KR20070007895A - Radiation-sensitive resin composition, spacer, and method of forming the same - Google Patents

Abstract

A radiation-sensitive resin composition which has high sensitivity and high resolution, can readily form a patterned thin film excellent in various performances including pattern shape, compression strength, rubbing resistance, and adhesion to transparent substrates, and is inhibited from emitting sublimates upon burning; a spacer formed from the composition; and a method of forming the spacer. The radiation-sensitive resin composition is characterized by comprising (A) a polymer which has carboxy and epoxy groups and in which the ratio of the weight-average molecular weight (Mw) in terms of polystyrene to the number-average molecular weight (Mn) in terms of polystyrene both measured by gel permeation chromatography, (Mw/Mn), is 1. 7 or lower, (B) a polymerizable unsaturated compound, and (C) a radiation- sensitive polymerization initiator. ® KIPO & WIPO 2007

Description

Radiation-sensitive resin composition, spacer and formation method thereof {RADIATION-SENSITIVE RESIN COMPOSITION, SPACER, AND METHOD OF FORMING THE SAME}

The present invention relates to a radiation sensitive resin composition, a spacer and a method for forming the same.

Conventionally, in the liquid crystal display element, spacer particles such as glass beads and plastic beads having a predetermined particle diameter are used in order to maintain a constant gap between two transparent substrates, but these spacer particles are placed on a transparent substrate such as a glass substrate. Since irregularly dispersed, when the spacer particles are present in the pixel formation region, there is a problem that the spacer particles are taken out or incident light is scattered and the contrast of the liquid crystal display element is lowered.

Therefore, in order to solve these problems, the method of forming a spacer by photolithography is used. In this method, a radiation-sensitive resin composition is applied onto a substrate, and then exposed to ultraviolet rays through a predetermined mask, followed by development to form spacers in the shape of dots or stripes, and the spacers are formed only at predetermined places other than the pixel formation region. Since it can be done, the above-mentioned problem is basically solved.

By the way, the radiation from a mercury lamp used as a light source in photolithography is usually near 436 nm (g line), near 404 nm (h line), around 365 nm (i line), near 335 nm, and near 315 nm. Since the intensity | strength strong spectrum is shown in (j line | wire), 303 nm vicinity, etc., as a radiation sensitive polymerization initiator which is a structural component of a radiation sensitive resin composition, what has the largest absorption wavelength in the wavelength range of these intensity | strength strong spectrums It is common to select and use, and in most cases, the radiation sensitive polymerization initiator which has the maximum absorption wavelength in the area | region below i line | wire from a viewpoint of transparency is used (refer Unexamined-Japanese-Patent No. 2001-261761). When a radiation sensitive polymerization initiator having a maximum absorption wavelength in the vicinity of g- and h-rays whose wavelength is longer than i-rays is used, the radiation-sensitive polymerization initiator can absorb in a wavelength range close to visible light, and therefore The radiation resin composition is colored, and transparency of the formed film falls. When the transparency of the film is low, the curing reaction proceeds on the surface of the film at the time of exposure, and the curing reaction in the depth direction of the film is insufficient. As a result, the shape of the spacer obtained after development is reverse tapered (cross-sectional shape as a cross-sectional shape). Since an inverted triangle is longer than the side of the substrate side, the spacer may be peeled off during the subsequent rubbing treatment of the alignment film.

However, including the one disclosed in Japanese Unexamined Patent Publication No. 2001-261761, the conventional radiation-sensitive resin composition may cause contamination of the process line or apparatus due to the sublimation generated during firing for forming the spacer. There is a desire for a radiation sensitive resin composition having reduced sublimation generated.

This invention is made | formed based on the above circumstances. Therefore, the object of the present invention is high sensitivity and high resolution, while it is possible to easily form a patterned thin film excellent in various performances such as pattern shape, compressive strength, rubbing resistance and adhesion to a transparent substrate, It is providing the radiation sensitive resin composition in which generation | occurrence | production was suppressed, the spacer formed therefrom, and its formation method.

The above object of the present invention firstly,

(A) A polymer which has a carboxyl group and an epoxy group, and ratio (Mw / Mn) of the polystyrene reduced weight average molecular weight (Mw) and the polystyrene reduced number average molecular weight (Mn) measured by gel permeation chromatography is 1.7 or less, (B) polymerizability Unsaturated compound and (C) radiation sensitive polymerization initiator

It is achieved by the radiation sensitive resin composition characterized by containing.

The term "radiation" in the present invention means ultraviolet rays, far ultraviolet rays, X rays, electron beams, molecular rays, gamma rays, synchrotron radiation, and proton beam rays.

The above object of the present invention is second,

(1) forming a coating film of the radiation-sensitive resin composition on a substrate;

(2) irradiating at least a part of the coating film with radiation;

(3) developing process, and

(4) heating process

Is achieved by the method of forming a spacer, which is carried out in the order described above.

The above object of the present invention is thirdly achieved by a spacer formed by the method.

1 is a schematic diagram illustrating a cross-sectional shape of a spacer.

Best Mode for Carrying Out the Invention

Radiation  Resin composition

Hereinafter, each component of the radiation sensitive resin composition of this invention is explained in full detail.

Copolymer (A)

The copolymer (A) in the radiation-sensitive resin composition of the present invention is preferably (a1) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride (hereinafter collectively referred to as "compound (a1)") (a2) living radicals containing a polymerizable mixture containing an epoxy group-containing unsaturated compound (hereinafter referred to as "compound (a2)") and (a3) other unsaturated compound (hereinafter referred to as "compound (a3)") radical) polymerization to obtain advantageously.

For example, copolymer (A) can be produced by living radical polymerization of a polymerizable mixture containing compound (a1), compound (a2) and compound (a3) in the presence of a polymerization initiator in a solvent.

The carboxyl group and epoxy group which the copolymer (A) thus obtained have are derived from the compound (a1) and the compound (a2), respectively.

As an initiator system of living radical polymerization, for example, an initiator system composed of a combination of a copper bromide and a bromine-containing ester compound proposed by TEMPO system, Matyjaszewski, etc. found by George et al. , An initiator system composed of a combination of carbon tetrachloride and ruthenium (II) complexes proposed by Higashimura et al., Japanese Patent Publication No. 2000-515181, Japanese Patent Publication No. 2002-500251 and Japanese Patent Publication Combinations of thiocarbonylthio compounds and radical initiators described in Japanese Patent Application Laid-Open No. 2004-518773 are preferably used.

