KR20170113457A - Alkally developable resin and photo-sensitive resin composition, photo spacer and display apparatus comprising the same - Google Patents

Abstract

The present invention relates to an alkali-soluble resin containing one or two or more units represented by the general formula (1), a photosensitive resin composition containing the same, a photo-spacer formed using the same, and a display device including the photo-spacer.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an alkali-soluble resin, a photosensitive resin composition containing the same, a photo-

This specification claims the benefit of Korean Patent Application No. 10-2016-0039711, filed on March 31, 2016, filed with the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference.

The present invention relates to an alkali-soluble resin and a photosensitive resin composition containing the alkali-soluble resin. The present application also relates to a photo-spacer formed of the composition and a display device including the photo-spacer.

A liquid crystal display (LCD) is an electro-optical element that applies a voltage to a liquid crystal material injected between upper and lower transparent substrates to drive the liquid crystal material.

At this time, it is important to maintain a constant gap between the upper and lower transparent substrates. If a constant gap can not be maintained, the applied voltage and the transmittance of the transmitted light are different, resulting in a defective spatially nonuniform brightness.

In recent years, as liquid crystal displays (LCDs) have become larger and larger in size, the importance of uniform spacing between transparent substrates has become greater. As described above, a photo spacer is used to maintain a space between transparent substrates, and a material having a solubility capable of reusing a developer as a photo-spacer material in order to lower the production cost is advantageous. The photo-spacers are prepared by coating a photosensitive resin composition on a substrate, exposing the photosensitive composition to ultraviolet rays or the like using a mask, and then developing the binder. The conventional binder for the photo-spacer includes a rigid structure, Has an elastic recovery rate, but tends to be poor in solubility in a developer.

Korean Patent Publication No. 10-2009-0081049

The present application is intended to provide an alkali-soluble resin, a photosensitive resin composition containing the same, and a photo-spacer formed from the composition.

An embodiment of the present application provides an alkali-soluble resin comprising one or two or more units represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

R ₁ to R ₄ are the same or different and each independently hydrogen or an alkyl group,

X ₁ is a trivalent linking group,

Y is CRR 'or O, wherein R and R' are hydrogen or an alkyl group.

According to another embodiment of the present application, the alkali-soluble resin further comprises one or two or more units represented by the following formula (2).

(2)

In Formula 2,

R ₅ to R ₈ are the same or different and each independently hydrogen or an alkyl group,

X ₂ is a trivalent linking group.

Another embodiment of the present application

1) an alkali-soluble resin according to the above-described embodiment,

2) Multifunctional monomers,

3) solvent, and

4) Photo initiator

The present invention provides a photosensitive resin composition.

Another embodiment of the present application provides a photo-spacer formed using the photosensitive resin composition.

Further, another embodiment of the present application provides a display device including the photo spacers.

The photosensitive resin composition according to the embodiments of the present invention described above is excellent in the resolution, solvent resistance, solvent resistance, and mechanical strength of the pattern, and at the same time forms a photo-spacer having a high elastic restoration rate by an acrylic resin containing a specific acid group And can provide a photosensitive resin composition for a photo-spacer having excellent solubility in a developing solution and improved processability.

1 is a SEM photograph of a photo spacer formed using the composition prepared in Experimental Example 2. FIG.
2 is a photograph showing the results of solubility test of the compositions prepared in Experimental Examples and Comparative Experimental Examples.

The present application will be described in more detail below.

One embodiment of the present application relates to an alkali-soluble resin, which comprises one or two or more units represented by the above formula (1). When the unit having the above structure is included, the resin has a rigid structure and has excellent elastic recovery rate, and exhibits excellent solubility in a developer, thereby lowering the processing cost.

According to one embodiment, R ₁ to R ₄ are the same or different and are each independently hydrogen or an alkyl group having 1 to 8 carbon atoms.

According to another embodiment, R ₁ to R ₄ are the same or different and each independently hydrogen or a methyl group.

According to another embodiment, R ₁ and R ₂ are hydrogen, R ₃ is hydrogen or a methyl group, and R ₄ is a methyl group.

According to one embodiment, X ₁ is a trivalent linear or branched aliphatic hydrocarbon group of 1 to 8 carbon atoms.

According to one embodiment, Y is O.

According to one embodiment, Y is CRR ', wherein R and R' are hydrogen.

According to one embodiment, the formula (1) may be represented by the following formula (3).

(3)

In Formula 3,

The definitions of R ₁ to R ₄ and Y are the same as those of the formula (1)

L ₁ and L ₂ are the same or different and are each independently alkylene; Or alkylcycloalkylene.

According to one example, L ₁ and L ₂ are the same or different from each other, and each independently is alkylene, alkylcyclopentyl or alkylcyclohexyl having 1 to 8 carbon atoms.

According to one example, L ₁ and L ₂ are the same or different and are each independently alkylene.

According to one example, L ₁ and L ₂ are the same or different and are each independently alkylene having 1 to 3 carbon atoms.

According to one example, L ₁ and L ₂ are methylene.

According to an exemplary embodiment, the alkali-soluble resin may contain the units R ₄ is an alkyl group of Formula 1 and the R ₄ is of the formula (1) hydrogen unit.

According to one embodiment, the alkali-soluble resin may include a unit wherein R ₄ in the formula (1) is hydrogen and a unit in which R ₄ in the formula (1) is a methyl group. In this case, the molar ratio of these units may be from 0: 100 to 100: 0, more preferably from 40:60 to 60:40, more preferably 50:50.

According to another embodiment of the present application, the alkali-soluble resin further comprises one or more units represented by the general formula (2).

According to one embodiment, R ₅ to R ₈ are the same or different and each independently hydrogen or an alkyl group having 1 to 8 carbon atoms.

According to another embodiment, R ₅ to R ₈ are the same or different and are each independently hydrogen or a methyl group.

According to another embodiment, R ₅ and R ₆ are hydrogen, R ₇ is hydrogen or a methyl group, and R ₈ is a methyl group.

According to one embodiment, X ₂ is a trivalent linear or branched aliphatic hydrocarbon group of 1 to 8 carbon atoms.

According to one embodiment, the formula (2) may be represented by the following formula (4).

[Chemical Formula 4]

In Formula 4,

The definitions of R ₅ to R ₈ are the same as those of the formula (2)

L ₃ and L ₄ , equal to or different from each other, are each independently alkylene; Or alkylcycloalkylene.

According to one example, L ₃ and L ₄ are the same or different from each other, and each independently is alkylene, alkylcyclopentyl, or alkylcyclohexyl having 1 to 8 carbon atoms.

According to one example, L < ₃ > and L < ₄ >, which are the same or different from each other, are each independently alkylene.

In accordance with one example, L ₃ and L ₄ are the same as or different from each other, and each independently represent an alkylene having 1 to 3 carbon atoms.

According to one example, L ₃ and L ₄ are methylene.

According to one embodiment, the alkali-soluble resin may include units wherein R ₈ in the formula (2) is hydrogen and R _{8 in} the formula (2) is an alkyl group.

