KR20120021488A - Negative photosensitive resin composition - Google Patents

Abstract

PURPOSE: A negative photo-sensitive resin composition, a display device pattern forming method using the same, and a display device including the pattern are provided to improve resolution, permeation, heat-resistance discoloration, and adhesive. CONSTITUTION: A negative photo-sensitive resin composition includes the following: 100 parts by weight of acryl-based copolymer, polyimide-based copolymer, siloxane-based copolymer, or the copolymer of the same; 0.1-30 parts by weight of a photo-initiator; and 0.1-30 parts by weight of a photo-sensitizer represented by chemical formula 1. In chemical formula 1, the n is the integer of 1 to 10. The acryl-based copolymer is obtained by radical-polymerizing acryl monomers under an azo-initiator. The polyimide-based copolymer is obtained from diamine and dianhydride. The siloxane copolymer is obtained by hydrolyzing and condensating silane monomers under acid or base.

Description

Negative photosensitive resin composition {NEGATIVE PHOTOSENSITIVE RESIN COMPOSITION}

The present invention relates to a negative photosensitive resin composition, more specifically, excellent in resolution, transmittance, heat discoloration resistance, adhesive strength, and the like, in particular, excellent sensitivity in UV long wavelength of 405 ~ 435nm, GH-line dedicated exposure machine or next-generation digital It relates to a negative photosensitive resin composition suitable for use in an exposure machine.

In the TFT type liquid crystal display device or integrated circuit device, not only a passivation insulating film, a gate insulating film, a planarizing film, etc. for insulating between the wirings disposed between the layers, but also a negative photosensitive resin for forming column spacers, overcodes, and color resists. The composition is mainly used.

As a negative photosensitive resin composition for forming an organic insulating film and a gate insulating film, a column spacer, an overcoat, a planarizing film, and a color resist of a display device such as a conventional TFT-LCD, a touch screen panel (TSP), an OLED, or an O-TFT, a binder, It consists of components such as a photoinitiator, a solvent, and the like, and an acrylic resin has been mainly used as the binder. However, the conventional negative photosensitive resin composition is sensitive sensitively to UV wavelengths of 365 nm (i-line), but not sensitively or slowly to UV long wavelengths of 405 to 435 nm, thus forming patterns in GH-line-exposed or next-generation digital exposure systems. There was a problem. In addition, the addition of photosensitizers, such as thioxanthone, was also significantly slower, causing problems in the process. Accordingly, there is an urgent need for a negative photosensitive resin composition having excellent sensitivity even at a UV wavelength of 405 to 435 nm.

In order to solve the problems of the prior art as described above, an object of the present invention is excellent in resolution, transmittance, heat discoloration resistance, adhesion, and the like, in particular, excellent sensitivity in the UV wavelength of 405 ~ 435nm, GH-line dedicated exposure machine or the next generation It is to provide a negative photosensitive resin composition which is very suitable for use in a digital exposure machine.

Another object of the present invention is to provide a pattern forming method of a display device using the negative photosensitive resin composition.

According to an aspect of the present invention,

a) an acrylic copolymer, a polyimide copolymer, a siloxane copolymer, or a copolymer thereof;

b) photoinitiators; And

c) Photosensitizer represented by the following formula (1)

It provides a negative photosensitive resin composition comprising a.

[Formula 1]

(In Formula 1, n is an integer of 1-10.)

Preferably the negative photosensitive resin composition is

a) 100 parts by weight of an acrylic copolymer, a polyimide copolymer, a siloxane copolymer, or a copolymer thereof;

b) 0.1 to 30 parts by weight of photoinitiator; And

c) 0.1 to 30 parts by weight of a photosensitizer represented by Formula 1 below.

In another aspect, the present invention provides a pattern forming method of a display device such as TFT-LCD, TSP (Touch Screen Panel), OLED, or O-TFT using the negative photosensitive resin composition.

The pattern may be used as a passivation insulating film, gate insulating film, planarization film, column spacer, overcoat or color resist of TFT-LCD, TSP (Touch Screen Panel), OLED, or O-TFT.

In addition, the present invention provides a display device comprising a cured negative photosensitive resin composition formed by the pattern forming method.

Hereinafter, the present invention will be described in detail.

The present invention relates to a negative photosensitive resin composition that can be used in various fields such as a passivation insulating film, a gate insulating film, a planarization film, a column spacer, an overcoat, a color resist, and the like, which are disposed between layers of an organic insulating film or an integrated circuit device of a liquid crystal display device.

