KR20130063715A - Photosensitive resin composition for spacer and spacer manufactured by the same - Google Patents

Abstract

PURPOSE: A photosensitive resin composition for forming a spacer and a spacer manufactured by the same are provided to improve solvent resistance properties and heat resistance properties. CONSTITUTION: A photosensitive resin composition for forming a spacer includes an oxime ester-based photo-initiator which is represented by chemical formula 1. The composition further includes one or more photo-initiators selected from a group including a triazine-based compound, an acetophenone-based compound, a biimidazol-based compound, an oxime-based compound, a benzoin-based compound, a benzophenone-based compound, a thioxanthone-based compound, and an anthracene-based compound. The composition further includes an alkali soluble resin, a photo-curable monomer, and a solvent. The spacer is made of the composition.

Description

Photosensitive resin composition for forming a spacer and a spacer produced therefrom {PHOTOSENSITIVE RESIN COMPOSITION FOR SPACER AND SPACER MANUFACTURED BY THE SAME}

The present invention relates to a photosensitive resin composition for forming a spacer and a spacer prepared therefrom, and more particularly, to a photosensitive resin composition for forming a spacer which can be applied to an image display device due to its excellent resilience and transparency. It is about.

In general display devices, silica beads or plastic beads having a certain diameter have been used to maintain constant spacing of the upper and lower substrates. However, when such beads are randomly dispersed on the substrate and located inside the pixel, there is a problem that the aperture ratio is lowered and light leakage phenomenon occurs. In order to solve these problems, a spacer formed by photolithography has been used in a display device. Currently, a spacer used in most display devices is formed by photolithography.

A method of forming a spacer by photolithography is a method in which a photosensitive resin composition is coated on a substrate, ultraviolet rays are irradiated through the mask, and a spacer is formed at a desired position on the substrate in accordance with a pattern formed on the mask.

Recently, as the demand for touch panels increases due to the popularization of smart phones and tablet PCs, the external pressure and the elastic recovery rate, which are the basic characteristics of the spacers that maintain the gap between the color filter substrate and the array substrate, which constitute the display device, Hard characteristics are demanded without pixel distortion. However, in the case of the conventional photosensitive resin composition for forming a spacer, the elastic recovery rate is sufficiently realized, but the rigid characteristics without pixel deformation due to external pressure are not realized to a satisfactory level.

On the other hand, it is also very important that the spacer has excellent transparency. By the way, the conventional photosensitive resin composition for spacer formation had a problem that transparency becomes low due to yellowing after curing.

In order to solve these problems, various studies on various photoinitiators have been carried out. Among them, oxime compounds absorb ultraviolet rays and have almost no color, have high radical generation efficiency, and have good stability in the composition.

As the oxime compounds, α-oxooxime derivatives have been disclosed in JP-A-61-118423, JP-A-1-068750 and JP-A-3-004226, and US Pat. No. 4,255,513 Discloses an oxime ester compound using p-dialkylaminobenzene. U.S. Patent No. 4,202,697 discloses an acrylamino-substituted oxime ester compound, and U.S. Patent No. 4,590,145 discloses a benzophenone oxime ester compound. U.S. Patent No. 5,776,996 discloses a β-aminooxime compound, and U.S. Patent No. 6,051,367 discloses an oxime ester compound in which an ethylenically unsaturated group is contained in a molecular structure. In addition, International Patent Publication No. 00/052530 discloses oxime ether, oxime ester, oxime sulfonate compounds, and International Patent Publication No. 02/100903 discloses a process for the production of oxycarboxylic acids by coupling with alkyl acyl ketones, diarylketones or ketocoumarines ≪ / RTI > is disclosed.

Of these oxime compounds, long conjugation compounds that absorb light having a long wavelength may have a slight color, which may affect the color when applied for optics. On the other hand, a compound that absorbs light of short wavelength has a disadvantage of low photoreactivity and low efficiency as a photoinitiator.

Japanese Unexamined Patent Application Publication No. 61-118423 (June 6, 1986) Japanese Laid-Open Patent Publication No. 1-068750 (Mar. 14, 1989) Japanese Unexamined Patent Application Publication No. 3-004226 (1991.01.10) U.S. Patent No. 4,255,513 (Mar. 3, 1981) U.S. Patent No. 4,202,697 (May 15, 1980) U.S. Patent No. 4,590,145 (May 5, 1986) U.S. Patent No. 5,776,996 (July 7, 1998) U.S. Patent No. 6,051,367 (Apr. 18, 2000) International Patent Publication No. 00/052530 (September 20, 2000) International Patent Publication No. 02/100903 (December 19, 2002)

An object of the present invention is to provide a photosensitive resin composition for forming a spacer which does not have a color upon curing or does not have a decrease in transparency such as yellowing even after curing.

Moreover, an object of this invention is to provide the photosensitive resin composition for spacer formation which has the rigid characteristic which has the outstanding elastic recovery rate and little deformation in external pressure.

Moreover, an object of this invention is to provide the spacer formed by apply | coating and hardening the said photosensitive resin composition for spacer formation in a predetermined pattern.

Moreover, an object of this invention is to provide the image display apparatus provided with the said spacer.

1. Photosensitive resin composition for spacer formation comprising an oxime ester photoinitiator represented by the following formula (1):

(Wherein R ₁ is an alkyl group having 0-10 carbon atoms; X is S or NH; R ₂ is an alkyl group having 1-13 carbon atoms, an acetyl group, an alkenyl group having 2-10 carbon atoms, or an alkynyl group having 2-10 carbon atoms) , 5 to 10 carbon atoms of the aryl group, having a carbon number of 5 to 10 heteroaryl group, having a carbon number of 5-10 aryloxy group, a 6 to 10 carbon atoms in the arylalkyl group, having a carbon number of 1-10 alkoxy group; R ₃ is a carbon number of 1 - 12 alkyl group).

2. In the above 1, R ₃ is an alkyl group having 1 to 6 carbon atoms, the photosensitive resin composition for spacer formation.

3. In the above 1, R ₃ is a methyl group for forming a photosensitive resin composition.

4. In the above 1, R ₁ is a photosensitive resin composition for spacer formation which is an alkyl group having 0-3 carbon atoms.

5. In the above 1, R ₂ is an alkyl group or an acetyl group having 1-3 carbon atoms, the photosensitive resin composition for spacer formation.

6. according to the above 1, selected from the group consisting of triazine compound, acetophenone compound, biimidazole compound, oxime compound, benzoin compound, benzophenone compound, thioxanthone compound and anthracene compound A photosensitive resin composition for forming a spacer, further comprising at least one photoinitiator.

7. according to the above 1, the photosensitive resin composition for spacer formation further comprising an alkali-soluble resin, a photocurable monomer and a solvent.

