KR20070070286A - Radiation sensitive resin composition, spacer for display panel, and display panel - Google Patents

Abstract

Provided is a radiation sensitive resin composition, which reproduces a desired dimension of a mask pattern with high sensitivity, has excellent adhesion to a substrate, and accomplishes a sufficient spacer shape and film thickness even under a low exposure dose, and imparts excellent compression strength to a spacer. The radiation sensitive resin composition comprises: [A] a copolymer of (a1) an ethylenically unsaturated carboxylic acid and/or ethylenically unsaturated carboxylic anhydride, (a2) an epoxy group-containing ethylenically unsaturated compound, and (a3) another ethylenically unsaturated compound; [B] a polymerizable compound having an ethylenically unsaturated bond; and [C] a radiation sensitive polymerization initiator essentially comprising a compound represented by the following formula(1) or (2). In formulae(1) and (2), each R^1 represents an alkyl or phenyl group, each R^2 represents H, an alkyl or phenyl group; and R^3 represents H or an alkyl group.

Description

Radiation sensitive resin composition, spacer for display panel, and display panel {Radiation Sensitive Resin Composition, Spacer for Display Panel, and Display Panel}

1 is a diagram illustrating a cross-sectional shape of a pattern.

The present invention relates to a radiation sensitive resin composition, a spacer for a display panel and a display panel, and more particularly, a radiation sensitive resin composition suitable as a material for forming a spacer used for a display panel such as a liquid crystal display panel or a touch panel, A display panel spacer formed from the composition, and a display panel comprising the spacer.

In the liquid crystal display panel, spacer particles such as glass beads and plastic beads having a predetermined particle diameter are conventionally used to maintain a constant gap (cell gap) between two substrates. However, these spacer particles are formed on a transparent substrate such as a glass substrate. Since the particles are irregularly distributed, the presence of the spacer particles in the pixel formation region causes a phenomenon in which the spacer particles are imprinted, or incident light is scattered and the contrast of the liquid crystal panel is lowered.

In order to solve these problems, a method of forming spacers by photolithography has been adopted. In this method, a photosensitive resin composition or a radiation sensitive resin composition (hereinafter, collectively referred to as "radiation sensitive resin composition") is applied onto a substrate and exposed to radiation such as ultraviolet rays through a predetermined mask. The above-described problem is basically solved because the spacers can be formed only at predetermined positions other than the pixel formation region by developing after the development.

By the way, when forming a spacer by photolithography on the board | substrate used for an actual spacer formation process, for example, a color filter, etc., a proximity exposure machine is often used. In the case of the proximity exposure, a constant cell gap is provided between the mask and a substrate on which a film such as a radiation-sensitive resin composition is formed. The cell gap is ideally exposed in the same pattern as the mask. Since the radiation filled with nitrogen and transmitted through the opening (transparent portion) of the mask diffuses and spreads in the gap portion, there is a problem that the exposure is wider than the design size of the mask pattern.

Thus, in order to solve such a problem, the present applicant has already disclosed in Japanese Patent Laid-Open No. 2001-261761 as 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (as a photopolymerization initiator of the photosensitive resin composition. By using O-benzoyl oxime), it is revealed that the design size of the mask pattern can be faithfully reproduced even by proximity exposure, and a display panel spacer excellent in strength, heat resistance, and the like can be formed.

In addition, although the cell gap needs to be controlled more accurately as the display panel is enlarged, when the adhesion of the film formed of the radiation-sensitive resin composition for spacers or the like to the substrate is insufficient, the formed spacer deviates from the substrate, resulting in a cell gap. It is impossible to keep accurate. In addition, in the display panel, the pixel aperture ratio is increasing, and as a result, the area of the black matrix region in which the spacer can be disposed is also getting smaller. Therefore, even in the case where the spacer enters the pixel region to some extent, higher transparency is required for the spacer in order not to damage the color tone of the pixel.

However, in the conventional radiation-sensitive resin composition and the like used in the formation of spacers, including those described in Japanese Patent Laid-Open No. 2001-261761, it cannot be said that they are still sufficient in terms of adhesion to the substrate and transparency. The development of the radiation sensitive resin composition etc. which had both was strongly desired.

In recent years, from the viewpoint of increasing the area of the display panel, improving the productivity, and the like, enlargement of mother glass substrates has been progressing. In the conventional substrate size (about 680 × 880 mm), since the substrate size is smaller than the mask size, it is possible to cope with the batch exposure method. However, in the case of a large substrate (for example, about 1,500 × 1,800 mm), the substrate size It is almost impossible to produce mask sizes of the same degree, and it is difficult to cope with the batch exposure method.

Therefore, a step exposure method is proposed as an exposure method that can cope with a large substrate. However, in the step exposure method, it is necessary to expose several times for each substrate, and since the time required for positioning and step movement at the time of each exposure, the work throughput may be reduced compared with the case of the batch exposure method. In addition, although the exposure sensitivity of about 3,000 J / m <2> was accepted with the package exposure system, it is calculated | required that the exposure sensitivity shall be 1,500 J / m <2> or less in the step exposure system. However, in the conventional radiation sensitive resin composition used for formation of a spacer, it was difficult to achieve sufficient spacer shape and film thickness in the exposure amount of 1,500 J / m <2> or less.

Therefore, the object of the present invention is to faithfully reproduce the design size of the mask pattern with high sensitivity, excellent adhesion to the substrate, and can achieve sufficient spacer shape and film thickness even at an exposure amount of 1,500 J / ㎡ or less, compressive strength, It is providing the radiation sensitive resin composition which can form the spacer for display panels excellent also in rubbing tolerance.

The present invention firstly,

[A] (a1) Copolymer of ethylenically unsaturated carboxylic acid and / or ethylenically unsaturated carboxylic anhydride with (a2) epoxy group-containing ethylenically unsaturated compound and (a3) other ethylenically unsaturated compound,

[B] a polymerizable compound having an ethylenically unsaturated bond, and

[C] A radiation-sensitive resin composition (hereinafter referred to as "radiation-sensitive resin composition (A)") containing a radiation-sensitive polymerization initiator containing as an essential component a compound represented by the following formula (1) or (2): ).

In formulas (1) and (2), each R ¹ independently of each other represents a linear, branched, or cyclic alkyl or phenyl group having 1 to 12 carbon atoms, and each R ² independently represents a hydrogen atom, a straight chain having 1 to 12 carbon atoms, Represents a branched or cyclic alkyl group or a phenyl group, and each R ³ independently represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, and each R ⁴ , each R ⁵ and each R ⁶ is Independently of each other, a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms is represented. Provided that the alkyl groups of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each a substituent selected from the group of linear, branched or cyclic alkoxyl groups, phenyl groups and halogen atoms having 1 to 6 carbon atoms, respectively. And a phenyl group of R ¹ and R ² may each be a straight, branched or cyclic alkyl group having 1 to 6 carbon atoms, a straight, branched or cyclic alkoxyl group having 1 to 6 carbon atoms, a phenyl group and a halogen atom, respectively. It may be substituted with a substituent selected from the group of.

