KR100736294B1 - Photosensitive resin composition, cured products thereof and spacer made from these cured products for display panel - Google Patents

Abstract

The photosensitivity which can form the display panel spacer which does not increase the viscosity of a photosensitive resin composition or gelatinizes even at room temperature, has sufficient storage stability, has the heat resistance and chemical-resistance required as a permanent film, and is excellent in compressive strength. Provided are a resin composition, a cured product thereof, and a spacer for a display panel formed by the cured product thereof.

The photosensitive resin composition of this invention is (A) carboxyl group-containing photosensitive resin which has a carboxyl group and 2 or more ethylenically unsaturated bond in 1 molecule, (B) polymeric compound which has 1 or more ethylenically unsaturated bond in 1 molecule, ( C) A photopolymerization initiator and a composition containing (D) an oxetane compound having two or more oxetanyl groups in one molecule, wherein the carboxyl group-containing photosensitive resin (A) has an unsaturated double bond represented by the following general formula (1): It is carboxyl group-containing photosensitive resin which contains a compound as a copolymerization component.

Photosensitive resin composition, carboxyl group-containing photosensitive resin, photoinitiator, oxetane compound, ethylenically unsaturated bond, polymeric compound

Description

Photosensitive resin composition and its hardened | cured material, and the spacer for display panels which consist of said hardened | cured material {PHOTOSENSITIVE RESIN COMPOSITION, CURED PRODUCTS THEREOF AND SPACER MADE FROM THESE CURED PRODUCTS FOR DISPLAY PANEL}

<Patent Document 1> Japanese Patent Application Laid-Open No. 11-133600 (claims)

<Patent Document 2> Japanese Unexamined Patent Publication No. 2001-324809 (claims)

This invention relates to the photosensitive resin composition, its hardened | cured material, and the display panel spacer which consists of the said hardened | cured material. More specifically, it relates to the photosensitive resin composition which is excellent in storage stability, compressive strength which is preferable as a material for forming spacers for display panels, such as a liquid crystal panel and a touch panel, its hardened | cured material, and the display panel spacer which consists of said hardened | cured material. will be.

In the conventional liquid crystal panel, spacer particles such as glass beads and plastic beads having a predetermined particle diameter have been used in order to keep the two substrate gaps constant. However, since these spacer particles are randomly scattered on the glass substrate, when the spacer is present in the effective pixel portion, there is a problem that the spacer is reflected or the incident light is scattered and the contrast of the liquid crystal panel is lowered. In order to solve these problems, the method of forming a spacer by photolithography using the photosensitive resin composition is used.

Such a spacer is required to withstand the compressive load when the liquid crystal panel is bonded. However, spacers formed using a conventional photosensitive resin composition composed of a photosensitive resin, a polyfunctional monomer and a photopolymerization initiator have insufficient hardness, and thus have a high temperature and high pressure at the time of assembly (cell compression) of a color filter and a TFT array substrate. There was a problem that the plastic deformation amount was large, which hindered the function as a spacer, and there was still room for improvement.

Moreover, since a spacer is used as a permanent film in a liquid crystal panel, heat resistance and chemical-resistance are also calculated | required. Therefore, in order to obtain the characteristic as a permanent film, the photosensitive resin composition used for this use uses the thermosetting resin which combines a carboxyl group and an epoxy group in the same molecule (refer patent document 1), or the epoxy resin which can react with binder resin, such as In some cases, a crosslinking agent is added (see Patent Document 2). However, in the case of the photosensitive resin composition which uses an epoxy crosslinking agent, since the reactivity of the epoxy group which produces a crosslinking reaction is high, there exists a fault, such as storage stability and a problem of reducing workability, and therefore the characteristic and workability of hardened | cured material It was difficult to make it compatible.

The present invention has been made on the basis of the above circumstances, and its object is not to increase viscosity or gelation of the photosensitive resin composition even at room temperature storage conditions, to have sufficient storage stability, and to have heat resistance and chemical resistance required as a permanent film. Moreover, it is providing the photosensitive resin composition which can form the spacer for display panels which is excellent in compressive strength. Another object of this invention is to provide the hardened | cured material obtained by irradiating an active energy ray and heat-hardening the said photosensitive resin composition, and the spacer for display panels formed with the hardened | cured material.

As a result of earnestly researching the inventors in order to achieve the above object, the basic aspect thereof is (A) a carboxyl group-containing photosensitive resin having a carboxyl group and two or more ethylenically unsaturated bonds in one molecule, and (B) one or more molecules in one molecule. A composition containing a polymerizable compound having an ethylenically unsaturated bond, (C) a photopolymerization initiator, and (D) an oxetane compound having two or more oxetanyl groups in one molecule, wherein the carboxyl group-containing photosensitive resin (A) The photosensitive resin composition which is a carboxyl group-containing photosensitive resin containing the compound which has an unsaturated double bond represented by following formula (1) as a copolymerization component is excellent in storage stability, and the hardened | cured material obtained by hardening the said photosensitive resin composition is hardness The present invention has been found to be excellent in heat resistance, chemical resistance, and compressive strength.

(Wherein x represents an integer of 0 to 2, R ¹ represents hydrogen or a methyl group, R ² represents a dicyclopentadiene derivative having 10 to 20 carbon atoms or a tricyclodecane derivative having 10 to 20 carbon atoms)

Moreover, according to this invention, an alkali developing solution after the photocuring process of apply | coating and drying the said photosensitive resin composition, the photocuring process of selectively irradiating an active energy ray to the coating film obtained through the said coating film formation process, and the photocuring process. The hardened | cured material obtained through the alkali image development process which removes an unirradiated part and obtains a pattern using the process, and the process of heating and hardening the pattern obtained at the alkali image development process is provided.

In addition, in this invention, an "active energy ray" means containing visible ray, an ultraviolet-ray, far ultraviolet ray, an electron beam, X-rays, etc.

Moreover, according to this invention, the spacer for display panels which consists of hardened | cured material excellent in the heat resistance and chemical-resistance obtained using the said photosensitive resin composition, and excellent in compressive strength is provided.

