TWI385485B - A photosensitive resin composition, a display panel spacer, and a display panel - Google Patents

Description

Photosensitive resin composition, spacer for display panel, and display panel

The present invention relates to a photosensitive resin composition, a spacer for a display panel, and a display panel. More specifically, the photosensitive resin composition for forming a spacer for a display panel such as a liquid crystal display panel or a touch panel, the spacer for a display panel formed of the photosensitive resin composition, and the spacer Become a display panel.

Conventionally, in order to keep the interval (cell gap) between two substrates constant, the liquid crystal display panel uses spacer particles such as glass beads or plastic beads having a predetermined particle diameter. Since these spacer particles are irregularly dispersed on a transparent substrate such as a glass substrate, when the pixel formation region contains spacer particles, a phenomenon in which spacer particles are reflected or scattered incident light is generated, and the contrast of the liquid crystal panel is lowered.

Therefore, in order to solve these problems, a method of forming a spacer by photo etching is employed. In this method, a photosensitive resin composition is applied onto a substrate, and after exposure to ultraviolet light through a predetermined mask, development is performed to form dots or strip-shaped spacers, which are only in a predetermined place other than the pixel formation region. Spacers can be formed, thus substantially solving the problems as described above.

In the actual spacer forming step, for example, when a spacer is formed by photolithography on a substrate used for a color filter or the like, a proximity exposure machine is often used. When the proximity exposure machine is exposed, a certain gap is exposed between the photomask and the substrate on which the photosensitive composition is applied, and the pattern exposure of the photomask is ideal. However, the gap is filled with air or nitrogen, and the light passing through the opening (transparent portion) of the mask is diffused by the gap portion, so that there is a problem that the exposure is wider than the design size of the mask pattern.

In order to solve such a problem, the present applicant has disclosed the use of 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-) in JP-A-2001-261761. As a photopolymerization initiator of the photosensitive composition, the design of the mask pattern can be faithfully achieved by the proximity exposure, and a spacer for a display panel excellent in strength, heat resistance, and the like can be formed.

With the enlargement of the liquid crystal display panel, it is necessary to precisely control the cell gap, but when the adhesion between the film formed by the photosensitive composition of the spacer and the substrate is insufficient, the spacer formed is deviated from the substrate, and the result is accurately maintained. Cell gap. The liquid crystal display panel performs high aperture ratio of pixels, and as a result, the area of the black matrix region in which the spacers can be arranged is gradually reduced. Therefore, even if the pixel area can be entered to some extent without affecting the hue of the pixel, higher transparency is required for the spacer.

However, as described in Japanese Laid-Open Patent Publication No. 2001-261761, the photosensitive composition for forming a spacer is insufficient in adhesion to the substrate and transparency, and it is necessary to develop a photosensitive composition having these characteristics.

In recent years, the size of the liquid crystal display device has increased, and productivity has increased. In the conventional substrate size (680 × 880 mm), the substrate size is smaller than that of the mask, so that one exposure method can be used.

However, a large substrate (for example, 1500 × 1800 mm) is almost impossible to produce the same mask size as the substrate, and it is difficult to use the one-time exposure method. The large substrate exposure method proposal uses a stage exposure method. However, the stage exposure method is to perform several exposures on the substrate, each time requiring alignment time and phase shift time. The stage exposure method may reduce productivity compared to the one-shot method. A permissible exposure method 3000J / m ² of exposure sensitivity, but the phase of the exposure method of claim ² or less exposure sensitivity 1500J / m. In the conventional materials, it is difficult to obtain a sufficient spacer shape and film thickness at an exposure amount of 1500 J/m ² or less.

The value of the controllability of the shape of the spacer and the thickness of the film has become more and more stringent in recent years, and there are still shapes and film thickness variations due to process variations in the formation of spacers, and shapes due to changes in the composition solution over time. The problem of thick stability. In particular, in the range of exposure amount of 1500 J/m ² or less, there is still a problem of controllability of the shape of the spacer and the film thickness of the exposure amount.

In recent years, the photosensitive composition for producing a liquid crystal display panel has a problem that the device is contaminated by impurities such as crystals of components in the composition during use, and a photosensitive composition which is expected to reduce such a problem is expected.

[disclosure of invention]

The subject of the present invention is high sensitivity, and can faithfully realize the design size of the mask pattern, and has excellent adhesion to the substrate, and a sufficient spacer shape and film thickness can be obtained at an exposure amount of 1500 J/m ² or less. It is excellent in formation strength and heat resistance, and is excellent in the shape of the spacer and the film thickness in the low-exposure region. In the storage period, foreign matter is less likely to be generated during use, and the display panel is excellent in process stability and stability over time. A photosensitive resin composition of a spacer, a spacer for a display panel, and a display panel.

According to the present invention, the first object can be achieved by the following photosensitive resin composition (hereinafter referred to as "photosensitive resin composition (A)").

A photosensitive resin composition comprising: [A] (a1) a copolymer of an ethylenically unsaturated carboxylic acid and/or an ethylenically unsaturated carboxylic anhydride and (a2) another ethylenically unsaturated compound, [B] a polymerizable compound having an ethylenically unsaturated bond and [C] a photopolymerization initiator composed of a compound represented by the following formula (1) or (2),

[R ₁ represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms or a phenyl group, and R ₂ and R ₃ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and a carbon number of 3 to 8 a cycloalkyl group, a substituted or unsubstituted phenyl group or an alicyclic group having 7 to 20 carbon atoms (except for a cycloalkyl group having 7 to 8 carbon atoms), and the substituent of the above substituted phenyl group is a carbon number of 1 to 6 An alkyl group, an alkoxy group having 1 to 6 carbon atoms, a phenyl group or a halogen atom, R ₄ is an oxygen-containing heterocyclic group having 4 to 20 carbon atoms, a nitrogen-containing heterocyclic group having 4 to 20 carbon atoms or a carbon number of 4~ a sulfur-containing heterocyclic group of 20, R ₅ represents hydrogen, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms, n is an integer of 1 to 5, m is an integer of 0 to 5, n + m ≦5,

The definitions of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , m and n are the same as above, and l is an integer of 0-6.

According to the invention, the second problem can be achieved by the spacer for a display panel formed by the photosensitive resin composition (A).

According to the invention, the third problem can be achieved by providing the display panel formed by the spacer for the display panel.

The invention is described in detail below.

Photosensitive resin composition (A)-copolymer [A] - The photosensitive resin composition (A) [A] is composed of (a1) an ethylenically unsaturated carboxylic acid and/or an ethylenically unsaturated carboxylic anhydride and A2) A copolymer of another ethylenically unsaturated compound (hereinafter referred to as "copolymer [A]").

Among the components constituting the copolymer [A], (a1) an ethylenically unsaturated carboxylic acid and/or an ethylenically unsaturated carboxylic acid anhydride (hereinafter collectively referred to as "unsaturated carboxylic acid monomer (a1)", for example, acrylic acid, Monocarboxylic acid of methacrylic acid, crotonic acid, 2-methylpropenyloxyethyl succinic acid, 2-methylpropenyloxyethyl hexahydrophthalic acid; maleic acid, anti-butene a dicarboxylic acid of diacid, citraconic acid, mesaconic acid, and itaconic acid; an acid anhydride of the above dicarboxylic acid; and the like.

Among these unsaturated carboxylic acid monomers (a1), acrylic acid, methacrylic acid, maleic anhydride, and the like are preferable from the viewpoints of copolymerization reactivity, solubility of the copolymer to an aqueous alkali solution, and ease of availability.

In the photosensitive resin composition (A), the unsaturated carboxylic acid monomer (a1) may be used singly or in combination of two or more.