8. In the above 7, the photoinitiator is a photosensitive resin composition for forming a spacer containing 0.1 to 40 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin and the photocurable monomer based on the solid content.

9. In the above 7, the alkali-soluble resin is a photosensitive resin composition for forming a spacer that is copolymerized including at least one or more of the monomers represented by the formula (8) and formula (9):

[Formula 8]

Wherein R ₁ is hydrogen or alkyl or cycloalkyl having 1 to 20 carbon atoms, with or without heteroatoms; R ₂ is alkylene or cycloalkylene having 1 to 20 carbon atoms, with or without heteroatoms R ₁ and R ₂ may be independently substituted with a hydroxy group)

[Chemical Formula 9]

Wherein R ₁ is hydrogen or alkyl or cycloalkyl having 1 to 20 carbon atoms, with or without heteroatoms; R ₂ is alkylene or cycloalkylene having 1 to 20 carbon atoms, with or without heteroatoms R ₁ and R ₂ may be independently substituted with a hydroxyl group.

10. In the above 9, the monomer represented by the formula (8) and formula (9) is epoxidized dicyclodecaneyl (meth) acrylate-3,4-epoxytricyclodecane-9-yl (meth) acrylate; 3,4-epoxytricyclodecane-9-yl (meth) acrylate; Epoxidized dicyclodecaneyl (meth) acrylate-3,4-epoxytricyclodecane-8-yl (meth) acrylate; 3,4-epoxytricyclodecane-8-yl (meth) acrylate; Epoxidized dicyclopentanyloxyethyl (meth) acrylate-2- (3,4-epoxytricyclodecane-9-yloxy) ethyl (meth) acrylate; Epoxidized dicyclopentanyloxyethyl (meth) acrylate-2- (3,4-epoxytricyclodecane-8-yloxy) ethyl (meth) acrylate; Epoxidized dicyclopentanyloxyhexyl (meth) acrylate; And a photosensitive resin composition for forming a spacer, which is at least one selected from the group consisting of epoxidized dicyclodecaneyl (meth) acrylate.

11. In the above 9, wherein the monomer represented by the formula (8) and formula (9) is 2 to 50 mol% of the total mole of the total monomer constituting the alkali-soluble resin, the photosensitive resin composition for spacer formation.

12. The spacer made of the photosensitive resin composition for spacer formation of any one of 1 to 11.

13. The image display device having the spacer of 12 above.

The photosensitive resin composition for spacer formation of this invention exhibits sufficient hardening characteristic even if it uses a small amount by using the photoinitiator which is excellent in sensitivity, and hardening is fully achieved even in the small exposure amount at the time of hardening.

In addition, after curing, it is excellent in adhesion and pattern formation characteristics to the substrate, not only excellent solvent resistance and heat resistance, but also high transparency does not affect the color implementation of the color filter.

In addition, the spacer made of the photosensitive resin composition for forming a spacer of the present invention has excellent elastic recovery rate, and has a hard property with little deformation in external pressure.

The present invention relates to a photosensitive resin composition for forming a spacer and a spacer prepared therefrom by including an oxime ester photoinitiator represented by the formula (1), which has excellent transparency and excellent elastic recovery and little deformation in external pressure.

Hereinafter, the present invention will be described in detail.

The photosensitive resin composition for forming a spacer of the present invention is characterized by comprising an oxime ester photoinitiator represented by the following formula (1):

[Formula 1]

In formula, R <_1> is a C0-10 alkyl group, Preferably it is good that it is a C0-3 alkyl group.

X is S or NH.

R ₂ is an alkyl group having 1 to 13 carbon atoms, an acetyl group, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 5 to 10 carbon atoms, a heteroaryl group having 5 to 10 carbon atoms, and a 5 to 10 carbon atoms. It is an aryloxy group, a C6-C10 arylalkyl group, a C1-C10 alkoxy group, Preferably it is a C1-C3 alkyl group or an acetyl group.

R ₃ is an alkyl group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group.

The oxime ester compound represented by the formula (1) may be exemplified by the compounds represented by the following formulas (2) to (6), but is not limited thereto.

The oxime ester compound according to the present invention can be obtained by substituting X, i.e., -S- or -NH-, which is an electron donating group (EDG) at the alpha position of the oxime to slightly shift the maximum absorption wavelength of ultraviolet to a short wavelength Stomach X increases solubility and is highly compatible with other ingredients. In addition, -COR ₃ group generates an alkyl radical after irradiation to improve light reactivity and maximize light efficiency. The shorter the length of the alkyl group, the more effective it is.

These oxime ester compounds can be synthesized by a known synthetic process.

Specific examples of the preparation of the oxime ester compound represented by the formula (1) according to the present invention are described in Korean Patent Application No. 10-2011-103977, which is incorporated herein by reference in its entirety.

The photosensitive resin composition for spacer formation of the present invention may further include a photoinitiator used in the art without departing from the present invention. For example, a triazine compound, an acetophenone compound, a nonimidazole compound, an oxime compound, a benzoin compound, a benzophenone compound, a thioxanthone compound, and an anthracene compound, Can be mixed and used.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) (Trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) Bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) -Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- Azine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- Methyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1 (2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] Propan-1-one oligomers and the like.

Examples of the acetophenone-based compounds usable in addition to the above-mentioned acetophenone-based compounds include compounds represented by the following general formula (7).

In Formula 7, R ₁ to R ₄ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group which may be substituted by an alkyl group having 1 to 12 carbon atoms, or a benzyl group which may be substituted by an alkyl group having 1 to 12 carbon atoms. Or a naphthyl group which may be substituted by an alkyl group having 1 to 12 carbon atoms.

Specific examples of the compound represented by Formula 7 include 2-methyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-ethyl- 1-one, 2-propyl-2-amino (4-morpholinophenyl) ethan- (4-morpholinophenyl) propane-1-one, 2-amino-2- 2-methyl-2-methylamino (4-morpholinophenyl) propane-1-one, 1-one, 2-methyl-2-dimethylamino (4-morpholinophenyl) propan- have.

Examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'- Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole or a phenyl group at the 4,4', 5,5 ' An imidazole compound substituted by an alkoxy group, and the like. Among them, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole or 2,2'-bis (2,3- , 5,5'-tetraphenylbiimidazole are preferably used.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Examples of the benzophenone compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4- .

Examples of the anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, .

Other examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylclyoxylic acid Methyl, titanocene compounds and the like can be mentioned as other photoinitiators.

Further, in the present invention, the photoinitiator may be used in combination with a photoinitiator. When a photoinitiator is used together with a photoinitiator, since the photosensitive resin composition for spacer formation containing these becomes more sensitive, productivity at the time of forming a spacer using this composition is preferable.

As photoinitiation adjuvant, an amine compound and a carboxylic acid compound are used preferably.