Secondly, the present invention includes a spacer for a display panel formed of the radiation-sensitive resin composition.

A third aspect of the present invention includes a display panel including the spacer for the display panel.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

Radiation-sensitive resin composition (A)

Copolymer [A]-

[A] component in a radiation sensitive resin composition (A) is (a1) ethylenically unsaturated carboxylic acid and / or ethylenically unsaturated carboxylic anhydride (henceforth "unsaturated carboxylic acid type compound (a1)"). ) And (a2) an epoxy group-containing ethylenically unsaturated compound (hereinafter referred to as "epoxy group-containing unsaturated compound (a2)") and (a3) other ethylenically unsaturated compounds (hereinafter referred to as "other unsaturated compounds (a3)") Copolymers (hereinafter referred to as "copolymer [A]").

Among the components constituting the copolymer [A], examples of the unsaturated carboxylic acid compound (a1) include acrylic acid, methacrylic acid, crotonic acid, succinic acid mono (2-acryloyloxyethyl) and succinic acid mono ( Monocarboxylic acids such as 2-methacryloyloxyethyl), phthalic acid mono (2-acryloyloxyethyl), and phthalic acid mono (2-methacryloyloxyethyl); Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; Anhydrides of the said dicarboxylic acid, etc. are mentioned.

Among these unsaturated carboxylic acid compounds (a1), acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity, solubility in an aqueous alkali solution of the obtained copolymer [A], and availability.

In copolymer [A], an unsaturated carboxylic acid compound (a1) can be used individually or in mixture of 2 or more types.

The content of the repeating unit derived from the unsaturated carboxylic acid compound (a1) in the copolymer [A] is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, particularly preferably 15 to 30% by weight. %to be. In this case, when the content rate of the repeating unit derived from an unsaturated carboxylic acid compound (a1) is less than 5 weight%, there exists a tendency for the solubility to aqueous alkali solution to fall, while exceeding 40 weight% to the aqueous alkali solution of the copolymer obtained. There is a fear that the solubility in water becomes too large.

As the epoxy group-containing unsaturated compound (a2), for example, glycidyl acrylate, 2-methylglycidyl acrylate, 3,4-epoxy acrylate, 6,7-epoxyheptyl acrylate, 3,4-epoxycyclo acrylate Hexyl, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl methacrylate, 3,4-epoxycyclohexyl methacrylate (Meth) acrylic acid epoxyalkyl esters such as these; α-ethyl acrylate glycidyl, α-ethyl acrylate 2-methylglycidyl, α-ethyl acrylate 3,4-epoxybutyl, α-ethyl acrylate 6,7-epoxyheptyl, α-ethyl acrylate 3,4-epoxy Α-alkylacrylic acid epoxyalkyl esters such as cyclohexyl, α-n-propyl acrylate glycidyl and α-n-butyl acrylate glycidyl; unsaturated glycidyl ethers such as o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether.

Among these epoxy group-containing unsaturated compounds (a2), methacrylate glycidyl, methacrylic acid 2-methylglycidyl, methacrylic acid 6,7-epoxyheptyl, o-vinyl from the viewpoint of copolymerization reactivity and the strength of the spacer. Benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, etc. are preferable.

In copolymer [A], an epoxy group containing unsaturated compound (a2) can be used individually or in mixture of 2 or more types.

The content of the repeating unit derived from the epoxy group-containing unsaturated compound (a2) in the copolymer [A] is preferably 10 to 70% by weight, more preferably 20 to 60% by weight, particularly preferably 30 to 50% by weight. to be. In this case, when the content rate of the repeating unit derived from an epoxy group containing unsaturated compound (a2) is less than 10 weight%, the compressive strength of the spacer obtained tends to fall, and when it exceeds 70 weight%, the storage stability of the copolymer obtained will fall. Tend to.

Moreover, as another unsaturated monomer (a3), for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, cyclohexyl acrylate, acrylic acid 2-methylcyclohexyl, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate Alkyl (meth) acrylates such as cyclohexyl methacrylate and 2-methylcyclohexyl methacrylate; Tricyclo [5.2.1.0 ^2,6 ] decane-8-yl, acrylic acid 2- (tricyclo [5.2.1.0 ^2,6 ] decane-8-yloxy) ethyl, isoboroyl acrylate, tricyclomethacrylate Other (meth) s, such as [5.2.1.0 ^2,6 ] decane-8-yl, methacrylic acid 2- (tricyclo [5.2.1.0 ^2,6 ] decane-8-yloxy) ethyl, isoboroyl methacrylate Acrylic acid alicyclic esters; Aryl esters or aralkyl esters of (meth) acrylic acid, such as phenyl acrylate, benzyl acrylate, phenyl methacrylate and benzyl methacrylate; (Meth) acrylic-acid hydroxyalkyl esters, such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate; Tetrahydrofuryl acrylate, tetrahydrofurfuryl acrylate, (tetrahydropyran-2-yl) methyl acrylate, tetrahydrofuryl methacrylate, tetrahydrofurfuryl methacrylate, (tetrahydropyran-2-yl) Hetero five-membered ring esters or hetero six-membered ring esters containing an oxygen atom of (meth) acrylic acid such as methyl methacrylate; Unsaturated dicarboxylic acid dialkyl esters such as diethyl maleate, diethyl fumarate and diethyl itaconic acid; vinyl aromatic compounds such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, and p-methoxystyrene ; In addition to conjugated diene-based compounds such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride, Vinyl acetate etc. are mentioned.

Among these other unsaturated compounds (a3), 2-methylcyclohexyl acrylate, t-butyl methacrylate and tricyclo methacrylate [5.2.2] from the viewpoint of copolymerization reactivity and solubility in the aqueous alkali solution of the copolymer [A] obtained. 1.0 ^2,6 ] decane-8-yl, tetrahydrofurfuryl methacrylate, styrene, p-methoxystyrene, 1,3-butadiene and the like are preferable.

In the copolymer [A], another unsaturated compound (a3) can be used individually or in mixture of 2 or more types.

The content of the repeating units derived from the other unsaturated compound (a3) in the copolymer [A] is preferably 10 to 70% by weight, more preferably 20 to 50% by weight, particularly preferably 30 to 50% by weight. In this case, when the content rate of the repeating unit derived from another unsaturated compound (a3) is less than 10 weight%, there exists a tendency for the storage stability of the copolymer obtained to fall, while when it exceeds 70 weight% with respect to the aqueous alkali solution of the copolymer obtained. Solubility tends to decrease.

The copolymer [A] has a carboxyl group and / or a carboxylic anhydride group and an epoxy group, has appropriate solubility in aqueous alkali solution, and can be easily cured by heating without using a special curing agent. The radiation-sensitive resin composition (a) containing the coalescence can easily form a spacer having a predetermined pattern without developing residue or film wear during development by a developer containing an aqueous alkali solution.

