KR20080004358A - Thermosetting resin composition, protective film and process for forming protective film - Google Patents

Abstract

A thermoplastic resin composition is provided to form a cured film with high smoothness even on a substrate having low smoothness, and to obtain a protective film for optical devices having high transparency, surface hardness, heat resistance, acid resistance, alkali resistance and sputtering resistance. A thermoplastic resin composition comprises a polymer and a solvent, wherein the polymer includes: (A) a copolymer comprising (a-1) repeating units derived from a polymerizable unsaturated compound having an oxylanyl group or oxetanyl group, and (a-2) a polymerizable unsaturated compound having at least one hydroxyl group. The copolymer (A) optionally further comprises: (a-3) repeating units derived from N-substituted maleimide, and (a-4) repeating units derived from an unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride.

Description

Thermosetting Resin Composition, Protective Film and Process for Forming Protective Film

[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

The present invention relates to a thermosetting resin composition, a method for forming a protective film from the composition, and a protective film. More specifically, the thermosetting resin composition 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 the composition, and its 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 deterioration or damage of an element 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 should have high adhesion to the substrate or lower layer on which the protective film should be formed, and furthermore, a layer formed on the protective film, the film itself should be smooth and strong, have transparency, high heat resistance and light resistance, and long term The performance which does not produce deterioration, such as coloring, yellowing, and whitening, is excellent in water resistance, solvent resistance, acid resistance, and alkali resistance, is calculated | required. As a material for forming the protective film which satisfy | fills these various characteristics, the thermosetting composition containing the polymer which has glycidyl group, for example is known (Unexamined-Japanese-Patent No. 5-78453 and Unexamined-Japanese-Patent No. 2001-). See publication 91732).

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-type spacer is disposed on a protective film in order to maintain uniform cell spacing of the liquid crystal layer. After spreading, joining of panels is performed. Thereafter, the liquid crystal cell is sealed by thermocompression bonding of the sealing material, and a phenomenon in which the protective film in the portion where the beads exist due to heat and pressure applied at this time is seen, and a cell gap is a problem.

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 a very high leveling leveling performance and heat resistance resistance performance are required for the protective film.

Moreover, 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 a strong acid or strong alkali is also employed. It is becoming. For this reason, the surface of a color filter protective film is locally exposed to high temperature at the time of sputtering, or many chemical treatments are performed. Therefore, adhesiveness with wiring electrodes is also required to withstand these treatments and to prevent ITO or IZO from peeling off on the protective film during chemical treatment.

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

A material that not only satisfies the general required performance as a protective film such as transparency, 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.

Japanese Unexamined Patent Publication (Kokai) No. 4-218561 discloses a thermosetting composition containing a latent carboxyl compound for use in paints, inks, adhesives, and molded articles, but the protective film of the color filter is not disclosed at all. Not.

The present invention has been made on the basis of the above circumstances, and an object thereof is to form a cured film having high flatness on the substrate even if the substrate has a low surface flatness, and also has high transparency and surface hardness, heat resistance, acid resistance, It is an object of the present invention to provide a composition having excellent storage stability as a composition while being preferably used to form a protective film for an optical device that is excellent in various resistances such as alkali resistance and sputtering resistance.

Another object of the present invention is to provide a method for forming a protective film using the composition.

Further, another object of the present invention is to provide a protective film formed from the composition.

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

According to the present invention, the above objects and advantages of the present invention are firstly a thermosetting resin composition comprising a polymer and a solvent, wherein the polymer has (A) (a-1) a polymerizable unsaturated compound having an oxylanyl group or oxetanyl group. It is achieved by the thermosetting resin composition characterized by the copolymer containing the polymer unit derived from the polymerizable unit derived from the polymerizable unsaturated compound which has a polymerized unit derived from (a-2), and at least one hydroxyl group.

According to the present invention, the above objects and advantages of the present invention are secondly achieved by a method of forming a protective film of a color filter, wherein the coating film is formed using the thermosetting resin composition, and then heat treated.

According to the present invention, the above objects and advantages of the present invention are thirdly achieved by the protective film of the color filter formed from the thermosetting resin composition.

Best Mode for Carrying Out the Invention

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

Copolymer (A)

The copolymer (A) of the present invention is a polymerizable unsaturated group having a polymerized unit derived from a polymerizable unsaturated compound having (a-1) an oxylalanyl group or an oxetanyl group as its copolymerization component and (a-2) at least one hydroxyl group. It includes a polymerization unit derived from a compound.

The polymerizable unsaturated compound (a-1) is not particularly limited as long as it has an oxylanyl group or an oxetanyl group and a polymerizable unsaturated group. Examples of the oxylanyl group-containing polymerizable unsaturated compounds include glycidyl acrylate, glycidyl methacrylate, 2-methyl glycidyl methacrylate, glycidyl α-ethyl acrylate, and glycerin α-n-propyl acrylate. Cydyl, α-n-butyl acrylate glycidyl, acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7- Epoxyheptyl, (alpha)-ethylacrylic-acid 6,7-epoxyheptyl, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, etc. are mentioned.

Examples of the oxetanyl group-containing polymerizable unsaturated compound include 3-methyl-3- (meth) acryloyloxymethyloxetane, 3-ethyl-3- (meth) acryloyloxymethyloxetane, and the like.

Of these, methacrylic acid glycidyl, methacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and the like are copolymerizable and reactive. And the point which raises the heat resistance and surface hardness of the protective film or insulating film which are obtained.

The copolymer (A) is a polymerizable unsaturated compound having at least one hydroxyl group different from the polymerizable unsaturated compound (a-1) in addition to the polymerized unit derived from the polymerizable unsaturated compound (a-1). It contains a polymerization unit derived from Examples of the polymerizable unsaturated compound (a-2) include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, and acrylic acid. Acrylic acid hydroxyalkyl esters such as 4-hydroxybutyl, 1,4-cyclohexanedimethanol monoacrylate, 1,2-dihydroxyethyl acrylate, 2- (6-hydroxy-hexanoyloxy) ethyl acrylate; Methacrylic acid 2-hydroxypropyl, methacrylic acid 3-hydroxypropyl, methacrylic acid 2-hydroxybutyl, methacrylic acid 3-hydroxybutyl, methacrylic acid 4-hydroxybutyl, 1,4-cyclo Methacrylic acid, such as hexanedimethanol monomethacrylate, 1,2-dihydroxyethyl methacrylate, 2-hydroxyethyl methacrylate, 2- (6-hydroxy-hexanoyloxy) ethyl methacrylate Hydroxyalkyl esters; 2-vinyl phenol, 3-vinyl phenol, 4-vinyl phenol, etc. are mentioned. Among them, 4-vinylphenol, 2-hydroxyethyl methacrylate and the like are preferable in view of heat resistance and ITO etching resistance, and particularly preferred is 2-hydroxyethyl methacrylate.