As a preferable living polymerization initiator system for obtaining the polymer (A) of the present invention, a system in which the growth terminal is not deactivated is appropriately selected depending on the type of monomer used, but in view of polymerization efficiency or the like, preferably It is a combination of a carbonylthio compound and a radical initiator. Here, as a thiocarbonylthio compound, dithio ester, dithiocarbonate, trithiocarbonate, xanthate, etc. are mentioned, for example.

As the specific example, the compound represented by a following formula is mentioned.

Of these, cumyldithiobenzoate, S-cyanomethyl-S-dodecyltrithiocarbonate, pyrazole-1-dithiocarboxylic acid phenyl-methyl ester, dithio ester used in Synthesis Example 5 below and the following The xanthate used by the synthesis example 6 is mentioned.

Moreover, as a radical initiator, what is generally known as a radical polymerization initiator can be used, For example, 2,2'- azobisisobutyronitrile, 2,2'- azobis- (2, 4- dimethylvalero Azo compounds such as nitrile) and 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile); Organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxy pivalate and 1,1'-bis- (t-butylperoxy) cyclohexane; Hydrogen peroxide; Examples thereof include redox initiators containing these peroxides and reducing agents.

These polymerization initiators can be used individually or in mixture of 2 or more types.

The amount of the thiocarbonylthio compound to be used is preferably 1 to 10,000 parts by weight, more preferably 10 to 1,000 parts by weight per 100 parts by weight of the polymerization initiator. The amount of the radical polymerization initiator used is preferably 0.01 to 100 parts by weight, more preferably 0.1 to 10 parts by weight, per 100 parts by weight of the monomer mixture containing the epoxy group-containing polymerizable unsaturated compound. Although the polymerization temperature at the time of the said living radical polymerization is not restrict | limited, Preferably it is 0 degreeC-100 degreeC, More preferably, it is 10 degreeC-85 degreeC.

Depending on the initiator system, the copolymer (A) may be obtained by polymerizing with an ester compound (a1 ') in which the carboxyl group of the compound (a1) is protected with an appropriate protecting group so as not to deactivate the polymerization initiator. .

Examples of the compound (a1) include acrylic acid, methacrylic acid, crotonic acid, mono succinate (2-acryloyloxyethyl), mono succinate (2-methacryloyloxyethyl), and hexahydrophthalic acid (2- Monocarboxylic acids such as acryloyloxyethyl) and hexahydrophthalic acid mono (2-methacryloyloxyethyl); Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; And anhydrides of these dicarboxylic acids.

Among these compounds (a1), acrylic acid, methacrylic acid, maleic anhydride, and the like are preferable in terms of copolymerization reactivity and availability.

The said compound (a1) can be used individually or in mixture of 2 or more types.

The content of the structural units derived from the compound (a1) in the copolymer (A) is preferably 5 to 50% by weight, particularly preferably 10 to 40% by weight. In this case, when the content rate of the structural unit is less than 5% by weight, the compressive strength, heat resistance or chemical resistance of the spacer obtained tends to decrease, whereas when it exceeds 50% by weight, the storage stability of the radiation-sensitive resin composition may be lowered. There is.

As the compound (a2), for example, glycidyl acrylate, glycidyl methacrylate, α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, α-ethyl acrylate 3,4-epoxybutyl acrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethyl 6,7-epoxyheptyl acrylate, β-methylglycidyl acrylate, β-methylglycidyl methacrylate, β-ethylglycidyl acrylate, β-ethylglycidyl methacrylate, β-n-propyl acrylate Carboxylic acid esters such as glycidyl, methacrylic acid β-n-propylglycidyl, acrylic acid 3,4-epoxycyclohexyl and methacrylic acid 3,4-epoxycyclohexyl; ethers such as o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether.

Of these compounds (a2), methacrylic acid glycidyl, methacrylic acid 6,7-epoxyheptyl, methacrylic acid 3,4-epoxycyclohexyl, methacrylic acid β-methylglycidyl, o-vinylbenzyl glycine Cydyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, and the like are preferred in terms of increasing the copolymerization reactivity and the strength of the spacer obtained.

The said compound (a2) can be used individually or in mixture of 2 or more types.

The content of the structural units derived from the compound (a2) in the copolymer (A) is preferably 10 to 70% by weight, particularly preferably 20 to 60% by weight. In this case, when the content rate of the structural unit is less than 10% by weight, the compressive strength, heat resistance or chemical resistance of the spacer obtained tends to decrease, whereas when it exceeds 70% by weight, the storage stability of the radiation-sensitive resin composition tends to decrease. There is this.

As the compound (a3), for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, sec-butyl acrylate and t- Acrylic acid alkyl esters such as butyl acrylate; Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, sec-butyl methacrylate and t-butyl methacrylate Methacrylic acid alkyl esters, such as a rate; Cyclohexylacrylate, 2-methylcyclohexylacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-ylacrylate (hereinafter referred to as “tricyclo [5.2.1.0 ^2,6 ] decane-8-yl Alicyclic esters of acrylic acid such as "dicyclopentanyl", 2-dicyclopentanyloxyethyl acrylate, isoboroyl acrylate and tetrahydrofuryl acrylate; Meta, such as cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentanyl methacrylate, 2-dicyclopentanyloxyethyl methacrylate, isobornyl methacrylate and tetrahydrofuryl methacrylate Cycloaliphatic esters of methacrylic acid; Acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate; Methacrylic acid aryl esters such as phenyl methacrylate and benzyl methacrylate; Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconic acid; Acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; Methacrylic acid hydroxyalkyl esters such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; Aromatic vinyl compounds such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene and p-methoxystyrene or acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide , Vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, N-cyclohexylmaleimide, N-phenylmaleimide, N-benzylmaleimide, N-succinimidyl-3 Maleimidebenzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimide propionate and N- (9 -Acridinyl) maleimide, etc. are mentioned.

Of these compounds (a3), 2-methylcyclohexyl acrylate, t-butyl methacrylate, dicyclopentanyl methacrylate, styrene, p-methoxy styrene, 1,3-butadiene, and the like are preferred in terms of copolymerization reactivity. Do.

The said compound (a3) can be used individually or in mixture of 2 or more types.

