KR101758393B1 - Photosensitive resin composition, method of forming pattern, color filter, and display device - Google Patents

Abstract

식 중, R¹ 및 R²는 각각 독립적으로 수소 원자 또는 유기기를 나타내지만, 적어도 한쪽은 유기기를 나타낸다. R¹ 및 R²는 이것들이 결합해 환상 구조를 형성하고 있어도 되고, 헤테로 원자의 결합을 포함하고 있어도 된다. R³은 단결합 또는 유기기를 나타낸다. R⁴~R⁹는 각각 독립적으로 수소 원자, 유기기 등을 나타내지만, R⁶ 및 R⁷이 수산기가 되는 경우는 없다. R¹⁰은 수소 원자 또는 유기기를 나타낸다. assignment
A pattern forming method using the photosensitive resin composition, a color filter formed by using the photosensitive resin composition, and a display device using the color filter. The present invention provides a photosensitive resin composition capable of forming a pattern having excellent light- Lt; / RTI >
Solution
The photosensitive resin composition according to the present invention contains a photopolymerizable compound, a photopolymerization initiator, a compound represented by the following formula (1), and a light shielding agent.

In the formulas, R ¹ and R ² each independently represent a hydrogen atom or an organic group, but at least one of them represents an organic group. R ¹ and R ² may combine with each other to form a cyclic structure or may contain a heteroatom bond. R ³ represents a single bond or an organic group. R ⁴ to R ⁹ each independently represent a hydrogen atom, an organic group or the like, but R ⁶ and R ⁷ do not form a hydroxyl group. R ¹⁰ represents a hydrogen atom or an organic group.

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition, a pattern forming method, a color filter, and a display device.

The present invention relates to a photosensitive resin composition, a pattern forming method using the photosensitive resin composition, a color filter formed using the photosensitive resin composition, and a display device using the color filter.

The negative-type photosensitive resin composition has properties of being cured by irradiation with electromagnetic waves such as ultraviolet rays. This photosensitive resin composition is widely used for various applications such as display devices, semiconductor devices, electronic parts, and microelectromechanical systems (MEMS) because it can obtain patterns of desired shapes by curing portions irradiated with electromagnetic waves. For example, the display device is used as a material such as a color filter or a black matrix in a liquid crystal display or an organic EL display.

In recent years, attempts have been made to improve the light-shielding property by the black matrix and further improve the display contrast in the manufacture of a liquid crystal display or an organic EL display. For this reason, it is necessary to incorporate a large amount of a light shielding agent into the photosensitive resin composition for forming the black matrix.

However, when a large amount of the light-shielding agent is contained in the photosensitive resin composition as described above, there is a problem that the sensitivity is lowered and the amount of exposure necessary for pattern formation is increased. Further, since hardening is less likely to occur in a portion closer to the substrate, there is a problem that the pattern is peeled off from the substrate during development, or the edge portion is eroded to lower the linearity of the pattern.

Japanese Patent Laid-Open No. 2011-052214

Accordingly, it is an object of the present invention to provide a photosensitive resin composition capable of forming a pattern that contains a light shielding agent and has excellent linearity and adhesion at a low exposure dose, a pattern forming method using the photosensitive resin composition, a color filter formed using the photosensitive resin composition, And a display device using the same.

The present inventors have studied hard to achieve the above object. As a result, they have found that the above problems can be solved by containing a specific compound in a photosensitive resin composition, and have accomplished the present invention. Specifically, the present invention provides the following.

A first aspect of the present invention is a photosensitive resin composition containing a photopolymerizable compound, a photopolymerization initiator, a compound represented by the following formula (1), and a light shielding agent.

(Shown in, R ¹ and R ² are a hydrogen atom or an organic each independently formula: provided that at least one of R ¹ and R ² represents an organic group. R ¹ and R ² form a cyclic structure by these binding It may be, or may include a combination of the hetero atom. R ³ represents a single bond or an organic. R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group , A silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group or an organic group R ⁶ , R ⁷ , R ⁸ And R ⁹ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonate group, A phosphonyl group, a phosphono group, a phosphonate group, an amino group Represents ammonia coming or an organic group. However, R ^6, and there is no case R ⁷ is where the hydroxyl group. R ^6, R ^7, R ⁸ and R ⁹ is may form a ring structure by combining more than these two, hetero And R ¹⁰ represents a hydrogen atom or an organic group.

As a compound having a structure similar to the compound represented by the above formula (1), Patent Document 1 discloses a base generator represented by the following formula. The base generator is cyclized by irradiation with electromagnetic waves and heating to produce a base (NHR ²¹ R ²² ).

(Wherein R ²¹ and R ²² are each independently a hydrogen atom or an organic group and may be the same or different), and R ²¹ and R ²² may be bonded to form a cyclic structure, or it may, and except, R ²¹ and the R ²² of the at least one is an organic group. R ²³ and R ²⁴ are playing each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol , a nitro group, alcohol is pinot group, sulfo group, sulfonate group, phosphino group, a phosphine P group, a phosphono group, phosphonate group or an organic group, may be the same or different. However, R ^23, and At least one of R ²⁴ is a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonate group, a phosphino group, , A phosphono group, a phosphonate group or an organic group R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ represents a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonate group, a phosphino group, A phosphono group, a phosphonate group, an amino group, an ammonium group or an organic group and may be the same or different from each other. R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ may combine with each other to form a cyclic structure, And may contain a bond of a hetero atom.)

However, the present inventors have found that good micropatterning characteristics can not be obtained because light energy is consumed for cyclization even when the base generator described in Patent Document 1 is contained in the photosensitive resin composition.

On the other hand, in the compound represented by the above formula (1), since R ⁶ and R ⁷ do not form a hydroxyl group, cyclization reaction does not occur and good fine patterning characteristics can be obtained.

Further, since the compound represented by the above formula (1) generates a base by irradiation with electromagnetic waves or heating, it also functions as a base generator. When the compound represented by the formula (1) is incorporated into the photosensitive resin composition, the compound exhibits an effect of enhancing the adhesion to the substrate and thus also functions as an adhesion enhancer.

A second aspect of the present invention is a pattern forming method for forming a coating film or a molded body using the photosensitive resin composition according to the present invention, and irradiating the coating film or the molded body with electromagnetic waves in a predetermined pattern shape for development.

A third aspect of the present invention is a color filter formed using the photosensitive resin composition according to the present invention, and the fourth aspect of the present invention is a display device using the color filter according to the present invention.

According to the present invention, there can be provided a photosensitive resin composition capable of forming a pattern having excellent light-shielding property and high linearity and adhesion at a low exposure amount, a pattern forming method using the photosensitive resin composition, a color filter formed using the photosensitive resin composition, Can be provided.

&Quot; Photosensitive resin composition &

The photosensitive resin composition according to the present invention contains at least a photopolymerizable compound, a photopolymerization initiator, a compound represented by the following formula (1), and a light shielding agent. Hereinafter, each component contained in the photosensitive resin composition will be described in detail.

≪ Photopolymerizable compound >

The photopolymerizable compound is not particularly limited, and conventionally known photopolymerizable compounds can be used. Among them, a resin or monomer having an ethylenic unsaturated group is preferable, and a combination thereof is more preferable. By combining a resin having an ethylenic unsaturated group and a monomer having an ethylenic unsaturated group, it is possible to improve the curability of the photosensitive resin composition and facilitate pattern formation.

[Resin Having Ethylenic Unsaturated Group]

As the resin having an ethylenic unsaturated group, for example, a resin obtained by reacting a reaction product of an epoxy compound and an unsaturated carboxylic acid with a polybasic acid anhydride can be used.

Among them, a resin having a cardo structure is preferable, and a resin represented by the following formula (a-1) is more preferable. The resin represented by the formula (a-1) is preferable in view of its high photocurability.

In the above formula (a-1), X ^a represents a group represented by the following formula (a-2).

