JPWO2007043430A1 - Active energy ray-curable composition - Google Patents

Abstract

When used as a composition for forming an active energy ray-curable pattern, the exposure sensitivity is high, the developability is good, and a precise and accurate pattern can be formed. Provided is an active energy ray-curable composition or a pattern forming method excellent in various physical properties such as chemical properties. The composition comprises a compound (a) obtained by adding an acid anhydride to a compound having three or more (meth) acryloyl groups and a hydroxyl group, and an acid anhydride or / and an acid anhydride hydrolyzate (b). It is a composition containing as an essential component, Comprising: (b) A component is contained in the ratio of 0.1-20 mass parts with respect to 100 mass parts of (a) component. In the method, the composition is applied to a substrate to form a coating film, and then the active energy ray is irradiated and cured from above through a mask having a specific pattern shape, and an uncured portion is developed with a developer. Consists of developing.

Description

  The present invention relates to an active energy ray-curable composition, and the composition of the present invention can be used for various uses of pattern forming compositions such as inks, paints and resists, and is particularly excellent in alkali developability. It can be preferably used as a forming composition and belongs to these technical fields.

  Conventionally, as color filters used in liquid crystal panel production, those in which pixels such as red, green, and blue are formed on a glass substrate by methods such as dyeing, printing, electrodeposition, and pigment dispersion are used. It has been.

Among conventional color filters, a color filter using a dyeing method is manufactured by forming an image using a photosensitive resin obtained by mixing dichromate as a photosensitizer with gelatin, polyvinyl alcohol, or the like, and then dyeing the image. In the case of this dyeing method, in order to form a multicolor image on the same substrate, there is a problem that an anti-dyeing process is essential and the process becomes complicated. In addition, since a dye is used, the light resistance is inferior, and there is a problem that dichromic acid used as a photosensitizer is not desirable from the viewpoint of pollution prevention.
A color filter by a printing method is manufactured by transferring a thermosetting ink or a photocurable ink to a glass substrate by a method such as screen printing or flexographic printing. Since the printing method does not require image formation and dyeing, the process is simple. However, on the other hand, a high-definition image cannot be obtained, and there is a problem in terms of ink smoothness.
A color filter by an electrodeposition method is manufactured by immersing a glass substrate provided with an electrode in a bath containing a pigment or dye, and attaching a hue by electrophoresis. The color filter by electrodeposition is excellent in smoothness, but has a problem that it is difficult to form a complicated pattern because it is necessary to previously provide an electrode on a glass substrate.

  On the other hand, a color filter by a pigment dispersion method is produced by forming an image with a colored resist in which a pigment is dispersed in a photocurable compound. The pigment dispersion method has an advantage that a highly heat-resistant color filter can be produced, dyeing is unnecessary, and a highly accurate image can be formed.

  For this reason, the pigment dispersion method is currently the mainstream of color filter manufacturing technology. However, in the pigment dispersion method, when an image is formed with a colored resist containing a large amount of pigment, the pigment tends to remain on the substrate (residues). Have the problem of adhesion). In manufacturing a color filter, red, green, and blue color pixels are sequentially formed. Therefore, the adhesion of the residue causes deterioration in color reproducibility of the color filter, smoothness of the coating film, and the like.

  In order to prevent such adhesion of residues, conventionally, methods such as control of development time, adjustment of developer concentration and removal with a brush or the like have been performed.

  In addition to the methods described above, a method of adding an organic carboxylic acid to a colored resist (Patent Documents 1 and 2), a method of improving solubility by increasing the acid value of a binder resin, or a molecular weight of 800 or less A method of adding an organic carboxylic acid anhydride to a colored resist (Patent Document 3) has also been proposed.

JP-A-4-369653 JP-A-5-343331 JP-A-8-292316

However, the control of the development time, the adjustment of the developer concentration, and the removal with a brush or the like cannot completely remove the occurrence of adhesion of residues, and the workability is reduced, the cost is increased, and the developer waste liquid It also had problems such as processing.
In addition, the method of adding organic carboxylic acid, the method of increasing the acid value of the binder resin, and the method of adding an acid anhydride completely prevent the occurrence of residue adhesion when the blending ratio of the binder resin is reduced. I couldn't.

  The object of the present invention is to provide an exposure pattern with high exposure sensitivity and good developability when used as an active energy ray-curable pattern forming composition, and can form a precise and accurate pattern. The object is to provide an active energy ray-curable composition or a pattern forming method which is excellent in various physical properties such as strength, heat resistance and chemical resistance. Furthermore, when used for color filter production in liquid crystal panel production, in addition to the above-mentioned performance, an active energy ray-curable coloring composition or pattern formation that can reduce the residue of the colored layer when the color filter pixels are formed It is to provide a method.

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

The present invention relates to a compound (a) obtained by adding an acid anhydride to a compound having three or more (meth) acryloyl groups and a hydroxyl group (hereinafter referred to as “component (a)”), an acid anhydride and / or an acid anhydride. A hydrolyzate of the product (b) [hereinafter referred to as “component (b)”] as an essential component, wherein the component (b) is 0.1 to 100 parts by mass of the component (a). It is related with the active energy ray hardening-type composition contained in the ratio of 20 mass parts.
Hereinafter, the component (a), the component (b) and other components will be described.

1. Component (a) Component (a) is a compound obtained by adding an acid anhydride to a compound having three or more (meth) acryloyl groups and a hydroxyl group (hereinafter referred to as “hydroxy polyfunctional (meth) acrylate”).
Specific examples of the hydroxy polyfunctional (meth) acrylate include ditrimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate.