In the copolymer (A), the content of the structural unit derived from the compound (a3) is preferably 10 to 80% by weight, particularly preferably 20 to 60% by weight. In this case, when the content rate of the said structural unit is less than 10 weight%, there exists a possibility that the storage stability of a radiation sensitive resin composition may fall, and when it exceeds 80 weight%, developability may fall.

The copolymer (A) used in the present invention is a ratio of the polystyrene reduced weight average molecular weight (hereinafter referred to as "Mw") and the polystyrene reduced number average molecular weight (hereinafter referred to as "Mn") measured by gel permeation chromatography. (Mw / Mn) is 1.7 or less, Preferably it is 1.5 or less. When Mw / Mn exceeds 1.7, the pattern shape of the spacer obtained may deteriorate. In addition, Mw is preferably 2x10 ³ to 1x10 ⁵ , and more preferably 5x10 ³ to 5x10 ⁴ . When Mw is less than 2x10 <^3> , image development margin may not become enough, the residual film ratio etc. of a film obtained may fall, or the pattern shape of a spacer obtained, heat resistance, etc. may deteriorate. On the other hand, when Mw exceeds 1 * 10 < ⁵ >, a sensitivity may fall or a pattern shape may deteriorate. Moreover, Mn becomes like this. Preferably it is 1.2 * 10 <^3> -1 * 10 <^5> , More preferably, it is 2.9 * 10 <^3> -5 * 10 <^4> . The radiation sensitive resin composition containing the said copolymer (A) can form a predetermined pattern shape easily, without developing developing residue at the time of image development.

Moreover, the residual monomer amount measured by the gel permeation chromatography of the copolymer (A) used in the present invention is preferably less than 5.0%, more preferably less than 3.0%, particularly preferably less than 2.0%. By using the copolymer of such residual monomer content, the coating film in which the sublimation at the time of baking is reduced can be obtained.

In this invention, a copolymer (A) can be used individually or in mixture of 2 or more types.

As a solvent used for manufacture of a copolymer (A), alcohol, ether, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol alkyl ether pro, for example Cypionate, aromatic hydrocarbons, ketones and esters;

Specific examples of these alcohols include alcohols such as methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol, and the like;

As ethers, For example, tetrahydrofuran etc .;

As glycol ether, For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc .;

As ethylene glycol alkyl ether acetate, For example, methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate, etc .;

As diethylene glycol, For example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc .;

As propylene glycol monoalkyl ether, For example, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, etc .;

As propylene glycol alkyl ether propionate, For example, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, etc .;

As propylene glycol alkyl ether acetate, For example, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate, etc .;

As an aromatic hydrocarbon, For example, toluene, xylene, etc .;

As the ketone, for example, methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone and the like;

Examples of the esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate and hydroxyacetic acid. Methyl, ethyl hydroxy acetate, butyl hydroxy acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxypropionate methyl, 3-hydroxypropionate, 3-hydroxypropionate, 3-hydroxy Butyl oxypropionate, methyl 2-hydroxy-3-methylbutyrate, methyl methoxyacetate, ethyl methoxyacetate, methoxyacetic acid propyl, butyl acetate, methyl ethoxyacetate, ethyl ethoxyacetate, ethoxyacetic acid propyl Butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, butoxyacetic acid Ethyl butoxy acetate, propyl butoxy acetate, butyl butoxy acetate, 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, 3-methoxy methyl propionate, 3-methoxy ethylpropionate, 3-methoxy propylpropionate, 3-methoxy butyl propionate, 3-ethoxy propylpropionate, 3-ethoxy propylpropionate, 3-ethoxy propylpropionate, 3 Butyl ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, 3-butoxypropionic acid Butyl, can be given a 3-butoxy-propionic acid and 3-propyl-butoxy-propionic acid butyl ester, etc., respectively.

Among them, ethylene glycol alkyl ether acetate, diethylene glycol, propylene glycol monoalkyl ether and propylene glycol alkyl ether acetate are preferred, of which diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol methyl ether and propylene are preferred. Glycol methyl ether acetate is particularly preferred.

(B) polymerizable unsaturated compound

As a polymerizable unsaturated compound (B) in the radiation sensitive resin composition of this invention, the bifunctional or more acrylate and methacrylate (henceforth "(meth) acrylate") are preferable.

As the bifunctional (meth) acrylate, for example, ethylene glycol acrylate, ethylene glycol methacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanedi Aldiacrylate, 1,9-nonanediol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, bisphenoxyethanol Fluorene diacrylate, bisphenoxyethanol fluorene dimethacrylate, and the like.

In addition, as a commercial item of a bifunctional (meth) acrylate, For example, Alonics M-210, M-240, M-6200 (above, manufactured by Toagosei Co., Ltd.), Kayarad HDDA, Kayarard HX-220, East R-604, UX-2201, UX-2301, UX-3204, UX-3301, UX-4101, UX-6101, UX-7101, UX-8101, MU-2100, MU-4001 (Above, Nippon Kayaku Co., Ltd. product), biscoat 260, copper 312, and copper 335HP (above, Osaka Kagaku Kogyo Co., Ltd. product) etc. are mentioned.

As (meth) acrylate more than trifunctional, for example, trimethylol propane triacrylate, trimethylol propane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate , Pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, tri (2-acrylo) Monooxyethyl) phosphate, tri (2-methacryloyloxyethyl) phosphate, or a (meth) acrylate having at least 9 functional groups, a compound having a linear alkylene group and an alicyclic structure and having two or more isocyanate groups; Having one or more hydroxyl groups in it, and three, four or five acryloyloxy groups and / or methacryl And urethane acrylate compounds obtained by reacting a compound having a royloxy group.

Moreover, as a commercial item of the (meth) acrylate more than trifunctional, for example, Alonics M-309, copper-400, copper-402, copper-405, copper-450, copper-1310, copper-1600, copper- 1960, East-7100, East-8030, East-8060, East-8100, East-8530, East-8560, East-9050, Alonics TO-1450 (above, manufactured by Toa Kosei Co., Ltd.), Kayard TMPTA, Copper DPHA, Copper DPCA-20, Copper DPCA-30, Copper DPCA-60, Copper DPCA-120, Copper MAX-3510 (above, manufactured by Nippon Kayaku Co., Ltd.), Biscot 295, Copper 300, Copper 360, Copper New frontier R-1150 (made by Daiichi Kogyo Seiyaku Co., Ltd.) and Kayarrad DPHA-40H as GPT, copper 3PA, copper 400 (above, manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.) or urethane acrylate compounds. Nippon Kayaku Co., Ltd. etc. are mentioned.