Specific examples of the amine compound in the photoinitiation aid include aliphatic amine compounds such as triethanolamine, methyl diethanolamine and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzoic acid isoamyl, 4 -Dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N, N-dimethyl paratoluidine, 4,4'-bis (dimethylamino) benzophenone (common name: Michler's ketone), 4,4'-bis Aromatic amine compounds, such as (diethylamino) benzophenone, are mentioned. As the amine compound, an aromatic amine compound is preferably used.

Specific examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid and dichlorophenylthioacetic acid. And aromatic heteroacetic acids such as N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

The photosensitive resin composition for forming a spacer of the present invention may include components conventionally used in the art to manufacture a spacer in addition to the photoinitiator described above. For example, alkali-soluble resins, photocurable monomers, solvents, and the like can be used without particular limitation.

At this time, the content of the photoinitiator according to the present invention described above is usually 0.1 to 40 parts by weight, preferably 1 to 30 parts by weight, based on solids, based on 100 parts by weight of the total amount of the alkali-soluble resin and the photocurable monomer. The content of the adjuvant is usually 0.1 to 50 parts by weight, preferably 1 to 40 parts by weight based on the above criteria. When the amount of photoinitiator used is in the above range, the photosensitive resin composition for forming a spacer is highly sensitive, and thus the strength of the spacer formed using the composition and the smoothness of the spacer surface are good. Moreover, when the usage-amount of a photoinitiation adjuvant exists in the said range, since the sensitivity of the photosensitive resin composition for spacer formation becomes higher, and productivity of the spacer formed using this composition improves, it is preferable.

Alkali-soluble resins usually have reactivity and alkali solubility by the action of light or heat and act as a dispersion medium of other components. Alkali-soluble resin contained in the photosensitive resin composition for spacer formation of the present invention is preferably prepared including a monomer having an epoxytricyclodecane ring structure and an unsaturated bond, these monomers are represented by the formulas (8) and (9) More preferably, it includes at least one of:

Wherein R ₁ is hydrogen or alkyl or cycloalkyl having 1 to 20 carbon atoms, with or without heteroatoms; R ₂ is alkylene or cycloalkylene having 1 to 20 carbon atoms, with or without heteroatoms; R ₁ and R ₂ may be independently substituted with a hydroxyl group,

Wherein R ₁ is hydrogen or alkyl or cycloalkyl having 1 to 20 carbon atoms, with or without heteroatoms; R ₂ is alkylene or cycloalkylene having 1 to 20 carbon atoms, with or without heteroatoms; R ₁ and R ₂ may be independently substituted with a hydroxyl group.

In Formulas 8 and 9, more specific examples of R ₁ , independently from each other, hydrogen; An alkyl group such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group; Hydroxy-n-propyl group, 3-hydroxy-n-propyl group, 1-hydroxy-1-hydroxypropyl group, N-butyl group, 3-hydroxy-n-butyl group, 4-hydroxy-n-butyl group, 2-hydroxy- -Butyl group and the like. Among them, R ₁ is preferably independently of each other hydrogen, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group or a 2-hydroxyethyl group, more preferably a hydrogen atom or a methyl group.

In Formulas 8 and 9, more specific examples of R ₂ , a single bond independently of each other; Alkylene groups such as a methylene group, an ethylene group and a propylene group; Containing alkylene groups such as a methylene group, an oxyethylene group, an oxyethylene group, an oxyethylene group, an oxypropylene group, a thiomethylene group, a thioethylene group, a thiopropylene group, an aminomethylene group, an aminoethylene group and an aminopropylene group. Among them, R ₂ is preferably a single bond, a methylene group, an ethylene group, an oxymethylene group or an oxyethylene group, more preferably a single bond or an oxyethylene group. In the present invention, when R ₂ is a single bond, it means that the carbon at the 8- or 9-position of the tricyclodecanyl group and the oxygen of the acrylate group are directly connected.

More specific examples of such a monomer having an epoxy tricyclodecane ring structure and an unsaturated bond include epoxidized dicyclodecaneyl (meth) acrylate-3,4-epoxytricyclodecane-9-yl (meth) acrylate; 3,4-epoxytricyclodecane-9-yl (meth) acrylate; Epoxidized dicyclodecaneyl (meth) acrylate-3,4-epoxytricyclodecane-8-yl (meth) acrylate; 3,4-epoxytricyclodecane-8-yl (meth) acrylate; Epoxidized dicyclopentanyloxyethyl (meth) acrylate-2- (3,4-epoxytricyclodecane-9-yloxy) ethyl (meth) acrylate; Epoxidized dicyclopentanyloxyethyl (meth) acrylate-2- (3,4-epoxytricyclodecane-8-yloxy) ethyl (meth) acrylate; Epoxidized dicyclopentanyloxyhexyl (meth) acrylate; Epoxidized dicyclodecaneyl (meth) acrylate etc. are mentioned, Preferably, epoxidized dicyclodecaneyl (meth) acrylate, epoxidized dicyclopentanyloxyethyl (meth) acrylate, etc. are mentioned. These can be used individually or in combination of 2 types or more, respectively.

In the present invention, (meth) acrylate means acrylate and / or methacrylate.

Alkali-soluble resins according to the present invention can be prepared by copolymerizing monomers including the monomer having the epoxytricyclodecane ring structure and an unsaturated bond. More specifically, (a) a monomer having an epoxytricyclodecane ring structure and an unsaturated bond, (b) a monomer copolymerizable with the monomer having the epoxytricyclodecane ring structure and an unsaturated bond, and (c) a carboxyl group and an unsaturated bond. It can be prepared by copolymerizing a monomer having.

Specific examples of the (b) monomer are as follows.

First, styrene, chlorostyrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether and aromatic vinyl monomers such as p-vinylbenzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, and indene. Toluene is preferable because it is excellent in developability and processability. Further, N-cyclohexyl maleimide, N-benzyl maleimide, N-phenyl maleimide, N-phenyl maleimide, No-hydroxyphenyl maleimide, Nm-hydroxyphenyl maleimide, Np-hydroxyphenyl maleimide N-substituted maleimide systems such as No, methylphenyl maleimide, Nm-methylphenyl maleimide, Np-methylphenyl maleimide, No-methoxyphenyl maleimide, Nm-methoxyphenyl maleimide and Np-methoxyphenyl maleimide Monomers; Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) ) Acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, acyloctyloxy-2-hydroxypropyl (meth) acrylic Ethylene, ethylhexyl acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, Methoxytripropylene Glycol (Meth) acrylate, methoxy polyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, p-nonyl phenoxy polyethylene glycol (meth) acrylate, p-nonyl phenoxy polypropylene glycol (meth) Acrylate, tetrafluoropropyl (meth) acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluoro Decyl (meth) acrylate, tribromophenyl (meth) acrylate, β- (meth) acyloloxyethylhydrogensuccinate, methylα-hydroxymethylacrylate, ethylα-hydroxymethylacrylate, propyl (meth) acrylate-based monomers such as α-hydroxymethyl acrylate and butyl α-hydroxymethyl acrylate; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethyl Unsaturated carboxylic acids such as aminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, and 3-dimethylaminopropyl methacrylate Alkyl ester monomers; Carboxylic acid vinyl ester monomers such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; Vinyl cyanide monomers such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and vinylidene cyanide; Unsaturated amides such as acrylamide, methacrylamide,? -Chloroacrylamide, N-2-hydroxyethyl acrylamide and N-2-hydroxyethyl methacrylamide; Aliphatic conjugated diene monomers such as, 3-butadiene, isoprene and chloroprene; And monoacryloyl or monomethacryloyl groups at the terminal of the polymer molecular chain of polystyrene, polymethylacrylate, polymethylmethacrylate, poly-n-butylacrylate, poly-n-butylmethacrylate, polysiloxane. The macromonomer which has, etc. are mentioned. These may be used alone or in combination of two or more.

