JP5194225B2 - Negative photosensitive resin composition - Google Patents

Description

  The present invention relates to a negative photosensitive resin composition.

In TFT type liquid crystal display elements and integrated circuit elements, an interlayer insulating film is used to insulate between the wirings arranged between the layers, and an overcoat for large area, high image quality and high contrast display of the liquid crystal color display. It is used as a material for liquid crystal display elements for image formation, such as resist for black matrix, resist for black matrix, resist for column spacer, resist for color filter.
When forming an interlayer insulating film, a photosensitive material having a small number of steps for obtaining an interlayer insulating film having a required pattern shape and excellent in flatness is used.

In addition, the structure of the TFT type liquid crystal display element is also changing due to the improvement of the display quality of the liquid crystal display (LCD), and the use of the interlayer insulating film with an increased flatness by increasing the film thickness of the interlayer insulating film is increasing. Furthermore, the interlayer insulating film applied to the LCD manufacturing process is required to have excellent transmittance.
Conventional interlayer insulating films are composed of components such as PAC, binder and solvent, and acrylic resin has been mainly used as the binder. However, in the case of the acrylic resin, since it is difficult to obtain the high heat resistance required for the interlayer insulating film, the photo equipment is damaged due to outgassing and the problem of afterimage occurs. In addition, it is difficult to obtain adhesive strength with ITO, SiNx, etc. that make up each layer, it is colored after thermosetting, it is difficult to achieve the high transmittance required for interlayer insulation films, and the molecular weight increases during storage at room temperature This causes the problem of storage stability such as sensitivity and pattern shape change.

  In the case of the resist resin for overcoat, the resist resin for black matrix, the resist resin for column spacer, and the resist resin for color filter that are used as materials for conventional liquid crystal elements for image formation, acrylic resin is mainly used. The acrylic resin has a problem that the curing rate by the polyfunctional monomer having a photoinitiator and an ethylenically unsaturated bond is slow, and volume shrinkage occurs after curing.

In order to solve such problems of the prior art, the present invention is superior in performance such as adhesive strength, heat resistance, insulation, flatness, chemical resistance, room temperature storage stability, etc. A negative photosensitive resin composition suitable for use as an interlayer organic insulating film because of its excellent sensitivity, residual film rate, and UV transmittance, particularly when forming an organic insulating film of a liquid crystal display device, It aims at providing the pattern formation method of the TFT type liquid crystal display element containing the hardened | cured material of photosensitive resin, and the TFT type liquid crystal display element using the said negative photosensitive resin composition.
Another object of the present invention is to provide a negative photosensitive resin which can be used as an overcoat resist resin, a black matrix resist resin, a column spacer resist resin, or a color filter resist resin to improve sensitivity and residual film ratio. It is providing the pattern formation method of the TFT type liquid crystal display element using the photosensitive resin composition, the TFT type liquid crystal display element containing the hardening body of the said photosensitive resin, and the said negative photosensitive resin composition.

（式中、Ｒはヒドロキシまたはカルボキシ基である。）
で表示されるフェニルマレイミド系化合物；
ｉｉ）アリルアクリル酸又はアリルメタクリル酸からなるアリルアクリル系化合物；および
ｉｉｉ）不飽和カルボン酸、不飽和カルボン酸無水物、またはこれらの混合物；
を共重合させて得られたアクリル系共重合体；
ｂ）光開始剤；
ｃ）エチレン性不飽和結合を有する多官能性モノマー；
ｄ）エポキシ基またはアミン基を含むシリコン系化合物；および
ｅ）溶媒
を含むことを特徴とするネガティブ感光性樹脂組成物を提供する。 In order to achieve the above object, the present invention provides a negative photosensitive resin composition,
a) i) the following formula (1)

(In the formula, R is a hydroxy or carboxy group .)
A phenylmaleimide compound represented by:
ii) allyl acrylic compounds comprising allyl acrylic acid or allyl methacrylic acid ; and iii) unsaturated carboxylic acids, unsaturated carboxylic acid anhydrides, or mixtures thereof;
An acrylic copolymer obtained by copolymerization of
b) a photoinitiator;
c) a polyfunctional monomer having an ethylenically unsaturated bond;
Provided is a negative photosensitive resin composition comprising d) a silicon-based compound containing an epoxy group or an amine group; and e) a solvent.