Such a negative photosensitive resin composition of the present invention comprises a) an acrylic copolymer, a polyimide copolymer, a siloxane copolymer or a copolymer thereof; b) photoinitiators; And c) a photosensitizer represented by the following formula (1).

[Formula 1]

(In Formula 1, n is an integer of 1-10.)

In the photosensitive resin composition of the present invention, the a) acrylic copolymer, polyimide copolymer, siloxane copolymer, or copolymers thereof are not particularly limited in kind, and those having ordinary skill in the art Well known copolymers can be used.

For example, the acrylic copolymer is prepared by radical polymerization of an acrylic monomer under an azo initiator, and a weight average molecular weight of 3000 to 50000 may be used. The polyimide copolymer is prepared from diamine and dione hydride, and a weight average molecular weight of 3000 to 50000 may be used. The siloxane copolymer is prepared by hydrolysis and condensation reaction of a silane monomer under an acid or a base, and a weight average molecular weight of 3000 to 50000 may be used.

In this case, the weight average molecular weight is based on the polystyrene converted average molecular weight measured using GPC.

In addition, the photoinitiator of b) used in the present invention may use compounds such as triazine, benzoin, acetophenone, imidazole, oxime or xanthone. Specific examples of photoinitiators include 2,4-bis (trichloromethyl) -6- (p-methoxystyryl) -s-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloro) Rhomethyl) -s-triazine, 2,4-trichloromethyl-6-triazine, 2,4-trichloromethyl-4-methylnaphthyl-6-triazine, 2- (o-chlorophenyl)- 4,5-diphenyl imidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5- Diphenyl imidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenyl imidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenyl imidazole dimer, 2 , 4-di (p-methoxy phenyl) -5-phenyl imidazole dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenyl imidazole dimer, or 2- (p-methyl 2,4,5-triaryl imidazole dimers, such as mercaptophenyl) -4,5-diphenyl imidazole dimer, [1- [9-ethyl-6- (2-methylbenzoyl) -9H-carba Zoyl-3-yl] -1- (O-acetyloxime), benzophenone, p- (diethylamino) benzophenone, 2,2-dichloro 4-phenoxyacetophenone, 2,2-diethoxyacetophenone, 2-dodecyl thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2,2-bis-2 Chlorophenyl-4,5,4,5-tetraphenyl-2-1,2-biimidazole, Irgacure 369, Irgacure 651, Irgacure 907, Darocur TPO, Irgacure 819 from Ciba Special Chemicals, etc. can be used. These can be used individually or in mixture of 2 or more types.

The photoinitiator may be included in an amount of 0.1 to 30 parts by weight, more preferably 0.1 to 20 parts by weight based on 100 parts by weight of the a) copolymer. In addition, if the content is less than 0.1 parts by weight, there is a problem that the residual film ratio becomes worse due to low sensitivity, and when the content exceeds 30 parts by weight, there may be a problem in storage stability, and the adhesion of the pattern during development due to the high curing degree There is a problem that this is lowered.

In particular, the photo-sensitizer of Formula 1 c) used in the present invention is an acridine compound having a specific structure, has an excellent sensitivity to the UV wavelength of 405 ~ 435nm, and to the photoinitiator through a photoinitiation reaction faster than the photoinitiator It has the characteristic of helping to speed photoinitiation reaction of photoinitiator by transferring energy. Such photosensitizers of the present invention may be used alone or in combination of two or more thereof. In this case, in the case of using a general acridine compound or a conventional photosensitizer instead of the photosensitizer having the specific structure of Formula 1, there is a problem in that the pattern is not formed when the sensitivity is slow or timed.

The photosensitizer is preferably included in 0.1 to 30 parts by weight, more preferably 0.5 to 20 parts by weight based on 100 parts by weight of the a) copolymer. Moreover, when the content is more preferable above, it is further more favorable in the photocuring speed improvement of a negative photosensitive resin composition. In addition, if the content is less than 0.1 parts by weight, there is a problem that the sensitivity is slow, if it exceeds 30 parts by weight there is a problem that the resolution is lowered.

In addition, the negative photosensitive resin composition of the present invention may further include a solvent, which does not generate flatness and coating stains of the interlayer insulating film to form a uniform pattern profile.

