KR20110038252A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE: A photosensitive resin composition is provided to improve the remaining rate of the composition or the transmitting rate of ultraviolet ray in addition to the adhesive property, the insulating property, and the flatness property. CONSTITUTION: A negative photosensitive resin composition includes a resin, a urethane resin, a crosslinkable monomer, a photo-polymerizable initiator, and a solvent. The crosslinkable monomer includes at least two ethylene-based double bonds. The resin is selected from an alkaline-soluble acrylate resin, a photo polymer, and the mixture of the same. The alkaline-soluble acrylate resin is the copolymer of monomer with ethylene-based acidic group and monomer without ethylene-based acidic group.

Description

Photosensitive Resin Composition {PHOTOSENSITIVE RESIN COMPOSITION}

This invention relates to the photosensitive resin composition, the liquid crystal display device which has its hardened | cured material, and the pattern formation method of the liquid crystal display device using the same.

Currently, an organic insulating film is used in a liquid crystal display for various purposes. In general, an organic insulating film of a liquid crystal display device is formed by applying a positive photosensitive resin composition on an insulating substrate and then performing exposure, development, and curing processes.

By the way, when forming the organic insulating film which is the hardened | cured material using the conventional positive photosensitive resin composition, the exposure time by a sensitivity fall increases, and productivity of a liquid crystal display device falls.

In addition, even if the positive photosensitive resin composition is uniformly coated on the insulating substrate, an organic insulating film having a uniform thickness can be obtained. Since an uneven coating is often generated, an organic insulating film having a non-uniform thickness is formed and in a liquid crystal display device. Due to its transmission and reflection properties, it is recognized as a stain.

When the organic insulating film is exposed to heat above a predetermined temperature for a predetermined time or absorbs short wavelengths such as ultraviolet rays, the organic insulating film is partially decomposed to cause coloration or a thickness difference. In this way, a part of the organic insulating film is partially decomposed to show coloration or a thickness difference is recognized as a stain in the LCD. In addition, an afterimage may occur in the liquid crystal display due to impurities generated due to partial decomposition of components of the organic insulating film.

An object of the present invention for solving the above problems is to provide a negative photosensitive resin composition which is excellent in heat resistance and / or light resistance and can improve the sensitivity.

Another object of the present invention for solving the above problems is to provide a liquid crystal display device having a cured product formed by the curing of the negative photosensitive resin composition.

Another object of the present invention for solving the above problems is to provide a pattern forming method of a liquid crystal display device using the negative photosensitive resin composition.

In order to achieve the above object, the present invention provides a negative photosensitive resin composition,

a) i) alkali soluble acrylate resin;

  Ii) photopolymers; And

  Iii) mixtures thereof

  Resin selected from the group which consists of;

b) urethane resins;

c) a crosslinkable monomer having at least two ethylenic double bonds;

d) photopolymerization initiator; And

e) solvent

It provides a negative photosensitive resin composition comprising a.

Preferably the present invention

a) i) alkali soluble acrylate resin;

  Ii) photopolymers; And

  Iii) mixtures thereof

  5 to 50% by weight of a resin selected from the group consisting of;

b) 1 to 20% by weight of urethane resin;

c) 1 to 20% by weight of a crosslinkable monomer having at least two ethylenic double bonds;

d) 0.1 to 10% by weight photopolymerization initiator; And

e) residual solvent

It includes.

In another aspect, the present invention provides a liquid crystal display device characterized in that the negative photosensitive resin composition is applied.

In another aspect, the present invention provides a pattern forming method of a liquid crystal display device using the negative photosensitive resin composition.

The negative photosensitive resin composition according to the present invention not only has adhesion, heat resistance, insulation, flatness, chemical resistance, etc. but also has improved sensitivity, residual film ratio, or UV transmittance.

Hereinafter, the present invention will be described in detail.