The monomer having an unsaturated bond with the (c) carboxyl group is not limited as long as it is a carboxylic acid compound having an unsaturated double bond that can be polymerized, and specific examples thereof include acrylic acid and methacrylic acid. Acrylic acid and methacrylic acid can be used individually or in combination of 2 types or more, respectively. In addition to these acrylic acid and methacrylic acid, at least one other acid may be used. As other acid, unsaturated monocarboxylic acid or unsaturated polyhydric carboxylic acid can be used, and specifically, it uses together the carboxylic acid selected from 1 or more types of other unsaturated carboxylic acids, such as crotonic acid, itaconic acid, mesaconic acid, citraconic acid, maleic acid, and fumaric acid together. It is also possible. The monomer having an unsaturated bond with the carboxyl group may be in the form of an acid anhydride, and the unsaturated polyhydric carboxylic anhydride may be, for example, maleic anhydride, itaconic anhydride, citraconic anhydride, or the like.

In addition, the unsaturated polyhydric carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester thereof, for example, monosuccinate mono (2-acryloyloxyethyl), monosuccinate mono (2-methacryloyloxyethyl ), Mono phthalate (2-acryloyloxyethyl), mono phthalate (2-methacryloyloxyethyl), etc. are mentioned.

The unsaturated polyhydric carboxylic acid may be a mono (meth) acrylate of the sock end dicarboxy polymer, and examples thereof include ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, and the like. .

Moreover, the said unsaturated polyhydric carboxylic acid may be unsaturated acrylate containing a hydroxyl group and a carboxyl group in the same molecule, For example, (alpha)-(hydroxymethyl) acrylic acid etc. are mentioned.

Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used because of high copolymerization reactivity.

According to the present invention, in the copolymers obtained by copolymerizing the above-mentioned (a) to (c) (which is included in the present invention even when a monomer other than a to c is further included and copolymerized), each of (a) to (c) The proportion of the constituents derived from is preferably in the following ranges in mole fraction with respect to the total moles of the constituents constituting the copolymer.

structural units derived from (a): 2-50 mol%,

structural units derived from (b): 2-50 mol%,

structural units derived from (c): 2 to 70 mole%

As described above, when the ratio of the constituents derived from each of (a) to (c) is within the above range, a good balance of developability, solubility and heat resistance can be obtained, so that a preferable copolymer can be obtained.

According to an embodiment of the present invention, the alkali-soluble resin is added to the copolymer obtained by the copolymerization reaction of the monomers (a) to (c) to add a compound having an unsaturated bond and an epoxy group in (d) 1 molecule to the alkali-soluble resin. Thermosetting property can be given.

Specific examples of the compound having an unsaturated bond and an epoxy group in the above (d) molecule include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and 3,4-epoxycyclohexylmethyl (meth). ) Acrylate, methylglycidyl (meth) acrylate, and the like. Of these, glycidyl (meth) acrylate is preferably used. These may be used alone or in combination of two or more. In the present invention, (meth) acrylate means acrylate and / or (meth) acrylate.

The compound having an unsaturated bond and an epoxy group in the (d) 1 molecule is preferably reacted at a molar fraction of 5 to 80 mol% with respect to the number of moles of the component derived from the compound having an unsaturated bond (c) in the copolymer. , And 10 to 70 mol% is more preferable. (d) When the compound which has an unsaturated bond and an epoxy group exists in the said range, since sufficient photocurability and thermosetting are obtained, a sensitivity and pencil hardness are compatible, and it is excellent in reliability, and it is preferable.

Alkali-soluble resins according to the present invention can be prepared by adopting a known method known in the art, a solution polymerization method is more preferable among known polymerization methods. The polymerization temperature and polymerization time vary depending on the type and ratio of the monomers to be introduced, the molecular weight of the target binder resin and the acid value, but preferably polymerization is carried out at 60 to 130 ° C for 1 to 10 hours.

As the solvent used in the above process, a solvent used in a normal radical polymerization reaction may be used, and specifically, tetrahydrofuran, dioxane, ethylene glycol dimethylethyl, diethylene glycol dimethylethyl, acetone, methyl ethyl ketone, Methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ethyl acetate, 3-methoxybutyl acetate, methanol, ethanol, propanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether , Toluene, xylene, ethylbenzene, chloroform, dimethyl sulfoxide and the like. These solvents may be used alone or in combination of two or more.

As the polymerization initiator to be used in the above step, a commonly used polymerization initiator may be added and is not particularly limited. Specifically, diisopropyl benzene hydroperoxide, di-t-butyl peroxide, benzoyl peroxide, t-butyl peroxy isopropyl carbonate, t-amyl peroxy-2-ethylhexanoate, t-butyl Organic peroxides such as peroxy-2-ethylhexyl carbonate; 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylbareronitoryl), dimethyl 2,2'-azobis (2-methylpropionate), etc. And nitrogen compounds. These can be used individually or in combination of 2 or more types.

In addition, the copolymer may use a mercapto-based chain transfer agent such as n-dodecyl mercapto, mercaptoacetic acid, methyl mercaptoacetate, α-methylstyrene dimer, or the like as a chain transfer agent in order to control the molecular weight or molecular weight distribution during the polymerization process. have. The amount of the α-methylstyrene dimer or mercapto compound is 0.005 to 5% by mass based on the total amount of monomers. In addition, the above-mentioned polymerization conditions may be appropriately adjusted depending on the production equipment or the amount of heat generated by polymerization, and the method of addition and the reaction temperature.

In the present invention, the acid value of the alkali-soluble resin is preferably in the range of 30 to 150 mgKOH / g based on solid content. When the acid value is less than 30 mgKOH / g, the developability against alkaline water is lowered and the residue may remain on the substrate. If the acid value exceeds 150 mgKOH / g, the possibility of desorption of the pattern increases.