The copolymer (A) further comprises (a-3) N-substituted maleimide and / or (a-4) unsaturated carboxylic acid and / or unsaturated carboxylic acid in addition to the component (a-1) and the component (a-2). It is preferable to contain the polymerization unit derived from each of the acid anhydrides.

As a polymerizable unsaturated compound (a-3), for example, N-phenylmaleimide, N-cyclohexyl maleimide, benzyl maleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl- 4-maleimide butyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimide propionate, N- (9-acridinyl) maleimide, and the like. . Of these, N-cyclohexylmaleimide and N-phenylmaleimide are preferably used in terms of heat resistance and ITO etching resistance.

As a polymerizable unsaturated compound (a-4), unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, and unsaturated dicarboxylic anhydride are mentioned, for example.

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

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

As unsaturated dicarboxylic anhydride, each anhydride of the said unsaturated dicarboxylic acid is mentioned, for example.

Of these, methacrylic acid is preferably used in terms of ITO etching resistance.

The copolymer (A) is a polymerization derived from a polymerizable unsaturated compound different from the components (a-5) (a-1) to (a-4), in addition to the components (a-1) to (a-4). It may contain units. As a polymerizable unsaturated compound (a-5), the cyclic alkyl part of (meth) acrylic-acid alkylester, (meth) acrylic-acid cyclic alkylester, (meth) acrylic-acid cyclic alkylester is a lactone structure, lactam structure, or acetal structure, for example. Substituted ester, (meth) acrylic-acid aryl ester, unsaturated dicarboxylic acid diester, a bicyclo unsaturated compound, unsaturated aromatic compound, conjugated diene type compound, an acetal structure, the unsaturated compound which has a ketal structure is mentioned.

As these specific examples, it is (meth) acrylic-acid alkylester, for example, 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-di Ethyl (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, For example, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acryl Latex, tricyclo [5.2.1.0 ^2,6 ] decane-8-yloxyethyl (meth) acrylate, isobornyl (meth) acrylate, 1-methylcyclopropane (meth) acrylate, 1-methylcycle Robutane (meth) acrylate, 1-methylcyclopentyl (meth) acrylate, 1-methylcyclohexyl (meth) acrylate, 1-methylcycloheptane (meth) acrylate, 1-methylcyclooctane (meth) acrylic Rate, 1-methylcyclononane (meth) acrylate, 1-ethylcyclodecane (meth) acrylate, 1-ethylcyclopropane (meth) acrylate, 1-ethylcyclobutane (meth) acrylate, 1-ethylcyclo Pentyl (meth) acrylate, 1-ethylcyclohexyl (meth) acrylate, 1-ethylcycloheptane ( -) Acrylate, 1-ethylcyclooctane (meth) acrylate, 1-ethylcyclononane (meth) acrylate, 1-ethylcyclodecane (meth) acrylate, 1- (iso) propylcyclopropane (meth) acrylic Rate, 1- (iso) propylcyclobutane (meth) acrylate, 1- (iso) propylcyclopentyl (meth) acrylate, 1- (iso) propylcyclohexyl (meth) acrylate, 1- (iso) propyl Cycloheptane (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) butylcyclo Octane (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) pentyl Cycloheptanyl (meth) acrylate, 1- (iso) pentylcyclooctanyl (meth) acrylate, 1- (iso) pentylcyclononanyl (meth) acrylate, 1- (iso) pentylcyclodecanyl ( 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- (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 Cyclohexyl (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 Cyclohexyl (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;

2-Ethyl- (gamma) -butyrolactone-2-yl- (meth) acrylate and 2-methyl- (gamma) which are cyclic alkyl parts of (meth) acrylic-acid cyclic alkylester substituted by lactone structure, lactam structure, and acetal structure. -Butyrolactone-2-yl- (meth) acrylate, 2-ethyl-γ-butyrolactone-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-methyl-δ-valerolactone-2-yl- (meth) acrylate, 2-ethyl-δ-valerolactone-3-yl- ( Meth) acrylate, 2-methyl-δ-valerolactone-3-yl- (meth) acrylate, 2-ethyl-δ-valerolactone-4-yl- (meth) acrylate, 2-methyl-δ -Valerolactone-4-yl- (meth) acrylate, 2-ethyl-δ-valerolactone-5-yl- (meth) acrylate, 2-methyl-δ-valerolactone-5-yl- ( Mat) Lactones, such as methacrylate:

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

Acetals such as tetrahydro-2H-pyran-2-yl- (meth) acrylate, and the like;

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

As unsaturated dicarboxylic acid diester, For example, diethyl maleate, diethyl fumarate, diethyl itaconate;

As the bicyclo unsaturated compound, for example, 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-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6 -Dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2'-hydrate 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 an unsaturated aromatic compound, For example, styrene, (alpha) -methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxy styrene etc .;

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

As another unsaturated compound, an acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate etc. are mentioned, for example.

Among them, styrene, N-cyclohexyl maleimide, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, p-methoxy styrene and 2-methylcyclohexyl acryl in terms of copolymerization reactivity and heat resistance Rate, 1,3-butadiene, bicyclo [2.2.1] hept-2-ene, 1-ethylcyclopentyl methacrylate, 2-methyl-2-propene tetrahydro-2H-pyran-2-ylester and the like This is preferred.

These are used alone or in combination.

In the copolymer (A), the content of the polymerized unit or the repeating unit derived from the polymerizable unsaturated compound having the (a-1) oxylanyl group or the oxetanyl group is preferably 5 to 5 based on the copolymer (A). 90 weight%, More preferably, it is 10-80 weight%.

In the copolymer (A), the content of the polymerized unit or the repeating unit derived from the polymerizable unsaturated compound having at least one hydroxyl group (a-2) is preferably 5 to 90% by weight, based on the copolymer (A), More preferably, it is 5 to 70 weight%.

In the copolymer (A), the content of the polymerized unit or the repeating unit derived from (a-3) N-substituted maleimide is preferably 0 to 90% by weight, more preferably based on the copolymer (A). Is 5 to 80% by weight.

In the copolymer (A), the content of the polymerized unit or the repeating unit derived from (a-4) unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride is preferably 0 to 40 based on the copolymer (A). It is weight%, More preferably, it is 1-30 weight%.

In this range, good ITO etching resistance and heat resistance can be realized.