According to one embodiment, the alkali-soluble resin may include a unit wherein R ₈ in the formula (2) is hydrogen and a unit in which R _{8 in} the formula (2) is a methyl group. In this case, the molar ratio of these units may be from 0: 100 to 100: 0, more preferably from 40:60 to 60:40, more preferably 50:50.

According to one embodiment of the present invention, when the unit represented by the formula (1) and the unit represented by the formula (2) are both included, the molar ratio of these units may be 1:99 to 99: 1, 95 to 50:50.

According to a further embodiment of the present application, in addition to the above formulas (1) and (2), a (meth) acrylate monomer may be further included. The (meth) acrylate-based monomer may be derived from the (meth) acrylate-based compounds known in the art by polymerization.

Examples of the (meth) acrylate-based compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) (Meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (beta) acrylate, (Meth) acrylate, cyclopentenyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, (Meth) acrylate, isobornyl (meth) acrylate, pinanyl (meth) acrylate, adamantyl (meth) acrylate, Unsaturated carboxylic acid ester compounds containing an alicyclic substituent such as acrylate and the like, mono-saturated carboxylic acid ester compounds of glycols such as oligoethylene glycol monoalkyl (meth) acrylate, benzyl (meth) acrylate, Unsaturated carboxylic acid ester compounds containing an aromatic ring such as cyano (meth) acrylate and rosin (meth) acrylate, aromatic vinyl compounds such as styrene,? -Methylstyrene and vinyl toluene, vinyl acetate, vinyl propionate , Vinyl cyanide compounds such as (meth) acrylonitrile and? -Chloroacrylonitrile, and maleimide compounds such as N-cyclohexylmaleimide and N-phenylmaleimide. Or a mixture of two or more thereof.

According to one embodiment of the present application, the weight average molecular weight of the alkali-soluble resin is 1,000 to 50,000 g / mol, preferably 5,000 to 45,000 g / mol, more preferably 5,000 to 30,000 g / mol, 100 mg KOH / g.

According to one embodiment, the resin containing the unit of the formula (1) has a monomer (A1) having an unsaturated bond and an epoxy group in the molecule, a monomer (A2) having an unsaturated double bond and a carboxyl group and an acid or an acid anhydride In the presence of a base.

The monomer (A1) is not particularly limited as long as it is a compound having an unsaturated bond and an epoxy group in the molecule, and specifically includes glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 4,5- (Meth) acrylate, 2-ethylhexyl (meth) acrylate, 5,6-epoxyhexyl (meth) acrylate, 6,7- Methyl (meth) acrylate,? -Ethyl glycidyl acrylate,? -N-propyl glycidyl acrylate,? -N-butyl glycidyl acrylate, 4-hydroxybutyl (meth) Diallyl ether, allyl glycidyl ether, 2-methylallyl glycidyl ether, and the like. These monomers may be used singly or in a mixture of two or more.

The monomer (A2) can be used without limitation as long as it is a compound which adds an unsaturated double bond to the polymer produced from the monomer (A1), preferably acrylic acid or methacrylic acid, or a mixture thereof .

The monomer (A2) can be used in combination with the monomer (A3) which is an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride. The unsaturated carboxylic acid or unsaturated carboxylic acid anhydride is not limited as long as it is a structure capable of providing the structure of formula (1) or (3). For example, a monomer having the following structure may be used as the monomer (A3).

In the above structural formula, the definition of Y is as described above.

The molecular weight regulator may be used in the production of the resin containing the unit of the formula (1). The molecular weight regulator is not particularly limited, but a mercaptan compound such as butylmercaptan, octylmercaptan or the like or? -Methylstyrene dimer may be used.

A polymerization initiator may be used in the production of the resin containing the unit of the formula (1). As the polymerization initiator, those known in the art may be used, and examples thereof include diisopropylbenzene hydroperoxide, di-t-butyl peroxide, benzoyl peroxide, t-butyl peroxyisopropylcarbonate, t- Amyl peroxy-2-ethylhexanoate and t-butyl peroxy-2-ethylhexanoate, and organic peroxides such as 2,2'-azobis (isobutyronitrile), 2,2'-azobis Dimethyl-2,2'-azobis (2-methylpropionate), and the like, or a mixture thereof may be used. It is not.

The polymerizable composition comprising the monomers may comprise any suitable solvent. For example, ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethyl glycol dimethyl ether, and propylene glycol monomethyl ether; Ketones such as acetone and methyl ethyl ketone; Esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate; Alcohols such as methanol and ethanol; Aromatic hydrocarbons such as toluene, xylene and ethylbenzene; chloroform; Dimethyl sulfoxide, and the like. These solvents may be used alone or in combination of two or more.

For example, the resin containing the unit of the formula (1) can be polymerized by a solution polymerization method, and the polymerization temperature at this time is preferably 40 to 150 ° C, more preferably 60 to 120 ° C.

The ratio of the constituent component derived from the monomer (A2) to the constituent component derived from the monomer (A3) in the production of the resin containing the unit represented by the formula (1) is not particularly limited and may be appropriately selected, Can be from 99: 1 to 1:99, and more preferably from 90:10 to 60:40.

Another embodiment of the present application provides a photosensitive resin composition comprising 1) an alkali-soluble resin according to the aforementioned embodiment, 2) a polyfunctional monomer, 3) a solvent, and 4) a photoinitiator. If desired, the composition may further comprise a coloring agent.

The content of the alkali-soluble resin is preferably 1 to 10% by weight based on the total weight of the photosensitive resin composition, but is not limited thereto.

The multifunctional monomer may comprise a multifunctional monomer known in the art. More specific examples include pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, But is not limited thereto.

The total content of the polyfunctional monomer is preferably 1 to 10% by weight based on the total weight of the photosensitive resin composition.

The solvent may comprise a solvent known in the art. 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 methyl ether acetate, propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, chloroform, methylene chloride, 1,2-dichloroethane, Trichloroethane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, methanol, ethanol, isopropanol, propanol, butanol, t-butanol, 2-ethoxypropanol, 2-methoxypropanol, 3-methoxybutanol, cyclohexanone, cyclopentanone, propylene glycol methyl ether acetate, propylene glycol ethyl At least one selected from the group consisting of ether acetate, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, methyl cellosolve acetate, and butyl acetate, dipropylene glycol monomethyl ether, But it is not limited thereto, and a solvent known in the art may be used.

The content of the solvent is preferably 65 to 90% by weight based on the total weight of the photosensitive resin composition.

The photoinitiator is a material which generates radicals by light to induce crosslinking, and may further include photoinitiators generally known in the art. The photoinitiator may be at least one selected from the group consisting of an acetophenone-based compound, a nonimidazole-based compound, a triazine-based compound, and an oxime-based compound.

Examples of the acetophenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2- - (2-hydroxyethoxy) -phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, 2-methyl-2- (4-methylthio) phenyl-2-morpholino-1-propan-1-one, 2-benzyl- Amino-1- (4-morpholinophenyl) -butan-1-one, 2- (4-bromo-benzyl- And 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one.