In the copolymer [A], the content of the repeating unit derived from the unsaturated carboxylic acid monomer (a1) is preferably from 5 to 50% by weight, more preferably from 10 to 40% by weight, particularly preferably from 15 to 30% by weight. %. When the content ratio of the repeating unit derived from the unsaturated carboxylic acid monomer (a1) is less than 5% by weight, the solubility in the aqueous alkali solution tends to decrease, and when it exceeds 50% by weight, the solubility in the aqueous alkali solution may be is too big.

Further, (a2) other ethylenically unsaturated compound may be an epoxy group-containing ethylenically unsaturated compound (hereinafter referred to as "epoxy group-containing monomer") and other ethylenically unsaturated compound not containing an epoxy group (hereinafter) Just called "other monomers"). These can be used singly or in combination. The epoxy group-containing monomer is, for example, glycidyl acrylate, 2-methylglycidyl acrylate, 3,4-epoxybutyl acrylate, 6,7-epoxyheptyl acrylate, acrylic acid 3,4. - epoxycycloalkyl acrylate of epoxy-cyclohexyl ester; glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl methacrylate, methyl 6,7-epoxyheptyl acrylate, 3,4-epoxycyclohexyl methacrylate, epoxy methacrylate, α-ethyl methacrylate, α-n-propyl acrylate Glycidyl acrylate, α-n-butyl acrylate propylene acrylate, α-alkyl acrylate epoxy methacrylate of α-ethyl acrylate 6,7-ethoxyheptyl ester; o-vinyl benzyl epoxide Epoxy ether, m-vinylbenzyl epoxy propyl ether, p-vinylbenzyl epoxy propyl ether epoxy propyl ether.

Among these epoxy group-containing monomers, from the viewpoints of copolymerization reactivity and strength of the spacer, glycidyl methacrylate, 2-methylglycidyl methacrylate, and methacrylic acid 6 are preferable. , 7-epoxyheptyl ester, o-vinylbenzyl epoxypropyl ether, m-vinylbenzyl epoxypropyl ether, p-vinylbenzyl epoxypropyl ether.

In the photosensitive resin composition (A), the epoxy group-containing monomers may be used singly or in combination of two or more.

In the copolymer [A], the content ratio of the repeating unit derived from the epoxy group-containing monomer is preferably from 10 to 70% by weight, more preferably from 20 to 60% by weight, particularly preferably from 30 to 50% by weight. When the content ratio of the repeating unit derived from the epoxy group-containing monomer is less than 10% by weight, the strength of the obtained spacer tends to decrease, and when it exceeds 70% by weight, the storage stability of the obtained copolymer is lowered. tendency.

(a3) other monomers of the ethylenically unsaturated compound, for example, alkyl acrylate such as methyl acrylate or isopropyl acrylate; methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, methyl Dibutyl acrylate, alkyl methacrylate of butyl methacrylate; cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclohexyl acrylate [5.2.1.0 ^{2 , 6} ] decane-8- Ester, 2-(tricyclo[5.2.1.0 ^{2 , 6} ]decane-8-oxy)ethyl acrylate, acrylate cyclic ester of isobornyl acrylate; cyclohexyl methacrylate, 2-methyl methacrylate cyclohexyl methacrylate, tricyclo [5.2.1.0 ^{2, 6]} decane-8-yl methacrylate, 2- (tricyclo [5.2.1.0 ^{2, 6]} decan-8-yloxy) acetate Esters, methacrylate alicyclic esters of isobornyl methacrylate; phenyl acrylate, aryl or aryl acrylate of benzyl acrylate; phenyl methacrylate, methacrylate methacrylate Or arylalkyl ester; diethyl maleate, diethyl fumarate, diethyl diconate dialkyl dicarboxylate 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate hydroxyalkyl methacrylate; tetrahydrofurfuryl methacrylate, tetrahydrofuran methacrylate, tetrahydropyran-2-methacrylate Oxygen-containing monoatomic unsaturated penta- and six-membered ring methacrylates of esters; ethylene of styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene Aromatic compound; conjugated diene compound of 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and acrylonitrile, methacrylonitrile, propylene oxime Amine, methacrylamide, vinyl chloride, vinylidene chloride, vinyl acetate, and the like.

Among these other monomers, from the viewpoints of copolymerization reactivity and solubility of the obtained copolymer to an aqueous alkali solution, 2-methylcyclohexyl acrylate, tert-butyl methacrylate, and methacrylic acid are preferable. Ring [5.2.1.0 ^{2 , 6} ] decane-8-ester, styrene, p-methoxystyrene, tetrahydrofurfuryl methacrylate, 1,3-butadiene, and the like.

In the photosensitive resin composition (A), the other monomers may be used singly or in combination of two or more.

In the copolymer [A], the content ratio of the repeating unit derived from the other monomer is preferably from 10 to 70% by weight, more preferably from 20 to 50% by weight, particularly preferably from 30 to 50% by weight. When the content ratio of the repeating unit derived from another monomer is less than 10% by weight, the storage stability of the obtained copolymer tends to be lowered, and when it exceeds 70% by weight, the solubility of the obtained copolymer to the aqueous alkali solution is lowered. Propensity.

The copolymer [A] has a carboxyl group and/or a carboxylic acid anhydride group and an epoxy group, and has an appropriate solubility in an aqueous alkali solution, and can be easily cured by heating without using a special curing agent, and the photosensitive film containing the copolymer When the resin composition (A) is developed, no development residue or film thinning occurs, and a spacer of a pattern can be easily formed.

The copolymer [A] can be produced by polymerizing an unsaturated carboxylic acid monomer (a1), an epoxy group-containing monomer, and/or another monomer (a2) in the presence of a suitable solvent and a radical polymerization initiator.

The solvent used for the production of the copolymer [A] is, for example, an alcohol, an ether, a glycol ether, an ethylene glycol alkyl ether acetate, a diethylene glycol, a dipropylene glycol, a propylene glycol monoalkyl ether, a propylene glycol alkyl ether acetate, Propylene glycol alkane propionate, aromatic hydrocarbon, ketone, ester, and the like.

Specific examples thereof include methanol, ethanol, benzyl alcohol, 2-phenylethanol, 3-phenyl-1-propanol, and the like; ethers such as tetrahydrofuran; and glycol ethers such as ethylene glycol monomethyl ether; Ethylene glycol monoethyl ether, etc.; ethylene glycol alkyl ether acetate such as methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether Acetate, etc.; 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. Dipropylene glycol is, for example, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl methyl ether, etc.; propylene glycol monoalkyl ether such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, Propylene glycol monopropyl ether, propylene glycol monobutyl ether, etc.; propylene glycol alkyl ether acetate such as propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, etc.; Propionates such as propylene glycol methyl ether propionate, propylene glycol diethyl ether propionate, propylene glycol Ether propionate, propylene glycol butyl ether propionate, etc.; aromatic hydrocarbons such as toluene, xylene, etc.; ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone Etc.; esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methyl Ethyl propionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, 3-hydroxypropionic acid Ester, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, methoxyacetic acid Ester, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate , propoxy propyl acetate, butyl propyl acetate, methyl butoxyacetate, ethyl butoxide, butyl butoxyacetate, butyl butoxyacetate, 2- Methyl oxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-B Ethyl oxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2-butyl Propyl oxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methyl Butyl oxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, 3-propane Methyl oxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, 3-butyl An ester of ethyl oxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate or the like.

Among these, ethylene glycol alkyl ether acetate, diethylene glycol, dipropylene glycol, dipropylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, more preferably diethylene glycol dimethyl ether, diethyl Glycol ethyl methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol ethyl methyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate.

These solvents may be used singly or in combination of two or more.