In this invention, a polymerizable unsaturated compound can be used individually or in mixture of 2 or more types.

(C) radiation sensitive polymerization initiator

A radiation sensitive polymerization initiator is a component which produces | generates the active species which can react with radiation and can start superposition | polymerization of (B) polymerizable unsaturated compound.

As such a radiation sensitive polymerization initiator, a radiation sensitive radical polymerization initiator is preferable, for example.

As said radiation sensitive radical polymerization initiator, For example, alpha-diketones, such as benzyl and diacetyl; Acyloins such as benzoin; Acyloin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; Thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-sulfonic acid, benzophenone, 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzo Benzophenones such as phenone; Acetophenone, p-dimethylaminoacetophenone, 4- (α, α'-dimethoxyacetoxy) benzophenone, 2,2'-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl Aceto, such as 2-morpholino-1- (4-methylthiophenyl) -1-propanone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one Phenones; Quinones such as anthraquinone and 1,4-naphthoquinone; Halogen compounds such as phenacyl chloride, tribromomethylphenyl sulfone, and tris (trichloromethyl) -s-triazine; 2,4,6-trimethylbenzoyldiphenylphosphineoxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphineoxide and bis (2,4,6-trimethylbenzoyl) phenylforce Acylphosphine oxides such as pinoxide; Peroxides, such as di-t- butyl peroxide, etc. are mentioned.

In addition, as a commercial item of a radiation sensitive radical polymerization initiator, Irgacure (IRGACURE) -124, copper-149, copper-184, copper-369, copper-500, copper-651, copper-819, copper-907 , East-1000, East-1700, East-1800, East-1850, East-2959, Darocur-1116, East-1173, East-1664, East-2959, East-4043 (above, Chiba Specialty Tea) Chemical Co., Ltd., KAYACURE-DETX, Copper-MBP, Copper-DMBI, Copper-EPA, Copper-OA (above, manufactured by Nippon Kayaku Co., Ltd.), LUCIRIN TPO (BASF) BASF Co., Ltd.), VICURE-10, copper-55 (above, STAUFFER Co., Ltd.), Trigonalp 1 (TRIGONALP1; manufactured by AKZO), SANDORAY 1000 (manufactured by Sandoz, Inc.), DEAP (manufactured by APJOHN), Quantacure (QUANTACURE) -PDO, copper-ITX and copper-EPD (above, manufactured by WARD BLEKINSOP) ), And the like.

These radiation-sensitive radical polymerization initiators can be used individually or in mixture of 2 or more types.

Moreover, by using together a radiation sensitive sensitizer with 1 or more types together with the said radiation sensitive radical polymerization initiator, it is also possible to obtain the highly sensitive radiation sensitive resin composition with little inactivation by oxygen in air.

As for the usage-amount of each component in the radiation sensitive resin composition of this invention, (B) polymeric unsaturated compound becomes like this. Preferably it is 10-150 weight part with respect to 100 weight part of copolymers (A), More preferably, it is 20-120 It is a weight part and (C) radiation sensitive polymerization initiator becomes like this. Preferably it is 1-40 weight part, More preferably, it is 3-35 weight part with respect to 100 weight part of copolymers (A).

When the usage-amount of (B) polymerizable unsaturated compound is less than 10 weight part, it will become difficult to form a coating film with a uniform film thickness, and when it exceeds 150 weight part, adhesiveness with a board | substrate will fall. Moreover, when the usage-amount of a (C) radiation sensitive polymerization initiator is less than 1 weight part, heat resistance, surface hardness, or chemical-resistance tends to fall, and when it exceeds 40 weight part, transparency tends to fall.

Arbitrary Additives

The radiation sensitive resin composition of this invention can mix | blend arbitrary additives other than the above, for example, an adhesion | attachment adjuvant, surfactant, a storage stabilizer, a heat resistance improving agent, etc. in the range which does not impair the effect of this invention as needed.

The adhesion assistant is a component used to improve adhesion between the formed spacer and the substrate.

As such an adhesion | attachment adjuvant, the functional silane coupling agent which has reactive functional groups, such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group, and an epoxy group, is preferable, The trimethoxysilyl benzoic acid, (gamma) -methacryloxypropyl trimethoxy as an example thereof is preferable. Silane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltri Methoxysilane, etc. are mentioned.

These adhesion aids can be used individually or in mixture of 2 or more types.

The compounding quantity of an adhesion | attachment adjuvant becomes like this. Preferably it is 20 weight part or less, More preferably, it is 15 weight part or less with respect to 100 weight part of copolymers (A). In this case, when the compounding quantity of an adhesion | attachment adjuvant exceeds 20 weight part, there exists a tendency for image development residue to occur easily.

In addition, the said surfactant is a component used in order to improve applicability | paintability.

As such a surfactant, a fluorine-type surfactant, a silicone type surfactant, etc. are preferable, for example.

As said fluorine-type surfactant, the compound which has a fluoroalkyl group and / or a fluoroalkylene group in 1 or more site | part of a terminal, a main chain, and a side chain is preferable, The example is 1,1,2,2- tetrafluoro-n-octyl (1,1,2,2-tetrafluoro-n-propyl) ether, 1,1,2,2-tetrafluoro-n-octyl (n-hexyl) ether, hexaethylene glycol di (1,1, 2,2,3,3-hexafluoro-n-pentyl) ether, octaethylene glycol di (1,1,2,2-tetrafluoro-n-butyl) ether, hexapropylene glycol di (1,1, 2,2,3,3-hexafluoro-n-pentyl) ether, octapropylene glycoldi (1,1,2,2-tetrafluoro-n-butyl) ether, perfluoro-n-dodecanesulfonic acid Sodium, 1,1,2,2,3,3-hexafluoro-n-decane, 1,1,2,2,8,8,9,9,10,10-decafluoro-n-dodecane Or sodium fluoroalkylbenzenesulfonate, sodium fluoroalkyl phosphate, sodium fluoroalkyl carboxylate, diglycerin tetrakis (fluoro Alkyl polyoxyethylene ether), fluoroalkyl ammonium iodide, fluoroalkyl betaine, other fluoroalkyl polyoxyethylene ether, perfluoroalkyl polyoxyethanol, perfluoroalkyl alkoxylate, fluoro carboxylic acid Low alkyl esters; and the like.