As a hydroxy polyfunctional (meth) acrylate in this invention, the compound which has a 4 or more (meth) acryloyl group which does not have the hydroxyl group byproduced in a manufacturing process may be included. Examples thereof include pentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate. In general, pentaerythritol tri (meth) acrylate is contained in pentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) acrylate is contained in dipentaerythritol hexa (meth) acrylate.
These compounds having 4 or more (meth) acryloyl groups not having a hydroxyl group may be contained in the hydroxy polyfunctional (meth) acrylate component in a proportion of 20 to 80% by mass.

  Examples of the method for producing the hydroxy polyfunctional acrylate include a method of heating and stirring (meth) acrylic acid and alcohol in the presence of an acidic catalyst. Examples of the acidic catalyst include sulfuric acid, paratoluenesulfonic acid, methanesulfonic acid, and the like. The reaction temperature may be appropriately set according to the compound to be used and the purpose, but is preferably 70 ° C to 140 ° C. When the reaction temperature is lower than 70 ° C., the reaction is slowed. On the other hand, when the reaction temperature exceeds 140 ° C., the reaction system becomes unstable, and impurities may be generated or gelation may occur.

  In the reaction, it is preferable to use an organic solvent having low solubility with water produced by the esterification reaction and promote dehydration while azeotropically distilling water. Preferred organic solvents include aromatic hydrocarbons such as toluene, benzene and xylene, aliphatic hydrocarbons such as hexane and heptane, and ketones such as methyl ethyl ketone and cyclohexanone. Further, the organic solvent may be distilled off under reduced pressure after the reaction, but when a solvent having no odor problem is used, it may be used as it is without being distilled off for adjusting the viscosity of the composition. .

  Specific examples of the alcohol in the reaction include polyols such as ditrimethylolpropane, pentaerythritol and dipentaerythritol, and alkylene oxide adducts of these polyols. Examples of the alkylene oxide include ethylene oxide and propylene oxide.

  Moreover, a polymerization inhibitor can be added to the reaction solution for the purpose of preventing polymerization of the resulting (meth) acrylic acid ester. Examples of such polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, 2,6-ditertiary butyl-p-cresol, and phenothiazine.

(A) A component is synthesize | combined by reaction of the said hydroxy polyfunctional (meth) acrylate and an acid anhydride.
Examples of the acid anhydride include succinic anhydride, 1-dodecenyl succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetramethylene maleic anhydride, One in the same molecule such as tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride and trimellitic anhydride Compounds having an acid anhydride group, as well as pyromellitic anhydride, phthalic anhydride dimer, diphenyl ether tetracarboxylic dianhydride, diphenyl sulfone tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride and 1,2 , 3,4 Tantetracarboxylic dianhydride, diphenyl ether tetracarboxylic anhydride and trimellitic anhydride / ethylene glycol ester (commercially available products include, for example, Shin Nippon Rika Co., Ltd., trade name Ricacid TMEG-100) Examples include compounds having two acid anhydride groups in the same molecule.
Among these, a compound having one acid anhydride group in the same molecule is preferable.

(A) As a manufacturing method of a component, what is necessary is just to follow a conventional method.
For example, a method in which a hydroxy polyfunctional (meth) acrylate and an acid anhydride are reacted at 60 to 110 ° C. for 1 to 20 hours in the presence of a catalyst can be used.
Examples of the catalyst in this case include N, N-dimethylbenzylamine, triethylamine, tributylamine, triethylenediamine, benzyltrimethylammonium chloride, benzyltriethylammonium bromide, tetramethylammonium bromide, cetyltrimethylammonium bromide, and zinc oxide.

  The proportion of the component (a) in the composition may be appropriately selected according to the purpose and application, but is preferably 10 to 80% by mass in the composition.

2. (B) Component (b) A component is an acid anhydride or / and a hydrolyzate of an acid anhydride.
Examples of the acid anhydride in the component (b) include the same compounds as the acid anhydrides mentioned as the raw material for the component (a). Examples of the acid anhydride hydrolyzate include dicarboxylic acids obtained by ring opening of an acid anhydride by hydrolysis.
The acid anhydride in component (b) may be the same compound or different compound used in the synthesis of component (a).
In addition, as the component (b), an unreacted acid anhydride when the component (a) is synthesized or a compound in which the unreacted acid anhydride is hydrolyzed during the reaction may be used as it is. You may mix | blend separately.

  The ratio of (b) component is 0.1-20 mass parts with respect to 100 mass parts of (a) component, Preferably it is 0.1-10 mass parts. (B) When the ratio of a component is less than 0.1 mass part, developability will run short and adhesion of a residue will increase. Moreover, when it exceeds 20 mass parts, the pigment dispersibility fall and the stability of a dispersion liquid will fall.

  Here, the content of (a) is a high-performance liquid chromatographic analysis, the area obtained by using a reverse phase silica column and using a water / methanol eluent, and using a calibration curve Thus, those obtained by compensation are preferred. The measurement conditions in this case can include the following.

[High-performance liquid chromatographic analysis conditions]
・ Device: SC-8010 manufactured by Tosoh Corporation
Column: ODS-100z manufactured by Tosoh Corporation
Reversed phase (ODS) column (inner diameter 4.6 mm, length 250 mm). Packed with reverse phase (ODS) silica particles with a particle size of 5 μm.
-Supply 5 μl of a solution of 100 mg of the composition in 10 ml of solvent to the column.
・ Analysis temperature: 40 ° C
Eluent: 0.015% phosphoric acid water: methanol (volume ratio) = 45: 55 (Initial) → 30: 70 (30 min) → 0: 100 (45-50 min)
・ Eluent flow rate: 1.0 ml / min
・ Detection wavelength: UV 210nm

  Next, the content of (b) was corrected by using an analytical curve for the area obtained by measurement using an anion exchange column and a carbonic acid-based eluent in ion chromatographic analysis. What was obtained was preferable. The measurement conditions in this case can include the following.