Copolymer [A] can be produced by, for example, polymerizing an unsaturated carboxylic acid compound (a1), an epoxy group-containing unsaturated compound (a2) and another unsaturated compound (a3) in a suitable solvent in the presence of a radical polymerization initiator.

As a solvent used for the said superposition | polymerization, for example,

Alcohols such as methanol, ethanol, n-propanol, i-propanol, benzyl alcohol, 2-phenylethanol and 3-phenyl-1-propanol;

Ethers such as tetrahydrofuran and dioxane;

Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether and ethylene glycol mono-n-butyl ether;

Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether acetate, and ethylene glycol mono-n-butyl ether acetate;

Diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate and diethylene glycol monoethyl ether acetate;

Ethylene glycol monoalkyl ether propionate, such as ethylene glycol monomethyl ether propionate, ethylene glycol monoethyl ether propionate, ethylene glycol mono-n-propyl ether propionate, and ethylene glycol mono-n-butyl ether propionate Nates;

Diethylene glycol alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol ethyl methyl ether;

Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether and propylene glycol mono-n-butyl ether;

Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate and propylene glycol mono-n-butyl ether acetate;

Propylene glycol monoalkyl ether propionate such as propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol mono-n-propyl ether propionate, and propylene glycol mono-n-butyl ether propionate Nates;

Aromatic hydrocarbons such as toluene and xylene;

Ketones such as methyl ethyl ketone, 2-pentanone, 3-pentanone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanone;

Methyl 2-methoxypropionate, 2-methoxy ethylpropionate, n-propyl 2-methoxypropionate, n-butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-ethoxy N-propyl propionate, n-butyl 2-ethoxypropionate, methyl 2-n-propoxypropionate, ethyl 2-n-propoxypropionate, n-propyl 2-n-propoxypropionic acid, 2-n-propoxypropionic acid n-butyl, 2-n-butoxypropionate, ethyl 2-n-butoxypropionic acid, 2-n-butoxypropionic acid n-propyl, 2-n-butoxypropionic acid n-butyl, 3-methoxypropionic acid Methyl, 3-methoxypropionate, 3-methoxypropionic acid n-propyl, 3-methoxypropionic acid n-butyl, 3-ethoxypropionic acid methyl, 3-ethoxypropionic acid, 3-ethoxypropionic acid n-propyl, 3-ethoxypropionate n-butyl, 3-n-propoxypropionate, 3-n-ethylpropoxypropionate, 3-n-propoxyprop N-propyl on-acid, n-butyl 3-n-propoxypropionate, methyl 3-n-butoxypropionate, ethyl 3-n-butoxypropionate, n-propyl 3-n-butoxypropionate, 3-n-part Alkyl alkoxypropionates such as n-butyl oxypropionate;

Methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl hydroxyacetate, ethyl hydroxyacetate, hydroxyacetic acid n-propyl, hydroxyacetic acid n-butyl, methyl lactate, ethyl lactate, n-propyl lactate , N-butyl lactate, 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, n-propyl 3-hydroxypropionate , 3-hydroxypropionic acid n-butyl, 2-hydroxy-3-methylbutyrate, methyl methoxyacetate, ethyl methoxyacetate, methoxyacetic acid n-propyl, methoxyacetic acid n-butyl, ethoxyacetic acid methyl Ethyl ethoxyacetate, ethoxyacetic acid n-propyl, ethoxyacetic acid n-butyl, n-propoxyacetic acid, n-propoxyacetic acid, n-propoxyacetic acid n-propyl, n-propoxyacetic acid n- Butyl, n-butoxy Set acids there may be mentioned methyl, ethyl, etc. n- butoxy, n- butoxy ethyl n- propyl, n- butoxy ethyl n- other esters such as butyl acids.

Among these solvents, diethylene glycol alkyl ethers, propylene glycol monoalkyl ether acetates, alkyl alkoxypropionates and the like are preferable.

The said solvent can be used individually or in mixture of 2 or more types.

Moreover, as a radical polymerization initiator used for the said superposition | polymerization, it does not specifically limit, For example, 2,2'- azobisisobutyronitrile, 2,2'- azobis- (2, 4- dimethylvalero Nitrile), 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile), 4,4'-azobis (4-cyanovaleric acid), dimethyl-2,2'- Azo compounds such as azobis (2-methylpropionate) 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 and the like. When using a peroxide as a radical polymerization initiator, you may use a reducing agent together and set it as a redox type initiator.

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

The copolymer [A] thus obtained may be used for the production of a radiation-sensitive resin composition (A) as it is, or may be separated from a solution and used for the production of a radiation-sensitive resin composition (A).

The polystyrene reduced weight average molecular weight (hereinafter referred to as "Mw") by gel permeation chromatography (GPC) of the copolymer [A] is usually 2,000 to 100,000, preferably 5,000 to 50,000. In this case, if Mw of copolymer [A] is less than 2,000, the developability and residual film rate of a film obtained may fall, or pattern shape and heat resistance may be impaired, whereas when it exceeds 100,000, resolution will fall or pattern shape will be It may be damaged.

In this invention, copolymer [A] can be used individually or in mixture of 2 or more types.

-Polymeric compound [B]-

[B] component in a radiation sensitive resin composition (a) contains the polymeric compound (henceforth "polymerizable compound [B]") which has an ethylenically unsaturated bond.

Although it does not specifically limit as a polymeric compound [B], Monofunctional, bifunctional, or trifunctional or more (meth) acrylic acid ester is preferable from a viewpoint that a polymerizability is favorable and the intensity | strength of the spacer obtained improves.

As said monofunctional (meth) acrylic acid ester, For example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol monoethyl ether acrylate, diethylene glycol monoethyl ether methacrylate, Isoboroyl acrylate, Isoboroyl methacrylate, 3-methoxybutyl acrylate, 3-methoxybutyl methacrylate, phthalic acid (2-acryloyloxyethyl) (2-hydroxypropyl) ester, phthalic acid (2- Methacryloyloxyethyl) (2-hydroxypropyl) ester etc. are mentioned.

Moreover, as a commercial item of monofunctional (meth) acrylic acid ester, For example, aronix-101, copper-111, copper-114 (above, Toagosei Co., Ltd. product); KAYARAD TC-110S, copper-120S (above, manufactured by Nippon Kayaku Co., Ltd.); Biscot 158, East 2311 (above, Osaka Yuki Kagaku Kogyo KK) etc. are mentioned.

As said bifunctional (meth) acrylic acid ester, For example, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate , Tetraethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate And bis (phenoxyethanol) fluorene diacrylate, bis (phenoxyethanol) fluorene dimethacrylate and the like.

In addition, as a commercial item of bifunctional (meth) acrylic acid ester, For example, aronix-210, copper-240, copper-6200 (above, Toagosei Co., Ltd.), KAYARAD HDDA, copper HX-220, East R-604 (above, manufactured by Nippon Kayaku Co., Ltd.), biscot 260, east 312, east 335 HP (above, manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.), and the like.