The negative photosensitive resin composition of the present invention is a resin selected from the group consisting of a) i) alkali-soluble acrylate resins, ii) photopolymer resins, and iii) mixtures thereof, b) urethane resins, c) at least two or more ethylenes. A crosslinkable monomer having a system double bond, d) a photopolymerization initiator, and e) a solvent.

The resin of a) used in the present invention may be used alone or in combination with an alkali-soluble acrylate resin, a photopolymer resin, or an alkali-soluble acrylate resin and a photopolymer resin, and in particular, an alkali-soluble acrylate resin and a photopolymer resin. It is preferable to mix and use.

The alkali-soluble acrylate resin of a) iii) is a copolymer of a monomer having an ethylene acidic group and a monomer not having an ethylene acidic group.

The monomer having an ethylenic acid group may be in the form of acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, vinyl acetic acid or an acid anhydride thereof, or 2-acryloxyethyl hydrogen phthalate, 2-acryloxyoxypropyl hydrogen Phthalate, 2-acrylooxypropyl hexahydro phthalate, and the like.

Examples of the monomer having no acidic group include isobutyl acrylate, tert-butyl acrylate, lauryl acrylate, methyl methacrylate, alkyl acrylate, steacrylate, cyclohexyl acrylate, isobornyl acrylate and benzyl methacrylate. Acrylate, benzyl acrylate, 2-hydroxy acrylate, trimethoxybutyl acrylate, ethyl carbidol acrylate, phenoxyethyl acrylate, 4-hydroxy butyl acrylate, phenoxy polyethylene glycol acrylate, 2 Hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-acryloxyethyl-2-hydroxypropyl phthalate, 2-hydroxy-3-phenoxypropyl acrylate and methacrylates thereof; Acrylates containing halogen compounds such as 3-floethyl acrylate and 4-flopropyl acrylate and methacrylates thereof; Acrylates containing siloxane groups such as triethylsiloxane ethyl acrylate and methacrylates thereof; Olefins having aromatics such as styrene and 4-methoxy styrene, and the like, and these may be used alone or in combination of two or more thereof.

In particular, the alkali-soluble acrylate resin is preferably polymerized benzyl methacrylate, methacrylic acid, and methyl methacrylate to have a weight average molecular weight of 10,000 to 35,000, more preferably benzyl methacrylate: methacrylic acid Methyl methacrylate is a copolymer having a weight average molecular weight of 20,000 by polymerization at a ratio of 60:20:20.

The photopolymer resin of a) ii) functions to improve the sensitivity of the negative photosensitive resin composition.

The photopolymer resin is a resin which is dissolved in an aqueous alkali solution, and at least one compound selected from the group consisting of compounds represented by the following Chemical Formula 1, Chemical Formula 2, and Chemical Formula 3 is preferable:

[Formula 1]

[Formula 2]

In the formula of Formula 1 or Formula 2,

Each R ₁ is independently hydrogen or an alkyl group having 1 to 2 carbon atoms,

R ₂ is an alkyl group having 2 to 5 carbon atoms which is unsubstituted or substituted with a hydroxy group,

a + b + c = 1, 0.1 <a <0,4, 0 <b <0.5, 0.1 <c <0.5.

(3)

In the formula (3),

R is alkyl or hydroxyalkyl having 1 to 20 carbon atoms,

Each X is independently hydrogen or methyl.

The weight average molecular weight of the photopolymer resin is preferably 10,000 to 80,000, more preferably 15,000 to 50,000. When the weight average molecular weight of the photopolymer is in the above range, the development time and the degree of removal of the residual film are better.

The alkali-soluble acrylate resin and the photopolymer resin as described above are preferably included in the photosensitive resin composition 5 to 50% by weight, alone or in combination, and when the content is within the above range, a negative photosensitive resin composition having an appropriate viscosity may be used. It can be obtained and has the advantage of easy thickness control.