[Ion chromatographic analysis measurement conditions]
・ Device: DIONEX DX-300 manufactured by DIONEX
Separation column: IonPacAS4A-SC (anion exchange column using ethylene vinylbenzene-divinylbenzene polymer as a base material and quaternary alkanolamine as an ion exchange group) manufactured by DIONEX Co., Ltd.
Guard column: IonPacAG4A-SC manufactured by DIONEX (anion exchange column using a quaternary alkanolamine as an ion exchange group based on an ethylene vinylbenzene-divinylbenzene polymer)
_{Eluent: 1.8mM-Na 2 CO 3 /1.7mM-NaHCO} 3
・ Flow rate: 1.5ml / min
・ Suppressor: ASRS-ULTRA-II (recycle mode, current value 50 mA)
・ Detector: Electrical conductivity ・ Sample injection volume: 50 μL
Procedure: After the sample was diluted with 10 times the amount of toluene, 5 times the amount of water was added and shaken for 10 minutes. After standing, the lower layer (aqueous layer) was separated and used as a measurement sample.

  In addition, when the component (b) is an acid anhydride, some may be partially hydrolyzed during ion chromatographic analysis, but if grasped as the total amount of the acid anhydride and the hydrolyzate of the acid anhydride, There is no problem in the present invention.

3. Other components The composition of this invention can mix | blend other components as needed.
Specifically, a photopolymerization initiator, an organic solvent, an unsaturated group-containing compound, an alkali-soluble resin, a pigment, a dye, an antifoaming agent, a leveling agent, an inorganic filler, an organic filler, and the like can be blended. If necessary, a small amount of an antioxidant, a light stabilizer, an ultraviolet absorber, a polymerization inhibitor, and the like may be added.
Hereinafter, the photopolymerization initiator, the organic solvent, the unsaturated group-containing compound, and the alkali-soluble resin will be described in detail.

3-1. Photopolymerization initiator The composition of the present invention is cured by irradiation with active energy rays. Examples of the active energy rays in this case include electron beams, visible rays, and ultraviolet rays. Among these, visible light or ultraviolet light is preferable because it does not require a special device and is simple.
When a visible light or ultraviolet curable composition is used, a photopolymerization initiator is added to the 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 “component (c)”] include biimidazole compounds, benzoin compounds, acetophenone compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, xanthone compounds. Thioxanthone compounds, triazine compounds and ketal compounds.

  Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 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 2,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′- Bis (2-bromophenyl) -4,4 ′, , 5′-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-tribromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole and the like.

When a biimidazole compound is used as the component (c), it is preferable to use a hydrogen donor in view of further improving sensitivity. The “hydrogen donor” as used herein means a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure.
As the hydrogen donor, mercaptan hydrogen donors and amine hydrogen donors are preferable.

  The mercaptan-based hydrogen donor is composed of a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having one or more, preferably 1 to 3, more preferably 1 to 2, mercapto groups directly bonded to the mother nucleus. Specific examples of mercaptan hydrogen donors include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2,5-dimercapto-1,3,4-thiadiazole and 2-mercapto-2,5. -Dimethylaminopyridine etc. can be mentioned. Of 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 heterocyclic ring as a mother nucleus and having 1 or more, preferably 1 to 3, more preferably 1 to 2 amino groups directly bonded to the mother nucleus. Specific examples of amine-based hydrogen donors include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, and ethyl-4. -Dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile, etc. can be mentioned.

  The hydrogen donors can be used alone or in admixture of two or more, but one or more mercaptan hydrogen donors and one or more amine hydrogen donors can be used in combination. The formed spacer or pixel is preferable because it is difficult to drop off from the substrate during development, and the strength and sensitivity of the spacer or pixel are high. Also, a hydrogen donor having a mercapto group and an amino group at the same time can be preferably used.

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

  Specific examples of acetophenone compounds include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1- ON, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-methylthiophenyl) -2-methyl-2-morpholinopropan-1-one, -[4- (2-hydroxyethoxy) phenyl] -2-methyl-2-hydroxypropan-1-one, 1- (4-morpholinophenyl) -2-benzyl-2-dimethylaminobutan-1-one, Examples include 1-hydroxycyclohexyl phenyl ketone and 2,2-dimethoxy-1,2-diphenylethane-1-one. You can.

  Specific examples of the benzophenone compounds 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, methylbenzoylformate, and the like.

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

  Specific examples of the xanthone compound include xanthone, thioxanthone, 2-chlorothioxanthone and the like.

  Specific examples of the triazine 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 and 2- (4-n-butoxyv) Yl) -4,6-bis (trichloromethyl) -s-triazine and the like.

Among these, 1-hydroxycyclohexyl phenyl ketone and 1- (4-methylthiophenyl) -2-methyl-2-morpholinopropan-1-one initiate and accelerate the polymerization reaction by irradiation with active energy rays even in a small amount. Therefore, it is preferably used in the invention.
(C) A component can be used individually or in combination of 2 or more types.

  (C) As a mixture ratio of a 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 parts by mass, the photocurability may be insufficient. On the other hand, if it exceeds 20 parts by mass, the exposed part may be easily broken during alkali development. Furthermore, as a ratio of (c) component, 2-10 mass% is more preferable at the point which can obtain a highly accurate pattern.

