KR101603845B1 - Copolymer, photosensitive resin composition comprising the same, photosensitive material manufactured by using the photosensitive resin composition and display device having the photosensitive material - Google Patents

Abstract

The present invention relates to a copolymer, a photosensitive resin composition containing the same, a photosensitive material made of the photosensitive resin composition, and a display device including the same.

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition, a photosensitive resin composition containing the photosensitive resin composition, a photosensitive material made of the photosensitive resin composition, and a display device including the same. BACKGROUND ART MATERIAL}

The present invention relates to a copolymer, a photosensitive resin composition containing the same, a photosensitive material made of the photosensitive resin composition, and a display device including the same.

A fine pattern of a color filter used in a display device such as a liquid crystal display device or a plasma display panel is usually formed by photolithography using a negative type photoresist, (Develop) -firing (Curing) process. The pattern formed by the development in the firing step is fired at a temperature of 220 ° C or more and 230 ° C or less for 20 minutes to 30 minutes by using a convection oven.

Currently, display manufacturers are making efforts to shorten the process time by improving the photolithography process. Recently, in order to shorten the process time, infrared (IR) And then proceeding to a high-speed curing process in which the material is fired for 5 minutes to 5 minutes, or a rapid curing process in which the material is fired for 2 to 3 minutes using a microwave. However, in the case of infrared curing, even if the time is shortened, it may occur due to deterioration of the material because it proceeds at a high temperature of 250 DEG C, and it is difficult to ensure the uniformity of infrared curing as the substrate size increases. In the case of curing using a microwave, it is necessary not only to contain a specific functional group capable of absorbing and oscillating a microwave of a specific wavelength in the material used for the pattern, but also because it proceeds at a high temperature There may arise a problem due to the deterioration of the film.

Particularly, in order to improve quality such as contrast ratio, brightness or reproducibility of color reproduction of a liquid crystal display device, it is necessary to use a dye other than a conventional pigment, or to apply it to a flexible display using a plastic substrate instead of a glass substrate as one of the next- It is required to be fired at a low temperature in consideration of the heat resistance of the dye or the heat resistance of the plastic substrate after pattern formation.

Korean Patent Publication No. 2001-0018075

The present invention provides a copolymer, a photosensitive resin composition containing the same, a photosensitive material made of the photosensitive resin composition, and a display device including the same.

This disclosure includes monomers comprising block isocyanate groups; Monomers having an ethylenically unsaturated double bond and an acid group; And a copolymer polymerized with a monomer having at least one ethylenically unsaturated double bond.

The present invention also provides a photosensitive resin composition comprising a binder resin containing the copolymer, a polyfunctional monomer having an ethylenically unsaturated double bond, and an initiator.

The present invention also provides a photosensitive material made of the photosensitive resin composition.

Further, the present specification provides a display device including the photosensitive material.

The present invention also provides a method for producing a photosensitive material produced using the photosensitive resin composition.

There is an advantage in that when the photosensitive resin composition according to the present invention is fired at a low temperature, it exhibits a high degree of curing within a short period of time.

The photosensitive material according to the present invention has an advantage of exhibiting a high degree of curing.

The photosensitive material according to the present invention has an advantage that the chemical resistance is increased.

Hereinafter, the present invention will be described in detail.

One embodiment of the present disclosure includes monomers comprising a block isocyanate group; Monomers having an ethylenically unsaturated double bond and an acid group; And a copolymer polymerized with a monomer having at least one ethylenically unsaturated double bond.

In one embodiment of the present invention, the monomer containing the block isocyanate group is not particularly limited as long as it contains a block isocyanate group in which an isocyanate group (-N = C = O) is blocked.

For example, the monomer containing the block isocyanate group may be a group derived from an isocyanate group (-N═C═O) from an alcohol, a group derived from a carboxyl group, a group derived from a malonate, or a group derived from a caprolactam A group originated from a pyrazole, or a block isocyanate group blocked with a group derived from a oxime.

In the monomers comprising a block isocyanate, wherein the isocyanate groups of blocks groups are OH-, a nucleophilic group, that can attract hydrogen atoms bonded to N in a specific temperature for -OCH _3, -COOCH _3, -CN, a halogen group, or -NH ₂ And the like.

The monomer containing the block isocyanate group can be activated by a deblocking reaction in which the nucleophilic group of the group blocking the isocyanate group at a certain temperature draws a hydrogen atom bound to N. [

In one embodiment of the present invention, the groups derived from the alcohols include groups derived from phenols, and groups derived from the alcohols may be represented by the following formula (2).