The negative photosensitive resin composition of the present invention comprises b) a urethane resin, the urethane resin is preferably a compound represented by the following formula (4):

[Formula 4]

In the formula (4),

R ₃ is aliphatic having 1 to 12 carbon atoms, cyclic aliphatic or aromatic compound having 6 to 12 carbon atoms, x is an integer of 1 to 20, preferably R ₃ is methylene (x = 1 to 6) or phenylene (x = 1-2),

R ₄ and R ₅ are each independently hydrogen and an alkyl group having 1 to 10 carbon atoms or an aromatic compound.

It is preferable that the urethane resin is included in the photosensitive resin composition in an amount of 1 to 20% by weight, and in the above range, the softness and reflow (flow) of the negative photosensitive resin composition may be satisfied at the same time.

The crosslinkable monomer having at least two or more ethylenic double bonds of c) used in the present invention is a urethane monomer represented by the following formula (5), 1,4-butanediol diacrylate, 1,3-butylene glycol diacryl Ethylene glycol diacrylate, pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, dipentaerythritol diacrylate, sorbitol triacrylate, bisphenol A diacrylate derivative, trimethyl propane triacrylic Elate, dipentaerythritol polyacrylate, methacrylates thereof, and the like can be used, and it is particularly preferable to use a urethane monomer represented by the following general formula (5):

[Chemical Formula 5]

In the formula (5),

R ₆ is an aliphatic, cyclic aliphatic, or aromatic compound having 1 to 12 carbon atoms, and y and z are each independently an integer of 1 to 6, preferably methylene (y = 1 to 6, z = 1 to 6). Or phenylene (y = 1 to 2, z = 1 to 6),

R ₇ is —C (CH ₃ ) ₂ C ₆ H ₄ C (CH ₃ ) = CH ₂ , -O (R) _x OC (O) C (R ') = CH ₂ , -O (R) _x OC ( O) C (R ') = CH ₂ , or -C ₆ H ₄ C (CH ₃ ) = CH, wherein R is an alkyl group having 1 to 5 carbon atoms, R' is hydrogen or an alkyl group having 1 to 5 carbon atoms, x Is an integer of 1 to 5.

The crosslinkable monomer having at least two or more ethylenic double bonds is preferably included in the photosensitive resin composition at 1 to 20% by weight. If the content is less than 1% by weight, there is a problem in that the softness of the negative photosensitive resin composition may not be realized. If the content is more than 20% by weight, the developability and adhesion may be reduced.

The photopolymerization initiator of d) used in the present invention has a function of initiating polymerization of the crosslinkable monomer by wavelengths such as visible light, ultraviolet light and far ultraviolet light.

The photopolymerization initiator may be a triazine compound, a benzoin compound, an acetophenone compound, a xanthone compound, or an imidazole compound, and specifically, 2,4-bistrichloromethyl-6-p-methoxysty Yl-s-triazine, 2-p-methoxystyryl-4,6-bistrichloromethyl-s-triazine, 2,4-trichloromethyl-6-triazine, 2,4-trichloromethyl Triazine compounds such as -4-methylnaphthyl-6-triazine; Benzoin compounds such as benzophenone and p- (diethylamino) benzophenone; 2,2-dichloro-4-phenoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone Acetophenone series compounds, such as these; Xane, such as xanthone, thioxanthone, 2-methyl thioxanthone, 2-isobutyl thioxanthone, 2-dodecyl thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone Ton compound; Or 2,2-bis-2-chlorophenyl-4,5,4,5-tetraphenyl-2-1,2-bisimidazole, 2,2-bis (2,4,6-tricyanophenyl)- Imidazole compounds such as 4,4,5,5-tetraphenyl-1,2-bisimidazole and the like can be used.

The photopolymerization initiator is preferably included in 0.1 to 10% by weight, more preferably 1 to 2% by weight in the photosensitive resin composition. If the content is less than 0.1% by weight, the degree of curing decreases, and there is a problem in that the straightness of the pattern is not good due to the low sensitivity. If the content exceeds 10% by weight, storage stability may occur and the resolution may be lowered due to the high degree of curing. And there is a problem that the residual film is likely to occur in portions other than the formed pattern.

