KR101224424B1 - Active energy ray-curable compositon - Google Patents

Abstract

When the present invention is used as a composition for forming an active energy ray-curable pattern, the exposure sensitivity is high, developability is good, precise and accurate patterns can be formed, and after curing, all of coating film strength, heat resistance and chemical resistance, etc. Provided is an active energy ray curable composition having excellent physical properties. The said composition is a compound (a) which added the acid anhydride to the compound which has 3 or more (meth) acryloyl group and a hydroxyl group, and 3 or more of at least 1 (meth) acryloyl group of the said (a) component. The compound (b) to which the hydroxyl group of the compound which has a (meth) acryloyl group and a hydroxyl group was added is contained as an essential component.

Active energy radiation curable composition

Description

ACTIVE ENERGY RAY-CURABLE COMPOSITON}

The present invention relates to an active energy ray-curable composition, the composition of the present invention can be used for various uses of the composition for forming a pattern, such as ink, paint, and resist, and in particular, as the composition for pattern formation because of excellent alkali developability It can be used preferably and belongs to these technical fields.

Conventionally, (meth) acrylate is used as a composition for pattern formation used by the etching resist, the soldering resist, and the color resist which forms the colored layer of a color filter. In this case, a compound having two or more (meth) acryloyl groups (hereinafter referred to as "polyfunctional (meth) acrylate") is used for the purpose of improving the sensitivity of the composition, improving the hardness of the cured product, and the like.

In this case, the polyfunctional (meth) acrylate is alkali insoluble, and there is a problem in that a film residue of the uncured portion coating film is generated at the time of development, so that sufficient resolution cannot be obtained. Examination of the carboxyl group-containing polyfunctional (meth) acrylate obtained by adding to a divalent carboxylic anhydride has been made | formed.

However, in order to add a large amount of divalent carboxylic anhydride in one molecule of polyfunctional (meth) acrylate, it is necessary to lower the ratio of the (meth) acryloyl group in one molecule in order to leave a hydroxyl group. It was not able to raise, and it was difficult to make developability and sclerosis compatible.

Therefore, in order to further improve hardness and developability, a carboxyl group-containing polyfunctional (meth) obtained by addition reaction of a compound having at least one hydroxyl group and at least two (meth) acryloyl groups with a dianhydride of a tetravalent carboxylic acid (meth The examination of acrylate is also made (patent document 1).

However, even when using the carboxyl group-containing polyfunctional (meth) acrylate of patent document 1, since the crosslinking density was insufficient, it had a problem that it was inferior to cured film strength, heat resistance, and chemical resistance.

On the other hand, the crosslinking density of hardened | cured material and alkali solubility are often requested | required in the composition for active energy ray hardening-type pattern formation for color filters used in manufacture of a liquid crystal panel.

As a composition for active energy ray hardening pattern formation for color filters, the composition containing the polyfunctional (meth) acrylate which does not have a carboxyl group, alkali-soluble resin, a photoinitiator, and the organic solvent is known (patent document 2).

Although the present invention increases the introduction ratio of photocurable groups and acidic functional groups of alkali-soluble resins to improve crosslinking density and alkali solubility of the cured product, the amount of photocurable groups and acidic functional groups that can be introduced is limited, and the viscosity of the composition The problem was that a rise would cause the coating aptitude to be impaired.

In order to solve this problem, the composition for pattern formation using the polyfunctional (meth) acrylate which has a carboxyl group is proposed (patent document 3). However, according to this composition, since the compound which has one carboxyl group is used in 1 molecule, alkali solubility improves, but it was not practical enough and the sensitivity was not enough.

Patent Document 1: Japanese Patent Application Laid-Open No. 2001-089416 (claims)

Patent Document 2: Japanese Patent Application Laid-Open No. 2000-105456 (claims)

Patent Document 3: Japanese Patent Application Laid-Open No. 2001-91954 (claims)

An object of the present invention is that when used as a composition for forming an active energy ray-curable pattern, the exposure sensitivity is high, developability is good, precise and accurate patterns can be formed, and after coating, coating film strength, heat resistance and chemical resistance, etc. In providing the active energy ray hardening-type composition excellent in all the physical properties of, Furthermore, it is used suitably as a coloring composition for forming the composition for color filter protective films in liquid crystal panel manufacture, the pixel, black matrix, etc. in a color filter. In addition to the above-described performance, there is provided a composition for forming a pattern or a method for forming a pattern which is highly elastic after curing and has an elastic behavior suitable for a columnar spacer.

Hereinafter, the present invention will be described in detail. In addition, in this specification, (meth) acryl means an acryl and / or methacryl, (meth) acrylate means an acrylate and / or methacrylate, and (meth) acryloyl means acryloyl and And / or methacryloyl.

The present invention provides a compound (a) (hereinafter referred to as "(a) component") in which an acid anhydride is added to a compound having three or more (meth) acryloyl groups and a hydroxyl group, and at least one of the components (a). Containing as essential components a compound (hereinafter referred to as "(b) component") in which a hydroxyl group of a compound having three or more (meth) acryloyl groups and a hydroxyl group is added to a number of (meth) acryloyl groups It relates to an active energy ray-curable composition.

Hereinafter, (a) component, (b) component, and another component are demonstrated.

1. (a) Component

(a) A component is a compound which added the acid anhydride to the compound (henceforth "hydroxy polyfunctional (meth) acrylate") which has three or more (meth) acryloyl group and a hydroxyl group.

Specific examples of the hydroxy polyfunctional (meth) acrylate include ditrimetholpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and the like.

Among these, dipentaerythritol penta (meth) acrylate is preferable because of its high pattern forming ability.

As a hydroxy polyfunctional (meth) acrylate in this invention, you may contain the compound which has four or more (meth) acryloyl groups which do not have the hydroxyl group by-produced in a manufacturing process. For example, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned. These usually include pentaerythritol tri (meth) acrylate in pentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) acrylate in dipentaerythritol hexa (meth) acrylate.

The compound which has four or more (meth) acryloyl groups which do not have these hydroxyl groups may be contained in the ratio of 20-80 mass% in the hydroxy polyfunctional (meth) acrylate component.