Moreover, as a commercial item of a fluorine-type surfactant, BM-1000, BM-1100 (above, BM CHEMIE company make), Megapack F142D, copper F172, copper F173, copper F183, copper F178, copper F191 , F471, F476 (above, Dai Nippon Ink Chemical Co., Ltd.), Flowride FC-170C, Copper-171, Copper-430, Copper-431 (above, Sumitomo 3M Corporation), Supron S-112, East-113, East-131, East-141, East-145, East-382, Surflon SC-101, East-102, East-103, East-104, East-105, East- 106 (above, Asahi Glass Co., Ltd.), f-top EF301, east 303, east 352 (above, new care Kasei Co., Ltd. make), aftergent FT-100, east -110, east -140A, east -150 , Copper-250, copper-251, copper-300, copper-310, copper-400S, Pleasant FTX-218 and copper-251 (above, manufactured by Neos).

As said silicone type surfactant, Toray silicon DC3PA, copper DC7PA, copper SH11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, copper SH-190, copper SH-193, copper SZ-6032, copper SF-8428 , DC-57, DC-190 (above, manufactured by Toray Dow Corning Silicon Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460 and TSF-4452 (more Commercially available, such as GE Toshiba Silicone Co., Ltd., may be mentioned.

Moreover, as surfactant other than the above, Polyoxyethylene alkyl ether, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene-n-octylphenyl ether and polyoxyethylene-n-nonylphenyl ether; Nonionic surfactant or organosiloxane polymer KP341 (made by Shin-Etsu Chemical Co., Ltd.), such as polyoxyethylene dialkyl ester, such as polyoxyethylene dilaurate and polyoxyethylene distearate, (meth) acryl Acid copolymer polyflow N0.57 and copper N0.95 (above, manufactured by Kyoeisha Chemical Co., Ltd.) and the like.

These surfactant can be used individually or in mixture of 2 or more types.

The blending amount of the surfactant is preferably 1.0 part by weight or less, more preferably 0.5 part by weight or less based on 100 parts by weight of the copolymer (A). In this case, when the compounding quantity of surfactant exceeds 1.0 weight part, there exists a tendency for film nonuniformity to arise easily.

Examples of the storage stabilizer include sulfur, quinones, hydroquinones, polyoxy compounds, amines and nitronitroso compounds, and more specifically, 4-methoxyphenol and N-nitroso-N-phenylhydride. Axyl amine aluminum etc. are mentioned.

These storage stabilizers can be used individually or in mixture of 2 or more types.

The compounding quantity of a storage stabilizer becomes like this. Preferably it is 3.0 weight part or less, More preferably, it is 0.5 weight part or less with respect to 100 weight part of copolymers (A). In this case, when the compounding quantity of a storage stabilizer exceeds 3.0 weight part, there exists a possibility that a sensitivity may fall and a pattern shape may deteriorate.

In addition, examples of the heat resistance improver include N- (alkoxymethyl) glycoluril compounds, N- (alkoxymethyl) melamine compounds, compounds having two or more epoxy groups, and the like.

Examples of the N- (alkoxymethyl) glycoluril compound include N, N, N, N-tetra (methoxymethyl) glycoluril, N, N, N, N-tetra (ethoxymethyl) glycoluril, N, N, N, N-tetra (n-propoxymethyl) glycoluril, N, N, N, N-tetra (i-propoxymethyl) glycoluril, N, N, N, N-tetra (n-butoxy Methyl) glycoluril, N, N, N, N-tetra (t-butoxymethyl) glycoluril, and the like.

Among these N- (alkoxymethyl) glycoluril compounds, N, N, N, N-tetra (methoxymethyl) glycoluril is preferable.

Examples of the N- (alkoxymethyl) melamine compound include N, N, N, N, N, N-hexa (methoxymethyl) melamine, N, N, N, N, N, N-hexa (ethoxymethyl ) Melamine, N, N, N, N, N, N-hexa (n-propoxymethyl) melamine, N, N, N, N, N, N-hexa (i-propoxymethyl) melamine, N, N And N, N, N, N-hexa (n-butoxymethyl) melamine and N, N, N, N, N, N-hexa (t-butoxymethyl) melamine and the like.

Among these N- (alkoxymethyl) melamine compounds, N, N, N, N, N, N-hexa (methoxymethyl) melamine is preferable, and as commercially available products thereof, for example, Nicarac N-2702 and MW-30M (As above, Sanwa Chemical Co., Ltd. product) etc. are mentioned.

Examples of the compound having two or more epoxy groups include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and propylene glycol di. Glycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycid Dil ether, glycerin diglycidyl ether, trimethylol propane triglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol A diglycidyl ether, and the like.

Moreover, as a commercial item of the compound which has two or more epoxy groups, for example, epolite 40E, copper 100E, copper 200E, copper 70P, copper 200P, copper 400P, copper 1500NP, copper 80MF, copper 100MF, copper 1600, copper 3002 and East 4000 (above, Kyoesha Chemical Co., Ltd. product) etc. are mentioned.

These heat resistance improvers can be used individually or in mixture of 2 or more types.

Radiation  Resin composition

The radiation sensitive resin composition of this invention is manufactured by mixing uniformly the above-mentioned copolymer (A), (B) component and (C) component, and the other component added arbitrarily as mentioned above. The radiation-sensitive resin composition of the present invention is preferably dissolved in a suitable solvent and used in a solution state. For example, the radiation sensitive resin composition of a solution state can be manufactured by mixing copolymer (A), (B) component, (C) component, and the other component added arbitrarily at predetermined ratio.

As a solvent used for manufacture of the radiation sensitive resin composition of this invention, each component of a copolymer (A), (B) component and (C) component, and the other component mix | blended arbitrarily is melt | dissolved uniformly, What does not react is used.

As such a solvent, the same thing as what was illustrated as a solvent which can be used in order to manufacture the copolymer (A) mentioned above is mentioned.

Among these solvents, for example, alcohols, glycol ethers, ethylene glycol alkyl ether acetates, esters, and diethylene glycol are preferably used in view of solubility of each component, reactivity with each component, and ease of coating film formation. Among them, for example, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethylmethyl Ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl methoxy propionate and ethyl ethoxypropionate can be particularly preferably used.