The radical polymerization initiator to be used in the above polymerization is not particularly limited, and examples thereof include 2,2'-azobisisobutyronitrile, 2,2'-azobis-(2,4-dimethylvaleronitrile), and 2 , 2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile), 4,4'-azobis(4-cyanovaleric acid), dimethyl 2,2' - azo compound of azobis(2-methylpropionate), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile); benzoguanidino peroxide , lauryl sulfhydryl peroxide, tert-butyl peroxytrimethyl acetate, organic peroxide of 1,1-bis(t-butylperoxy)cyclohexane; hydrogen peroxide and the like. When a peroxide is used as a radical polymerization initiator, it can be used together with a reducing agent as a redox type initiator.

These radical polymerization initiators can be used alone or in combination of two or more.

The copolymer [A] obtained above may be in the form of a solution, and may be used as a composition for modulating a radiation-sensitive resin, or may be separated from a solution for modulating a composition of a radiation-sensitive resin.

The polystyrene-equivalent weight average molecular weight (hereinafter referred to as "Mw") of the gel permeation chromatography (GPC) of the copolymer [A] is preferably 2,000 to 100,000, more preferably 5,000 to 50,000. When the Mw is less than 2,000, the development of the obtained film, the residual film ratio, and the like may be lowered, and the shape, heat resistance, and the like may be impaired. When the Mw exceeds 100,000, the resolution is lowered or the pattern shape may be affected.

- Polymerizable Compound [B] - The component [B] in the photosensitive resin composition (A) is a polymerizable compound having an ethylenically unsaturated bond (hereinafter referred to as "polymerizable compound [B]").

The polymerizable compound [B] is not particularly limited, but a monofunctional, bifunctional or trifunctional or higher (meth) acrylate is preferred because it has good polymerizability and can increase the strength of the resulting spacer.

Monofunctional (meth) acrylates are, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol monoethyl acrylate, diethylene glycol monoethyl methacrylate, and Borne based acrylate, isobornyl methacrylate, 3-methoxybutyl acrylate, 3-methoxybutyl methacrylate, 2-propenyloxyethyl-2-hydroxypropyl phthalate Formate, 2-methylpropenyloxyethyl-2-hydroxypropyl phthalate, etc., and commercially available products such as Aronix M-101, M-111, and M-114 (East Asia Synthetic (stock) system; KAYARAD TC-110S, same as TC-120S (Nippon Chemical Co., Ltd.); Viscoat 158, same 2311 (Osaka Organic Chemical Industry Co., Ltd.).

The bifunctional (meth) acrylates are, for example, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, butanediol diacrylic acid. Ester, butylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9 - decanediol dimethacrylate, bisphenoxyethanol hydrazine diacrylate, bisphenoxyethanol hydrazine dimethacrylate, etc., and commercially available products such as Aronix M-210, same M-240, same M-6200 (East Asia Synthetic Co., Ltd.), KAYARAD HDDA, HX-220, R-604 (Nippon Chemical Co., Ltd.), Viscoat 260, 312, and 335HP (Osaka Organic Chemical Industry Co., Ltd.) System) and so on.

The trifunctional or higher (meth) acrylate is, for example, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, neopentyl alcohol triacrylate, neopentyl alcohol trimethacrylate, new Pentaerythritol tetraacrylate, neopentyl alcohol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol Alcohol hexamethacrylate, tris(2-propenyl methoxyethyl) phosphate, tris(2-methylpropenyl oxyethyl) phosphate, and the like.

In particular, the hexa-functional or higher (meth) acrylate has a linear alkyl chain and an alicyclic structure, and a compound containing two or more isocyanate groups and a trifunctional, tetrafunctional, and pentafunctional group having one or more hydroxyl groups in the molecule. The (meth) acrylate compound produces a urethane acrylate compound obtained by the reaction.

The above-mentioned commercial products include, for example, Aronix M-309, the same M-400, the same M-405, the same M-450, the same M-7100, the same M-8030, the same M-8060, the same TO-1450 (East Asian synthesis) )), KAYARAD TMPTA, with DPHA, with DPCA-20, with DPCA-30, with DPCA-60, with DPCA-120 (Nippon Chemical Co., Ltd.), Viscoat 295, with 300, with 360, with GPT , the same as 3PA, the same 400 (Osaka Organic Chemical Industry Co., Ltd.) and so on. A commercial product of a polyfunctional urethane acrylate having a ninth or more functional group, for example, New Frontier R-1150 (above, manufactured by Daiichi Kogyo Co., Ltd.), KAYARAD DPHA-40H (above, Nippon Kayaku Co., Ltd.) ))).

Among these monofunctional, bifunctional or trifunctional or higher functional (meth) acrylates, a trifunctional or higher (meth) acrylate is preferable, and particularly preferably trimethylolpropane triacrylate or neopentyl alcohol Acrylate, neopentyl alcohol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate.

The above-mentioned monofunctional, bifunctional or trifunctional or higher functional (meth) acrylate may be used alone or in combination of two or more.

In the photosensitive resin composition (A), the amount of the polymerizable compound [B] used is preferably from 50 to 140 parts by weight, more preferably from 60 to 120 parts by weight, per 100 parts by weight of the copolymer [A]. When the amount of the polymerizable compound [B] is less than 50 parts by weight, development residue may occur during development, and when it exceeds 140 parts by weight, the hardness of the obtained spacer tends to decrease.

- Photopolymerization Initiator [C] - The component [C] of the photosensitive resin composition (A) is composed of an O-fluorenyl hydrazine type photopolymerization initiator, and is particularly represented by the above formula (1) or (2). A compound (hereinafter referred to as "photopolymerization initiator [C]") is preferred.

The photopolymerization initiator of the present invention is a component which can cause an active species which polymerizes the start of the polymerizable compound [B] by exposure to visible light, ultraviolet rays, far ultraviolet rays, charged particle rays, X-rays or the like.

In the "photopolymerization initiator [C]" represented by the above formula (1) or (2), R ₁ represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms or a phenyl group, and R ₂ is R ₃ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a substituted or unsubstituted phenyl group or an alicyclic group having 7 to 20 carbon atoms (but a carbon number of 7 to 8) Except for the cycloalkyl group). The substituent of the above substituted phenyl group is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group and a halogen atom. These substituents may be 1 to 5, and R ₄ is an oxygen-containing heterocyclic group having 4 to 20 carbon atoms, a nitrogen-containing heterocyclic group having 4 to 20 carbon atoms or a sulfur-containing heterocyclic group having 4 to 20 carbon atoms. R ₅ represents hydrogen, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. n is an integer from 1 to 5, m is an integer from 0 to 5, n + m ≦ 5, and l is an integer from 0 to 6.

The alkyl group having 1 to 20 carbon atoms of R ₁ of the formula (1) or (2) may be a linear or branched alkyl group, and specific examples thereof are a methyl group, an ethyl group, a n-propyl group, and an isopropyl group. , n-butyl, t-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl, n-undecyl, n-dodecyl. The cycloalkyl group having 3 to 8 carbon atoms is, for example, a cyclopentyl group or a cyclohexyl group.

The alkyl group having 1 to 20 carbon atoms of R ₂ and R ₃ may be a linear or branched alkyl group, and specific examples thereof are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, and the like. Dibutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl, n-undecyl, n-dodecyl. The cycloalkyl group having 3 to 8 carbon atoms is, for example, a cyclopentyl group or a cyclohexyl group.

The alkyl group having 1 to 6 carbon atoms of the substituent of the substituted phenyl group of R ₂ and R ₃ may be a linear, branched or cyclic alkyl group, and specific examples thereof are a methyl group, an ethyl group, and a n-propyl group. , isopropyl, n-butyl, t-butyl, tert-butyl, n-pentyl, n-hexyl, cyclopentyl, cyclohexyl and the like.