Moreover, as said trifunctional or more than (meth) acrylic acid ester, a trimethylol propane triacrylate, a trimethylol propane trimethacrylate, a pentaerythritol triacrylate, a pentaerythritol trimethacrylate, Pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol Hexamethacrylate, tri (2-acryloyloxyethyl) phosphate, tri (2-methacryloyloxyethyl) phosphate or 9 or more functional (meth) acrylic acid esters having alkylene chains and alicyclic structures. , Trifunctional, tetrafunctional or 5-functional (meth) acrylic compounds having two or more isocyanate groups and one or more hydroxyl groups in the molecule The urethane acrylate type compound etc. which are obtained by making a compound react are mentioned.

Moreover, as a commercial item of the trifunctional or more than trifunctional (meth) acrylic acid ester, For example, aronix M-309, copper-400, copper-405, copper-450, copper-7100, copper-8030, copper-8060, aro Knicks TO-1450 (above, Doa Kosei Co., Ltd.), KAYARAD TMPTA, East DPHA, East DPCA-20, East DPCA-30, East DPCA-60, East DPCA-120 (above, Nippon Kayaku Co., Ltd.) New frontier as a commercial item containing the biscoat 295, the copper 300, the copper 360, the copper GPT, the copper 3PA, the copper 400 (above, Osaka Yuki Kagaku Kogyo Co., Ltd.), and a urethane acrylate compound. R-1150 (made by Daiichi Kogyo Seiyaku Co., Ltd.), KAYARAD DPHA-40H (made by Nippon Kayaku Co., Ltd.), etc. are mentioned.

Among these monofunctional, bifunctional or trifunctional or higher (meth) acrylic acid esters, trifunctional or higher (meth) acrylic acid esters are more preferable, and trimethylolpropane triacrylate, pentaerythritol triacrylate and pentae are particularly preferred. Rithritol tetraacrylate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate are preferred.

In this invention, polymeric compound [B] can be used individually or in mixture of 2 or more types.

The use amount of the polymerizable compound [B] in the radiation sensitive resin composition (A) is preferably 50 to 140 parts by weight, more preferably 60 to 120 parts by weight based on 100 parts by weight of the copolymer [A]. In this case, when the usage-amount of polymeric compound [B] is less than 50 weight part, there exists a possibility that the development residue may arise at the time of image development by the developing solution containing aqueous alkali solution, On the other hand, when it exceeds 140 weight part, the hardness of the spacer obtained will fall. There is a tendency.

Polymerization initiator [C]-

Component [C] in the radiation-sensitive resin composition (A) is essentially an O-acyl oxime type carbazole compound represented by the formula (1) or (2) (hereinafter referred to as "carbazole compound (C1)"). A radiation sensitive polymerization initiator which is a component and generates active species capable of initiating polymerization of the polymerizable compound [B] by exposure to radiation such as visible light, ultraviolet light, far ultraviolet ray, charged particle beam, or X-ray ( Hereinafter, the "polymerization initiator [C]" is referred to).

Examples of the linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms of R ¹ , R ^2, and R ³ in Formula 1 and Formula 2 include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n -Butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n -Dodecyl group, cyclopentyl group, cyclohexyl group, etc. are mentioned.

Moreover, as a C1-C6 linear, branched or cyclic alkyl group of R <^4> , R <^5> and R <^6> , a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, etc. are mentioned.

Linear, branched or cyclic having 1 to 6 carbon atoms in the substituent for each alkyl group of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ , and the substituent for each phenyl group of R ¹ and R ² As an alkoxyl group, a methoxy group, an ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, t-butoxy group, etc. are mentioned, for example, As a halogen atom, For example, a fluorine atom And a chlorine atom.

Moreover, as a C1-C6 linear, branched, or cyclic alkyl group in the substituent with respect to each phenyl group of R <^1> and R <^2> , For example, a methyl group, an ethyl group, n-propyl group, i-propyl group, n -Butyl group, t-butyl group, etc. are mentioned.

One or more of these substituents may be present in each alkyl group and each phenyl group.

In formulas (1) and (2), R ¹ is preferably a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, phenyl group and the like, and R ² is hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, etc. are preferable, As R <^3> , a hydrogen atom, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, etc. are preferable, and as R <^4> , R <^5> and R <^6> , a hydrogen atom, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, etc. are preferable.

Preferred carbazole compound (C1) is, for example, 1- [9-ethyl-6-benzoyl-9.H.-carbazol-3-yl] -nonane-1,2-nonane-2-oxime-O -Benzoate, 1- [9-ethyl-6-benzoyl-9.H.-carbazol-3-yl] -nonane-1,2-nonane-2-oxime-O-acetate, 1- [9-ethyl -6-benzoyl-9.H.-carbazol-3-yl] -pentane-1,2-pentane-2-oxime-O-acetate, 1- [9-ethyl-6-benzoyl-9.H.- Carbazol-3-yl] -octane-1-onoxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane- 1-onoxime-O-benzoate, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-onoxime-O-acetate, 1- [9-ethyl-6- (1,3,5-trimethylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9- n-butyl-6- (2-ethylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-benzoate and the like.

Among these carbazole compounds (C1), in particular, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-acetate Is preferred.

In this invention, a carbazole type compound (C1) can be used individually or in mixture of 2 or more types.

In addition, in the photosensitive resin composition (a), another radiation sensitive polymerization initiator (henceforth a "other polymerization initiator") can also be used together with a carbazole type compound (C1).

As another polymerization initiator, an O-acyl oxime type compound (henceforth "other O-acyl oxime type polymerization initiator") is preferable.

As another O-acyl oxime type polymerization initiator, For example, 1,2-octadione-1- [4- (phenylthio) phenyl] -2- (O-benzoyl oxime), 1,2-butanedione-1 [4- (phenylthio) phenyl] -2- (O-benzoyloxime), 1,2-butanedione-1- [4- (phenylthio) phenyl] -2- (O-acetyloxime), 1, 2-octadione-1- [4- (methylthio) phenyl] -2- (O-benzoyloxime), 1,2-octadione-1- [4- (phenylthio) phenyl] -2- (O- (4-methylbenzoyl oxime)) etc. are mentioned.

Among these other O-acyl oxime type polymerization initiators, 1,2-octadione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) is particularly preferable.

The said other O-acyl oxime type polymerization initiator can be used individually or in mixture of 2 or more types.

In the present invention, by using a carbazole compound (C1) or another O-acyl oxime type polymerization initiator as the polymerization initiator [C] component, it is highly sensitive even at an exposure amount of 1,500 J / m 2 or less, and is excellent in adhesion to the substrate. The spacer for a panel can be formed.

The total amount of the carbazole compound (C1) and the other O-acyl oxime type polymerization initiator in the radiation sensitive resin composition (A) is preferably 5 to 30 parts by weight, based on 100 parts by weight of the polymerizable compound [B], More preferably, it is 5-20 weight part. In this case, when the total amount is less than 5 parts by weight, the residual film ratio at the time of development by a developer containing an aqueous alkali solution tends to decrease, while when it exceeds 30 parts by weight, the solubility of the unexposed part in the developer is lowered. There is this.