Best Mode for Carrying Out the Invention

The oxetane compound added as a crosslinking component to the photosensitive composition of the present invention has a four-membered ring oxetanyl group, which reacts with the carboxyl group of the alkali-soluble photosensitive resin at the time of thermosetting, and mainly produces a primary hydroxyl group. Hardened | cured material which is excellent in adhesiveness is obtained compared with the case where the epoxy resin which a grade hydroxyl group generate | occur | produces is used. Moreover, since an oxetane compound has a slow reaction at low temperature compared with an epoxy resin, since the photosensitive composition containing this has a long self-life (preservation life), it is advantageous at the point of workability and economy.

Hereinafter, each component of the photosensitive composition of this invention is demonstrated in detail.

The carboxyl group-containing photosensitive resin (A) having a carboxyl group and two or more ethylenically unsaturated bonds in the molecule of the present invention is a carboxyl group-containing photosensitive resin containing a compound having an unsaturated double bond represented by the following formula (1) as a copolymerization component.

<Formula 1>

(Wherein x represents an integer of 0 to 2, R ¹ represents hydrogen or a methyl group, R ² represents a dicyclopentadiene derivative having 10 to 20 carbon atoms or a tricyclodecane derivative having 10 to 20 carbon atoms)

Such carboxyl group-containing photosensitive resin (A) contains the compound which has an unsaturated double bond represented by the said Formula (1) as a component, and since glass transition temperature can be improved and transparency is high, it is obtained from the photosensitive resin composition using this. It becomes possible to remarkably improve the hardness, compressive strength, heat resistance, and chemical resistance of the cured product.

Although such a carboxyl group-containing photosensitive resin (A) is not limited to a specific thing, Photosensitive resin synthesize | combined by copolymerization of an unsaturated monomer especially listed below can be used preferably.

In the copolymer containing (1) (a) unsaturated carboxylic acid and (b) a compound having an unsaturated double bond represented by the formula (1) (and) or (c) a compound having another unsaturated double bond, an ethylenically unsaturated group Carboxyl group-containing photosensitive resin obtained by adding as a pendant,

(2) a copolymer comprising (d) a compound having an epoxy group with an unsaturated double bond, (b) a compound having an unsaturated double bond represented by the formula (1), and / or (c) a compound having another unsaturated double bond carboxyl group-containing photosensitive resin obtained by reacting (a) unsaturated carboxylic acid and reacting the produced secondary hydroxyl group with (e) saturated or unsaturated polybasic acid anhydride,

(3) a copolymer comprising (f) an acid anhydride having an unsaturated double bond, (b) a compound having an unsaturated double bond represented by the formula (1), and / or (c) a compound having another unsaturated double bond, (g) Carboxyl group containing photosensitive resin etc. which are obtained by making a compound which has a hydroxyl group and unsaturated double bond react are mentioned.

As unsaturated carboxylic acid (a) used for the synthesis | combination of the said carboxyl group-containing photosensitive resin (1) and (2), for example, acrylic acid, methacrylic acid, itaconic acid, (beta) -carboxyl ethyl acrylate, (beta) -carboxyl The compound etc. which added polybasic acid anhydride to ethyl methacrylate and the (meth) acrylate containing a hydroxyl group are mentioned. Among them, acrylic acid or methacrylic acid is particularly preferable in view of photosensitivity, reactivity, and storage stability. These unsaturated monocarboxylic acids (a) can also be used individually or in mixture of 2 or more types.

In addition, in this specification, a (meth) acrylate is a term which generically mentions acrylate and methacrylate, and is the same also about another similar expression.

As a specific example of the compound (b) which has an unsaturated double bond represented by the said Formula (1) which is the characteristic of the carboxyl group-containing photosensitive resin of this invention, dicyclopentenyl (meth) acrylate and dicyclopentenyloxyethyl (meth) acrylate And dicyclopentanyl (meth) acrylate. Examples of the commercially available products include Pankrill FA-511A, FA-512A, FA-513A, FA-512M, FA-513M and the like manufactured by Hitachi Kasei Kogyo Co., Ltd., for example.

As a compound (c) which has another unsaturated double bond used for the synthesis | combination of the said carboxyl group-containing photosensitive resin (1), (2), and (3), a well-known conventional monofunctional monomer can be used. For example, styrene, chlorostyrene, α-methylstyrene; As substituents methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, amyl, 2-ethylhexyl, octyl, capryl, nonyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, isobo Acrylate, methacrylate or fumarate having substituents such as ronyl, methoxyethyl, butoxyethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-chloro-2-hydroxypropyl and the like; Monoacrylate or monomethacrylate of polyethylene glycol, or monoacrylate or monomethacrylate of polypropylene glycol; Vinyl acetate, vinyl butyrate or vinyl benzoate; Olefins such as ethylene and propylene; Acrylonitrile etc. are mentioned.

As a compound (d) which has an epoxy group and unsaturated double bond used for the synthesis | combination of the said carboxyl group-containing photosensitive resin (2), glycidyl (meth) acrylate, (beta) -methyl glycidyl (meth) acrylate, and (beta) -ethyl Glycidyl (meth) acrylate, N- [4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl] acrylamide, N- [4- (2,3-epoxypropoxy) -3 , 5-dimethyl benzyl] methacrylamide, crotonic acid glycidyl, 3, 4- epoxycyclohexyl methyl (meth) acrylate, etc. are mentioned. Among these, glycidyl (meth) acrylate is preferable at the point of reactivity.

Examples of the saturated or unsaturated polybasic acid anhydride (e) used in the synthesis of the carboxyl group-containing photosensitive resin (2) include methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride and nadine anhydride. Alicyclic dibasic acid anhydrides such as acid, 3,6-endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride and tetrabromophthalic anhydride; Aliphatic or aromatic polybasic acid anhydrides such as succinic anhydride, maleic anhydride, itaconic anhydride, octenyl succinic anhydride, pentadodecenyl succinic anhydride, phthalic anhydride, trimellitic anhydride, and the like, and the like. More than one species can be used. Among these, alicyclic dibasic acid anhydride is especially preferable at the point of developability.