Preferably, the present invention provides: a) i) 5 to 80% by weight of a phenylmaleimide compound represented by the formula (1);
ii) 5-80% by weight of allyl acrylic compound; and iii) 5-40% by weight of unsaturated carboxylic acid, unsaturated carboxylic acid anhydride, or a mixture thereof;
100 parts by weight of an acrylic copolymer obtained by copolymerizing
b) 0.001 to 30 parts by weight of photoinitiator;
c) 10 to 100 parts by weight of a polyfunctional monomer having an ethylenically unsaturated bond;
d) 0.0001 to 5 parts by weight of a silicon-based compound containing an epoxy group or an amine group; and e) a solvent so that the solid content in the photosensitive resin composition is 10 to 50% by weight.

The present invention also provides a TFT-type liquid crystal display device comprising a cured product of the negative photosensitive resin composition.
Furthermore, the present invention provides a method for forming a pattern of a TFT-type liquid crystal display element, wherein the negative photosensitive resin composition is used.

The negative photosensitive resin composition according to the present invention is excellent in performance such as adhesive strength, heat resistance, insulation, flatness, chemical resistance, and room temperature storage stability, and should be suitably used as an image forming material for liquid crystal display elements. Can do. In particular, when forming an organic insulating film of a liquid crystal display element, it is excellent in sensitivity, remaining film ratio, and UV transmittance, and therefore can be suitably used as an interlayer organic insulating film.
In addition, it can be suitably used as resist resin for overcoat, resist resin for black matrix, resist resin for column spacer, or resist resin for color filter, improving sensitivity and heat resistance, adhesive strength, and room temperature storage stability. There is an effect that can be.

Hereinafter, the present invention will be described in detail.
The negative photosensitive resin composition of the present invention comprises: a) i) a phenylmaleimide compound represented by the formula (1), ii) an allylacrylic compound, and iii) an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride. Or an acrylic copolymer obtained by copolymerizing a mixture thereof, b) a photoinitiator, c) a polyfunctional monomer having an ethylenically unsaturated bond, d) a silicon system containing an epoxy group or an amine group A compound, and e) a solvent.

The acrylic copolymer of a) used in the present invention acts to easily form a predetermined pattern in which no scum is generated during development.
The acrylic copolymer of a) includes a) i) a phenylmaleimide compound represented by the formula (1), ii) an allylacrylic compound, and iii) an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride. Or a mixture thereof as a monomer can be produced by radical reaction in the presence of a solvent and a polymerization initiator.

The phenylmaleimide compound represented by formula (1) in a) i) functions to improve heat resistance, adhesive strength, and storage stability at room temperature.
As the phenylmaleimide compound, 4-hydroxyphenylmaleimide or 4-carboxyphenylmaleimide can be used.
When the content of the phenylmaleimide-based compound is too small, the heat resistance and the adhesive strength are lowered, and when the content is too large, the solubility in alkaline water solubility is lowered to 5 to 80 wt. %, Preferably 5 to 40% by weight.

The allyl acrylic compound of a) ii) used in the present invention increases the curing rate with a polyfunctional monomer having an ethylenically unsaturated bond by a photoinitiator and decreases the solubility in a developer. It works to improve the remaining film rate.
The allyl acrylate-based compound, or the like can be used A drill acrylate or allyl methacrylate.
The allylacrylic compound is 5 to 80% by weight based on the total monomer from the viewpoint that if the content is too small, the photocuring rate is slow, and if the content is too large, the resolution decreases due to contact hole generation and pattern formation. %, Preferably 20 to 70% by weight.

  The unsaturated carboxylic acid, unsaturated carboxylic acid anhydride or mixture thereof of a) iii) is an unsaturated monocarboxylic acid such as acrylic acid or methacrylic acid; maleic acid, fumaric acid, citraconic acid, methaconic acid, itaconic acid, etc. These unsaturated dicarboxylic acids; or anhydrides of these unsaturated dicarboxylic acids can be used alone or in admixture of two or more, and in particular, acrylic acid, methacrylic acid, or maleic anhydride is used. It is further preferable in terms of polymerization reactivity and solubility of the developer in an alkaline aqueous solution.

  From the viewpoint that the unsaturated carboxylic acid, the unsaturated carboxylic acid anhydride, or a mixture thereof is difficult to dissolve in the alkaline aqueous solution if the content is too small, and that the solubility in the alkaline aqueous solution is excessively large if the content is too large, It is preferably contained at 5 to 40% by weight, more preferably 10 to 30% by weight with respect to the monomer.