As a manufacturing method of hydroxy polyfunctional acrylate, the method of heating and stirring (meth) acrylic acid and alcohol in presence of an acidic catalyst is mentioned. Examples of acidic catalysts include sulfuric acid, paratoluenesulfonic acid and methanesulfonic acid. Moreover, although reaction temperature may be set suitably according to the compound to be used and the objective, Preferably it is 70 degreeC-140 degreeC. When this reaction temperature is less than 70 degreeC, reaction will be delayed. On the other hand, when reaction temperature exceeds 140 degreeC, reaction system may become unstable and an impurity may produce | generate or gelatinize.

In the above reaction, it is preferable to use an organic solvent having a low solubility with water produced by the esterification reaction and to promote dehydration while azeotropic water. As a preferable organic solvent, aromatic hydrocarbons, such as toluene, benzene, and xylene, aliphatic hydrocarbons, such as hexane and heptane, ketones, such as methyl ethyl ketone and cyclohexanone, are mentioned, for example. In addition, although an organic solvent may be distilled off under reduced pressure after reaction, when using the solvent which does not have a bad smell problem, you may use it as it is without distilling off for the viscosity adjustment of a composition.

Specific examples of the alcohol in the reaction include polyols such as ditrimethyrolpropane, pentaerythritol, and dipentaerythritol, and alkylene oxide adducts of these polyols. Ethylene oxide, a propylene oxide, etc. are mentioned as said alkylene oxide.

Moreover, a polymerization inhibitor can be added to a reaction liquid for the purpose of preventing superposition | polymerization of the obtained (meth) acrylic acid ester. Examples of such a polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-p-cresol, phenothiazine, and the like.

(a) A component is synthesize | combined by reaction of the said hydroxy polyfunctional (meth) acrylate with an acid anhydride. As acid anhydride, succinic anhydride, 1-dodecenyl succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, hexahydro phthalic anhydride, methylhexahydro phthalic anhydride, tetramethylene anhydride, tetrahydro phthalic anhydride, methyl Compound having one acid anhydride group in the same molecule, such as tetrahydro phthalic anhydride, endmethylenetetrahydro phthalic anhydride, methylendmethylenetetrahydro phthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride and trimellitic anhydride, and anhydrous Pyromellitic acid, phthalic anhydride dimer, diphenyl ether tetracarboxylic dianhydride, diphenyl sulfontetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride and 1,2,3,4-butane tetracarboxylic Acid dianhydride, diphenyl ether tetracarboxylic anhydride, trimellitic anhydride, ethylene glycol anhydride The compound which has two acid anhydride groups in the same molecule | numerators, such as a collester (The commercial item contains, for example, the Shin-Nihon Rika Co., Ltd. product, brand name RikashitTM TMEG-100) is mentioned.

Among these, the compound which has one acid anhydride group in the same molecule is preferable.

As a manufacturing method of (a) component, it is good according to the conventional method.

For example, the method of making hydroxy polyfunctional (meth) acrylate and an acid anhydride react at 60-110 degreeC for 1 to 20 hours in presence of a catalyst, etc. are mentioned.

Examples of the catalyst in this case include N, N-dimethylbenzylamine, triethylamine, tributylamine, triethylenediamine, benzyltrimethylammonium chloride, benzyltriethylammonium bromide, tetramethylammonium bromide, cetyltrimethylammonium bromide, zinc oxide and the like. Can be mentioned.

Although the ratio in the composition of (a) component should just select suitably according to the objective and a use, Preferably it is 10-80 mass% in a composition.

2. (b) Component

(b) A component is a compound in which the hydroxyl group of the hydroxy polyfunctional (meth) acrylate was added to the at least 1 (meth) acryloyl group of the said (a) component. As (b) component, the compound in which the hydroxyl group of the hydroxy polyfunctional (meth) acrylate of Michael was added to one (meth) acryloyl group of the said (a) component.

As (b) component, the thing obtained by the various manufacturing methods can be used, The method of adding a hydroxyl group of a hydroxy polyfunctional (meth) acrylate to the (meth) acryloyl group of (a) component, two hydroxides The acid anhydride is added after the hydroxyl group of one hydroxy polyfunctional (meth) acrylate is Michael-added to the acrylate group of another hydroxy polyfunctional (meth) acrylate among the hydroxy polyfunctional (meth) acrylates. A method of adding is mentioned. The two production methods differ only in the order of reaction, and the compounds produced are the same.

In addition, as (b) component, the thing by-produced in manufacture of (a) component can also be used.

The first by-product is a hydroxy polyfunctional (meth) group as one of the (meth) acryloyl groups in the hydroxy polyfunctional (meth) acrylate as the raw material hydroxy polyfunctional (meth) acrylate in the preparation of the component (a). It is the case where the thing containing the compound to which the hydroxyl group of the acrylate contains Michael addition (henceforth a compound b ') is used.

Compound b 'is produced | generated as a side reaction in the process of heating and stirring (meth) acrylic acid and alcohol in manufacture of raw material hydroxy polyfunctional (meth) acrylate.

In this case, the ratio of the compound b 'produced in the reaction system can be arbitrarily adjusted by the reaction temperature, the reaction time or the injection ratio of alcohol and (meth) acrylic acid. Generally, in order to increase the conversion of hydroxyl groups in alcohol, it is preferable to inject 1.5 times or more of (meth) acrylic acid, but in the case of producing compound b ', the injection amount of (meth) acrylic acid is preferable to the injection amount of alcohol. Preferably it is 1.3 mol or less, More preferably, it is 1.2 times or less. The reaction can also be promoted by setting the reaction temperature higher than usual or by lengthening the reaction time.

As reaction temperature in this case, 90 degreeC or more is preferable, More preferably, it is 100 degreeC or more.

Compound b 'is added to an acid anhydride, and (b) component is produced | generated.

The second by-product is a hydroxyl of a hydroxy polyfunctional (meth) acrylate in one of the (meth) acryloyl groups in the (a) component produced in the step of adding an acid anhydride in the production of the component (a). It is created when the actual skill is added to Michael.

In this case, the ratio of (b) component produced in the reaction system can be arbitrarily adjusted by reaction temperature, reaction time, or injection ratio of unreacted hydroxyl group and acid anhydride. When producing component (b), slightly less acid anhydride is used for unreacted hydroxyl groups. Specifically, 0.95 times mole of acid anhydride is preferable with respect to an unreacted hydroxyl group, More preferably, it is 0.9 times mole or less. The reaction can also be promoted by setting the reaction temperature higher than usual or by lengthening the reaction time.