Examples of the acid anhydride (f) having an unsaturated double bond used in the synthesis of the carboxyl group-containing photosensitive resin (3) include maleic anhydride, itaconic anhydride, pyromellitic anhydride, 2-hydroxyethyl (meth) acrylate, Partial reaction products with unsaturated compounds having hydroxyl groups, such as hydroxyalkyl (meth) acrylates, such as 2-hydroxypropyl (meth) acrylate, etc. are mentioned, These can be used individually or in combination of 2 or more types. Can be. Among these, maleic anhydride which can synthesize | combine a polymer stably is preferable.

As a compound (g) which has a hydroxyl group and unsaturated double bond used for the synthesis | combination of the said carboxyl group-containing photosensitive resin (3), 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4- Hydroxyalkyl (meth) acrylates such as hydroxybutyl (meth) acrylate; Diethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipenta Erythritol penta (meth) acrylate etc. are mentioned. Moreover, the compound which added cyclic ester, such as (epsilon) -caprolactone, to the hydroxyl group of the said compound can also be used. These can be used individually or in combination of 2 or more types.

Although these carboxyl group-containing photosensitive resin (A) may be used individually or in mixture, in either case, it is preferable to mix | blend them in the ratio of 5-80 mass% of the whole composition whole quantity, Preferably it is 10-60 mass%. If necessary, a small amount of a resin such as a polybasic acid anhydride added to a carboxyl group-containing photosensitive resin other than the above, for example, epoxy acrylate, may be added.

The acid value of the said carboxyl group-containing photosensitive resin (A) is 30-250 mg KOH / g, Preferably it is 50-150 mg KOH / g. When the acid value of the said carboxyl group-containing photosensitive resin is less than 30 mg KOH / g, sufficient hardening reaction with the said oxetane compound (D) becomes difficult to advance, and its solubility with respect to aqueous alkali solution is inadequate, and it is easy to produce development defect. On the other hand, when it exceeds 250 mg KOH / g, it is unpreferable since adhesive deterioration of a film and dissolution of a photo hardening part (exposure part) arise at the time of image development.

In addition, the double bond equivalent of carboxyl group-containing photosensitive resin (A) can use preferably 350-2,000, Preferably it is 400-1,500. When the double bond equivalent of carboxyl group-containing photosensitive resin (A) is less than 350, since storage stability falls or the strength of hardened | cured material becomes weak, it is unpreferable. On the other hand, when the double bond equivalent exceeds 2,000, since the work margin at the time of image development is narrow and high exposure amount is required at the time of photocuring, it is unpreferable.

As a polymeric compound (B) which has one or more ethylenically unsaturated bond in 1 molecule used by this invention, a monofunctional, bifunctional, or trifunctional or more than (meth) acrylate has good polymerizability, and It is used preferably at the point which improves strength and heat resistance.

As said monofunctional (meth) acrylate, 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isoboroyl (meth) acrylate, 3-methoxybutyl (meth), for example Acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, etc. are mentioned. As its commercial item, for example, an Alonics M-101, copper M-111, copper M-114 (above, manufactured by Toagosei Co., Ltd.), KAYARAD TC-110S, copper TC-120S (above, Nippon Kayaku Co., Ltd.) ), Biscot 158, East 2311 (above, manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.).

As said bifunctional (meth) acrylate, for example, ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polypropylene Glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, bisphenoxyethanol fluorene diacrylate, and the like. As its commercial item, for example, Alonics M-210, copper M-240, copper M-6200 (above, Toagosei Co., Ltd.), KAYARAD HDDA, copper HX-220, copper R-604 (more, Nippon Kaya) Cub Co., Ltd., Biscot 260, 312, 335 HP (above, Osaka Yuki Kagaku Kogyo Co., Ltd.), etc. are mentioned.

As said trifunctional or more than (meth) acrylate, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri (meth) acryloyloxyethyl) phosphate, pentaerythritol tetra (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned. As its commercially available product, for example, Alonics M-309, M-400, M-402, M-405, M-450, M-7100, M-8030, M-8060, M -1310, M-1600, M-1960, M-8100, M-8530, M-8560, M-9050, TO-1450 (above, manufactured by Toa Kosei Co., Ltd.), KAYARAD TMPTA, East DPHA, East DPCA-20, East DPCA-30 , East DPCA-60, East DPCA-120 (above, Nippon Kayaku Co., Ltd.), Biscot 295, East 300, East 360, East GPT, East 3PA, East 400 (above, Osaka Yuki Kagaku Kogyo Co., Ltd. ) Production). These monofunctional, difunctional or trifunctional or more (meth) acrylates are used alone or in combination.

As a compounding quantity of these polymeric compounds (B), 5-100 mass parts is preferable with respect to 100 mass parts of said carboxyl group-containing photosensitive resin (A), Especially preferably, it is 5-50 mass parts. When (B) component is less than 5 mass parts, sufficient sclerosis | hardenability will not be obtained. On the other hand, when it becomes 100 parts or more, since touch-drying property worsens or hardened | cured material becomes weak, it is not preferable.

As said photoinitiator (C), the well-known compound which generate | occur | produces a radical by irradiation of an active energy ray can be used, For example, acetophenone, 2, 2- dimethoxy- 2-phenylacetophenone, 2, 2- Diethoxy-2-phenylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butyltrichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1 -[4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, N, Acetophenones, such as N-dimethylamino acetphenone; Benzophenone, methylbenzophenone, 2-chlorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, Michler's ketone, 4 Benzophenones such as -benzoyl-4'-methyldiphenyl sulfide; Benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Thioxanthones, such as thioxanthone, 2-chloro thioxanthone, 2, 4- dimethyl thioxanthone, 2, 4- diethyl thioxanthone, and 2, 4- diisopropyl thioxanthone; Anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-aminoanthraquinone and 2,3-diphenyl anthraquinone; Organic peroxides such as benzoyl peroxide and cumene peroxide; Thiol compounds such as 2,4,5-triarylimidazole dimer, riboflavin tetrabutylate, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole; Organic halogen compounds such as 2,4,6-tris-s-triazine, 2,2,2-tribromoethanol and tribromomethylphenyl sulfone; 2,4,6-trimethylbenzoyl diphenylphosphine oxide etc. are mentioned. Moreover, an acridine compound, oxime ester, etc. are mentioned as another example. These compounds may be used alone or in combination of two or more thereof.

