KR20170054898A - Active energy ray-curable compositon - Google Patents

Abstract

The present invention relates to an active energy ray-curable composition and, more specifically, to an active energy ray-curable composition having excellent elastic modulus, adhesion and developability, a color filter comprising a spacer produced by using the composition, and a liquid crystal display device having the color filter.

Description

[0001] ACTIVE ENERGY RAY-CURABLE COMPOSITON [0002]

More specifically, the present invention relates to an active energy ray curable composition having excellent elastic modulus, adhesion and developability, a color filter including a spacer made using the composition, And a liquid crystal display device.

BACKGROUND ART Conventionally, (meth) acrylate has been widely used as a composition for pattern formation used in a color resist forming a colored layer of an etching resist, a solder resist and a color filter. In this case, a compound having two or more (meth) acryloyl groups (hereinafter also referred to as "multifunctional (meth) acrylate") is used for the purpose of improving the sensitivity of the composition and improving the hardness of the cured product. At this time, the polyfunctional (meth) acrylate is insoluble in alkali, and a film residue of the uncured part coating film is generated at the time of development, and sufficient resolution can not be obtained. Accordingly, studies have been made on a carboxyl group-containing polyfunctional (meth) acrylate obtained by adding a compound having a hydroxyl group and a (meth) acryloyl group to a dicarboxylic anhydride.

However, in order to add a large number of carboxyl groups by adding a large number of dicarboxylic anhydrides to one molecule of a compound having a hydroxyl group and a (meth) acryloyl group, it is required to leave a large amount of hydroxyl groups in the reaction compound. For this reason, it is necessary to lower the ratio of (meth) acryloyl groups in one molecule, and as a result, the crosslinking density can not be increased, and it is difficult to achieve both development and curability.

 To solve this problem, studies have also been made on a carboxyl group-containing polyfunctional (meth) acrylate obtained by reacting a compound having at least one hydroxyl group and at least two (meth) acryloyl groups with an anhydride of a tetravalent carboxylic acid ( Patent Document 1).

However, even when the carboxyl group-containing polyfunctional (meth) acrylate described in Patent Document 1 is used, there is a problem that the strength of the cured film, the heat resistance and the chemical resistance are inferior because the crosslinking density is insufficient.

Further, when a compound having at least one hydroxyl group and at least two (meth) acryloyl groups is reacted with an anhydride of a tetravalent carboxylic acid as described above, it is preferable that the equivalent of a carboxyl group is more than the equivalent of the hydroxyl group And there is a limit to improving the developability to a desired level.

Japanese Patent Laid-Open No. 2001-089416

Disclosure of the Invention The present invention has been made in order to solve the problems of the prior art, and it is an object of the present invention to provide an active energy ray which is not only excellent in generally required physical properties such as hardenability, chemical resistance, heat resistance and adhesion, And to provide a curable composition.

It is another object of the present invention to provide a color filter including a spacer manufactured using the composition and a liquid crystal display device having the color filter.

In order to achieve the above object,

(A) in which a polyvalent acid (A2) is added to a compound (A1) having at least three (meth) acryloyl groups and hydroxyl groups and which can not be in the form of an anhydride is added to the active energy ray curable composition .

The present invention also provides a color filter comprising a spacer made using the active energy ray curable composition.

Further, the present invention provides a liquid crystal display device provided with the color filter.

The active energy ray curable composition of the present invention comprises a compound (A) obtained by adding a polyvalent acid (A2) which can not be an anhydride form to a compound (A1) having at least three (meth) acryloyl groups and a hydroxyl group , Excellent elastic modulus, adhesion, and developability.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows the shape of a side surface of a columnar spacer used for evaluation of an elastic strain rate by an electron microscope. Fig.

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, (meth) acryloyl means acryloyl and / Or methacryloyl.

Hereinafter, components constituting the active energy ray-curable composition of the present invention will be described.

Three or more ( Meta ) Acryloyl group  And Hydroxyl group  (A1) having no anhydride form The polyvalent acid (A2)  The compound (A)

The active energy ray-curable composition of the present invention is a compound having three or more (meth) acryloyl groups and a hydroxyl group (hereinafter also referred to as a 'hydroxy-functional (meth) acrylate' or ' (Hereinafter also referred to as "component (A)") to which a polyvalent acid which can not be an anhydride form (hereinafter also referred to as "component (A2)") is added.

Specific examples of the hydroxyfunctional (meth) acrylate (A1) include ditrimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) have. Of these, dipentaerythritol penta (meth) acrylate and pentaerythritol tri (meth) acrylate are more preferable because of their good pattern forming ability.

The composition of the present invention may contain a compound having at least four (meth) acryloyl groups which do not have a hydroxyl group as a by-product in the production process of hydroxydifunctional (meth) acrylate. Examples of the compound include pentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate.

The component (A) and the compound having four or more (meth) acryloyl groups having no hydroxyl group may be compounded in a weight ratio of 1: 4 to 4: 1.

Examples of the method for producing the hydroxyfunctional (meth) acrylate (A1) include a method in which (meth) acrylic acid and an alcohol are reacted by heating and stirring under an acidic catalyst. Examples of the acidic catalyst include sulfuric acid, paratoluenic acid and methanesulfonic acid. The temperature of the reaction can be appropriately set according to the compound to be used and the purpose, and is preferably 70 to 140 캜. When the reaction temperature is lower than 70 ° C, the reaction is delayed. When the reaction temperature is higher than 140 ° C, the reaction system becomes unstable, and impurities are generated or gelated.