As reaction temperature in this case, 90 degreeC or more is preferable, More preferably, it is 100 degreeC or more.

In this invention, as for the ratio of (b) component, 1-50 mass parts is preferable with respect to 100 mass parts of (a) component, More preferably, it is 10-50 mass parts. When the ratio of (b) component does not reach 1 mass part and exceeds 50 mass parts, developability may be inadequate.

In addition, when mix | blending polyfunctional (meth) acrylates other than (a) component and (b) component, the total amount of (a) component and (b) component is 100 mass parts of all the polyfunctional (meth) acrylates. 5-80 mass% is preferable. If the total amount of (a) component and (b) component is less than 5 mass%, developability will run out, and when it exceeds 80 mass%, crosslinking density may fall.

Herein, the contents of the components (a) and (b) are obtained by using a reverse phase silica column by high-performance liquid chromatography analysis and correcting the area obtained by using an eluent of water / methanol system using a calibration curve. It is preferable. Examples of the measurement conditions in this case include the following.

[High-Speed Liquid Chromatograph Analysis Conditions]

Apparatus: SC-8010, manufactured by Tosso Corporation

Column: ODS-100z, manufactured by Tosso Corporation

  Inverse phase (ODS) column (inner diameter 4.6 mm, length 250 mm). Filled with reverse phase (ODS) silica particles having a particle diameter of 5 mu m.

5 μl of a solution of 100 mg of the composition dissolved in 10 ml of a solvent was fed to the column.

Analytical temperature: 40 ° C.

Eluent: 0.015% Phosphate: Methanol (volume ratio) = 45:55 (Initial) → 30:70 (30min) → 0: 100 (45-50min)

Flow rate of eluent: 1.0 ml / min

Detection wavelength: UV 210 nm

3. Other Ingredients

The composition of this invention can mix | blend other components as needed.

Specifically, you may mix | blend a photoinitiator, an organic solvent, an unsaturated group containing compound, alkali-soluble resin, a pigment, dye, an antifoamer, a leveling agent, an inorganic filler, an organic filler, etc. Moreover, you may add a small amount of antioxidant, a light stabilizer, a ultraviolet absorber, a polymerization inhibitor, etc. as needed.

Hereinafter, a photoinitiator, an organic solvent, an unsaturated group containing compound, and alkali-soluble resin are demonstrated in detail.

3-1 .Photoinitiator

Although the composition of this invention hardens | cures by irradiation of an active energy ray, as an active energy ray in this case, an electron beam, a visible ray, an ultraviolet-ray, etc. are mentioned. Among them, visible light or ultraviolet light is preferable because it does not require a special device and is simple.

When it is set as a visible light or ultraviolet curable composition, a photoinitiator is mix | blended with a composition. In addition, when setting it as an electron beam curable composition, it is not necessary to mix | blend a photoinitiator.

Examples of the photopolymerization initiator (hereinafter referred to as "(c) component") include a biimidazole compound, a benzoin compound, an acetophenone compound, a benzophenone compound, an α-diketone compound, a polynuclear quinone compound, and a xane Ton compounds, thioxanthone compounds, triazine compounds, ketal compounds, and the like.

Specific examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimi Dazole, 2,2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2 '-Bis (2-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'-tetraphenyl- 1,2'-biimidazole, 2,2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'- Bis (2,4-dibromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and 2,2'-bis (2,4,6-tribromo Phenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, etc. are mentioned.

When using a biimidazole type compound as (c) component, using a hydrogen donor together is more preferable at the point which can improve a sensitivity. The "hydrogen donor" as used here means the compound which can donate a hydrogen atom with respect to the radical generate | occur | produced from the biimidazole type compound by exposure.

Preferred hydrogen donors are mercaptan-based hydrogen donors, amine-based hydrogen donors and the like.

The mercaptan-based hydrogen donor is composed of a compound having a benzene ring or a heterocycle as a mother nucleus and having at least one, preferably one to three, more preferably one to two mercapto groups directly bonded to the mother nucleus. . Specific examples of the mercaptan-based hydrogen donor include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2,5-dimercapto-1,3,4-thiadiazole and 2-mercapto-2,5-dimethylaminopyridine etc. are mentioned. Among these mercaptan-based hydrogen donors, 2-mercaptobenzothiazole and 2-mercaptobenzoxazole are preferable, and 2-mercaptobenzothiazole is particularly preferable.

The amine-based hydrogen donor is composed of a compound having a benzene ring or a heterocycle as a mother nucleus, and having at least one, preferably 1 to 3, more preferably 1 to 2 amino groups directly bonded to the mother nucleus. Specific examples of the amine hydrogen donor include 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, Ethyl-4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile and the like.

Hydrogen donors may be used alone or in combination of two or more thereof, but spacers or pixels formed by using one or more mercaptan-based hydrogen donors and one or more amine-based hydrogen donors in combination are difficult to fall off from the substrate during development. In addition, the intensity and sensitivity of the spacer or the pixel are also preferable. Moreover, the hydrogen donor which has a mercapto group and an amino group simultaneously can also be used preferably.

Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin i-propyl ether, benzoin i-butyl ether, methyl 2-benzoylbenzoate and the like.

Specific examples of acetophenone compounds include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenyl Propane-1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-methylthiophenyl) -2-methyl-2-morpholino Propane-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-methyl-2-hydroxypropan-1-one, 1- (4-morpholinophenyl) -2-benzyl 2-dimethylaminobutan-1-one, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, etc. are mentioned.

Specific examples of the benzophenone compound include benzyl dimethyl ketone, benzophenone, 4,4'-bis (dimethylbenzophenone), 4,4'-bis (diethylbenzophenone), and the like.

Specific examples of the α-diketone compound include diacetyl, dibenzoyl, methylbenzoyl formate, and the like.

Specific examples of the multinuclear quinone compound include anthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1,4-naphthoquinone, and the like.

As a specific example of a xanthone type compound, xanthone, a thioxanthone, 2-chloro thioxanthone, etc. are mentioned.