3-2. Organic Solvent In the present invention, an organic solvent can be blended for the purpose of improving the coating property of the composition.
The organic solvent [hereinafter referred to as “component (d)”] may be any one that does not react with each component of the composition. An organic solvent having a boiling point of 80 to 200 ° C. is preferable, and an organic solvent having a boiling point of 100 to 170 ° C. is more preferable because the coating property is excellent and the drying speed of the obtained coating film is moderate.
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; propylene glycol monomethyl ether Alcohol glycol ethers such as ethanol, alcohols such as 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; γ-butyrolactam and N-methyl-2 -Lactams such as pyrrolidone; and lactones such as γ-butyrolactone.
(D) A component can be used individually or in combination of 2 or more types.
(D) As a mixture ratio of a component, the ratio from which the solid content concentration of a composition will be 10-50 mass% is preferable.

3-3. Unsaturated Group-Containing Compound An unsaturated group-containing compound other than the component (a) [hereinafter referred to as “component (e)”] can be blended in the composition of the present invention, if necessary.
Examples of the component (e) include phenoxyethyl (meth) acrylate, carbitol (meth) acrylate, N-vinylcaprolactone, acryloylmorpholine, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl. (Meth) acrylate, 1,4-butanediol mono (meth) acrylate, 1,6-hexanediol di (meth) acrylate, nonanediol diacrylate, polyethylene glycol di (meth) acrylate, 2-hydroxy-3-phenyloxy Propyl (meth) acrylate, tribromophenyl (meth) acrylate, 2,2-bis (4- (meth) acryloyloxyethoxyphenyl) -propane, 2,2-bis (4- (meth) acryloyloxydie) Xylphenyl) -propane, 2,2-bis (4- (meth) acryloyloxytriethoxyphenyl) -propane, ethylene glycol di (meth) acrylate, tribromophenyloxyethyl (meth) acrylate, trimethylolpropane tri (meth) Examples include acrylate, pentaerythritol tetra (meth) acrylate, di (meth) acrylate of bisphenol A type epoxy resin, various polyurethane poly (meth) acrylates, and polyester poly (meth) acrylate.
(E) The preferable mixture ratio of a component is the range of 0-50 mass% in a composition.

3-4. Alkali-soluble resin In the present invention, the alkali-soluble resin [hereinafter referred to as “component (f)”] acts as a binder for the component (f) and is preferably used as a developer, particularly preferably an alkali developer, in the development processing step. If it has solubility with respect to it, it will not specifically limit.
Examples of the component (f) include addition polymers, polyesters, epoxy resins, and polyethers, and addition polymers obtained by polymerizing ethylenically unsaturated monomers are preferred.
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 “carboxyl group-containing unsaturated monomer”) and this A copolymer (hereinafter referred to as “carboxyl group-containing copolymer”) with an ethylenically unsaturated monomer copolymerizable with (hereinafter referred to as “copolymerizable unsaturated monomer”) is preferred.

Examples of the carboxyl group-containing unsaturated monomer include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α-chloroacrylic acid and cinnamic acid; maleic acid, maleic anhydride, fumaric acid, itacon Unsaturated dicarboxylic acids such as acid, itaconic anhydride, citraconic acid, citraconic anhydride and mesaconic acid or their anhydrides; trivalent or higher unsaturated polycarboxylic acids or their anhydrides; succinic acid mono (2- ( Mono [(meth) acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids such as (meth) acryloyloxyethyl) and phthalic acid mono (2- (meth) acryloyloxyethyl); and ω-carboxy Examples include mono (meth) acrylates of polymers having a carboxy group and a hydroxyl group at both ends, such as polycaprolactone mono (meth) acrylate. Can. Of these carboxyl group-containing unsaturated monomers, ω-carboxypolycaprolactone monoacrylate and mono (2-acryloyloxyethyl) phthalate are Aronix M-5300 and M-5400 [Toagosei Co., Ltd.], respectively. It is marketed with the brand name.
The carboxyl group-containing unsaturated monomers can be used alone or in admixture of two or more.

  The copolymerizable unsaturated monomer may be any copolymerizable with a carboxyl group-containing unsaturated monomer, such as an aromatic vinyl compound, an unsaturated carboxylic acid ester, an unsaturated imide, and a terminal. Macromonomers having a mono (meth) acryloyl group are preferred.

  Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, 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, etc. are mentioned.

As unsaturated carboxylic acid esters, 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, methoxytriethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, methoxydi Propylene glycol (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate and Examples include glycerol mono (meth) acrylate.

  Examples of unsaturated imides include maleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

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

As the copolymerizable unsaturated monomer, in addition to the above, 2- (3,4,5,6-tetrahydrophthalimido) ethyl (meth) acrylate, 2- (2,3-dimethylmaleimido) ethyl (meth) Imide (meth) acrylates such as acrylate; 2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 2-dimethylaminopropyl acrylate, 3-aminopropyl ( Unsaturated carboxylic acid aminoalkyl esters such as meth) acrylate and 3-dimethylaminopropyl (meth) acrylate; Unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate; Indens such as indene and 1-methylindene; Vinyl acetate, vinyl propionate, butyric acid Carboxylic acid vinyl esters such as nyl 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 alone or in admixture of two or more.

  As the carboxyl group-containing copolymer, (meth) acrylic acid is an essential component, and in some cases, from the group of succinic acid mono (2- (meth) acryloyloxyethyl), ω-carboxypolycaprolactone mono (meth) acrylate. Carboxyl group-containing unsaturated monomer component further containing at least one selected compound, styrene, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate , A copolymer with at least one selected from the group consisting of glycerol mono (meth) acrylate, N-phenylmaleimide, polystyrene macromonomer and polymethylmethacrylate 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 copolymer, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (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 (meta ) Acrylate / polystyrene macromonomer copolymer, (meta Acrylic acid / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic Acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / styrene / benzyl (meth) 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) acryloyloxy Ethyl] / still / Allyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / Ω-carboxypolycacrolactone mono (meth) acrylate / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate / N-phenylmaleimide copolymer.