In formula (a-2), R ^a1 independently represents a hydrogen atom, a hydrocarbon group of 1 to 6 carbon atoms or a halogen atom, R ^a2 each independently represents a hydrogen atom or a methyl group, and W ^a represents ^a single bond or Represents a group represented by the following formula (a-3).

In the formula (a-1), Y ^a represents a residue other than an acid anhydride group (-CO-O-CO-) from ^a dicarboxylic acid anhydride. Examples of the dicarboxylic acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl endmethylenetetrahydrophthalic anhydride, chlorodic anhydride, methyltetrahydrophthalic anhydride, And glutaric acid.

In the above formula (a-1), Z ^a represents a residue other than the two acid anhydride groups from the tetracarboxylic acid dianhydride. Examples of the tetracarboxylic acid dianhydride include pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, and biphenyl ether tetracarboxylic dianhydride.

In the above formula (a-1), m represents an integer of 0 to 20.

Examples of the resin having an ethylenic unsaturated group include a polyester (meth) acrylate obtained by reacting a (meth) acrylic acid with a polyester prepolymer obtained by condensing a polyhydric alcohol with a monobasic acid or a polybasic acid; (Meth) acrylate obtained by reacting a compound with a (meth) acrylic acid and then reacting with the (meth) acrylic acid; a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a phenol or cresol novolak type epoxy resin, An epoxy resin such as a sol-type epoxy resin, a triphenolmethane-type epoxy resin, a polycarboxylic acid polyglycidyl ester, a polyol polyglycidyl ester, an aliphatic or alicyclic epoxy resin, an amine epoxy resin and a dihydroxybenzene- (Meth) acrylic acid obtained by reacting an epoxy (meth) Sites may use a resin, or the like.

In the present specification, "(meth) acrylic acid" means both acrylic acid and methacrylic acid. Likewise, "(meth) acrylate" means both acrylate and methacrylate.

The acid value of the resin having an ethylenic unsaturated group is preferably 10 to 150 mgKOH / g, more preferably 70 to 110 mgKOH / g, in terms of resin solid content. Within the above range, sufficient curability can be obtained while achieving good developability.

The weight average molecular weight of the resin having an ethylenic unsaturated group is preferably from 1,000 to 40,000, more preferably from 2,000 to 30,000. Within the above range, sufficient heat resistance and film strength can be obtained while satisfactory developability is obtained.

The content of the resin having an ethylenic unsaturated group is preferably 5 to 80% by weight, more preferably 15 to 50% by weight, based on the solid content of the photosensitive resin composition. When the amount is in the above range, there is a tendency that balance of developability is easily obtained.

[Monomer having an ethylenically unsaturated group]

Monomers having an ethylenic unsaturated group include monofunctional monomers and polyfunctional monomers.

Examples of the monofunctional monomer include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxy (Meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, maleic anhydride, maleic anhydride, Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, (Meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl ) Acrylate, 2-phenoxy-2-hydroxypropyl (meth) (Meth) acrylate, glycidyl (meth) acrylate, trimethylolpropyl (meth) acrylate, dimethylamino (Meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, and half . These monofunctional monomers may be used alone or in combination of two or more.

Examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (Meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, butyleneglycol di (meth) acrylate, neopentyl glycol di (Meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (Meth) acryloxypolyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxy diethoxyphenyl) propane, (Meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (Meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (i.e., tolylene diisocyanate), trimethylhexamethylene diisocyanate (Meth) acrylamide, (meth) acrylamide methylene ether, a reaction product of a polyhydric alcohol and N-methylol (meth) acrylamide, a reaction product of hexamethylene diisocyanate and 2-hydroxyethyl There may be mentioned polyfunctional monomer and, triacrylate Pro words such compounds and the like. These multifunctional monomers may be used alone or in combination of two or more.

The content of the monomer having an ethylenic unsaturated group is preferably 1 to 30% by weight, more preferably 5 to 20% by weight, based on the solid content of the photosensitive resin composition. When the content is in the above range, there is a tendency to balance the sensitivity, developability and resolution.

<Photopolymerization initiator>

The photopolymerization initiator is not particularly limited and conventionally known photopolymerization initiators can be used.

Specific examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2- hydroxyethoxy) Methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy- (4-dimethylaminophenyl) ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethylsulfide, 2- Dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino- benzyldimethylketal, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, 2,4- , 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, 2-isopropylanthraquinone, octamethylanthraquinone, 1,2-benzoyl peroxide, 2-ethylhexanoic acid, 2-chlorothioxanthone, Anthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzoimidal, 2-mercaptobenzooxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o- (O-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- , 5-diphenylimidazole dimer, 2,4,5-triarylimidazole dimer, benzophenone, 2-chlorobenzophenone, 4,4'-bisdimethylaminobenzophenone (that is, ), 4,4'-bisdiethylaminobenzophenone (i.e., ethylhexyl ketone), 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzo Benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p- P-tert-butyltrichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p- Butyldichloroacetophenone,?,? -Dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate , 9-phenylacridine, 1,7-bis- (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane, (Trichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl- [2- (5-methylfuran-2-yl) ether (Trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (Trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethyl] (Trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (Trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis , 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl- -Triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl- IRGACURE OXE02 "," IRGACURE OXE01 "," IRGACURE 369 "," IRGACURE 651 "," IRGACURE 907 ", and" IRGACURE 907 " (Trade name, manufactured by BASF) and "NCI-831" (trade name, manufactured by ADEKA). These photopolymerization initiators may be used alone or in combination of two or more.

Among them, it is particularly preferable to use an oxime-based photopolymerization initiator in terms of sensitivity, and it is particularly preferable to use a oxime-based photopolymerization initiator having a carbazole skeleton.

A preferred example of the oxime-based photopolymerization initiator is a photopolymerization initiator represented by the following formula (b-1).

In the above formula (b-1), R ^b1 represents a heterocyclic group, a condensed cyclic aromatic group or an aromatic group which may have a substituent. R ^b2 to R ^b4 each independently represent a monovalent organic group.

The heterocyclic group for R &lt; ^b1 &gt; includes a heterocyclic group having 5 or more ring members, preferably a 5-membered ring or 6-membered ring including at least one atom selected from a nitrogen atom, a sulfur atom and an oxygen atom. Examples of the heterocyclic group include a nitrogen-containing five-membered ring group such as a pyrrolyl group, an imidazolyl group and a pyrazolyl group, a nitrogen-containing six-membered ring group such as pyridyl group, pyridinyl group, pyrimidyl group, and pyridadinyl group, A nitrogen-containing heterocyclic group such as an isothiazolyl group, a nitrogen-containing oxygen group such as an oxazolyl group and an isoxazolyl group, a heterocyclic group such as a thienyl group and a thiopyranyl group, an oxygen atom such as a furyl group and a pyranyl group, . Among them, it is preferable to include one nitrogen atom or sulfur atom. The heterocyclic ring may contain a condensed ring. Examples of the heterocyclic group containing a condensed ring include a benzothienyl group and the like.

^Examples of the condensed cyclic aromatic group in R ^b1 include a naphthyl group, an anthryl group, and a phenanthryl group. The aromatic group in R ^b1 includes a phenyl group.

The heterocyclic group, the condensed ring aromatic group or the aromatic group may have a substituent. Particularly, when R ^b1 is an aromatic group, it is preferable to have a substituent. Examples of such substituents include -NO ₂ , -CN, -SO ₂ R ^b5 , -COR ^b5 , -NR ^b6 R ^b7 , -R ^b8 , -OR ^b8 , -OR ^b9 -OR ^b10 and the like.

R ^b5 each independently represents an alkyl group, which may be substituted with a halogen atom, or may be interrupted by an ether bond, a thioether bond or an ester bond. The alkyl group in R ^b5 preferably has 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group.