(2)

In Formula 2, R1 is H, substituted or unsubstituted C ₁ to C ₁₀ alkyl groups, substituted or unsubstituted C ₆ to C ₂₀ aryl _{group, -OH, -OCH 3, -COOCH 3} , -CN, A halogen group or -NH ₂ .

In one embodiment of the present invention, the group derived from the above-mentioned carboxy group may be represented by the following formula (3).

(3)

In Formula 3, R2 is H, substituted or unsubstituted C ₁ to C ₁₀ alkyl groups, substituted or unsubstituted C ₆ to C ₂₀ aryl _{group, -OH, -OCH 3, -COOCH 3} , -CN, A halogen group or -NH ₂ .

In one embodiment of the present invention, the group derived from the malonate may be represented by the following formula (4).

[Chemical Formula 4]

In the formula 4, R3 is H, substituted or unsubstituted C ₁ to C ₁₀ alkyl groups, substituted or unsubstituted C ₆ to C ₂₀ aryl _{group, -OH, -OCH 3, -COOCH 3} , -CN, A halogen group or -NH ₂ .

In one embodiment of the present invention, the group derived from the caprolactam species may be represented by the following formula (5).

[Chemical Formula 5]

In Formula 5, R4 is H, substituted or unsubstituted C ₁ to C ₁₀ alkyl groups, substituted or unsubstituted C ₆ to C ₂₀ aryl _{group, -OH, -OCH 3, -COOCH 3} , -CN, A halogen group or -NH ₂ .

In one embodiment of the present specification, the group resulting from the pyrazoles may be represented by the following formula (6).

[Chemical Formula 6]

In Formula 6, R5 is H, substituted or unsubstituted C ₁ to C ₁₀ alkyl groups, substituted or unsubstituted C ₆ to C ₂₀ aryl _{group, -OH, -OCH 3, -COOCH 3} , -CN, A halogen group or -NH ₂ .

In one embodiment of the present invention, the group derived from the oxime group may be represented by the following formula (7).

(7)

In Formula 7, R6 and R7 are each independently H, substituted or unsubstituted C ₁ to C ₁₀ alkyl groups, substituted or unsubstituted C ₆ to C ₂₀ aryl group, -OH, -OCH _3, -COOCH ₃ , -CN, a halogen group or -NH ₂ .

In one embodiment of the present specification, the monomer containing the block isocyanate group is not particularly limited as long as it can be polymerized with a monomer having an ethylenically unsaturated double bond.

For example, the monomer containing the block isocyanate group may be a monomer represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

And G1 is an alkylene group of C ₁ to C _10,

G2, G3 and G4 are the same or are different and each independently represents a hydrogen or C ₁ to about C ₁₀ to each other,

A is any one of the following formulas (2) to (7)

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

In the above formulas 2 to 7,

Each of R 1, R 2, R 3, R 4, R 5, R 6 and R 7 is independently H, a substituted or unsubstituted C ₁ to C ₁₀ alkyl group, a substituted or unsubstituted C ₆ to C ₂₀ aryl group, OCH ₃ , -COOCH ₃ , -CN, a halogen group or -NH ₂ .

Of the substituents of Formula 1 A is an _{OH-, -OCH 3, -COOCH 3,} -CN, halogen, or -NH ₂ nucleophilic groups that can attract the hydrogen atoms bonded to N at a certain temperature And the like.

 The monomer containing the block isocyanate group can activate the isocyanate group due to a deblocking reaction in which the nucleophilic group A of the substituent of the general formula (1) at a certain temperature pulls the hydrogen atom bound to N.

As used herein, the term "derived from a specific compound or functional group" means that the functional group in the specific compound or compound has a state of being bonded to another compound or functional group by the reaction.

In one embodiment of the present invention, the monomer having an ethylenically unsaturated double bond and an acid group is not particularly limited as long as it has an ethylenically unsaturated double bond and an acid group.

For example, the monomer having an ethylenically unsaturated double bond and an acid group may be at least one selected from the group consisting of (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethyl maleic acid, isoprenesulfonic acid, styrenesulfonic acid, But is not limited thereto.

In one embodiment of the present invention, the monomer having at least one ethylenically unsaturated double bond is not particularly limited as long as it contains an ethylenically unsaturated double bond.