Examples of the nonimidazole-based compounds include 2,2-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'- 4 ', 5,5'-tetrakis (3,4,5-trimethoxyphenyl) -1,2'-biimidazole, 2,2'-bis (2,3-dichlorophenyl) ', 5,5'-tetraphenylbiimidazole, and a group consisting of 2,2'-bis (o-chlorophenyl) -4,4,5,5'-tetraphenyl-1,2'-biimidazole Lt; / RTI >

Examples of the triazine compound include 3- {4- [2,4-bis (trichloromethyl) -s-triazin-6-yl] phenylthio} propionic acid, 1,1,1,3,3,3- (Trichloromethyl) -s-triazine-6-yl] phenylthio} propionate, ethyl 2- {4- [2,4 Bis (trichloromethyl) -s-triazin-6-yl] phenylthio} acetate, 2- epoxyethyl-2- {4- [ Yl] phenylthio} acetate, benzyl-2- {4- [2- (4-fluorophenyl) (Trichloromethyl) -s-triazine-6-yl] phenylthio} acetate, 3- {chloro-4- [ (Phenylthio) propionic acid, 2,4- bis (trichloromethyl) -s-triazine-6-yl] Methyl) -6- p-methoxystyryl-s-triazine, 2,4-bis (trichloromethyl) -6- (1-p- Aminophenyl) -1,3-butadienyl -s- triazine, and 2-trichloromethyl-4-amino -6-p- methoxy styryl -s- will selected from the group consisting of a triazine,

Examples of the oxime compounds include 1,2-octadione-1- (4-phenylthio) phenyl-2- (o-benzoyloxime) (Ciba Geigy, CGI 124), and ethanone- (2-methylbenzoyl-3-yl) -1- (o-acetyloxime) (CGI 242).

The photoinitiator is preferably used in an amount of 1 to 300 parts by weight based on 100 parts by weight of the sum of the alkali-soluble binder resin and the unsaturated double bond contained in the multifunctional monomer. In particular, 1 to 30 parts by weight of the acetophenone compound, 1 to 30 parts by weight of a triazine compound, 1 to 30 parts by weight of a triazine compound, or 1 to 30 parts by weight of a oxime compound.

The photoinitiator may further include 0.01 to 10 parts by weight of a photo-crosslinking sensitizer and 0.01 to 10 parts by weight of a curing accelerator for accelerating the curing, relative to 100 parts by weight of the photoinitiator.

The photo-crosslinking sensitizer may be at least one selected from the group consisting of benzophenone, 4,4-bis (dimethylamino) benzophenone, 4,4-bis (diethylamino) benzophenone, 2,4,6-trimethylaminobenzophenone, Benzoate compounds such as benzoate, 3,3-dimethyl-4-methoxybenzophenone, and 3,3,4,4-tetra (t-butylperoxycarbonyl) benzophenone; Fluorene-based compounds such as 9-fluorenone, 2-chloro-9-proprenone and 2-methyl-9-fluorenone; Thioxanthone systems such as thioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 1-chloro-4-propyloxytioxanthone, 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-acridinylpentane), 1,3-bis (9-acridinyl) propane, and the like Acridine-based compounds; Dicarbonyl compounds such as benzyl, 1,7,7-trimethyl-bicyclo [2,2,1] heptane-2,3-dione, and 9,10-phenanthrenequinone; Phosphine oxide-based compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide; Benzophenone compounds such as methyl-4- (dimethylamino) benzoate, ethyl-4- (dimethylamino) benzoate and 2-n-butoxyethyl-4- (dimethylamino) benzoate; (4-diethylaminobenzal) cyclopentanone, 2,6-bis (4-diethylaminobenzal) cyclohexanone, 2,6-bis Amino-synergists such as methyl-cyclopentanone; (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- Pyran o [6,7,8-ij] -quinolizine-11-one; Chalcone compounds such as 4-diethylaminokalone and 4-azidobenzalacetophenone; 2-benzoylmethylene, or 3-methyl-b-naphthothiazoline.

Examples of the curing accelerator include 2-mercaptobenzoimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2,5-dimercapto-1,3,4-thiadiazole, 2- (3-mercaptopropionate), pentaerythritol-tris (3-mercaptopropionate), pentaerythritol-tetrakis (2-mercaptoacetate) , Trimethylolpropane-tris (2-mercaptoacetate), trimethylolpropane-tris (3-mercaptopropionate), pentaerythritol-tris Can be used.

The content of the photoinitiator is preferably 0.5 to 5% by weight based on the total weight of the photosensitive resin composition, but is not limited thereto.

The photosensitive resin composition may further include a colorant. The colorant may be those known in the art. For example, a black pigment may be used. More specifically, the colorant can be used by preparing a colored dispersion in which black pigment alone, black pigment alone, or a black pigment and a first color pigment are mixed and milled to prepare a colored dispersion. When the coloring pigment is mixed and used, the content of the coloring pigment may be 50% by weight or less and 30% by weight or less based on the total weight of the coloring agent. If the content of the coloring pigment exceeds 50% by weight based on the total weight of the coloring agent, OD (optical density) may be lowered.

As the black pigment, carbon black can be used, and examples of the carbon black include cis-to 5HIISAF-HS, cis-to-KH, cis-totho-3HHAF-HS, cis- toto- 300 HAF-LS, Cysto 116 HMMAF-HS, Cysto 116 MAF, Cysto FMFEF-HS, Cysto SOFEF, Cysto VGPF, Cysto SVHSRF-HS, and Cysto SSRF; 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, # 2600, # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 900, MCF88, # 52, # 50, # 47, # 45, # 45L, CF9, # 95, # 3030, # 3050, MA7, MA77, MA8, MA11, OIL7B, OIL9B, OIL11B, OIL30B, and OIL31B; PRINTEX-55, PRINTEX-55, PRINTEX-45, PRINTEX-35, PRINTEX-55, PRINTEX-85, PRINTEX-75, PRINTEX- SPECIAL BLACK-350, SPECIAL BLACK-250, SPECIAL BLACK-100, and LAMP BLACK-101; PRINTEX-25, PRINTEX-200, PRINTEX-40, PRINTEX-30, PRINTEX-3, PRINTEX-A; SPECIAL BLACK-550; RAVEN-1080 ULTRA, RAVEN-1060ULTRA, RAVEN-1060ULTRA, RAVEN-1040, RAVEN-1035, RAVEN-1020, RAVEN-1000, RAVEN-890H, RAVEN-890, RAVEN- 420, RAVEN-410, RAVEN-850, RAVEN-820, RAVEN-790ULTRA, RAVEN-780ULTRA, RAVEN-760ULTRA, RAVEN-520, RAVEN-500, RAVEN-460, RAVEN- RAVEN-1250, RAVEN-1200, RAVEN-1190ULTRA, and RAVEN-1170 can be used.

As the black pigment, at least one organic black pigment such as lactam black, perylene black, aniline black and the like can be used.

