JP4483371B2 - Photosensitive resin composition - Google Patents

Description

  The present invention relates to a positive photosensitive resin composition suitable for forming a light-shielding separator or a black matrix of an organic electroluminescent device or a liquid crystal display device which is a flat panel display.

  Non-light-emitting liquid crystal displays (LCDs) are widely used as flat panel displays, but organic electroluminescence devices as self-light-emitting displays are highly researched and developed due to their high brightness and full-color display capability. .

  The organic electroluminescence element operates by applying a voltage between the opposed first electrode and second electrode, or by passing a current. At this time, since the electric field tends to concentrate on the edge portion of the electrode having a small radius of curvature, undesirable phenomena such as dielectric breakdown and generation of leakage current are likely to occur in the edge portion.

  In order to suppress these phenomena, it is known to cover the edge portion of the first electrode with an insulating layer (also referred to as a separator) (see Patent Document 1). This technique can alleviate electric field concentration at the edge portion of the electrode. Furthermore, the thickness of the insulating layer at the exposed boundary portion on the first electrode gradually increases as the distance from the boundary increases so that the organic insulating layer and the second electrode deposited after the formation of the insulating layer are smoothly deposited. By increasing the thickness, that is, by making the cross section into a forward tapered shape, it is possible to suppress electric field concentration at the edge portion of the electrode. Recently, for the purpose of increasing the contrast in an organic electroluminescent device, an attempt has been made to add light shielding properties to an insulating film and / or an element isolation structure by adding carbon black to a non-photosensitive polyimide resin (Patent Document 2). reference). In addition, the specific black matrix material is a negative photosensitive resin comprising an alkali-soluble resin obtained by condensing phenols and aldehydes, an acid-crosslinkable methylolated melamine compound, a photoacid generator, a specific dispersant, and a black pigment. Material (refer to Patent Document 3), polyimide precursor vehicle and solvent, light absorbing dye or mixture thereof, non-photosensitive material comprising carbon black pigment or non-carbon black metal oxide pigment and Newton dispersant (Patent Documents 4 and 5) See).

  In general, polyimide, novolac, acrylic resin, or the like is used for the insulating layer of the display. These resins are non-photosensitive, negative-type photosensitive, and positive-type photosensitive. However, in order to suppress electric field concentration at the edge portion of the electrode, the insulating layer is preferably a positive photosensitive resin. Usually, the radiation effective intensity to the inside of the coating film in exposure gradually decreases from the coating film surface toward the bottom. Therefore, in the positive photosensitive resin in which the exposed portion is dissolved and removed, the shape of the exposed portion is likely to be forward tapered as compared with the negative type and non-photosensitive, and the forward tapered shape can be easily formed.

  As a positive photosensitive resin composition for a black matrix of an LCD, a method of adding a quinonediazide compound and a black pigment to an alkali-soluble resin made of a novolak resin or a vinyl polymer (see Patent Document 6), or shielding light from an organic EL device. As a conductive insulating film, there is a method of adding a quinonediazide compound and a colorant to an alkali-soluble resin made of a polymer of a novolak resin or a radical polymerizable monomer (see Patent Document 7).

  However, the light-shielding positive photosensitive resin prepared by adding a colorant to the resin composition described above has an exposure wavelength region of 350 nm to a mercury lamp generally used as an exposure light source in order to provide sufficient light-shielding properties. Since it has an absorption maximum at 450 nm, there is a problem of deteriorating exposure sensitivity.

  On the other hand, it contains a novolak resin and a naphthoquinonediazide-based photosensitizer, and by performing exposure or / and heat treatment, the light transmittance of the coating film is reduced to about 10% or less in the visible region (400 to 700 nm). There is a method of adding a pigment to a black matrix photoresist (see Patent Document 8). In this method, by performing exposure and heat treatment, the light transmittance of the coating film can be reduced to about 10% or less in the visible region (400 to 700 nm), and cresol novolac resin and naphthoquinone diazide type are used as coloring means. A photoresist containing a photosensitizer is used.