In addition, the photoinitiator (C) as described above is N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine, or the like. Tertiary amines; thioethers such as β-thiodiglycol; Sensitizing dyes such as (keto) coumarin and thioxanthene; It can be used in combination with one kind or two or more kinds of photosensitizers or accelerators such as alkyl borate salts such as cyanine, rhodamine, safranin, malachite green, methylene blue and the like.

Preferred combinations of the photopolymerization initiator (C) are 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one (for example, from Ciba Specialty Chemicals, Irugacure 907 and 2-chloro-thioxanthone (for example, Kayak CTX manufactured by Nippon Kayaku Co., Ltd.) and 2,4-diethyl thioxanthone (for example, Nippon Kayakaku Co., Ltd.) Cure DETX), 2-isopropyl thioxanthone, 4-benzoyl-4'-methyldiphenyl sulfide and the like. Moreover, the preferable range of the photoinitiator (C) usage-amount as mentioned above is a ratio which becomes 0.01-30 mass parts with respect to 100 mass parts of said carboxyl group-containing photosensitive resin (A), Preferably it becomes 0.1-15 mass parts. When the compounding ratio of a photoinitiator is less than 0.01 mass part, photocurability worsens, On the other hand, when it is more than 30 mass parts, the characteristic of a cured coating film worsens and storage stability worsens, and it is unpreferable.

As the oxetane compound (D), any substance may be used as long as it is an oxetane compound having two or more oxetanyl groups in one molecule, and the organic solvent (described later) in terms of transparency of the cured product ( Soluble in E) is preferably used.

Examples of the bifunctional oxetane compound include bisoxetanes represented by the following general formula (2).

(In Formula 2, R ³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ⁴ represents an oxygen atom, a sulfur atom, and linear or branched saturated hydrocarbons having 1 to 12 carbon atoms, 1 to 12 carbon atoms. Linear or branched unsaturated hydrocarbons, aromatic hydrocarbons represented by the following formulas (I), (II), (III), (IV) and (V), and carbonyl groups represented by the following formulas (VI) and (VII) A linear or cyclic alkylene to be included, a group having two valences selected from aromatic hydrocarbons containing a carbonyl group represented by the following formulas (VIII) and (IX)), and other bifunctional oxetane compounds And naphthalene type.

(Wherein R ⁵ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group or an aralkyl group, and R ⁶ represents —O—, —S—, —CH ₂ —, —NH—, —SO ₂ —, -CH (CH ₃ )-, -C (CH ₃ ) ₂ -or -C (CF ₃ ) _2- , and R ⁷ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms)

(Wherein n represents an integer of 1 to 12)

As a polyfunctional oxetane compound, hydroxyl groups, such as oxetane alcohol, novolak resin, poly (hydroxy styrene), the calix arene, and silicone resins, such as a silsesquioxane, in addition to the compound represented by following formula (3) And etherified resins with resins. In addition, the copolymer etc. of the unsaturated monomer which has an oxetane ring, and an alkyl (meth) acrylate are mentioned.

(In the above formula (3), R ³ is the same meaning as above, and R ⁸ is a carbon number of 1 to 12 as represented by the hydroxyl group-containing residue of the ether, the following formula (X), (XI) and (XII)) Branched alkylene groups, aromatic hydrocarbons represented by the formulas (XIII), (XIV) and (XV), and m represents the number of functional groups to which the residue R ⁸ is bonded, and an integer of 3 or more, preferably 3 to Is an integer of 100)

(Wherein R ⁹ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having a substituent)

The action of the oxetane compound (D) is to form a crosslinked structure by reacting with a carboxyl group in the carboxyl group-containing photosensitive resin to form a solid cured product having improved chemical resistance and heat resistance. As for the compounding quantity of an oxetane compound (D), the ratio of 5-100 mass parts is suitable with respect to 100 mass parts of said carboxyl group-containing photosensitive resin (A), Preferably it is 15-60 mass parts.

In order to accelerate reaction of the oxetane compound (D) and the carboxyl group in carboxyl group-containing photosensitive resin (A), you may add the reaction promoter shown below.

As the reaction accelerator, it is possible to arbitrarily select among tertiary amines, imidazoles, quaternary onium salts, tertiary phosphines, phosphoniumlides, acetylacetone metal complexes, or crown ether complexes, and these alone or in combination. You may use combining a species or more.

Examples of tertiary amines include triethylamine, tributylamine, DBU (1,8-diazabicyclo [5.4.0] undeca-7-ene), DBN (1,5-diazabicyclo [4.3.0] nona -5-ene), DABCO (1,4-diazabicyclo [2.2.2] octane), pyridine, N, N-dimethyl-4-aminopyridine, etc. are mentioned.

As imidazole, imidazole, 2-methylimidazole, 2-undecylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2 -Phenyl imidazole, 2-phenyl imidazole, isocyanuric acid adduct, etc. are mentioned.