R ^b6 and R ^b7 each independently represent a hydrogen atom, an alkyl group or an alkoxy group, which may be substituted with a halogen atom, and the alkylene moiety of the alkyl group and the alkoxy group may be interrupted by an ether bond, a thioether bond or an ester bond, . R ^b6 and R ^b7 may combine to form a ring structure. The alkyl group or the alkoxy group in R ^b6 and R ^b7 preferably has 1 to 5 carbon atoms, and examples thereof include a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, methoxy group, ethoxy group, Time and so on.

The ring structure that R ^b6 and R ^b7 can combine to form is a heterocycle. The heterocyclic ring may be a 5-membered ring or more, preferably a 5- to 7-membered heterocyclic ring containing at least a nitrogen atom. The heterocyclic ring may contain a condensed ring. Examples of the heterocycle include a piperidine ring, a morpholine ring, and a thiomorpholine ring. Among them, a morpholine ring is preferable.

R ^b8 represents an alkyl group in which some or all of the hydrogen atoms may be substituted with a halogen atom. The alkyl group in R ^b8 preferably has 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and an isobutyl group.

R ^b9 and R ^b10 each independently represent an alkyl group, which may be substituted with a halogen atom, or may be interrupted by an ether bond, a thioether bond or an ester bond. The preferred number of carbon atoms or a specific example thereof is the same as that of R ^b1 .

Among them, preferable examples of R ^b1 include a pyrrolyl group pyridyl group, a thienyl group, a thiopyraryl group, a benzothienyl group, a naphthyl group and a phenyl group having a substituent group.

In the above formula (b-1), R ^b2 represents a monovalent organic group. The organic group is preferably a group represented by -R ^b11 , -OR ^b11 , -COR ^b11 , -SR ^b11 , or -NR ^b11 R ^b12 . R ^b11 and R ^b12 each independently represent an alkyl group, an alkenyl group, an aryl group, an aralkyl group or a heterocyclic group, which may be substituted with a halogen atom, an alkyl group or a heterocyclic group, May be interrupted by an unsaturated bond, an ether bond, a thioether bond, or an ester bond. R ^b11 and R ^b12 may combine with each other to form a ring structure together with the nitrogen atom.

The alkyl group for R ^b11 and R ^b12 preferably has 1 to 20 carbon atoms, more preferably 1 to 5 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec- n-hexyl group, n-heptyl group, n-octyl group, isooxyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, , And the like. The alkyl group may have a substituent. Examples of the substituent include a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propoxyethoxyethyl group, and a methoxypropyl group.

The alkenyl group in R ^b11 and R ^b12 preferably has 1 to 20 carbon atoms, more preferably 1 to 5 carbon atoms. Examples of the alkenyl group include a linear or branched group such as a vinyl group, an allyl group, a butenyl group, an ethenyl group, and a propynyl group. The alkenyl group may have a substituent. Examples of the substituent include a 2- (benzoxazol-2-yl) ethenyl group and the like.

The aryl group in R ^b11 and R ^b12 preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms. Examples of the aryl group include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl and phenanthryl groups.

The aralkyl group in R ^b11 and R ^b12 preferably has 7 to 20 carbon atoms, more preferably 7 to 12 carbon atoms. Examples of the aralkyl group include benzyl group,? -Methylbenzyl group,?,? - dimethylbenzyl group, phenylethyl group, phenylethenyl group and the like.

As the heterocyclic group for R ^b11 and R ^b12 , a heterocyclic group having 5 or more members, preferably 5 to 7 member rings, containing at least one atom of a nitrogen atom, a sulfur atom and an oxygen atom can be mentioned. The heterocyclic group may contain a condensed ring. Examples of the heterocyclic group include a pyrrolyl group pyridyl group, a pyrimidyl group, a furyl group, and a thienyl group.

Among these R ^b11 and R ^b12 , the alkylene moiety of the alkyl group and the aralkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond, or an ester bond.

The ring structure that R ^b11 and R ^b12 may combine to form may include a heterocyclic ring. The heterocyclic ring may be a 5-membered ring or more, preferably a 5- to 7-membered heterocyclic ring containing at least a nitrogen atom. The heterocyclic ring may contain a condensed ring. Examples of the heterocycle include a piperidine ring, a morpholine ring, and a thiomorpholine ring.

Among them, R ^b2 is most preferably a methyl group, an ethyl group, a propyl group or a phenyl group.

In the above formula (b-1), R ^b3 represents a monovalent organic group. The organic group is preferably an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms which may have a substituent, a group represented by the following formula (b-2) or a heterocyclic group optionally having a substituent. Examples of the substituent include the same groups as those in the case of R ^b1 . Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group.

In the formula (b-2), R ^b13 represents an alkylene group having 1 to 5 carbon atoms which may be interrupted by an oxygen atom. Examples of such alkylene groups include methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, sec-butylene, n-pentylene, A straight chain or branched chain group. Among them, R ^b13 is most preferably an isopropylene group.

In the formula (b-2), R ^b14 represents a monovalent organic group represented by -NR ^b15 R ^b16 (R ^b15 and R ^b16 each independently represent a monovalent organic group). Among these organic ^groups , it is preferable that the structure of R ^b14 is represented by the following formula (b-3) in that the solubility of the photopolymerization initiator can be improved.

In the formula (b-3), R ^b17 and R ^b18 each independently represent an alkyl group having 1 to 5 carbon atoms. Examples of such alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, , tert-pentyl group, and the like. Among them, R ^b17 and R ^b18 are most preferably a methyl group.

The heterocyclic group in R ^b3 includes a heterocyclic group having 5 or more members, preferably a 5-membered ring or 6-membered ring containing at least one atom selected from a nitrogen atom, a sulfur atom and an oxygen atom. Examples of the heterocyclic group include a nitrogen-containing five-membered ring group such as a pyrrolyl group, an imidazolyl group and a pyrazolyl group, a nitrogen-containing six-membered ring group such as pyridyl group, pyridinyl group, pyrimidyl group, and pyridadinyl group, A nitrogen-containing heterocyclic group such as an isothiazolyl group, a nitrogen-containing oxygen group such as an oxazolyl group and an isoxazolyl group, a heterocyclic group such as a thienyl group and a thiopyranyl group, an oxygen atom such as a furyl group and a pyranyl group, . Among them, it is preferable to include one nitrogen atom or sulfur atom. The heterocyclic ring may contain a condensed ring. Examples of the heterocyclic group containing a condensed ring include a benzothienyl group and the like.

The heterocyclic group may have a substituent. Examples of the substituent include the same groups as those in the case of R ^b1 .

In the above formula (b-1), R ^b4 represents a monovalent organic group. Among them, an alkyl group having 1 to 5 carbon atoms is preferable. Examples of such alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, , tert-pentyl group, and the like. Among them, R ^b4 is most preferably a methyl group.

Another preferable example of the oxime-based photopolymerization initiator is a photopolymerization initiator represented by the following formula (c-1) proposed in Japanese Patent Application Laid-Open No. 2010-15025.

In the formula (c-1), R ^c1 and R ^c2 each independently represent R ^c11 , OR ^c11 , COR ^c11 , SR ^c11 , CONR ^c12 R ^c13 or CN.

R ^c11 , R ^c12 and R ^c13 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. Hydrogen atoms of the alkyl group, aryl group, arylalkyl group and heterocyclic group may also ^c21 OR, COR ^{c21, c21} SR, NR ^c22 R ^c23, CONR ^c22 R ^c23, -NR ^{c22 c23} -OR, -OCOR -NCOR ^{c22 c23,} -C (= N-OR ^c21 ) -R ^c22 , -C (= N-OCOR ^c21 ) -R ^c22 , CN, a halogen atom, -CR ^c21 = CR ^c21 R ^c23 , -CO-CR ^c21 = CR ^c22 R ^c23 , Or an epoxy group. R ^c21 , R ^c22 and R ^c23 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.