Examples of color pigments that can be used in combination with the black pigment include carmine 6B (CI12490), phthalocyanine green (CI 74260), phthalocyanine blue (CI 74160), Mitsubishi carbon black MA100, perylene black (BASF K0084.K0086) , Linol Yellow (CI 21090), Linol Yellow GRO (CI 21090), Benzidine Yellow 4T-564D, Mitsubishi Carbon Black MA-40, Victoria Pure Blue (CI42595) PIGMENT RED97, 122, 149, 168, 177, 180, 192, 215, C.I. PIGMENT GREEN 7, 36, C.I. PIGMENT 15: 1, 15: 4, 15: 6, 22, 60, 64, C.I. PIGMENT 83, 139 C.I. PIGMENT VIOLET 23, etc. In addition, white pigments, fluorescent pigments, etc. may be used.

As the color pigment, one or two kinds of blue pigments, red pigments and yellow pigments may be used, but the present invention is not limited thereto. The blue pigment, the red pigment, the yellow pigment and the like may be made of materials known in the art.

The content of the colorant is preferably 5 to 20% by weight based on the total weight of the photosensitive resin composition.

The photosensitive resin composition may further include at least one additive selected from the group consisting of a dispersant, an adhesion promoter, an antioxidant, an ultraviolet absorber, a thermal polymerization inhibitor, and a leveling agent.

The adhesion promoter may be 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, and 3-mercaptopropyltrimethoxysilane, And trimethoxysilane can be used.

The antioxidant may be 2,2-thiobis (4-methyl-6-t-butylphenol), or 2,6-g, t-butylphenol, -Butyl-5-methyl-2-hydroxyphenyl) -5-chloro-benzotriazole, or alkoxybenzophenone.

The thermal polymerization inhibitor may be at least one selected from the group consisting of hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t- butylcatechol, benzoquinone, 4,4- -Butylphenol), 2,2-methylenebis (4-methyl-6-t-butylphenol), or 2-mercaptoimidazole.

The leveling agent can serve to improve the chemical resistance of the photosensitive resin composition, and UV curing leveling agents known in the art can be used. As the leveling agent, MCF 350SF, F-475, F-488 or F-552, F-562, F554, RS-72K, RS-75, RS-76E and RS- However, the present invention is not limited thereto.

In addition, the photosensitive resin composition may further include at least one additive selected from the group consisting of a radiation-sensitive compound and other additives.

Still another embodiment of the present application provides a photo-spacer formed using the photosensitive resin composition. The photo spacers can be easily applied to a liquid crystal display device or the like. Here, the fact that the photo-sensitive resin composition is used means that the photo-sensitive resin composition includes the dried or hardened photosensitive resin composition, that is, the dried or cured product of the photosensitive resin composition.

The photo-spacer can be produced by a method including, for example, a) coating a tactile photosensitive resin composition on a substrate, and b) exposing and developing the applied photosensitive resin composition.

The step a) may be a step of applying the photosensitive resin composition, for example, on a substrate using a method known in the art. More specifically, the method of applying the photosensitive resin composition may be a spraying method, a roll coating method, a spin coating method, a bar coating method, a slit coating method, or the like. However, the present invention is not limited thereto.

At this time, the substrate may be made of metal, paper, glass, plastic, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide and the like. Treatment, plasma treatment, ion plating, sputtering, gas phase reaction, vacuum deposition, or the like. In addition, the substrate may have an optional thin film transistor for driving, and a nitrided silicon film may be sputtered.

The step b) is a step of exposing and developing the applied photosensitive resin composition.

More specifically, the prebaked coating film can be patterned by irradiating ultraviolet rays through a predetermined pattern mask and developing it with an aqueous alkaline solution to remove unnecessary portions. At this time, as a developing method, a dipping method, a shower method, and the like can be applied without limitation. The developing time is usually about 30 to 180 seconds. Examples of the developer include aqueous alkaline solutions such as sodium hydroxide, potassium hydroxide, sodium silicate, sodium metasilicate and ammonia; Primary amines such as ethylamine and N-propylamine; Secondary amines such as diethylamine and di-n-propylamine; Tertiary amines such as trimethylamine, methyldiethylamine and dimethylethylamine; Tertiary alcohol amines such as dimethylethanolamine, methyldiethanolamine and triethanolamine; Diazabicyclo [4.3.0] hept-2-ene, 1,1-diazabicyclo [5.4.0] Cyclic tertiary amines such as cyclohexane-5-nonene; Aromatic tertiary amines such as pyridine, coridine, lutidine and quinoline; An aqueous solution of a quaternary ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide can be used.

After the development, washing with water for about 30 to 90 seconds and drying with air or nitrogen can be carried out. This pattern can be obtained through a post-bake using a heating device such as a hot plate or an oven. At this time, it is preferable to heat post-baking at 150 to 230 DEG C for 10 to 90 minutes.

Examples of the light source for curing the above-mentioned photosensitive resin composition include, but are not limited to, a mercury vapor arc, a carbon arc, and an Xe arc, which emit light having a wavelength of 250 to 450 nm, for example.

The photo-spacers according to the embodiments of the present application have a rigid structure and not only have excellent elastic recovery, but also exhibit excellent solubility in developer.

Another embodiment of the present application includes a display device including the photo spacers. For example, the display device may include a liquid crystal cell including a transparent substrate and a photo spacer provided between the transparent substrate. The display device includes structures and materials known in the art, except that it includes photo spacers according to the embodiments of the present application.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

Synthetic example  One

20 g of glycidyl methacrylate and 0.7 g of 1-dodecanethiol as a chain transfer agent were dissolved in 74 g of propylene glycol monomethyl ether acetate (PGMEA) as a solvent, and the mixture was heated to 65 DEG C under a nitrogen atmosphere, Minute. After the reaction temperature was stabilized, 0.6 g of a thermal polymerization initiator V-65 was diluted in 6 g of a PGMEA solvent, charged into a reaction vessel, and maintained at 65 캜 for 15 hours under a nitrogen atmosphere.

After completion of the reaction for 15 hours, the reaction temperature was raised to 80 캜 and stirred for 1 hour. Then, 0.27 g of tetrabutylammonium bromide and 0.06 g of 4-methoxyphenol as a thermal polymerization inhibitor were added together with 8.13 g of PGMEA as a solvent, Followed by stirring at 90 DEG C for 2 hours. Thereafter, 5.05 g of acrylic acid and 6.03 g of methacrylic acid were added, and then the temperature was raised to 120 캜 and the reaction was carried out in an air atmosphere for 24 hours. After the reaction for 24 hours, the temperature of the reactor was lowered to 90 占 폚, 3.49 g of 5-norbornene-2,3-dicarboxylic anhydride and 2.71 g of PGMEA were added and the reaction was carried out in an air atmosphere for 16 hours. (Acid value: 52.3 mg KOH / g, solid content: 24.4%, weight average molecular weight: 17,300 g / mol).