The solvent is alcohol, such as methanol and ethanol; Ethers such as tetrahydrofuran; Glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol dimethyl ether; Propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, and propylene glycol butyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, and propylene glycol butyl ether acetate; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate and propylene glycol butyl ether propionate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, and 4-hydroxy 4-methyl 2-pentanone; Or methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2-hydroxy propionate, methyl 2-hydroxy 2-methylpropionate, ethyl 2-hydroxy 2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, Butyl hydroxy acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl hydroxypropionate, 2-hydroxy 3 Methyl methyl butyrate, methyl methoxy acetate, ethyl methoxy acetate, methoxy propyl acetate, methoxy butyl acetate, ethoxy acetate, ethyl ethoxy acetate, ethoxy propyl acetate, butyl ethoxy acetate, methyl propoxy acetate Ethyl propoxy acetate, propyl propoxy acetate, butyl propoxy acetate, methyl butoxy acetate, ethyl butoxy acetate, propyl butoxy acetate, butyl butoxy acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxy Propyl propionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, 2 Ethyl butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate ethyl 3-methoxypropionate, propyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3- Ethyl ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, 3-part Ester, such as methyl oxy propionate, ethyl 3-butoxy propionate, propyl 3-butoxy propionate, and butyl 3-butoxy propionate, etc. can be used, These can be used 1 or more types as needed.

In particular, it is preferable to select and use at least 1 type of said solvent from the group which consists of solubility, reactivity with each component, and easy to form a coating film, glycol ethers, ethylene alkyl ether acetates, and diethylene glycols.

The solvent is preferably included so that the solid content of the entire negative photosensitive resin composition is 10 to 50% by weight, and the composition having a solid content in the above range is preferably used after filtering with a Millipore filter of 0.1 to 0.2 μm. . More preferably, it is preferable to include the solvent so that the solid content is 15 to 40% by weight. When the solids content of the entire negative photosensitive resin composition is less than 10% by weight, the coating thickness becomes thin, and there is a problem that the coating flatness is lowered. When it exceeds 50% by weight, the coating thickness becomes thick, and the coating equipment is coated. There is a problem that can be overwhelming.

The negative photosensitive resin composition of this invention which consists of such a component as needed is selected from the group which consists of d) the polyfunctional monomer which has an ethylenically unsaturated bond, e) the silicone type compound which has an epoxy group or an amine group, and f) surfactant as needed. The above additive may be further included.

In addition, the multifunctional monomer having the ethylenically unsaturated bond of d) used in the present invention may generally use a crosslinkable monomer having at least two or more ethylenic double bonds. Examples of the polyfunctional monomer of d) include 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, ethylene glycol diacrylate, trimethylolpropanediacrylate, and trimethylolpropane triacrylic. Latene, pentaerythritol triacrylate, pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, dipentaerythritol hexadiacrylate, dipentaerythritol tridiacrylate, dipentaerythritol diacrylate, Sorbitol triacrylate, a bisphenol A diacrylate derivative, dipentaerythritol polyacrylate, these methacrylates, etc. can be used.

It is preferable that the polyfunctional monomer which has the said ethylenically unsaturated bond is contained 5-50 weight part with respect to 100 weight part of a) copolymers. If the content is less than 5 parts by weight, there is a problem in that the contact hole and the pattern is difficult to implement due to the low degree of curing with the photosensitive resin, and if the content exceeds 50 parts by weight, the resolution of the contact hole and the pattern is reduced during development. There is a problem.

In addition, the silicone-based compound having an epoxy group or an amine group of the e) used in the present invention is (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, (3-gly Seedoxypropyl) methyldimethoxysilane, (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) dimethylethoxysilane, (3-glycidoxypropyl) dimethylethoxysilane Phosphorus, 3,4-epoxybutyltrimethoxysilane, 3,4-epoxybutyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyl triethoxy silane, aminopropyl trimethoxy silane, etc. can be used individually or in mixture of 2 or more types.

The silicon-based compound including the epoxy group or the amine group is preferably included in 0.0001 to 5 parts by weight based on 100 parts by weight of the copolymer. If the content is less than 0.0001 parts by weight, the adhesion between the ITO electrode and the photosensitive resin is inferior, and there is a problem in that the heat resistance after curing is inferior. There is a problem that a scum of a hole or a pattern is generated.