Wherein R ^c11, R ^c12, R ^c13, R ^c21, R methylene groups are unsaturated bond of the alkylene portion of the substituent in the ^c22 and R ^c23, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond or a urethane bond , The alkyl moiety of the substituent may be branched or cyclic, the alkyl terminus of the substituent may be an unsaturated bond, and R ^c12 and R ^c13 and R ^c22 and R ^c23 may be bonded to each other to form a ring structure.

R ^c3 and R ^c4 are each independently selected from the group consisting of R ^c11 , OR ^c11 , COR ^c11 , SR ^c11 , CONR ^c12 R ^c13 , NR ^c11 COR ^c12 , OCOR ^c11 , COOR ^c11 , SCOR ^c11 , OCSR ^c11 , COSR ^c11 , CSOR ^c11 , CN, a halogen atom or a hydroxyl group. a and b each independently represent an integer of 0 to 4;

R ^c3 may be bonded to one of the carbon atoms of adjacent benzene rings through -X ^c2 - to form a ring structure, or R ^c3 and R ^c4 may be combined to form a ring structure.

In the formula (c-1), X ^c1 represents a single bond or CO.

In the formula (c-1), X ^c2 represents an oxygen atom, a sulfur atom, a selenium atom, CR ^c31 R ^c32 , CO, NR ^c33 or PR ^c34 . R ^c31 , R ^c32 , R ^c33 and R ^c34 each independently represent R ^c11 , OR ^c11 , COR ^c11 , SR ^c11 , CONR ^c12 R ^c13 or CN. R ^c31 , R ^c33 and R ^c34 may independently be ^bonded to any adjacent benzene ring to form a ring structure.

Examples of the alkyl group in R ^c11 , R ^c12 , R ^c13 , R ^c21 , R ^c22 and R ^c23 in the formula (c-1) include a methyl group, ethyl group, n-propyl group, isopropyl group, Butyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group and tert-pentyl group.

The aryl group in R ^c11 , R ^c12 , R ^c13 , R ^c21 , R ^c22 and R ^c23 in the formula (c-1) is preferably a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a chlorophenyl group, A trityl group, a phenanthrenyl group and the like.

Examples of the arylalkyl group in R ^c11 , R ^c12 , R ^c13 , R ^c21 , R ^c22 and R ^c23 in the formula (c-1) include a benzyl group, a chlorobenzyl group, A benzyl group, a phenylethyl group, and a phenylethenyl group.

The heterocyclic group in R ^c11 , R ^c12 , R ^c13 , R ^c21 , R ^c22 and R ^c23 in the formula (c-1) includes a pyridyl group, a pyrimidyl group, a furyl group, a thienyl group, a tetrahydrofuryl group, A thiazolyl group, an isoxazolyl group, an isoxazolyl group, an isoxazolyl group, a piperazino group, a benzooxazol-2-yl group, a tetrahydropyranyl group, a pyrrolidyl group, an imidazolididyl group, A 5- to 7-membered ring such as a furanyl group, a furfuryl group, a furfuryl group, a furfuryl group, a furfuryl group,

In the formula (c-1), a ring which R ^c12 and R ^c13 can bond together to form a ring, a ring which R ^c22 and R ^c23 can bond to form, and R ^c3 can be formed with an adjacent benzene ring, Examples of the ring include 5- to 7-membered rings such as a cyclopentane ring, cyclohexane ring, cyclopentene ring, benzene ring, piperidine ring, morpholine ring, lactone ring, and lactam ring.

When X ^c2 is NR ^c33 and R ^c3 is bonded to one of the carbon atoms of the adjacent benzene ring to form a 5-membered ring structure together with X ^c2 , the photopolymerization initiator has a carbazole skeleton.

In the formula (c-1), the halogen atom which may be substituted for R ^c11 , R ^c12 , R ^c13 , R ^c21 , R ^c22 and R ^c23 and the halogen atom for R ^c4 and R ^c5 include fluorine, chlorine, bromine Atoms, and iodine atoms.

The methylene group of the alkylene moiety of the substituent may be interrupted one to five times by an unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond or a urethane bond. In this case, the coupler to be stopped may be one kind or two or more kinds of contributing units, and in the case of a group capable of being continuously stopped, two or more of them may be continuously discontinued. The alkyl moiety of the substituent may be branched or cyclic alkyl, and the alkyl terminus of the substituent may be an unsaturated bond.

The content of the photopolymerization initiator is preferably 0.5 to 20 parts by weight based on 100 parts by weight of the solid content of the photosensitive resin composition. When the content is in the above range, sufficient heat resistance and chemical resistance can be obtained, and coating film forming ability can be improved, and curing defects can be suppressed.

&Lt; Compound represented by formula (1) &gt;

The photosensitive resin composition according to the present invention contains a compound represented by the following formula (1).

In the formula (1), R ¹ and R ² each independently represent a hydrogen atom or an organic group, but at least one of R ¹ and R ² represents an organic group.

Examples of the organic group for R ¹ and R ² include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, and an aralkyl group. This organic group may contain a bond or a substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be any of linear, branched and cyclic.

This organic group is usually monovalent, but in the case of forming a cyclic structure, it may be a divalent or higher-valent organic group.

R ¹ and R ² may combine with each other to form a cyclic structure or may further include a bond of a heteroatom. Examples of the cyclic structure include a heterocycloalkyl group and a heteroaryl group, and condensed rings may be used.

The bond other than the hydrocarbon group in the organic group of R ¹ and R ² is not particularly limited as long as the effect of the present invention is not impaired and includes a bond including a hetero atom such as an oxygen atom, a nitrogen atom or a silicon atom . Specific examples thereof include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, an imino bond (-N═C (-R) R represents a hydrogen atom or an organic group), a carbonate bond, a sulfonyl bond, a sulfinyl bond, and an azo bond.

From the viewpoint of heat resistance, examples of the bond other than the hydrocarbon group in the organic group of R ¹ and R ² include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, -N═C (-R) -, -C (═NR) -: R represents a hydrogen atom or a monovalent organic group), a carbonate bond, a sulfonyl bond and a sulfinyl bond are preferable.

Substituents other than the hydrocarbon group in the organic group of R ¹ and R ² are not particularly limited as long as the effect of the present invention is not impaired, and examples thereof include a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, A silanol group, an alkoxy group, an alkoxycarbonyl group, a carbamoyl group, a thiocarbamoyl group, a nitro group, a nitroso group, a carboxyl group, a carboxylate group, a carboxylate group, an isocyanate group, a thiocyanate group, an isothiocyanate group, An acyl group, an acyloxy group, a sulfino group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, a hydroxyimino group, an alkyl ether group, an alkenyl ether group , An alkylthioether group, an alkenylthioether group, an arylether group, an arylthioether group, an amino group (-NH ₂ , -NHR, -NRR ': R and R' each independently represents a hydrocarbon group) have. The hydrogen atom contained in the substituent may be substituted by a hydrocarbon group. The hydrocarbon group contained in the substituent may be any of straight chain, branched chain and cyclic.

Examples of substituents other than the hydrocarbon group in the organic group of R ¹ and R ² include a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, an isocyanato group, a cyanate group, an isocyanate group, a thiocyanate group, A carbamoyl group, a nitrocarbamoyl group, a nitro group, a carboxyl group, a carboxylate group, an acyl group, an acyloxy group, a sulfino group, a sulfo group, a sulfonyl group, a sulfonyl group, A sulfonate group, a phosphono group, a phosphonyl group, a phosphono group, a phosphonate group, a hydroxyimino group, an alkyl ether group, an alkenyl ether group, an alkylthioether group, an alkenylthioether group, Group and an arylthioether group are preferable.

Of these, at least one of R ¹ and R ² is preferably an alkyl group having 1 to 12 carbon atoms or an aryl group having 1 to 12 carbon atoms, or may be bonded to each other to form a heterocycloalkyl group or a heteroaryl group having 2 to 20 carbon atoms Do. Examples of the heterocycloalkyl group include a piperidino group and a morpholino group. Examples of the heteroaryl group include an imidazolyl group and a pyrazolyl group.