Specific examples of the triazine-based compound include 1,3,5-tris (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2'-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (4'-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2'-methoxyphenyl) -s- Triazine, 1,3-bis (trichloromethyl) -5- (4'-methoxyphenyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s -Triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, and the like.

Among these, 1-hydroxycyclohexylphenyl ketone and 1- (4-methylthiophenyl) -2-methyl-2-morpholinopropane-1-one start polymerization reaction by irradiation of active energy ray even in a small amount. Since it promotes, it is preferably used in the invention.

(c) A component can be used individually or in combination of 2 or more types.

As a compounding ratio of (c) component, 0.5-20 mass parts is preferable with respect to 100 mass parts of solid content other than the photoinitiator in a composition. If it is less than 0.5 mass part, photocurability may become inadequate, and when it exceeds 20 mass parts, an exposure part may become easy to be damaged at the time of alkali image development. Moreover, as a ratio of (c) component, 2-10 mass% is more preferable at the point which can obtain the pattern with high precision.

3-2. Organic solvent

In this invention, an organic solvent can be mix | blended for the purpose of improving the applicability | paintability of a composition.

The organic solvent (hereinafter referred to as "(d) component") should just not react with each component of a composition. The organic solvent which has the boiling point of 80-200 degreeC is preferable at the point which is excellent in applicability | paintability, and the drying speed of the coating film obtained is suitable, and the organic solvent which has a boiling point of 100-170 degreeC is especially more preferable.

Specifically, For example, aromatic compounds, such as toluene and xylene; Fatty acid esters such as butyl acetate, benzyl acetate, propylene glycol monomethyl ether acetate and ethoxyethyl propionate; Cellosolves such as ethyl cellosolve and butyl cellosolve; Alkylene glycol ethers such as propylene glycol monomethyl ether; Alcohols such as ethanol, ethylene glycol and diethylene glycol; Ethers such as diethylene glycol dimethyl ether; Ketones such as methyl isobutyl ketone and cyclohexanone; Formamides such as N, N-dimethylformamide; lactams such as γ-butyrolactam and N-methyl-2-pyrrolidone; And lactones such as γ-butyrolactone.

(d) A component can be used individually or in combination of 2 or more types.

As a compounding ratio of (d) component, the ratio by which solid content concentration of a composition becomes 10-50 mass% is preferable.

3-3. Unsaturated group-containing compound

The composition of this invention can mix | blend unsaturated group containing compound (henceforth "(e) component") other than (a) component as needed.

As (e) component, for example, phenoxyethyl (meth) acrylate, carbitol (meth) acrylate, N-vinyl caprolactone, acryloyl morpholine, glycidyl (meth) acrylate, 2-hydride, for example Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, nonanediol diacrylate, Polyethylene glycol di (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, tribromophenyl (meth) acrylate, 2,2-bis (4- (meth) acryloyloxy Ethoxyphenyl) -propane, 2,2-bis (4- (meth) acryloyloxydiethoxyphenyl) -propane, 2,2-bis (4- (meth) acryloyloxytriethoxyphenyl)- Propane, ethylene glycol di (meth) acrylate, tribromophenyloxyethyl (meth) acrylate, trimetholpropane tri (meth) acrylate And pentaerythritol tetra (meth) acrylate, di (meth) acrylate of bisphenol A epoxy resin, various polyurethane poly (meth) acrylates, polyester poly (meth) acrylates, and the like.

The preferable compounding ratio of (e) component is the range of 0-50 mass% in a composition.

3-4. Alkali-soluble resin

As alkali-soluble resin (henceforth "(f) component") in this invention, it acts as a binder with respect to (f) component, and especially solubility with respect to the developing solution used in a developing process process, Especially preferably an alkaline developing solution It will not specifically limit, if it has.

Examples of the component (f) include an addition polymer, polyester, epoxy resin, polyether, and the like, and an addition polymer obtained by using an ethylenically unsaturated monomer as a polymer is preferable.

As the component (f), an alkali-soluble resin having a carboxyl group is preferable, and in particular, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as a "carboxyl group-containing unsaturated monomer") and an ethylenically unsaturated monomer copolymerizable therewith (" Copolymer (hereinafter referred to as "carboxyl group-containing copolymer") is preferred.

Examples of the carboxyl group-containing unsaturated monomers include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α-chloroacrylic acid and cinnamic acid; Unsaturated dicarboxylic acids or anhydrides thereof such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride and mesaconic acid; Trivalent or higher unsaturated polyvalent carboxylic acid or its anhydrides; Mono ((meth) acryloyloxyalkyl] of divalent or higher polyhydric carboxylic acid, such as succinic acid mono (2- (meth) acryloyloxyethyl) and phthalic acid mono (2- (meth) acryloyloxyethyl) Esters; And mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both terminals, such as? -Carboxypolycaprolactone mono (meth) acrylate. Of these carboxyl group-containing unsaturated monomers, ω-carboxypolycaprolactone monoacrylate and phthalic acid mono (2-acryloyloxyethyl) are sold under the trade names of Aronix M-5300 and M-5400 (Doagosei Co., Ltd.), respectively. It is becoming.

A carboxyl group-containing unsaturated monomer can be used individually or in mixture of 2 or more types.

Moreover, what is necessary is just to copolymerize with a carboxyl group-containing unsaturated monomer as a copolymerizable unsaturated monomer, Aromatic vinyl compound, unsaturated carboxylic ester, unsaturated imides, macromonomer which has a mono (meth) acryloyl group at the terminal, etc. are preferable. .

As an aromatic vinyl compound, styrene, (alpha) -methylstyrene, o-vinyl toluene, m-vinyl toluene, p-vinyl toluene, p-chlor styrene, o-methoxy styrene, m-methoxy styrene, p-methoxy styrene, 2 -Vinyl benzyl methyl ether, 3-vinyl benzyl methyl ether, 4-vinyl benzyl methyl ether, 2-vinyl benzyl glycidyl ether, 3-vinyl benzyl glycidyl ether, 4-vinyl benzyl glycidyl ether, and the like. have.

As unsaturated carboxylic acid ester, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl ( Meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (Meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) Acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, Methoxy triethylene glycol (meth) acrylate, Methoxy propylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6] decane-8-yl (meth) acrylate, 2 -Hydroxy-3-phenoxypropyl (meth) acrylate, glycerol mono (meth) acrylate, and the like.