As a preferable specific example of a copolymer (A), For example, styrene / glycidyl methacrylate / 2-hydroxyethyl methacrylate, styrene / glycidyl methacrylate / methacrylic acid 2- (6- Hydroxy-hexanoyloxy) ethyl copolymer, styrene / glycidyl glycidyl / 4-vinylphenol copolymer, styrene / methacrylate tricyclo [5.2.1.0 ^2,6 ] decane-8-yl / methacryl Shanglycidyl / methacrylate 2-hydroxyethyl copolymer, styrene / methacrylate tricyclo [5.2.1.0 ^2,6 ] decane-8-yl / glycidyl methacrylate / methacrylic acid 2- ( 6-hydroxy-hexanoyloxy) ethyl copolymer, styrene / methacrylic tricyclo [5.2.1.0 ^2,6 ] decane-8-yl / glycidyl / 4-vinylphenol copolymer, styrene / N-cyclohexyl maleimide / glycidyl methacrylate / 2-hydroxyethyl copolymer methacrylate, styrene / N-cyclohexyl maleimide / glycidyl methacrylate / 2-methacrylate Roxy -Hexanoyloxy) ethyl copolymer, styrene / N-cyclohexylmaleimide / glycidyl glycidyl / 4-vinylphenol copolymer, styrene / N-phenylmaleimide / methacrylate glycidyl / methacrylic acid 2-hydroxyethyl copolymer, styrene / N-phenylmaleimide / glycidyl methacrylate / methacrylic acid 2- (6-hydroxy-hexanoyloxy) ethyl copolymer, styrene / N-phenylmaleimide / Glycidyl methacrylate / 4-vinylphenol copolymer, N-cyclohexyl maleimide / methacrylate glycidyl / methacrylate 2-hydroxyethyl copolymer, N-cyclohexyl maleimide / methacrylate Cydyl / methacrylic acid 2- (6-hydroxy-hexanoyloxy) ethyl copolymer, N-cyclohexylmaleimide / methacrylate glycidyl / 4-vinylphenol copolymer, N-phenylmaleimide / meta Glycidyl methacrylate / 2-hydroxyethyl methacrylate copolymer, N-phenylmaleimide / Glycidyl methacrylate / 2-methacrylic acid Hydroxy-hexanoyl) ethyl copolymer, N- phenylmaleimide / glycidyl methacrylate / 4-vinyl phenol copolymers, styrene / methacrylate, tricyclo [5.2.1.0 ^2,6] decane-8-yl / Methacrylic acid / methacrylic acid glycidyl / methacrylate 2-hydroxyethyl copolymer, styrene / methacrylate tricyclo [5.2.1.0 ^2,6 ] decane-8-yl / methacrylic acid / methacrylic Shanglycidyl / methacrylic acid 2- (6-hydroxy-hexanoyloxy) ethyl copolymer, styrene / methacrylic tricyclo [5.2.1.0 ^2,6 ] decan-8-yl / methacrylic acid / meta Glycidyl Glycidyl / 4-Vinylphenol Copolymer, Styrene / N-cyclohexylmaleimide / methacrylic acid / methacrylate Glycidyl / methacrylic acid 2-hydroxyethyl copolymer, styrene / N-cyclohexyl Maleimide / methacrylic acid / methacrylate glycidyl / methacrylic acid 2- (6-hydroxy- hexanoyloxy) ethyl copolymer, styrene / N-cyclohexyl maleimide / methacrylic acid / methacrylate city / 4-Vinylphenol copolymer, styrene / N-phenylmaleimide / methacrylic acid / methacrylate glycidyl / methacrylic acid 2-hydroxyethyl copolymer, styrene / N-phenylmaleimide / methacrylic acid / Glycidyl methacrylate / methacrylic acid 2- (6-hydroxy-hexanoyloxy) ethyl copolymer, styrene / N-phenylmaleimide / methacrylic acid / methacrylic acid glycidyl / 4-vinylphenol aerial Copolymerization, styrene / methacrylate tricyclo [5.2.1.0 ^2,6 ] decane-8-yl / 1-ethylcyclohexyl methacrylate / glycidyl methacrylate / methacrylic acid 2-hydroxyethyl copolymer, Styrene / methacrylate tricyclo [5.2.1.0 ^2,6 ] decane-8-yl / 1-ethylcyclohexyl methacrylate / methacrylic acid glycidyl / methacrylic acid 2- (6-hydroxy-hexanoyl Oxy) ethyl copolymer, styrene / methacrylate tricyclo [5.2.1.0 ^2,6 ] decane-8-yl / 1-ethylcyclohexyl methacrylate / glycidyl methacrylate / 4-vinylphenol copolymer, Sti Ethylene / N-cyclohexylmaleimide / 1-ethylcyclohexyl methacrylate / methacrylic acid glycidyl / methacrylate 2-hydroxyethyl copolymer, styrene / N-cyclohexylmaleimide / 1-ethylcyclohexyl Methacrylate / Glycidyl methacrylate / Methacrylic acid 2- (6-hydroxy-hexanoyloxy) ethyl copolymer, styrene / N-cyclohexyl maleimide / 1-ethylcyclohexyl methacrylate / methacrylate Shanglycidyl / 4-vinylphenol copolymer, styrene / N-phenylmaleimide / 1-ethylcyclohexyl methacrylate / methacrylate glycidyl / methacrylate 2-hydroxyethyl copolymer, styrene / N -Phenylmaleimide / 1-ethylcyclohexyl methacrylate / glycidyl methacrylate / methacrylic acid 2- (6-hydroxy-hexanoyloxy) ethyl copolymer, styrene / N-phenylmaleimide / 1- Ethylcyclohexyl methacrylate / glycidyl methacrylate / 4-vinylphenol copolymer, styrene / methacrylate Tricyclo [5.2.1.0 ^2,6] decane-8-yl / 1-ethylcyclopentyl methacrylate / glycidyl methacrylate / 2-hydroxyethyl methacrylate copolymer, a styrene / methacrylic acid tricyclo [ 5.2.1.0 ^2,6 ] decane-8-yl / 1-ethylcyclopentylmethacrylate / methacrylic acid glycidyl / methacrylic acid 2- (6-hydroxy-hexanoyloxy) ethyl copolymer, styrene / Tricyclo methacrylate [5.2.1.0 ^2,6 ] decane-8-yl / 1-ethylcyclopentyl methacrylate / glycidyl methacrylate / 4-vinylphenol copolymer, styrene / N-cyclohexylmalee Mid / 1-ethylcyclopentyl methacrylate / glycidyl methacrylate / methacrylic acid 2-hydroxyethyl copolymer, styrene / N-cyclohexylmaleimide / 1-ethylcyclopentyl methacrylate / methacrylic acid Glycidyl / methacrylic acid 2- (6-hydroxy-hexanoyloxy) ethyl copolymer, styrene / N-cyclohexylmaleimide / 1-ethylcyclopentylmethacrylate / methac Glycidyl / 4-vinylphenol copolymer, styrene / N-phenylmaleimide / 1-ethylcyclopentyl methacrylate / methacrylic acid glycidyl / methacrylate 2-hydroxyethyl copolymer, styrene / N -Phenylmaleimide / 1-ethylcyclopentylmethacrylate / glycidyl methacrylate / methacrylic acid 2- (6-hydroxy-hexanoyloxy) ethyl copolymer, styrene / N-phenylmaleimide / 1- Ethylcyclopentyl methacrylate / glycidyl methacrylate / 4-vinylphenol copolymer, styrene / methacrylate tricyclo [5.2.1.0 ^2,6 ] decane-8-yl / 1-methylcyclohexyl methacrylate Glycidyl methacrylate / 2-hydroxyethyl methacrylate copolymer, styrene / methacrylate tricyclo [5.2.1.0 ^2,6 ] decane-8-yl / 1-methylcyclohexyl methacrylate / meth Glycidyl methacrylate / methacrylic acid 2- (6-hydroxy-hexanoyloxy) ethyl copolymer, styrene / methacrylate tricyclo [5.2.1.0 ^2,6 ] decane-8-yl / 1-meth Methylcyclohexyl methacrylate / glycidyl methacrylate / 4-vinylphenol copolymer, styrene / N-cyclohexyl maleimide / 1-methylcyclohexyl methacrylate / methacrylate glycidyl / methacrylate -Hydroxyethyl copolymer, styrene / N-cyclohexylmaleimide / 1-methylcyclohexyl methacrylate / glycidyl methacrylate / methacrylic acid 2- (6-hydroxy-hexanoyloxy) ethyl copolymer , Styrene / N-cyclohexylmaleimide / 1-methylcyclohexyl methacrylate / glycidyl glycidyl / 4-vinylphenol copolymer, styrene / N-phenylmaleimide / 1-methylcyclohexyl methacrylate Glycidyl methacrylate / 2-hydroxyethyl methacrylate copolymer, styrene / N-phenylmaleimide / 1-methylcyclohexyl methacrylate / methacrylate glycidyl / methacrylate 2- (6 -Hydroxy-hexanoyloxy) ethyl copolymer, styrene / N-phenylmaleimide / 1-methylcyclohexylme Methacrylate / glycidyl methacrylate / 4-vinyl phenol copolymers, styrene / methacrylate, tricyclo [5.2.1.0 ^2,6] decane-8-yl / tetrahydro -2H- pyran-2-yl ester / Glycidyl methacrylate / methacrylic acid 2-hydroxyethyl copolymer, styrene / methacrylate tricyclo [5.2.1.0 ^2,6 ] decan-8-yl / tetrahydro-2H-pyran-2-ylester Glycidyl methacrylate / methacrylate 2- (6-hydroxy-hexanoyloxy) ethyl copolymer, styrene / methacrylate tricyclo [5.2.1.0 ^2,6 ] decane-8-yl / tetrahydro -2H-pyran-2-ylester / glycidyl methacrylate / 4-vinylphenol copolymer, styrene / N-cyclohexylmaleimide / tetrahydro-2H-pyran-2-ylester / glymethacrylate Dyl / methacrylic acid 2-hydroxyethyl copolymer, styrene / N-cyclohexylmaleimide / tetrahydro-2H-pyran-2-ylester / methacrylic acid glycidyl / methacrylic acid 2- (6-hydroxy Roxy-hexanoyloxy) Copolymer, styrene / N-cyclohexylmaleimide / tetrahydro-2H-pyran-2-ylester / glycidyl methacrylate / 4-vinylphenol copolymer, styrene / N-phenylmaleimide / tetrahydro-2H -Pyran-2-yl ester / Glycidyl methacrylate / 2-hydroxyethyl methacrylate, Styrene / N-phenylmaleimide / Tetrahydro-2H-pyran-2-yl ester / Gly methacrylate Cydyl / methacrylic acid 2- (6-hydroxy-hexanoyloxy) ethyl copolymer, styrene / N-phenylmaleimide / tetrahydro-2H-pyran-2-ylester / glycidyl methacrylate / 4 -Vinylphenol copolymer etc. are mentioned.