In the above formula (1), R ³ represents a single bond or an organic group.

Examples of the organic group for R ³ include a group excluding one hydrogen atom from an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group or an aralkyl group. This organic group may contain a substituent in the organic group. Examples of the substituent include those exemplified as R ¹ and R ² . The organic group may be either straight chain or branched chain.

Among them, R ³ is preferably a single bond, an alkyl group having 1 to 12 carbon atoms, or an aryl group having 1 to 12 carbon atoms, which is a group excluding one hydrogen atom.

Wherein R ⁴ and R ⁵ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, , A sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group or an organic group.

The organic groups in R ⁴ and R ⁵ include those exemplified as R ¹ and R ² . As in the case of R ¹ and R ² , this organic group may contain a bond or a substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be any of linear, branched and cyclic.

Among them, R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, a cycloalkenyl group having 4 to 13 carbon atoms, an aryloxyalkyl group having 7 to 16 carbon atoms, An aralkyl group having 7 to 20 carbon atoms, an alkyl group having 2 to 11 carbon atoms having a cyano group, an alkyl group having 1 to 10 carbon atoms having a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an amide group having 2 to 11 carbon atoms, An acyl group having from 1 to 10 carbon atoms, an ester group having from 2 to 11 carbon atoms (-COOR, -OCOR: R representing a hydrocarbon group), an aryl group having from 6 to 20 carbon atoms, an electron donating group and / An aryl group having 6 to 20 carbon atoms which is substituted, a benzyl group substituted with an electron-donating group and / or an electron-withdrawing group, a cyano group, or a methylthio group. More preferably R &lt; ⁴ &gt; And R ⁵ are both hydrogen atoms, or R ⁴ is a methyl group and R ⁵ is a hydrogen atom.

R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, A sulfonyl group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, an amino group, an ammonium group or an organic group.

Examples of the organic group at R ⁶ , R ⁷ , R ⁸ and R ⁹ include those exemplified as R ¹ and R ² . As in the case of R ¹ and R ² , this organic group may contain a bond or a substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be any of linear, branched and cyclic.

In the above formula (1), R ⁶ and R ⁷ do not form a hydroxyl group. When R ⁶ or R ⁷ is a hydroxyl group, a cyclization reaction occurs by electromagnetic wave irradiation and heating as described in Patent Document 1. Therefore, even when such a compound is contained in the photosensitive resin composition, the light energy is consumed for cyclization and good fine patterning characteristics can not be obtained. In contrast, the compound represented by the above formula (1) does not cause a cyclization reaction because R ⁶ and R ⁷ do not form a hydroxyl group, and it is possible to obtain good minute patterning characteristics when contained in the photosensitive resin composition .

R ⁶ , R ⁷ , R ⁸ and R ⁹ may combine with each other to form a cyclic structure or may contain a heteroatom bond. Examples of the cyclic structure include a heterocycloalkyl group and a heteroaryl group, and condensed rings may be used. For example, R ⁶ , R ⁷ , R ^8, and R ⁹ may be bonded to each other to form a bond between the benzene ring atoms to which R ⁶ , R ⁷ , R ^8, and R ⁹ are bound to form naphthalene, anthracene, phenanthrene, Condensed rings such as indene may be formed.

Of the above groups, R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, a cycloalkenyl group having 4 to 13 carbon atoms, An aralkyl group having 7 to 20 carbon atoms, an alkyl group having 2 to 11 carbon atoms having a cyano group, an alkyl group having 1 to 10 carbon atoms having a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an amide group having 2 to 11 carbon atoms, An alkyl group having 1 to 10 carbon atoms, an acyl group having 1 to 10 carbon atoms, an ester group having 2 to 11 carbon atoms, an aryl group having 6 to 20 carbon atoms, an electron donating group and / An aryl group, an electron-donating group and / or a benzyl group substituted with an electron-withdrawing group, cyano group, methylthio group or nitro group.

In addition, R ^6, R ^7, R ⁸ and R ⁹ roneun combination of these 2 or more, R ^6, R ^7, R ⁸ and R ⁹ are sharing a benzene ring atom bonded naphthalene, anthracene, phenanthrene, indene, etc. Condensed ring is also formed from the viewpoint that the absorption wavelength becomes long.

More preferably, all of R ⁶ , R ⁷ , R ⁸ and R ⁹ are hydrogen atoms, or any one of R ⁶ , R ⁷ , R ⁸ and R ⁹ is a nitro group, and the remaining three are hydrogen atoms.

In the above formula (1), R ¹⁰ represents a hydrogen atom or an organic group.

Examples of the organic group at R ¹⁰ include those exemplified as R ¹ and R ² . As in the case of R ¹ and R ² , this organic group may contain a bond or a substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be any of linear, branched and cyclic.

The compound represented by the above formula (1) has a -OR ¹⁰ group at the para position of the benzene ring, and therefore has good solubility in an organic solvent.

Among them, R ¹⁰ is preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably a methyl group.

Particularly preferred specific examples among the compounds represented by the above formula (1) include compounds represented by the following formulas.

The compound represented by the above formula (1) has good solubility in an organic solvent and can obtain good fine patterning characteristics when contained in a photosensitive resin composition. Further, this compound can be synthesized in the same manner as in Examples described later.

The content of the compound represented by the formula (1) is preferably 35 to 200 parts by weight, more preferably 50 to 150 parts by weight, and still more preferably 50 to 100 parts by weight based on 100 parts by weight of the photopolymerization initiator. By setting the thickness within the above range, good fine patterning characteristics can be obtained while satisfactory developability is obtained.

<Shading agent>

As the light shielding agent, it is preferable to use a black pigment. Examples of the black pigments include carbon black, titanium black, metal oxides such as copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium and silver, complex oxides, metal sulfides, metal sulfates, metal carbonates, And various pigments. Among these, it is preferable to use carbon black having high light shielding properties.

As the carbon black, known carbon black such as channel black, furnace black, thermal black and lamp black can be used, but it is preferable to use channel black excellent in light shielding property. Resin-coated carbon black may also be used.

Since the resin-coated carbon black has a lower conductivity than carbon black having no resin coating, a display with low power consumption and high reliability can be manufactured with less current leakage when used in a photosensitive resin composition for forming a black matrix.

In order to adjust the color tone of the carbon black, an organic pigment may be appropriately added as an auxiliary pigment.

In order to uniformly disperse the colorant in the negative-type photosensitive resin composition, a dispersant may be further used. As such a dispersing agent, it is preferable to use a polymeric dispersant of a polyethylene imine type, a urethane resin type or an acrylic resin type. Particularly when carbon black is used as a light-shielding agent, it is preferable to use an acrylic resin-based dispersant as a dispersant.

The content of the light-shielding agent may be appropriately determined depending on the use of the photosensitive resin composition, but is preferably 5 to 70 parts by weight, more preferably 25 to 60 parts by weight, based on 100 parts by weight of the solid content of the photosensitive resin composition.

Particularly, in the case of forming a black matrix using a photosensitive resin composition, it is preferable to adjust the amount of the light-shielding agent in the photosensitive resin composition so that the OD value per 1 m of the thickness of the black matrix is 4 or more. When the OD value per 1 m of the film thickness in the black matrix is 4 or more, sufficient display contrast can be obtained when the black matrix is used for a black matrix.

It is preferable that the light-shielding agent is added to the photosensitive resin composition after preparing a dispersion in which the light-shielding agent is dispersed at a suitable concentration using a dispersant.