In addition, the use ratio of the other O-acyl oxime type polymerization initiator at the time of using a carbazole type compound (C1) and another O-acyl oxime type polymerization initiator together is O-acyl oxime type different from a carbazole type compound (C1). The total amount with the polymerization initiator is preferably 50% by weight or less, more preferably 1 to 30% by weight. In this case, when the use ratio of another O-acyl oxime type polymerization initiator exceeds 50 weight%, there exists a possibility that the pattern shape of the spacer obtained may be impaired.

In addition, as other polymerization initiators other than other O-acyl oxime type polymerization initiators, for example, a biimidazole type compound, a benzoin type compound, an acetophenone type compound, a benzophenone type compound, the (alpha)-diketone type compound, a polynuclear quinine Non-based compounds, xanthone-based compounds, phosphine-based compounds, triazine-based compounds, and the like, among these, acetophenone-based compounds and biimidazole-based compounds are preferable.

As said acetophenone type compound, the (alpha)-hydroxy ketone type compound, the (alpha)-amino ketone type compound, etc. are mentioned, for example.

As said (alpha)-hydroxy ketone type compound, 1-phenyl- 2-hydroxy- 2-methyl-propan- 1-one, 1- (4-i-propylphenyl) -2-hydroxy- 2-, Methyl propan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, etc. are mentioned, The said alpha-amino ketone Examples of the compound include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1- (4-mor Polynophenyl) -butan-1-one etc. are mentioned.

Moreover, as an acetophenone type compound other than an (alpha)-hydroxy ketone type compound and the (alpha)-amino ketone type compound, 2, 2- dimethoxy acetophenone, 2, 2- diethoxy acetophenone, 2, 2-, Dimethoxy-2-phenylacetophenone and the like.

These acetophenone type compounds can be used individually or in mixture of 2 or more types.

In this invention, by using an acetophenone type compound as another polymerization initiator, the sensitivity, the shape of the spacer obtained, compressive strength, etc. can be further improved.

As said biimidazole type compound, it is, for example

2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2-chlorophenyl ) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetra Phenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole , 2,2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dibro Mophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-tribromophenyl) -4,4', 5,5'- tetraphenyl-1,2'-biimidazole etc. are mentioned.

Among these biimidazole compounds, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis ( 2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4, 4 ', 5,5'-tetraphenyl-1,2'-biimidazole and the like are preferable, and particularly preferably 2,2'-bis (2,4-dichlorophenyl) -4,4', 5, 5'-tetraphenyl-1,2'-biimidazole.

The said biimidazole type compound can be used individually or in mixture of 2 or more types.

In this invention, by using a biimidazole type compound as another polymerization initiator, the sensitivity, the resolution, adhesiveness with the board | substrate of the spacer obtained, etc. can be further improved.

In addition, when using a biimidazole type compound as another polymerization initiator, in order to sensitize it, you may use together the aromatic type compound which has a dialkylamino group (henceforth "dialkylamino group containing sensitizer").

Examples of the dialkylamino group-containing sensitizer include 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, ethyl p-dimethylaminobenzoate and p-diethylamino. Ethyl benzoate, p-dimethylaminobenzoic acid i-amyl, p-diethylaminobenzoic acid i-amyl and the like.

Of these dialkylamino group-containing sensitizers, 4,4'-bis (diethylamino) benzophenone is preferable.

The said dialkylamino group containing sensitizer can be used individually or in mixture of 2 or more types.

The use amount of the dialkylamino group-containing sensitizer is preferably 0.1 to 50 parts by weight, more preferably 1 to 20 parts by weight based on 100 parts by weight of the copolymer [A]. In this case, when the amount of the dialkylamino group-containing sensitizer is less than 0.1 part by weight, the resulting spacer film may be worn or the pattern shape may be damaged. On the other hand, when the amount of the dialkylamino group-containing sensitizer is used, the pattern shape of the spacer may be damaged.

In addition, when using a biimidazole type compound and a dialkylamino group containing sensitizer together as another polymerization initiator, a thiol type compound can be added as a hydrogen donor compound. The biimidazole compound is sensitized and cleaved by a dialkylamino group-containing sensitizer to generate an imidazole radical, but at this time, a high polymerization initiation capacity is not necessarily expressed, and a spacer obtained is not preferable such as an inverse taper shape. Often, the shape is not. This problem can be alleviated by adding a thiol compound to the system in which the biimidazole compound and the dialkylamino group-containing sensitizer coexist. That is, the hydrogen radicals are donated from the thiol-based compound to the imidazole radicals, thereby converting the imidazole radicals into neutral imidazoles, thereby generating a component having a sulfur radical having a high polymerization initiation capacity. It becomes tapered shape.

As said thiol type compound, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mer, for example Aromatic compounds such as capto-5-methoxybenzoimidazole; 3-mercaptopropionic acid, 3-mercaptopropionic acid methyl, 3-mercaptopropionic acid ethyl, 3-mercaptopropionic acid n-octyl, or a bifunctional or higher functional compound, 3,6-dioxa-1,8-octanedithiol And aliphatic compounds such as pentaerythritol tetra (mercaptoacetate) and pentaerythritol tetra (3-mercaptopropionate).

These thiol type compounds can be used individually or in mixture of 2 or more types.

The amount of the thiol compound to be used is preferably 0.1 to 50 parts by weight, more preferably 1 to 20 parts by weight based on 100 parts by weight of the carbazole compound (C1). In this case, when the amount of the thiol-based compound is less than 0.1 part by weight, the resulting spacer film may be worn or the pattern shape may be damaged. On the other hand, when the amount of the thiol compound is more than 50 parts by weight, the pattern shape of the spacer may be damaged.

The use ratio of the other polymerization initiator in the radiation-sensitive resin composition (A) is preferably 100 parts by weight or less, more preferably 80 parts by weight or less, particularly preferably 60 parts by weight with respect to 100 parts by weight of the total polymerization initiator. It is as follows. In this case, when the use ratio of another polymerization initiator exceeds 100 weight part, the desired effect of this invention may be impaired.

-additive-

To the radiation-sensitive resin composition (a), additives other than the above components, for example, surfactants, adhesion aids, storage stabilizers, heat resistance enhancers, and the like, may be blended, if necessary, within the range not impairing the desired effects of the present invention. It may be.

The said surfactant is a component used in order to improve applicability | paintability, A preferable surfactant is a fluorine-type surfactant and silicone type surfactant.