Synthetic example  2

20 g of glycidyl methacrylate and 0.7 g of 1-dodecanethiol as a chain transfer agent were dissolved in 74 g of propylene glycol monomethyl ether acetate (PGMEA) as a solvent, and the mixture was heated to 65 DEG C under nitrogen atmosphere to obtain 30 Minute. After the reaction temperature was stabilized, 0.6 g of a thermal polymerization initiator V-65 was diluted in 6 g of a PGMEA solvent and charged into the reaction vessel. The reaction was maintained at 65 캜 for 15 hours in a nitrogen atmosphere.

After completion of the reaction for 15 hours, the reaction temperature was raised to 80 캜 and stirred for 1 hour. Then, 0.27 g of tetrabutylammonium bromide and 0.06 g of 4-methoxyphenol as a thermal polymerization inhibitor were added together with 8.13 g of PGMEA as a solvent, Followed by stirring at 90 DEG C for 2 hours. Thereafter, 5.05 g of acrylic acid and 6.03 g of methacrylic acid were added, and then the temperature was raised to 120 캜 and the reaction was carried out in an air atmosphere for 24 hours. After the reaction for 24 hours, the temperature of the reactor was lowered to 90 ° C, and 3.32 g of 7-oxabicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid anhydride and 2.71 g of PGMEA were added, , And the reaction was completed to prepare a copolymer containing the following four units (acid value: 51.3 mg KOH / g, solid content: 25.6%, weight average molecular weight: 17,700 g / mol).

Synthetic example  3_Molecular weight control

20 g of glycidyl methacrylate and 0.8 g of 1-dodecanethiol as a chain transfer agent were dissolved in 68 g of propylene glycol monomethyl ether acetate (PGMEA) as a solvent, and the mixture was heated to 65 DEG C under a nitrogen atmosphere to obtain 30 Minute. After the reaction temperature was stabilized, 1.26 g of a thermal polymerization initiator V-65 was diluted in 6 g of a PGMEA solvent and put in a reaction vessel, and the reaction was maintained at 75 캜 for 15 hours under a nitrogen atmosphere.

After completion of the reaction for 15 hours, the reaction temperature was raised to 80 캜 and stirred for 1 hour. Then, 0.27 g of tetrabutylammonium bromide and 0.06 g of 4-methoxyphenol as a thermal polymerization inhibitor were added together with 8.13 g of PGMEA as a solvent, Followed by stirring at 90 DEG C for 2 hours. Thereafter, 5.3 g of acrylic acid and 6.4 g of methacrylic acid were charged, and then the temperature was raised to 120 DEG C and the reaction was carried out in an air atmosphere for 24 hours. After the reaction for 24 hours, the temperature of the reactor was lowered to 90 DEG C, 1.6 g of 7-oxabicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid anhydride and 2.86 g of PGMEA were added, (Acid value: 34 mg KOH / g, solid content: 27.6%, weight average molecular weight: 9,100 g / mol).

Synthetic example  4_Molecular weight control

20 g of glycidyl methacrylate and 0.8 g of 1-dodecanethiol as a chain transfer agent were dissolved in 68 g of propylene glycol monomethyl ether acetate (PGMEA) as a solvent, and the mixture was heated to 65 DEG C under a nitrogen atmosphere to obtain 30 Minute. After the reaction temperature was stabilized, 1.0 g of thermal polymerization initiator V-65 was diluted in 6 g of PGMEA solvent and charged into the reaction vessel. The reaction was maintained at 65 占 폚 for 15 hours under a nitrogen atmosphere.

After completion of the reaction for 15 hours, the reaction temperature was raised to 80 캜 and stirred for 1 hour. Then, 0.27 g of tetrabutylammonium bromide and 0.06 g of 4-methoxyphenol as a thermal polymerization inhibitor were added together with 8.13 g of PGMEA as a solvent, Followed by stirring at 90 DEG C for 2 hours. Thereafter, 5.3 g of acrylic acid and 6.4 g of methacrylic acid were charged, and then the temperature was raised to 120 DEG C and the reaction was carried out in an air atmosphere for 24 hours. After the reaction for 24 hours, the temperature of the reactor was lowered to 90 DEG C, 1.6 g of 7-oxabicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid anhydride and 2.86 g of PGMEA were added, (Acid value 31 mg KOH / g, solid content 26.6%, weight average molecular weight 11,500 g / mol) after completion of the reaction.

Synthetic example  5_ molecular weight control

20 g of glycidyl methacrylate and 0.4 g of 1-dodecanethiol as a chain transfer agent were dissolved in 68 g of propylene glycol monomethyl ether acetate (PGMEA) as a solvent, and the mixture was heated to 65 DEG C under a nitrogen atmosphere to obtain 30 Minute. After the reaction temperature was stabilized, 0.6 g of a thermal polymerization initiator V-65 was diluted in 6 g of a PGMEA solvent and put in a reaction vessel, and the reaction was maintained at 75 캜 for 15 hours under a nitrogen atmosphere.

After completion of the reaction for 15 hours, the reaction temperature was raised to 80 캜 and stirred for 1 hour. Then, 0.27 g of tetrabutylammonium bromide and 0.06 g of 4-methoxyphenol as a thermal polymerization inhibitor were added together with 8.13 g of PGMEA as a solvent, Followed by stirring at 90 DEG C for 2 hours. Thereafter, 5.3 g of acrylic acid and 6.4 g of methacrylic acid were charged, and then the temperature was raised to 120 DEG C and the reaction was carried out in an air atmosphere for 24 hours. After the reaction for 24 hours, the temperature of the reactor was lowered to 90 DEG C, 1.6 g of 7-oxabicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid anhydride and 2.86 g of PGMEA were added, (Acid value 30 mg KOH / g, solid content 25.8%, weight average molecular weight 19,200 g / mol) after completion of the reaction.

Synthetic example  6_ molecular weight control

20 g of glycidyl methacrylate and 0.2 g of 1-dodecanethiol as a chain transfer agent were dissolved in 68 g of propylene glycol monomethyl ether acetate (PGMEA) as a solvent, and the mixture was heated to 65 DEG C under a nitrogen atmosphere to obtain 30 Minute. After the reaction temperature was stabilized, 0.5 g of thermal polymerization initiator V-65 was diluted in 6 g of PGMEA solvent, and the mixture was poured into a reaction vessel. The reaction was maintained at 75 캜 for 15 hours under a nitrogen atmosphere.

After completion of the reaction for 15 hours, the reaction temperature was raised to 80 캜 and stirred for 1 hour. Then, 0.27 g of tetrabutylammonium bromide and 0.06 g of 4-methoxyphenol as a thermal polymerization inhibitor were added together with 8.13 g of PGMEA as a solvent, Followed by stirring at 90 DEG C for 2 hours. Thereafter, 5.3 g of acrylic acid and 6.4 g of methacrylic acid were charged, and then the temperature was raised to 120 DEG C and the reaction was carried out in an air atmosphere for 24 hours. After the reaction for 24 hours, the temperature of the reactor was lowered to 90 DEG C, 1.6 g of 7-oxabicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid anhydride and 2.86 g of PGMEA were added, (Acid value 30 mg KOH / g, solid content 25.2%, weight average molecular weight 41,300 g / mol) after completion of the reaction.