The alkali-soluble resin preferably has a weight average molecular weight in terms of polystyrene in the range of 3,000 to 100,000, more preferably in the range of 5,000 to 50,000. When the weight average molecular weight of alkali-soluble resin exists in the range of 3,000-100,000, film | membrane decrease does not occur at the time of image development, and since the missing property of a non-pixel part at the time of image development is preferable, it is preferable.

It is preferable that it is 1.5-6.0, and, as for the molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of alkali-soluble resin, it is more preferable that it is 1.8-4.0. The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of 1.5 to 6.0 is preferable because it is excellent in developability.

The content of the alkali-soluble resin is preferably contained in a mass fraction of 10 to 95% by mass, more preferably 20 to 70% by mass relative to the total solids of the composition. If it is the said range, since the residue can remain at the time of image development, and a desired coating film can be formed, it is preferable.

The photocurable monomer contained in the photosensitive resin composition for spacer formation of this invention is a compound which can superpose | polymerize by the action of light and the said photoinitiator, A monofunctional monomer, a bifunctional monomer, another polyfunctional monomer, etc. are mentioned.

The photocurable monomer used in the present invention may be used by mixing two or more photocurable monomers having different functional groups or functional groups in order to improve the developability, sensitivity, adhesion, and surface problems of the photosensitive resin composition for spacer formation. Does not limit its scope

Specific examples of monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N- Money and so on.

Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like.

Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, and pentaerythritol tree. (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol Hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned.

Of these, multifunctional monomers having two or more functional groups are preferably used.

The photocurable monomer is normally used in the range of 1-60 mass%, Preferably it is 5-50 mass% with respect to solid content in the photosensitive resin composition for spacer formation. Since the intensity | strength and smoothness of a pixel part become it favorable that a photocurable monomer is the range of 1-60 mass% on the said reference | standard, it is preferable.

The solvent contained in the photosensitive resin composition for spacer formation of the present invention is not particularly limited and various solvents used in the art can be used without limitation. Specific examples include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate; Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate; Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether; Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol dipropyl ether, propylene glycol propyl methyl ether and propylene glycol ethyl propyl ether; Propylene glycol alkyl ether propionates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate and propylene glycol butyl ether propionate; Butyldiol monoalkyl ethers such as methoxybutyl alcohol, ethoxybutyl alcohol, propoxybutyl alcohol and butoxybutyl alcohol; Butanediol monoalkyl ether acetates such as methoxybutyl acetate, ethoxybutyl acetate, propoxybutyl acetate and butoxybutyl acetate; Butanediol monoalkyl ether propionates such as methoxy butyl propionate, ethoxy butyl propionate, propoxy butyl propionate and butoxy butyl propionate; Dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether and dipropylene glycol methyl ethyl ether; Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin; Methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate , Butyl hydroxy acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxypropionate methyl, 3-hydroxypropionate ethyl, 3-hydroxypropionate propyl, 3-hydroxypropionate butyl, 2-hydroxy 3-Methyl methyl butyrate, methyl methoxy acetate, ethyl methoxy acetate, methoxy acetate propyl, butyl acetate, ethoxy acetate methyl, ethoxy acetate, ethoxy acetate propyl, butyl ethoxy acetate, propoxy Methyl acetate, ethyl propoxy acetate, propyl propoxy acetate, butyl propoxy acetate, methyl butoxy acetate, ethyl butoxy acetate, Propyl acetate, butyl butoxy acetate, methyl 2-methoxypropionate, 2-methoxy ethylpropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate Propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, 3-methoxy ethylpropionate, 3-methoxy propylpropionate, 3-methoxy propylpropionate, 3-ethoxy propylpropionate, 3-ethoxy propylpropionate, 3-ethoxy propylpropionate, 3-ethoxy propylpropionate, 3 Methyl propoxypropionate, 3-propoxy propionate, 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, 3-butoxypropionic acid Esters such as ropil, 3-butoxy-propionic acid butyl; Cyclic ethers such as tetrahydrofuran and pyran; Cyclic esters, such as (gamma) -butyrolactone, etc. can be used individually or in mixture of 2 or more types, respectively.

Among the above solvents, organic solvents having a boiling point of 100 ° C. to 200 ° C. are preferably used in the above solvents in terms of applicability and drying properties, and more preferably alkylene glycol alkyl ether acetates, ketones and butanediol alkyl ether acetates. Esters such as butanediol monoalkyl ethers, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate may be preferably used, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Cyclohexanone, methoxybutyl acetate, methoxybutanol, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like may be used alone or in combination of two or more thereof.

The content of the solvent in the photosensitive resin composition for forming a spacer of the present invention is 60 to 90 mass%, preferably 70 to 85 mass% with respect to the total mass of the photosensitive resin composition for forming a spacer. If the solvent content is in the range of 60 to 90% by mass, the applicability becomes good when applied with a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as die coater), inkjet, or the like. It is preferable because of that.

Optionally, the photosensitive resin composition for forming a spacer of the present invention may further include additives such as fillers, other polymer compounds, curing agents, leveling agents, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomerates, chain transfer agents, and the like. .

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

Specific examples of the other high molecular compound include curable resins such as epoxy resins and maleimide resins; And thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane.

The curing agent is used to increase the core hardening and mechanical strength, and specific examples of the curing agent include epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, oxetane compounds and the like.

Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, noblock type epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin, Aliphatic, cycloaliphatic or aromatic epoxy compounds other than glycidyl ester resins, glycidylamine resins, or brominated derivatives of these epoxy resins, epoxy resins and their brominated derivatives, butadiene (co) polymer epoxides, isoprene A polymer epoxide, glycidyl (meth) acrylate (co) polymer, a triglycidyl isocyanurate, etc. are mentioned.

Specific examples of the oxetane compound in the curing agent include carbonate bis oxetane, xylene bis oxetane, adipate bis oxetane, terephthalate bis oxetane, and cyclohexane dicarboxylic acid bis oxetane.

The curing agent may be used together with a curing agent in combination with a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound. As said hardening auxiliary compound, polyhydric carboxylic acid, polyhydric carboxylic anhydride, an acid generator, etc. are mentioned, for example.

The carboxylic acid anhydrides may be those commercially available as an epoxy resin curing agent. Examples of the epoxy resin curing agents include epoxy resins such as those available under the trade names (ADEKA HARDONE EH-700) (ADEKA INDUSTRY CO., LTD.), Trade names (RICACIDO HH) Manufactured by Shin-Etsu Chemical Co., Ltd.). The hardeners illustrated above can be used individually or in mixture of 2 or more types.