<Organic solvents>

The photosensitive resin composition according to the present invention preferably contains an organic solvent for dilution. Examples of the organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether Diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono propyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono- (Poly) alkylene glycol moiety such as propylene glycol monomethyl ether, tripropylene glycol monoethyl ether and the like Alkyl ethers such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and the like Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, tetrahydrofuran and the like; alcohols such as methyl ethyl ketone, cyclohexanone, 2- Methyl propionate, methyl 3-methoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-hydroxypropionate, Ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, acetic acid n &lt; RTI ID = 0.0 & Butyl, isobutyl acetate, n-pentyl acetate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, Methyl ethyl ketone, ethyl lactate, ethyl lactate, ethyl lactate, ethyl lactate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; Amides such as amide and N, N-dimethylacetamide, and the like. These organic solvents may be used alone or in combination of two or more.

Among the organic solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 3 -Methoxybutyl acetate is preferable because it exhibits excellent solubility in the above photopolymerizable compound, the photopolymerization initiator and the compound represented by the formula (1), and the dispersibility of the light-shielding agent can be improved, and propylene glycol mono It is particularly preferable to use methyl ether acetate, 3-methoxybutyl acetate.

The content of the organic solvent is preferably such that the solid concentration of the photosensitive resin composition is 1 to 50% by weight, more preferably 5 to 30% by weight.

&Lt; Other components &gt;

The photosensitive resin composition according to the present invention may contain various additives as required. Examples of the additive include a sensitizer, a curing accelerator, a filler, an adhesion promoter, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, a thermal polymerization inhibitor, a defoaming agent, and a surfactant.

&Lt; Preparation method of photosensitive resin composition &gt;

The photosensitive resin composition according to the present invention is prepared by mixing each of the above components with a stirrer. Further, it may be filtered using a membrane filter or the like so that the prepared photosensitive resin composition becomes uniform.

«Pattern formation method»

The pattern forming method according to the present invention forms a coating film or a molded product using the photosensitive resin composition according to the present invention and irradiates the coated film or the molded product with electromagnetic waves in a predetermined pattern shape to develop the coated film or the molded product.

More specifically, first, a coating film or a molded product is formed by an appropriate coating method or molding method. For example, a photosensitive resin composition is applied on a substrate using a non-contact type coating device such as a roll coater, a reverse coater, a bar coater, or the like, a spinner (rotary coating device), or a curtain flow coater, . The drying method is not particularly limited and includes, for example, (1) a method of performing prebaking on a hot plate at a temperature of 80 to 120 ° C, preferably 90 to 100 ° C for 60 to 120 seconds, (2) And (3) a method of removing the solvent by putting it in a warm air heater or an infrared heater for several minutes to several hours, and the like.

Next, the coated film or the molded product is exposed by irradiating electromagnetic waves in a predetermined pattern shape. The electromagnetic wave may be irradiated through a negative type mask or directly irradiated. The exposure dose varies depending on the composition of the photosensitive resin composition but is preferably, for example, about 5 to 500 mJ / cm 2.

Next, the coated film or the molded product after exposure is developed with a developing solution to be patterned into a desired shape. The developing method is not particularly limited, and for example, a dipping method, a spraying method, or the like can be used. Examples of the developing solution include organic ones such as monoethanolamine, diethanolamine and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and quaternary ammonium salts.

Post-baking is preferably performed at about 200 to 250 ° C for the pattern after development.

«Color filter, display device»

The color filter according to the present invention is formed using the photosensitive resin composition according to the present invention.

For example, a black matrix in a color filter of a liquid crystal display or an organic EL display can be formed by forming a coating film using the photosensitive resin composition according to the present invention and irradiating the coating film with electromagnetic waves in a predetermined pattern shape have.

The display device according to the present invention includes such a color filter. Examples of the display device include a liquid crystal display and an organic EL display.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited to these Examples.

<Compounds represented by the above formula (1) and comparative compounds>

As the compound represented by the above formula (1), compounds 1 to 20 represented by the following formulas were prepared. The synthesis methods of the compounds 1 to 20 are shown below. For comparison, comparative compounds 1 to 10 represented by the following formulas were prepared.

[Synthesis method of Compound 1]

5.90 g (30 mmol) of 3- (4-methoxyphenyl) acrylic acid chloride were dissolved in 50 ml of dry ether, 4.59 ml (equivalent ratio 1.1) of triethylamine and 2.41 ml (equivalent ratio 1.1) Stirring time. Washed with 50 ml of water, 50 ml of a saturated aqueous solution of NaHCO ₃ and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was carried out by column chromatography using ethyl hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 1 (4.65 g, 20 mmol). The yield based on acrylic acid chloride was 67%.

[Synthesis method of Compound 2]

5.90 g (30 mmol) of 3- (4-methoxyphenyl) acrylic acid chloride were dissolved in 50 ml of dry ether, 4.59 ml (equivalent ratio 1.1) of triethylamine and 3.07 ml (an equivalent ratio 1.1) of aniline were added thereto and stirred at room temperature for 1 hour did. Washed with 50 ml of water, 50 ml of a saturated aqueous solution of NaHCO ₃ and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was carried out by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 2 (6.31 g, 25 mmol). The yield based on acrylic acid chloride was 83%.

[Synthesis method of Compound 3]

5.90 g (30 mmol) of 3- (4-methoxyphenyl) acrylic acid chloride were dissolved in 50 ml of dry ether, 4.59 ml (equivalent ratio 1.1) of triethylamine and 2.25 ml (equivalent ratio 1.1) Lt; / RTI &gt; Washed with 50 ml of water, 50 ml of a saturated aqueous solution of NaHCO ₃ and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was carried out by column chromatography using ethyl hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 3 (3.41 g, 15 mmol). The yield based on acrylic acid chloride was 50%.

[Synthesis method of Compound 4]

5.90 g (30 mmol) of 3- (4-methoxyphenyl) acrylic acid chloride were dissolved in 50 ml of dry ether, 4.59 ml (equivalent ratio 1.1) of triethylamine and 2.25 ml (morpholine ratio 1.1) Lt; / RTI &gt; Washed with 50 ml of water, 50 ml of a saturated aqueous solution of NaHCO ₃ and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was carried out by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 4 (3.41 g, 15 mmol). The yield based on acrylic acid chloride was 50%.

[Synthesis method of Compound 5]

7.25 g (30 mmol) of 3- (2-nitro-4-methoxyphenyl) acrylic acid chloride were dissolved in 50 ml of dry ether, 4.59 ml (equivalent ratio 1.1) of triethylamine and 2.25 ml (equivalent ratio 1.1) And the mixture was stirred at room temperature for 1 hour. Washed with 50 ml of water, 50 ml of a saturated aqueous solution of NaHCO ₃ and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was carried out by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 5 (4.08 g, 15 mmol). The yield based on acrylic acid chloride was 50%.

[Synthesis method of Compound 6]

(30 mmol) of 3- (3-nitro-4-methoxyphenyl) acrylic acid chloride were dissolved in 50 ml of dry ether, 4.59 ml (equivalent ratio 1.1) of triethylamine and 2.25 ml (equivalent ratio 1.1) And the mixture was stirred at room temperature for 1 hour. Washed with 50 ml of water, 50 ml of a saturated aqueous solution of NaHCO ₃ and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was performed by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 6 (4.08 g, 15 mmol). The yield based on acrylic acid chloride was 50%.

[Synthesis method of Compound 7]

(30 mmol) of 2-methyl-3- (2-nitro-4-methoxyphenyl) acrylic acid chloride was dissolved in 50 ml of dry ether. 4.59 ml (equivalent ratio 1.1) of triethylamine and 2.25 ml 1.1), which was stirred for 1 hour at room temperature. Washed with 50 ml of water, 50 ml of a saturated aqueous solution of NaHCO ₃ and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was carried out by column chromatography using ethyl hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 7 (4.29 g, 15 mmol). The yield based on acrylic acid chloride was 50%.