Synthetic example  7_ Acid value  control( Acid value Approximately 30 mg  KOH / g)

20 g of glycidyl methacrylate and 1.7 g of 1-dodecanethiol as a chain transfer agent were dissolved in 74 g of propylene glycol monomethyl ether acetate (PGMEA) as a solvent, and the mixture was heated to 65 DEG C under a nitrogen atmosphere to obtain 30 Minute. After the reaction temperature was stabilized, 0.6 g of a thermal polymerization initiator V-65 was diluted in 6 g of a PGMEA solvent and charged into the reaction vessel. The reaction was maintained at 65 캜 for 15 hours in a nitrogen atmosphere.

After completion of the reaction for 15 hours, the reaction temperature was raised to 80 캜 and stirred for 1 hour. Then, 0.27 g of tetrabutylammonium bromide and 0.06 g of 4-methoxyphenol as a thermal polymerization inhibitor were added together with 8.13 g of PGMEA as a solvent, Followed by stirring at 90 DEG C for 2 hours. Thereafter, 5.05 g of acrylic acid and 6.03 g of methacrylic acid were added, and then the temperature was raised to 120 캜 and the reaction was carried out in an air atmosphere for 24 hours. After the reaction for 24 hours, the temperature of the reactor was lowered to 90 ° C, 1.4 g of 7-oxabicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid anhydride and 2.71 g of PGMEA were added, (Acid value 32 mg KOH / g, solid content 28.8%, weight average molecular weight 17,300 g / mol) after completion of the reaction.

Synthetic example  8_ Acid value  control( Acid value Approximately 70 mg  KOH / g)

20 g of glycidyl methacrylate and 1.7 g of 1-dodecanethiol as a chain transfer agent were dissolved in 74 g of propylene glycol monomethyl ether acetate (PGMEA) as a solvent, and the mixture was heated to 65 DEG C under a nitrogen atmosphere to obtain 30 Minute. After the reaction temperature was stabilized, 0.6 g of a thermal polymerization initiator V-65 was diluted in 6 g of a PGMEA solvent and charged into the reaction vessel. The reaction was maintained at 65 캜 for 15 hours in a nitrogen atmosphere.

After completion of the reaction for 15 hours, the reaction temperature was raised to 80 캜 and stirred for 1 hour. Then, 0.27 g of tetrabutylammonium bromide and 0.06 g of 4-methoxyphenol as a thermal polymerization inhibitor were added together with 8.13 g of PGMEA as a solvent, Followed by stirring at 90 DEG C for 2 hours. Thereafter, 5.05 g of acrylic acid and 6.03 g of methacrylic acid were added, and then the temperature was raised to 120 캜 and the reaction was carried out in an air atmosphere for 24 hours. After the reaction for 24 hours, the temperature of the reactor was lowered to 90 ° C, 4.82 g of 7-oxabicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid anhydride and 2.71 g of PGMEA were added, (Acid value: 66 mg KOH / g, solid content: 26.7%, weight average molecular weight: 17,600 g / mol) for 16 hours.

Synthetic example  9_ Acid value  control( Acid value About 90  mg KOH / g)

20 g of glycidyl methacrylate and 1.7 g of 1-dodecanethiol as a chain transfer agent were dissolved in 74 g of propylene glycol monomethyl ether acetate (PGMEA) as a solvent, and the mixture was heated to 65 DEG C under a nitrogen atmosphere to obtain 30 Minute. After the reaction temperature was stabilized, 0.6 g of a thermal polymerization initiator V-65 was diluted in 6 g of a PGMEA solvent and charged into the reaction vessel. The reaction was maintained at 65 캜 for 15 hours in a nitrogen atmosphere.

After completion of the reaction for 15 hours, the reaction temperature was raised to 80 캜 and stirred for 1 hour. Then, 0.27 g of tetrabutylammonium bromide and 0.06 g of 4-methoxyphenol as a thermal polymerization inhibitor were added together with 8.13 g of PGMEA as a solvent, Followed by stirring at 90 DEG C for 2 hours. Thereafter, 5.05 g of acrylic acid and 6.03 g of methacrylic acid were added, and then the temperature was raised to 120 캜 and the reaction was carried out in an air atmosphere for 24 hours. After 24 hours of reaction, the temperature of the reactor was lowered to 90 ° C, 6.86 g of 7-oxabicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic anhydride and 2.71 g of PGMEA were added, (Acid value: 99 mg KOH / g, solid content: 26.0%, weight average molecular weight: 16,200 g / mol).

Comparative Synthetic Example  One

20 g of glycidyl methacrylate and 0.7 g of 1-dodecanethiol as a chain transfer agent were dissolved in 74 g of propylene glycol monomethyl ether acetate (PGMEA) as a solvent, and the mixture was heated to 65 DEG C under nitrogen atmosphere to obtain 30 Respectively. After the reaction temperature was stabilized, 0.6 g of a thermal polymerization initiator V-65 was diluted in 6 g of a PGMEA solvent, put into a reaction vessel, and maintained at 65 캜 for 15 hours under a nitrogen atmosphere.

After completion of the reaction for 15 hours, the reaction temperature was raised to 80 캜 and stirred for 1 hour. Then, 0.27 g of tetrabutylammonium bromide and 0.06 g of 4-methoxyphenol as a thermal polymerization inhibitor were added together with 8.13 g of PGMEA as a solvent, Followed by stirring at 90 DEG C for 2 hours. Thereafter, 5.05 g of acrylic acid and 6.03 g of methacrylic acid were added, and then the temperature was raised to 120 캜 and the reaction was carried out in an air atmosphere for 24 hours. After reacting for 24 hours, the temperature of the reactor was lowered to 90 占 폚, 1.93 g of succinic anhydride and 2.71 g of PGMEA were added and the reaction was allowed to proceed in an air atmosphere for 16 hours. The reaction was completed to obtain a copolymer containing the following four units . (Acid value 61.6 mg KOH / g, solid content 30.1%, weight average molecular weight 21,900 g / mol)

Comparative Synthetic Example  2

20 g of glycidyl methacrylate and 0.7 g of 1-dodecanethiol as a chain transfer agent were dissolved in 74 g of propylene glycol monomethyl ether acetate (PGMEA) as a solvent, and the mixture was heated to 65 DEG C under nitrogen atmosphere to obtain 30 Minute. After the reaction temperature was stabilized, 0.6 g of a thermal polymerization initiator V-65 was diluted in 6 g of a PGMEA solvent, put into a reaction vessel, and maintained at 65 캜 for 15 hours under a nitrogen atmosphere.