For example, the monomer having at least one ethylenically unsaturated double bond is an unsaturated carboxylic acid ester; Aromatic vinyl monomers; Unsaturated ethers; N-substituted maleimides and maleic anhydrides.

Specific examples of the unsaturated carboxylic acid esters include benzyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dimethylaminoethyl Acrylates such as butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, ethylhexyl (Meth) acrylate, tetrahydrofurfuryl (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2- (Meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, , Ethoxydiethylene glycol (Meth) acrylate, methoxytriethyleneglycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, poly (ethylene glycol) methylether (meth) acrylate, p-nonylphenoxypolypropylene glycol (meth) acrylate, glycidyl (meth) acrylate, tetrafluoropropyl (meth) (Meth) acrylate, hexafluoroisopropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, tribromophenyl , Methyl [alpha] -hydroxymethyl acrylate, ethyl [alpha] -hydroxymethyl acrylate, propyl [alpha] -hydroxymethyl acrylate and butyl [alpha] -hydroxymethyl acrylate Can.

Specific examples of the aromatic vinyl monomers include styrene,? -Methylstyrene, p-styrenesulfonic acid, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p- Methoxy styrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p - < / RTI > vinyl benzyl glycidyl ether.

Specific examples of the unsaturated ethers may be selected from the group consisting of vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether.

Specific examples of the N-substituted maleimide include N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm-methylphenyl Maleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide and Np-methoxyphenylmaleimide.

Specific examples of the maleic anhydride include maleic anhydride, methylmaleic anhydride, tetrahydrophthalic anhydride, and phthalic anhydride, but are not limited thereto.

In one embodiment of the present invention, the monomer having at least one ethylenically unsaturated double bond may include at least one of the monomers represented by the following formulas (8) to (10).

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

In the above formulas (8) to (10)

R8, R9, R10, R14, R15 and R16 are the same or are different and each independently represents a hydrogen or C ₁ to about C ₁₀ to each other,

R11 is a direct connection or an alkylene group of C ₁ to C _10,

R12 is hydrogen; A substituted or unsubstituted C ₁ to C ₁₀ alkyl group; Or an aryl group, a substituted or unsubstituted C ₆ to C _20,

R13 and R17 each independently represent a substituted or unsubstituted C ₁ to C ₁₀ alkyl group; Or a substituted or unsubstituted C ₆ to C ₂₀ aryl group.

In the present specification, the C ₁ to C ₁₀ alkyl group may be linear or branched, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or a t-butyl group, no.

In the present specification, specific examples of the C ₆ to C ₂₀ aryl group include, but are not limited to, phenyl, benzyl, biphenyl, naphthyl, anthracene or phenanthrene.

Examples of the halogen group include, but are not limited to, a fluorine group, a chlorine group, a bromine group or an iodine group.

This disclosure includes monomers comprising block isocyanate groups; Monomers having an ethylenically unsaturated double bond and an acid group; And polymerizing a monomer having at least one ethylenically unsaturated double bond.

In one embodiment of the present invention, at least one of a thermal polymerization initiator and a solvent may be further added during the polymerization.

In the copolymer of the present invention, the molar ratio of the monomer having the block isocyanate group: monomer having the ethylenically unsaturated double bond and the acid group: the monomer having the ethylenic unsaturated double bond is 10:40 to 10:40 to 40:40, Lt; / RTI >

In the present specification, the weight average molecular weight of the copolymer may be 5,000 or more and 30,000 or less, but is not limited thereto.

In the present specification, the acid value (A.V.) of the copolymer may be 10 KOH mg / g or more and 70 KOH mg / g or less, but is not limited thereto.

The polymerized copolymer contains a block isocyanate group and an acid group.

The nucleophilic group in the group which blocks the isocyanate group of the copolymer at a certain temperature pulls the hydrogen atom bonded to N of the block isocyanate group, so that the block isocyanate group is deblocked. At this time, the deblocked isocyanate group reacts with the acid group of the copolymer and is cured.

The temperature at which the block isocyanate group is deblocked in the copolymer may be 180 ° C or lower and may be 150 ° C or lower as required. When the temperature at which the block isocyanate group is deblocked is low, there is an advantage that curing of the copolymer can proceed at a low temperature. Specifically, depending on the kind of the isocyanate group-blocking group, the deblocking temperature may be 100 ° C or more and 180 ° C or less.

The copolymer of the present invention can be used as a binder resin of a photosensitive resin composition.

The present invention provides a photosensitive resin composition comprising a binder resin containing the copolymer, a polyfunctional monomer having an ethylenically unsaturated double bond, and an initiator.