The surfactant of f) serves to improve the applicability and developability of the photosensitive composition. The surfactant may be polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, F171, F172, F173 (trade name: Japan Nippon Ink Company), FC430, FC431 (trade name: Sumitomo Triem, Inc.), or KP341 (trade name: Shinwol) Chemical industry) and the like.

The surfactant is preferably included in 0.0001 to 2 parts by weight with respect to 100 parts by weight of the a) copolymer, and when the content is within the above range, it is more preferable in the applicability or developability of the negative photosensitive composition. At this time, if the content is less than 0.0001, there is a problem in coating uniformity, and if it exceeds 2 parts by weight, there is a problem that defects may occur due to bubbles.

Moreover, the negative photosensitive resin composition of this invention can add compatible additives, such as a thermal polymerization inhibitor and an antifoamer, to said composition as needed, and can add a pigment according to a use.

In another aspect, the present invention provides a method of forming a pattern of a display device such as TFT-LCD, TSP (Touch Screen Panel), OLED, or O-TFT using the negative photosensitive resin composition as described above.

Preferably, the present invention provides a method of forming a pattern of a display device, comprising the steps of coating the negative photosensitive resin composition of the present invention on a substrate, and after prebaking, exposing and developing.

The pattern may be used as a passivation insulating film, gate insulating film, planarization film, column spacer, overcoat or color resist of TFT-LCD, TSP (Touch Screen Panel), OLED, or O-TFT.

In another aspect, the present invention can provide a display device comprising a cured negative photosensitive resin composition formed by the pattern forming method of the display device such as TFT-LCD, TSP (Touch Screen Panel), OLED, or O-TFT.

At this time, the thickness and the conditions of the pattern formed by the above method is not particularly limited, and may be set in a range used for manufacturing a conventional device. Therefore, matters other than the negative photosensitive resin composition may be applied to those skilled in the art by appropriately selecting a known method. More specifically, in a display element, an example of the method of forming a pattern using a negative photosensitive resin composition is as follows.

First, the negative photosensitive resin composition of this invention is apply | coated to the surface of a board | substrate by the spray method, the roll coater method, the rotary coating method, etc., A solvent is removed by prebaking, and a coating film is formed. At this time, the prebaking is preferably carried out for 1 to 15 minutes at a temperature of 70 ~ 110 ℃.

Then, a predetermined pattern is formed by irradiating visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, and the like on the formed coating film according to a previously prepared pattern, and developing with a developer to remove unnecessary portions.

The developer is preferably an aqueous alkali solution, specifically, inorganic alkalis such as sodium hydroxide, potassium hydroxide and sodium carbonate; primary amines such as n-propylamine; Secondary amines such as diethylamine and n-propylamine; Tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine and triethylamine; Alcohol amines such as dimethylethanolamine, methyl diethanolamine and triethanolamine; Or an aqueous solution of a quaternary ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide can be used. In this case, the developer is used by dissolving the alkaline compound at a concentration of 0.1 to 10% by weight, and may be added an appropriate amount of a water-soluble organic solvent and a surfactant such as methanol, ethanol and the like.

In addition, after developing with the developer as described above, it is washed with ultrapure water for 30 to 90 seconds to remove unnecessary parts and dried to form a pattern, and after irradiating the formed pattern with light such as ultraviolet rays, the pattern is applied to a heating apparatus such as an oven. By heating at a temperature of 150 to 250 ℃ for 30 to 90 minutes to obtain a final pattern.

The negative photosensitive resin composition according to the present invention has excellent resolution, transmittance, heat discoloration resistance, adhesive strength, and the like, and particularly has excellent sensitivity at UV wavelengths of 405 to 435 nm, so that it can be used in a GH-line exposure machine or a next-generation digital iron exposure machine. Suitable. Furthermore, the negative photosensitive resin composition of this invention can be used for formation of the passivation insulating film, gate insulating film, planarization film, column spacer, overcoat, or color resist of TFT-LCD, TSP (Touch Screen Panel), OLED, or O-TFT.

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.

Synthesis Example 1 (Preparation of Acrylic Copolymer)

A mixed solution of 400 parts by weight of propylene glycol monoethyl acetate, 30 parts by weight of methacrylic acid and 30 parts by weight of styrene, and 40 parts by weight of aryl methacrylate was added to a flask equipped with a cooler and a stirrer. The liquid composition was sufficiently mixed at 600 rpm in a mixing vessel, and then 15 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) was added. The polymerization mixture solution was slowly raised to 70 ° C., held at this temperature for 8 hours, cooled to room temperature, and 500 ppm of hydrobenzophenone was added as a polymerization inhibitor to obtain an acrylic copolymer having a solid content of 20% by weight. The weight average molecular weight of the obtained acrylic copolymer was 10,000. In this case, the weight average molecular weight is a polystyrene converted average molecular weight measured using GPC.