As a specific method for imparting light shielding properties to the insulating layer, there is a method of adding a heat-sensitive material and a developer to a diazoquinone-novolak resin-based positive resist (see Patent Document 9). In this method, a heat-sensitive material that develops a black color when heat is applied and a positive photosensitive resin in which a developer is added in advance are used. Therefore, the photosensitive resin does not have a light shielding property and does not deteriorate the exposure sensitivity. However, a general heat-sensitive material composed of a developer and a color former has a color development temperature of 100 to 180 ° C., and there is a problem in heat resistance at the final heat treatment temperature after pattern processing (generally 200 ° C. or more). . For this reason, the thermosensitive material that has developed color is faded by the final heat treatment, and sufficient light shielding properties cannot be obtained. In addition, when blackening is performed using a general heat-sensitive material group composed of a developer and a color former, there is a problem with light resistance after the final heat treatment, and the color may fade due to long-term visible-ultraviolet irradiation. In many cases, it is difficult to continue to use the display device as a black matrix.
JP-A-11-97182 (page 1-3) JP-A-11-273870 (page 1-3) JP 2000-47378 A JP-A-10-232302, JP 2001-525561 A Japanese Patent Laid-Open No. 6-230215 (page 1-2) JP 2002-116536 A (page 1-3) JP-A-8-137098 (page 2-3) JP-A-10-170715 (page 2-4)

  In light of the above-described problems, the present invention provides a photosensitive resin composition capable of obtaining a light-shielding and light-resistant cured film suitable for forming a light-shielding separator or a black matrix of an organic electroluminescence device or a liquid crystal display device. It is.

      That is, the present invention includes (a) an alkali-soluble resin, (b) a quinonediazide compound, (c) a thermochromic compound that develops color when heated and exhibits an absorption maximum at 350 nm to 700 nm, and (d) 350 nm to less than 500 nm. A photosensitive resin composition comprising a compound having no absorption maximum and having an absorption maximum at 500 nm or more and 750 nm or less.

  According to the present invention, not only can a positive type in which a portion exposed to ultraviolet rays is dissolved in an alkaline aqueous solution, but also an optical density suitable for forming a light-shielding separator or a black matrix of an organic electroluminescent device or a liquid crystal display device. A cured film having a light shielding property of at least 0.3 and an optical density retention after 50 hours of light irradiation of 50% or more can be obtained. Further, when the photosensitive resin composition of the present invention is used for a light-shielding separator or a black matrix, a high-quality organic electroluminescence device or a liquid crystal display element can be supplied.

  The component (a) in the present invention needs to be soluble in an alkaline aqueous solution used as a developer. Examples of the alkali-soluble resin include, but are not limited to, a phenol resin, a polymer containing a radical polymerizable monomer having an alkali-soluble group, a polyimide precursor, a polyimide, and a polybenzoxazole precursor. The polymer preferably has an alkali-soluble group in the molecule. The type of polymer in the present invention is excellent in heat resistance and exhibits excellent characteristics as a separator of an organic electroluminescence device. Therefore, after heat treatment, those having a small degassing amount at a high temperature of 200 ° C. or higher are preferable. Polyimide, polyhydroxyamide There are polyimide precursors such as polyamic acid or polyamic acid ester or polybenzoxazole precursors.

  Examples of the alkali-soluble group include a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group.

  Examples of the phenolic resin that can be used in the present invention include novolak phenolic resins and resol phenolic resins, which are obtained by polycondensation of various phenols alone or a mixture of a plurality of them with aldehydes such as formalin.

  Examples of phenols constituting the novolak phenol resin and resol phenol resin include phenol, p-cresol, m-cresol, o-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, and 2,5-dimethylphenol. 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, , 4,5-trimethylphenol, methylene bisphenol, methylene bis p-cresol, resorcin, catechol, 2-methyl resorcin, 4-methyl resorcin, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3-dichloro Phenol m-methoxyphenol, p-methoxyphenol, p-butoxyphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, 2,3-diethylphenol, 2,5-diethylphenol, p-isopropylphenol, α -Naphthol, (beta) -naphthol etc. are mentioned, These can be used individually or as a mixture of several.

  In addition to formalin, examples of aldehydes include paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde, and the like. These can be used alone or as a mixture of a plurality of them.

  The preferred weight average molecular weight of the phenol resin used in the present invention is preferably in the range of 2,000 to 50,000, preferably 3,000 to 30,000 in terms of polystyrene using gel permeation chromatography. When the weight average molecular weight exceeds 50,000, the developability and sensitivity tend to deteriorate. When the weight average molecular weight is less than 2,000, the pattern shape, resolution, developability, and heat resistance tend to deteriorate.