  The copolymerization ratio of the carboxyl group-containing unsaturated monomer in the carboxyl group-containing copolymer is usually 5 to 50% by mass, preferably 10 to 40% by mass. In this case, if the copolymerization ratio is less than 5% by mass, the solubility of the resulting composition in an alkaline developer tends to decrease, whereas if it exceeds 50% by mass, the solubility in an alkaline developer becomes excessive, When developing with an alkali developer, the spacer layer and the pixels tend to fall off the substrate and the spacer surface becomes rough.

As the component (f) in the present invention, the alkali-soluble resin having an ethylenically unsaturated group in the side chain improves the crosslink density of the resulting cured film, and improves the coating strength, heat resistance, and chemical resistance. Since it becomes the thing excellent in the point, it is preferable.
The alkali-soluble resin having an ethylenically unsaturated group in the side chain is preferably an alkali-soluble resin having a carboxyl group. Examples of the resin include those obtained by adding an unsaturated compound having an epoxy group (hereinafter referred to as “epoxy unsaturated compound”) to the carboxyl group-containing copolymer.
Examples of the epoxy unsaturated compound include epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate and cyclohexene oxide-containing (meth) acrylate.
As a method for the addition reaction, a conventional method may be followed, and it can be produced by adding an epoxy unsaturated compound to a carboxyl group-containing copolymer in an organic solvent or without a solvent. As conditions for the addition reaction, the reaction temperature, reaction time, and catalyst may be appropriately selected according to each 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. The number average molecular weight (hereinafter referred to as “Mn”) is usually 3,000 to 60,000, preferably 5,000 to 25,000.
In addition, in this invention, Mw and Mn mean the value which converted the molecular weight measured by the gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) in polystyrene conversion.
In the present invention, by using the component (e) having such specific Mw and Mn, a photosensitive resin composition excellent in developability can be obtained, thereby forming a pattern having sharp pattern edges. In addition to being able to be formed, residues, background stains, film residues, and the like are less likely to occur on the unexposed portion of the substrate and the light shielding layer during development. Moreover, the ratio (Mw / Mn) of Mw and Mn of the component (e) is usually 1 to 5, preferably 1 to 4.
(F) A component can be used individually or in combination of 2 or more types.

When blending component (a) or component (e), the proportion of component (a) and component (e) (hereinafter collectively referred to as (meth) acrylate component) and component (f) is (meth) Based on the total amount of the acrylate component and the component (f), the component (f) is preferably 10 to 90% by mass, and more preferably 30 to 80% by mass. When the proportion of the component (f) exceeds 90% by mass, the cross-linking density decreases, so that the coating strength, heat resistance, and chemical resistance tend to decrease.
As a ratio in the composition of the total amount of (meth) acrylate component and (f) component, 10-50 mass% is preferable in a composition. If this ratio is less than 10% by mass, the film thickness after pre-baking becomes too thin. On the other hand, if it exceeds 50% by mass, the viscosity of the composition becomes too high, resulting in poor coating properties, The film thickness becomes too thick.

4). Applications The composition of the present invention can be used for various applications. Examples thereof include a pattern forming composition such as a resist, and coating materials such as ink and paint.
Among these, since the composition of the present invention is excellent in alkali developability, it can be preferably used as a pattern forming pattern forming composition.
The composition of the present invention can be preferably used as a pattern forming composition because it has a high exposure sensitivity and is extremely excellent in developability and can form a precise and accurate pattern.
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 composition, it is sufficient to follow a conventional method, and after applying the composition to a substrate and drying to form a coating film, a mask having a specific pattern shape is formed thereon. Examples include a method of curing by irradiating active energy rays and developing an uncured portion with a developer.
Examples of the substrate include glass and plastic. As the developer, an alkaline developer is preferable, and specific examples are as described below.

  Examples of the composition for pattern formation include resists such as etching resists and solder resists, columnar spacers in the production of liquid crystal panels, coloring compositions for forming pixels and black matrices in color filters, and color filter protective films. It is done.

  Among these uses, the composition of the present invention can be preferably used as a coloring composition for forming a pixel, a black matrix and the like in liquid crystal panel production.

4-1. Coloring composition When the composition of the present invention is used as a coloring composition, a pigment and a pigment dispersant are further blended. Hereinafter, these components will be described.

The pigment is not particularly limited, and various organic or inorganic pigments can be used.
Specific examples of organic pigments include compounds classified as Pigments in the Color Index (CI; published by The Society of Dyers and Colorists), ie, the following Color Index (CI) numbers. You can list what you have. CI Pigment Yellow 1, CI Pigment Yellow 3, CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180, CI Pigment Yellow 185, etc. CI pigment red 1, CI pigment red 2, CI pigment red 3, CI pigment red 177, CI pigment red 254 and other red pigments; and CI pigment blue 15 and CI pigment blue 15: 3, CI CI pigment blue 15: 4, CI pigment blue 15: 6 and other blue pigments; CI pigment green 7, CI pigment green 36 and other green pigments; CI pigment violet 23, CI pigment violet 23 19, and the like.
In addition, phthalocyanines with high bromination rates, such as Monastral Green 6YC and 9YC (manufactured by Avicia Co., Ltd.), which are difficult to disperse in the past, high brightness G pigments, metals whose central metal is other than copper, such as Mg, Al, Si , Ti, V, Mn, Fe, Co, Ni, Zn, Ge, Sn, and other high-purity G pigments made of different metal phthalocyanine pigments can be used.