The solvent of e) used in the present invention is selected by solubility, coating property, and the like, and specifically, propylene glycol monoethyl ether acetate, ethyl ethoxypropionate, butyl acetic acid, ethylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether , Propylene glycol methyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate and the like can be used, and in particular, propylene glycol monoethyl ether Preference is given to using acetate, ethyl ethoxypropionate or butyl acetic acid.

The solvent may be included in the remaining amount except the solids used in the photosensitive resin composition of the present invention by varying the content according to the viscosity or the total solids content in the composition, and in particular, propylene glycol monoethyl ether It is preferable to include 40 to 80% by weight of acetate, 15 to 40% by weight of ethyl ethoxypropionate, and 1 to 20% by weight of butyl acetic acid, more preferably propylene glycol monoethyl ether acetate: ethyl ethoxypropionate: butylacetic acid It is used by mixing in the ratio of 6 = 3: 1. When the solvent is included in the above range, there is a problem that the thickness deviation cannot be overcome and the uniformity of the negative photosensitive resin composition is lowered.

The negative photosensitive resin composition of this invention which consists of such a component as above may further contain f) the crosslinkable acrylic monomer containing at least 2 or more double bonds as needed.

The crosslinkable acrylic monomer including at least two or more double bonds may be 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, ethylene glycol diacrylate, pentaerythritol tetraacrylate, triethylene Glycol diacrylate, polyethylene glycol diacrylate, dipentaerythritol diacrylate, sorbitol triacrylate, bisphenol A diacrylate derivative, trimethyl propane triacrylate, dipentaerythritol polyacrylate, or methacrylates thereof Etc. can be used.

The crosslinkable acrylic monomer including at least two or more double bonds is preferably included in the photosensitive resin composition at 2 to 10% by weight, more preferably at 5% by weight. If the content is less than 2% by weight, there is a problem in that the pattern is not formed due to insufficient hardening degree and adhesive strength, and when the content is more than 10% by weight, the deformation amount decreases due to the increase in the degree of hardening, which makes it impossible to implement a soft pattern. There is this.

In addition, the negative photosensitive resin composition of the present invention may further include additives such as a surfactant, a sensitizer, a curing accelerator, and a pigment as necessary. In particular, the surfactant may be a silicone-based or fluorine-based surfactant.

Preferably, the additive is included in the photosensitive resin composition at a maximum of 2% by weight. If the content exceeds 2% by weight, a residual film may occur or stability may decrease, and ions and impurities may be eluted into the liquid crystal. There is a problem.

As described above, the negative photosensitive resin composition of the present invention is excellent in adhesiveness, heat resistance, insulation property, flatness, chemical resistance, and the like, and thus is suitable as an image forming material of a liquid crystal display device, and especially when forming an organic insulating film of a liquid crystal display device. Because of its excellent properties in terms of residual film rate and UV transmittance, the cured product is suitable as an organic insulating film of a liquid crystal display device.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.

[Example]

Example 1

With an alkali-soluble acrylate resin, benzyl methacrylate: methacrylic acid: methyl methacrylate is 60: 20: is polymerized in a proportion of 30% by weight of a copolymer of 20,000 weight-average molecular weight of 20, R ₃ is hexamethylene in the general formula (4) Methylene, 5% by weight of a urethane-based resin having a molecular weight of 3,000, wherein R ₄ and R ₅ are methyl, a crosslinkable monomer having at least two or more ethylene-based double bonds.In Formula 5, R ₆ is methylene and R ₇ is -C ( CH ₃ ) ₂ C ₆ H ₄ C (CH ₃ ) = CH ₂ , y is 6 and z is 2 5% by weight urethane monomer, 0.5% by weight of Irgacure 907 (manufactured by Ciba Specialty Chemical) as a photopolymerization initiator and 4,4 0.2% by weight of bisdiethylaminobenzophenone, 37% by weight of propylene glycol methyl ether acetate as a solvent, 17% by weight of ethyl 3-ethoxypropionate, and 5.3% by weight of butylacetic acid were uniformly mixed to form a liquid negative photosensitive resin composition. Prepared.