Examples of the unsaturated imides include maleimide, N-phenylmaleimide, N-cyclohexyl maleimide, and the like.

Examples of macromonomers having a mono (meth) acryloyl group at the terminal include polymer molecular chains such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane. .

As a copolymerizable unsaturated monomer, in addition to the above, 2- (3,4,5,6- tetrahydrophthalimide) ethyl (meth) acrylate, 2- (2, 3- dimethyl maleimide) ethyl (meth) acrylate, etc. Imide (meth) acrylates; 2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 2-dimethylaminopropyl acrylate, 3-aminopropyl (meth) acrylate and 3 Unsaturated carboxylic acid aminoalkyl esters such as -dimethylaminopropyl (meth) acrylate; Unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate; Indenes such as indene and 1-methylindene; Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; Vinyl cyanide compounds such as (meth) acrylonitrile, α-chloroacrylonitrile and vinylidene cyanide; Unsaturated amides such as (meth) acrylamide, α-chloroacrylamide and N-2-hydroxyethyl (meth) acrylamide; And aliphatic conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene.

These copolymerizable unsaturated monomers can be used individually or in mixture of 2 or more types.

As the carboxyl group-containing copolymer, (meth) acrylic acid is an essential component, and optionally selected from the group of succinic acid mono (2- (meth) acryloyloxyethyl) and ω-carboxypolycaprolactone mono (meth) acrylates. A carboxyl group-containing unsaturated monomer component which further contains at least 1 sort (s) compound, styrene, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, At least one copolymer selected from the group of glycerol mono (meth) acrylate, N-phenylmaleimide, polystyrene macromonomer and polymethyl methacrylate macromonomer (hereinafter referred to as "carboxyl group-containing copolymer (α)"). Is preferred.

Specific examples of the carboxyl group-containing copolymer (α) include (meth) acrylic acid / methyl (meth) acrylate copolymers, (meth) acrylic acid / benzyl (meth) acrylate copolymers, and (meth) acrylic acid / 2-hydroxyethyl (meth). ) Acrylate / benzyl (meth) acrylate copolymer, (meth) acrylic acid / glycidyl (meth) acrylate copolymer, (meth) acrylic acid / glycidyl (meth) acrylate / styrene copolymer, (meth) Acrylic acid / methyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / methyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polystyrene Macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) a Acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethylmethacrylate macromonomer copolymer, methacrylic acid / styrene / benzyl ( Meta) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / styrene / allyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / styrene / benzyl (meth) acrylate / Glycerol mono (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylic Rate / N-phenylmaleimide And copolymers.

The copolymerization ratio of the carboxyl group-containing unsaturated monomer in a carboxyl group-containing copolymer is 5-50 mass% normally, Preferably it is 10-40 mass%. In this case, when the said copolymerization ratio is less than 5 mass%, the solubility with respect to the alkaline developing solution of the composition obtained tends to fall, while when it exceeds 50 mass%, the solubility with respect to an alkaline developing solution will become excessive, and when developing with alkaline developing solution, It tends to be easy to cause the spacer layer or the pixel to fall off from the substrate and to cause film roughness on the surface of the spacer.

As (f) component in this invention, since the crosslinking density of the cured film from which alkali-soluble resin which has an ethylenically unsaturated group in a side chain improves, it becomes excellent in the point which improves coating film strength, heat resistance, and chemical resistance, is preferable.

As alkali-soluble resin which has an ethylenically unsaturated group in a side chain, alkali-soluble resin which has a carboxyl group is preferable. As said resin, what added the unsaturated compound which has an epoxy group (henceforth "epoxy unsaturated compound") to the said carboxyl group-containing copolymer is mentioned.

Examples of the epoxy unsaturated compounds include epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate and cyclohexene oxide-containing (meth) acrylate.

As a method of addition reaction, it is good according to a conventional method, and can be manufactured by adding an epoxy unsaturated compound to a carboxyl group-containing copolymer in an organic solvent or a solvent free. What is necessary is just to select reaction temperature, reaction time, and a catalyst suitably according to each reaction as conditions of an addition reaction.

The weight average molecular weight (hereinafter, referred to as "Mw") of the component (f) is usually 3,000 to 300,000, preferably 5,000 to 100,000. In addition, a number average molecular weight (henceforth "Mn") is 3,000-60,000 normally, Preferably it is 5,000-25,000.

In addition, in this invention, Mw and Mn mean the value which carried out polystyrene conversion of the molecular weight measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran).

In the present invention, by using the (e) component having such specific Mw and Mn, a photosensitive resin composition excellent in developability can be obtained, whereby a pattern having a sharp pattern edge can be formed, and at the time of development, an unexposed part Residues, greasing, film residues, etc., on the substrates and the light shielding layers of the substrates are less likely to occur. In addition, ratio (Mw / Mn) of Mw and Mn of (e) component is 1-5 normally, Preferably it is 1-4.

(f) A component can be used individually or in combination of 2 or more types.

When (a) component, (b) component, or (e) component are mix | blended, (a) component, (b) component, and (e) component (hereinafter, these are collectively called a (meth) acrylate component) and (f As a ratio of a component, 10-90 mass% of (f) components are preferable based on the total amount of a (meth) acrylate component and (f) component, More preferably, it is 30-80 mass%. When the ratio of (f) component exceeds 90 mass%, since crosslinking density falls, there exists a tendency for coating film strength, heat resistance, and chemical-resistance to fall.

As a ratio in the composition of the total amount of a (meth) acrylate component and (f) component, 10-50 mass% is preferable in a composition. If this ratio is less than 10 mass%, the film thickness after prebaking will become too thin. On the other hand, if it exceeds 50 mass%, the viscosity of a composition will become high too much and applicability | paintability will become bad, or the film thickness after prebaking will become too thick.

4. Usage

The composition of the present invention can be used for various purposes. For example, coating materials, such as a composition for pattern formation, such as a resist, ink, and a coating material, etc. are mentioned.

Since the composition of this invention is excellent in alkali developability among these, it can be used suitably as a composition for pattern formation.