Synthesis Example 2 (Preparation of Polyimide Copolymer)

50 parts by weight of 2,2, -bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 4,4- (hexafluoro-isopropylidene) diphthalic anhydride in a flask equipped with a cooler and a stirrer 50 parts by weight was added, and 400 parts by weight of NMP was added at room temperature, followed by stirring for 24 hours. At this time, the concentration of the solution was to be 20% by weight solids. Thereafter, in order to remove the water generated in the imidization reaction, xylene was added in the same amount as the NMP to the polyamic acid produced by the reaction and reacted at 160 ° C. for 5 hours to prepare a polyimide. Soluble polyimide (6FDA / BAPAF) was dissolved in DMAc under a nitrogen atmosphere, and then a photosensitive group methacryl oil-chloride and the same equivalent of triethylamine (TEA) were added dropwise and reacted at 0 ° C. for 12 hours to prepare a photosensitive polyimide copolymer. Prepared. The weight average molecular weight of the obtained polyimide copolymer was 15,000. In this case, the weight average molecular weight is a polystyrene converted average molecular weight measured using GPC.

Synthesis Example 3 (Production of siloxane copolymer)

In a flask equipped with a cooler and a stirrer, 40 parts by weight of phenyltriethoxysilane, 20 parts by weight of tetraethoxysilane and 40 parts by weight of methacryloxypropyltrimethoxysilane were added as reactive silanes, respectively, and propylene glycol monoethyl acetate 100 was used as a solvent. Part by weight, nitrogen was substituted, and then gently stirred. 40 parts by weight of ultrapure water and 3 parts by weight of oxalic acid were added to the reaction solution, followed by gentle stirring. After 1 hour, the reaction solution was heated to 60 ° C., maintained at this temperature for 10 hours, solution polymerized, and cooled to room temperature to terminate the reaction. Subsequently, the solvent and residual water of the alcohols produced during the reaction were removed through vacuum drying, and then diluted with 300 parts by weight of propylene glycol monoethyl acetate to prepare a siloxane copolymer having a solid concentration of 20% by weight. The weight average molecular weight of the obtained siloxane copolymer was 5,000. In this case, the weight average molecular weight is a polystyrene converted average molecular weight measured using GPC.

Example 1

100 parts by weight of the acrylic copolymer solution prepared in Synthesis Example 1, as a photoinitiator [1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O- Acetyl oxime) 5 parts by weight, 3 parts by weight of 10-butyl-2-chloroacridin-9 (10H) -one (10-butyl-2-chloroacridin-9 (10H) -one) as a photosensitizer, polyfunctional monomer 10 parts by weight of dipentaerythritol hexaacrylate and 10 parts by weight of trimethylolpropanetriacrylate were mixed. Propylene glycol monoethyl acetate was added to dissolve the mixture so that the solid content was 20% by weight, followed by filtration through a 0.2 μm millipore filter to prepare a negative photosensitive resin composition coating solution.

Example 2

A photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the polyimide copolymer of Synthesis Example 2 was used instead of the acrylic copolymer of Synthesis Example 1 in Example 1.

Example 3

A photosensitive resin composition coating solution was prepared in the same manner as in Example 1, except that the siloxane copolymer of Synthesis Example 3 was used instead of the acrylic copolymer of Synthesis Example 1 in Example 1.

Example 4

2- (o-) in place of the photoinitiator [1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime) in Example 1 Photosensitive resin composition in the same manner as in Example 1, except that chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer (HABI-1311, manufactured by Daelim Chemical Co., Ltd.) was used. Coating solution was prepared.

Example 5

Irgacure 819 (manufactured by Ciba) in place of the photoinitiator [1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime) in Example 1 Except for using), a photosensitive resin composition coating solution was prepared in the same manner as in Example 1.

Example 6

Except for using 10-propyl-2-chloroacridin-9 (10H) -one in place of 10-butyl-2-chloroacridin-9 (10H) -one as a photosensitizer in Example 1 Was prepared in the same manner as in Example 1, the photosensitive resin composition coating solution.