As said leveling agent, commercially available surfactants can be used, For example, surfactants, such as a silicone type, a fluorine type, ester type, a cation type, an anion type, a nonionic type, an amphoteric, etc., are mentioned, These are each independently, either You may use in combination of 2 or more type.

As said surfactant, For example, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol diester, sorbitan fatty acid ester, fatty acid modified polyester, tertiary amine modified polyurethane, In addition to polyethyleneimines, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), polyflow (manufactured by Kyoi Chemical Co., Ltd.), F-Top (manufactured by Tochem Products Co., Ltd.), MegaPac (Dainippon Ink Chemical Co., Ltd.) Co., Ltd., Florade (manufactured by Sumitomo 3M Co., Ltd.), Asahigard, Saffron (above, Asahigarasu Co., Ltd.), Soapaspa (Geneka Co., Ltd.), EFKA (EFKA CHEMICALS Co., Ltd.) Manufacture), PB821 (made by Ajinomoto Co., Ltd.), etc. are mentioned.

As said adhesion promoter, a silane type compound is preferable, Specifically, a vinyl trimethoxysilane, a vinyl triethoxysilane, a vinyl tris (2-methoxyethoxy) silane, N- (2-aminoethyl)- 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-gly Cidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxy Propyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, etc. are mentioned.

Specific examples of the antioxidant include 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate, 2- [1- (2-hydroxy -3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenylacrylate, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) prop Foxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosphine, 3,9-bis [2- {3- (3-tert -Butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,2'-methylenebis ( 6-tert-butyl-4-methylphenol), 4,4'-butylidenebis (6-tert-butyl-3-methylphenol), 4,4'-thiobis (2-tert-butyl-5- Methylphenol), 2,2'-thiobis (6-tert-butyl-4-methylphenol), dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate , Distearyl 3,3'-thiodipropionate, pentaerythritol tetrakis (3-laurylthiopropionate), 1,3,5-tris (3,5-di-te (3H, 3H, 5H) -triene, 3,3 ', 3 ", 5,5' 5 '' - hexa-tert-butyl-a, a ', a' '- (mesitylene-2,4,6-triyl) tri-p-cresol, pentaerythritol tetrakis [3- Di-tert-butyl-4-hydroxyphenyl) propionate], 2,6-di-tert-butyl-4-methylphenol and the like.

Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, alkoxybenzophenone and the like.

As said aggregation inhibitor, sodium polyacrylate etc. are mentioned specifically ,.

Specific examples of the chain transfer agent include dodecyl mercaptan, 2,4-diphenyl-4-methyl-1-pentene, and the like.

The photosensitive resin composition for spacer formation of this invention can be manufactured, for example by the method of adding and mixing alkali-soluble resin, a photocurable monomer, a photoinitiator, and other additives used as needed to a solvent. However, the present invention does not limit this method.

The present invention provides a spacer formed by forming a photosensitive resin composition in a predetermined pattern and then exposing and developing the same, and a display device having the same. The display device spacer can be produced, for example, by applying a photosensitive resin composition on a substrate as described below, photocuring and developing to form a pattern.

First, a photosensitive resin composition is apply | coated on a board | substrate (usually glass) or the layer which consists of solid content of the photosensitive resin composition formed previously, and heat-drying removes volatile components, such as a solvent, and obtains a smooth coating film.

The coating method can be carried out by, for example, a spin coating method, a flexible coating method, a roll coating method, a slit and spin coat method or a slit coat method. It heats after application | coating and heat-drying (prebaking) or drying under reduced pressure, and volatilizes volatile components, such as a solvent. Here, heating temperature is 70-200 degreeC normally, Preferably it is 80-130 degreeC. The coating film thickness after heat drying is about 1-8 micrometers normally. Ultraviolet rays are applied to the thus obtained coating film through a mask for forming a desired pattern. At this time, it is preferable to use an apparatus such as a mask aligner or a stepper so as to uniformly irradiate a parallel light beam onto the entire exposed portion and accurately align the mask and the substrate. When ultraviolet light is irradiated, the site irradiated with ultraviolet light is cured.

The ultraviolet rays may be g-line (wavelength: 436 nm), h-line, i-line (wavelength: 365 nm), or the like. The dose of ultraviolet rays can be appropriately selected according to need, and the present invention is not limited thereto. When the coating film after curing is brought into contact with a developing solution to dissolve and develop the non-visible portion, a spacer having a desired pattern shape can be obtained.

The developing method may be any of a liquid addition method, a dipping method, a spray method and the like. Further, the substrate may be inclined at an arbitrary angle during development. The developer is usually an aqueous solution containing an alkaline compound and a surfactant. The alkaline compound may be either an inorganic or an organic alkaline compound. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, sodium dihydrogen phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate And sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, ammonia and the like. Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, Monoisopropylamine, diisopropylamine, ethanolamine, and the like. These inorganic and organic alkaline compounds may be used alone or in combination of two or more. The concentration of the alkaline compound in the alkaline developer is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass.

The surfactant in the alkaline developer may be at least one selected from the group consisting of nonionic surfactants, anionic surfactants or cationic surfactants.

Specific examples of the nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.

Specific examples of the anionic surfactant include higher alcohol sulfuric acid ester salts such as sodium lauryl alcohol sulfate ester and sodium oleyl alcohol sulfate ester, alkylsulfates such as sodium laurylsulfate and ammonium laurylsulfate, sodium dodecylbenzenesulfonate And alkylarylsulfonic acid salts such as sodium dodecylnaphthalenesulfonate.

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts. Each of these surfactants may be used alone or in combination of two or more.

The concentration of the surfactant in the developer is usually from 0.01 to 10% by mass, preferably from 0.05 to 8% by mass, more preferably from 0.1 to 5% by mass. After development, it is washed with water and optionally 150 to 230 ° C. Post-baking of 10 to 60 minutes can also be performed.

Using the photosensitive resin composition of this invention, a pattern can be formed on a board | substrate or a color filter substrate through each process as mentioned above. This pattern is useful as a photospacer used for a display device.

Therefore, the spacer having the pattern thus obtained can be usefully used in an image display device such as a liquid crystal display device, and has excellent transparency, high crosslinking density even at a low exposure amount, and excellent adhesion to a substrate. Solvent resistance) and has high elastic recovery rate.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to examples. However, the embodiments according to the present invention can be modified into various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of the present invention are provided to enable those skilled in the art to more fully understand the present invention.