Among them, styrene / N-cyclohexyl maleimide / methacrylic acid / glycidyl methacrylate / methacrylic acid 2-hydroxyethyl copolymer, styrene / N-cyclohexyl maleimide, etc. in terms of copolymerization reactivity and heat resistance 1-Methylcyclohexyl methacrylate / glycidyl methacrylate / 2-hydroxyethyl copolymer methacrylate, styrene / N-cyclohexylmaleimide / 1-ethylcyclohexyl methacrylate / glycmethacrylate Dyl / methacrylic acid 2-hydroxyethyl copolymer, styrene / N-cyclohexylmaleimide / 1-ethylcyclopentyl methacrylate / methacrylic acid glycidyl / methacrylic acid 2-hydroxyethyl copolymer, styrene / N-cyclohexylmaleimide / tetrahydro-2H-pyran-2-ylester / methacrylic acid glycidyl / methacrylic acid 2-hydroxyethyl copolymer, styrene / N-phenylmaleimide / methacrylic acid / Glycidyl Methacrylic Acid / Methacrylic Acid 2-hydroxyethyl Copolymer , Styrene / N-phenylmaleimide / 1-methylcyclohexyl methacrylate / glycidyl methacrylate / methacrylate 2-hydroxyethyl copolymer, styrene / N-phenylmaleimide / 1-ethylcyclohexyl meta Acrylate / glycidyl methacrylate / 2-hydroxyethyl methacrylate, styrene / N-phenylmaleimide / 1-ethylcyclopentyl methacrylate / methacrylate glycidyl / methacrylate 2- Preference is given to hydroxyethyl copolymers, styrene / N-phenylmaleimide / tetrahydro-2H-pyran-2-ylester / glycidyl methacrylate / 2-hydroxyethyl methacrylate.

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. Is 2,000 to 50,000, and particularly preferably 3,000 to 40,000. 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. On the other hand, when Mw exceeds 100,000, the film roughness at the time of baking may generate | occur | produce.

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

Such copolymers can be synthesized in copolymer (A) by polymerizing unsaturated compounds (a-1) to (a-5) by known methods, for example radical polymerization, in the presence of a suitable solvent and a suitable polymerization initiator. have.

In addition to the copolymer (A), the composition of the present invention further contains an acid anhydride (B), a curing accelerator (C), a cationic polymerizable compound (D), an adhesion aid (E), a surfactant (F) and a thermosensitive acid generator. (G) can be contained as needed.

Acid Anhydride (B)

The composition of this invention can contain an acid anhydride (B) in order to improve the heat resistance and hardness of the protective film to form. As the acid anhydride (B), for example, a polymer containing a repeating unit derived from a polymerizable unsaturated compound having an acid anhydride group (except for copolymer (A)), and (b-2 ) Polyhydric carboxylic acid anhydride is mentioned as a preferable thing.