In the photosensitive resin composition according to the present specification, the binder resin may be composed solely of the copolymer according to the present specification, and may further include a binder resin known in the art in addition to the polymer.

In the photosensitive resin composition according to the present invention, the content of the binder resin may be 1% by weight or more and 20% by weight or less based on the total weight of the photosensitive resin composition, but is not limited thereto.

In the photosensitive resin composition according to the present invention, the polyfunctional compound containing an ethylenically unsaturated bond includes an ethylenically unsaturated bond and is not particularly limited as long as it functions as a crosslinking agent in the photosensitive resin composition.

Examples thereof include ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) A compound obtained by esterifying a polyhydric alcohol such as pentaerythritol tri (meth) acrylate and propylene glycol di (meth) acrylate having 2 to 14 propylene groups with an?,? - unsaturated carboxylic acid; A compound obtained by adding (meth) acrylic acid to a compound containing a glycidyl group such as trimethylolpropane triglycidyl ether acrylic acid adduct and bisphenol A diglycidyl ether acrylic acid adduct; ester compounds of a compound having a hydroxyl group or an ethylenically unsaturated bond such as a phthalic acid diester of? -hydroxyethyl (meth) acrylate and a toluene diisocyanate adduct of? -hydroxyethyl (meth) acrylate with a polyvalent carboxylic acid , Or adducts with polyisocyanates; And at least one selected from the group consisting of alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and 2-ethylhexyl .

The content of the polyfunctional compound containing an ethylenically unsaturated bond may be 2% by weight or more and 30% by weight or less based on the total weight of the photosensitive resin composition, but is not limited thereto.

In the photosensitive resin composition according to the present specification, the initiator may be 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine, 2,4-trichloromethyl- (4'- 6-triazine, 2,4-trichloromethyl- (3 ', 4'-dimethoxyphenyl) -6- Triazine compounds such as triazine, 3- {4- [2,4-bis (trichloromethyl) -s-triazin-6-yl] phenylthio} propanoic acid; Bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- , 5'-tetraphenylbiimidazole; 2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy- Benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, benzoin butyl ether, 2,2-dimethoxy-benzoin methyl ether, (4-methylthiophenyl) -2-morpholino-1-propan-1-one, 2-benzyl-2-dimethylamino- ) -Butan-1-one; Benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 2,4,6-trimethylaminobenzophenone, methyl- , 3-dimethyl-4-methoxybenzophenone, and 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; Fluorene compounds such as 9-fluorenone, 2-chloro-9-fluorenone and 2-methyl-9-fluorenone; Thioxanthones such as thioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 1-chloro-4-propyloxyoctanoate, isopropylthioxanthone and diisopropylthioxanthone compound; Xanthone compounds such as xanthone and 2-methylxanthone; Anthraquinone compounds such as anthraquinone, 2-methyl anthraquinone, 2-ethyl anthraquinone, t-butyl anthraquinone, and 2,6-dichloro-9,10-anthraquinone; (9-acridinyl) pentane, 1,3-bis (9-acridinyl) propane, and the like. Acridine-based compounds; Dicarbonyl compounds such as benzyl, 1,7,7-trimethyl-biscuit [2,2,1] heptane-2,3-dione, and 9,10-phenanthrenequinone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,6-dichlorobenzoyl) propylphosphine oxide Phosphine oxide-based compounds; (Dimethylamino) benzoate, 2-n-butoxyethyl 4- (dimethylamino) benzoate, 2,5-bis (4-diethylaminobenzal) Amine-based synergists such as cyclopentanone, 2,6-bis (4-diethylaminobenzal) cyclohexanone, and 2,6-bis (4-diethylaminobenzal) -4-methyl-cyclohexanone; (Diethylamino) coumarin, 3- (2-benzothiazolyl) -7- (diethylamino) coumarin, 3-benzoyl- Benzoyl-7-methoxy-coumarin, 10,10'-carbonylbis [1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H, 5H, 11H- -Benzopyrano [6,7,8-ij] -quinolizine-11-one; Chalcone compounds such as 4-diethylaminokalone and 4-azidobenzalacetophenone; 2-benzoylmethylene; And 3-methyl-β-naphthothiazoline. However, it is not limited to these, and initiators known in the art may also be used.

The content of the initiator may be 0.1 wt% or more and 5 wt% or less based on the total weight of the photosensitive resin composition, but is not limited thereto.