As the fluorine-based surfactant, a compound having a fluoroalkyl group and / or a fluoroalkylene group in at least one of terminal, main chain and side chain is preferable, and examples thereof include 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, octaethylene glycol di ( 1,1,2,2-tetrafluoro-n-butyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoro-n-pentyl) ether, octapropylene glycol di (1 , 1,2,2-tetrafluoro-n-butyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoro-n-pentyl) ether, perfluoro-n- Sodium dodecanesulfonate, 1,1,2,2,8,8,9,9,10,10-decafluoro-n-dodecane, 1,1,2,2,3,3-hexafluoro- n-decane, sodium fluoroalkylbenzenesulfonic acid, sodium fluoroalkylphosphonic acid, sodium fluoroalkyl carboxylic acid, fluoroalkyl polyjade Cyethylene ether, diglycerin tetrakis (fluoroalkyl polyoxyethylene ether), fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl polyoxyethylene ether, perfluoroalkyl polyoxyethanol And perfluoroalkyl alkoxylates and fluorine alkyl esters.

Moreover, as a commercial item of a fluorine-type surfactant, BM-1000, copper-1100 (above, BM CHEMIE company make), Megapack F 142D, copper 172, copper 173, copper 183, copper 178, copper 191, copper, for example 471, East 476 (above, Dai Nippon Ink Chemical Co., Ltd.), Fluoride FC-170C, East-171, East-430, East-431 (above, Sumitomo 3M Co., Ltd.), Suplon S-112, East-113, East-131, East-141, East-145, East-382, Suflon SC-101, East-102, East-103, East-104, East-105, East-106 ( Asahi Glass Co., Ltd., F-Top EF301, copper 303, copper 352 (above, Shin-Kase Kasei Co., Ltd.), Butagent FT-100, Copper-110, Copper-140 A, Copper-150, Copper-250, copper-251, butanegent FTX-251, copper-218, copper-300, copper-310, copper-400S (above, made by Neos) etc. are mentioned.

As said silicone type surfactant, Toray silicon DC3PA, copper 7 PA, Toray silicon SH11PA, copper 21 PA, copper 28 PA, copper 29 PA, copper 30 PA, Toray silicon SH-190, copper-193, Toray silicon SZ-6032, Toray Silicon SF-8428, Toray Silicon DC-57, Copper-190 (above, manufactured by Toray Dow Corning Silicon Co., Ltd.), TSF-4300, Copper-4440, Copper-4445, Copper-4446, What is marketed by brand names, such as 4-4452 and 4460 (above, GE Toshiba Silicone Co., Ltd.), are mentioned.

Moreover, as surfactant other than the above, For example, Polyoxyethylene alkyl ether, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene n-octylphenyl ether and polyoxyethylene n-nonylphenyl ether; Nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate and KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) and Polyflop No. 57, East No. 95 (above, Kyoeisha Chemical Co., Ltd. product) etc. are mentioned.

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

The blending amount of the surfactant is preferably 5 parts by weight or less, more preferably 2 parts by weight or less, based on 100 parts by weight of the copolymer [A]. In this case, when the compounding quantity of surfactant exceeds 5 weight part, there exists a tendency for a film | membrane to become rough easily at the time of application | coating.

The said adhesion aid is a component used in order to further improve adhesiveness with a board | substrate, A functional adhesion silane coupling agent is mentioned as a preferable adhesion aid.

As said functional silane coupling agent, For example, the silane coupling agent which has reactive functional groups, such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group, an epoxy group, More specifically, trimethoxysilyl benzoic acid, (gamma) -methacryl Royloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclo Hexyl) ethyl trimethoxysilane 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 10 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 developing residue to arise easily at the time of image development by the developing solution containing aqueous alkali solution.

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

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

The compounding quantity of storage stability is preferably 3.0 parts by weight or less, more preferably 0.5 parts by weight or less based on 100 parts by weight of the copolymer [A]. In this case, when the compounding quantity of storage stability exceeds 3.0 weight part, a sensitivity may fall and the pattern shape of the spacer obtained may be damaged.

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, N-tetra (i-propoxymethyl) glycoluril, N, N, N, N-tetra (n- Butoxymethyl) glycoluril, N, N, N, N-tetra (t-butoxymethyl) glycoluril, and the like, among which N, N, N, N-tetra (methoxymethyl) glycoluril desirable.

Examples of the N- (alkoxymethyl) melamine compound include N, N, N, N, N, N-hexa (methoxymethyl) melamine, N, N, N, N, N, N-hexa (e) Methoxymethyl) melamine, N, N, N, N, N, N-hexa (n-propoxymethyl) melamine, N, N, N, N, N, N-hexa (i-propoxymethyl) melamine, N , N, N, N, N, N-hexa (n-butoxymethyl) melamine, N, N, N, N, N, N-hexa (t-butoxymethyl) melamine, and the like can be given. N, N, N, N, N, N-hexa (methoxymethyl) melamine is preferred.

Moreover, as a commercial item of an N- (alkoxymethyl) melamine compound, Nikarak N-2702, Nikarak MW-30M (made by Sangwa Chemical Co., Ltd.), etc. are mentioned, for example.

Examples of the compound having two or more epoxy groups include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and tripropylene glycol. Diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylol propane triglycidyl ether And 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 3,002 And 4,000 (more than Kyueisha Chemical Co., Ltd.) are mentioned.

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

Composition solution

When using the radiation sensitive resin composition (A), components, such as a copolymer [A], a polymeric compound [B], and a polymerization initiator [C], are normally melt | dissolved in a suitable solvent and are manufactured as a composition solution.

As a solvent used for manufacture of the said composition solution, the thing which melt | dissolves each component which comprises a radiation sensitive resin composition (A) uniformly, does not react with each component, and has moderate volatility is used, for example, the copolymer The same thing as the solvent illustrated about the superposition | polymerization which manufactures [A] is mentioned.

Among these solvents, alcohols, ethylene glycol monoalkyl ether acetates, diethylene glycol monoalkyl ether acetates, diethylene glycol alkyl ethers, from the viewpoint of solubility of each component, reactivity with each component, and ease of film formation, Propylene glycol monoalkyl ether acetates, alkyl alkoxypropionates, and the like are preferable, and benzyl alcohol, 2-phenylethanol, 3-phenyl-1-propanol, ethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether Acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and the like are preferable.

The said solvent can be used individually or in mixture of 2 or more types.

Moreover, when manufacturing a composition solution, you may use a high boiling point solvent together with the said solvent.

As the high boiling point solvent, for example, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone , Dimethyl sulfoxide, benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, Diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate, and the like.

These high boiling point solvents can be used individually or in mixture of 2 or more types.

The composition solution thus prepared can be used, if necessary, by filtration with a Millipore filter having a pore size of, for example, about 0.2 to 0.5 µm.

Here, when the composition of the preferable radiation sensitive resin composition (a) in this invention is illustrated more concretely, it is as follows (i)-(v).

(i) The component constituting the copolymer [A] includes an unsaturated carboxylic acid compound (a1) containing a single or a mixture of two or more of acrylic acid, methacrylic acid and maleic anhydride groups, and an epoxy group-containing unsaturated compound (a2 ) Is a monovalent or 2 group of glycidyl methacrylate, 6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether and p-vinylbenzyl glycidyl ether group Mixtures of two or more species; other unsaturated compounds (a3) are 2-methylcyclohexyl acrylate, t-butyl methacrylate, tricyclo methacrylate [5.2.1.0 ^2,6 ] decan-8-yl, tetrahydrofur A composition comprising sole or a mixture of two or more of furyl methacrylate, styrene, p-methoxystyrene and 1,3-butadiene groups.