In the above reaction, it is preferable to use an organic solvent having a low solubility with water produced by the esterification reaction and accelerate dehydration while azeotropically watering. Preferred examples of the organic solvent 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; And the like. The organic solvent may be distilled off under reduced pressure after the reaction. If a solvent free from odor or the like is used, the organic solvent may be used as it is without removing to adjust the viscosity of the composition.

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

In addition, in the above reaction, a polymerization inhibitor may be added to the reaction solution for the purpose of preventing polymerization of the resulting (meth) acrylic acid ester. Examples of such a polymerization inhibitor include 2,5-bis (1,1,3,3-tetramethylbutylhydro (DOHQ), hydroquinone, hydroquinone monomethyl ether, 2,6-di-tert- - cresol and phenothiazine, and the like.

When the component (A1) reacts with the polybasic acid (A2) which can not be in the form of an anhydride, an acid-containing polyfunctional acrylate compound can be prepared as the component (A).

As the compound which reacts with the component (A1) for introducing a carboxyl group as an acid group in the polyfunctional acrylate, a polyvalent acid which can be in the form of an acid anhydride or anhydride can be used. However, in the case of using an acid anhydride or a polyhydric acid which may be an anhydride form, a side reaction occurs due to a side reaction in which an acid anhydride is hydrolyzed, making it difficult to produce a target compound, It grows longer. In addition, since introduction of the acid group limits the equivalent amount of the hydroxyl group contained in the component (A1), there are restrictions on introduction of the carboxyl group to the desired level.

On the other hand, in the case of using a polyhydric acid (A2) which can not form an anhydride as a component reacting with the component (A1) for introducing an acid group into the polyfunctional acrylate, the glass transition temperature T _g ), it is possible to easily adjust the acidity or the equivalent of the acid by selecting a suitable type of polyvalent acid. In addition, the desired effect can be expressed by controlling the kind and characteristics of the substituted acid. In other words, when the component (A2) is used to introduce an acid group into the polyfunctional acrylate, the acid can be introduced regardless of the equivalent amount of the hydroxyl group contained in the component (A1) , Adhesion, and the like.

The kind of the polyvalent acid (A2) which can not be in the form of the anhydride is not particularly limited and can be appropriately selected and used according to the purpose. Specific examples thereof include maleic acid, biphenyl-3,3 ', 5,5'-tetracarboxylic acid, isophthalic acid, Terephthalic acid, benzene-1,3,5-tricarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, furan-2,5-dicarboxylic acid, 2,5-dicarboxylic acid, and a compound represented by the following formula (1), and at least one selected from the foregoing can be used.

[Chemical Formula 1]

In the above formula (1), R ₁ is a single bond, a C1-alkylene group or a C5-C20 alkylene group.

The component (A) can be prepared by the reaction of a compound (A1) having three or more (meth) acryloyl groups and hydroxyl groups with a polyvalent acid (A2) which can not be in the form of an anhydride.

In the above reaction, the compounding ratio of the component (A1) and the component (A2) is not particularly limited and may be appropriately combined in a stoichiometric equivalent ratio. In general, the molar ratio of the component (A1) to the component (A2) is preferably 1: 0.1 to 1: 2, more preferably 1: 0.3 to 1: 1.1.

The compound (A) obtained by adding the polyvalent acid (A2), which can not be an anhydride form, to the compound (A1) having three or more (meth) acryloyl groups and hydroxyl groups is added to the solid component Preferably 70 wt%, more preferably 10 wt% to 30 wt%. It is advantageous in that it exhibits excellent developability and elastic recovery rate within the above range.

The active energy ray-curable composition of the present invention may further contain other components than those described above, if necessary. Specifically, at least one selected from an alkali-soluble resin, a photopolymerization initiator, an organic solvent, an unsaturated group-containing compound, a pigment, a dye, a defoaming agent, a leveling agent, an inorganic filler and an organic filler. It is also possible to contain a small amount of an antioxidant, a light stabilizer, an ultraviolet absorber, a polymerization inhibitor and the like.

Hereinafter, the alkali-soluble resin (B), the photopolymerization initiator (C) and the organic solvent (D) will be described in detail.

(B) an alkali-soluble resin

The composition of the present invention may further comprise an alkali-soluble resin (hereinafter also referred to as 'component (B)'). The alkali-soluble resin is not particularly limited as long as it acts as a binder and is soluble in a developing solution used in a developing treatment step, particularly preferably in an alkali developing solution.

Examples of the alkali-soluble resin include an addition polymer, a polyester resin, an epoxy resin and a polyether resin, and an addition polymer obtained by polymerizing an ethylenic unsaturated monomer may be more preferable.

As the alkali-soluble resin, an alkali-soluble resin having a carboxyl group is preferable, and an ethylenically unsaturated monomer having at least one carboxyl group (hereinafter also referred to as a "carboxyl group-containing unsaturated monomer") and an ethylenically unsaturated monomer copolymerizable therewith Copolymerizable unsaturated monomer ") (hereinafter also referred to as a" carboxyl group-containing copolymer ") is preferable.