  Solvents used to polymerize the above monomers into acrylic copolymers are methanol, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether. , Diethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl Ether ace , Propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, propylene glycol methyl ethyl propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate, toluene, xylene, methyl ethyl ketone , Cyclohexanone, 4-hydroxy 4-methyl 2-pentanone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methylpropionic acid Ethyl, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, lactic acid Lopyr, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, Propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propylpropoxyacetate, butylpropoxyacetate, methylbutoxyacetate, ethylbutoxyacetate Propyl, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, 2 -Methyl ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, 2- Butyl propoxyate butyl, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-ethoxy Propyl propionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, 3-butoxy Ethers such as methyl propionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, or butyl 3-butoxypropionate can be used, and the above compounds can be used alone or in combination of two or more. Can be used.

  The polymerization initiator used to polymerize such a monomer into an acrylic copolymer can be a radical polymerization initiator, specifically 2,2-azobisisobutyronitrile, 2-azobis (2,4-dimethylvaleronitrile), 2,2-azobis (4-methoxy2,4-dimethylvaleronitrile), 1,1-azobis (cyclohexane-1-carbonitrile), or dimethyl 2,2 -Azobisisobutyrate or the like can be used.

In addition, the copolymer may further include an olefin unsaturated compound of iv) at the time of manufacturing the acrylic copolymer of the present invention to manufacture an acrylic copolymer. The olefinic unsaturated compound of iv) is methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, methyl acrylate, isopropyl acrylate, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentenyl. Acrylate, dicyclopentanyl acrylate, dicyclopentenyl methacrylate, dicyclopentanyl methacrylate, 1-adamantyl acrylate, 1-adamantyl methacrylate, dicyclopentanyloxyethyl methacrylate, isobornyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate Dicyclopentanyloxyethyl acrylate, Minced sulfonyl acrylate, phenyl methacrylate, phenyl acrylate, benzyl acrylate, 2-hydroxyethyl methacrylate, styrene, o - methylstyrene, m- methylstyrene, p- methyl styrene, vinyl toluene, p- methoxystyrene, 1,3-butadiene, Isoprene, 2,3-dimethyl 1,3-butadiene, or the like can be used, and the above compounds can be used alone or in admixture of two or more.

In particular, it is more preferable to use styrene, dicyclopentanylmethyl methacrylate, or p-methoxystyrene as the olefinically unsaturated compound in terms of copolymerization reactivity and solubility in an aqueous alkali solution.
The olefinically unsaturated compound is preferably contained in 10 to 70% by weight relative to the total monomers, more preferably from 20 to 50 wt%. When the content is within the above range, it is possible to solve simultaneously the problems such as a decrease in the storage safety of the acrylic copolymer and the difficulty in dissolving the acrylic copolymer in the alkaline aqueous solution of the developer.
The acrylic copolymer of a) produced by radical reaction of the above monomers in the presence of a solvent and a polymerization initiator has a polystyrene equivalent weight average molecular weight (Mw) of 6,000 to 90,000. It is preferable that it is 6,000 to 40,000. In the case of the negative photosensitive resin composition having a polystyrene-reduced weight average molecular weight that is too small, the developability, the remaining film ratio, etc. may decrease, or the pattern shape, heat resistance, etc. may be inferior. Is inferior.

As the photoinitiator of b) used in the present invention, compounds such as Irgacure 369, Irgacur 651, Irgacure 907, Darocur TPO, Irgacure 819, triazine, benzoin, acetophenone, imidazole, or xanthone are used. be able to.
Specifically, the photoinitiator 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-di Ethoxyacetophenone, 2-dodecylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, or 2,2-bis-2-chlorophenyl-4,5,4,5-tetraphenyl-1,2- Compounds such as biimidazole can be used alone or in admixture of two or more.

  If the content of the photoinitiator is too low, the remaining film rate may be deteriorated due to low sensitivity, and if it is too high, a problem may occur in storage stability, and a high degree of curing reduces the adhesion of the pattern during development. From the standpoint of the possibility, it is preferably contained in an amount of 0.001 to 30 parts by weight, more preferably 0.01 to 20 parts by weight with respect to 100 parts by weight of the acrylic copolymer of a).

The polyfunctional monomer having an ethylenically unsaturated bond of c) used in the present invention is generally a crosslinkable monomer having at least two ethylenic double bonds, and is 1,4-butanediol diacrylate. 1,3-butylene glycol diacrylate, ethylene glycol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, dipenta Erythritol hexadiacrylate, dipentaerythritol tridiacrylate, dipentaerythritol diacrylate, sorbitol triacrylate, bisphenol A Acrylate derivatives, dipentaerythritol polyacrylate or methacrylates thereof, i.e., 1,4-butanediol dimethacrylate, 1,3-butylene glycol dimethacrylate, ethylene glycol dimethacrylate, trimethylol propane dimethacrylate, Trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, dipentaerythritol hexadimethacrylate, dipentaerythritol tridimethacrylate, dipentaerythritol Dimethacrylate, sorbitol trimethacrylate, bisphenol A dimethacrylate derivative, dipentaerythritol polymethacrylate and the like can be used.