Example  1-8 and Comparative example  1-2

< Synthetic example  1: Synthesis of Alkali-Soluble Resin (A-1)>

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen introduction tube was prepared, and as a monomer dropping lot, 3,4-epoxycyclodecane-8-yl (meth) acrylate and 3,4- 40 parts by weight of a mixture of epoxytricyclodecane-9-yl (meth) acrylate (50:50 molar ratio), 50 parts by weight of methyl methacrylate, 40 parts by weight of acrylic acid, 70 parts by weight of vinyltoluene, t-butylperoxy- 4 parts by weight of 2-ethylhexanoate and 40 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) were added and prepared by stirring and mixing. As a chain transfer agent dropping tank, 6 parts by weight of n-dodecanethiol and 24 parts by weight of PGMEA were added thereto. The thing which stirred and mixed was prepared. Thereafter, 395 parts by weight of PGMEA was introduced into the flask, the atmosphere in the flask was changed to nitrogen in air, and the temperature of the flask was raised to 90 DEG C while stirring. Then, the monomer and the chain transfer agent were added dropwise from the dropping funnel. The dropwise addition was carried out for 2 hours while maintaining 90 ° C, and after 1 hour, the temperature was raised to 110 ° C and maintained for 5 hours to obtain a resin (A-1) having a solid acid value of 75 mgKOH / g. The weight average molecular weight measured by GPC in terms of polystyrene was 17,000 and the molecular weight distribution (Mw / Mn) was 2.3.

< Synthetic example  2: Synthesis of Alkali-Soluble Resin (A-2)>

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen introduction tube was prepared, and as a monomer dropping lot, 3,4-epoxycyclodecane-8-yl (meth) acrylate and 3,4- 40 parts by weight of a mixture of epoxytricyclodecane-9-yl (meth) acrylate (50:50 molar ratio), 50 parts by weight of methyl methacrylate, 40 parts by weight of acrylic acid, 70 parts by weight of benzylmaleimide, t-butylperoxy 4 parts by weight of -2-ethylhexanoate and 40 parts by weight of propylene glycol monomethyl ether acetate were prepared, followed by stirring and mixing. As a chain transfer agent dropping tank, 6 parts by weight of n-dodecanethiol and 24 parts by weight of PGMEA were added and stirred and mixed. I prepared one thing. Thereafter, 395 parts by weight of PGMEA was introduced into the flask, the atmosphere in the flask was changed to nitrogen from air, and the temperature of the flask was raised to 90 ° C. while stirring. Subsequently, dropping of the monomer and the chain transfer agent was started from the dropping lot. The dropwise addition was performed for 2 hours while maintaining 90 ° C, and after 1 hour, the temperature was raised to 110 ° C and maintained for 5 hours to obtain a resin (A-2) having a solid acid value of 73 mgKOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 18,000, and molecular weight distribution (Mw / Mn) was 2.2.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the alkali-soluble resin were measured by the GPC method under the following conditions.

Apparatus: HLC-8120GPC (manufactured by TOSOH CORPORATION)

Column: TSK-GELG4000HXL + TSK-GELG2000HXL (Serial Connection)

Column temperature: 40 ℃

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0 ml / min

Injection amount: 50 μl

Detector: RI

Measurement sample concentration: 0.6 mass% (solvent = tetrahydrofuran)

Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by TOSOH CORPORATION)

The ratio of the weight average molecular weight and number average molecular weight obtained above was made into molecular weight distribution (Mw / Mn).

< Spacer  Production of Photosensitive Resin Composition for Formation>

The photosensitive resin composition for spacer formation was produced with the component and composition of following Table 1 (unit is a weight part).

Example Comparative example One 2 3 4 5 6 7 8 One 2 Alkali-soluble resin (A) A-1 55.00 55.00 55.00 55.00 55.00 A-2 55.00 55.00 55.00 55.00 55.00 Photocurable
Monomer (B) 45.0 45.00 45.00 45.00 45.00 45.00 45.00 45.00 45.00 45.00 Photoinitiator
(C) C-1 4.00 4.00 C-2 4.00 4.00 C-3 4.00 4.00 C-4 4.00 4.00 C-5 4.00 4.00 Photoinitiation
Supplements (CC) 3.0 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 Solvent (D) D-1 53.00 53.00 53.00 53.00 53.00 53.00 53.00 53.00 53.00 53.00 D-2 42.00 42.00 42.00 42.00 42.00 42.00 42.00 42.00 42.00 42.00 D-3 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 D-4 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Additive (E) 0.80 0.80 0.80 0.80 0.80 0.80 0.80 0.80 0.80 0.80
Photocurable monomer (B): dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Photoinitiator (C-1): Oxime ester compound represented by the formula (2)
Photoinitiator (C-2): Oxime ester compound represented by the formula (3)
Photoinitiator (C-3): Oxime ester compound represented by the formula (4)
Photoinitiator (C-4): Oxime ester compound represented by the formula (5)
Photoinitiator (C-5): 1,2-octanedione-1- [4- (phenylthio) phenyl] -2-O-benzoyloxime (OXE-01; BASF)
Photoinitiation adjuvant (CC): 4,4'-bis (diethylamino) benzophenone (EAB-F; manufactured by Hodogaya Kagaku Co., Ltd.)
Solvent (D-1): Propylene glycol monomethyl ether acetate
Solvent (D-2): 3-ethoxyethylpropionate
Solvent (D-3): 3-methoxy-1-butanol
Solvent (D-4): 3-methoxybutyl acetate
Additives (F-antioxidants): 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (Irganox3114; manufactured by Ciba Specialty Chemicals)

Test Example

< Test Specimen  Production>

A glass substrate (Eagle 2000; Corning) having an aspect ratio of 2 inches was sequentially washed with a neutral detergent, water and alcohol, and then dried. The photosensitive resin compositions prepared in the above Examples and Comparative Examples were each spin-coated on this glass substrate, and then prebaked in a clean oven at 90 캜 for 3 minutes. After cooling the prebaked substrate to room temperature, the distance from the quartz glass photomask was set to 10 μm, and light was emitted at an exposure amount (405 nm standard) of 60 mJ / cm 2 using an exposure machine (TME-150RSK; Topcon Co., Ltd.). Investigate. The irradiation to the polymerizable resin composition at this time passed the light emitted from an ultra-high pressure mercury lamp through an optical filter (LU0400; manufactured by Asahi Spectroscopy Co., Ltd.), and cut and used light of 400 nm or less. In this case, a photomask in which the next pattern was formed on the same plane was used.

One side has a square light-transmitting part (pattern) which is 10 micrometers, and the said space | interval is 100 micrometers.

After the light irradiation, the coating film was immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide for 100 seconds at 25 ° C for development. After washing with water, postbaking was carried out at 220 ° C for 20 minutes in an oven. The obtained film thickness was 3 micrometers. The film thickness was measured using a film thickness measuring device (DEKTAK 6M; manufactured by Veeco). The physical properties were evaluated for the pattern thus obtained as follows, and the results are shown in Table 2 below.

1. Transmittance

The transmittance | permeability (%) in 400 nm of the cured film obtained above was measured using the microscope spectrophotometer (OSP-SP200; the product made by OLYMPUS). The transmittance is shown in Table 2 below in terms of transmittance at a film thickness of 3.0 μm. The transmittance is better near 100%.