Examples of the quaternary onium salts include ammonium salts, phosphonium salts, arsonium salts, stibonium salts, oxonium salts, sulfonium salts, selenium salts, stannonium salts, and iodonium salts. Especially preferred are ammonium salts and phosphonium salts. Specific examples of the ammonium salt include tetra n-butylammonium halides such as tetra n-butylammonium chloride (TBAC), tetra n-butylammonium bromide (TBAB), tetra n-butylammonium iodide (TBAI), and tetra n-butyl Ammonium acetate (TBAAc) and the like. Specific examples of the phosphonium salt include tetra n-butylphosphonium halides such as tetra n-butylphosphonium chloride (TBPC), tetra n-butylphosphonium bromide (TBPB), tetra n-butylphosphonium iodide (TBBI), Tetraphenylphosphonium halides such as tetraphenylphosphonium chloride (TPPC), tetraphenylphosphonium bromide (TPPB), tetraphenylphosphonium iodide (TPPI), ethyltriphenylphosphonium bromide (ETPPB), ethyltriphenyl Phosphonium acetate (ETPPAc) and the like.

As tertiary phosphine, the trivalent organophosphorus compound which has a C1-C12 alkyl group or an aryl group is mentioned. Specific examples include triethyl phosphine, tributyl phosphine, triphenyl phosphine and the like.

In addition, quaternary onium salts formed by addition reactions of tertiary amines or tertiary phosphines with carboxylic acids or highly acidic phenols can also be used as reaction accelerators. These may be any method of forming a quaternary salt prior to addition to the reaction system, or adding each separately to form a quaternary salt in the reaction system. Specifically, the tributylamine acetate obtained from tributylamine and acetic acid, the triphenyl phosphine acetate formed from triphenylphosphine and acetic acid, etc. are mentioned.

As the phosphonium illide, any known substance can be used as long as it is a compound obtained by the reaction of a phosphonium salt with a base. However, a substance having high stability is preferable because of its ease of handling. Specific examples include (formylmethylene) triphenylphosphine, (acetylmethylene) triphenylphosphine, (pivaloylmethylene) triphenylphosphine, (benzoylmethylene) triphenylphosphine, (p-methoxybenzoylmethylene) Triphenylphosphine, (p-methylbenzoylmethylene) triphenylphosphine, (p-nitrobenzoylmethylene) triphenylphosphine, (naphthoyl) triphenylphosphine, (methoxycarbonyl) triphenylphosphine, ( Diacetyl methylene) triphenyl phosphine, (acetyl cyano) triphenyl phosphine, (dicyano methylene) triphenyl phosphine, etc. are mentioned.

Examples of the acetylacetone metal complexes include acetylacetone vanadium complexes, acetylacetone chromium complexes, acetylacetone manganese complexes, acetylacetone iron complexes, acetylacetone cobalt complexes, acetylacetone nickel complexes, and acetylacetone aluminum complexes.

It is preferable that the usage-amount of these reaction promoters is 0.1-25 mol% with respect to 1 mol of oxetanyl groups, More preferably, it is 0.5-20 mol%, More preferably, it is 1-15 mol%. . When the amount of the reaction accelerator is less than 0.1 mol% relative to the oxetanyl group, the reaction is less likely to proceed at a practical rate, and even when present in a large amount exceeding 25 mol%, no significant reaction promoting effect is observed. It is not preferable at this point.

The photosensitive resin composition of this invention can use the (E) organic solvent in order to melt | dissolve the said photosensitive resin composition uniformly as needed, or to adjust a viscosity. In particular, each component of the said carboxyl group-containing photosensitive resin (A), the polymeric compound (B) which has at least 1 ethylenically unsaturated bond in 1 molecule, a photoinitiator (C), and an oxetane compound (D) is melt | dissolved uniformly. It is preferable to make it do not react with each component. When the solubility of each component with respect to the said organic solvent (E) is low, since it becomes difficult to melt | dissolve uniformly and it becomes difficult to ensure transparency required for a spacer, it is unpreferable.

As a specific example of these organic solvents (E), For example, Alcohol, such as methanol and ethanol; Ethers such as tetrahydrofuran; Glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol dimethyl ether; Propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether and propylene glycol butyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and propylene glycol butyl ether acetate; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate and propylene glycol butyl ether propionate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone and 4-hydroxy-4-methyl-2-pentanone; And methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, hydroxy Ethyl acetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, methyl 3-hydroxypropionate, 3- Esters such as ethyl butoxypropionate, propyl 3-butoxypropionate and butyl 3-butoxypropionate.

Among these organic solvents (E), glycol ethers, ethylene glycol alkyl ether acetates, esters and diethylene glycols are preferably used because of their solubility, reactivity with each component, and ease of formation of a coating film. These organic solvents (E) can be used individually or in mixture of 2 or more types, Although the usage-amount is not specifically limited, Usually, it is 30-90 mass% in the photosensitive resin composition of this invention, Preferably it becomes 40-85 mass%. Range.

The photosensitive resin composition of this invention may contain other components other than the above as needed in the range which does not impair the objective of this invention.

For example, surfactant for improving applicability | paintability is mentioned. As surfactant, a fluorochemical surfactant and silicone type surfactant can be used preferably. As the fluorine-based surfactant, a compound having a fluoroalkyl or a fluoroalkylene group at any one or more of the terminal, main chain and side chain can be preferably used, and specific examples thereof include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether, octaethylene glycol di (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 di ( 1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate, 1,1,2,2,8,8,9,9,10,10-decafluorodo Decane, 1,1,2,2,3,3-hexafluorodecane, sodium fluoroalkylbenzenesulfonate, sodium fluoroalkylphosphonate, sodium fluoroalkylcarboxylic acid, fluoroalkylpolyoxyethylene ether, Glycerin tetrakis (fluoroalkylpolyoxyethylene ether), fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl polyoxyethylene ether, perfluoroalkyl polyoxyethanol, perfluoroalkyl alkoxylate And fluorine-based alkyl esters.