The photosensitive resin composition of the present specification may further include at least one of a colorant and a solvent.

As the colorant, one or more pigments, dyes, or mixtures thereof may be used.

Specifically, for example, carbon black, graphite, metal oxide, or the like can be used as the black pigment. Examples of carbon blacks are cysteine 5HIISAF-HS, cysto KH, cysteo 3HHAF-HS, cysteo NH, cysto 3M, cysto 300HAF-LS, cysto 116HMMAF-HS, , SISTO SOFEF, SISTO VGPF, SISTO SVHSRF-HS and SISTO SSRF (Donghae Carbon Co., Ltd.); Diagram Black II, Diagram Black N339, Diagram Black SH, Diagram Black H, Diagram LH, Diagram HA, Diagram SF, Diagram N550M, Diagram M, Diagram E Diagram G Diagram R Diagram N760M Diagram LR, # 2700, # 25, # 45, # 45, # 45, # 45, # 45, # 25, # CF9, # 95, # 20, # 2300, # 2350, # 2300, # 2200, # 1000, # 980, # 900, 3030, # 3050, MA7, MA77, MA8, MA11, MA100, MA40, OIL7B, OIL9B, OIL11B, OIL30B and OIL31B (Mitsubishi Chemical); PRINTEX-25, PRINTEX-25, PRINTEX-55, PRINTEX-55, PRINTEX-45, PRINTEX-35, PRINTEX- 200, PRINTEX-40, PRINTEX-30, PRINTEX-3, PRINTEX-A, SPECIAL BLACK-550, SPECIAL BLACK-350, SPECIAL BLACK-250, SPECIAL BLACK-100 and LAMP BLACK-101 (Daegu; 890, RAVEN-880ULTRA, RAVEN-880ULTRA, RAVEN-850R, RAVEN-1080ULTRA, RAVEN-1080ULTRA, RAVEN-1080ULTRA, RAVEN-1080ULTRA, RAVEN-1040ULTRA, RAVEN-1040, RAVEN-1035, RAVEN-1020, RAVEN- 820, RAVEN-790ULTRA, RAVEN-780ULTRA, RAVEN-760ULTRA, RAVEN-520, RAVEN-500, RAVEN-460, RAVEN-450, RAVEN-430ULTRA, RAVEN- RAVEN-1500, RAVEN-1255, RAVEN-1250, RAVEN-1200, RAVEN-1190ULTRA, RAVEN-1170 (Colombia Carbon) or mixtures thereof.

Also, examples of coloring agents that are colored include carmine 6B (C.I.12490); Phthalocyanine green (CI 74260); Phthalocyanine blue (CI 74160); Perylene Black (BASF K0084.K0086); Cyanine black; Linol Yellow (CI 21090); Linol Yellow GRO (CI 21090); Benzidine yellow 4T-564D; Victoria Pure Blue (C.I.42595); C.I. PIGMENT RED 3, 23, 97, 108, 122, 139, 140, 141, 142, 143, 144, 149, 166, 168, 175, 177, 180, 185, 189, 190, 192, 220, 221, 224, 230, 235, 242, 254, 255, 260, 262, 264, 272; C.I. PIGMENT GREEN 7, 36; C.I. PIGMENT blue 15: 1, 15: 3, 15: 4, 15: 6, 16, 22, 28, 36, 60, 64; C.I. PIGMENT yellow 13, 14, 35, 53, 83, 93, 95, 110, 120, 138, 139, 150, 151, 154, 175, 180, 181, 185, 194, 213; Or C.I. PIGMENT VIOLET 15, 19, 23, 29, 32, 37, etc. In addition, white pigments and fluorescent pigments can be used. As the phthalocyanine-based complex compound used as the pigment, a material having zinc as a central metal in addition to copper may be used.

The content of the colorant may be 1 wt% or more and 50 wt% or less based on the total weight of the photosensitive resin composition, but is not limited thereto.

In the photosensitive resin composition according to the present specification, examples of the solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether , Ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, chloroform, methylene chloride, 1,2-dichloroethane, Trichloroethane, 1,1,2-trichloroethane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, methanol, ethanol, Propanol, butanol, t-butanol, 2-ethoxypropanol, 2-methoxypropanol, 3-methoxybutanol, cyclohexanone, cyclopentanone, propylene glycol methyl ether acetate, propel At least one member selected from the group consisting of glycol ethyl ether acetate, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, methyl cellosolve acetate, butyl acetate and dipropylene glycol monomethyl ether, But it is not limited thereto, and a solvent known in the art may also be used.