  In order to synthesize a polymer containing a radically polymerizable monomer having an alkali-soluble group, the following monomers may be mentioned. Examples of the radical polymerizable monomer having a phenolic hydroxyl group or a carboxyl group include o-hydroxystyrene, m-hydroxystyrene and p-hydroxystyrene, and alkyl, alkoxy, halogen, haloalkyl, nitro, cyano, amide, ester, Carboxy-substituted products; polyhydroxyvinylphenols such as vinylhydroquinone, 5-vinylpyrogallol, 6-vinylpyrogalol, 1-vinylphlorogricinol; o-vinylbenzoic acid, m-vinylbenzoic acid, and p-vinylbenzoic acid Acids and their alkyl, alkoxy, halogen, nitro, cyano, amide, ester substituents, methacrylic acid and acrylic acid, and their alpha-position haloalkyl, alkoxy, halogen, nitro, cyano substitution Divalent unsaturated carboxylic acids such as maleic acid, maleic anhydride, fumaric acid, fumaric anhydride, citraconic acid, mesaconic acid, itaconic acid and 1,4-cyclohexenedicarboxylic acid, and their methyl, ethyl, propyl, i-Propyl, n-butyl, sec-butyl, ter-butyl, phenyl, o-, m-, p-toluyl half ester and half amide are preferred.

  Of these, o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene, and alkyl and alkoxy substituted products thereof are sensitive to patterning, remaining film ratio after resolution development, heat distortion resistance, solvent resistance, groundwork It is preferably used from the viewpoints of adhesion to the solution and storage stability of the solution. These can be used alone or in combination of two or more.

  Other radical polymerizable monomers include, for example, styrene, and alkyl, alkoxy, halogen, haloalkyl, nitro, cyano, amide, ester-substituted products at the α-position, o-position, m-position, or p-position of styrene. Diolefins such as butadiene, isoprene and chloroprene; methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, ter-butyl, pentyl, neopentyl, isoamylhexyl and cyclohexyl methacrylates or acrylic acid , Adamantyl, allyl, propargyl, phenyl, naphthyl, anthracenyl, anthraquinonyl, piperonyl, salicyl, cyclohexyl, benzyl, phenethyl, cresyl, glycidyl, 1,1,1-trifluoroethyl, perfluoroethyl, perfluoro-n- Propyl, perfluoro-i-propyl, triphenylmethyl, tricyclo [5.2.1.02,6] decan-8-yl (common name: “dicyclopentanyl”), cumyl, 3- (N, N -Dimethylamino) propyl, 3- (N, N-dimethylamino) ethyl, furyl, furfuryl esters, methacrylic or acrylic acid anilides, amides, or N, N-dimethyl, N, N-diethyl, N , N-dipropyl, N, N-diisopropyl, anthranilamide, acrylonitrile, acrolein, methacrylonitrile, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, N-phenyl Maleimide, N- (4-hydroxyphenyl) maleimide, N-methacryloylphthalimide N- acryloyl phthalimide and the like can be used. These can be used alone or in combination of two or more.

  Of these, styrene, and styrene α-, o-, m-, and p-alkyl, alkoxy, halogen, haloalkyl substituents; butadiene, isoprene; methacrylic acid, or methyl, ethyl of acrylic acid, Each ester of n-propyl, N-butyl, glycidyl, and tricyclo [5.2.1.02,6] decan-8-yl is sensitive to patterning, remaining film ratio after resolution development, and heat deformation. It is particularly preferably used from the viewpoints of properties, solvent resistance, adhesion to the substrate, storage stability of the solution, and the like. When a copolymer of a radical polymerizable monomer having a phenolic hydroxyl group and another radical polymerizable monomer is used as the alkali-soluble resin, the preferred ratio of the other radical polymerizable monomer is that the radical polymerizable monomer having a phenolic hydroxyl group and the other It is preferably 30% by weight or less, particularly preferably 5 to 20% by weight, based on the total amount with the radical polymerizable monomer. Further, when a copolymer of a radical polymerizable monomer having a carboxyl group and another radical polymerizable monomer is used as the alkali-soluble resin, the preferred ratio of the other radical polymerizable monomer is that the radical polymerizable monomer having a carboxyl group and the other It is preferably 90% by weight or less, particularly preferably 10 to 80% by weight, based on the total amount of the radically polymerizable monomer. If the ratio of these radically polymerizable monomers exceeds the above-mentioned ratio with respect to the radically polymerizable monomer having a phenolic hydroxyl group or a carboxyl group, alkali development may be difficult.