Examples of the carboxyl group-containing unsaturated monomer include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid,? -Crotonic 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;

An unsaturated polycarboxylic acid having three valencies or more or anhydrides thereof;

Mono [(meth) acryloyloxyalkyl] dibasic carboxylic acid such as succinic acid mono (2- (meth) acryloyloxyethyl) and phthalic acid mono (2- (meth) acryloyloxyethyl) Esters; And mono (meth) acrylates of a polymer having a carboxyl group and a hydroxyl group at both ends such as? -Carboxypolycaprolactone mono (meth) acrylate. Of these carboxyl group-containing unsaturated monomers,? -Carboxypolycaprolactone monoacrylate or phthalic acid mono (2-acryloyloxyethyl) are respectively referred to as Aronix M-5300 or M-5400 (trade name, Commercially available products may also be used.

These carboxyl group-containing unsaturated monomers may be used alone or in combination of two or more.

The copolymerizable unsaturated monomer is not particularly limited as long as it is copolymerizable with the carboxyl group-containing unsaturated monomer. Specific examples thereof include aromatic vinyl compounds, unsaturated carboxylic acid esters, unsaturated imides and macro monomers having a mono (meth) acryloyl group at the terminal May be preferable.

Examples of the aromatic vinyl compound include styrene,? -Methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p- , 2-vinylbenzyl methyl ether, 3-vinyl benzyl methyl ether, 4-vinyl benzyl methyl ether, 2-vinyl benzyl glycidyl ether, 3-vinyl benzyl glycidyl ether, .

Examples of the unsaturated carboxylic acid esters include unsaturated carboxylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxy (Meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl Acrylate, 2-methoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxy diethylene glycol (meth) acrylate, Acrylate, methoxy tri Ethylene glue glycol (meth) acrylate, methoxy propylene glue glycol (meth) acrylate, methoxy dipropylene glue glycol (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^{2, 6]} (Meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate and glycerol mono (meth) acrylate.

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

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

Examples of the copolymerizable unsaturated monomer include 2- (3,4,5,6-tetrahydrophthalimide) ethyl (meth) acrylate, 2- (2,3-dimethylmaleimide) ethyl (meth) Imide (meth) acrylates such as acrylate; (Meth) acrylate, 2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2- Unsaturated carboxylic acid aminoalkyl esters such as dimethylaminopropyl (meth) acrylate; Unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate; Indene 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,? -Chloroacrylonitrile and vinylidene cyanide; Unsaturated amides such as (meth) acrylamide,? -Chloroacrylamide and N-2-hydroxyethyl (meth) acrylamide; And aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene.

These copolymerizable unsaturated monomers may be used singly or in a mixture of at least one thereof.

Specific examples of the carboxyl group-containing copolymer include (meth) acrylic acid as an essential component, and optionally a group of succinic acid mono (2- (meth) acryloyloxyethyl), omega-carboxypolycaprolactone mono (meth) (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate and the like, and at least one compound selected from the group consisting of styrene, (Hereinafter also referred to as a " carboxyl group-containing copolymer ") selected from the group consisting of acrylate, acrylate, glycerol mono (meth) acrylate, N-phenylmaleimide, polystyrene macromonomer and polymethylmethacrylate macromonomer ).

Specific examples of the carboxyl group-containing copolymer include (meth) acrylic acid / methyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / (Meth) acrylic acid / glycidyl (meth) acrylate / styrene copolymer, (meth) acrylic acid / glycidyl (meth) acrylate copolymer, (Meth) acrylate / polystyrene macromonomer copolymer, a (meth) acrylic acid / methyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, a (meth) acrylic acid / benzyl (Meth) acrylate / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl Acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / styrene / benzyl Styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylate / N-phenylmaleimide copolymer, (Meth) acrylate / styrene / benzyl (meth) acrylate / styrene / allyl (meth) acrylate / N-phenylmaleimide copolymers, mono [2- (meth) acryloyloxyethyl] (Meth) acrylate / glycerol mono (meth) acrylate / glycerol mono (meth) acrylate / N-phenylmaleimide copolymer, N-phenylmaleimide And the like.

The copolymerization ratio of the carboxyl group-containing unsaturated monomer in the carboxyl group-containing copolymer is usually 5 to 50% by weight, preferably 10 to 40% by weight. When the copolymerization ratio is less than 5% by weight, the solubility of the resulting composition in an alkali developing solution tends to be lowered. When it exceeds 50% by weight, solubility in an alkali developing solution becomes excessively high, Tends to cause the film to come off from the substrate or to become rough on the surface of the spacer.

As the alkali-soluble resin component in the present invention, when an alkali-soluble resin having an ethylenic unsaturated group in its side chain is used, the crosslinked density, film strength, heat resistance and chemical resistance of the resulting cured film are preferably improved.

As the alkali-soluble resin having an ethylenic unsaturated group in the side chain, an alkali-soluble resin having a carboxyl group is preferable. Examples of the resin include those obtained by adding an unsaturated compound having an epoxy group (hereinafter also referred to as an " epoxy-based unsaturated compound ") to the above carboxyl group-containing copolymer.

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

The addition reaction can be carried out according to a conventional method, and can be produced by adding an epoxy-based unsaturated compound to a carboxyl group-containing copolymer in an organic solvent or by using a solvent. As the conditions of the addition reaction, the reaction temperature, the reaction time and the catalyst may be appropriately selected depending on each reaction.

The weight average molecular weight (hereinafter, also referred to as 'Mw') of the alkali-soluble resin is usually 3,000 to 300,000, preferably 5,000 to 100,000. The number average molecular weight (hereinafter also referred to as " Mn ") is usually 3,000 to 60,000, preferably 5,000 to 25,000.

In the present invention, Mw and Mn mean values obtained by converting a molecular weight measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) into polystyrene.