2. Line width Cross-sectional shape

The line width was measured for the cured film obtained above using the scanning electron microscope (S-4200; the Hitachi Corporation make), and the cross-sectional shape was evaluated as follows. The cross sectional shape was determined as a reverse taper when the angle of the pattern with respect to the substrate was less than 90 degrees and as a reverse taper when the angle was greater than 90 degrees.

A forward taper is preferable because disconnection of the ITO wiring hardly occurs at the time of forming the display device.

3. Mechanical characteristics (total displacement and recovery rate)

The cured film obtained above was measured using a dynamic ultra-micro hardness tester (DUH-W201; manufactured by Shimadzu Corporation) and its total displacement (µm) and elastic displacement (µm) were measured according to the following measurement conditions. The recovery rate (%) was calculated as follows. It was judged that the total recovery was hard and the recovery rate was large.

Recovery rate (%) = [elastic displacement amount (占 퐉)] / [total displacement amount (占 퐉)] 占 100

The measurement conditions are as follows.

Test Mode: Load-Unload Test

Test force: 5gf [SI unit conversion value; 49.0mN]

Load speed: 0.45gf / sec [SI unit conversion value; 4.41 mN / sec]

Retention time: 5sec

Indenter: truncated indenter (diameter 50㎛)

4. Sensitivity

Development adhesiveness is the size of the mask with 100% of the pattern formed with the thickness of 3㎛ by the photomask with 1000 circular patterns with the diameter of 1㎛ interval from 5㎛ to 20㎛. Evaluated. The smaller the mask size, the better the sensitivity.

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Comparative Example 2 Transmittance (%) 99 99 97 98 98 98 96 98 95 96 pattern Line width (탆) 14.3 14.2 14.7 14.5 14.4 14.5 14.8 14.6 13.0 13.2 shape Forward taper Forward taper Forward taper Forward taper Forward taper Forward taper Forward taper Forward taper Reverse taper Reverse taper Mechanical characteristics Total displacement
(Μm) 0.77 0.75 0.71 0.74 0.75 0.74 0.70 0.75 1.03 1.20 Recovery rate
(%) 62.7 63.5 64.1 63.8 63.7 63.8 64.5 64.0 57.7 55.7 Sensitivity
(Mask Size, ㎛) 7 7   5 6 6 6 5   6 10 11

As shown in Table 2, in the case of using the photoinitiator according to the present invention, it can be confirmed that the transmittance is superior to the comparative examples that do not include it. In addition, it can be confirmed that the adhesion to the substrate and the pattern shape at the low exposure amount is good, the elastic recovery rate is excellent, the total displacement is not only mechanical properties but also the sensitivity is excellent.

Claims (13)

A photosensitive resin composition for forming a spacer comprising an oxime ester photoinitiator represented by Formula 1 below:
[Formula 1]

(Wherein R ₁ is an alkyl group having 0-10 carbon atoms; X is S or NH; R ₂ is an alkyl group having 1-13 carbon atoms, an acetyl group, an alkenyl group having 2-10 carbon atoms, or an alkynyl group having 2-10 carbon atoms) , 5 to 10 carbon atoms of the aryl group, having a carbon number of 5 to 10 heteroaryl group, having a carbon number of 5-10 aryloxy group, a 6 to 10 carbon atoms in the arylalkyl group, having a carbon number of 1-10 alkoxy group; R ₃ is a carbon number of 1 - 12 alkyl group).
The photosensitive resin composition for spacer formation of Claim 1 whose R <_3> is a C1-C6 alkyl group.
The photosensitive resin composition for spacer formation of Claim 1 whose R <_3> is a methyl group.
The photosensitive resin composition for spacer formation of Claim 1 whose R <_1> is a C0-3 alkyl group.
The photosensitive resin composition for spacer formation of Claim 1 whose R <_2> is a C1-C3 alkyl group or an acetyl group.
The method according to claim 1, at least one selected from the group consisting of triazine compound, acetophenone compound, biimidazole compound, oxime compound, benzoin compound, benzophenone compound, thioxanthone compound and anthracene compound The photosensitive resin composition for spacer formation containing the above photoinitiator further.
The photosensitive resin composition for spacer formation of Claim 1 which further contains alkali-soluble resin, a photocurable monomer, and a solvent.
The photosensitive resin composition for forming a spacer according to claim 7, wherein the photoinitiator is included in an amount of 0.1 to 40 parts by weight based on 100 parts by weight of the total of the alkali-soluble resin and the photocurable monomer based on the solid content.
The photosensitive resin composition for forming a spacer according to claim 7, wherein the alkali-soluble resin is copolymerized including at least one or more of monomers represented by the following Chemical Formulas 8 and 9.
[Chemical Formula 8]

Wherein R ₁ is hydrogen or alkyl or cycloalkyl having 1 to 20 carbon atoms, with or without heteroatoms; R ₂ is alkylene or cycloalkylene having 1 to 20 carbon atoms, with or without heteroatoms R ₁ and R ₂ may be independently substituted with a hydroxy group)
[Chemical Formula 9]

Wherein R ₁ is hydrogen or alkyl or cycloalkyl having 1 to 20 carbon atoms, with or without heteroatoms; R ₂ is alkylene or cycloalkylene having 1 to 20 carbon atoms, with or without heteroatoms R ₁ and R ₂ may be independently substituted with a hydroxyl group.
The method of claim 9, wherein the monomer represented by the formula (8) and formula (9) is epoxidized dicyclodecaneyl (meth) acrylate-3,4-epoxytricyclodecane-9-yl (meth) acrylate; 3,4-epoxytricyclodecane-9-yl (meth) acrylate; Epoxidized dicyclodecaneyl (meth) acrylate-3,4-epoxytricyclodecane-8-yl (meth) acrylate; 3,4-epoxytricyclodecane-8-yl (meth) acrylate; Epoxidized dicyclopentanyloxyethyl (meth) acrylate-2- (3,4-epoxytricyclodecane-9-yloxy) ethyl (meth) acrylate; Epoxidized dicyclopentanyloxyethyl (meth) acrylate-2- (3,4-epoxytricyclodecane-8-yloxy) ethyl (meth) acrylate; Epoxidized dicyclopentanyloxyhexyl (meth) acrylate; And a photosensitive resin composition for forming a spacer, which is at least one selected from the group consisting of epoxidized dicyclodecaneyl (meth) acrylate.
The photosensitive resin composition for forming a spacer according to claim 9, wherein the monomers represented by the formulas (8) and (9) are 2 to 50 mol% based on the total number of moles of the entire monomers constituting the alkali-soluble resin.
The spacer made from the photosensitive resin composition for spacer formation of any one of Claims 1-11.
An image display device provided with the spacer of claim 12.