The content of the solvent may be 45% by weight or more and 95% by weight or less based on the total weight of the photosensitive resin composition, but is not limited thereto.

The photosensitive resin composition of the present invention may further comprise at least one additive selected from the group consisting of a surfactant, a curing accelerator, a plasticizer, a filler, a coupling agent, a photosensitizer and a dispersant.

The surfactant may be a silicone surfactant or a fluorine surfactant. Specifically, the silicone surfactant is BYK-077, BYK-085, BYK-300, BYK-301, BYK-302, BYK-306, BYK-307, BYK-310, BYK- , BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-335, BYK-341v344, BYK-345v346, BYK-348, BYK-354, BYK-355, BYK-370, BYK-371, BYK-370, BYK-380 and BYK-390 may be used. Examples of the fluorine surfactant include DIC (Dai Nippon Ink & Chemicals) F-177, F-410, F-411, F-450, F-493, F-494, F-443, F-444, F- F-474, F-477, F-478, F-479, F-480SF, F-482, F-483, F- MCF-350SF, TF-1025SF, TF-1117SF, TF-1026SF, TF-1128, TF-1127, TF-1129, TF- 1126, TF- 1441 or TF-1442 may be used, but the present invention is not limited thereto.

The content of the surfactant may be 0.02 wt% or more and 1 wt% or less based on the total weight of the photosensitive resin composition, but is not limited thereto. In this case, there is an advantage that the coating is smooth because of the leveling property or wetting property when the ink is coated.

The coupling agent is selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) -silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- 2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, 3- glycidoxypropylmethyldimethoxysilane, 2- 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, or 3-mercaptopropyltrimethoxysilane, Trimethoxysilane, and the like, but the present invention is not limited thereto.

The dispersant may be used either in a manner of internally adding to the pigment in the form of surface-treating the pigment in advance, or in a method of externally adding the pigment. As the dispersing agent, a polymer type, a nonionic, an anionic, or a cationic dispersing agent can be used. Examples thereof include polyalkylene glycols and esters thereof, polyoxyalkylene polyhydric alcohols, ester alkylene oxide adducts, But are not limited to, at least one member selected from the group consisting of an oxide adduct, a sulfonic acid ester, a sulfonic acid salt, a carboxylic acid ester, a carboxylate, an alkylamide alkylene oxide adduct, and an alkylamine.

The surfactants, cure accelerators, plasticizers, fillers, coupling agents, photosensitizers, and dispersants may include those generally known in the art.

The content of the other additives may independently be 0.01 wt% or more and 5 wt% or less based on the total weight of the photosensitive resin composition, but is not limited thereto.

There is provided a photosensitive material produced using the photosensitive resin composition according to the present specification.

More specifically, the photosensitive resin composition of the present invention is applied onto a substrate by a suitable method to form a photosensitive material in the form of a thin film or a pattern.

The coating method is not particularly limited, but a spray method, a roll coating method, or a spin coating method can be used. In general, a spin coating method is widely used. After the coating film is formed, a part of the residual solvent may be removed under reduced pressure as occasion demands.

Examples of the light source for curing the photosensitive resin composition according to the present invention include, but are not limited to, mercury vapor arc, carbon arc or Xe arc, which emits light having a wavelength of 250 to 450 nm .

The photosensitive resin composition according to the present invention can be used for forming a black matrix of a pigment-dispersed photosensitive material, a thin film transistor liquid crystal display (TFT-LCD) or an organic light emitting diode for manufacturing a thin film transistor liquid crystal display (TFT-LCD) color filter A photoresist for forming an overcoat layer, a photoresist for a column spacer, a photocurable material, a photocurable ink, a photocurable adhesive, a printing plate, a photosensitive material for a printed wiring board, and a photosensitive material for a plasma display panel (PDP) There is no restriction on usage.

A display device including the photosensitive material according to the present invention is provided.

The display device may be a plasma display panel (PDP), a light emitting diode (LED), an organic light emitting diode (OLED), a liquid crystal display (LCD) A liquid crystal display (TFT-LCD), and a cathode ray tube (CRT).

There is provided a color filter comprising a photosensitive material according to the present specification.

The present invention provides a method for producing a photosensitive material using the photosensitive resin composition.

1) applying the photosensitive resin composition to a substrate; 2) pre-baking the applied photosensitive resin composition; And 3) post-baking the applied photosensitive resin composition after the heat treatment.