[Synthesis method of Compound 8]

7.67 g (30 mmol) of 2-methyl-3- (3-nitro-4-methoxyphenyl) acrylic acid chloride was dissolved in 50 ml of dry ether. 4.59 ml (equivalent ratio 1.1) of triethylamine and 2.25 ml 1.1), which was stirred for 1 hour at room temperature. Washed with 50 ml of water, 50 ml of a saturated aqueous solution of NaHCO ₃ and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was carried out by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 8 (3.41 g, 15 mmol). The yield based on acrylic acid chloride was 50%.

[Synthesis method of Compound 9]

(30 mmol) of 3- (2-nitro-4-methoxyphenyl) acrylic acid chloride were dissolved in 50 ml of dry ether. 4.59 ml (equivalent ratio 1.1) of diethylamine and 2.41 ml (equivalent ratio 1.1) And the mixture was stirred at room temperature for 1 hour. Washed with 50 ml of water, 50 ml of a saturated aqueous solution of NaHCO ₃ and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was carried out by column chromatography using ethyl hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 9 (5.55 g, 20 mmol). The yield based on acrylic acid chloride was 67%.

[Synthesis method of Compound 10]

(30 mmol) of 3- (3-nitro-4-methoxyphenyl) acrylic acid chloride was dissolved in 50 ml of dry ether. 4.59 ml (equivalent ratio 1.1) of diethylamine and 2.41 ml (equivalent ratio 1.1) And the mixture was stirred at room temperature for 1 hour. Washed with 50 ml of water, 50 ml of a saturated aqueous solution of NaHCO ₃ and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was carried out by column chromatography using ethyl hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 9 (5.55 g, 20 mmol). The yield based on acrylic acid chloride was 67%.

[Synthesis method of Compound 11]

7.67 g (30 mmol) of 2-methyl-3- (2-nitro-4-methoxyphenyl) acrylic acid chloride was dissolved in 50 ml of dry ether. 4.59 ml (equivalent ratio: 1.1) of triethylamine and 2.41 ml Equivalent ratio 1.1) was added and the mixture was stirred at room temperature for 1 hour. Washed with 50 ml of water, 50 ml of a saturated aqueous solution of NaHCO ₃ and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was carried out by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 11 (5.83 g, 20 mmol). The yield based on acrylic acid chloride was 67%.

[Synthesis method of Compound 12]

7.67 g (30 mmol) of 2-methyl-3- (3-nitro-4-methoxyphenyl) acrylic acid chloride was dissolved in 50 ml of dry ether. 4.59 ml (equivalent ratio: 1.1) of triethylamine and 2.41 ml Equivalent ratio 1.1) was added and the mixture was stirred at room temperature for 1 hour. Washed with 50 ml of water, 50 ml of a saturated aqueous solution of NaHCO ₃ and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was carried out by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 12 (5.83 g, 20 mmol). The yield based on acrylic acid chloride was 67%.

[Synthesis method of Compound 13]

(30 mmol) of 3- (2-nitro-4-methoxyphenyl) acrylic acid chloride were dissolved in 50 ml of dry ether, 4.59 ml (equivalent ratio 1.1) of triethylamine and 2.81 ml (equivalent ratio 1.1) And the mixture was stirred at room temperature for 1 hour. Washed with 50 ml of water, 50 ml of a saturated aqueous solution of NaHCO ₃ and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was carried out by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 13 (5.62 g, 23 mmol). The yield based on acrylic acid chloride was 77%.

[Synthesis method of Compound 14]

(30 mmol) of 3- (3-nitro-4-methoxyphenyl) acrylic acid chloride were dissolved in 50 ml of dry ether. 4.59 ml (equivalent ratio 1.1) of triethylamine and 2.81 ml (equivalent ratio 1.1) And the mixture was stirred at room temperature for 1 hour. Washed with 50 ml of water, 50 ml of a saturated aqueous solution of NaHCO ₃ and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was carried out by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 14 (5.62 g, 23 mmol). The yield based on acrylic acid chloride was 67%.

[Synthesis method of Compound 15]

7.67 g (30 mmol) of 2-methyl-3- (2-nitro-4-methoxyphenyl) acrylic acid chloride was dissolved in 50 ml of dry ether. 4.59 ml (equivalent ratio 1.1) of triethylamine and 2.81 ml Equivalent ratio 1.1) was added and the mixture was stirred at room temperature for 1 hour. Washed with 50 ml of water, 50 ml of a saturated aqueous solution of NaHCO ₃ and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was carried out by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 15 (5.83 g, 23 mmol). The yield based on acrylic acid chloride was 67%.

[Synthesis method of Compound 16]

7.67 g (30 mmol) of 2-methyl-3- (3-nitro-4-methoxyphenyl) acrylic acid chloride was dissolved in 50 ml of dry ether. 4.59 ml (equivalent ratio 1.1) of triethylamine and 2.81 ml Equivalent ratio 1.1) was added and the mixture was stirred at room temperature for 1 hour. Washed with 50 ml of water, 50 ml of a saturated aqueous solution of NaHCO ₃ and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was carried out by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 16 (5.83 g, 23 mmol). The yield based on acrylic acid chloride was 67%.

[Synthesis method of compound 17]

5.90 g (30 mmol) of 3- (4-methoxyphenyl) acrylic acid chloride was dissolved in 50 ml of dry ether, 4.59 ml (equivalent ratio 1.1) of triethylamine and 2.81 ml (equivalent ratio 1.1) Stirring time. Washed with 50 ml of water, 50 ml of a saturated aqueous solution of NaHCO ₃ and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was performed by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 17 (3.41 g, 15 mmol). The yield based on acrylic acid chloride was 50%.

[Synthesis method of Compound 18]

(30 mmol) of 2-methyl-3- (4-methoxyphenyl) acrylic acid chloride was dissolved in 50 ml of dry ether, 4.59 ml (equivalent ratio 1.1) of triethylamine and 2.25 ml (equivalent ratio 1.1) And the mixture was stirred at room temperature for 1 hour. Washed with 50 ml of water, 50 ml of a saturated aqueous solution of NaHCO ₃ and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was carried out by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 18 (3.62 g, 15 mmol). The yield based on acrylic acid chloride was 50%.

[Synthesis method of Compound 19]

(30 mmol) of 2-methyl-3- (4-methoxyphenyl) acrylic acid chloride was dissolved in 50 ml of dry ether, 4.59 ml (equivalent ratio 1.1) of diethylamine and 2.41 ml (equivalent ratio 1.1) And the mixture was stirred at room temperature for 1 hour. Washed with 50 ml of water, 50 ml of a saturated aqueous solution of NaHCO ₃ and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was carried out by column chromatography using hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 19 (4.93 g, 20 mmol). The yield based on acrylic acid chloride was 67%.

[Synthesis method of Compound 20]

(30 mmol) of 2-methyl-3- (4-methoxyphenyl) acrylic acid chloride was dissolved in 50 ml of dry ether, 4.59 ml of triethylamine (equivalent ratio 1.1) and 3.07 ml of aniline (equivalent ratio 1.1) Lt; / RTI &gt; for 1 hour. Washed with 50 ml of water, 50 ml of a saturated aqueous solution of NaHCO ₃ and 1N hydrochloric acid, dried over magnesium sulfate, and concentrated under reduced pressure. Purification was carried out by column chromatography using ethyl hexane-ethyl acetate as a developing solvent and silica gel as a support carrier to obtain the corresponding compound 20 (4.29 g, 25 mmol). The yield based on acrylic acid chloride was 83%.

&Lt; Preparation of Photosensitive Resin Composition &gt;

[ Example  One]

The following components were dissolved in a mixed solvent of 3-methoxybutyl acetate (MA) / propylene glycol monomethyl ether acetate (PM) / cyclohexanone (AN) = 60/20/20 (weight ratio) The mixture was filtered through a membrane filter having a pore diameter of 5 탆 to prepare a photosensitive resin composition having a solid concentration of 15% by weight.