Moreover, in order to raise the in-plane uniformity of a film thickness with the said solvent, a high boiling point solvent can be used together. As a high boiling point solvent which can be used together, it is N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpi, for example. Ralidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, male Diethyl acid, gamma -butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate. Of these, N-methylpyrrolidone, γ-butyrolactone and N, N-dimethylacetamide are preferable.

When using a high boiling point solvent together as a solvent of the radiation sensitive resin composition of this invention, the usage-amount is preferably 50 weight% or less, More preferably, 40 weight% or less, More preferably, 30 weight% with respect to solvent whole quantity. It can be set as follows. When the usage-amount of a high boiling point solvent exceeds this usage-amount, the film thickness uniformity, a sensitivity, and a residual film ratio of a coating film may fall.

When producing the radiation-sensitive resin composition of the present invention as a solution state, the total amount of components other than the solvent occupied in the solution, that is, the copolymer (A), (B) component and (C) component and other components optionally added The ratio can be arbitrarily set according to the purpose of use or the value of the desired film thickness, and the like, for example, 5 to 50% by weight, preferably 10 to 40% by weight, more preferably 15 to 35% by weight.

The composition solution thus prepared can be used after being filtered using a Millipore filter having a pore size of about 0.5 μm or the like.

Spacer  Formation method

Next, the method of forming the spacer of this invention using the radiation sensitive resin composition of this invention is demonstrated.

The method of forming the spacer of the present invention,

(1) process of forming the coating film of the radiation sensitive resin composition of this invention on a board | substrate,

(2) irradiating at least a part of the coating film with radiation;

(3) developing process, and

(4) heating process

It is characterized by performing in the order described above.

Hereinafter, each of these steps will be described in order.

(1) of the present invention Radiation  Process of forming coating film of resin composition on board

A transparent conductive film is formed on one surface of a transparent substrate, and after apply | coating the composition solution of the radiation sensitive resin composition of this invention on the said transparent conductive film, a film is formed by heating (prebaking) a coating surface.

As a transparent substrate used for formation of a spacer, a glass substrate, a resin substrate, etc. are mentioned, for example, More specifically, Glass substrates, such as a soda-lime glass and an alkali free glass; And resin substrates containing plastics such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate and polyimide.

Examples of the transparent conductive film provided on one surface of the transparent substrate include an NESA film containing tin oxide (SnO ₂ ) (registered trademark of US PPG), and an ITO containing indium tin oxide (In ₂ O ₃ -SnO ₂ ). And the like.

It does not specifically limit as a coating method of a composition solution, For example, suitable methods, such as a spraying method, the roll coating method, the spin coating method (spin coating method), the slit die coating method, the bar coating method, and the inkjet coating method, can be used, In particular, the spin coating method and the slit die coating method are preferable.

In addition, although the conditions of prebaking differ according to the kind, compounding ratio, etc. of each component, it is about 1 to 15 minutes at 70-120 degreeC normally.

(2) irradiating at least a part of the coating film with radiation

Subsequently, at least part of the formed film is exposed to radiation. In this case, when exposing to a part of film, it exposes through the photomask which has a predetermined pattern.

As the radiation used for the exposure, visible light, ultraviolet light and far ultraviolet light can be used. Radiation with a wavelength in the range of 190 to 450 nm is preferred, particularly radiation comprising 365 nm ultraviolet radiation.

The exposure dose is a value measured by an illuminometer (OAI Model 356, manufactured by OAI Optical Associates Inc.) of the intensity at a wavelength of 365 nm of the radiation to be exposed, and preferably 100 to 10,000 J / m 2. More preferably, it is 1,500-3,000 J / m <2>.

(3) developing process

Next, by developing the film after exposure, an unnecessary part is removed and a predetermined pattern is formed.

As a developing solution used for image development, For example, inorganic alkalis, such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; Aliphatic primary amines such as ethylamine and n-propylamine: aliphatic secondary amines such as diethylamine and di-n-propylamine; Aliphatic tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine and triethylamine; Pyrrole, piperidine, N-methylpiperidine, N-methylpyrrolidine, 1,8-diazabicyclo [5.4.0] -7-undecene and 1,5-diazabicyclo [4.3.0] Alicyclic tertiary amines such as -5-nonene; Aromatic tertiary amines such as pyridine, collidine, lutidine and quinoline; Alkanolamines such as dimethylethanolamine, methyldiethanolamine and triethanolamine; Aqueous solutions of alkaline compounds, such as quaternary ammonium salts, such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, can be used.

In addition, a suitable amount of water-soluble organic solvents and / or surfactants such as methanol and ethanol can be added to the aqueous solution of the alkaline compound.

The developing method may be any one of a puddle method, a dipping method and a shower method, and the developing time is usually about 10 to 180 seconds at room temperature.

After the development, for example, washing with running water is performed for 30 to 90 seconds, and then a desired pattern is formed by, for example, air drying with compressed air or compressed nitrogen.

(4) heating process

Subsequently, the obtained pattern is heated at a predetermined temperature, for example, 100 to 160 ° C. for a predetermined time, for example, 5 to 30 minutes on a hot plate, for example 30 to 180 in an oven, by a heating device such as a hot plate and an oven. By heating for a minute (post-baking), a predetermined spacer can be obtained.

In the conventional radiation-sensitive resin composition used for forming the spacer, the obtained spacer cannot exhibit sufficient performance unless the heat treatment is performed at a temperature of about 180 to about 200 ° C. or more, but the radiation-sensitive resin composition of the present invention has a conventional heating temperature. It can be made at a lower temperature, and as a result, a spacer excellent in various performances such as compressive strength, rubbing resistance at the time of liquid crystal alignment, and adhesion to a transparent substrate can be obtained without causing yellowing or deformation of the resin substrate.

Although a synthesis example and an Example are shown to the following and this invention is demonstrated to it further more concretely, this invention is not limited to a following example.

<Measurement of Molecular Weight of Copolymer by Gel Permeation Chromatography>

Device: GPC-101 (manufactured by Showa Denko Co., Ltd.)

Column: GPC-KF-801, GPC-KF-802, GPC-KF-803, and GPC-KF-804

Mobile phase: Tetrahydrofuran comprising 0.5% by weight phosphoric acid.