  Solvents used for the production of a polymer containing a radically polymerizable monomer having an alkali-soluble group are, for example, alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether; propylene glycol monomethyl ether, propylene glycol Mo Propylene glycol monoalkyl ethers such as ethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate propylene glycol butyl ether acetate Propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol alkyl ether acetates such as propylene glycol butyl ether propionate; toluene, xylene, etc. Aromatic hydrocarbons; ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone; and methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, 2-hydroxy- Methyl 2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, 3 -Ethyl hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, methoxyacetate Chill, methyl ethoxy acetate, ethyl ethoxy acetate, propyl ethoxy acetate, butyl ethoxy acetate, methyl propoxy acetate, ethyl propoxy acetate, propyl propoxy acetate, butyl propoxy acetate, methyl butoxy acetate, ethyl butoxy acetate, propyl butoxy acetate, butyl butoxy acetate, Methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, 2 -Butyl ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, 3-methoxypropionate Methyl onate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, 3-ethoxypropion Acid butyl, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, 3-butoxypropionic acid Examples include esters such as propyl and butyl 3-butoxypropionate. The amount of these solvents used is preferably 20 to 1,000 parts by weight per 100 parts by weight of the reaction raw material.

  The polymerization initiator used for the production of a polymer containing a radically polymerizable monomer having an alkali-soluble group is, for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvalero). Nitrile), azo compounds such as 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1'-bis- ( organic peroxides such as (t-butylperoxy) cyclohexane; and hydrogen peroxide. When a peroxide is used as the radical polymerization initiator, the peroxide may be used together with a reducing agent to form a redox initiator.

  The preferable weight average molecular weight of the polymer containing the radically polymerizable monomer having an alkali-soluble group is preferably 2,000 to 100,000, more preferably 3,000 to 50, in terms of polystyrene using gel permeation chromatography. 000, particularly preferably 5,000 to 30,000. When the weight average molecular weight exceeds 100,000, the developability and sensitivity tend to deteriorate. When the weight average molecular weight is less than 2,000, the pattern shape, resolution, developability, and heat resistance tend to deteriorate.

  These polymers containing a radically polymerizable monomer having an alkali-soluble group may be used alone or in admixture of two or more. Alternatively, an alkali-soluble resin may be synthesized by a method of imparting alkali solubility by introducing a protecting group into a carboxyl group or a phenolic hydroxyl group before the polymerization and deprotecting after the polymerization. Further, the transparency and softening point in visible light may be changed by hydrogenation or the like.

In the formula, R ¹ is a divalent to octavalent organic group having 2 or more carbon atoms, R ² is a divalent to hexavalent organic group having 2 or more carbon atoms, and R ³ and R ⁴ are the same. Or may be different and represents hydrogen or an organic group having 1 to 20 carbon atoms. R ⁵ is a divalent organic group, X and Y are C 1 to C 10 containing at least one organic group selected from a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a thiol group, and an unsaturated hydrocarbon group An organic group having one or more substituents selected from a hydrocarbon group, a nitro group, a methylol group, an ester group, a hydroxyalkynyl group, and a hydrocarbon group having 1 to 10 carbon atoms. n is a range from 5 to 100,000, m is an integer from 0 to 10, p and q are integers from 0 to 4, and r and s are integers from 0 to 2, respectively. p + q> 0.

  The alkali-soluble resin containing as a main component the structural units represented by the general formulas (1) to (5) in the present invention becomes a polymer having an imide ring, an oxazole ring, or other cyclic structure by heating or an appropriate catalyst. obtain. It is also a heat resistant resin precursor whose heat resistance and solvent resistance are drastically improved by having a ring structure.

  The above general formulas (1) to (5) represent a polyamic acid having a hydroxyl group, and the hydroxyl group makes the solubility in an alkaline aqueous solution better than that of a polyamic acid having no hydroxyl group. In particular, a phenolic hydroxyl group is more preferable among hydroxyl groups from the viewpoint of solubility in an alkaline aqueous solution. In addition, by having 10% by weight or more of fluorine atoms in each of the general formulas (1) to (5), when developing with an alkaline aqueous solution, water repellency appears moderately at the film interface. Etc. are suppressed. However, if the fluorine atom content exceeds 20% by weight, the solubility in an alkaline aqueous solution is reduced, the organic solvent resistance of the polymer having a cyclic structure by heat treatment is reduced, and the solubility in fuming nitric acid is reduced. It is not preferable. Accordingly, the fluorine atom is preferably contained in an amount of 10% by weight to 20% by weight.