In the present invention, by using such an alkali-soluble resin having the specific Mw and Mn, a composition having excellent developability is obtained, whereby a pattern having a sharp pattern edge can be formed. Further, it is possible to provide an effect that residues, greasing, film residue, and the like are less likely to be generated on the substrate and the light-shielding layer of the unexposed portion at the time of development. The ratio (Mw / Mn) of Mw and Mn of the alkali-soluble resin is usually 1 to 5, preferably 1 to 4.

The above-described alkali-soluble resins may be used alone or in combination of two or more.

The alkali-soluble resin is preferably 10 to 90% by weight, more preferably 20 to 80% by weight, based on 100% by weight of the component (A) and the alkali-soluble resin. When the content of the alkali-soluble resin exceeds 90% by weight on the basis of the above-mentioned criteria, the crosslinking density is lowered, and thus the film strength, heat resistance and chemical resistance tend to be lowered.

The alkali-soluble resin is preferably contained in an amount of 20 to 80% by weight, and more preferably 30 to 50% by weight, based on the solid content in the composition of the present invention. If it is less than 20% by weight, the film thickness becomes too thin after pre-baking. If it exceeds 80% by weight, the viscosity of the composition becomes excessively high and the coatability becomes poor or the film thickness after pre-baking becomes too thick.

(C) Light curing Initiator

The composition of the present invention is cured by irradiation of active energy rays, and examples of the active energy ray include electron beams, visible rays, ultraviolet rays, and the like. Among these, a special device is not required, and it is preferable to use visible light or ultraviolet light because of simplicity.

In the composition of the present invention, when a visible ray or an ultraviolet ray curable composition is prepared, a photopolymerization initiator (hereinafter also referred to as a 'component (C)') is added to the composition. On the other hand, in the case of an electron beam curable composition, it is not always necessary to blend a photopolymerization initiator.

The photopolymerization initiator may be any of those used in the art without any particular limitation, and specific examples thereof include non-imidazole compounds, benzoin compounds, acetophenone compounds, benzophenone compounds,? -Diketone compounds, Compounds, xanthone compounds, thioxanthone compounds, oxime compounds, triazine compounds, ketal compounds and the like. One or more of these compounds can be selected and used.

Specific examples of the imidazole-based compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) 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) ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'- 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 and the like.

When a non-imidazole-based compound is used as a photopolymerization initiator, it may be more preferable to use a hydrogen donor in combination because the sensitivity can be improved. Here, the hydrogen donor refers to a compound capable of donating a hydrogen atom to a radical generated from a non-imidazole-based compound by exposure.

As the hydrogen donor, for example, a mercaptan-based hydrogen donor and an amine-based hydrogen donor are preferable.

The mercaptan-based hydrogen donor is composed of a compound having a benzene ring or a heterocycle as a parent nucleus and having at least one, preferably 1 to 3, more preferably 1 to 2, mercapto groups directly bonded to the mother nucleus . Specific examples of the mercapan-based hydrogen donor include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2,5-dimercapto-1,3,4-thiadiazole and 2-mercapto-2,5-dimethylaminopyridine, and the like. 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 parent 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-based hydrogen donor include 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, Ethyl-4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, and 4-dimethylaminobenzonitrile.

The hydrogen donors may be used alone or in combination of two or more. However, the spacers or pixels formed by using one or more kinds of mercaptan-based hydrogen donors in combination with one or more amine-based hydrogen donors are difficult to be removed from the substrate at the time of development , The spacer or the pixel is high in strength and sensitivity. Also, a hydrogen donor having both a mercapto group and an amino group can be preferably used.

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

Specific examples of the acetophenone-based compound include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy- 1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan- Propan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-methyl- 2-dimethylaminobutan-1-one, 1-hydroxycyclohexyl phenyl ketone and 2,2-dimethoxy-1,2-diphenylethan-1-one.

Specific examples of the benzophenone-based compound include benzyldimethylketone, benzophenone, 4,4'-bis (dimethylbenzophenone), and 4,4'-bis (diethylbenzophenone).

Specific examples of the? -diketone-based compound include diacetyl, dibenzoyl, methylbenzoylformate and the like.

Specific examples of the polynuclear quinone-based compound include anthraquinone, 2-ethyl anthraquinone, 2-t-butyl anthraquinone, and 1,4-naphthoquinone.

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

Specific examples of the oxime-based compounds include o-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one and the like. Commercially available products include OXE-01 and OXE-02 from BASF.

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

Among them, 1-hydroxycyclohexyl phenyl ketone and 1- (4-methylthiophenyl) -2-methyl-2-morpholinopropane-1-one initiate a polymerization reaction by irradiation of active energy rays And therefore it is preferably used in the invention.

One or more of the photopolymerization initiators may be selected and used.

The photopolymerization initiator is preferably used in an amount of 0.5 to 20 parts by weight based on 100 parts by weight of solid components other than the photopolymerization initiator in the composition. When the amount is less than 0.5 part by weight, the photocuring property may be insufficient. When the amount is more than 20 parts by weight, the exposed part may be easily broken during alkali development.

Further, the content of the photopolymerization initiator is more preferably 1 to 30% by weight based on the solid content in the composition in that a pattern with high precision can be obtained.

(D) Organic solvents

In the present invention, an organic solvent (hereinafter also referred to as "component (D)") may be further blended in the composition for the purpose of improving the applicability of the composition. The organic solvent may be any one that does not react with each component of the composition. Further, an organic solvent having a boiling point of 80 to 200 캜 is preferable from the viewpoint of excellent coatability and a drying rate of the obtained coating film, and an organic solvent having a boiling point of 100 to 170 캜 is more preferable.