  If the content of the polyfunctional monomer having an ethylenically unsaturated bond is too small, it is difficult to realize a contact hole and a pattern due to a low degree of curing with the photosensitive resin. From the viewpoint that the resolving power of the pattern may be lowered, it is preferably contained in 10 to 100 parts by weight, more preferably 10 to 60 parts by weight with respect to 100 parts by weight of the acrylic copolymer of a). .

  The silicon compound containing an epoxy group or an amine group of d) used in the present invention is (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, (3-glycidyl). Sidoxypropyl) methyldimethoxysilane, (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) dimethylethoxysilane, (3-glycidoxypropyl) dimethylethoxysilane, 3,4-epoxybutyl Trimethoxysilane, 3,4-epoxybutyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, aminopropyltrimethoxysilane, etc. Singly or in combination of two or more It is possible to use Te.

When the content of the silicon-based compound containing an epoxy group or an amine group is too small, the adhesive force between the ITO electrode and the photosensitive resin is inferior, the heat resistance after curing may be inferior, and the developer is too much in the developer. In view of the whitening phenomenon of the non-exposed area and the occurrence of contact hole and pattern scum after development, the content is 0.0001 to 5 parts by weight with respect to 100 parts by weight of the acrylic copolymer of a). The amount is preferably 0.005 to 2 parts by weight.
The solvent e) used in the present invention does not cause flatness of the interlayer insulating film and coating stain, and forms a uniform pattern profile.

  Examples of the solvent include alcohols 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 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 methyl ether Propylene glycol alkyl ether acetates such as teracetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate; propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propio , Propylene glycol alkyl ether acetates such as propylene glycol butyl ether propionate; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy 4-methyl 2-pentanone; or methyl acetate, Ethyl acetate, propyl acetate, butyl acetate, 2-hydride Ethyl xylpropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3 -Methyl hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, methoxyacetic acid Butyl, methyl ethoxy acetate, ethyl ethoxy acetate, propyl ethoxy acetate, butyl ethoxy acetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, butoxy Methyl diacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 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, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, 3- Butyl xypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, 3-butoxy Esters such as propyl propionate and butyl 3-butoxypropionate can be used.

In particular, the solvent may be used by selecting one or more from the group consisting of glycol ethers, ethylene alkyl ether acetates, and diethylene glycols that are soluble, reactive with each component, and easy to form a coating film. preferable.
The solvent is preferably included so that the total photosensitive resin composition has a solid content of 10 to 50% by weight, and the composition having the solid content in the above range is a 0.1 to 0.2 μm Millipore filter or the like. It is good to use after filtering with. More preferably, it is 15 to 40% by weight. If the solid content of the whole composition is too small, the coating thickness becomes thin and the coating flatness is deteriorated. If it exceeds 50% by weight, the coating thickness becomes thick and the coating is coated at the time of coating. This is because it may impair the equipment.

The negative photosensitive resin composition of the present invention comprising the above components can additionally contain f) a photosensitizer and g) a surfactant, if necessary.
The photosensitizer of f) has an appropriate sensitivity to the ultraviolet wavelength to be used, and transfers the energy to the photoinitiator by a photoinitiation reaction faster than the photoinitiator, thereby assisting the photoinitiator reaction rate of the photoinitiator.
As the photosensitizer , ITX, n-butylacridone, 2-ethylhexyl-dimethylaminobenzoate, or the like can be used alone or in admixture of two or more.
The photosensitizer is preferably contained in an amount of 0.001 to 70 parts by weight with respect to 100 parts by weight of the photoinitiator of b), and when the content is within the above range, the negative photosensitive resin composition. It is even better in improving the photocuring speed of the product.

The surfactant of g) functions to improve the coating property and developability of the photosensitive composition.
The surfactant is polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, F171, F172, F173 (trade name: Dainippon Ink & Chemicals, Inc.), FC430, FC431 (trade name: Sumitomo 3M Limited). Alternatively, KP341 (trade name: Shin-Etsu Chemical Co., Ltd.) or the like can be used.

