at this temperature for 5 hours to obtain a polymer solution containing a copolymer (A-7). Solid content concentration of the obtained polymer solution was 29.7 weight%.

Hardener Synthesis Example 1

In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were placed. Subsequently, 50 parts by weight of maleic anhydride and 50 parts by weight of styrene (ST) were added thereto, followed by nitrogen substitution, followed by gentle stirring. The temperature of the solution was raised to 70 ° C. and maintained at this temperature for 5 hours to obtain a polymer solution containing a copolymer (B-3). Solid content concentration of the obtained polymer solution was 32.7 weight%.

 Hardener Synthesis Example 2

In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were placed. Subsequently, 40 parts by weight of maleic anhydride, 50 parts by weight of styrene (ST) and 10 parts by weight of N-cyclohexylmaleimide (CHMI) were added thereto, followed by nitrogen substitution, followed by gentle stirring. The temperature of the solution was raised to 70 ° C. and maintained at this temperature for 5 hours to obtain a polymer solution containing a copolymer (B-4). Solid content concentration of the obtained polymer solution was 32.8 weight%.

Preparation and Evaluation of Resin Compositions

Example 1

Solution containing copolymer (A-1) obtained in Synthesis Example 1 (amount corresponding to 100 parts by weight (solid content) of copolymer (A-1)), (B) 40.0 parts by weight of hexahydrophthalic anhydride, and (C) 0.1 weight part of 1-benzyl-2-phenylimidazole, 5.0 weight part of (E)-glycidoxy propyl trimethoxysilane, and (F) surfactant SH-28PAA (made by Dow Corning Toray Co., Ltd.) 0.1 Add weight parts, and further add propylene glycol monomethyl ether acetate (S-1) and diethylene glycol ethylmethyl ether (S-2) at a weight ratio of 8 to 2 so that the solid content concentration is 20% by weight, and then the pore size is 0.5. The resin composition was prepared by filtering with a millimeter pore filter.

The composition was applied onto a SiO ₂ dip glas substrate using a spinner, and then prebaked at 80 ° C. for 5 minutes on a hot plate to form a coating film, followed by further heat treatment at 230 ° C. for 60 minutes in an oven to form a film thickness. A protective film having a thickness of 2.0 μm 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 in 400-800 nm was measured using the spectrophotometer (150-20 type double beam (made by Hitachi, Ltd.)). The minimum value of the transmittance | permeability in 400-800 nm is shown in Table 1. When this value is 95% or more, the transparency of a protective film can be said to be favorable.

(2) Evaluation of heat resistance stability

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

Thermal Dimension Stability = [(Film Thickness After Heating) / (Film Thickness Before Heating)] × 100 (%)

(3) Evaluation of alkali-resistant stability

The board | substrate with a protective film formed as mentioned above was immersed for 30 minutes in 5weight% sodium hydroxide aqueous solution heated at 30 degreeC, and it wash | cleaned in pure water. The mixture was heated in an oven at 120 ° C. for 2 minutes to remove moisture and to measure the film thickness. Table 1 shows alkali dimensional stability calculated by the following formula. When this value is 95% or more, alkali-resistant stability is favorable.

Heat-resistant alkali stability = [(film thickness after alkali immersion and washing) / (film thickness before alkali immersion)] × 100 (%)

(4) evaluation of heat discoloration resistance

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

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

 (5) measurement of surface hardness

About the board | substrate which has 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 JIS W-5400-1990. This value is shown in Table 1. When this value is 4H or harder, the surface hardness can be said to be good.

(6) Measurement of dynamic microhardness

The substrate having the protective film formed as described above was subjected to a test of inserting a ridge angle 115 ° triangular indenter (triangular pyramid) using Shimadzu dynamic microhardness meter DUH-201 (manufactured by Shimadzu Corporation) to obtain a microscopic protective film. Hardness was measured under load conditions of 0.1 gPa, speed: 0.0145 gf / sec, holding time: 5 seconds, and temperature at 23 ° C and 140 ° C. The results are shown in Table 1.

(7) Evaluation of adhesiveness

The pressure cooker test (120 degreeC, 100% of humidity, 4 hours) was performed on the board | substrate with a protective film formed as mentioned above, and then 8.5.3 adhesive checker tape method of JISK-5400-1990. The adhesion of the protective film (adhesion to SiO ₂ ) was evaluated through the test. Table 2 shows the remaining number of checkerboard eyes.

In addition, in evaluating 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. Evaluated. The results are shown in Table 1.