Example  7

In Example 1, 10 parts by weight of 10-butyl-2-chloroacridin-9 (10H) -one was used instead of 3 parts by weight of 10-butyl-2-chloroacridin-9 (10H) -one as a photosensitizer. Except that, a photosensitive resin composition coating solution was prepared in the same manner as in Example 1.

Comparative Example 1

Except not using a photosensitizer in Example 1, a photosensitive resin composition coating solution was prepared in the same manner as in Example 1.

Comparative Example 2

Example 1, except that 2-isopropylthioxanthone was used in place of 10-butyl-2-chloroacridin-9 (10H) -one as a photosensitizer. A photosensitive resin composition coating solution was prepared in the same manner as in Example 1.

Comparative Example 3

Except that 2,4-diethylthioxanthone was used in place of 10-butyl-2-chloroacridin-9 (10H) -one as a photosensitizer in Example 1, A photosensitive resin composition coating solution was prepared in the same manner as in Example 1.

Experimental Example

Using the negative photosensitive resin composition prepared in Examples 1 to 7 and Comparative Examples 1 to 3, the physical properties were evaluated by the following method, and the results are shown in Table 1 below.

a) Sensitivity-After application of the negative photosensitive composition solution prepared in Examples 1 to 7 and Comparative Examples 1 to 3 using a spin coater on a glass substrate on which SiNx was deposited, it was free on a hot plate at 100 ° C. for 2 minutes. It baked and formed the 4.0 micrometer film.

The film obtained above was irradiated with the ultraviolet-ray whose intensity | strength is 10 mW / cm <2> at 405-435 nm for 1 to 30 second using the predetermined pattern mask. Thereafter, the solution was developed at 23 ° C. for 2 minutes in an aqueous solution of 2.38% by weight of tetramethyl ammonium hydroxide, and then washed with ultrapure water for 1 minute.

The pattern film was obtained by heating at 220 degreeC for 60 minutes in oven for final hardening. Sensitivity was measured based on the amount of exposure that the residual film ratio saturates based on 20 μm Line & Space CD using SEM.

b) Resolution-Measured by the minimum size of the pattern film formed when the sensitivity of the a).

c) Half-tone adhesive strength-The case where the minimum residual film of the pattern film formed at the time of the sensitivity measurement of a) was less than 1.2 micrometers (circle), and the case where 1.2-1.8 micrometers were (triangle | delta) and 1.8 micrometers or more were marked with x.

d) Transmittance-Transparency was measured by using a spectrophotometer on the pattern film formed during the sensitivity measurement of a) using a spectrophotometer to measure the transmittance of 400 nm. (Circle) and the case where the transmittance | permeability at this time is 90% or more, (triangle | delta) and the case where it is 85 to 90%, and the case were represented by x.

e) Heat discoloration resistance-The measurement at the time of evaluating the transparency of d) The substrate was further cured in an oven at 300 ° C. for 40 minutes to evaluate heat discoloration resistance by 400 nm transmittance change of the pattern film before and after curing. (Circle) and the case where the change rate at this time are less than 5%, (triangle | delta) and the case exceeding 10% were represented by x as the case where it was 5-10%.

Sensitivity (mJ / ㎠) Resolution (μm) Adhesion Permeability Heat discoloration resistance Example 1 40 3 ○ ○ ○ Example 2 39 3 ○ ○ ○ Example 3 41 3 ○ ○ ○ Example 4 40 3 ○ ○ ○ Example 5 40 3 ○ ○ ○ Example 6 41 3 ○ ○ ○ Example 7 35 3 ○ ○ ○ Comparative Example 1 No pattern formation No pattern formation No pattern formation No pattern formation No pattern formation Comparative Example 2 200 8 ○ ○ ○ Comparative Example 3 200 8 ○ ○ ○

Through Table 1, Examples 1 to 7 prepared by using the photosensitizer of the formula 1 according to the present invention is excellent in adhesion, transmittance, heat discoloration resistance, in particular the sensitivity is 35-41 mJ / ㎠ It was very excellent compared to 1 to 3, it was confirmed that the excellent 3㎛ in resolution.

Through this, the present invention was excellent in sensitivity at UV long wavelength of 405 ~ 435nm, it can be seen that it is suitable for use in GH-line dedicated exposure machine or next-generation digital iron exposure machine.