In the present invention, the solvent is not particularly limited, but ethers, aromatic hydrocarbons, ketones, alcohols, esters or amide solvents are preferably used.

Examples of the ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Dipropyl ether and diethylene glycol dibutyl ether.

Examples of the aromatic hydrocarbon solvents include benzene, toluene, xylene, and mesitylene.

Examples of the ketone solvent include methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone.

Examples of the alcoholic solvent include ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin.

Examples of the ester solvents include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl But are not limited to, lactate, butyl lactate, 3-methoxybutyl acetate, 3-methyl-3-methoxy-1-butyl acetate, methoxypentyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, Amino-2-ethyl-1,3-propanediol, ethyl lactate, propylene glycol, n-propyleneglycol methyl ether acetate, Propyl ester, ethyl-3-ethoxypropionate, propylene glycol monobutyl ether, 3-methoxy-1-butyl acetate, ethylene glycol monobutyl ether, diethylene glycol methyl ethyl ether, , 2-propylene glycol Diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether, gamma butyrolactone, diethylene glycol monoethyl ether acetate, dipropylene glycol Methyl ether acetate, diethylene glycol monobutyl ether, 1,3-butylene glycol diacetate, diethylene glycol monobutyl ether acetate ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol mono Propylene glycol monoacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate, propylene carbonate, and? -Butyrolactone And tirolactone.

In view of the coatability and dryness of the solvents exemplified above, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butalactate, ethyl 3-ethoxypropionate , Methyl 3-methoxypropionate, diethylene glycol monoethyl ether acetate, 1,3-butylene glycol diacetate, and diethylene glycol monobutyl ether acetate.

The organic solvent may be used alone or in combination of two or more.

The content of the solvent is preferably 20 to 90% by weight, more preferably 30 to 85% by weight based on the total weight of the composition of the present invention.

(E) Additive

The active energy ray-curable composition of the present invention may further include UV stabilizers, fillers, other polymer compounds, curing agents, dispersants, adhesion promoters, antioxidants, and antiflocculants as necessary in addition to the above components.

The UV stabilizer is included in the curable composition to ensure light resistance.

Specific examples of the UV stabilizer include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranilate derivatives and dibenzoylmethane derivatives.

Specific examples of the benzophenone derivative include 2-hydroxy-4-methoxy-benzophenone 2-hydroxy-4-methoxybenzophenone, 2-hydroxy- Dihydroxy-4-methoxybenzophenone, and 2,4-dihydroxybenzophenone.

Specific examples of the benzoate derivative include 2-ethylhexyl salicylate, phenyl salicylate, p-tart-butylphenyl salicylate, 2,4-di-tart- -4-hydroxybenzoate, and hexadecyl-3,5-di-tart-butyl-4-hydroxybenzoate.

Specific examples of the benzotriazole derivatives include 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- 5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di- Benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tart-amylphenyl) benzotriazole and the like .

Specific examples of the triazine derivatives include hydroxyphenyltriazine and bisethylhexyloxyphenol methoxyphenyltriazine.

The UV stabilizer may also be a commercially available one such as TINUVIN PS, TINUVIN 99-2, INUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479, TINUVIN 1577 , CHIMASSORB81 (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name), and the like.

The UV stabilizer may preferably have a maximum absorption region at 350 nm or less (inclusive of j-line) in the wavelength region. A UV stabilizer having a maximum absorption region of 350 nm or more may weaken the irradiation intensity of i-line. From the viewpoint of the structure of the UV stabilizer, benzophenone derivatives and triazine derivatives have a good absorption region at 350 nm or less. Commercially available products include TINUVIN 400, TINUVIN 1577, CHIMASSORB81, and the like.

The above-mentioned UV stabilizers can be used singly or in combination of two or more kinds, and the light resistance and yellowing of the curable composition of the present invention can be prevented.

Specific examples of the filler include glass, silica, and alumina.

Specific examples of the other polymer compound include a curable resin such as an epoxy resin and a maleimide resin, a thermoplastic resin such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester and polyurethane .

The curing agent is used for increasing the hardness of the deep portion and the mechanical strength. Examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, and an oxetane compound.

Examples of the epoxy compound in the curing agent include a bisphenol A epoxy resin, a hydrogenated bisphenol A epoxy resin, a bisphenol F epoxy resin, a hydrogenated bisphenol F epoxy resin, a Novolak epoxy resin, an aromatic epoxy resin, Based epoxy resins, glycidyl ester-based resins, glycidylamine-based resins, aliphatic, alicyclic or aromatic epoxy compounds other than the brominated derivatives, epoxy resins and brominated derivatives of such epoxy resins, butadiene (co) polymeric epoxides , Isoprene (co) polymer epoxides, glycidyl (meth) acrylate (co) polymers, and triglycidyl isocyanurate.

Examples of the oxetane compound in the curing agent include carbonates such as carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexanedicarboxylic acid bisoxetane, and the like. have.

The curing agent may further comprise a curing auxiliary compound capable of ring-opening polymerization of an epoxy group of an epoxy compound and an oxetane skeleton of an oxetane compound together with a curing agent. Examples of the curing aid compound include polyvalent carboxylic acids, polyvalent carboxylic anhydrides, acid generators, and the like. As the carboxylic acid anhydrides, those commercially available as epoxy resin curing agents can be used. As the epoxy resin curing agent, for example, there may be mentioned epoxy resin curing agents such as trade name (ADEKA HARDONE EH-700) (ADEKA INDUSTRY CO., LTD.), Trade name (RICACIDO HH) Manufactured by Shin-Etsu Chemical Co., Ltd.). These curing agents may be used alone or in combination of two or more.