The surfactant is preferably contained in an amount of 0.0001 to 2 parts by weight based on 100 parts by weight of the acrylic polymer of a), and when the content is within the above range, the negative photosensitive composition. It is even better in improving the coating property and developing property.
Moreover, the negative photosensitive resin composition of this invention can add compatible additives, such as a thermal-polymerization inhibitor and an antifoamer, to the said composition as needed, and a pigment is added according to a use. be able to. For example, a black matrix resist and a color filter resist, which are image forming materials for TFT-type liquid crystal display elements, are obtained by blending a pigment with the above-described composition. It can be appropriately selected depending on the application of the color filter resist, and both inorganic and organic pigments can be used.

In addition, the present invention provides a TFT type liquid crystal display element comprising the cured product of the negative photosensitive resin as described above and a method for forming a pattern of the TFT type liquid crystal display element using the negative photosensitive resin composition.
The pattern forming method of the TFT type liquid crystal display element of the present invention comprises forming a negative photosensitive resin composition as an organic insulating film, an overcoat resist, a black matrix resist, a column spacer resist, or a color filter resist. In the method of forming a liquid crystal display element, the negative photosensitive resin composition is used.
Specifically, an example of a method for forming a pattern of a TFT type liquid crystal display element using the negative photosensitive resin composition is as follows.

First, the photosensitive resin composition of the present invention is applied to the substrate surface by a spray method, a roll coater method, a spin coating method, or the like, and the solvent is removed by pre-baking to form a coating film. At this time, the pre-bake is preferably performed at a temperature of 70 to 110 ° C. for 1 to 15 minutes.
Thereafter, the formed coating film is irradiated with visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, etc. according to a pattern prepared in advance, and developed with a developer to remove unnecessary portions. Form a pattern.

  The developer is preferably an alkaline aqueous solution, specifically inorganic alkalis such as sodium hydroxide, potassium hydroxide and sodium carbonate; primary amines such as n-propylamine; diethylamine and n-propylamine. Secondary amines such as: trimethylamine, methyldiethylamine, dimethylethylamine, triethylamine and other tertiary amines; dimethylethanolamine, methyldiethanolamine, triethanolamine and other alcohol amines; or tetramethylammonium hydroxide, tetraethylammonium hydroxide An aqueous solution of a quaternary ammonium salt such as can be used. At this time, the developer is used by dissolving an alkaline compound in a concentration of 0.1 to 10% by weight, and a water-soluble organic solvent such as methanol and ethanol and a surfactant can be added in appropriate amounts. .

Moreover, after developing with such a developing solution, it is washed with ultrapure water for 30 to 90 seconds to remove unnecessary portions, dried to form a pattern, and the pattern is 150 to 250 by a heating device such as an oven. The final pattern can be obtained by heat treatment at a temperature of 30 ° C. for 30 to 90 minutes.
The negative photosensitive resin composition according to the present invention as described above is excellent in performance such as adhesive strength, heat resistance, insulation, flatness, chemical resistance, and room temperature storage stability, and is used as an image forming material for liquid crystal display elements. It can be preferably used. In particular, since the sensitivity, residual film ratio, and UV transmittance at the time of forming an organic insulating film of a liquid crystal display element are excellent, it can be suitably used as an interlayer organic insulating film. Also suitable for improving sensitivity and heat resistance, adhesive strength, and room temperature storage stability by using as overcoat resist resin, black matrix resist resin, column spacer resist resin, or color filter resist resin. Material.
Hereinafter, preferred examples will be presented for the understanding of the present invention. However, the following examples are merely illustrative of the present invention, and the scope of the present invention is not limited to the following examples.

Example 1
(Acrylic copolymer production)
In a flask equipped with a condenser and a stirrer, 10 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile), 400 parts by weight of propylene glycol monomethyl ether acetate, 30 parts by weight of methacrylic acid, 30 parts by weight of allyl methacrylate, 10 parts by weight of 4-hydroxyphenylmaleimide of the formula (1) and 30 parts by weight of styrene were added, and after nitrogen substitution, the mixture was gently stirred. The reaction solution was heated to 55 ° C., and a polymer solution containing an acrylic copolymer was produced while maintaining this temperature for 24 hours.
The acrylic copolymer produced as described above was dropped into 5,000 parts by weight of hexane, precipitated, and filtered and separated, and then 200 parts by weight of propionate was added and heated to 30 ° C. A polymer solution having a weight average molecular weight of 18,000 and a polymer weight of 45% was produced. The weight average molecular weight at this time is an average molecular weight in terms of polystyrene measured using GPC.