  Specific examples of the inorganic pigment include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red rose (red iron oxide (III)), cadmium red, ultramarine blue, and chromium oxide green. , Cobalt green, amber, titanium black, synthetic iron black, carbon black and the like. In this invention, a pigment can be used individually or in mixture of 2 or more types.

  Among these pigments, the pigment dispersion can impart excellent dispersibility to various pigments widely used in color filters for liquid crystal display devices. Specifically, CI pigment yellow 150, CI CI Pigment Green 36, CI Pigment Green 7, CI Pigment Yellow 138 CI Pigment Yellow 83, CI Pigment Blue 15: 6, CI Pigment Violet 23, CI Pigment Red 177, CI Pigment Red 254, CI Pigment Yellow 139, Bromination Rate It can be suitably used when preparing a pigment dispersion containing at least one selected from the group consisting of the above-mentioned phthalocyanine pigment having a high molecular weight and the different metal phthalocyanine pigment.

The pigment dispersant is not particularly limited, and various pigment dispersants can be used.
Specific examples of usable pigment dispersants include amide compounds such as nonanoamide, decanamide, dodecanamide, N-dodecylhexamide, N-octadecylpropioamide, N, N-dimethyldodecanamide and N, N-dihexylacetamide. , Amine compounds such as diethylamine, diheptylamine, dibutylhexadecylamine, N, N, N ′, N′-tetramethylmethanamine, triethylamine, tributylamine and trioctylamine, monoethanolamine, diethanolamine, triethanolamine, N, N, N ′, N ′-(tetrahydroxyethyl) -1,2-diaminoethane, N, N, N′-tri (hydroxyethyl) -1,2-diaminoethane, N, N, N ′, N'-tetra (hydroxyethylpolyoxyethylene) -1,2-diaminoethane, 1,4-bis (2-hydroxyethyl) pipera Can be exemplified amines having emissions and 1- (2-hydroxyethyl) hydroxy groups, such as piperazine, Other nipecotamide, mention may be made of isonipecotamide, the compound such as nicotinamide.

  Furthermore, (co) polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; (partial) amine salts, (partial) ammonium salts of (co) polymers of unsaturated carboxylic acid esters such as polyacrylic acid (Partial) alkylamine salts; (co) polymers of hydroxyl group-containing unsaturated carboxylic acid esters such as hydroxyl group-containing polyacrylic acid esters and their modified products; polyurethanes; unsaturated polyamides; polysiloxanes; long-chain polyaminoamides Phosphate salts: Amides obtained by reacting poly (lower alkyleneimine) with free carboxyl group-containing polyesters and salts thereof can be mentioned.

  In addition, commercially available dispersants include Shigenox-105 (trade name, manufactured by Hakkol Chemical), Disperbyk-101, -130, -140, -170, -171, -182, and -2001. [Above, manufactured by Big Chemie Japan Co., Ltd.], EFKA-49, -4010, -9900 (above, manufactured by EFKA CHEMICALS), Solsperse 12000, 13240, 11394, 17000, 20000, 24000GR, 24000SC, 27000, 28000, 33500 [above, manufactured by Geneca Co., Ltd.], PB821, 822 [above, manufactured by Ajinomoto Co., Inc.], and the like.

  The pigment dispersant is usually used at a ratio of 10 to 90 parts by mass, preferably 20 to 80 parts by mass with respect to 100 parts by mass of the pigment.

  If necessary, the coloring composition may further contain an ultraviolet blocking agent, an ultraviolet absorber, a surface conditioner (leveling agent) and other components.

  The coloring composition may be produced by directly mixing the (meth) acrylate component, the pigment, the pigment dispersant and, if necessary, the other components into the component (d) and dispersing the mixture using a known disperser. Although good, the pigment dispersion may be insufficient, so a method of preparing a pigment dispersion in advance is preferred.

  According to this method, a photosensitive coloring composition having excellent pigment dispersibility can be easily obtained. In this method, particularly when the component (f) is blended, it is mixed and dispersed in a pigment, a pigment dispersant and, if necessary, a solvent for dispersing a part of the component (f) (hereinafter referred to as “dispersion solvent”). To prepare a pigment dispersion in advance. Separately, the (meth) acrylate component and, if necessary, the component (f) and other components are mixed with a solvent for dilution (hereinafter referred to as “diluting solvent”) and dissolved or dispersed, thereby clearing. Prepare a resist solution. And the coloring composition excellent in pigment dispersibility is easily obtained by mixing the obtained pigment dispersion liquid and a clear resist liquid, and performing a dispersion process as needed. According to this method, since the dispersion solvent and the diluting solvent can be selected separately, the range of solvent selection is expanded.

  If the pigment dispersion is not pre-prepared, first add the pigment, pigment dispersant, and, if necessary, the alkali-soluble resin to the organic solvent, and mix and stir to disperse the pigment. By adding and mixing the remaining components such as the polyfunctional acrylate, the pigment dispersibility is not inhibited by the other compounding components in the pigment dispersion step, and the stability is also excellent.

  The colored composition thus obtained is applied to a support to form a coating film, dried, and then a part of the coating film is selected by irradiating the coating film with light in a predetermined pattern. After being cured, the film is developed with an alkaline solution, post-baked, and further heat-cured to obtain a colored coating film having a predetermined pattern.