Since the composition of this invention has high exposure sensitivity, is very excellent in developability, and can form a precise and accurate pattern, it can be used suitably as a composition for pattern formation.

When using the composition of this invention as a composition for pattern formation, the composition which consists of (a), (b), (c), (d), and (f) component is preferable.

As a pattern formation method using the said composition, it is good according to the conventional method, after apply | coating a composition to a board | substrate and drying it to form a coating film, it irradiates and hardens an active energy ray through the mask which has a specific pattern shape from this, The method of developing an unhardened part with a developing solution, etc. are mentioned.

Glass and plastics etc. are mentioned as a board | substrate. As a developing solution, an alkaline developing solution is preferable and it is as showing later in a specific example.

As a composition for pattern formation, resist, such as an etching resist and a soldering resist, a columnar spacer in liquid crystal panel manufacture, the coloring composition for forming the pixel, a black matrix, etc. in a color filter, a color filter protective film, etc. are mentioned.

The composition of this invention can be used suitably for the columnar spacers in liquid crystal panel manufacture among these uses.

When using for a columnar spacer use, nonionic surfactant, such as polyoxyethylene lauryl ether, and fluorine-type surfactant can also be added to a composition in order to improve applicability | paintability and developability. Or you may add an adhesion | attachment adjuvant, a storage stabilizer, an antifoamer, etc. suitably as needed.

Hereinafter, the use of a columnar spacer (hereinafter, simply referred to as "spacer") will be described.

4-1. Spacer

The spacer is formed by the photocurable coating film of the composition by the port lithography method. Although the said spacer can be formed in arbitrary locations of a liquid crystal panel board | substrate, it is generally formed in the black matrix area | region which is a light shielding part of a color filter, or a TFT electrode.

As a method of forming a spacer, according to the conventional method, it is good, for example, after apply | coating the composition of this invention to the film thickness necessary for forming a cell gap on a board | substrate, such as glass, and heating (simplified by "prebaking" hereafter). And) to dry the coating film, and to form the coating film through a process of exposure, development, and post-heating (hereinafter, simply referred to as "post baking").

When apply | coating a composition on a board | substrate, it apply | coats a little thick with respect to the design value of a cell gap in consideration of film | membrane reduction or deformation by image development, postbaking, etc. Specifically, the thickness after the prebaking is more preferably set to 6 to 7 µm so as to be 5 to 10 µm.

Examples of the coating method include a printing method, a spray method, a roll coating method, a bar coating method, a curtain coating method, a spin coating method, a die coating method (slit coat method), and the like. The die coat method is used.

After apply | coating a composition on a board | substrate, prebaking is performed. As temperature and time in this case, about 5 to 15 minutes are mentioned at 50-150 degreeC.

Light is irradiated through the mask which has a predetermined pattern shape for forming a spacer in the coating film surface after prebaking.

Ultraviolet light or visible light is preferable, and the light to be used uses wavelength light of 240 nm-410 nm obtained from a high pressure mercury lamp, a metal halide lamp, or the like.

Although light irradiation conditions depend on the kind of light source, the absorption wavelength of the photoinitiator to be used, the film thickness of a coating film, etc., it is preferable to make the light irradiation amount into 50-600mJ / cm <2> in general. If the amount of light irradiation is less than 50 mJ / cm 2, it becomes poor in curing and the exposed portion tends to fall off during development. On the other hand, if the amount of light irradiation is larger than 600 mJ / cm 2, a precise spacer pattern tends to be difficult to be obtained.

After irradiating the said coating film surface, the unexposed part is removed with a developing solution.

As a developing solution, the aqueous solution of an alkali compound can be used. As an alkaline compound, potassium hydroxide, sodium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, ammonia, tetramethylammonium hydroxide, etc. are mentioned, for example. In addition, in order to accelerate the development speed, an appropriate amount of a water-soluble organic solvent such as methanol, ethanol, isopropanol and benzyl alcohol and various surfactants may be added to the developing solution.

The developing method may be any of a puddle method, a dipping method and a spray method. After the development, the pattern portion is washed with water for 0.5 to 1.5 minutes, dried by compressed air or the like to obtain a spacer pattern.

The obtained spacer pattern is post-baked in the temperature range of 150-350 degreeC with heating apparatuses, such as a hotplate and oven, and the liquid crystal panel spacer of this invention is obtained.

Post-baking can volatilize the residual solvent and the water absorbed at the time of image development, and can improve the heat resistance of a spacer. Although the film thickness of a spacer changes with the cell gap setting value of a liquid crystal panel, it is designed so that it may become 3 to 5 micrometers generally after postbaking.

When using the composition of this invention for spacer manufacture, compression of a planar indenter (indenter which formed the plane of 100 micrometer x 100 micrometers) at room temperature using the ultramicro hardness tester (made by Pitsin Instruments, H-100C) It is preferable that the elastic strain ((elastic strain / total strain amount) × 100) measured when the load is 0.2 GPa is 60% or more.

By using such a composition, it has sufficient hardness which is hard to be plastically deformed with respect to a compressive load at room temperature, and has the flexibility to be able to follow liquid crystal shrinkage and expansion in the use environment temperature range of a liquid crystal display device. Therefore, the liquid crystal panel substrate obtained by the present invention can form an accurate and uniform cell gap without causing plastic deformation when the substrate is adhered by the room temperature cell crimping method, and particularly the room temperature cell crimping in the ODF method. Also when using, it can use preferably.

(Effects of the Invention)

Since the composition of this invention requires (a) component and (b) component which are excellent in sclerosis | hardenability and alkali developability, when used as a composition for active-energy-ray-curable pattern formation, exposure exposure is high, developability is good, and it is precise Accurate pattern can be formed, and after curing, all physical properties such as coating film strength, heat resistance and chemical resistance are excellent.

In addition, the composition of the present invention is excellent in that the spacer shape after curing tends to be tapered and the elasticity is high, so that plastic deformation of the pattern is unlikely to occur, and is particularly suitable for forming columnar spacers. Since the property is excellent, the ratio of component (f) to solid content of the composition except component (d) can be reduced.

FIG. 1: shows the shape of the side surface which observed the columnar spacer used for evaluation of an elastic strain with the electron microscope.

This invention relates to the active-energy-ray-curable composition containing the said (a) component and (b) component as an essential component.