Examples 2-4

A liquid negative photosensitive resin composition was prepared in the same manner as in Example 1, except that Example 1 was used as a component and a composition ratio shown in Table 1 below. At this time, the unit of Table 1 is weight%. In Table 1, in Formulas 1 and 2, R ₁ is methyl, R ₂ is methylene, a: b: c = 20: 20: 60, each having a molecular weight of 20,000, and in Formula 3, R is methyl and X is A compound which is hydrogen was used, and dipentaerythritol polyacrylate was used as the crosslinkable acrylic monomer.

division Example One 2 3 4 Alkali Soluble Acrylate Resin 30 - 15 15
Photopolymer resin Formula 1 - 30 - - Formula 2 - - 15 - Formula 3 - - - 15 Urethane Resin of Formula 4 5 5 3 5 Uthetan Monomer of Formula 5 5 5 10 20 Crosslinkable acrylic monomer - - 3 5 Photopolymerization initiator Irgacure 907 0.5 0.5 0.5 0.5 4,4-bisdiethylaminobenzophenone 0.2 0.2 0.2 0.2
solvent Propylene Glycol Methyl Ether Acetate 37 37 35 24 Ethyl ethoxypropionate 17 17 15 12 Butyl Acetic Acid 5.3 5.3 3.3 3.3

[Experimental Example]

After evaluating the physical properties by the following method using the negative photosensitive resin composition and the conventional positive photoresist composition coating solution prepared in Examples 1 to 4, the results are shown in Table 1 below.

A) sensitivity

After coating the negative photosensitive resin composition and the conventional positive photoresist composition coating solution prepared in Examples 1 to 4 using a spin coater on the insulating substrate, and prebaked at 90 ℃ for 2 minutes on a hot plate to form a coating film It was.

The coating film obtained above was irradiated with the ultraviolet-ray whose intensity | strength at 365 nm is 15 microseconds / cm <2> for 6 second using the predetermined pattern mask. Thereafter, the solution was developed at 25 ° C. for 2 minutes with an aqueous solution of 0.38 parts by weight of tetramethylammonium hydroxide, and then washed with ultrapure water for 1 minute.

Subsequently, the developed pattern was irradiated with ultraviolet rays having a intensity of 15 mA / cm 2 at 365 nm for 34 seconds, midbaked at 120 ° C. for 3 minutes, and then cured by heating at 220 ° C. for 60 minutes in an oven. Got it.

B) residual rate

The height of the bottom of the pattern film formed at the time of the sensitivity measurement of a) and the top of the pattern were measured. At this time, based on the thickness of the film obtained by prebaking the thickness change rate, 0 to 10% was good, 10 to 40% was good, and 40% was bad.

C) transmittance

When measuring the sensitivity of (a), the light absorption spectrum of visible light of the coating film having a thickness of 3 microns after prebaking was measured, and it was very excellent when the light transmittance was 98% or more at 400 nm, and was excellent when 94 to 98%. , 92 to 94% of cases were usually shown as bad, 92% or less.

TABLE 1

Example 1 Example 2 Example 3 Example 4 existing Sensitivity (mJ / ㎠) 29 19 16 11 55 to 200 Residual rate Great Great Good Good Good Transmittance Great Great Great Good Normal or
Bad Stain Good Good Great Great Bad

Through Table 1, Examples 1 to 4 according to the present invention has a sensitivity of 11 to 29 mJ / ㎠ and very excellent compared to the sensitivity of 55 to 200 mJ / ㎠ of the organic insulating film obtained with a conventional positive photoresist composition, In particular, the transmittance was significantly superior to that of the organic insulating film obtained with the conventional positive photoresist composition.

From this, when the negative photosensitive resin composition according to the present invention is used as the organic insulating film of the liquid crystal display device, it was possible to contribute to the improvement of the very excellent sensitivity, residual film rate and transmittance.