The light to be used is preferably ultraviolet light or visible light, and light having a wavelength of 240 nm to 410 nm obtained from a high pressure mercury lamp, a metal halide lamp or the like is used. The irradiation energy required for curing is usually about 10 to 500 mJ / cm ² . In the exposure step, a predetermined position of the coating film can be selectively exposed and cured by irradiating the surface of the coating film with laser light or irradiating light through a mask.
As the developer, an aqueous solution of an alkali compound can be used. Examples of the alkaline compound include potassium hydroxide, sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate, ammonia, tetramethylammonium hydroxide, and the like. In order to accelerate the development speed, water-soluble organic solvents such as methanol, ethanol, isopropanol and benzyl alcohol, and various surfactants may be added to the developer.
The developing method may be any of a liquid piling method, a dipping method, a spray method, and the like. After development, the pattern portion is washed with water for 0.5 to 1.5 minutes and air-dried with compressed air or the like to obtain a colored pattern.

  In addition, the thermosetting is usually performed by drying at 50 to 200 ° C. using a vacuum dryer, oven, hot plate, or other device to which heat is applied, and then heating and curing at a temperature of about 120 to 250 ° C. .

  The cured part in the coating film has a structure in which the pigment is uniformly dispersed in the matrix formed by the cross-linking network formed by the photocuring reaction and the thermosetting reaction according to the present invention. .

  This colored composition is excellent in curability, has an increased crosslink density and hardens uniformly to the inside, so that it is difficult to reverse taper during development, and a pattern with a forward taper shape, sharp edges and good surface smoothness is formed. The

  In addition, the colored composition of the present invention can provide a colored cured film having high electrical reliability because impurities are confined in a matrix having a high crosslinking density that is hardened to the inside during curing and is not easily eluted into the liquid crystal layer. In particular, when a colored layer of a liquid crystal panel is produced using this colored composition, the voltage of the display portion can be stably maintained and electric reliability is high.

  In addition, the colored composition can disperse a high concentration pigment finely and uniformly, and has high colorability. Therefore, even if it is thin, it can form a colored pattern having a large color concentration, and has a wide color reproduction range. .

  The colored composition can be used to form various colored coatings, and is particularly suitable for forming a colored layer constituting the details of a color filter, that is, a pixel or a black matrix.

Since the composition of the present invention requires the components (a) and (b) excellent in alkali developability, when used as an active energy ray-curable pattern forming composition, the exposure sensitivity is high and the developability is good. Thus, a precise and accurate pattern can be formed, and after curing, it has excellent physical properties such as coating film strength, heat resistance and chemical resistance.
Further, since the composition of the present invention does not deteriorate the alkali developability even when the blending ratio of the component (f) is reduced, a polyfunctional (meth) acrylate or pigment containing the component (a) which is a relatively crosslinkable component Therefore, it is suitable for forming a colored layer.

This invention is a composition which contains the said (a) component and (b) component as an essential component, Comprising: 0.1-20 mass parts of (b) component is with respect to 100 mass parts of (a) component. It is related with the active energy ray hardening-type composition contained in a ratio.
As the component (a), an acid anhydride adduct of dipentaerythritol pentaacrylate is preferable.
The composition of the present invention preferably further contains a photopolymerization initiator, and preferably contains an organic solvent.
The composition of the present invention can be used for various uses of pattern forming compositions such as inks, paints and resists, and is particularly excellent in alkali developability, and therefore can be preferably used as a pattern forming composition.
As the pattern forming composition, those further containing an alkali-soluble resin are preferable.
Furthermore, among the compositions for pattern formation, it can be preferably used as a coloring composition.
Further, in the present invention, the composition is applied to a substrate to form a coating film, and then the active energy ray is irradiated and cured from above through a mask having a specific pattern shape, and the uncured portion is developed as a developer. The present invention relates to a pattern forming method in which development is performed.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples.
In the following, “part” means mass part, and “%” means mass% unless otherwise specified.

○ Production Example 1 [Production of (a-1)]
In a 500 ml glass flask equipped with a stirrer, thermometer, and water-cooled condenser, 110 g of propylene glycol monomethyl ether monoacetate [manufactured by Kuraray Co., Ltd .: trade name PGMAC, hereinafter referred to as “PGMAC”], dipentaerythritol penta and hexaacrylate Acrylate mixture containing 30:70 (mass ratio), hydroxyl value 36 mg KOH / g] 250 g, 16 g succinic anhydride and 0.13 g methoquinone were added, and the temperature was raised to 85 ° C. The reaction was carried out for 3 hours after adding 1.3 g of the catalyst triethylamine. 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 for component (a), and analyzed by ion chromatography under the following conditions for component (b): 100 parts of total acrylate ester, 30 parts and component (b) was 0.2 parts.

● High-performance liquid chromatograph measurement conditions and equipment: SC-8010 manufactured by Tosoh Corporation
Column: ODS-100z manufactured by Tosoh Corporation
Reversed phase (ODS) column (inner diameter 4.6 mm, length 250 mm). Filled with ODS silica with a particle size of 5 μm.
・ Analysis temperature: 40 ° C
Eluent: 0.015% phosphoric acid water: methanol (volume ratio) = 45: 55 (Initial) → 30: 70 (30 min) → 0: 100 (45-50 min)
・ Eluent flow rate: 1.0 mL / min
・ Detector: UV 210nm

● Ion chromatographic analysis measurement conditions]
・ Device: DIONEX DX-300 manufactured by DIONEX
Separation column: IONEPacAS4A-SC manufactured by DIONEX
Guard column: DIONEX Co., Ltd. IonPacAG4A-SC
_{Eluent: 1.8mM-Na 2 CO 3 /1.7mM-NaHCO} 3
・ Flow rate: 1.5ml / min
・ Suppressor: ASRS-ULTRA-II (recycle mode, current value 50 mA)
・ Detector: Electrical conductivity ・ Sample injection volume: 50 μL
Procedure: After the sample was diluted with 10 times the amount of toluene, 5 times the amount of water was added and shaken for 10 minutes. After standing, the lower layer (aqueous layer) was separated and used as a measurement sample.