The polymer containing the repeating unit derived from the polymerizable unsaturated compound which has the said acid anhydride group (b-1) can be a copolymer of unsaturated polyhydric carboxylic anhydride and an olefinic unsaturated compound, for example. As unsaturated polyhydric carboxylic anhydride, 1 or more types chosen from the group which consists of itaconic anhydride, a citraconic anhydride, a maleic anhydride, and a cis 1,2,3,4- tetrahydro phthalic anhydride, are mentioned, for example. have.

Moreover, as an olefinic unsaturated compound, styrene, p-methylstyrene, p-methoxy styrene, methyl methacrylate, t-butyl methacrylate, tricyclo methacrylate [5.2.1.0 ^2,6 ] decane, for example And at least one selected from the group consisting of -8-yl, 2-methylcyclohexyl acrylate, phenylmaleimide and cyclohexyl.

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. It is wealth. By using such a copolymer, the protective film excellent in planarization property can be obtained.

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

The polystyrene reduced weight average molecular weight of the copolymer of the polymerizable unsaturated compound having the acid anhydride group and the olefinically unsaturated compound is 500 to 50,000, more preferably 500 to 10,000. By using the copolymer of such a molecular weight range, the protective film excellent in planarization property can be obtained.

As said polyhydric carboxylic acid anhydride (b-2), itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarvalic acid anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride Aliphatic dicarboxylic acid anhydrides such as anhydrous acid; 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; Ester group-containing acid anhydrides such as ethylene glycol bis anhydrous trimellitate and glycerin tris anhydrous trimellitate. Among these, aromatic polyhydric carboxylic anhydride, particularly trimellitic anhydride, is preferable in that a cured film having high heat resistance is obtained.

2-100 weight part is preferable with respect to 100 weight part of copolymers (A), and, as for content of an acid anhydride (B), 5-60 weight part is more preferable.

Cure Accelerator (C)

In order to improve the heat resistance and hardness of the protective film formed, a hardening accelerator (C) can be used together with an acid anhydride (B), and can be contained in the composition of this invention.

Specific examples of the curing accelerator (C) include 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 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-hydroxymethylimidazole, 2-phenylimidazole isocyanuric acid adduct, 2,4-diamino-6- [2 ' -Methyl imidazolyl- (1 ')]-ethyl-s-triazine isocyanuric acid addition product etc. are mentioned.

As for content of a hardening accelerator (C), 0.0001-10 weight part is preferable with respect to 100 weight part of copolymers (A), and 0.001-1 weight part is more preferable from a heat resistance or storage stability viewpoint.

Cationically polymerizable compound (D)

A cationically polymerizable compound (D) can be contained in the composition of this invention in order to improve the ITO etching tolerance of the protective film formed. As the cationically polymerizable compound (D), for example, a compound having two or more oxylanyl groups or oxetanyl groups in the molecule (except the copolymer (A-1) described above) is preferably used. As a compound which has two or more oxylanyl groups or an oxetanyl group in a molecule | numerator, the compound which has two or more epoxy groups in a molecule | numerator, or the compound which has two or more 3, 4- epoxycyclohexyl groups in a molecule | numerator is mentioned, for example. have.

As a compound which has two or more epoxy groups in a molecule | numerator, for example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenation Digs of bisphenol compounds such as bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, and brominated bisphenol S diglycidyl ether Glycidyl ethers;

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

Polyglycidyl ethers of polyether polyols obtained by 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 a molecule | numerator, it is a bisphenol-A epoxy resin, for example, Epicoat 1001, copper 1002, copper 1003, copper 1004, copper 1007, copper 1009, copper 1010, copper 828 (above, Japan) Epoxy resins);

Epicoat 807 (Japan Epoxy Resin Co., Ltd.) etc. 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), EPPN 201, Copper 202 (above, Nippon Kayaku Co., Ltd. product) etc .;

EOCN 102, copper 103S, copper 104S, copper 1020, copper 1025, copper 1027 (above, manufactured by Nippon Kayaku Co., Ltd.), epicoat 180S75 (manufactured by Japan Epoxy Resin Co., Ltd.), and the like;

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

As cyclic aliphatic epoxy resin, CY-175, copper 177, copper 179, araldite CY-182, copper 192, copper 184 (above, manufactured by Ciba Specialty Chemicals), ERL-4234, copper 4299, copper 4221, 4206 (above, manufactured by UCC), Shodine 509 (manufactured by Showa Denko Co., Ltd.), Epiclone 200, copper 400 (above, manufactured by Dai Nippon Ink Co., Ltd.), Epicoat 871, East 872 (more, Japan Epoxy Resin Co., Ltd.), ED-5661, copper 5662 (above, manufactured by Celanese Co., Ltd.), etc .;

Examples of the aliphatic polyglycidyl ethers include epolite 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) 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 cationic polymerizable compounds (D), phenol novolak type epoxy resins and polyphenol type epoxy resins are preferable.

The content of the cationic polymerizable compound (D) 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 100 parts by weight of the copolymer (A). 10 to 50 parts by weight. When the usage-amount of a cationically polymerizable compound (D) is more than 200 weight part, a problem may arise in the coating property of a composition, and when it is less than 3 weight part, the hardness of the protective film obtained may be insufficient.

(E) Adhesion Aids

(E) An adhesive adjuvant can be contained in the 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.

As a specific example of (E) adhesion | attachment adjuvant, For example, trimethoxy silyl benzoic acid, (gamma)-methacryloxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, (gamma) -isocyanate propyl triethoxysilane, (gamma) -glycidoxypropyl 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, based on 100 parts by weight of the copolymer (A). When the amount of the (E) adhesion assistant exceeds 30 parts by weight, the heat resistance of the protective film obtained may be insufficient.

(F) surfactant

Surfactant can be added in order to improve the application | coating performance of the resin composition of this invention.

As such surfactant, a fluorochemical surfactant, silicone type surfactant, nonionic surfactant, other surfactant is mentioned, for example.

As said fluorine-type surfactant, the brand names of BM CHIMIE company make, for example: BM-1000, BM-1100, the Dai Nippon Ink Chemical Co., Ltd. brand name: Megapack F142 D, copper F172, copper F173, copper F183 , The product name of Sumitomo 3M Co., Ltd .: Florade FC-135, the copper FC-170C, the copper FC-430, the copper FC-431, the brand name of neos Co., Ltd. make: 250, copper 251, copper 222F, Product name of FTX-218, Asahi Glass Co., Ltd .: suffron S-112, copper S-113, copper S-131, copper S-141, copper S-145, copper S-382, copper SC-101, Commercial items, such as SC-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, PAINTAD 19 , FZ-2101, East 77, East 2118, L-7001, L-7002, Big Chemi Japan Co., Ltd., Byk-300, East 306, East 310, East 335, East 341, East 344, East 370, Shin The brand name of Etsu Chemical Co., Ltd. make: KP341, The brand name of Shin-Akita Kasei Co., Ltd. make: Commercial items, such as F-Top EF301, EF 303, and EF 352, are mentioned.