The alkoxy group having 1 to 6 carbon atoms may be a linear, branched or cyclic alkyl group, and specific examples thereof are a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, and a n-butoxy group. Base, third butoxy, and the like. The halogen atom is, for example, a fluorine atom or a chlorine atom.

An alicyclic group having 7 to 20 carbon atoms (except for a cycloalkyl group having 7 to 8 carbon atoms), for example, a bicycloalkyl group, a tricycloalkyl group, a spiroalkyl group, a third cycloalkyl group, and a group containing a fluorene skeleton. , the base of the adamantane skeleton, and the like.

a nitrogen-containing heterocyclic group having 4 to 20 carbon atoms of R ₄ , an oxygen-containing heterocyclic group having 4 to 20 carbon atoms, and a sulfur-containing heterocyclic group having 4 to 20 carbon atoms, for example, a tetrahydrothiophenyl group or an azepine group , dihydroazepine, dioxolane, triazinyl, oxathiazyl, thiazolyl, oxadiazinyl, dioxaindanyl, dithianaphthyl, furyl , phenylthio, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyrazolyl, furazolyl, pyranyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, Pyrrolinyl, morpholinyl, piperazinyl, quinuclidinyl, fluorenyl, isodecyl, benzofuranyl, benzophenylthio, pyridazinyl, chromenyl, quinolyl, Isoquinolyl, fluorenyl, quinazolinyl, isoquinazolinyl, pyridazinyl, acridinyl, oxazolyl, acridinyl, phenanthroline, thioxanthyl, phenazinyl, phenothiazine Azinyl, phenoxazinyl, phenothionyl, thioxyl, tetrahydrofuranyl, tetrahydropyranyl and the like. Preferred among them are tetrahydrofuranyl group, tetrahydropyranyl group and the like.

The alkyl group having 1 to 12 carbon atoms of R ₅ may be a linear, branched or cyclic alkyl group, and specific examples thereof are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, and the like. Dibutyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, n-decyl, n-undecyl, n-dodecyl, cyclopentyl, cyclohexyl and the like.

The alkoxy group having 1 to 12 carbon atoms may be a linear, branched or cyclic alkyl group, and specific examples thereof are a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, and a n-butoxy group. Base, third butoxy, n-pentyloxy and the like.

Preferred among R ₅ is a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, a methoxy group or an ethoxy group.

It is preferable that n is 1. m is one of 0, 1, 2, and more preferably 1. l is one of 0, 1, 2, and more preferably 1.

A specific example of the compound [C] is ethyl ketone, 1-[9-ethyl-6-(2-methyl-2-tetrahydrofuranyloxyphenyl)-9.H.-carbazol-3-yl]- , 1-(O-acetamidine); ethyl ketone, 1-[9-ethyl-6-(2-methyl-2-tetrahydropyranyloxyphenyl)-9.H.-carbazole 3-yl]-, 1-(O-acetamidine); ethyl ketone, 1-[9-ethyl-6-(2-methyl-2-tetrahydrofuranylmethoxyphenyl)--9. H.-carbazol-3-yl]-, 1-(O-acetamidine); ethyl ketone, 1-[9-ethyl-6-(2-methyl-2-tetrahydropyranylmethoxy) Benzo hydrazino)-9.H.-carbazol-3-yl]-, 1-(O-acetamidine); ethyl ketone, 1-[9-ethyl-6-(2-methyl-3) -tetrahydrofuranyloxybenzoyl)-9.H.-carbazol-3-yl]-, 1-(O-acetamidine); ethyl ketone, 1-[9-ethyl-6-(2-methyl Benzyl-3-tetrahydropyranyloxyphenyl)-9.H.-carbazol-3-yl]-, 1-(O-acetamidine); ethyl ketone, 1-[9-ethyl- 6-(2-methyl-3-tetrahydrofuranylmethoxyphenyl)-9.H.-carbazol-3-yl]-, 1-(O-acetamidine); ethyl ketone, 1- [9-ethyl-6-(2-methyl-3-tetrahydropyranylmethoxyphenyl)-9.H.-carbazol-3-yl]-, 1-(O-acetamidine)乙); ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranyloxyphenyl)-9.H.-carbazol-3-yl]-, 1-(O -acetamidine); ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydropyranyloxyphenyl)-9.H.-carbazol-3-yl] -, 1-(O-acetamidine); ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxyphenyl)--9.H.-carbazole 3-yl]-, 1-(O-acetamidine); ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylmethoxyphenyl) -9.H.-carbazol-3-yl]-, 1-(O-acetamidine); ethyl ketone, 1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranoxybenzene Mercapto)-9.H.-carbazol-3-yl]-, 1-(O-acetamidine); ethyl ketone, 1-[9-ethyl-6-(2-methyl-5-tetra Hydropyridyloxyphenylhydrazino)-9.H.-carbazol-3-yl]-, 1-(O-acetamidine); ethyl ketone, 1-[9-ethyl-6-(2- Methyl-5-tetrahydro Furyl methoxyphenyl fluorenyl)-9.H.-carbazol-3-yl]-, 1-(O-acetamidine); ethyl ketone, 1-[9-ethyl-6-(2- Methyl-5-tetrahydropyranylmethoxybenzoinyl-9.H.-carbazol-3-yl]-, 1-(O-acetamidine); ethyl ketone, 1-[9- Ethyl-6-(2-methyl-2-tetrahydrofuranyloxyphenyl)-9.H.-carbazol-3-yl]-, 1-(O-phenylhydrazinyl); ethyl ketone , 1-[9-ethyl-6-(2-methyl-2-tetrahydropyranyloxyphenyl)-9.H.-carbazol-3-yl]-, 1-(O-benzene Ethyl ketone); ethyl ketone, 1-[9-ethyl-6-(2-methyl-2-tetrahydrofurylmethoxyphenyl)-9.H.-carbazol-3-yl] -, 1-(O-phenylhydrazinyl); ethyl ketone, 1-[9-ethyl-6-(2-methyl-2-tetrahydropyranylmethoxyphenyl)--9 .H.-carbazol-3-yl]-, 1-(O-phenylhydrazinyl); ethyl ketone, 1-[9-ethyl-6-(2-methyl-3-tetrahydrofuranyloxy) Benzoyl)-9.H.-carbazol-3-yl]-, 1-(O-phenylhydrazinyl); ethyl ketone, 1-[9-ethyl-6-(2-methyl -3-tetrahydropyranoxyphenyl fluorenyl)-9.H.-carbazol-3-yl]-, 1-(O-phenylhydrazinyl); ethyl ketone, 1-[9-B -6-(2-methyl-3-tetrahydrofurylmethoxyphenyl)-9.H.-carbazol-3-yl]-, 1-(O-benzoinylhydrazine Ethylketone, 1-[9-ethyl-6-(2-methyl-3-tetrahydropyranylmethoxyphenyl)-9.H.-carbazol-3-yl]-, 1-(O-phenylhydrazinium); ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranyloxyphenyl)-9.H.-carbazole- 3-yl]-, 1-(O-phenylhydrazinyl); ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydropyranyloxyphenyl) -9.H.-carbazol-3-yl]-, 1-(O-phenylhydrazinyl); ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran) Methoxy phenyl hydrazino)-9.H.-carbazol-3-yl]-, 1-(O-acetamidine); ethyl ketone, 1-[9-ethyl-6-(2-methyl 4--4-hydropyranylmethoxyphenylhydrazino)-9.H.-carbazol-3-yl]-, 1-(O-acetamidine); ethyl ketone, 1-[9-B -6-(2-methyl-5-tetrahydrofuranyloxyphenyl)-9.H.-oxazol-3-yl]-, 1-(O-acetamidine); ethyl ketone, 1-[ 9-ethyl-6-(2-methyl-5-tetrahydropyranyloxyphenyl)-9.H.-oxazol-3-yl]-, 1-(O-acetyl); Ethyl ketone, 1-[9-ethyl-6-(2-methyl-5-tetrahydrofurylmethoxyphenyl)--9.H.-carbazole-3- ]-, 1-(O-acetamidine); ethyl ketone, 1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylmethoxyphenyl)--9.H .-carbazol-3-yl]-, 1-(O-acetamidine); ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-(2,2-dimethyl) -1,3-dioxolyl)methoxybenzoinyl-9-H.-carbazol-3-yl]-, 1-(O-acetamidine) and the like.