(ii) In the above (i), the content of the repeating unit derived from the unsaturated carboxylic acid compound (a1) in the copolymer [A] is 5 to 40% by weight, more preferably 10 to 30% by weight, and an epoxy group The content rate of the repeating unit derived from a containing unsaturated compound (a2) is 10 to 70 weight%, More preferably, it is 20 to 60 weight%, and the content rate of the repeating unit derived from another unsaturated compound (a3) is 10 to 70 weight% , More preferably 20 to 50% by weight.

(iii) In the above (i) or (ii), the polymerizable compound [B] is a monofunctional, difunctional or trifunctional or higher (meth) acrylic acid ester, more preferably trifunctional or higher (meth) acrylic acid ester Particularly preferably trimethylolpropanetriacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate alone or in groups A composition that is a mixture of species or more.

(iv) The composition according to any one of (i) to (iii), wherein the polymerization initiator [C] further comprises a single type or a mixture of two or more kinds of other O-acyl oxime type polymerization initiators.

(v) In any one of (i)-(vi), the usage-amount of a polymeric compound [B] is 50-140 weight part with respect to 100 weight part of copolymers [A], More preferably, it is 60-120 weight Part, and the usage-amount of a polymerization initiator [C] is 5-30 weight part with respect to 100 weight part of polymeric compounds [B], More preferably, it is 5-20 weight part.

The radiation sensitive resin composition (a) can be used very preferably especially as a material for forming spacers for display panels, such as a liquid crystal panel and a touch panel.

Display panel spacer

When forming a spacer for display panels using a radiation sensitive resin composition (A), after apply | coating a composition solution to the surface of a board | substrate, a film is formed by prebaking and removing a solvent.

As a coating method of the composition solution, for example, an appropriate method such as spraying, roll coating, rotary coating (spin coating), slit die coating, bar coating, inkjet, or the like can be adopted. Method, the slit die coating method is preferred.

In addition, although the conditions of prebaking differ also with kinds, compounding ratio, etc. of each structural component, it is about 1 to 15 minutes at 70-90 degreeC normally.

Subsequently, the prebaked film is exposed to light through a mask of a predetermined pattern and polymerized, and then developed by a developing solution to remove unnecessary portions to form a pattern.

As radiation used for exposure, radiation, such as visible light, an ultraviolet-ray, an ultraviolet-ray, a charged particle beam, X-rays, etc. can be selected suitably, but the radiation in the range of 190-450 nm is preferable.

As a developing method, any of a paddle method, an immersion method, a shower method, etc. may be sufficient, for example, and developing time is about 30 to 180 second normally at normal temperature.

As said developing solution, For example, inorganic alkalis, such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia; Primary amines such as ethylamine and n-propylamine; Secondary amines such as diethylamine and di-n-propylamine; Tertiary amines such as trimethylamine, methyldiethylamine, ethyldimethylamine and triethylamine; Tertiary alkanolamines such as dimethylethanolamine, methyldiethanolamine and triethanolamine; Pyrrole, piperidine, N-methylpiperidine, N-methylpyrrolidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] Alicyclic tertiary amines such as -5-nonene; Aromatic tertiary amines such as pyridine, collidine, lutidine and quinoline; An aqueous solution (alkali aqueous solution) of alkaline compounds, such as quaternary ammonium salts, such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, can be used.

In addition, an appropriate amount of a water-soluble organic solvent such as methanol and ethanol and / or a surfactant may be added to the aqueous alkali solution.

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

Thereafter, the pattern is heated by a heating device such as a hot plate or an oven at a predetermined temperature, for example, 150 to 250 ° C. for a predetermined time, for example, for 5 to 30 minutes on the hot plate, for example, in an oven, for example, 30 to 90 degrees. By heating for a minute (hereinafter, referred to as "post-baking"), a target spacer can be obtained.

<Example>

Although an Example is shown to the following and embodiment of this invention is demonstrated more concretely, this invention is not limited to these Examples.

Synthesis Example 1

In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile), 200 parts by weight of diethylene glycol methylethyl ether, followed by 18 parts by weight of methacrylic acid and meta 40 parts by weight of glycidyl methacrylate, 5 parts by weight of styrene, and 32 parts by weight of tricyclo methacrylate [5.2.1.0 ^2,6 ] decane-8-yl were substituted for nitrogen, and then 5 parts of 1,3-butadiene were added. Part was added, the temperature of the solution was raised to 70 ° C. while stirring slowly, and the temperature was maintained for 5 hours to polymerize to obtain a solution of the copolymer [A] (solid content concentration = 33.0 wt%). Mw of this copolymer [A] was 11,000. This copolymer [A] is called "copolymer [A-1]".

Synthesis Example 2

In a flask equipped with a cooling tube and a stirrer, 7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile), 200 parts by weight of diethylene glycol methylethyl ether, 18 parts by weight of methacrylic acid and meta 20 parts by weight of glycidyl methacrylate, 5 parts by weight of styrene, 32 parts by weight of tricyclo methacrylate [5.2.1.0 ^2,6 ] decane-8-yl, 25 parts by weight of tetrahydrofurfuryl methacrylate were substituted with nitrogen. Thereafter, the temperature of the solution was raised to 70 ° C. while stirring slowly, and the temperature was maintained for 5 hours to polymerize to obtain a solution of the copolymer [A] (solid content concentration = 33.4 wt%). Mw of this copolymer [A] was 9,000. This copolymer [A] is called "copolymer [A-2]".

<Example 1>

Preparation of Composition Solution

Amount corresponding to 100 parts by weight (solid content) of the copolymer (A-1) with the solution of the copolymer [A-1] as the component [A], and dipentaerythritol hexaacrylate as the component [B] (trade name KAYARAD DPHA , Nippon Kayaku Co., Ltd.) 80 parts by weight, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1 as [C] component Onoxime-O-acetate (trade name CGI-242, manufactured by Ciba Specialty Chemicals Co., Ltd.) was dissolved in propylene glycol monomethyl ether acetate so that the solid content concentration was 35% by weight, followed by a millipore filter having a pore diameter of 0.2 μm. Filtration gave a composition solution (hereinafter referred to as "composition (S-1)").

Formation of spacers

After apply | coating composition solution (S-1) using a spinner on an alkali free glass substrate, it baked preliminarily on a hotplate for 3 minutes at 90 degreeC, and formed the film of 6.0 micrometers in thickness.

Subsequently, the obtained film was exposed to 150 micrometers of exposure gaps through the mask of the remaining pattern of a 10 micrometer side, and it exposed by the ultraviolet-ray whose exposure intensity in wavelength 365nm is 300 W / m <2>. Thereafter, the solution was developed at 25 DEG C for 60 seconds with 0.05% by weight aqueous potassium hydroxide solution, and then washed with pure water for 1 minute. Thereafter, baking was performed at 150 ° C. for 120 minutes in an oven to form a spacer having a predetermined pattern.