Moreover, as these commercial items, for example, BM-1000, BM-1100 (above, manufactured by BM CHEMIE Co., Ltd.), Megapack F142D, East F172, East F173, East F183, East F178, East F191, East F 471 (above, Dainippon Ink & Chemicals Co., Ltd.), Floroid FC170C, FC-171, FC-430, FC-431 (above, Sumitomo 3M Co., Ltd.), Saffron S-112, Copper S-113, S-131, S-l41, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 ( Asahi Glass Co., Ltd., F-Top EF301, copper 303, copper 352 (above, Shinsegae Kasei Co., Ltd.), pgentant FT-100, copper FT-110, copper FT-140A, copper FT- 150, FT-250, FT-251, FTX-251, FTX-218, FT-300, FT-310, FT-400S (above, manufactured by Neos), and the like. . Moreover, as silicone type surfactant, Toray silicon DC3PA, copper DC7PA, copper SH11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, copper SH-190, copper SH-193, copper SZ-6032, copper SF- 8428, copper DC-57, copper DC-190 (above, manufactured by Toray Silicone Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (above, Toshiba Silicon Co., Ltd.), BYK-300, BYK-302, BYK-306, BYK-307, BYK-310, BYK-315, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, What is marketed by brand names, such as BYK-331, BYK-332, BYK-333, BYK-337, BYK-344, BYK-370, BYK-375 (made by Big Chemie), etc. are mentioned.

In addition, polyoxyethylene alkyl ether, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; Nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; Organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid-based copolymer polyflow No. 57, 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.), BYK-352, BYK-354, BYK-355, BYK-356, BYK-357, BYK-358, BYK-359, BYK-361, BYK -390, BYK-392 (above, made by Big Chemie), etc. are mentioned. These surfactant is used 5 mass parts or less, Preferably it is 2 mass parts or less with respect to 100 mass parts of carboxyl group-containing photosensitive resin (A). When the amount of the surfactant exceeds 5 parts by mass, film roughness tends to occur at the time of coating.

Moreover, in order to improve adhesiveness with a board | substrate, an adhesion | attachment adjuvant can also be used. As this adhesion | attachment adjuvant, a functional silane coupling agent is used preferably, For example, the silane coupling agent which has reactive substituents, such as a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, is mentioned, Specifically, trimethoxysilyl is mentioned. Benzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3 And 4-epoxycyclohexyl) ethyltrimethoxysilane. Such adhesion aid is used in an amount of 20 parts by mass or less, preferably 10 parts by mass or less, based on 100 parts by mass of the carboxyl group-containing photosensitive resin (A). When the amount of the adhesion assistant exceeds 20 parts by mass, development residues tend to occur.

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

As a method of forming a pattern using the photosensitive resin composition of this invention, the coloring photosensitive resin composition layer of solid which previously formed the photosensitive resin composition of this invention on a board | substrate or a board | substrate (henceforth this is called a board | substrate etc.) And a volatile component such as a solvent is removed from the applied photosensitive resin composition layer, and a layer is removed after exposing the layer from which the volatile component is removed through a photomask.

As a board | substrate, the board | substrate with flat surfaces, such as a glass substrate, a silicon substrate, a polycarbonate board | substrate, a polyester board | substrate, an aromatic polyamide board | substrate, a polyamideimide board | substrate, a polyimide board | substrate, Al substrate, GaAs board | substrate, is mentioned, for example. have. These substrates may be subjected to pretreatment such as chemical treatment with a chemical such as a silane coupling agent, plasma treatment, ion plating treatment, sputtering treatment, vapor phase reaction treatment, vacuum deposition treatment, or the like. When a silicon substrate or the like is used as the substrate, a charge coupling element (CCD), a thin film transistor (TFT), or the like may be formed on the surface of the silicon substrate or the like.

In order to apply the photosensitive resin composition on the substrate, for example, the photosensitive resin composition of the present invention may be a liquid such as a rotary coating method (spin coating method), a flexible coating method, a roll coating method, a slit & spin coating method, a spinless coater, or the like. It can apply | coat on board | substrates etc. by a well-known coating method, such as apply | coating using a saving coater, and can then volatilize volatile components, such as a solvent, by heating. In this way, the layer which consists of solid content of the photosensitive resin composition is formed on substrates etc. Next, the layer (henceforth this may be called photosensitive resin composition layer) which consists of solid content of the photosensitive resin composition is exposed. For example, the active energy ray can be selectively irradiated through a photomask. As an exposure light source, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a xenon lamp, a metal halide lamp etc. are suitable normally. Moreover, a laser beam etc. can also be used as an active energy ray for exposure. In addition, electron beams, alpha rays, beta rays, gamma rays, X rays, neutron rays and the like can also be used. The active energy ray is irradiated through the photomask, wherein the photomask is provided with a light shielding layer for shielding the active energy ray, for example, on the surface of the glass plate. The part in which the light shielding layer is not provided in a glass plate is a light transmission part which an active energy ray permeate | transmits, The photosensitive resin composition layer is exposed by the pattern according to the pattern of this light transmission part, and the unirradiated area | region to which an active energy ray was not irradiated, and active energy There is an irradiation area where the line is irradiated. The irradiation amount of the active energy ray in the irradiation region is appropriately determined by the weight average molecular weight, monomer ratio, content of the binder polymer, the kind and content of the photopolymerizable compound, the kind and content of the photopolymerization initiator, the kind and content of the photopolymerization initiation aid, and the like. Is selected.

The substrate exposed as mentioned above is developed by the diluted alkali aqueous solution. To develop, for example, the photosensitive resin composition layer after exposure can be contacted with a diluted alkali aqueous solution, specifically, the board | substrate of the state in which the photosensitive resin composition layer was formed on the surface was immersed in the diluted alkali aqueous solution, or the diluted alkaline aqueous solution, for example. In the form of a shower. As dilute aqueous alkali solution, aqueous solution of alkaline compounds, such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, an organic amine, etc. are mentioned, for example. By development, the unirradiated area | region to which the active energy ray in the photosensitive resin composition layer was not irradiated is removed. On the other hand, the active energy ray irradiation area remains as it is and forms a pattern.