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 Octyl phenyl ether and polyoxyethylene nonyl phenyl ether are mentioned, As a 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 copolymer polyflow No. 57, copper No. 90, etc. are mentioned.

The amount of these (F) surfactants added is preferably 5 parts by weight or less, more preferably 2 parts by weight or less based on 100 parts by weight of the polymer (A). When the quantity of surfactant exceeds 5 weight part, the film roughness of a coating film may become easy in a coating process.

(G) thermosensitive acid generator

The composition of the present invention may contain a thermosensitive acid generator. Examples of the thermosensitive acid generator include sulfonium salts, benzothiazonium salts, ammonium salts and phosphonium salts. Among these, sulfonium salts and benzothiazonium salts are preferably used.

menstruum

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, what dissolves or disperse | distributes each component of a composition and does not react with each component is used preferably.

As such a solvent, for example, alcohol, ether, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol alkyl ether Propionate, aromatic hydrocarbons, ketones, esters and the like.

As these specific examples, As alcohol, For example, methanol, ethanol, benzyl alcohol, etc .;

As the ether, for example, tetrahydrofuran and the like;

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

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

As diethylene glycol monoalkyl ether, For example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, etc .;

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

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

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

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

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

As the ketone, for example, 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 hydroxyacetic acid. Methyl, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxypropionate methyl, 3-hydroxypropionate, 3-hydroxypropionic acid propyl, 3-hydroxypropionic acid Butyl, 2-hydroxy-3-methyl butyrate, methyl methoxyacetate, ethyl methoxyacetate, methoxyacetic acid propyl, butyl acetate, ethoxyacetic acid, ethyl ethoxyacetate, ethoxyacetic acid propyl Butyl oxyacetate, methyl propoxy acetate, ethyl propoxy acetate, propyl propoxy acetate, butyl propoxy acetate, methyl butoxy acetate Ethyl butoxy acetate, propyl butoxy acetate, butyl butoxy acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate Ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, 3-methoxy methyl propionate, 3-methoxy ethylpropionate, 3-methoxy propylpropionate, 3-methoxy butyl propionate, 3-ethoxy propylpropionate, 3-ethoxy propylpropionate, 3-ethoxy propylpropionate, 3 Butyl ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, 3-butoxypropionic acid Butyl, and 3-butoxy-propyl propionate, butyl propionate, 3-butoxy respectively.

Among these, alcohol, diethylene glycol, propylene glycol alkyl acetate, ethylene glycol alkyl ether acetate and diethylene glycol dialkyl ether are preferable, and benzyl alcohol, diethylene glycol ethyl methyl ether, propylene glycol methyl ether acetate and propylene glycol ethyl ether are particularly preferred. Acetate, diethylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-methoxypropionate This is preferred.

The amount of the solvent used is preferably 1 to 50% by weight, more preferably 5 to 40% by weight of the total solids (the amount of the solvent excluding the amount of the solvent from the total amount of the composition including the solvent) in the composition of the present invention. 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-methylacetamide, N, N-dimethylacetamide, and N-methyl Pyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, Diethyl maleate, gamma -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 preferably used after being filtered using a Millipore filter having a pore size of about 0.2 to 3.0 μm, more preferably about 0.2 to 0.5 μm, and the like.

Formation of protective film of color filter

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

After forming the coating film by apply | coating the resin composition solution of this invention to the board | substrate surface, prebaking, and removing a solvent, the protective film of the target color filter can be formed by heat processing.

As what can be used as said board | substrate, board | substrates, such as glass, quartz, a silicone, resin, can be used, for example. As resin, resin, such as a ring-opening polymer of polyethylene terephthalate, a polybutylene terephthalate, a polyether sulfone, a polycarbonate, a polyimide, and a cyclic olefin, and its hydrogenated substance, is mentioned, for example.

As the coating method, for example, a spraying method, a roll coating method, a rotary coating method, a bar coating method, an inkjet method or the like can be adopted, and in particular, coating using a spin coater, a spinless coater, or a slit die coater is preferable. Can be used.

The conditions for the prebaking also vary depending on the type, blending ratio, and the like of each component. Preferably, conditions for about 1 to 15 minutes can be adopted at 70 to 90 ° C. 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. 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 appropriate heating apparatuses, 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 of 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, the said resin composition is apply | coated to the surface of a board | substrate, a solvent is removed by prebaking, it is made into a coating film, and the radiation irradiation process (exposure process) is performed for the purpose A protective film can be formed. If necessary, heat treatment may be further performed after the exposure treatment.

As radiation which can be used by the said irradiation process, visible light, an ultraviolet-ray, an ultraviolet-ray, an electron beam, an X-ray, etc. are mentioned, for example. Preference is given to ultraviolet rays comprising light of a wavelength of 190 to 450 nm.

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

The heat treatment may optionally be further performed after irradiation. As heating temperature at this time, about 150-250 degreeC is preferable. As a heating apparatus, an appropriate 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 in the case of using a hotplate, and 30 to 90 minutes in the case of using an oven.

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. On the other hand, when the protective film of the present invention is formed on a substrate having a step of the color filter, the film thickness should be understood as the thickness from the top of the color filter.

<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 1

5 parts by weight of 2,2'-azobis-isobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate were charged into a flask equipped with a cooling tube and a stirrer. Subsequently, 50 parts by weight of glycidyl methacrylate, 30 parts by weight of styrene and 20 parts by weight of 2-hydroxyethyl methacrylic acid were added thereto, followed by nitrogen replacement, followed by gentle stirring. The solution temperature was raised to 70 ° C, and the temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-1). Solid content concentration of the obtained polymer solution was 33.0 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 charged into a flask equipped with a cooling tube and a stirrer. Subsequently, 60 parts by weight of 3-ethyl-3-methacryloyloxymethyloxetane, 20 parts by weight of styrene, and 20 parts by weight of 2-hydroxyethyl methacrylic acid were added thereto, followed by nitrogen replacement, followed by gentle stirring. The solution temperature was raised to 70 ° C., and the temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (A-2). Solid content concentration of the obtained polymer solution was 32.8 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 charged into a flask equipped with a cooling tube and a stirrer. Subsequently, 50 parts by weight of glycidyl methacrylate, 10 parts by weight of styrene, 10 parts by weight of N-cyclohexylmaleimide, 10 parts by weight of methacrylic acid, and 20 parts by weight of methacrylic acid were substituted with nitrogen. Slowly starting stirring. The solution temperature was raised to 70 ° C., and the temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (A-3). Solid content concentration of the obtained polymer solution was 32.9 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 charged into a flask equipped with a cooling tube and a stirrer. Subsequently, 50 parts by weight of glycidyl methacrylate, 10 parts by weight of styrene, 10 parts by weight of N-phenylmaleimide, 10 parts by weight of methacrylic acid, and 20 parts by weight of methacrylic acid were substituted with nitrogen, and then gently replaced. Agitation was initiated. The solution temperature was raised to 70 ° C., and the temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (A-4). Solid content concentration of the obtained polymer solution was 32.9 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 charged into a flask equipped with a cooling tube and a stirrer. Subsequently, 50 parts by weight of glycidyl methacrylate, 10 parts by weight of styrene, 10 parts by weight of N-phenylmaleimide, 10 parts by weight of methacrylic acid, and 20 parts by weight of methacrylic acid 1,2-dihydroxyethyl were substituted. After gently stirring was started. The solution temperature was raised to 70 ° C., and the temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (A-5). Solid content concentration of the obtained polymer solution was 33.0 weight%.