Preferred among them are ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxyphenyl)-9.H.-carbazol-3-yl]-, 1-(O-acetamidine); ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylmethoxyphenylhydrazino)-9.H.-咔Zyrid-3-yl]-, 1-(O-acetamidine); ethyl ketone, 1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylmethoxyphenyl)--9 .H.-carbazol-3-yl]-, 1-(O-acetamidine); ethyl ketone, 1-[9-ethyl-6-(2-methyl-5-tetrahydropyranyl) Oxyphenyl phenyl)-9.H.-carbazol-3-yl]-, 1-(O-acetamidine); and ethyl ketone, 1-[9-ethyl-6-(2-methyl 4-(2,2-dimethyl-1,3-dioxolanyl)methoxyphenylhydrazino)-9.H.-carbazol-3-yl]-, 1-(O-醯肟)).

These photoinitiators (C) may be used alone or in combination of two or more.

As the photopolymerization initiator [C], an O-acetonitrile type photopolymerization initiator other than the above formula (1) (hereinafter referred to as "photopolymerization initiator [C-2]") may be used in combination.

Specific examples of the photopolymerization initiator [C-2] are 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoinhydrazino), 1,2 -butanedione-1-[4-(phenylthio)phenyl]-2-(O-phenylhydrazinyl), 1,2-butanedione-1-[4-(phenylthio)phenyl -2-(O-ethylindenyl), 1,2-octanedione-1-[4-(methylthio)phenyl]-2-(O-phenylhydrazinyl), 1,2- Octanedione-1-[4-(phenylthio)phenyl]-2-(O-(4-methylphenylhydrazinyl)) and the like. The preferred one is 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-phenylhydrazinyl). The photopolymerization initiator [C-2] can be used in an amount of 30% by weight or less based on the photopolymerization initiator [C].

By using these photopolymerization initiators [C], a spacer having sufficient sensitivity and adhesion can be obtained even at an exposure amount of 1500 J/m ² or less.

The amount of the photopolymerization initiator [C] used in the photosensitive resin composition (A) is preferably from 1 to 20 parts by weight, more preferably from 2 to 15 parts by weight, per 100 parts by weight of the polymerizable compound [B]. . When the amount of the photopolymerization initiator [C] used is less than 1 part by weight, the residual film ratio at the time of development tends to decrease, and when it exceeds 20 parts by weight, the unexposed portion is dissolved in the alkaline developing solution at the time of development. Sex has a tendency to decrease.

In the photosensitive resin composition (A), a photopolymerization initiator [C] and at least one photopolymerization initiator other than the O-acetonitrile type photopolymerization initiator may be used in combination.

Examples of the other photopolymerization initiator include a bisimidazole compound, a benzoin compound, an acetophenone compound, a benzophenone compound, an α-diketone compound, a polynuclear oxime compound, and a xanthone compound. A phosphine compound, a triazine compound, or the like. Among them, an acetaminophen compound (hereinafter sometimes referred to as "(D) component)" or a bisimidazole compound (hereinafter sometimes referred to as "(E) component") is preferred.

(D) component: acetonitrile-based compound The acetaminophen-based compound may, for example, be an α-hydroxyketone compound or an α-amino ketone compound or a compound other than these.

Specific examples of the α-hydroxyketone-based compound, for example, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl Propane-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 1-hydroxycyclohexyl phenyl ketone, and the like. Specific examples of the α-aminoketone compound are, for example, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one, 2-benzyl-2-di Methylamino-1-(4-morpholinylphenyl)-butanone-1, 2-(4-methylbenzyl)-2-dimethylamino-1-(4-morpholinylbenzene Base)-butanone-1 and the like. Specific examples of the compounds other than these include, for example, 2,2-dimethoxyacetamidine, 2,2-diethoxyethyl benzene, 2,2-dimethoxy-2-phenylethyl benzene, and the like. .

These acetophenone-based compounds may be used singly or in combination of two or more.

The use of these acetophenone compounds can improve the sensitivity, the shape of the spacer, and the compressive strength.

(E) component: specific examples of the biimidazole-based compound diimidazole-based compound, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonyl) Phenyl)-1,2'-bisimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1, 2'-bisimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole, 2,2'-bis (2 ,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole, 2,2'-bis(2,4,6-trichlorophenyl)- 4,4',5,5'-tetraphenyl-1,2'-bisimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetraphenyl- 1,2'-bisimidazole, 2,2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole, 2,2 '-Bis(2,4,6-tribromophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole.

Among the above bisimidazole compounds, preferred is 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole, 2,2 '-Bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole, 2,2'-bis(2,4,6-three Chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole, etc., more preferably 2,2'-bis(2,4-dichlorophenyl)-4, 4',5,5'-Tetraphenyl-1,2'-bisimidazole.

These biimidazole-based compounds may be used singly or in combination of two or more.

The use of these biimidazole-based compounds improves sensitivity, resolution, and adhesion.

Further, in order to sensitize the bisimidazole compound, an aliphatic or aromatic compound having a dialkylamine group (hereinafter sometimes referred to as "sensitizer [E-2]") may be used.

Specific examples of the above sensitizer [E-2], such as N-methyldiethanolamine, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamine) Base) benzophenone, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester, and the like. Of these sensitizers, preferred is 4,4'-bis(diethylamino)benzophenone.

These sensitizers [E-2] may be used alone or in combination of two or more.

The amount of the sensitizer [E-2] used is preferably from 0.1 to 50 parts by weight, more preferably from 1 to 20 parts by weight, per 100 parts by weight of [A].

When the amount of the sensitizer [E-2] is less than 0.1 part by weight, the obtained spacer tends to have a thin film or a poor pattern shape, and when it exceeds 50 parts by weight, the pattern shape tends to be poor.

When a bisimidazole compound is used, a thiol compound which provides a hydrogen compound (hereinafter sometimes referred to as "thiol compound [E-3]) may be used. The diimidazole compound is a benzophenone having a dialkylamine group. The compound is sensitized to cause the imidazole compound to be cleaved to generate an imidazole radical. At this time, no high radical polymerization initiation energy is produced, and a poor shape of an inverted conical shape is often formed. This problem can be caused by a diimidazole compound and a dialkylamine. The addition of the thiol compound [E-3] to the coexistence system of the benzophenone compound is moderated. The hydrogen radical of the thiol compound is supplied to the imidazole radical to produce a neutral imidazole group and the polymerization initiation energy. A compound of high sulfur radicals whereby a preferred conical shape can be formed from an inverted conical shape.

The use ratio of the above-mentioned thiol compound [E-3] is preferably 0.1 to 50 parts by weight, more preferably 1 to 20 parts by weight, per 100 parts by weight of the compound [C]. When the amount of the thiol compound [E-3] is less than 0.1 part by weight, the obtained spacer tends to have a thin film or a poor pattern shape, and when it exceeds 50 parts by weight, the pattern shape tends to be poor.