The substrate which has been developed in this manner can be washed with water and dried, thereby obtaining a desired pattern. It may be heated after drying. The pattern can be cured by heating to further improve its mechanical strength. Heating temperature is 180 degreeC or more normally, Preferably it is 200 degreeC or more, and is 250 degrees C or less normally. If heating temperature is 180-250 degreeC, the mechanical strength of a coating film will improve, solvent resistance and liquid crystal resistance will improve, and it is preferable. The heating time is usually 5 minutes to 120 minutes, preferably 10 minutes to 90 minutes, more preferably 15 minutes to 60 minutes. If heating time is 5 minutes-120 minutes, the mechanical strength of a coating film will improve and it is preferable. In this way, a spacer made of the photosensitive resin composition is formed.

<Example>

Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples. In addition, "part" means a mass part unless there is particular notice below.

Preparation of carboxyl group-containing photosensitive resin solution

Synthesis Example 1

4.1 parts of azobisisobutyronitrile and 286 g of propylene glycol monomethyl ether acetate were put into the detachable flask provided with the stirrer, the reflux condenser, and the thermometer, and it heated in the water bath, and made internal temperature 70 degreeC. A mixture of 124.5 parts of dicyclopentanyl methacrylate, 10.4 parts of styrene, and 58.9 parts of glycidyl methacrylate represented by the formula (1) was added dropwise thereto over 3 hours to conduct a polymerization reaction. Furthermore, it stirred for 3 hours at 70 degreeC, and confirmed that there was no unreacted monomer by GPC. 31.2 parts of acrylic acid and 1 part of triphenylphosphine were added to the polymer and reacted at 80 to 90 ° C. for 24 hours. After confirming the disappearance of the epoxy group in the IR spectrum, 60.9 parts of tetrahydrophthalic anhydride was added and further reacted at 80 ° C. for 12 hours to obtain a carboxyl group-containing photosensitive resin (A-1) varnish. In addition, the solid acid value of the carboxyl group-containing photosensitive resin (A-1) of this invention was 79 mg KOH / g, and the molecular weight (Mw) in GPC was 18000. Solid content concentration of this carboxyl group-containing photosensitive resin (A-1) varnish was 50 mass%.

Comparative Synthesis Example 1

4.1 parts of azobisisobutyronitrile and 125 g of propylene glycol monomethyl ether acetates were put into the detachable flask provided with the stirrer, the reflux condenser, and the thermometer, and it heated in the water bath to make internal temperature 70 degreeC. A mixture of 55 parts of methyl methacrylate, 20.8 parts of styrene, and 42.7 parts of glycidyl methacrylate was added dropwise thereto to carry out a polymerization reaction. In addition, by stirring for 3 hours at 70 ℃ it was confirmed that there is no unreacted monomer in GPC. 23.4 parts of acrylic acid and 0.8 parts of triphenylphosphine were added to the polymerized product and reacted at 80 to 90 ° C. for 16 hours. After confirming the disappearance of the epoxy group in the IR spectrum, 45.7 parts of tetrahydrophthalic anhydride was added, and further reacted at 80 ° C. for 8 hours, whereby a carboxyl group-containing photosensitive resin (R-1) varnish containing no compound represented by Formula 1 was prepared. Got it. In addition, the acid value of the carboxyl group-containing photosensitive resin (R-1) was 90 mg KOH / g, and the molecular weight (Mw) by GPC was 15000. Solid content concentration of this carboxyl group-containing photosensitive resin (R-1) varnish was 60 mass%.

Below, the raw material used by the Example and the comparative example is shown in Table 1.

ingredient Chemical name or trade name Carboxyl group-containing photosensitive resin Varnish (A-1) obtained in Synthesis Example 1 Varnish (R-1) obtained in Comparative Synthesis Example 1 Polymerizable compound Dipentaerythritol hexaacrylate Photopolymerization initiator 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one Oxetane compound ①xylylene-type dioxetane ^{1 )} ② biphenyl type dioxetane ^{2 )} ③Phenyl novolak type oxetane (the number of nucleus bodies = 5) ^{3 )} Epoxy resin ① Epicoat 828 ⁴⁾ ②EPPN-201 ⁵⁾ Organic solvent Propylene Glycol Monomethyl Ether Acetate

Remarks:

1) Bifunctional oxetane compound made by Toagosei Co., Ltd. (brand name: OXT-121)

2) Bifunctional oxetane compound manufactured by Ube Koyama (brand name: Eternacoll 0XBP)

3) Polyfunctional oxetane compound manufactured by Toagosei Co., Ltd. (brand name: PNOX-1009)

4) Bifunctional epoxy resin manufactured by Japan Epoxy Resin Co., Ltd.

5) Nippon Kayaku Co., Ltd. polyfunctional epoxy resin

(Examples 1 to 3, and Comparative Examples 1 to 4)

Preparation of Photosensitive Resin Composition

Each component was mix | blended in the mixing | blending ratio shown in Table 2, and it stirred for 1 hour at room temperature, melt | dissolved each component, and filtered with the Millipore filter of 0.45 micrometer of pore diameters, and obtained the photosensitive resin composition (one-component composition).

(1) evaluation of resolution

The photosensitive resin composition solution was applied on the glass substrate at a rotational speed of 1000 rpm for 20 seconds using a spin coater, and then prebaked at 90 ° C. for 3 minutes on a hot plate to form a dry coating film. The coating film obtained above was irradiated with 100 mJ / cm <^2> of ultraviolet-rays with the intensity of 12 mW / cm <^2> in 365 nm through the mask of the dot pattern of (phi) 10micrometer by accumulated light quantity. The ultraviolet irradiation at this time was performed in oxygen atmosphere (in air), and the exposure gap was 100 micrometers. Subsequently, it developed for 120 second at 25 degreeC using the tetramethylammonium hydroxide 0.4 mass% aqueous solution, and wash | cleaned with flowing water for 30 second with pure water. The spacer pattern formed above was cured by heating at 230 ° C. for 60 minutes in an oven.

(Circle) and the case where it was not resolved were made into the case where the pattern of 10 micrometers of dot diameters are resolved as the spacer pattern obtained above. The results are shown in Table 3.