As the dispersing agent, a commercially available surfactant can be used, and examples thereof include surfactants such as silicone, fluorine, ester, cationic, anionic, nonionic, and amphoteric surfactants. These may be used alone or in combination of two or more. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes (Manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by TOKEM PRODUCTS CO., LTD.), And polyethyleneimine, (Manufactured by Asahi Glass Co., Ltd.), Surfon (manufactured by Asahi Glass Co., Ltd.), Mitsubishi Kasei Kogyo Co., Ltd., MEGAFAC (manufactured by Dainippon Ink and Chemicals Inc.), Flourad (manufactured by Sumitomo 3M Limited), Asahi guard, Surflon SOLSPERSE (manufactured by Genene), EFKA (manufactured by EFKA Chemical), PB 821 (manufactured by Ajinomoto), and the like.

These dispersing agents may be used alone or in combination of two or more, and may be contained in an amount of usually 0.01 to 15% by weight based on the solid content in the curable composition.

Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane , N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- Propyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and the like. These adhesion promoters may be used alone or in combination of two or more, and may contain 0.01 to 10% by weight, preferably 0.05 to 2% by weight, based on the solid content in the curable composition.

Specific examples of the antioxidant include 2,2'-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butyl-4-methylphenol.

Specific examples of the anti-flocculant include sodium polyacrylate and the like.

The composition of the present invention can be used for various purposes. For example, a composition for pattern formation such as a resist, a coating material such as an ink and a coating material, and the like can be given. Among them, the composition of the present invention is preferably used as a composition for pattern formation because of its excellent alkali developability.

The composition of the present invention can be preferably used as a composition for forming an active energy ray-curable pattern because it has a high exposure sensitivity and is highly developable and can form an accurate and precise pattern.

When the composition of the present invention is used as a composition for pattern formation, the components (A), (B), (C) and (D) are mixed at appropriate ratios, Can be obtained.

 The pattern forming method using the above composition may be carried out according to a conventional method. The composition may be applied to a substrate and dried to form a coating film. Then, an active energy ray is irradiated from above onto a mask having a specific pattern shape, And a method of developing the uncured portion with a developing solution.

Examples of the substrate include glass and plastic. As the developing solution, an alkaline developing solution is preferable, and concrete examples are as shown later.

As the composition for forming a pattern, 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 can be given.

The composition of the present invention can be preferably used for columnar spacers in the production of liquid crystal panels among these applications.

In the case of using as a columnar spacer, a nonionic surfactant such as polyoxyethylene lauryl ether or a fluorine surfactant may be added to the composition in order to improve coatability and developability. Alternatively, an adhesive preparation, a storage stabilizer, a defoaming agent, and the like may be appropriately added as necessary.

Hereinafter, the use of columnar spacers (hereinafter also referred to as "spacers") will be described.

Spacer

The spacer is formed by the photo-cured coating film of the composition by a photolithography method. The spacers can be formed in arbitrary sizes at arbitrary positions in a liquid crystal panel substrate, but are often formed on a black matrix region or a TFT electrode, which is generally a light shielding portion of a color filter.

The spacer may be formed according to a conventional method. For example, the composition of the present invention may be applied on a substrate such as glass to a thickness required for forming a cell gap, and then heated (hereinafter also referred to as "prebaking" , A method of drying the coating film and forming the coating film through exposure, development, and post-heating (hereinafter, also referred to as post-baking).

When the composition is applied on a substrate, it is applied to a slightly larger thickness of the cell gap in consideration of reduction and deformation of the film due to development, post-baking, and the like. Concretely, it is preferable that the film thickness after pre-baking is 5 to 10 탆, more preferably 6 to 7 탆.

Examples of the application method include a printing method, a spraying method, a roll coating method, a bar coating method, a curtain coating method, a spin coating method and a die coating method (slit coat method) Die coating method is used.

After the composition is applied onto the substrate, pre-baking is performed. In this case, the temperature and time conditions for prebaking may be about 5 to 15 minutes at 50 to 150 ° C. Light is irradiated through a mask having a predetermined pattern shape for forming a spacer on the coated film surface after prebaking.

The light used is preferably ultraviolet light or visible light, and wavelength light of 240 to 410 nm obtained from a high-pressure mercury lamp or a metal halide lamp may be used.

The light irradiation conditions are preferably such that the light irradiation amount is generally from 50 to 600 mJ / cm < 2 > although it depends on the type of the light source, the absorption wavelength of the photopolymerization initiator used or the film thickness of the coating film. If the irradiation amount is less than 50 mJ / cm < 2 >, the exposed portion tends to be detached at the time of development due to defective curing. If the irradiation amount exceeds 600 mJ / cm < 2 >, a precise spacer pattern tends to be difficult to obtain.

After irradiating the coating film surface with light, the unexposed portion is removed by a developer.

As the developer, an aqueous solution of an alkaline compound can be used. Examples of the alkaline compound include potassium hydroxide, sodium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, ammonia, tetramethylammonium hydroxide, and the like. In order to accelerate the developing rate, a water-soluble organic solvent such as methanol, ethanol, isopropanol, and benzyl alcohol or various surfactants may be added in an appropriate amount to the developing solution.