In the detailed description of the present invention described above with reference to the preferred embodiment of the present invention, those skilled in the art or those skilled in the art can be variously modified and changed the present invention. I can understand that.

Claims (17)

In the negative photosensitive resin composition, a) i) alkali soluble acrylate resin;   Ii) photopolymers; And   Iii) mixtures thereof   Resin selected from the group which consists of; b) urethane resins; c) a crosslinkable monomer having at least two ethylenic double bonds; d) photopolymerization initiator; And e) solvent Negative photosensitive resin composition comprising a. The method of claim 1, a) i) alkali soluble acrylate resin;   Ii) photopolymers; And   Iii) mixtures thereof   5 to 50% by weight of a resin selected from the group consisting of; b) 1 to 20% by weight of urethane resin; c) 1 to 20% by weight of a crosslinkable monomer having at least two ethylenic double bonds; d) 0.1 to 10% by weight photopolymerization initiator; And e) residual solvent Negative photosensitive resin composition comprising a. The method of claim 1, The negative photosensitive resin composition of the above-mentioned a) iii) is a copolymer of a monomer having an ethylene acidic group and a monomer having no ethylene acidic group. The method of claim 3, The monomer having an ethylene-based acid group is acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, vinyl acetic acid or acid anhydrides thereof, 2-acryloxyethyl hydrogen phthalate, 2-acrylooxypropyl hydrogen phthalate, and Negative photosensitive resin composition, It is selected from the group which consists of 2-acrylooxypropyl hexahydro phthalate. The method of claim 3, Monomers having no acidic groups include isobutyl acrylate, tert-butyl acrylate, lauryl acrylate, methyl methacrylate, alkyl acrylate, steacrylate, cyclohexyl acrylate, isobornyl acrylate and benzyl methacrylate. , Benzyl acrylate, 2-hydroxy acrylate, trimethoxybutyl acrylate, ethyl carbidol acrylate, phenoxyethyl acrylate, 4-hydroxy butyl acrylate, phenoxy polyethylene glycol acrylate, 2- hydrate Hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-acryloxyethyl-2-hydroxypropyl phthalate, 2-hydroxy-3-phenoxypropyl acrylate and methacrylates thereof; 3-floethyl acrylate, 4-flopropyl acrylate and their methacrylates; Acrylates containing siloxane groups and methacrylates thereof; Or at least one member selected from the group consisting of olefins having an aromatic composition. The method of claim 1, The alkali-soluble acrylate resin of a) iii) is a copolymer of benzyl methacrylate, methacrylic acid, and methyl methacrylate, and has a weight average molecular weight of 15,000 to 35,000. The method of claim 1, The photopolymer resin of a) ii) is a compound having a weight average molecular weight of 10,000 to 80,000 selected from the group consisting of compounds represented by the following formulas (1), (2) and (3). Composition: [Formula 1]

[Formula 2]

In Formula 1 or Formula 2, Each R ₁ is independently hydrogen or an alkyl group having 1 to 2 carbon atoms, R ₂ is an alkyl group having 2 to 5 carbon atoms which is unsubstituted or substituted with a hydroxy group, a + b + c = 1, 0.1 <a <0,4, 0 <b <0.5, 0.1 <c <0.5, (3)

In the formula (3), R is alkyl or hydroxyalkyl having 1 to 20 carbon atoms, X is hydrogen or methyl. The method of claim 1, The negative photosensitive resin composition, wherein the urethane resin of b) is a compound represented by the following general formula (4): [Formula 4]

In the formula (4), R ₃ is an aliphatic, cyclic aliphatic, or aromatic compound having 1 to 12 carbon atoms, x is an integer from 1 to 20, R ₄ and R ₅ are each independently hydrogen and an alkyl group having 1 to 10 carbon atoms or an aromatic compound having 6 to 10 carbon atoms. The method of claim 1, A negative photosensitive resin composition, characterized in that the crosslinkable monomer having at least two or more ethylenic double bonds of c) is a urethane monomer represented by the following formula (5): [Chemical Formula 5]