· Resin having ethylenic unsaturated group

Resin (A-1) (solid content 55%, solvent: 3-methoxybutyl acetate) 310 parts by weight

· Monomers having an ethylenic unsaturated group

Dipentaerythritol hexaacrylate (DPHA) 175 parts by weight

· Photopolymerization initiator

Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -, 1- (O-acetyloxime) "IRGACURE OXE02" 100 parts by weight

The compound represented by the above formula (1)

Compound 3 ... 100 parts by weight

·coloring agent

Carbon dispersion "CF Black" (trade name: Mikuni Color, solid content 25%, solvent: 3-methoxybutyl acetate) 450 parts by weight

The synthesis method of the resin (A-1) is as follows.

235 g of bisphenol fluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol and 72.0 g of acrylic acid were placed in a 500 ml four- , And the mixture was heated and dissolved at 90 to 100 ° C while blowing air at a rate of 25 ml / min. Then, the solution was gradually warmed to a cloudy state and heated to 120 DEG C to be completely dissolved. At this time, the solution gradually became a transparent point group, but stirring was continued. In the meantime, the acid value was measured, and the heating and stirring were continued until it was less than 1.0 mg KOH / g. It took 12 hours until the acid value reached the target value. Then, the mixture was cooled to room temperature to obtain a bisphenol fluorene-type epoxy acrylate represented by the following formula (a-4) which was colorless transparent and solid.

Then, 600 g of 3-methoxybutyl acetate was added and dissolved in 307.0 g of the bisphenol fluorene-type epoxy acrylate thus obtained, and then 80.5 g of benzophenonetetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed, The reaction was allowed to proceed at 110 to 115 ° C for 4 hours. After disappearance of the acid anhydride group was confirmed, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 DEG C for 6 hours to obtain a resin (A-1). The disappearance of the acid anhydride group was confirmed by IR spectrum.

The resin (A-1) corresponds to the resin represented by the above formula (a-1).

[ Example  2-6]

IRGACURE OXE01 "(product name: manufactured by BASF)," NCI-831 "(product name: manufactured by ADEKA)," IRGACURE 369 "," IRGACURE 651 "," IRGACURE OXE02 " A photosensitive resin composition was prepared in the same manner as in Example 1 except that &quot; IRGACURE 907 &quot; (trade name, all manufactured by BASF) was used. Details of the photopolymerization initiator used are as follows.

IRGACURE OXE01: 1,2-octanedione, 1- [4- (phenylthio) -, 2- (O-benzoyloxime)]

· "NCI-831": See the following formula

IRGACURE 369: 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1

IRGACURE 651: 2,2-dimethoxy-1,2-diphenylethan-1-one

[ Example  7-12]

As shown in the following Table 1, a photosensitive resin composition was prepared in the same manner as in Examples 1 to 6 except that Compound 1 was used instead of Compound 3.

[ Example  13-24]

As shown in the following Table 2, a photosensitive resin composition was prepared in the same manner as in Examples 1 to 12 except that the content of the compound represented by the formula (1) was changed to 50 parts by weight.

[ Example  25 ~ 42]

As shown in the following Table 3, a photosensitive resin composition was prepared in the same manner as in Example 1 except that Compound 2, 4 to 20 were used in place of Compound 3, respectively.

[ Comparative Example  1-6]

As shown in the following Table 4, a photosensitive resin composition was prepared in the same manner as in Example 1, except that Compound 3 was not used.

[ Comparative Example  7 ~ 14]

As shown in the following Table 4, a photosensitive resin composition was prepared in the same manner as in Example 1 except that the above-mentioned Comparative Compounds 1 to 8 were used instead of the above-mentioned Compound 3.

[evaluation]

The photosensitive resin compositions of Examples 1 to 42 and Comparative Examples 1 to 14 were coated on a glass substrate (100 mm x 100 mm) using a spin coater and prebaked at 90 캜 for 120 seconds to give a coating film having a thickness of 1.0 탆 . Next, the coating film was irradiated with ultraviolet rays through a negative mask in which a line pattern of 20 mu m was formed with an exposure gap of 50 mu m using a mirror projection aligner (product name: TME-150RTO, Topcon Co., Ltd.). The exposure amounts were 20, 40, 60, and 120 mJ / cm &lt; 2 &gt; After the exposure, the coated film was developed with a 0.04 wt% KOH aqueous solution at 26 DEG C for 40 seconds and post-baked at 230 DEG C for 30 minutes to form a line pattern.

Similarly, ultraviolet rays were irradiated to the coating film with an exposure gap of 50 占 퐉 through a negative mask in which line patterns of 2, 5, 10 and 20 占 퐉 were formed. The exposure dose was 10 mJ / cm 2. After the exposure, the coated film was developed with a 0.04 wt% KOH aqueous solution at 26 DEG C for 40 seconds and post-baked at 230 DEG C for 30 minutes to form a line pattern.

With respect to the formed line pattern, the OD value per 1 mu m of the film thickness was measured using an OD measuring apparatus D-200II (manufactured by GretagMarkbeth).

In addition, the line pattern was observed with an optical microscope to evaluate the pattern straightness. The pattern straightness was evaluated as &quot; good &quot; with no shaking at the edge of the line, and &quot; defective &quot; with shaking.

Further, the line pattern was observed by an optical microscope, and the pattern adhesion was evaluated. The pattern adhesion was evaluated as &quot; good &quot; when the line pattern was not peeled off the substrate, &quot; poor &quot; when the line pattern was formed but the pattern defect occurred, and &quot; .

The presence or absence of the residue in the unexposed portion after development was evaluated.

The results are shown in Tables 5 to 8 below.

As can be seen from the table, when the photosensitive resin compositions of Examples 1 to 24 containing the compound represented by the above formula (1) were used in addition to the photopolymerization initiator, the photosensitive resin composition containing no compound represented by the formula (1) The pattern straightness and the pattern adhesion were significantly improved as compared with the case of using the photosensitive resin compositions of Comparative Examples 1 to 6. In particular, as can be seen from Examples 25 to 42, when "IRGACURE OXE02" is used as a photopolymerization initiator, a line pattern excellent in straightness can be formed even at a low exposure dose of 20 mJ / A line pattern of 5 mu m was adhered to the substrate. Further, when the photosensitive resin compositions of Examples 1 to 42 were used, there was no development residue.

On the other hand, when the photosensitive resin compositions of Comparative Examples 7 to 14 containing Comparative Compounds 1 to 8 were used instead of the compound represented by the formula (1), pattern straightness and pattern adhesion were evaluated in Examples 1, 7, 13, 19 and 25 to 42, and good fine patterning characteristics could not be obtained.

Claims (6)

A photosensitive resin composition comprising a photopolymerizable compound, a photopolymerization initiator, a compound represented by the following formula (1), and a light-shielding agent.

(Shown in, R ¹ and R ² are a hydrogen atom or an organic each independently formula: provided that at least one of R ¹ and R ² represents an organic group. R ¹ and R ² form a cyclic structure by these binding It may be, or may include a combination of the hetero atom. R ³ represents a single bond. R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol A nitro group, a nitro group, a sulfino group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group or an organic group, R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonate group, A phosphono group, a phosphonate group, an amino group, an ammonia group Or it represents an organic group. However, R ^6, and there is no case R ⁷ is where the hydroxyl group. R ^6, R ^7, R ⁸ and R ⁹ is may form a ring structure by combining more than these two, a combination of heteroatoms And R ¹⁰ represents a hydrogen atom or an organic group. The method according to claim 1,
Wherein the content of the compound represented by the formula (1) is 35 to 200 parts by weight based on 100 parts by weight of the photopolymerization initiator. The method according to claim 1,
Wherein the photopolymerizable compound contains a resin having a cardo structure. A pattern forming method for forming a coating film or a molded body by using the photosensitive resin composition according to any one of claims 1 to 3 and irradiating the coating film or the molded body with electromagnetic waves in a predetermined pattern shape for development. A color filter formed using the photosensitive resin composition according to any one of claims 1 to 3. A display device using the color filter according to claim 5.