Specific examples thereof are 2-hydrothiobenzothiazole, 2-hydrothiobenzoxazole, 2-hydrothiobenzimidazole, 2-hydrothio-5-methoxybenzothiazole, 2-hydrogen An aromatic thiol such as thio-5-methoxybenzimidazole, 3-hydrothiopropionic acid, methyl 3-hydrothiopropionate, ethyl 3-hydrothiopropionate, 3-hydrogen An aliphatic monothiol such as octyl thiopropionate. An aliphatic thiol having 2 or more functional groups such as 3,6-dioxa-1,8-octanedithiol, pentaerythritol tetrakis (hydrothioacetate), pentaerythritol tetrakis(3-hydrothiopropionate) Wait.

The ratio of use of the other photopolymerization initiator is preferably 100 parts by weight or less, more preferably 80 parts by weight or less, even more preferably 60 parts by weight or less, per 100 parts by weight of the all-photopolymerization initiator. In this case, when the ratio of use of the other photopolymerization initiator exceeds 100 parts by weight, the effects of the present invention may be affected.

- Additive - In the photosensitive resin composition (A), an additive other than the above components may be used as needed within a range that does not impair the effects of the present invention.

For example, in order to improve coatability, a surfactant may be blended. As the surfactant, a fluorine-based surfactant and a polyoxyn-based surfactant can be suitably used.

As the fluorine-based surfactant, a compound having a fluoroalkyl group or a fluorine-extended alkyl group in at least any one of a terminal, a main chain and a side chain can be used. Specific examples thereof include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl)ether, 1,1,2,2-tetrafluorooctylhexyl ether, and octaethylene. Alcohol bis(1,1,2,2-tetrafluorobutyl)ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl)ether, octapropylene glycol di(1,1, 2,2-tetrafluorobutyl)ether, hexapropylene glycol bis(1,1,2,2,3,3-hexafluoropentyl)ether, sodium perfluorododecylsulfonate, 1,1,2, 2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, sodium fluoroalkylbenzenesulfonate, fluoroalkylphosphonic acid Sodium, sodium fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, diglyceryl tetrakis(fluoroalkyl polyoxyethylene ether), fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl polyoxyethylene Ether, perfluoroalkylpolyoxyethanol, perfluoroalkylalkylate, fluoroalkyl ester, and the like.

Further, these commercially available products include, for example, BM-1000, BM-1100 (above, BMCHEMIE), Megafac F142D, F172, F173, F183, F178, F191, F471, and F476 (above, large Japan Ink Chemical Industry Co., Ltd., Fulorad FC-170C, FC-171, FC-430, FC-431 (above, Sumitomo 3M (share) system), Surflon S-112, same S-113, same S- 131, with S-141, with S-145, with S-382, with SC-101, with SC-102, with SC-103, with SC-104, with SC-105, with SC-106 (above, Asahi Glass) (share) system), Ftop EF301, same 303, same 352 (above, new Akita Chemicals Co., Ltd.), Ftergent FT-100, same FT-110, same FT-140A, same FT-150, same FT-250 , with FT-251, with FTX-251, with FTX-218, with FT-300, with FT-310, with FT-400S (above, (share) Neos) and so on.

Further, the polyoxo-type surfactants such as Toray polyoxyl DC3PA, the same DC7PA, the same SH11PA, the same SH21PA, the same SH28PA, the same SH29PA, the same SH30PA, the same SH-190, the same SH-193, the same SZ-6032, the same SF-8428, same DC-57, same DC-190 (above, Toray.DowCorning.Silicone), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (The above, GE Toshiba Silicone (share) system) and other commercial names.

Further, the surfactant other than the above is, for example, polyoxyethylene lauryl ether, polyoxyethylene stearyl allyl ether, polyoxyethylene alkyl ether of polyoxyethylene oleyl ether; polyoxyethylene n-octylbenzene Polyoxyethylene aryl ether of ether, polyoxyethylene n-decyl phenyl ether; nonionic surfactant such as polyoxyethylene dilaurate, polyoxyethylene dialkyl ester of polyoxyethylene distearate Or KP341 (Shin-Etsu Chemical Co., Ltd.), Polyflow No. 57, 95 (manufactured by Kyoeisha Oil Chemical Industry Co., Ltd.), etc., which are commercially available.

These surfactants can be used singly or in combination of two or more.

When the amount of the surfactant is 100 parts by weight based on the copolymer [A], it is preferably 5 parts by weight or less, more preferably 2 parts by weight or less. At this time, when the amount of the surfactant is more than 5 parts by weight, the film tends to be rough at the time of coating.

Further, in order to improve the adhesion to the substrate, a bonding aid may be blended.

The adhesion aid is preferably a functional decane coupling agent such as a decane coupling agent having a reactive functional group such as a carboxyl group, a methacryl group, an isocyanate group or an epoxy group. More specifically, for example, trimethoxydecyl benzoic acid, γ-methyl propylene methoxy propyl trimethoxy decane, vinyl triethoxy decane, vinyl trimethoxy decane, γ-isocyanate propyl triethyl Oxydecane, γ-glycidylpropyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, and the like.

These adjunct agents may be used singly or in combination of two or more.

When the amount of the auxiliary agent is 100 parts by weight based on the copolymer [A], it is preferably 20 parts by weight or less, more preferably 10 parts by weight or less. When the amount of the auxiliary agent exceeds 20 parts by weight, the development of the developer tends to be likely to occur.

Other additives can be added. Additives added to improve stability, etc., are specifically sulfur, anthraquinone, hydroquinone, polyoxyl compound, amine, nitronitroso compound. Examples thereof include 4-methoxyphenol, N-nitroso-N-phenylhydroxylamine aluminum, and the like. These are preferably used in an amount of 3.0 parts by weight or less, more preferably 0.001 to 0.5 parts by weight, per 100 parts by weight of the copolymer [A]. When it exceeds 3.0 parts by weight, sufficient sensitivity cannot be obtained and the pattern shape is deteriorated.

Further, in order to improve heat resistance, a N-(alkoxymethyl)glycoluride compound, an N-(alkoxymethyl)melamine compound, and a compound having a bifunctional or higher functional group in one molecule may be added. Specific examples of the above N-(alkoxymethyl)glycoluric compound, N,N,N,N-tetrakis(methoxymethyl)glycoluril, N,N,N,N-tetra(ethoxymethyl) Glycoluril, N, N, N, N-tetrakis (n-propoxymethyl) glycoluril, N, N, N, N-tetrakis(isopropoxymethyl) glycoluril, N, N, N N-tetrakis(n-butoxymethyl) glycoluril, N,N,N,N-tetrakis(t-butoxymethyl)glycoluril and the like. Among these, N, N, N, N-tetrakis(methoxymethyl) glycoluril is particularly preferred. Specific examples of the above N-(alkoxymethyl)melamine compound are 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(isopropoxy Methyl) melamine, N, N, N, N, N, N-hexa(n-butoxymethyl) melamine, N, N, N, N, N, N-hexa (t-butoxymethyl) ) melamine and the like. Among these, especially N, N, N, N, N, N-hexa(methoxymethyl) melamine is preferred. Commercially available products of these are, for example, Nikalac N-2702, MW-30M (manufactured by Sanwa Chemical Co., Ltd.) and the like.