In the formula (5), R ₆ is an aliphatic, cyclic aliphatic, or aromatic compound having 1 to 12 carbon atoms, y and z are each independently an integer from 1 to 6, R ₇ is —C (CH ₃ ) ₂ C ₆ H ₄ C (CH ₃ ) = CH ₂ , -O (R) _x OC (O) C (R ') = CH ₂ , -O (R) _x OC ( O) C (R ') = CH ₂ , or -C ₆ H ₄ C (CH ₃ ) = CH, wherein R is an alkyl group having 1 to 5 carbon atoms, R' is hydrogen or an alkyl group having 1 to 5 carbon atoms, x is It is an integer of 1-5. The method of claim 1, The crosslinkable monomer having at least two or more ethylenic double bonds of c) may be a urethane monomer, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, ethylene glycol diacrylate, pentaerythritol tetra Acrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, dipentaerythritol diacrylate, sorbitol triacrylate, bisphenol A diacrylate derivative, trimethyl propane triacrylate, dipentaerythritol polyacrylate, and these At least 1 sort (s) is chosen from the group which consists of methacrylates, The negative photosensitive resin composition characterized by the above-mentioned. The method of claim 1, The photoinitiator of d) is 2,4-bistrichloromethyl-6-p-methoxystyryl-s-triazine, 2-p-methoxystyryl-4,6-bistrichloromethyl-s- Triazine, 2,4-trichloromethyl-6-triazine, 2,4-trichloromethyl-4-methylnaphthyl-6-triazine, benzophenone, p- (diethylamino) benzophenone, 2, 2-dichloro-4-phenoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, x Santone, thioxanthone, 2-methyl thioxanthone, 2-isobutyl thioxanthone, 2-dodecyl thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, or 2, 2-bis-2-chlorophenyl-4,5,4,5-tetraphenyl-2-1,2-bisimidazole, and 2,2-bis (2,4,6-tricyanophenyl) -4, The negative photosensitive resin composition characterized by selecting 1 or more types from the group which consists of 4,5,5- tetraphenyl- 1, 2-bisimidazole. water. The method of claim 1, The solvent of e) is propylene glycol monoethyl ether acetate, ethoxy propionate, butyl acetic acid, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl At least one selected from the group consisting of ethyl ether, cyclohexanone, ethyl 3-methoxypropionate, and methyl 3-ethoxypropionate is a negative photosensitive resin composition. The method of claim 1, 40 to 80% by weight of propylene glycol monoethyl ether acetate, 15 to 40% by weight of ethyl ethoxypropionate, and 1 to 20% by weight of butyl acetic acid, based on the total amount of the solvent used in the e) solvent. Negative photosensitive resin composition. The method of claim 1, The photosensitive resin composition is 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, ethylene glycol diacrylate, pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate At least one selected from the group consisting of dipentaerythritol diacrylate, sorbitol triacrylate, bisphenol A diacrylate derivative, trimethylpropane triacrylate, dipentaerythritol polyacrylate, and methacrylates thereof F) A negative photosensitive resin composition, further comprising 2 to 10% by weight of a crosslinkable acrylic monomer comprising at least two or more double bonds in the photosensitive resin composition. The method of claim 1, The photosensitive resin composition further comprises a surfactant, a sensitizer, a curing accelerator, or a pigment in the photosensitive resin composition at a maximum of 2% by weight. The negative photosensitive resin composition of Claim 1 was applied, The liquid crystal display element characterized by the above-mentioned. Applying the negative photosensitive resin composition of claim 1 on an insulating substrate; Performing an exposure process on the insulating substrate coated with the negative photosensitive resin composition; Performing a developing process on the insulating substrate on which the exposure process is performed; And Performing a curing process on the insulating substrate on which the developing process is performed; Pattern forming method of a liquid crystal display device comprising a.