○ Production Example 2
Except that the raw material succinic anhydride was charged in an amount of 20 g, synthesis was carried out according to Production Example 1 to obtain a compound having an acid value of 50 mg KOH / g (hereinafter referred to as “ab2”).
The obtained compound was analyzed in the same manner as in Production Example 1. As a result, in 100 parts of the total acrylic ester, the component (a) was 30 parts and the component (b) was 1.5 parts.

* Production Example 3
Synthesis was performed in accordance with Production Example 1 except that the raw material succinic anhydride was charged in an amount of 13 g and the reaction time was 8 hours, and a compound having an acid value of 28 mg KOH / g (hereinafter referred to as “ab3”) was prepared. Obtained.
When the obtained compound was analyzed in the same manner as in Production Example 1, the component (a) was 25 parts and the component (b) was 0.015 part in 100 parts of the total acrylic ester.

○ Production Example 4 [Production of component (f)]
In a separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, benzyl methacrylate is 52%, acrylic acid is 23%, PGMAC is twice the total amount of monomers, 2, 2 '-Azobis (2-methylbutyronitrile) was added in an amount of 5% based on the total amount of the monomers and dissolved uniformly. Then, it stirred at 85 degreeC under nitrogen stream for 2 hours, and also was made to react at 100 degreeC for 1 hour. Furthermore, the resulting solution is 25% glycidyl methacrylate, 10% triethylamine with respect to glycidyl methacrylate, 1% with respect to hydroquinone glycidyl methacrylate, and 35% of the combined monomer and glycidyl methacrylate weight. DMDG was added to and stirred at 100 ° C. for 5 hours to obtain the desired copolymer solution (solid content concentration 31.5%).
Mw of the obtained component (f) (hereinafter referred to as “f1”) was 21,200, the acid value was 84 mgKOH / g, and the hydroxyl value was 96 mgKOH / g.

○ Examples 1-3, Comparative Examples 1-2
The components (a) to (c), the component (e), the pigment and the pigment dispersant were mixed according to a conventional method so as to obtain the ratio shown in Table 1 below, thereby preparing a colored composition.
Using the obtained composition, developability was evaluated in the same manner as in Examples 1 to 3 and Comparative Examples 1 and 2. The residue was evaluated according to the following method. The results are shown in Table 1.

<Developability>
The composition described in Tables 1 and 2 was applied onto a 10 cm chrome mask glass substrate by a spin coater, and this coating film was dried for 10 minutes with an air dryer at 80 ° C. to form a coating film having a dry film thickness of 2 μm. Formed. The obtained coating film was spray-developed with a 0.5 wt% sodium carbonate aqueous solution, and the time until complete dissolution was measured.

<Residue>
The substrate surface after the evaluation of developability was wiped 10 times with a cotton swab containing ethanol, the presence or absence of coloring of the swab was examined, and the following criteria were evaluated.
○: Cotton swabs are not colored at all.
-: The swab is slightly colored.
*: Cotton swabs are colored.

The numbers in the column of the composition in Table 1 mean parts, and ab1 to ab3 and f1 are shown as solid content ratios.
In addition, the symbol in Table 1 means the following.
Irg907: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, Irgacure 907 manufactured by Ciba Specialty Chemicals
M-402: Dipentaerythritol pentaacrylate / dipentaerythritol hexaacrylate mixture (ratio: about 30/70) Aronix M-402 manufactured by Toagosei Co., Ltd.
PB: Pigment, C.I. I. Pigment Blue 15: 6
DIS: pigment dispersant, Disperbyk-2001, solid content 46% (main solvent: methoxypropyl acetate, methoxypropanol, butyl cellosolve)

  The components (a) and (b) contained in the composition of Table 1 are summarized in Table 2 below.

The compositions of Examples 1 to 3 had very good developability and no residue on the substrate.
On the other hand, Comparative Example 1 in which the ratio of the component (b) was less than 0.1 part was a result that the developability and the residue were slightly inferior. Moreover, in the comparative example 2 which uses a commercially available polyfunctional (meth) acrylate and does not contain the component (b), both developability and residue were insufficient.

The composition of the present invention can be used for various applications such as inks, paints, and resists, and can be preferably used as a composition for pattern formation of resists and the like.
Furthermore, the composition of the present invention can be preferably used as a colored composition for forming a pixel of a color filter, a black matrix, or the like in liquid crystal panel production.

Claims (8)

It contains a compound (a) obtained by adding an acid anhydride to a compound having three or more (meth) acryloyl groups and a hydroxyl group, and an acid anhydride or / and an acid anhydride hydrolyzate (b) as essential components. It is a composition, Comprising: The active energy ray hardening-type composition which contains (b) component in the ratio of 0.1-20 mass parts with respect to 100 mass parts of (a) component. The active energy ray-curable composition according to claim 1, wherein the component (a) is an acid anhydride adduct of 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 any one of claims 1 to 3, further comprising an organic solvent. An active energy ray-curable pattern forming composition comprising the composition according to claim 1. The composition for forming an active energy ray-curable pattern according to claim 5, further comprising an alkali-soluble resin. The coloring composition for active energy ray hardening-type pattern formation which consists of a composition of Claim 5 or Claim 6. After applying the composition according to any one of claims 5 to 7 to a substrate to form a coating film, it is cured by irradiating an active energy ray from above through a mask having a specific pattern shape. The pattern formation method which develops an uncured part with a developing solution.