Subsequently, various evaluation was performed about the obtained spacer by the following method. The evaluation results are shown in Table 3 below.

(I) evaluation of sensitivity

With respect to the obtained pattern, the exposure amount such that the residual film ratio after development (film thickness after development x 100 / initial film thickness. The same applies below) was 90% or more as the sensitivity. When the sensitivity is 1,500 J / m 2 or less, it can be said that the sensitivity is good.

(II) evaluation of resolution

The obtained pattern was evaluated by the minimum pattern size at the exposure amount such that the residual film ratio after development was 90% or more. The smaller the pattern size, the better the resolution.

(III) Evaluation of Pattern Shape

The cross-sectional shape of the obtained pattern was observed with the scanning electron microscope, and the shape was evaluated according to which of A to C shown in FIG. At this time, when the pattern edge is a forward taper like A, the pattern shape is good, and when the pattern edge is vertical like B, the pattern shape is slightly good. In addition, in the case where the pattern edge is in an inverted tape shape (inverse cross-section in which the side of the film surface is longer in the cross-sectional shape than the side on the substrate side) as in C, the pattern is very likely to be peeled off during the subsequent rubbing treatment. It can be said to be bad.

(IV) evaluation of compressive strength

Deformation amount when a load of 10 mN was applied by a planar indenter having a diameter of 50 µm using a microcompression tester (trade name MCTM-200, manufactured by Shimadzu Corporation) as the compressive strength of the obtained pattern was measured at 23 ° C. Measured at When this value is 0.55 micrometer or less, it can be said that compressive strength is favorable.

(V) evaluation of rubbing resistance

After apply | coating AL3046 (brand name, JSR Corporation make) with the liquid crystal aligning film coating machine to the board | substrate with which the spacer was formed, it dried at 180 degreeC for 1 hour, and formed the aligning agent coating film of 0.05 micrometer in thickness. .

Subsequently, the rubbing process was performed on the conditions of the rotation speed of a roll of 500 rpm, and the moving speed of 1 cm / sec by the rubbing machine which has the roll wound the polyamide cloth to this coating film. At this time, the pattern was evaluated by the presence or absence of shaving or peeling.

(VI) Evaluation of adhesiveness

Except not using a pattern mask, it carried out similarly to the case of the said spacer formation, and formed the cured film for adhesive evaluation.

Subsequently, during the adhesion test of JIS K-5400 (1900) 8.5, a 8.5 · 2 checker taping method was performed, and evaluation was made according to the number of remaining checkerboard eyes in 100 checkerboard eyes.

<Examples 2 to 18>

Each composition solution was produced like Example 1 except having carried out the [A] component, the [B] component, and the [C] component as shown in following Table 1, the spacer was formed, and various evaluation was performed. Table 3 shows the results of the evaluation.

Example 19

[A] component, [B] component and [C] component similar to Example 3 were melt | dissolved in diethylene glycol ethylmethyl ether so that solid content concentration might be 17.5 weight%, and the composition was filtered by the Millipore filter of 0.2 micrometer of pore diameters. A solution (hereinafter referred to as "composition (S-19)") was prepared.

A spacer was formed and various evaluations were performed in the same manner as in Example 1 except that the composition (S-19) was used instead of the composition (S-1) and applied using a slit die coater instead of the spinner. Table 3 shows the results of the evaluation.

Example 20

[A] component, [B] component and [C] component similar to Example 5 were melt | dissolved in the mixture of diethylene glycol ethylmethyl ether / benzyl alcohol = 90/10 (weight ratio) so that solid content concentration might be 15 weight%, A composition solution (hereinafter referred to as "composition (S-20)") was prepared by filtration with a Millipore filter having a pore diameter of 0.2 mu m.

A spacer was formed and various evaluations were carried out in the same manner as in Example 1 except that the composition (S-20) was used instead of the composition (S-1) and applied using a slit die coater instead of the spinner. Table 3 shows the results of the evaluation.

<Comparative Examples 1 to 10>

Each composition solution was produced, the spacer was formed, and various evaluation was performed like Example 1 except having carried out the [A] component, the [B] component, and the polymerization initiator as shown in following Table 2. The evaluation results are shown in Table 4 below.

In Table 1 and Table 2, each component other than a [A] component is as follows.

[B] component

B-1: dipentaerythritol hexaacrylate (trade name KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.)

B-2: Brand name KAYARAD DPHA-40H (product made by Nippon Kayaku Co., Ltd.)

Polymerization initiator

C-1: 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-

     Acetate (brand name CGI-242, Ciba specialty chemicals company make)

γ-1: 1,2-octadione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime (brand name CGI-

      124, Shiba specialty chemicals company made)

γ-2: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one

      Rugacure 907, product made by Ciba specialty chemicals company)

γ-3: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one (trade name Ir

      Cure 369, Shiba specialty chemicals company made)

γ-4: 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole

γ-5: 4,4'-bis (diethylamino) benzophenone

γ-6: 2-mercaptobenzothiazole

The radiation-sensitive resin composition (a) of the present invention can faithfully reproduce the design size of the mask pattern with high sensitivity, excellent adhesion to the substrate, and obtain sufficient spacer shape and film thickness even at an exposure amount of 1,500 J / m 2 or less. The display panel spacer can also be formed with excellent compressive strength, rubbing resistance, and the like.

Claims (3)

[A] (a1) Copolymer of ethylenically unsaturated carboxylic acid and / or ethylenically unsaturated carboxylic anhydride with (a2) epoxy group-containing ethylenically unsaturated compound and (a3) other ethylenically unsaturated compound, [B] a polymerizable compound having an ethylenically unsaturated bond, and [C] A radiation sensitive resin composition containing a radiation sensitive polymerization initiator containing as an essential component a compound represented by the following formula (1) or (2). <Formula 1>

<Formula 2>

In formula, each R <^1> represents a C1-C12 linear, branched or cyclic alkyl group or a phenyl group each independently, and each R <^2> represents a hydrogen atom, a linear, branched or A cyclic alkyl group or a phenyl group, each R ³ independently represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, and each R ⁴ , each R ⁵ and each R ⁶ independently of one another; A hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, and the alkyl groups of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each linear, minute It may be substituted with a substituent selected from the group of terrestrial or cyclic alkoxyl groups, phenyl groups and halogen atoms, and the phenyl groups of R ¹ and R ² are linear, branched or cyclic alkyl groups having 1 to 6 carbon atoms, and 1 to C carbon atoms, respectively. 6, linear It may be substituted with substituents selected from the ground or an alkoxyl group, a phenyl group and a group of the halogen atom of the cyclic. The display panel spacer formed from the radiation sensitive resin composition of Claim 1. The display panel provided with the display panel spacer of Claim 2.

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