(2) Evaluation of NMP Resistance

The photosensitive resin composition solution was applied on the glass substrate at a rotational speed of 1000 rpm for 20 seconds using a spin coater, and then prebaked at 90 ° C. for 3 minutes on a hot plate to form a dry coating film. The whole surface of the coating film obtained above was irradiated with 100 mJ / cm <^2> of ultraviolet-rays with an intensity of 12 nW / cm <^2> in 365 nm in accumulated light quantity. The ultraviolet irradiation at this time was performed in oxygen atmosphere (in air), and the exposure gap was 100 micrometers. Then, it hardened | cured by heating for 60 minutes at 230 degreeC in oven.

The cured coating film was rubbed with a piece of cloth infiltrated with N-methyl-2-pyrrolidone (NMP) to observe the surface state. (Circle) and the case where the surface melt | dissolved or softened and the case where there was no change were made into x.

(3) γ-butyrolactone resistance

The surface condition was observed by rubbing the cured coating film manufactured similarly to said (2) with the piece of cloth which permeated (gamma) -butyrolactone. (Circle) and the case where the surface melt | dissolved or softened and the case where there was no change were made into x.

(4) evaluation of transparency

The cured coating film manufactured similarly to said (2) was observed visually, and transparency evaluation was performed. (Circle) and the case where the coating film had a blur and were opaque even if it was completely transparent were made into x.

(5) compressive strength

A pattern having a film thickness of 5 mu m and a dot diameter of 30 mu m was formed, and the spacer pattern thermally cured at 230 deg. C for 60 minutes was evaluated using a microhardness meter. The amount of deformation when a 50 mN load was applied by a plane indenter having a diameter of 50 µm was measured. (Circle) and the case larger than 0.6 were made into the case where this value is 0.6 or less.

(6) storage stability

The case where the said photosensitive resin composition was preserve | saved for 14 days in 40 degreeC oven, and showed gelation-the remarkable viscosity rise was made into x and the viscosity rise was small and it was not gelatinized.

The test results are shown in Table 3.

As is apparent from the results shown in Table 3, Examples 1 to 3, which are the photosensitive resin compositions of the present invention, exhibited excellent storage stability, and their cured products exhibited excellent chemical resistance and compressive strength, and were found to have transparency. lost.

Since the photosensitive resin composition of this invention is a hardening system containing an oxetane compound as a crosslinking component, it is excellent in storage stability, and the hardened | cured material obtained has sufficient heat resistance and chemical resistance. That is, the photosensitive resin composition of this invention does not have a problem that storage stability is inferior to the case of using an epoxy resin as a conventional crosslinking component, and can form hardened | cured material excellent in various characteristics, such as heat resistance and chemical-resistance. Moreover, since the photosensitive resin composition of this invention provides the hardened | cured material excellent in transparency, it is effective for uses, such as a spacer and a planarization film. Moreover, since it is excellent in storage stability, it is very useful also from an economic point, such as being excellent in workability and reducing the disposal of the photosensitive resin composition which reached end of life. That is, according to the photosensitive resin composition of this invention, since the trouble of the two-liquid mixing immediately before use is skipped because it is excellent in storage stability, the one-component photosensitive resin composition excellent in workability can be provided.

Claims (6)

(A) carboxyl group-containing photosensitive resin which has a carboxyl group and 2 or more ethylenically unsaturated bond in 1 molecule, (B) polymeric compound which has 1 or more ethylenically unsaturated bond in 1 molecule, (C) photoinitiator, and (D) A composition containing an oxetane compound having two or more oxetanyl groups in one molecule, wherein the carboxyl group-containing photosensitive resin (A) contains a compound having an unsaturated double bond represented by the following formula (1) as a copolymerization component: It is a carboxyl group-containing photosensitive resin, The photosensitive resin composition characterized by the above-mentioned. <Formula 1>

(Wherein x represents an integer of 0 to 2, R ¹ represents hydrogen or a methyl group, and R ² represents dicyclopentadiene or tricyclodecane) (A) carboxyl group-containing photosensitive resin which has a carboxyl group and 2 or more ethylenically unsaturated bond in 1 molecule, (B) polymeric compound which has 1 or more ethylenically unsaturated bond in 1 molecule, (C) photoinitiator, and (D) A composition containing an oxetane compound having two or more oxetanyl groups in one molecule, wherein the carboxyl group-containing photosensitive resin (A) contains a compound having an unsaturated double bond represented by the following formula (1) as a copolymerization component: It is carboxyl group-containing photosensitive resin, The photosensitive resin composition for display panels characterized by the above-mentioned. <Formula 1>

(Wherein x represents an integer of 0 to 2, R ¹ represents hydrogen or a methyl group, and R ² represents dicyclopentadiene or tricyclodecane) The compounding quantity of the said polymeric compound (B) is 5-100 mass parts with respect to 100 mass parts of said photosensitive resin (A), and the compounding quantity of the said photoinitiator (C) is 100 said photosensitive resin (A) 100 0.01-30 mass parts with respect to mass part, and the compounding quantity of the said oxetane compound (D) is 5-100 mass parts with respect to 100 mass parts of said photosensitive resin (A), The photosensitive resin composition characterized by the above-mentioned. The compounding quantity of the said polymeric compound (B) is 5-100 mass parts with respect to 100 mass parts of said photosensitive resin (A), and the compounding quantity of the said photoinitiator (C) is 100 said photosensitive resin (A) 100 0.01-30 mass parts with respect to mass part, and the compounding quantity of the said oxetane compound (D) is 5-100 mass parts with respect to 100 mass parts of said photosensitive resin (A), The photosensitive resin composition characterized by the above-mentioned. The photocuring process of apply | coating and drying the photosensitive resin composition of any one of Claims 1-4, the photocuring process of selectively irradiating an active energy ray to the coating film obtained through the said coating film formation process, and photocuring process The hardened | cured material obtained through the alkali developing process of removing the unirradiated part using an alkali developing solution after a process, and obtaining a pattern, and the process of heating and hardening the pattern obtained by the said alkali developing process. The spacer for display panels obtained using the photosensitive resin composition of any one of Claims 1-4.