Synthesis Example 6

5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were charged into a flask equipped with a cooling tube and a stirrer. 50 parts by weight of glycidyl methacrylate, 10 parts by weight of styrene, 10 parts by weight of N-phenylmaleimide, 10 parts by weight of methacrylic acid and 2- (6-hydroxyhexanoyloxy) methacrylate 20 After adding the parts by weight and replacing with nitrogen, stirring was started gently. The solution temperature was raised to 70 ° C., and the temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (A-6). Solid content concentration of the obtained polymer solution was 32.7 weight%.

Synthesis Example 7

5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were charged into a flask equipped with a cooling tube and a stirrer. Subsequently, 50 parts by weight of glycidyl methacrylate, 10 parts by weight of styrene, 10 parts by weight of N-phenylmaleimide, 10 parts by weight of methacrylic acid, and 20 parts by weight of 4-vinylphenol were added thereto, followed by nitrogen replacement, followed by gentle stirring. . The solution temperature was raised to 70 ° C., and the temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-7). Solid content concentration of the obtained polymer solution was 33.2 weight%.

Synthesis Example 8

5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were charged into a flask equipped with a cooling tube and a stirrer. 50 parts by weight of 3-ethyl-3-methacryloyloxymethyloxetane, 10 parts by weight of styrene, 10 parts by weight of N-phenylmaleimide, 10 parts by weight of methacrylic acid and 20 parts by weight of 2-hydroxyethyl methacrylic acid After adding the parts and replacing with nitrogen, stirring was started gently. The solution temperature was raised to 70 ° C., and the temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (A-8). Solid content concentration of the obtained polymer solution was 33.0 weight%.

Synthesis Example 9

5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were charged into a flask equipped with a cooling tube and a stirrer. Subsequently, 50 parts by weight of 2-methylglycidyl methacrylic acid, 10 parts by weight of styrene, 10 parts by weight of N-phenylmaleimide, 10 parts by weight of methacrylic acid, and 20 parts by weight of methacrylic acid are substituted with nitrogen. After gently stirring was started. The solution temperature was raised to 70 ° C., and the temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (A-9). Solid content concentration of the obtained polymer solution was 32.8 weight%.

Synthesis Example 10

5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were charged into a flask equipped with a cooling tube and a stirrer. Subsequently, 50 parts by weight of 2-methylglycidyl methacrylate, 10 parts by weight of styrene, 10 parts by weight of N-phenylmaleimide, 10 parts by weight of 1-ethylcyclohexyl methacrylate and 2-hydroxyethyl methacrylic acid 20 After adding the parts by weight and replacing with nitrogen, stirring was started gently. The solution temperature was raised to 70 ° C., and the temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (A-10). Solid content concentration of the obtained polymer solution was 32.7 weight%.

Synthesis Example 11

5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were charged into a flask equipped with a cooling tube and a stirrer. 50 parts by weight of 2-methylglycidyl methacrylate, 10 parts by weight of styrene, 10 parts by weight of N-phenylmaleimide, 10 parts by weight of 1-ethylcyclopentyl methacrylate, and 2-hydroxyethyl methacrylic acid 20 After adding the parts by weight and replacing with nitrogen, stirring was started gently. The solution temperature was raised to 70 ° C., and the temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (A-11). Solid content concentration of the obtained polymer solution was 32.7 weight%.

Comparative Synthesis Example 1

5 parts by weight of 2,2'-azobis-isobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate were charged into a flask equipped with a cooling tube and a stirrer. Subsequently, 70 parts by weight of glycidyl methacrylate and 30 parts by weight of styrene were added thereto, followed by nitrogen replacement, followed by gentle stirring. The solution temperature was raised to 70 ° C, and the temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (a-1). Solid content concentration of the obtained polymer solution was 32.9 weight%.

Comparative Synthesis Example 2

5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were charged into a flask equipped with a cooling tube and a stirrer. Subsequently, 50 parts by weight of glycidyl methacrylate, 20 parts by weight of styrene, 20 parts by weight of N-cyclohexylmaleimide, and 10 parts by weight of methacrylic acid were added thereto, followed by nitrogen replacement, followed by gentle stirring. The solution temperature was raised to 70 ° C., and the temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (a-2). Solid content concentration of the obtained polymer solution was 32.8 weight%.

Preparation and Evaluation of Resin Compositions

Example 1

A solution containing the copolymer (A-1) obtained in Synthesis Example 1 (amount corresponding to 100 parts by weight (solid content) of the copolymer (A-1)) and (E-1) γ-glycidoxypropyltrimeth 5.0 parts by weight of oxysilane, 0.1 part by weight of SH-28PA (manufactured by Toray Dow Corning Silicone Co., Ltd.) as a (F-1) surfactant, and a propylene glycol monomethyl ether acetate (S -1) and diethylene glycol ethyl methyl ether (S-2) were added at a ratio of 8 to 2, and then filtered with a Millipore filter having a pore size of 0.5 µm to prepare a resin composition.

After applying the composition on a SiO ₂ immersed glass substrate using a spinner, the film was prebaked at 80 ° C. for 5 minutes on a hot plate to form a coating film, and further heated in 230 minutes at 230 ° C. for a film thickness of 2.0. A protective film of 탆 was formed.

Evaluation of the shield

(1) transparency evaluation

The transmittance | permeability of 400-800 nm was measured using the spectrophotometer (150-20 type double beam (made by Hitachi Seisakusho Co., Ltd.)) with respect to the board | substrate which has the protective film formed as mentioned above. 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 the transparency of a protective film is favorable.

(2) Evaluation of heat resistance dimensional stability

The board | substrate with a protective film formed as mentioned above was heated in 250 degreeC in conditions of 1 hour in oven, and the film thickness before and behind heating was measured. Table 1 shows the heat-resistant dimensional stability calculated according to Equation 1 below. 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) x 100 (%)

(3) Evaluation of heat discoloration resistance

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

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

(4) measurement of surface hardness

The surface hardness of the protective film was measured by the 8.4.1 pencil drawing test of JISK-5400-1990 with respect to the board | substrate which has the protective film formed as mentioned above. This value is shown in Table 1. When this value is 4H or harder, the surface hardness can be said to be good.