After completion of the reaction for 15 hours, the reaction temperature was raised to 80 캜 and stirred for 1 hour. Then, 0.27 g of tetrabutylammonium bromide and 0.06 g of 4-methoxyphenol as a thermal polymerization inhibitor were added together with 8.13 g of PGMEA as a solvent, Followed by stirring at 90 DEG C for 2 hours. Thereafter, 5.05 g of acrylic acid and 6.03 g of methacrylic acid were charged, and the temperature was raised to 120 캜 and the reaction was carried out in an air atmosphere for 24 hours. After the reaction for 24 hours, the temperature of the reactor was lowered to 90 ° C, 3.49 g of 4-cyclohexene-1,2-dicarboxylic acid anhydride and 2.71 g of PGMEA were added and the reaction was carried out in an air atmosphere for 16 hours. , And a copolymer containing the following four units was prepared. (Acid value 47.8 mg KOH / g, 31.7%, weight average molecular weight 16,600 g / mol)

Experimental Example  One

2.23 g of the above copolymer solution (Synthesis Example 1), 6.03 g of pentaerythritol triacrylate (Japanese Gunpowder) as a polyfunctional monomer and 2-benzyl-2- (dimethylamino) -1- [4- (O-chlorophenyl) -4,4,5,5'-tetraphenyl-l, 2 ', 5'-tetramethyluronium hexafluorophosphate (trade name: Irgacure 369, I369) , 0.011 g of nonimidazole (BCIM), 0.011 g of 4,4'-bis (dimethylamino) benzophenone (EAB-F manufactured by Hodogaya Chemical Co., Ltd.), 5.91 g of inorganic dispersant (CHJ35, Renko, solid content 20.4% 0.055 g of silane coupling agent KBM503, 0.548 g of surfactant TF1697 and 5.11 g of solvent PGMEA according to a conventional method and stirred for 5 hours to prepare a composition for each photo-spacer.

Experimental Example  2

2.96 g of the copolymer solution (Synthesis Example 2), 5.96 g of pentaerythritol triacrylate (Japanese explosive) as a multifunctional monomer and 2.96 g of 2-benzyl-2- (dimethylamino) -1- [4- (O-chlorophenyl) -4,4,5,5'-tetraphenyl-l, 2 '-naphthol (trade name: Irgacure 369, I369) 0.011 g of diimidazole (BCIM), 0.011 g of 4,4'-bis (dimethylamino) benzophenone (EAB-F, manufactured by Hodogaya Chemical Co., Ltd.), 0.008 g of MEHQ, an inorganic dispersant (CHJ35, RENKO solid content 20.4% ), 0.054 g of a silane coupling agent KBM-503, 0.54 g of a surfactant TF-1697 and 5.23 g of a solvent PGMEA according to a conventional method and stirred for 5 hours to prepare a composition for each photo-spacer.

Experimental Example  3

2.96 g of the copolymer solution (Synthesis Example 3), 5.96 g of pentaerythritol triacrylate (Japanese explosive) as a multifunctional monomer and 2.96 g of 2-benzyl-2- (dimethylamino) -1- [4- (O-chlorophenyl) -4,4,5,5'-tetraphenyl-1,2'-bis (trimethylsilyl) phenyl] -1-butanone (trade name: Irgacure 369, I369) , 0.081 g of imidazole (BCIM), 0.011 g of 4'-bis (dimethylamino) benzophenone (EAB-F, manufactured by Hodogaya Chemical Co., Ltd.), 0.008 g of MEHQ, 5.84 g of inorganic dispersant (CHJ35, RENKO solid content 20.4% 0.054 g of a silane coupling agent KBM-503, 0.54 g of a surfactant TF-1697 and 5.23 g of a solvent PGMEA according to a conventional method, and the mixture was stirred for 5 hours to prepare a composition for each photo-spacer.

Experimental Example  4 to 9

A composition for a photo-spacer was prepared in the same manner as in Experimental Example 3, except that the copolymer solution prepared in Synthesis Examples 4 to 9 was used.

Comparative Experimental Example  One

1.97 g of the above copolymer solution (Comparative Synthesis Example 1), 5.92 g of pentaerythritol triacrylate (Japanese explosive) as a multifunctional monomer and 2.92 g of 2-benzyl-2- (dimethylamino) -1- [4- (O-chlorophenyl) -4,4,5,5 ' -tetraphenyl-1,2 (4-morpholinyl) phenyl] -1-butanone (trade name Irgacure 369, I369) 0.043 g of bisimidazole (BCIM), 0.043 g of 4,4'-bis (dimethylamino) benzophenone (EAB-F, manufactured by Hodogaya Kagaku), an inorganic dispersant (CHJ20, solid content 20.2% ), 0.054 g of silane coupling agent KBM-503, 0.032 g of surfactant BYK307, 0.022 g of BYK331, 5.88 g of solvent PGMEA and 0.063 g of DPM according to a conventional method and stirred for 5 hours for each photo spacer A composition was prepared.

Comparative Experimental Example  2

2.03 g of the copolymer solution (Comparative Synthesis Example 2), 6.43 g of pentaerythritol triacrylate as a multifunctional monomer, and 2.43 g of 2-benzyl-2- (dimethylamino) -1- [4- ) Phenyl] -1-butanone (trade name Irgacure 369, I369), 0.105 g of 2,2'-bis (o-chlorophenyl) -4,4,5,5'-tetraphenyl- (CHEM 37, RENKO, solid content 21.0%) 6.13 (product name), 0.033 g of benzotriazole (BCIM), 0.012 g of 4,4'-bis (dimethylamino) benzophenone (EAB-F, manufactured by Hodogaya Chemical Co., , 0.056 g of silane coupling agent KBM-503, 0.58 g of surfactant TF-1697 and 4.58 g of solvent PGMEA according to a conventional method and stirred for 5 hours to prepare a composition for each photo-spacer.

Photo spacers were prepared using the compositions for the photo-spacers prepared in Experimental Examples 1 to 9 and Comparative Experimental Examples 1 and 2. SEM photographs of the photo-spacers prepared using the composition of Experimental Example 2 are shown in Fig. Regarding the manufactured photo spacers, the width, height and elastic restoration ratio were measured in the following manner. The solubility of the composition was measured by the following method.

1) The width of the photo spacer (diameter in the horizontal direction) and height

The size and height of the photo spacers were measured using a laser microscope, and the results are shown in Tables 1 and 2 below.