(Manufacture of negative photosensitive resin composition)
100 parts by weight of the polymer solution containing the acrylic copolymer prepared, 15 parts by weight of Irgacure 819 as a photoinitiator, 5 parts by weight of 2-ethylhexyl-4-dimethylaminobenzoate as a photosensitizer, and n-butylacridone 5 parts by weight, 40 parts by weight of dipentaerythritol hexaacrylate and 10 parts by weight of trimethylolpropane triacrylate as a polyfunctional monomer having an ethylenically unsaturated bond, and 2- (3,4-epoxycyclohexyl) ethyltri as a silicon compound 1 part by weight of methoxysilane and 2 parts by weight of F171 as a silicon-based surfactant were mixed. Diethylene glycol dimethyl ether was added to the mixture so as to have a solid concentration of 35% by weight and dissolved, and then filtered through a 0.2 μm Millipore filter to prepare a negative photosensitive resin composition coating solution.

Example 2
In production of the acrylic copolymer of Example 1, 20 parts by weight of 4-hydroxyphenylmaleimide of the formula (1) is used, 30 parts by weight of methacrylic acid, 30 parts by weight of allyl methacrylate, and 20 parts by weight of styrene are used. The negative photosensitive resin was prepared in the same manner as in Example 1 except that an acrylic copolymer having a solid content of 45% by weight and a weight average molecular weight of 17,800 was produced. A composition coating solution was prepared.

Example 3
In the production of the acrylic copolymer of Example 1, 30 parts by weight of 4-hydroxyphenylmaleimide of formula (1) is used, 30 parts by weight of methacrylic acid, 30 parts by weight of allyl methacrylate, and 10 parts by weight of styrene are used. In the same manner as in Example 1 except that an acrylic copolymer having a solid content of 45% by weight and a weight average molecular weight of 18,100 was produced, negative photosensitivity was obtained. A resin composition coating solution was prepared.

Example 4
In production of the acrylic copolymer of Example 1, 40 parts by weight of 4-hydroxyphenylmaleimide of the formula (1) was used, and 30 parts by weight of methacrylic acid and 30 parts by weight of allyl methacrylate were used. The negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 except that an acrylic copolymer having a concentration of 45% by weight and a weight average molecular weight of 18,210 was produced. Manufactured.

Example 5
In production of the acrylic copolymer of Example 1, 10 parts by weight of 4-carboxyphenylmaleimide of the formula (1) is used, 30 parts by weight of methacrylic acid, 30 parts by weight of allyl methacrylate, and 30 parts by weight of styrene are used. In the same manner as in Example 1 except that an acrylic copolymer having a solid content of 45% by weight and a weight average molecular weight of 17,700 was produced, negative photosensitivity was obtained. A resin composition coating solution was prepared.

Example 6
In production of the acrylic copolymer of Example 1, 20 parts by weight of 4-carboxyphenylmaleimide of the formula (1) is used, 30 parts by weight of methacrylic acid, 30 parts by weight of allyl methacrylate, and 20 parts by weight of styrene are used. In the same manner as in Example 1 except that an acrylic copolymer having a solid content of 45% by weight and a weight average molecular weight of 17,500 was produced, negative photosensitivity was obtained. A resin composition coating solution was prepared.

Example 7
In the production of the acrylic copolymer of Example 1, 30 parts by weight of 4-carboxyphenylmaleimide of formula (1) is used, 30 parts by weight of methacrylic acid, 30 parts by weight of allyl methacrylate, and 10 parts by weight of styrene are used. In the same manner as in Example 1 except that an acrylic copolymer having a solid content of 45% by weight and a weight average molecular weight of 17,300 was produced, negative photosensitivity was obtained. A resin composition coating solution was prepared.

Example 8
In the production of the acrylic copolymer of Example 1, 40 parts by weight of 4-carboxyphenylmaleimide of the formula (1) was used, and 30 parts by weight of methacrylic acid and 30 parts by weight of allyl methacrylate were used. The negative photosensitive resin composition coating solution was prepared in the same manner as in Example 1 except that an acrylic copolymer having a concentration of 45% by weight and a weight average molecular weight of 18,100 was produced. Manufactured.

Comparative Example 1
In the preparation of the acrylic copolymer of Example 1, 20 parts by weight of glycidyl methacrylate was used, 30 parts by weight of methacrylic acid, 30 parts by weight of allyl methacrylate, and 20 parts by weight of styrene were used. A negative photosensitive resin composition coating solution was produced in the same manner as in Example 1 except that an acrylic copolymer having a weight average molecular weight of 17,400 was produced. did.