(5) measurement of dynamic microhardness

The substrate having the protective film formed as described above was prepared by using a Shimadzu dynamic microhardness meter DUH-201 (manufactured by Shimadzu Seisakusho Co., Ltd.) by a press-fit test of a ridge angle 115 ° triangular indenter (Herkovitch type). The dynamic microhardness was measured under the measurement conditions of load: 0.1 gf, speed: 0.0145 gf / second, holding time: 5 seconds, and temperature of 23 ° C and 140 ° C. The results are shown in Table 1.

(6) Evaluation of adhesiveness

After the pressure cooker 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, it carries out the protective film by 8.5.3 adhesive checkerboard graduation tape method of JISK-5400-1990. Adhesion (adhesion to SiO ₂ ) was evaluated. Table 1 shows the number of remaining checkerboard ticks among the checkerboard tickers.

In addition, adhesion was evaluated as an evaluation of the Cr, SiO ₂ glass was immersed, except for using the Cr substrate instead of the substrate and in the same manner as described above to form a protective film having a thickness of 2.0 ㎛, likewise by the checkerboard grid tape method. The results are shown in Table 1.

(7) Evaluation of ITO Etch Resistance

With respect to the substrate having the protective film formed as described above, the ITO target (ITO filling rate of 95% or more and In ₂ O ₃ / SnO ₂ ==) was obtained using a high rate sputtering apparatus SH-550-C12 manufactured by Nippon Shinku Kijutsu Co. 90/10 weight ratio) was used for ITO sputtering at 60 ° C. 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 / h, and an O ₂ gas flow rate of 1.2 × 10 ⁻⁵ m 3 / h. The board | substrate after sputtering was heated in 240 degreeC x 60 minutes in the said clean oven, and it annealed. Subsequently, the board | substrate was set to the spinner, the positive resist PFR3650-21cp for G-ray made by JSR Corporation was dripped on the board | substrate, and it coated at 3,500 rpm x 30 second. The substrate was warmed at 90 ° C for 2 minutes on a hot plate to remove the solvent. Subsequently, the ghi line (wavelength 436 nm, 405 nm, 365 nm intensity ratio = 2.7: 2.5: 4.8) was exposed using a exposure machine Canon PLA501F (manufactured by Canon Corporation) through a pattern mask of 10 mu m / 10 mu m. Irradiation was carried out at an exposure amount of roughness 23 mW / m 2 and 25 mJ / m 2 in terms of linear conversion, immersion development was carried out for 60 seconds using a 2.4% TMAH aqueous solution at room temperature, and washed with ultrapure water for 60 seconds, followed by air drying. It was then post-baked in a clean oven at 150 ° C. × 60 minutes. The etchant was provided by mixing nitric acid / hydrochloric acid in a weight ratio of 1/3. The substrate was immersed in an etchant, the substrate was taken out every 10 seconds to determine the just etching time for forming a 10 μm ITO line, the ITO line width 1.2 times the just etching time was measured by an optical microscope, and the results are shown in Table 1. Indicated. It was assumed that the higher the retention rate of the 10 µm ITO line, the better the ITO etching resistance.

(8) Evaluation of storage stability

The viscosity in the resin composition for protective film formation manufactured in Example 1 was measured using the Tokyo Keiki Corporation ELD viscometer. Thereafter, the composition was measured at 25 ° C. while the solution viscosity at 25 ° C. was measured daily. 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. When this number of days is 20 days or more, it can be said that storage stability is favorable.

(9) Evaluation of flatness

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

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

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

The unevenness | corrugation of the protective film surface was measured with the contact film thickness measuring apparatus (alpha) -step (made by Tencor Japan Co., Ltd.) with respect to the board | substrate which has a protective film on the color filter formed as mentioned above. However, it measured by 2,000 micrometers in measurement length, 2,000 micrometers in measurement range, and the number of measurement points n = 5. That is, the measurement direction is made into two directions of the stripe line short axis direction in the red, green, and blue directions, and the stripe line major axis direction of the same color of red, red, green, green, blue, and blue, and n = 5 for each direction. It was measured (the total number of n was 10). In Table 1, ten average values of the height difference (nm) of the highest part and the lowest part at the time of each measurement are shown. When this value is smaller than 200 nm, it can be said that planarization property is favorable.

Examples 2 to 13 and Comparative Examples 1 to 3

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

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.

Example 14

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

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

In Table 1, the abbreviations of acid anhydride (B), curing accelerator (C), cationic polymerizable compound (D), adhesion aid (E), surfactant (F), and solvent (S) are as follows. Indicates.

B-1: trimellitic anhydride

C-1: 2-phenyl-4-methylimidazole

D-1: Bisphenol A novolak-type epoxy resin (brand name of Japan epoxy resin Co., Ltd. make: Epicoat 828)

D-2: novolak-type epoxy resin (brand name of Japan epoxy resin Co., Ltd. make: Epicoat 154)

E-1: γ-glycidoxypropyltrimethoxysilane

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

F-2: Silicone type surfactant (Bic-chemy Japan Co., Ltd. brand name: Byk-344)

F-3: Fluorine-type surfactant (Neos Co., Ltd. brand name: Pgentgent FTX-218)

F-4: Silicone type surfactant (Toray Dow Corning Silicone Co., Ltd. brand name: PAINTAD19)

S-1: Propylene Glycol Monomethyl Ether Acetate

S-2: diethylene glycol ethyl methyl ether

As is apparent from the above 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 under heat, and also on the base substrate. 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 can be exposed to heating exceeding 250 ° C. in the panel manufacturing process, having sufficient heat resistance even in that case is ensured by having sufficient dimensional stability at 270 ° C.

Claims (5)

A thermosetting resin composition comprising a polymer and a solvent, wherein the polymer has a polymerized unit derived from a polymerizable unsaturated compound having (A) (a-1) an oxylalanyl group or an oxetanyl group and (a-2) at least one hydroxyl group. It is a copolymer containing the polymerization unit derived from a polymerizable unsaturated compound, The thermosetting resin composition characterized by the above-mentioned. The copolymer according to claim 1, wherein the copolymer (A) is further derived from (a-3) polymerized units derived from N-substituted maleimide and (a-4) unsaturated carboxylic acids and / or unsaturated carboxylic anhydrides. The thermosetting resin composition containing the polymerized unit which becomes. The thermosetting resin composition according to claim 1 or 2, wherein the thermosetting resin composition is for forming a protective film of a color filter. The coating film is formed on the board | substrate using the thermosetting resin composition of Claim 3, and then heat-processed, The formation method of the protective film of a color filter characterized by the above-mentioned. The protective film of a color filter formed from the thermosetting resin composition of Claim 3.