In the method of manufacturing a photosensitive material according to one embodiment of the present invention, the post-heat treatment in the step 3) refers to a baking step, and the post-baking (baking) temperature may be less than 200 ° C.

In the method for producing a photosensitive material according to one embodiment of the present invention, the baking time in the step 3) may be more than 2 minutes but not more than 30 minutes. If necessary, it may be more than 5 minutes and less than 15 minutes. In this case, the pattern can be uniformly fired without defects due to deterioration.

The method of applying the composition to the substrate is not particularly limited, and a method generally used in the art can be employed.

In the method for manufacturing a photosensitive material according to an embodiment of the present invention, in the step 2), the electrothermal treatment is a step of evaporating the photosensitive resin composition solvent, and the electrothermal treatment temperature may be 50 ° C or more and 100 ° C or less.

The treatment time of the electrothermal treatment step is not limited, but may be, for example, 30 seconds to 5 minutes.

There is an advantage that the photosensitive resin composition according to the present invention exhibits a high degree of curing within a short period of time in the case of post-heat treatment (firing) at a low temperature.

The photosensitive material may further include a step of forming a pattern on the photosensitive resin composition applied before the heat treatment step.

The method for forming the pattern is not particularly limited, and a method generally used in the art can be employed. For example, a patterned photosensitive resin composition can be formed on the substrate by exposure and development using a photomask.

The present specification will be described in more detail by way of the following examples. It is to be understood, however, that the embodiments are illustrative of the present specification and the scope of the present invention is not limited thereto.

Example  One

Based on the total weight of the composition, 7.038% by weight of Pigment Red 177, 0.612% by weight of Pigment Y139 as a colorant, benzyl (meth) acrylate, N-phenylmaleimide, styrene, resin containing a (meth) acrylic acid and a block isocyanate group as a resin binder, (O- [1'-methylpropylideneamino] carboxyamino) ethyl acrylate), 37.1: 10.6: 12.7: 14.8: 24.7 2.242% by weight of a polyfunctional (meth) acrylate monomer (Mw = 15,000, AV = 55.5), 0.04% by weight of F-475 (DaiNippon Ink & Chemicals) as a surfactant, 0.15 wt% of 3-methacryloxypropyltrimethoxysilane as coupling agent, 0.383 wt% of I369 (BASF) and 0.63 wt% of CGI124 (BASF) as photoinitiators, 0.113 wt% of EMK (Hodogaya, Japan) as photosensitizer, And 86.55% by weight of propylene glycol monomethyl ether acetate were mixed, and the mixture was stirred for 5 hours to prepare a photosensitive resin composition.

Example  2

(O- [1'-methylpropylideneamino] carboxyamino (meth) acrylate containing benzyl (meth) acrylate, N-phenylmaleimide, styrene, (meth) acrylic acid and a block isocyanate group in place of the binder resin of Example 1 ) 2.242% by weight of a copolymer (Mw = 8,000, AV = 55.7) formed at a molar ratio of 37.1: 10.6: 12.7: 14.8: 24.7 and 2-ethyl- And the other components were the same as in Example 1 to prepare a photosensitive resin composition.

Comparative Example  One

(Mw = 8500, AV = 105) formed in a molar ratio of benzyl (meth) acrylate, N-phenylmaleimide, styrene and (meth) acrylic acid in the ratio of 37.1: 10.6: 12.7: 39.5 instead of the binder resin of Example 1 ) And 2.242% by weight of a multifunctional (meth) acrylate monomer was used to make the same weight of the multifunctional (meth) acrylate monomer, and the other components were the same as Example 1 To prepare a photosensitive resin composition.

Experimental Example

On light irradiation  Pattern formation by

When the low-temperature molded photosensitive resin composition prepared in accordance with the present invention was used, it was compared with the photosensitive resin composition of Comparative Example 1 that a pattern was formed by light irradiation. Each of the low-temperature small-sized photosensitive resin compositions prepared in Examples 1 to 2 and Comparative Example 1 was spin-coated on glass and pre-baked at about 90 캜 for 100 seconds. Photomask was prepared on the substrate prepared by spin coating, and light of 365 nm wavelength was irradiated to 40 mJ / cm ² and developed for about 60 seconds using potassium hydroxide (KOH) solution. Then, the pattern was formed by post-heat treatment at 150 캜 for another time.

Experimental results of the pattern formation are shown in Table 1 below.