Although only the specific examples of the present invention have been described in detail above, it will be apparent to those skilled in the art that various modifications and variations are possible within the technical spirit of the present invention, and such modifications and modifications belong to the appended claims. .

Claims (13)

a) an acrylic copolymer, a polyimide copolymer, a siloxane copolymer, or a copolymer thereof;
b) photoinitiators; And
c) a photosensitizer represented by the following formula (1)
Negative photosensitive resin composition comprising a.
[Formula 1]

(In Formula 1, n is an integer of 1-10.) The method of claim 1,
a) 100 parts by weight of an acrylic copolymer, a polyimide copolymer, a siloxane copolymer, or a copolymer thereof;
b) 0.1 to 30 parts by weight of photoinitiator; And
c) 0.1 to 30 parts by weight of a photosensitizer represented by Formula 1
Negative photosensitive resin composition comprising a. The negative photosensitive resin composition of claim 1, wherein the acrylic copolymer is prepared by radical polymerization of an acrylic monomer under an azo initiator, and has a weight average molecular weight of 3000 to 50000. The negative photosensitive resin composition of claim 1, wherein the polyimide copolymer is prepared from diamine and dione hydride, and has a weight average molecular weight of 3000 to 50000. The negative photosensitive resin composition of claim 1, wherein the siloxane copolymer is prepared by hydrolysis and condensation of a silane monomer under an acid or a base, and has a weight average molecular weight of 3000 to 50000. The method of claim 1,
The photoinitiator of b) is 2,4-bis (trichloromethyl) -6- (p-methoxystyryl) -s-triazine, 2- (p-methoxystyryl) -4,6-bis ( Trichloromethyl) -s-triazine, 2,4-trichloromethyl-6-triazine, 2,4-trichloromethyl-4-methylnaphthyl-6-triazine, 2- (o-chlorophenyl) -4,5-diphenyl imidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5 -Diphenyl imidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenyl imidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenyl imidazole dimer, 2,4-di (p-methoxy phenyl) -5-phenyl imidazole dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenyl imidazole dimer, 2- (p-methyl Mercaptophenyl) -4,5-diphenyl imidazole dimer, [1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime ), Benzophenone, p- (diethylamino) benzophenone, 2,2-dichloro-4-phenoxyacetophenone, 2,2-diethoxyacetophenone, 2- Dodecyl thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2,2-bis-2-chlorophenyl-4,5,4,5-tetraphenyl-2-1, A negative photosensitive resin composition which is at least one selected from the group consisting of 2-biimidazole, Irgacure 369, Irgacure 651, Irgacure 907, Darocur TPO, and Irgacure 819. The negative photosensitive resin composition of claim 1, wherein the composition further comprises a solvent such that a solid content is 10 to 50 wt%. The method of claim 1,
The composition is a negative photosensitive resin composition further comprises at least one additive selected from the group consisting of d) a polyfunctional monomer having an ethylenically unsaturated bond, e) a silicone-based compound having an epoxy group or an amine group, and f) a surfactant. The method of claim 8,
The polyfunctional monomer having an ethylenically unsaturated bond is 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, ethylene glycol diacrylate, trimethylolpropanediacrylate, trimethylolpropane triacrylate , Pentaerythritol triacrylate, pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, dipentaerythritol hexadiacrylate, dipentaerythritol tridiacrylate, dipentaerythritol diacrylate, sorbitol The negative photosensitive resin composition chosen from the group which consists of a triacrylate, a bisphenol A diacrylate derivative, dipentaarithol polyacrylate, and these methacrylates. The method of claim 8,
The silicone-based compound having the epoxy group or the amine group may be (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane , (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) dimethylethoxysilane, (3-glycidoxypropyl) dimethylethoxysilane, 3,4-epoxybutyltri Methoxysilane, 3,4-epoxybutyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri The negative photosensitive resin composition chosen from the group which consists of ethoxysilane and aminopropyl trimethoxy silane. Coating and negatively prebake, exposing and developing the negative photosensitive resin composition of any one of claims 1 to 10 on a substrate.
Pattern forming method of the display device comprising a. The passivation insulating film, gate insulating film, planarization film, column spacer, overcoat of the TFT-LCD, TSP (Touch Screen Panel), OLED, or O-TFT pattern using the negative photosensitive resin composition of any one of Claims 1-11. Or a pattern formation method of a display element used as a color resist. The display element containing the pattern using the negative photosensitive resin composition of any one of Claims 1-11.