The developing method may be any one selected from a puddle method, a dipping method and a spraying method. After development, the pattern portion is cleaned with water for 0.5 to 1.5 minutes, and is dried by air with compressed air or the like to obtain a spacer pattern. The obtained spacer pattern is post-baked by a heating device such as a hot plate or oven at a temperature of 150 to 350 占 폚 to obtain a liquid crystal panel spacer of the present invention.

The post baking can volatilize the residual solvent and moisture absorbed at the time of development, and can improve the heat resistance of the spacer. The thickness of the spacer is designed to be 3 to 5 占 퐉 after post-baking, though it depends on the cell gap set value of the liquid crystal panel.

When the composition of the present invention is used in the production of a spacer, compression of a planar indenter (indenter formed with a plane of 100 m x 100 m) at room temperature is measured using an ultra-small microhardness tester (H-100C available from Fisher Instruments Co., It is preferable that the elastic deformation ratio [(elastic deformation ratio / total amount of displacement) x 100] measured under the condition that the load becomes 0.2 GPa is 60% or more.

That is, the active energy ray-curable composition of the present invention can be preferably used for producing a spacer, and provides a color filter including the spacer.

Further, the present invention provides a liquid crystal display device provided with the color filter.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the following examples illustrate the present invention and the present invention is not limited by the following examples, and various modifications and changes may be made. The scope of the present invention will be determined by the technical idea of the following claims.

< Manufacturing example >

Manufacturing example  1. Acid content Multifunctional Acrylate  Produce

An acid-containing polyfunctional acrylate was prepared by the ingredients and contents shown in Table 1 below.

100 g (0.335 mol) of pentaerythritol triacrylate (PETA) and 31.5 g (0.35 mol) of oxalic acid as a raw material were dissolved in 200 g of toluene, and the mixture was stirred at 80 DEG C for 1 hour. Thereafter, 5 g of triethylamine as a catalyst was added, and the esterification reaction was carried out at 90 DEG C for 3 hours. To the reaction mixture was added 0.5 g of 2,5-bis (1,1,3,3-tetramethylbutyl hydrocue (DOHQ) Followed by stirring at 90 DEG C for 3 hours to prepare the desired acid-containing polyfunctional acrylate.

Manufacturing example  2 to 7. Acid content Multifunctional Acrylate  Produce

An acid-containing polyfunctional acrylate was prepared in the same manner as in Preparation Example 1, but with the composition shown in Table 1 below.

Production Example 1 Production Example 2 Production Example 3 Production Example 4 Production Example 5 Production Example 6 Production Example 7 Hydroxy-functional (meth) acrylate a-1 100g
(0.335 mol) 100g
(0.335 mol) 100g
(0.335 mol) 100g
(0.335 mol) 100g
(0.335 mol) 100g
(0.335 mol) a-2 100g
(0.19 mol) Polyvalent acid b-1 31.5 g
(0.35 mol) 18g
(0.2 mol) b-2 36.4g
(0.35 mol) b-3 56.1 g
(0.35 mol) b-4 58.1 g
(0.35 mol) b-5 115.5g
(0.35 mol) Acid anhydride c 35g
(0.35 mol) a-1: pentaerythritol triacrylate (molecular weight: 298)
a-2: dipentaerythritol monohydroxypentaacrylate (molecular weight: 524.5)
b-1: Oxalic acid (molecular weight: 90)
b-2: Malonic acid (molecular weight: 104)
b-3: Pimelic acid (molecular weight: 160)
b-4: p-phthalic acid (molecular weight: 166)
b-5: Biphenyl-3,3 ', 5,5'-tetracarboxylic acid (molecular weight: 330)
c: succinic anhydride (molecular weight: 100)

< Synthetic example >

Synthetic example  1. Synthesis of alkali-soluble resin (B-1)

A separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 72 parts by weight of methyl methacrylate, 3 parts by weight of acrylic acid, and propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA" 5 parts by weight of 2,2'-azobis (2-methylbutyronitrile) was added to the total amount of the monomers (100 parts by weight), and dissolved homogeneously. Thereafter, the mixture was stirred at 85 DEG C for 2 hours under a nitrogen stream, and then reacted at 100 DEG C for 1 hour. To the obtained solution, 25 parts by weight of glycidyl methacrylate, 10 parts by weight of triethylamine with respect to glycidyl methacrylate, 1 part by weight of hydroquinone with respect to glycidyl methacrylate, And glycidyl methacrylate were added in an amount of 35% by weight, and the mixture was stirred at 100 캜 for 5 hours to obtain a desired copolymer solution (solid content concentration: 31.5%).

The Mw of the obtained alkali-soluble resin was 22,000, the acid value was 84 mgKOH / g, and the hydroxyl value was 96 mgKOH / g.

< Example  And Comparative Example >

Example  1 to 6 and Comparative Example  1-2. activation Energy line  Curable composition

And the compositions shown in Table 2 were combined to prepare an active energy ray curable composition.