Comparative Example 2
In the acrylic copolymer production of Example 1, 40 parts by weight of glycidyl methacrylate was used, 30 parts by weight of methacrylic acid and 30 parts by weight of allyl methacrylate were used, and the solid content was 45% by weight. A negative photosensitive resin composition coating solution was produced in the same manner as in Example 1 except that an acrylic copolymer having a weight average molecular weight of 18,100 was produced.

Using the negative photosensitive resin composition coating solutions prepared in Examples 1 to 8 and Comparative Example 1 or 2, the physical properties were evaluated by the following methods. The results are shown in Table 1 below.
A) Sensitivity—After applying the photosensitive resin composition solutions prepared in Examples 1 to 8 and Comparative Examples 1 and 2 on a glass substrate using a spin coater, the glass substrate was heated on a hot plate at 90 ° C. for 2 minutes. Pre-baked to form a film.
The film obtained above was irradiated with ultraviolet rays having an intensity at 365 nm of 15 mW / cm ² and a sensitivity of 10 μm line and space 1: 1 CD reference dose for 15 seconds using a predetermined pattern mask. Thereafter, development was performed with an aqueous solution of 0.38% by weight of tetramethylammonium hydroxide at 23 ° C. for 2 minutes and washed with ultra pure water for 1 minute.
Subsequently, the pattern developed above was irradiated with ultraviolet rays having an intensity at 365 nm of 15 mW / cm ² for 34 seconds, and heated and cured in an oven at 220 ° C. for 60 minutes to obtain a pattern film.

  B) Heat resistance—The widths of the upper, lower, left and right sides of the pattern film formed during the sensitivity measurement in the above a) were measured. At this time, the case where the angle change rate was 0 to 20% based on the pre-mid-bake basis was indicated as ◯, the case where it was 20 to 40% as Δ, and the case where it exceeded 40% as ×.

  C) Adhesiveness--When the pattern film formed at the time of sensitivity measurement in the above a) is reciprocated once at the same speed by using a manual roller crimping device, the entire area of the substrate is divided into 100 equal parts. The area to be peeled was measured and displayed as a percentage.

D) Storage stability at room temperature-After leaving for 1 day to 2 weeks in a clean room maintaining 40% humidity at 23 ° C, the sensitivity (mJ / sqcm) change was checked. At this time, the case where the change rate for 2 weeks was less than 10% was indicated by ◯, the case where it was 10-20% was indicated by Δ, and the case where it exceeded 20% was indicated by ×.

As shown in Table 1, in Examples 1 to 8 using an acrylic copolymer produced by including a phenylmaleimide compound according to the present invention, the sensitivity is excellent at 100 to 160 mJ / cm ^2, and heat resistance In addition, the adhesiveness was very good, and there was little influence on the afterimage formation of the liquid crystal. Therefore, when applied to the interlayer insulating film in the LCD process, higher reliability can be obtained. On the other hand, in the case of Comparative Examples 1 and 2, heat resistance, adhesive strength, and room temperature storage stability are inferior, and it is difficult to apply to the interlayer insulating film.

From the above, when the negative photosensitive resin composition according to the present invention is used as an interlayer insulating film of an image forming material, it is possible to obtain very excellent sensitivity, heat resistance, adhesiveness, and storage stability at room temperature. When used as a resist resin for coating, a resist resin for black matrix, a resist resin for column spacers, or a resist resin for color filters, it could be predicted that it will contribute to the improvement of heat resistance, adhesiveness, and room temperature storage stability. .
Although only specific examples of the present invention have been described in detail, it is obvious to those skilled in the art that various modifications and alterations are possible within the scope of the technical idea of the present invention. Of course, it is within the scope of the appended claims.

Claims (14)

A negative photosensitive resin composition comprising:
a) i) the following formula (1)