The compound having a bifunctional or higher epoxy group in one molecule is, for example, ethylene glycol diepoxypropyl ether, diethylene glycol diepoxypropyl ether, polyethylene glycol diepoxypropyl ether, propylene glycol diepoxy Propyl ether, tripropylene glycol diepoxypropyl ether, polypropylene glycol diepoxypropyl ether, neopentyl glycol diepoxypropyl ether, 1,6-hexanediol diepoxypropyl ether, glycerol bicyclo Oxypropyl propyl ether, trimethylolpropane triepoxypropyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol A diglycidyl ether, and the like. Specific examples of these commercial products include EPOLIGHT 40E, EPOLIGHT 100E, EPOLIGHT 200E, EPOLIGHT 70P, EPOLIGHT 200P, EPOLIGHT 400P, EPOLIGHT 40E, EPOLIGHT 1500NP, EPOLIGHT 1600, EPOLIGHT 80MF, EPOLIGHT 100MF, EPOLIGHT 4000, EPOLIGHT 3002 (above Social chemistry (shares) system, etc. These can be used individually or in combination of 2 or more types.

When the photosensitive resin composition (a) of the composition solution is used, the constituent components such as the copolymer [A], the polymerizable compound [B], and the photopolymerization initiator [C] polymer are dissolved in a suitable solvent to form a composition. The solution is preferably prepared. The solvent used for the preparation of the above-mentioned composition solution is used to uniformly dissolve the components constituting the photosensitive resin composition (A), and does not react with each component.

Such a solvent is exemplified, for example, as a solvent for producing the above copolymer [A].

Among these solvents, alcohol, glycol ether, ethylene glycol alkyl ether acetate, ester, and the like are preferably used from the viewpoints of solubility of each component, reactivity with each component, and ease of formation of a coating film. Diethylene glycol. Among them, preferred are benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, and Ethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl methoxypropionate, Ethyl ethoxypropionate.

In order to increase the uniformity in the film thickness plane, the above solvent may be used in combination with a high boiling point solvent. High-boiling solvents which can be used in combination are, for example, N-methylformamide, N,N-dimethylformamide, N-methylanilide, N-methylacetamide, N,N-dimethylacetamidine Amine, N-methylpyrrolidone, dimethyl hydrazine, benzyl ethyl ether, dihexyl ether, acetone acetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, Benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenylethylene glycol ethyl ether acetate, and the like. Preferred among them are N-methylpyrrolidone, γ-butyrolactone, and N,N-dimethylacetamide.

The composition solution prepared as described above may be used after being filtered by a millipere filter having a pore diameter of, for example, 0.2 to 0.5 μm, if necessary. The photosensitive resin composition (A) is particularly suitable for forming a material for a spacer for a display panel such as a liquid crystal panel or a touch panel.

When a spacer for a display panel is formed using a photosensitive resin composition (A) for a spacer for a display panel, a composition solution is applied onto the surface of the substrate, and then the solvent is removed by prebaking to form a coating film.

The coating method of the composition solution is, for example, a suitable method such as a spray method, a roll coating method, a spin coating method, a slit die coating method, a bar coating method, or an inkjet coating method, and particularly preferably a spin coating method. Slot die coating method.

Further, the prebaking conditions vary depending on the type of the constituent components, the blending ratio, and the like, and are, for example, pre-baked at 70 to 90 ° C for 1 to 15 minutes.

Then, the film is exposed to the pre-baked coating film through a predetermined pattern mask, and after polymerization, the developing solution is developed to remove unnecessary portions to form a pattern.

The radiation used for exposure may be appropriately selected from visible light, ultraviolet light, far ultraviolet light, charged particle beam, X-ray, etc., and is preferably a radiation having a wavelength in the range of 190 to 450 nm.

The development method is, for example, a stirring method, a dipping method, a rinsing method, or the like, and the development time is usually 30 to 180 seconds.

The developing solution can use, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, and an inorganic base of ammonia; ethylamine, a primary amine of n-propylamine; diethylamine, di-n-propylamine. Grade 2 amine; tertiary amine of trimethylamine, methyldiethylamine, ethyldimethylamine, triethylamine; octaethanolamine of methylethanolamine, methyldiethanolamine, triethanolamine; pyrrole, piperazine Pyridine, N-methylpiperidine, N-methylpyrrolidine, 1,8-diazabicyclo [5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]- 5-decene alicyclic tertiary amine; pyridine, trimethylpyridine, lutidine, quinoline aromatic tertiary amine; tetramethylammonium hydroxide, tetraethylammonium hydroxide 4-grade ammonium salt, etc. An aqueous solution of a basic compound.

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

After the development, for example, by washing with running water, for example, after washing for 30 to 90 seconds, the unnecessary portion is removed, and compressed air or compressed nitrogen is blown and dried to form a predetermined pattern.

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, 5 to 30 minutes on a hot plate, for example, 30 to 90 minutes in an oven. Get the spacer for the purpose.

The photosensitive resin composition (A) of the present invention is highly sensitive, and can faithfully realize the design size of the mask pattern, and has excellent adhesion to the substrate, and a sufficient spacer can be obtained at an exposure amount of 1500 J/m ² or less. The shape and the film thickness are excellent in strength and heat resistance, and are excellent in the shape of the spacer and the film thickness in the low-exposure region, and during the storage period, foreign matter is less likely to be generated during use.

Example

Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples, but the present invention is not limited to these Examples.

Synthesis Example 1

5 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol methyl ethyl ether were placed in a flask equipped with a cooling tube and a stirrer, followed by addition of a methyl group. 18 parts by weight of acrylic acid, 40 parts by weight of glycidyl methacrylate, 5 parts by weight of styrene, and 32 parts by weight of tricyclo [5.2.1.0 ^{2 , 6} ]decane-8-yl methacrylate, after nitrogen substitution Further, 5 parts by weight of 1,3-butadiene was added, and the temperature of the solution was gradually increased to 70 ° C while stirring, and the temperature was maintained for 5 hours to carry out polymerization to obtain a solution of the copolymer [A-1].

The solid content concentration of this solution was 33.0% by weight, and the Mw of the copolymer [A-1] was 11,000.

Synthesis Example 2

7 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol methyl ethyl ether were placed in a flask equipped with a cooling tube and a stirrer, followed by addition of a methyl group. 15 parts by weight of acrylic acid, 20 parts by weight of glycidyl methacrylate, 25 parts by weight of 2-methylglycidyl methacrylate, 5 parts by weight of styrene, tricyclomethacrylate [5.2.1.0 ^{2 , 6} ] 20 parts by weight of decane-8-yl ester and 10 parts by weight of tetrahydrofurfuryl methacrylate, after nitrogen substitution, 5 parts by weight of 1,3-butadiene was added, and the temperature of the solution was raised to 70 by stirring slowly. At ° C, the temperature was maintained for 5 hours to carry out polymerization to obtain a solution of the copolymer [A-2].

The solid content concentration of this solution was 33.4% by weight, and the Mw of the copolymer [A-2] was 7,000.

Synthesis Example 3

5 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 250 parts by weight of diethylene glycol methyl ethyl ether were placed in a flask equipped with a cooling tube and a stirrer, followed by addition of a methyl group. 10 parts by weight of acrylic acid, 30 parts by weight of 2-methacryloxyethyl succinic acid, 25 parts by weight of n-butyl methacrylate, and 30 parts by weight of benzyl methacrylate, and after nitrogen substitution, 1 is added. 5 parts by weight of 3-butadiene was slowly stirred to raise the temperature of the solution to 80 ° C, and the temperature was maintained for 5 hours to carry out polymerization to obtain a solution of the copolymer [A-3] having a solid content of 28.0% by weight. The Mw of the obtained copolymer [A-3] was 9,000.

Example 1

Preparation of a solution solution: Copolymer [A]: 100 parts by weight of a solution of the copolymer [A-1] obtained in Synthesis Example 1 (solid content), polymerizable compound [B]: KAYARAD DPHA (Nippon Chemical Co., Ltd. )) 80 parts by weight, photopolymerization initiator [C]: ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylmethoxyphenyl)--9 5 parts by weight of H.-carbazol-3-yl]-, 1-(O-acetyl ketone oxime) was dissolved in propylene glycol monomethyl ether acetate to have a solid content of 35% by weight, and a pore diameter of 0.2. The milipore filter of μ m was filtered to prepare a composition solution (S-1).