Of copolymer (A) Synthesis Example

Synthesis Example 1

1 part by weight of 2,2'-azobis (2,4-dimethylvaleronitrile), 4 parts by weight of cumyldithiobenzoate and 50 parts by weight of diethylene glycol ethylmethyl ether were charged into a flask equipped with a cooling tube and a stirrer. It was. Subsequently, 20 parts by weight of styrene, 17 parts by weight of methacrylic acid, 18 parts by weight of tricyclodecanyl methacrylate, and 45 parts by weight of glycidyl methacrylate were replaced with nitrogen, followed by slowly stirring. The temperature of the solution was raised to 60 ° C. and maintained at this temperature for 24 hours, followed by the addition of 3 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) for an additional 4 hours at 60 ° C. It stirred, and added 200 weight part of diethylene glycol ethyl methyl ether, and obtained the polymer solution containing a copolymer (A-1). As for the polystyrene reduced weight average molecular weight (Mw) of copolymer (A-1), 11,000 and molecular weight distribution (Mw / Mn) were 1.4 and the residual monomer was 2.0 weight%. Solid content concentration of the polymer solution was 28.4 weight%.

Synthesis Example 2

A flask equipped with a cooling tube and a stirrer was charged with 1 part by weight of 2,2'-azobis (2,4-dimethylvaleronitrile), 4 parts by weight of cumyldithiobenzoate and 50 parts by weight of diethylene glycol ethylmethyl ether. . Subsequently, 5 parts by weight of styrene, 16 parts by weight of methacrylic acid, 34 parts by weight of tricyclodecanyl methacrylate, 35 parts by weight of glycidyl methacrylate and 5 parts by weight of methylglycidyl methacrylate were injected, followed by nitrogen substitution. After slowly stirring was started. The temperature of the solution was raised to 60 ° C. and maintained at this temperature for 24 hours, followed by addition of 3 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) for an additional 4 hours at 60 ° C. Stirring was carried out, and 200 weight part of diethylene glycol ethyl methyl ether was added, and the polymer solution containing a copolymer (A-2) was obtained. Mw of the copolymer (A-2) was 12,000, molecular weight distribution (Mw / Mn) was 1.4 and the residual monomer was 2.0 wt%. Solid content concentration of the polymer solution was 28.6 weight%.

Synthesis Example 3

In Synthesis Example 1, a solution of Copolymer (A-3) was obtained according to Synthesis Example 1 except that S-cyanomethyl-S-dodecyltrithiocarbonate was used instead of cumyldithiobenzoate. As for the polystyrene reduced weight average molecular weight (Mw) of copolymer (A-3), 10,000, molecular weight distribution (Mw / Mn) were 1.2, and the residual monomer was 1.5 weight%. Solid content concentration of the polymer solution was 28.2 weight%.

Synthesis Example 4

In the synthesis example 2, the polymer solution containing copolymer (A-4) was obtained according to the synthesis example 2 except having used pyrazole-1-dithiocarboxylic acid phenyl-methyl ester instead of cumyldithiobenzoate. . The polystyrene reduced weight average molecular weight (Mw) of the copolymer (A-4) was 1.3, and the molecular weight distribution (Mw / Mn) was 1.3 and the residual monomer was 1.4 wt%. Solid content concentration of the polymer solution was 28.5 weight%.

Synthesis Example 5

In the synthesis example 1, the polymer solution containing a copolymer (A-5) was obtained according to the synthesis example 1 except having used the following dithio ester instead of cumyldithiobenzoate. The polystyrene reduced weight average molecular weight (Mw) of the copolymer (A-5) was 12,000, the molecular weight distribution (Mw / Mn) was 1.2, and the residual monomer was 1.4 wt%. Solid content concentration of the polymer solution was 28.0 weight%.

Synthesis Example 6

In the synthesis example 2, the polymer solution containing copolymer (A-6) was obtained according to the synthesis example 2 except having used the following xanthate instead of cumyldithiobenzoate. As for the polystyrene reduced weight average molecular weight (Mw) of copolymer (A-6), 11,500, molecular weight distribution (Mw / Mn) were 1.3, and the residual monomer was 1.4 weight%. Solid content concentration of the polymer solution was 28.5 weight%.

Comparative Synthesis Example 1

5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol methylethyl ether were introduced into a flask equipped with a cooling tube and a stirrer, followed by 20 parts by weight of styrene and methacryl 17 parts by weight of acid, 18 parts by weight of dicyclopentanyl methacrylate, and 45 parts by weight of glycidyl methacrylate were introduced and replaced with nitrogen, and then the temperature of the reaction solution was raised to 70 ° C. with slow stirring, and the temperature was increased for 4 hours. The polymer solution containing copolymer (a-1) was obtained by hold | maintaining and polymerizing for a while. Mw of the copolymer (a-1) was 13,000, the molecular weight distribution (Mw / Mn) was 2.4, and the residual monomers were 7.1 wt%. Solid content concentration of the polymer solution was 29.5 weight%.

Example 1

(I) Preparation of a radiation sensitive resin composition

A solution containing the polymer (A-1) as the component (A) synthesized in Synthesis Example 1, corresponding to 100 parts by weight (solid content) of the polymer (A-1), and dipentaerythritol as the component (B) 80 parts by weight of hexaacrylate (trade name Kayarrad DPHA, manufactured by Nippon Kayaku Co., Ltd.), (C) component 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5' -10 parts by weight of tetraphenylbiimidazole, 15 parts of 2-methyl [4- (methylthio) phenyl] -2-morpholino-1-propane (trade name Irugacure 907, manufactured by Chiba Specialty Chemical Co., Ltd.) Part, 10 parts by weight of 4,4'-bis (dimethylamino) benzophenone as a radiation sensitizer, 5 parts by weight of 2-mercaptobenzothiazole, and γ-glycidoxypropyltrimethoxysilane 5 as an adhesion aid. 0.5 parts by weight of FTX-218 (trade name, manufactured by Neos) as a weight part, surfactant, 0.5 parts by weight of 4-methoxyphenol as a storage stabilizer were mixed, and the profile was changed to a solid content concentration of 30% by weight. It was dissolved in monomethyl ether acetate, and an opening diameter of 0.5 mm ㎛ filtered through a pore filter to prepare a composition solution.

(II) Formation of spacer

After apply | coating the said composition solution using a spinner on the alkali free glass substrate, it prebaked for 3 minutes on the 90 degreeC hotplate, and formed the film of 6.0 micrometers in film thicknesses.