As a ratio of each component in a composition, it is preferable to contain 1-50 mass parts of (b) component with respect to 100 mass parts of (a) component.

Moreover, as hydroxy polyfunctional (meth) acrylate in (a) component and (b) component, dipentaerythritol pentaacrylate is preferable.

It is preferable to contain a photoinitiator further as a composition of this invention, and it is preferable to contain an organic solvent further.

The composition of the present invention can be used for various uses of pattern forming compositions such as inks, paints, and resists, and in particular, it is preferably used as a pattern forming composition because of its excellent alkali developability.

It is preferable to further contain alkali-soluble resin as a composition for pattern formation.

Moreover, it can use suitably for manufacture of a columnar spacer also in the composition for pattern formation.

Moreover, after this composition is apply | coated to a board | substrate and a coating film is formed, pattern formation which irradiates and hardens an active energy ray through the mask which has a specific pattern shape from this, and develops an uncured part with a developing solution It is about a method.

(Example)

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

In addition, below, a "part" means a mass part and "%" means the mass%.

○ Production example 1

(1) Esterification reaction

As a starting material, 400 g (1.58 mol) of dipentaerythritol and 821 g (11.4 mol) of acrylic acid were used. 775 g of toluene is used as a solvent, and the raw material, 17 g of sulfuric acid as a catalyst, and 2.2 g of hydroquinone monomethyl ether (hereinafter referred to as "MQ") as a polymerization inhibitor are esterified at 90 ° C for 6 hours. Reaction was carried out.

(2) neutralization treatment

After completion of the reaction, 1690 g of toluene was added, the reaction solution was filtered using a filter paper, and then washed with distilled water 875 g. Then, 800 g of 10% aqueous NaOH solution was added to the reaction solution after washing with water, and at room temperature for 1 hour. The neutralization process was performed on condition of.

(3) water treatment

After the neutralization treatment, the organic layer and the water layer were separated, and then the water layer was removed, and further 360 g of distilled water was added for the purpose of removing excess NaOH. Thereafter, the organic layer and the water layer were separated, and then the water layer was removed. Then, toluene which is a solvent was distilled off under reduced pressure of 50 mmHg or less, and the acrylic acid ester (hydroxyl value 36 mgKOH / g) was obtained.

(4) acid denaturation

250 g of the acrylic acid ester obtained in (3) was injected into a glass flask, 16 g of succinic anhydride and 0.13 g of MQ were added thereto, and the temperature was raised to 85 ° C. After adding 1.3 g of triethylamine which is a catalyst therein, reaction was performed for 4 hours. The reaction was carried out in a mixed atmosphere of air / nitrogen to obtain a compound having an acid value of 34 mg KOH / g (hereinafter referred to as "ab1").

The obtained compound was analyzed by high performance liquid chromatography under the following conditions. As a result, (a) component was 30% and (b) component was 8% in 100 parts of all the acrylic acid esters.

High-speed liquid chromatograph measurement condition

Apparatus: SC-8010, manufactured by Tosso Corporation

Column: ODS-100z

  Toso Corporation brand name ODS-100z, diameter 4.6 mm, length 250 mm reverse phase (ODS) column. Filled with ODS Silica with a particle diameter of 5 μm.

· Temperature: 40 ℃

Eluent: 0.015% Phosphoric acid water: Methanol = 45:55 (Initial) → 30:70 (30min) → 0: 100 (45-50min)

Flow rate: 1.0 mL / min

Detector: UV 210 nm

○ Production Example 2

(1) Esterification reaction

Except having made acrylic acid which is a raw material into 683g (9.48mol), all esterification reaction was performed according to manufacture example 1.

(2) neutralization treatment

In each case, neutralization treatment was performed.

(3) water treatment

Both were washed with water according to Production Example 1 to obtain an acrylic acid ester (a hydroxyl value of 72 mgKOH / g).

(4) acid denaturation

250 g of the acrylic acid ester obtained in (3) was injected into a glass flask, 32 g of succinic anhydride and 0.13 g of metoquinone were added thereto, and the temperature was elevated to 85 ° C. After adding 1.3 g of triethylamine which is a catalyst therein, reaction was performed for 4 hours. The reaction was carried out in a mixed atmosphere of air / nitrogen to obtain a compound having an acid value of 68 mgKOH / g (hereinafter referred to as "ab2"). As a result of analyzing the obtained compound by a high performance liquid chromatography, (a) component was 50% and (b) component was 15% in 100 parts of all acrylic acid esters.

○ Production Example 3 [Production of (f) Component]

In a separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping lot, and a nitrogen inlet tube, 52% benzyl methacrylate, 23% acrylic acid, and diethylene glycol dimethyl ether (hereinafter referred to as "DMDG") are monomers. 2 times and 2,2'- azobis (2-methylbutyronitrile) were added 5% with respect to the total amount of a monomer with respect to the total amount, and it melt | dissolved uniformly. Then, it stirred at 85 degreeC for 2 hours under nitrogen stream, and made it react at 100 degreeC again for 1 hour. The obtained solution was 25% glycidyl methacrylate, triethylamine was 10% to glycidyl methacrylate, hydroquinone was 1% to glycidyl methacrylate, and the injected monomer and glycy DMDG was further added so that the combined weight of dimethyl methacrylate could be 35%, and it stirred at 100 degreeC for 5 hours, and obtained the target copolymer solution (solid content concentration 31.5%).

Mw of the obtained (f) component (henceforth "f1") was 21,200, and the acid value was 84 mgKOH / g and the hydroxyl value was 96 mgKOH / g.

○ Comparative Production Example 1 [Preparation of (a) Component]

20 g of the acrylic acid ester [compound before acid modification] prepared in Preparation Example 2 was changed from 9/1% to 6/4% of hexane / ethyl acetate as a developing solution and fed to a silica gel column. Fractions containing dipentaerythritol hexaacrylate (I) and dipentaerythritol pentaacrylate (II) were fractionated, respectively. 0.020 g of metoquinone was added to each of the obtained fractions, and the resultant was concentrated. As a result, dipentaerythritol pentaacrylate (II) having a hydroxyl value of 1 or less of dipentaerythritol hexaacrylate (I) and a hydroxyl value of 103 mgKOH / g was obtained. 8.0g was obtained. In addition, according to the high performance liquid chromatography analysis, the purity of both compounds was 95 area% or more.