 (8) Evaluation of ITO Etch Resistance

For the substrate having the protective film formed as described above, an ITO target (ITO filling rate of 95% or more, In ₂ O ₃ / SnO ₂ = 90/10) was used in the high-speed sputtering apparatus SH-550-C12 manufactured by Nippon Vacuum Engineering Co., Ltd. ITO sputtering was performed at 60 degreeC using the weight ratio). At this time, the atmosphere had a reduced pressure of 1.0 × 10 ⁻⁵ Pa, an Ar gas flow rate of 3.12 × 10 ⁻³ m ³ /, and an O ₂ gas flow rate of 1.2 × 10 ⁻⁵ m ³ / ｈ. The board | substrate after sputter | heating was heated in 240 degreeC x 60 minutes in said clean oven, and it annealed. Next, the board | substrate was attached to the spinner, the JSR G line positive resistor PFR3650-21cp was dripped on the board | substrate, and it coated at 3,500 rpm x 30 second. The board | substrate was heated at 90 degreeCx 2 minutes on the hotplate, and the solvent was removed. Next, a ghi line (wavelength of 436 nm, 405 nm, and 365 nm intensity ratio = 2.7: 2.5: 4.8) was applied using an exposure machine Canon PLA 501F (manufactured by Canon Corporation) through a pattern mask of 10 μm / 10 μm. the line in terms of lighting, road 23mW / m ^2, using a 2.4 wt% TMAH (tetramethylammonium hydroxide) aqueous solution at room temperature in view of the exposure dose of 25mJ / m ^2, washed 60 seconds immersion development, and the second in pure water 60 seconds Then dried in the wind. It was then baked in a clean oven at 150 ° C. × 60 minutes. Corrosion solution was provided by mixing acetic acid / hydrochloric acid in a weight ratio of 1/3. The substrate was immersed in a corrosion solution and the substrate was taken out every 10 seconds to determine the just etching time for forming a 10 μm ITO line, and the ITO line width was measured by an optical microscope at 1.2 times the just etching time. Is shown in Table 1. The higher the ITO line retention of 10 μm, the better the ITO etching resistance.

 (9) Evaluation of flatness

Pigment-based color registers (trade names [JCR RED 689], [JCR GREEN 706], [CR 8200B], and above, manufactured by JSR Corporation) were coated on a SiO ₂ dip glass substrate using a spinner, and then hot plated. It prebaked at 90 degreeC for 150 second from the top, and formed the coating film. Subsequently, a ghi line (wavelength ratio of 436 nm, 405 nm, 365 nm) of ghi line (wavelength: 436 nm, 405 nm, 365 nm) using an exposure machine Canon PLA501F (manufactured by Canon Co., Ltd.) through a predetermined pattern mask was added at 2,000 kV / m ² , stripe color filter of red, green, and blue color, developed with 0.05 wt% aqueous potassium hydroxide solution, washed with ultrapure water for 60 seconds, and further heated at 230 ° C. for 30 minutes in an oven. (Stripe width 100 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 Tester [(alpha) -step] (brand name: Tencor company make). In addition, the measurement length 2,000 micrometers and the measurement range 2,000 micrometers each measured by measurement score n = 5. That is, the measurement direction was made into two directions of the stripe line short axis direction of red, green, and blue direction and the stripe line major axis direction of the same color of red, red, green, green, blue, and blue, and measured by n = 5 for each direction. (The total number of n is 10).

The protective film-forming composition was applied thereon with a spinner, followed by prebaking at 90 ° C. for 5 minutes on a hot plate to form a coating film, followed by heat treatment at 230 ° C. for 60 minutes in an oven to form a film thickness from above the color filter. A protective film having a thickness of 2.0 μm was formed. However, the film thickness here means the thickness from the uppermost surface of the color filter formed on the substrate.

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

 (10) Evaluation of storage stability

The viscosity in the resin composition for protective film formation manufactured in Example 1 was measured using the Tokyo Metro Instruments Co., Ltd. ELD type viscometer. The solution viscosity at 25 ° C. was then measured daily while the composition was left at 25 ° C. The number of days required for 5% thickening based on the viscosity immediately after preparation was calculated | required, and this date number is shown in Table 1. When this date is 20 days or more, storage stability is favorable.

Examples 2 to 32 and Comparative Examples 1 to 3

The type and amount of each component of the composition were as described in Tables 1 to 3, and the resins were prepared in the same manner as in Example 1 except that the solids concentrations shown in Tables 1 to 3 were adjusted using the solvents shown in Tables 1 to 3. The composition was prepared.

The protective film was formed and evaluated like Example 1 using the resin composition for protective film formation manufactured as mentioned above. The results are shown in Tables 1-3.

Examples 33-40

The composition was prepared like Example 1 except having adjusted the kind and quantity of each component of a composition as shown in Table 3, and using the solvent of Table 3 and adjusting to solid content concentration shown in Table 3.

Except having apply | coated using the slit die coater instead of a spin coater, the resin composition was produced like Example 1, and the protective film was formed and evaluated. The results are shown in Table 3.

Examples 41-68

The type and amount of each component of the composition was as described in Table 4 or Table 5, and was adjusted as in Example 1 except that the solvents described in Table 4 or Table 5 were used to adjust the solid content concentrations described in Table 4 or Table 5. To prepare a composition.

The composition whose solid content concentration of Examples 54, 56, 66-68 was less than 15 weight% was manufactured like Example 1 except having apply | coated using the slit die coater instead of a spin coater, and evaluated by forming a protective film. . Moreover, in Examples other than the said Example 54, 56, 66-68, the resin composition was produced like Example 1, the protective film was formed and evaluated. The results are shown in Tables 4 to 5.