(In the formula, R is a hydroxy or carboxy group.)
A phenylmaleimide compound represented by:
ii) allyl acrylic compounds comprising allyl acrylic acid or allyl methacrylic acid; and iii) unsaturated carboxylic acids, unsaturated carboxylic acid anhydrides, or mixtures thereof;
An acrylic copolymer obtained by copolymerization of
b) a photoinitiator;
c) a polyfunctional monomer having an ethylenically unsaturated bond;
a negative photosensitive resin composition comprising d) a silicon-based compound containing an epoxy group or an amine group; and e) a solvent. a) i) 5 to 80% by weight of a phenylmaleimide compound represented by the formula (1);
ii) 5-80% by weight of allyl acrylic compound; and iii) 5-40% by weight of unsaturated carboxylic acid, unsaturated carboxylic acid anhydride, or a mixture thereof;
100 parts by weight of an acrylic copolymer obtained by copolymerizing
b) 0.001 to 30 parts by weight of photoinitiator;
c) 10 to 100 parts by weight of a polyfunctional monomer having an ethylenically unsaturated bond;
d) a silicon compound containing an epoxy group or an amine group in an amount of 0.0001 to 5 parts by weight; and e) a solvent so that the solid content in the photosensitive resin composition is 10 to 50% by weight. The negative photosensitive resin composition as described in 2. The unsaturated carboxylic acid, unsaturated carboxylic acid anhydride or mixture thereof of a) iii) is acrylic acid, methacrylic acid, maleic acid, fumaric acid, citraconic acid, methaconic acid, itaconic acid, and unsaturated dicarboxylic acids thereof. The negative photosensitive resin composition of Claim 1 selected from the group which consists of an anhydride of these. The negative photosensitive resin composition according to claim 1, comprising an olefinic unsaturated compound as a monomer at a content of 10 to 70% by weight of the monomer used during the production of the acrylic copolymer. The olefinically unsaturated compound is methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, methyl acrylate, isopropyl acrylate, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentenyl acrylate, di- Cyclopentanyl acrylate, dicyclopentenyl methacrylate, dicyclopentanyl methacrylate, 1-adamantyl acrylate, 1-adamantyl methacrylate, dicyclopentanyloxyethyl methacrylate, isobornyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclo Pentanyloxyethyl acrylate, isoboro Acrylate, phenyl methacrylate, phenyl acrylate, benzyl acrylate, 2-hydroxyethyl methacrylate, styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, vinyl toluene, p-methoxy styrene, 1,3-butadiene, isoprene And one or more selected from the group consisting of 2,3-dimethyl-1,3-butadiene. 2. The negative photosensitive resin composition according to claim 1, wherein the acrylic copolymer of a) has a polystyrene equivalent weight average molecular weight (Mw) of 6,000 to 90,000. The photoinitiator of b) is Irgacure 369, Irgacure 651, Irgacure 907, Darocur TPO, Irgacure 819, 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-dodecylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,2-bis-2-chlorophenyl-4,5 , Negative photosensitive resin composition of claim 1 wherein at least one selected from the group consisting of 5-tetraphenyl -2-1,2- biimidazole. The polyfunctional monomer having an ethylenically unsaturated bond of c) is 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, ethylene glycol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate. Acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate , dipentaerythritol diacrylate, sorbitol triacrylate, bisphenol A diacrylate derivative, dipentaerythritol polyacrylate, 1,4-butane Diol dimethacrylate, 1,3-butylene glycol dimethacrylate, ethylene glycol dimethacrylate Rate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, dipentaerythritol dimethacrylate, sorbitol tri 2. The negative photosensitive resin composition according to claim 1, which is at least one compound selected from the group consisting of methacrylate, bisphenol A dimethacrylate derivative, and dipentaerythritol polymethacrylate. The silicon compound containing an epoxy group or an amine group of d) is (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, (3-glycidoxypropyl) methyldimethoxy. Silane, (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) dimethylethoxysilane, (3-glycidoxypropyl) dimethylethoxysilane, 3,4-epoxybutyltrimethoxysilane, 3, Selected from the group consisting of 4-epoxybutyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and aminopropyltrimethoxysilane. One or more compounds Negative photosensitive resin composition of claim 1. The negative photosensitive resin composition is one or more f) photosensitizers selected from the group consisting of ITX, n-butylacridone, and 2-ethylhexyl-dimethylaminobenzoate; The negative photosensitive resin composition according to claim 1, further comprising 0.001 to 70 parts by weight with respect to 100 parts by weight of the agent. The negative photosensitive resin composition is one or more selected from the group consisting of polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, F171, F172, F173, FC430, FC431, and KP341 g) Surface activity 2. The negative photosensitive resin composition according to claim 1, further comprising an agent in an amount of 0.0001 to 2 parts by weight based on 100 parts by weight of the acrylic polymer of a). The negative photosensitive resin composition according to claim 1, wherein the negative photosensitive resin composition further comprises at least one additive selected from the group consisting of a thermal polymerization inhibitor, an antifoaming agent, and a pigment. A TFT type liquid crystal display device comprising a cured product of the negative photosensitive resin composition according to claim 1. A pattern forming method for a TFT type liquid crystal display element, wherein the negative photosensitive resin composition according to any one of claims 1 to 12 is used.