9.0 g of (II), 1.47 g of succinic anhydride and 0.01 g of metoquinone were put into a 25 ml glass flask equipped with a stirring device, a thermometer, and a water-cooled condenser, and the temperature was raised to 80 ° C. After adding 0.05 g of triethylamine as a catalyst therein, the reaction was carried out for 4 hours under a mixed atmosphere of air / nitrogen. The obtained reactant (III) had an acid value of 91 mgKOH / g. In addition, the ratio of the component (a) contained in the reaction material was 95 area% according to the high performance liquid chromatography analysis, and the ratio of the component (b) was 0.5 area%.

The obtained polyfunctional (meth) acrylate (a1) containing about 40% of component (a) without mixing component (b) by mixing the obtained (I) and (III) by weight part at a ratio of 6: 4 Got it.

○ Examples 1-3, Comparative Examples 1-3 (spacer composition)

(A)-(d) component and (f) component were mixed according to the conventional method, and the composition for spacers or a protective film was adjusted so that it may become the ratio which the following Tables 1 and 2 show.

Evaluation shown below was performed using the obtained composition. These results are shown in Tables 1 and 2.

<Developing>

The composition shown in Tables 1 and 2 was apply | coated with a spin coater on the 10-cm-square chrome mask glass substrate, this coating film was dried for 10 minutes with the 80 degreeC ventilation dryer, and the coating film of 5 micrometers of dry film thicknesses was formed. The obtained coating film was spray-developed by 0.5 wt% sodium carbonate aqueous solution, and time until it melt | dissolved completely was measured, and the following reference | standard evaluated.

○: dissolves within 30 seconds.

?: Dissolves within 60 seconds.

X: It does not melt | dissolve within 60 second.

<Evaluation of Elastic Strain>

The composition shown in Tables 1 and 2 was apply | coated with a spin coater on the 10-cm-square chrome mask glass substrate, this coating film was dried for 10 minutes with the 80 degreeC ventilation dryer, and the coating film of 6 micrometers of dry film thicknesses was formed. The photomask was arrange | positioned at the distance of 100 micrometers from this coating film, and the ultraviolet-ray was irradiated with the intensity | strength (365 nm roughness conversion) of 300mJ / cm <2> with an ultrahigh pressure mercury lamp by a proximity aligner. Subsequently, it immersed for 60 second in 0.5 wt% sodium carbonate aqueous solution of 23 degreeC of liquid temperature, and developed alkali, and removed only the unhardened part of the coating film. Then, heat processing was performed by leaving a board | substrate to stand in 200 degreeC atmosphere for 30 minutes, and the columnar spacer of 5 micrometers in height and 10-20 micrometers in diameter was formed.

Compression load using an ultra-small hardness meter (manufactured by Fitzshine Instruments Co., Ltd., H-100C) equipped with a planar indenter (a indenter having a plane of 100 µm x 100 µm) at room temperature of the obtained columnar spacer at room temperature. It calculated as [(elastic deformation amount / total deformation amount) x100] when measured on the conditions which become this 0.2GPa.

<Shape>

The ratio (S2 / S1) of the upper surface area S2 and the lower surface area S1 which measured and measured the columnar spacer used for evaluation of elastic strain by the electron microscope was calculated (refer FIG. 1). When this value exceeds 100, since it becomes a reverse taper shape, elastic strain will fall easily.

The number of the column of the composition in Table 1 means a part, and ab1-ab2, a1, and f1 were shown as ratio of solid content.

In addition, the symbol in Table 1 and 2 means the following.

Irg907: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, Irgacure907 manufactured by Chiba Specialty Chemicals Co., Ltd.

M-402: Dipentaerythritol pentaacrylate / dipentaerythritol hexaacrylate mixture (ratio: about 30/70) Aaronia M-402 manufactured by Toagosei Co., Ltd.

The (a) and (b) component contained in the composition of Table 1 were put together in the following Table 2.

The compositions of Examples 1-3 were very excellent in developability and there was no residue on a board | substrate at all. In addition, these hardened | cured materials had sufficient elastic strain for spacers or a protective film.

On the other hand, Comparative Examples 1-2 which do not have component (b) are inferior to developability and a residue a little, and Comparative Example 3 using commercially available polyfunctional acrylate had insufficient residue and developability.

The composition of this invention can be used for various uses, such as an ink, a paint, and a resist, and can be used suitably as a composition for pattern formation, such as a resist.

Moreover, the composition of this invention can be used suitably as a coloring composition for forming the columnar spacer in the liquid crystal panel manufacture, the composition for color filter protective films, the pixel, black matrix, etc. in a color filter.

Claims (9)

Compound (a) which added an acid anhydride to the compound which has three or more (meth) acryloyl groups and a hydroxyl group, and three or more (meth) s to the (meth) acryloyl group of one or more (meth) acryloyl groups of the said (a) component. An active energy ray-curable composition comprising a compound (b) in which a hydroxyl group of a compound having an acryloyl group and a hydroxyl group is added as an essential component. The active energy ray-curable composition according to claim 1, wherein 1 to 50 parts by mass of the component (b) is contained with respect to 100 parts by mass of the component (a). The active energy ray-curable composition according to claim 1 or 2, wherein the compound having at least three (meth) acryloyl groups and hydroxyl groups is dipentaerythritol pentaacrylate. The active energy ray-curable composition according to claim 1 or 2, further comprising a photopolymerization initiator. The active energy ray-curable composition according to claim 1 or 2, further comprising an organic solvent. It consists of the composition of Claim 1 or 2, The composition for active energy ray hardening type pattern formation characterized by the above-mentioned. The composition for forming an active energy ray-curable pattern according to claim 6, further comprising an alkali-soluble resin. It consists of the composition of Claim 6, The composition for active energy ray hardening type pattern formation for columnar spacer manufacture. After apply | coating the composition of Claim 6 to a board | substrate and forming a coating film, from this, an active energy ray is irradiated and hardened | cured through the mask which has a specific pattern shape, and the uncured part is developed with the developing solution, It is characterized by the above-mentioned. Pattern formation method.

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