TABLE 1

TABLE 2

TABLE 3

TABLE 4

TABLE 5

In addition, in Tables 1-4, the [C] hardening accelerator, the [D] cationically polymerizable compound, the [E] adhesion | attachment adjuvant, the [F] surfactant, the [G] polyfunctional acrylate monomer, and the [S] solvent Abbreviated-name shows that it is each below.

C-1: 1-benzyl-2-phenylimidazole

C-2: 2-phenylimidazole

C-3: 2-phenyl-4-methylimidazole

C-4: 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine

C-5: 2,4-diamino-6- [2'-undecylimidazolyl- (1 ')]-ethyl-s-triazine

C-6: 2-phenyl-4-methyl-5-hydroxymethylimidazole

C-7: 2-phenyl-1 (H) -benzoimidazole

c-1: 1-benzyl-2-methylimidazole

D-1: bisphenol A novolak type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., product name: EPIKOTE 157S65)

D-2: novolac type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., brand name: EPIKOTE 152)

E-1: γ-glycidoxypropyl trimethoxysilane

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

F-2: silicone surfactant (BYK-Kemi Japan Co., Ltd., brand name: BYK-344)

F-3: Fluorine-type surfactant [Neo Co., Ltd. make, brand name: FTX-218]

F-4: Silicone Surfactant (manufactured by Dow Corning Toray Co., Ltd., trade name: PAINTAD 19)

F-5: Fluorine-type surfactant (made by Nippon Ink Chemical Co., Ltd. product name: MEGAFACE R-08)

G-1: pentaacryloyloxy dipentaerythritol succinic acid {alias: [3- (3-acryloyloxy-2,2-bisacryloyloxymethyl-propyl) -2,2-bis-acrylo Iloxymethyl-propyl] ester, abbreviated: PADPS}

G-2: dipentaerythritol hexaacrylate (made by Nippon Kayaku Co., Ltd., brand name: KAYARAD DPHA)

S-1: Propylene Glycol Monomethyl Ether Acetate

S-2: diethylene glycol ethyl methyl ether

S-3: Methyl-3-methoxypropionate

S-4: cyclohexyl acetate

Industrial availability

The resin composition of the present invention can form a cured film having a high flatness even on a substrate having a low surface flatness, high transparency and high surface hardness, excellent heat resistance, acid resistance, alkali resistance, sputter resistance, and various resistances. It 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 a substrate having a low surface flatness can form a cured film having a high flatness on the substrate, high transparency and surface hardness, and excellent color resistance such as heat resistance, acid resistance, alkali resistance and sputter resistance. The resin composition which is used very suitably for forming the protective film for a use, and is excellent in the storage stability as a composition, the formation method of the color filter protective film using this resin composition, and the protective film formed by the said composition are provided.

Claims (8)

(A) (a1) Polymerizable unsaturated compound which has an oxylanyl group or an oxetanyl group, (a2) (meth) acrylic-acid alkylester, (meth) acrylic-acid cyclic alkylester, (meth) acrylic-acid aryl ester, unsaturated dicarboxylic acid di Esters, bicyclo unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic anhydrides, and unsaturated having an acetal structure or a ketal structure At least one copolymer selected from the group consisting of compounds and [B] a polymerizable unsaturated compound having an acid anhydride group having from 1 to 200 parts by weight based on 100 parts by weight of the copolymer [A] and an olefinically unsaturated compound 0.000 to 100 parts by weight of the copolymer, (b2) an acid anhydride formed from a polyhydric carboxylic anhydride, or a mixture thereof, and [C] 100 parts by weight of the copolymer [A]. A resin composition comprising 1 to 10 parts by weight of a curing accelerator formed from a compound represented by the following formula (3), a compound represented by the following formula (4), or a mixture thereof. <Formula 3>

<Formula 4>

R ₁ or R ₂ of Formula 3 or 4 represents a hydrogen atom, an alkyl group of 1 to 8 carbon atoms, an alkyl group of 1 to 8 carbon atoms having a C 1 to 4 alkoxy group, a phenyl group, a benzyl group or a hydroxy methyl group, and Or R ₁ and R ₂ of Formula 4 may be combined to be a phenyl ring and a cycloalkane ring having 4 to 8 carbon atoms, and R ₃ of Formula 3 may have a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms. An alkyl group having 1 to 8 carbon atoms, a phenyl group, a benzyl group or a cyanoethyl group is represented, and R ₄ in Formula 4 represents an alkyl group having 1 to 18 carbon atoms, an alkyl group having 1 to 18 carbon atoms or a phenyl group having an alkoxy group having 1 to 4 carbon atoms. delete delete The resin composition according to claim 1, further comprising a compound having two or more oxylanyl groups or oxetanyl groups in the molecule [D], except for the copolymer [A]. The resin composition according to claim 4, wherein the compound having two or more oxylanyl groups or oxetanyl groups in the molecule [D] is 3 to 200 parts by weight based on 100 parts by weight of the [A] copolymer. The resin composition of Claim 1 which is for formation of the protective film of a color filter. A coating film is formed on a board | substrate using the resin composition of Claim 6, and then heat-processed, The formation method of the protective film of a color filter characterized by the above-mentioned. The protective film of the color filter formed from the resin composition of Claim 6.