Evaluation of Chemical Resistance of Photosensitive Resin Composition

The chemical resistance of each of the low-temperature molding photosensitive resin compositions was measured by cutting the color-coated film formed on the glass substrate into 5 cm x 1 cm by the above method, immersing it in 8 g of propylene glycol monomethyl ether acetate solvent and shaking at 1200 rpm for about 10 minutes. ) To determine whether a pattern remained on the glass substrate.

The results of the chemical resistance test are shown in Table 2 below.

Claims (17)

Monomers comprising block isocyanate groups; Monomers having an ethylenically unsaturated double bond and an acid group; And a monomer having at least one ethylenically unsaturated double bond,
The monomer having at least one ethylenically unsaturated double bond may be a monomer represented by the following formula (8); A monomer represented by the following formula (9); And a monomer represented by the following formula (10):
[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

In the above formulas (8) to (10)
R8, R9, R10, R14, R15 and R16 are the same or are different and each independently represents a hydrogen or C ₁ to about C ₁₀ to each other,
R11 is a direct connection or an alkylene group of C ₁ to C _10,
R12 is hydrogen; A substituted or unsubstituted C ₁ to C ₁₀ alkyl group; Or an aryl group, a substituted or unsubstituted C ₆ to C _20,
R13 and R17 each independently represent a substituted or unsubstituted C ₁ to C ₁₀ alkyl group; Or a substituted or unsubstituted C ₆ to C ₂₀ aryl group. The monomer containing a block isocyanate group according to claim 1, wherein the monomer containing the block isocyanate group is a group derived from an isocyanate group (-N═C═O) from an alcohol, a group derived from a carboxy group, a group derived from a malonate or a group derived from a caprolactam A block derived from a pyrazole group, or a block isocyanate group blocked with a group derived from a oxime group. The copolymer according to claim 1, wherein the monomer containing the block isocyanate group is a monomer represented by the following formula (1):
[Chemical Formula 1]

In Formula 1,
And G1 is an alkylene group of C ₁ to C _10,
G2, G3 and G4 are the same or are different and each independently represents a hydrogen or C ₁ to about C ₁₀ to each other,
A is any one of the following formulas (2) to (7)
(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

In the above formulas 2 to 7,
Each of R 1, R 2, R 3, R 4, R 5, R 6 and R 7 is independently H, a substituted or unsubstituted C ₁ to C ₁₀ alkyl group, a substituted or unsubstituted C ₆ to C ₂₀ aryl group, OCH ₃ , -COOCH ₃ , -CN, a halogen group or -NH ₂ . [4] The composition of claim 1, wherein the monomer having at least one ethylenically unsaturated double bond is selected from the group consisting of unsaturated carboxylic acid esters; Aromatic vinyl monomers; Unsaturated ethers; N-substituted maleimides; And maleic anhydride. delete A photosensitive resin composition comprising a binder resin comprising a copolymer according to any one of claims 1 to 4, a polyfunctional monomer having an ethylenically unsaturated double bond, and an initiator. The photosensitive resin composition according to claim 6, wherein the photosensitive resin composition further comprises at least one of a colorant and a solvent. The photosensitive resin composition according to claim 6, wherein the photosensitive resin composition further comprises at least one of a surfactant, a curing accelerator, a plasticizer, a filler, a coupling agent, a photosensitizer and a dispersant. A photosensitive material produced from the photosensitive resin composition of claim 6. A display device comprising the photosensitive material of claim 9. A process for producing a photosensitive material produced by using the photosensitive resin composition of claim 6. 12. The method of claim 11,
Applying the photosensitive resin composition to a substrate;
Pre-baking the applied photosensitive resin composition; And
And post-baking the applied photosensitive resin composition after the electro-thermal treatment. The method of manufacturing a photosensitive material according to claim 12, wherein, in the post-heat treatment step, the post-heat treatment temperature is less than 200 ° C. The method of manufacturing a photosensitive material according to claim 12, wherein, in the post-heat treatment step, the post-heat treatment time is more than 2 minutes but not more than 30 minutes. 14. The method of manufacturing a photosensitive material as set forth in claim 12, wherein in the electrothermal treatment step, the electrothermal treatment temperature is 50 DEG C or more and 100 DEG C or less. 13. The method of manufacturing a photosensitive material as set forth in claim 12, wherein in said electrothermal treatment step, the electrothermal treatment time is from 30 seconds to 5 minutes. [14] The method of claim 12, wherein the method further comprises the step of forming a pattern on the photosensitive resin composition applied before the heat treatment step.