TOP CD PSH (μm) TOP (μm) Bottom (μm) B-T (μm) Experimental Example 1 TOP 5 3.253 5.6 10.4 4.8 TOP 7 3.256 6.9 11.5 4.6 TOP 10 3.189 10.0 14.8 4.8 Experimental Example 2 TOP 5 3.207 5.6 9.8 4.2 TOP 7 3.196 6.8 10.9 4.1 TOP 10 3.105 10.0 4.2 4.2 Comparative Experimental Example 1 TOP 5 3.263 4.9 9.2 4.4 TOP 7 3.240 7.3 11.4 4.1 TOP 10 3.164 10.4 14.7 4.3 Comparative Experimental Example 2 TOP 5 3.101 4.1 10.36 5.8 TOP 7 3.110 7.0 12.7 5.7 TOP 10 3.047 10.2 15.9 5.7 PSH: Photo-Spacer Height
TOP 5: Characteristics at the top 5 μm
TOP 7: Characteristics at the top 7 μm
TOP 10: Characteristics at the top 10 μm

Mask (μm) PSH (μm) TOP (μm) Bottom (μm) B-T (μm) Experimental Example 3 10.5 3.158 5.3 9.7 4.4 12 3.155 7.1 11.6 4.6 15 3.124 9.9 14.5 4.6 Experimental Example 4 7.5 3.359 5.0 9.1 4.2 9.5 3.420 7.0 12.2 5.2 12 3.410 10.3 15.9 5.6 Experimental Example 2 8 3.440 5.4 10.0 4.5 9.5 3.464 7.3 12.0 4.7 12 3.460 10.4 15.8 5.4 Experimental Example 5 7.5 3.417 5.1 9.5 4.4 9.5 3.505 7.2 12.0 4.8 12 3.353 10.3 15.8 5.5 Experimental Example 6 7.5 3.568 4.8 9.3 4.5 9.5 3.625 6.8 11.7 5.0 12 3.353 10.3 15.8 5.5  Mask (μm): Mask size used to manufacture the photo spacer

2) Elastic Restoration Rate of Photo Spacer

The elastic recovery rate of the photo spacers was measured using a micro compression tester. After the load was applied to the formed photo-spacers at a rate of 5 mN / sec, the load was maintained for 5 seconds, and the strain (Hmax) was confirmed. Then, the load was removed to 1.96 mN at a rate of 5 mN / (Hf) was measured to prepare an elastic restoration rate curve. The measured elastic recovery value was calculated from the following equation.

Elastic restoration rate = (Hmax-Hf) / (Hmax-Hmin)

Hmax: strain at 40 mN load

Hf: deformation at 1.96 mN when removing load

Hmin: strain at 1.96 mN when load is applied

3) Solubility of the composition

The composition was applied on a 10 cm ² glass substrate, baked at 100 ° C for 3 minutes, pretreated, and a photomask having a circular pattern of 1 to 50 μm in diameter was placed on the glass substrate. Respectively. This was immersed in KOH aqueous solution to check the time and developer conditions.

Transparent recording: OK

Not transparent but does not form precipitate: OK (sprinkled)

Precipitation Formation: NG

The measurement results are shown in Tables 3 and 4. A photograph showing the results of the solubility measurement is shown in FIG. 2, and the results of the solubility measurement of Synthesis Examples 2 and 7 to 9 are shown in Table 5 below.

TOP CD Recovery Rate (%) Solubility TOP5 TOP7 TOP10 0h 24h 48h Comparative Synthesis Example 1 67.2 74.5 86.1 NG NG NG Comparative Synthesis Example 2 69.3 78.8 89.9 NG NG NG Synthesis Example 1 69.4 74.6 87.5 OK OK NG Synthesis Example 2 69.2 79.3 90.1 OK OK OK TOP 5: Elastic restoration rate value at the upper 5 μm
TOP 7: Elastic restoration rate value at the upper 7 μm
TOP 10: Elastic restoration rate value at the upper 10 μm

As shown in Table 3, the elastic restoration ratio due to the change of the acid period was the same level. However, there was a large difference in solubility in developer. In addition, it was confirmed that the resins prepared in Synthesis Examples 1 and 2 were more effective in terms of elastic restoration due to the introduction of RS (reactive site).

TOP CD Recovery Rate (%) Solubility TOP5 TOP7 TOP10 0h 24h 48h Synthesis Example 3 58.3 64.4 80.4 OK (sprinkled) OK (sprinkled) OK (sprinkled) Synthesis Example 4 57.5 63.2 80.3 OK (sprinkled) OK OK Synthesis Example 2 58.8 65.1 79.5 OK (sprinkled) OK OK Synthesis Example 5 57.6 65 81.8 OK (sprinkled) OK OK Synthesis Example 6 58.5 66.1 80.3 OK (sprinkled) OK OK

As shown in Table 4, the resins prepared in Synthesis Examples 3, 4, 5 and 6 had elastic recovery rates and solubilities of the same level as those of Synthesis Example 2 having the best elastic recovery and solubility in Table 3 there was.

bookbinder Sample Binder acid 0h 0.5h 3.5h
ETX100

Synthesis Example 7 AV30 OK OK OK Synthesis Example 2 AV50 OK (sprinkled) OK (sprinkled) NG Synthesis Example 8 AV70 OK (sprinkled) OK (sprinkled) NG Synthesis Example 9 AV90 OK (sprinkled) NG NG

As shown in Table 5, it was confirmed from the results of solubility tests of Synthesis Examples 2, 7, 8 and 9 that the acid value of the binder was about 30 mg KOH / g to 90 mg KOH / g, and the lower the acid value of the binder, the better the solubility .

Claims (11)

An alkali-soluble resin comprising one or two or more units represented by the following formula (1):
[Chemical Formula 1]

In Formula 1,
R ₁ to R ₄ are the same or different and each independently hydrogen or an alkyl group,
X ₁ is a trivalent linking group,
Y is CRR 'or O, wherein R and R' are hydrogen or an alkyl group. An alkali-soluble resin according to claim 1, wherein the chemical formula 1 is represented by Chemical Formula 3:
(3)

In Formula 3,
The definitions of R ₁ to R ₄ and Y are the same as those of the formula (1)
L ₁ and L ₂ are the same or different and are each independently alkylene; Or alkylcycloalkylene. The alkali-soluble resin according to claim 1, wherein the alkali-soluble resin comprises a unit wherein R ₄ in the formula (1) is hydrogen and a unit in which R ₄ in the formula (1) is an alkyl group. The alkali-soluble resin according to claim 1, wherein the alkali-soluble resin further comprises one or two or more units represented by the following formula (2):
(2)

In Formula 2,
R ₅ to R ₈ are the same or different and each independently hydrogen or an alkyl group,
X ₂ is a trivalent linking group. [4] The method according to claim 4, wherein the alkali-soluble resin represented by Chemical Formula 2 is represented by Chemical Formula 4:
[Chemical Formula 4]

In Formula 4,
The definitions of R ₅ to R ₈ are the same as those of the formula (2)
L ₃ and L ₄ , equal to or different from each other, are each independently alkylene; Or alkylcycloalkylene. [Claim 4] The alkali-soluble resin according to claim 4, wherein the alkali-soluble resin comprises units wherein R < ₈ > is hydrogen and R < ₈ > The alkali-soluble resin according to claim 1, wherein the alkali-soluble resin has a weight average molecular weight of 1,000 to 50,000 g / mol. 1) an alkali-soluble resin according to any one of claims 1 to 7,
2) Multifunctional monomers,
3) solvent, and
4) Photo initiator
. The photosensitive resin composition according to claim 8, further comprising a colorant. A photo-spacer formed using the photosensitive resin composition according to claim 8. A display device comprising a photo spacer according to claim 10.

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