(I) Formation of a spacer The above composition solution was applied onto an alkali-free glass substrate using a spinner, and then prebaked on a hot plate at 90 ° C for 3 minutes to form a coating film having a film thickness of 6.0 μm.

Ultraviolet rays having an exposure gap of 150 μm and an exposure intensity of 300 W/m ^{2 having a} wavelength of 365 nm were exposed on the above-prepared coating film via a pattern mask having a residual 10 μm square. Subsequently, the mixture was washed with pure water at a temperature of 25 ° C for 60 seconds in a 0.05 wt% aqueous solution of potassium hydroxide, and then washed with pure water for 1 minute. The mixture was further heated in an oven at 150 ° C for 120 minutes to form a spacer.

(II) Evaluation of resolution In the pattern obtained in the above (1), the residual film ratio after development (thickness after development/initial film thickness × 100) was evaluated as the minimum pattern size of sensitivity of 90% or more. The smaller the pattern size, the better the resolution. The results are shown in Table 2.

(III) Sensitivity evaluation In the pattern obtained in the above (1), when the residual film ratio after development is 90% or more and the sensitivity is 1,500 J/m ² or less, the sensitivity is good.

(IV) Evaluation of Pattern Cross-Section Shape The result of observing the cross-sectional shape of the pattern obtained in the above (1) by a scanning electron microscope was as shown in Fig. 1 and corresponds to any of A to C. As shown in A, when the pattern edge is a conical shape, the pattern shape is good. As shown by B, when the pattern edges are formed vertically, the pattern shape is slightly good.

Further, as shown by C, the shape in which the inverted cone (the side of the film surface having the cross-sectional shape is longer than the side of the substrate side, and the inverted triangular shape) is formed is highly likely to be peeled off during the subsequent polishing step. This shape is not good.

(V) Evaluation of Compressive Strength The compressive strength of the spacer obtained in the above (1) was evaluated using a micro compression tester (MCTM-200, manufactured by Shimadzu Corporation). The amount of deformation (measuring temperature: 23 ° C) at which a load of 10 mN was applied was measured by a flat head having a diameter of 50 μm. When the value is 0.5 or less, the compressive strength is good. The results are shown in Table 2.

(VI) Evaluation of the polishing resistance The liquid crystal alignment agent AL3046 (manufactured by JSR) was applied onto the substrate obtained in the above (1), and dried at 180 ° C for 1 hour to form a liquid crystal alignment film coating printer. A coating film of an alignment agent having a film thickness of 0.05 μm was dried.

This coating film was subjected to a grinding treatment by a grinding machine having a drum wound with a nylon fabric at a number of revolutions of the drum of 500 rpm and a moving speed of the polishing table of 1 cm/sec. The presence or absence of cutting or peeling of the spacer pattern at this time is as shown in Table 2.

(VII) Evaluation of Adhesiveness A cured film for adhesion evaluation was formed in the same manner as in the above (1) except that the pattern mask was not used, and the adhesion test was performed. The test method is based on the checkerboard tape method of 8.5.2 in the adhesion test of JIS K-5400 (1900) 8.5. The number of remaining checkerboards is shown in Table 2.

(VIII) Evaluation of Preservation Stability After modulating the composition, the composition was stored at -15 ° C, and the change in the necessary exposure amount after the development of the residual film ratio after the development was 90% or more was traced as in the above (III) sensitivity evaluation. The relative value of the sensitivity after storage for 3 months and the sensitivity after the preparation was measured. A light scattering type particle detector (KS-28B, manufactured by Lion Co., Ltd.) was used to measure the occurrence of foreign matter of 0.5 μm or more in the solution after 3 months. The results are shown in Table 2.

(IX) Heat resistance was evaluated except that the mask was not used, and the formation of the spacer was the same. After the cured film was formed, it was heated in an oven at 240 ° C for 60 minutes, and the film thickness before and after the heating was measured to evaluate the residual film rate (heating). After film thickness × 100 / initial film thickness). The results are shown in Table 2.

Examples 2 to 12 and Comparative Examples 1 to 4

In the same manner as in Example 1, except that the components [A] to [E] in the first embodiment were used in the same manner as in Example 1, the composition solution was prepared to form a spacer and evaluated. The addition amount of [B] to [E] is a weight ratio of 100 parts by weight of the copolymer [A].

In Table 1, the abbreviations of the ingredients mean the following compounds.

(B-1): (KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) (B-2): KAYARAD DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.) (B-3): Diethylene glycol diacrylate (C-1): ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydropyranyloxyphenyl)-9.H.-carbazol-3-yl] -, 1-(O-acetylhydrazinone) (C-2): ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxyphenyl)- 9.H.-carbazol-3-yl]-, 1-(O-acetylhydrazinone) (C-3): ethyl ketone, 1-[9-ethyl-6-(2-methyl- 5-tetrahydropyranylmethoxyphenylhydrazino)-9.H.-carbazol-3-yl]-,1-(O-ethylmercapto oxime) (C-4): ethyl ketone, 1 -[9-ethyl-6-(2-methyl-5-tetrahydrofurylmethoxyphenyl)-9.H.-carbazol-3-yl]-, 1-(O-ethenyl ketone肟)(C-5): Ethyl ketone, 1-[9-ethyl-6-[2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl) A Oxyl phenyl hydrazino)-9.H.-carbazol-3-yl]-, 1-(O-acetyl ketone oxime) (D-1): 2-methyl-1-[4-(A Thio)phenyl]-2-morpholinylpropane 1-ketone (Irgacure 907, manufactured by Ciba Geigy Chemical Co., Ltd.) (D-2): 2-(4-methylbenzyl)-2-dimethylamino-1-(4-morpholinylphenyl) Keto-1 (Irgacure 306, manufactured by Ciba Geigy chemicals) (E-1): 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1 , 2'-bisimidazole (E-2): 4,4'-bis(diethylamino)benzophenone (E-3): 2-hydrothiobenzothiazole, in Table 1, the mark of - Indicates that the ingredient has not been added.

The evaluation results are shown in Table 2.

Fig. 1 is a cross-sectional view showing an example of a pattern.

Claims (3)

A photosensitive resin composition comprising: [A] (a1) a copolymer of an ethylenically unsaturated carboxylic acid and/or an ethylenically unsaturated carboxylic anhydride and (a2) another ethylenically unsaturated compound, [B] a polymerizable compound having an ethylenically unsaturated bond and [C] a photopolymerization initiator composed of a compound represented by the following formula (2), [R ₁ is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms or a phenyl group; and R ₂ and R ₃ are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and a carbon number of 3 to 8; a cycloalkyl group, a substituted or unsubstituted phenyl group or an alicyclic group having 7 to 20 carbon atoms (except for a cycloalkyl group having 7 to 8 carbon atoms), and the substituent of the above substituted phenyl group is a carbon number of 1 to 6 An alkyl group, an alkoxy group having 1 to 6 carbon atoms, a phenyl group or a halogen atom, R ₄ is an oxygen-containing heterocyclic group having 4 to 20 carbon atoms, a nitrogen-containing heterocyclic group having 4 to 20 carbon atoms or a carbon number of 4~ a sulfur-containing heterocyclic group of 20, R ₅ is hydrogen, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms, n is an integer of 1 to 5, m is an integer of 0 to 5, n+ m ≦ 5, 1 is an integer from 0 to 6. A spacer for a display panel, which is characterized in that it is formed of a photosensitive resin composition of the first application of the patent scope. A display panel comprising the spacer for a display panel according to item 2 of the patent application scope.