(Parts by weight) Example Comparative Example One 2 3 4 5 6 One 2 article
castle
water Alkali-soluble resin B-1 40 40 40 40 40 40 40 40 Multifunctional
Acrylate Production Example 1 60 Production Example 2 60 Production Example 3 60 Production Example 4 60 Production Example 5 60 Production Example 6 60 Production Example 7 60 M-402 60 Photopolymerization initiator I-907 15 15 15 15 15 15 15 15 Organic solvent PGMEA 250 250 250 250 250 250 250 250 Sum 365 365 365 365 365 365 365 365 B-1: The resin of Synthesis Example 1
M-402: dipentaerythritol pentaacrylate / dipentaerythritol hexaacrylate mixture
&Lt; (Ratio: about 30/70) Aronix M-402 manufactured by Toagosei Co., Ltd.>
I-907: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, IRGACURE 907 manufactured by Ciba Specialty Chemicals
PGMEA: Propylene glycol monomethyl ether acetate

< Experimental Example >

Experimental Example  One. Developability  evaluation

A composition shown in Table 2 was coated on a chromium mask glass substrate of 10 cm square by a spin coater and the coating film was dried for 10 minutes by an air dryer at 80 占 폚 to form a coating film having a dry film thickness of 5 占 퐉. The obtained coating film was spray-developed with a 0.5 wt% aqueous solution of sodium carbonate to measure the time until complete dissolution, and was evaluated according to the following criteria.

[Evaluation Criteria for Developability]

○: dissolve within 30 seconds

Δ: Dissolve within 60 seconds

X: Not dissolved within 60 seconds

Experimental Example  2. Elasticity Strain rate  evaluation

Chromium mask with 10 cm square A composition shown in Tables 1 and 2 was coated on a glass substrate by a spin coater and the coating film was dried for 10 minutes by an air dryer at 80 DEG C to form a coating film having a dry film thickness of 6 mu m . A photomask was placed at a distance of 100 mu m from the coating film, and ultraviolet rays were irradiated by a proximity aligner with an ultrahigh pressure mercury lamp at an intensity of 300 mJ / cm2 (365 nm in terms of illuminance). Subsequently, the substrate was immersed in a 0.5 wt% sodium carbonate aqueous solution at a liquid temperature of 23 DEG C for 60 seconds to undergo alkali development to remove only the uncured portion of the coating film. Thereafter, the substrate was allowed to stand in an atmosphere at 200 캜 for 30 minutes to carry out heat treatment to form a columnar spacer having a height of 5 탆 and a diameter of 10 to 20 탆.

The elastic strain rate of the obtained columnar spacer at room temperature was measured using a micro-hardness tester (H-100C, manufactured by Fisher Instruments Co., Ltd.) equipped with a planar indenter (indenter with a plane of 100 m x 100 m) (Elastic deformation amount / total displacement amount) x 100] under the condition that the load becomes 0.2 GPa.

Experimental Example  3. Evaluation of Shape

The ratio (S2 / S1) of the area (S2) measured by observing the columnar spacers used for the evaluation of the elastic strain rate by an electron microscope and the lower limit (S1) was calculated (see FIG. When this value exceeds 100, it means that the elastic deformation rate is easily lowered because it becomes a reverse tapered phase.

Item Example Comparative Example One 2 3 4 5 6 One 2 Developability ○ ○ ○ ○ ○ ○ X X Elastic strain (%) 73 77 74 74 71 76 42 39 S2 / S1 (%) 75 71 80 76 82 84 121 134

As can be seen from Table 3, the compositions of Examples 1 to 6 were excellent in developability and had an elastic deformation rate of 70% or more and had a sufficient elastic deformation rate for a spacer or a protective film. The shape evaluation result was also confirmed to be less than 100% and no reverse taper phase was observed.

On the other hand, the compositions of Comparative Examples 1 and 2 were inferior in developability evaluation result, and the shape evaluation result was more than 100%, and an inverse tapered image was observed. The evaluation of the elastic strain was also poor at 40%.

Claims (9)

(A) in which a polyvalent acid (A2) is added to a compound (A1) having three or more (meth) acryloyl groups and a hydroxyl group and which can not be in the form of an anhydride is added to the active energy ray curable composition . The method according to claim 1,
Wherein the compound having at least three (meth) acryloyl groups and hydroxyl groups and the polybasic acid which can not be in the form of an anhydride are compounded at a molar ratio of 1: 0.1 to 1: 2. The method according to claim 1,
The compound (A) obtained by adding the polyvalent acid (A2), which can not be an anhydride form, to the compound (A1) having three or more (meth) acryloyl groups and hydroxyl groups is added to the solid component By weight of the active energy ray curable composition. The method according to claim 1,
The polybasic acid which can not be in the form of an anhydride may be selected from the group consisting of maleic acid, biphenyl-3,3 ', 5,5'-tetracarboxylic acid, Isophthalic acid, terephthalic acid, benzene-1,3,5-tricarboxylic acid, 1,3-cyclohexanedicarboxylic acid (1 Cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, 2,5-dicarboxylic acid, and a compound represented by the following formula (1): &quot; (1) &quot;
[Chemical Formula 1]

In the above formula (1), R ₁ is a single bond, a C1-alkylene group or a C5-C20 alkylene group. The method according to claim 1,
An alkali-soluble resin, an alkaline-soluble resin, a photopolymerization initiator, and an organic solvent. The method of claim 5,
With respect to the total weight of solids in the composition,
20 to 80% by weight of an alkali-soluble resin and
Further comprising 1 to 30% by weight of a photopolymerization initiator,
With respect to the total weight of the composition,
And 20 to 90% by weight of an organic solvent. The method of claim 5,
(A) which is a compound obtained by adding a polyvalent acid which can not form an anhydride form to a compound having three or more (meth) acryloyl groups and a hydroxyl group, and a component (A) To 90% by weight of the total weight of the active energy ray curable composition. A color filter comprising a spacer made from the composition of any one of claims 1 to 7. A liquid crystal display device comprising the color filter of claim 8.

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