Subsequently, an ultraviolet-ray having an intensity of 250 W / m 2 at 365 nm was exposed for 10 seconds through a photomask having a remaining pattern of 10 µm each side on the obtained film. Then, after developing for 60 second at 25 degreeC with the 0.05 weight% aqueous solution of potassium hydroxide, it wash | cleaned with pure water for 1 minute. Thereafter, post-baking was performed at 150 ° C. for 120 minutes in an oven to form a spacer of a predetermined pattern.

(III) evaluation of resolution

When forming a pattern in said (II), the case where the remaining pattern was resolved was evaluated as good ((circle)) and the case where it was not resolved as defect (x). The evaluation results are shown in Table 2.

(IV) evaluation of sensitivity

With respect to the pattern obtained in the above (II), the case where the residual film ratio (film thickness after development x 100 / initial film thickness) after development was 90% or more was evaluated as good (○) and less than 90% as poor (×). The evaluation results are shown in Table 2.

(V) Evaluation of pattern shape

The cross-sectional shape of the pattern obtained by said (II) was observed with the scanning electron microscope, and it evaluated by any of A-D shown in FIG. At this time, when the pattern edge is a forward taper shape or a vertical shape like A or B, it can be said that the pattern shape as a spacer is favorable. On the other hand, as shown in C, the sensitivity is insufficient, the residual film ratio is low, the cross-sectional dimensions are smaller than those of A and B, and the pattern shape as a spacer when the bottom of the cross-sectional shape is a flat semiconvex lens image This defect is poor, and even when the cross-sectional shape is reverse tapered as shown in D, there is a high possibility that the pattern is peeled off during the subsequent rubbing treatment, so that the pattern shape as a spacer is made poor. The evaluation results are shown in Table 2.

(VI) Evaluation of compressive strength.

About the pattern obtained by said (II), the deformation amount at the time of applying the load of 10 mN by 50 micrometer diameter planar indenter using a micro compression tester (MCTM-200, the Shimadzu Corporation make) It measured at the temperature of 23 degreeC. When this value is 0.5 or less, it can be said that compressive strength is favorable. The evaluation results are shown in Table 2.

(VII) evaluation of rubbing resistance

After apply | coating AL3046 (brand name, JSR Corporation make) to the board | substrate with the pattern obtained by said (II) using a liquid crystal aligning film coating machine as a liquid crystal aligning agent, it dried at 180 degreeC for 1 hour, and dried The coating film of the aligning agent of the film thickness of 0.05 micrometer was formed. Then, using the rubbing machine which has the roll which wound the cloth made from polyamide to this coating film, the rubbing process was performed at roll rotation speed of 500 rpm and stage movement speed of 1 cm / sec. At this time, the presence or absence of shaving or peeling of the pattern was evaluated. The evaluation results are shown in Table 2.

(VIII) Evaluation of adhesion

Except not using the mask of the remaining pattern, it carried out similarly to said (II), and formed the cured film. Then, during the adhesion test of JISK-5400 (1900) 8.5, it evaluated by the 8.5 * 2 checker scale tape method. At this time, Table 2 shows the number of remaining checkerboard ticks among the 100 checkerboard ticks.

(IX) Evaluation of Sublimation

The composition solution was applied onto the silicon substrate using a spinner, and then prebaked at 90 ° C. on a hot plate for 2 minutes to form a coating film having a film thickness of 3.0 μm. It exposed to the obtained coating film so that accumulated irradiation amount might be 3,000 J / m <2> with Canon PLA-501F exposure machine (ultra high pressure mercury lamp), and this silicon substrate was heated at 220 degreeC in the clean oven for 1 hour, and the cured film was obtained. A bare silicon wafer for cooling was mounted at an interval of one centimeter above the obtained cured film, and the heating treatment was performed at 230 ° C. for 1 hour on a hot plate. After continuously processing 20 sheets of the silicon substrate on which the cured film was formed separately without replacing the cooling bare silicon wafer, the presence or absence of a sublimation adhered to the bare silicon was visually verified. When the sublimation is not confirmed, it can be said that the sublimation evaluation is good. The evaluation results are shown in Table 2.

Examples 2-14 and Comparative Examples 1-3

Each composition solution was produced and evaluated similarly to Example 1 except having used each component shown in Table 1 as (A)-(C) component and a radiation sensitive sensitizer. The evaluation results are shown in Table 2.

In Table 1, each component other than a copolymer (A-1), a copolymer (A-2), and a copolymer (a-1) is as follows.

(B) component

B-1: dipentaerythritol hexaacrylate

(C) component

C-1: 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole

C-2: 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole

C-3: 2-methyl [4- (methylthio) phenyl] -2-morpholino-1-propanone

C-4: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1

(Radiation sensitizer)

D-1: 4,4'-bis (dimethylamino) benzophenone

D-2: 2-mercaptobenzothiazole

D-3: pentaerythritol tetra (mercaptoacetate)

The radiation-sensitive resin composition of the present invention has a high sensitivity and high resolution, and can easily form a spacer excellent in various performances such as pattern shape, compressive strength, rubbing resistance, and adhesion to a transparent substrate, and heating after development at the time of spacer formation. Not only is it possible to lower the temperature, but also does not cause yellowing or deformation of the resin substrate, so that the amount of sublimation is low and the possibility of contaminating the device or panel is reduced.

Claims (6)

(A) A copolymer which has a carboxyl group and an epoxy group, and ratio (Mw / Mn) of the polystyrene reduced weight average molecular weight (Mw) and the polystyrene reduced number average molecular weight (Mn) measured by gel permeation chromatography is 1.7 or less, (B) superposition | polymerization A radiation sensitive resin composition containing a sex unsaturated compound and (C) a radiation sensitive polymerization initiator, and for spacer formation. The copolymer (A) according to claim 1, wherein the copolymer (A) is other than (a1) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride, (a2) epoxy group-containing unsaturated compound, and (a3) component (a1) and component (a2) A radiation sensitive resin composition obtained by living radical polymerization of the polymerizable mixture containing an unsaturated compound of. The radiation sensitive resin composition of Claim 1 or 2 whose copolymer (A) is a copolymer obtained by the living radical polymerization which used the thiocarbonylthio compound as a control agent. (delete) (1) process of forming the coating film of the radiation sensitive resin composition of Claim 1 on a board | substrate, (2) irradiating at least a part of the coating film with radiation; (3) developing process, and (4) heating process Is carried out in the order described above. The spacer formed by the method of Claim 5.

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