R ¹ contained in the dicarboxylic acid units of the general formula (1) to (5) represents a structural component of an acid dianhydride, a divalent to 8-valent organic group having two or more carbon atoms The acid dianhydride is preferably a trivalent or tetravalent organic group having 6 to 30 carbon atoms and containing an aromatic ring or an aliphatic ring and having 0 to 2 hydroxyl groups. R ¹ is preferably an organic group having 6 to 30 carbon atoms containing an aromatic ring or an aliphatic ring and having 0 to 2 hydroxyl groups.

  When a specific acid dianhydride has no hydroxyl group, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′- Biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3 , 3′-benzophenonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane Anhydride, bis (2,3- Carboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 2,2-bis (4- (4-amino) Phenoxy) phenyl) propane, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic acid Dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis (4- ( 3,4-dicarboxyphenoxy) phenyl) hexafluoropropane dianhydride, 2,2-bis (4- (3,4-dicarboxybenzoyloxy) phenyl) hexafluoro Aromatic tetracarboxylic dianhydrides such as lopan dianhydride, 2,2′-bis (trifluoromethyl) -4,4′-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride, cyclobutanetetra Carboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5,6-cyclohexanetetracarboxylic dianhydride, 5- (2,5-dioxotetrahydro- 3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylicsan anhydride and aliphatic tetracarboxylics such as “TDA100, Rica Resin TMEG” (trade name, manufactured by Shin Nippon Rika Co., Ltd.) Mention may be made of acid dianhydrides. Of these, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′- Biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenonetetracarboxylic dianhydride, 2,2-bis ( 3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, Screw (3,4-di Ruboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 2,2-bis (3 4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis (4- (3,4-dicarboxybenzoyloxy) phenyl) hexafluoropropane dianhydride, 2,2′-bis (trifluoromethyl) ) -4,4'-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride is preferred.

  In the case of having a hydroxyl group, examples of preferred compounds include those shown below, but are not limited thereto.

  These are used alone or in combination of two or more.

R ² contained in the diamine units of the general formulas (1) to (5) represents a divalent to hexavalent organic group having 2 or more carbon atoms. R ² is preferably an organic group having 6 to 30 carbon atoms containing an aromatic ring or an aliphatic ring. As a preferred example, those having aromaticity are preferred from the heat resistance of the resulting polymer. Specific examples of the diamine having no hydroxyl group include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'- Diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfide, 4,4′-diaminodiphenylsulfide, 1,4-bis (4-aminophenoxy) benzene, benzine, m- Phenylenediamine, P-phenylenediamine, 3,5-diaminobenzoic acid, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, Bis (4-aminophenoxy) biphenyl, bis {4- ( -Aminophenoxy) phenyl} ether, 1,4-bis (4-aminophenoxy) benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-diethyl-4,4′-diaminobiphenyl, 2,2 ′, 3,3′-tetramethyl-4,4′-diamino Biphenyl, 3,3 ′, 4,4′-tetramethyl-4,4′-diaminobiphenyl, 2,2′-di (trifluoromethyl) -4,4′-diaminobiphenyl, or aromatic rings thereof Examples include, but are not limited to, compounds substituted with an alkyl group or a halogen atom, aliphatic cyclohexyldiamine, methylenebiscyclohexylamine and the like. The above compound may be a single species or a mixture of two or more species.

2,2-bis [4- (amino-3-hydroxyphenyl) hexafluoropropane, 2,2-bis [4- (4-amino-3-hydroxyphenoxy) phenyl having a fluorine atom when having a hydroxyl group ] Hexafluoropropane, diaminodihydroxypyrimidine, diaminodihydroxypyridine, hydroxy-diamino-pyrimidine, diaminophenol, dihydroxybenzidine and "ABCH", "ABPS" (trade name, Nippon Kayaku Co., Ltd.) And the like, and those having a structure such that R ^{2 in the} general formulas (1) to (5) is as shown below, are not limited thereto.

  These are used alone or in combination of two or more.

  The heat resistant resin precursor represented by the general formulas (1) to (5) of the present invention is, for example, a method in which tetracarboxylic dianhydride and a diamine compound are reacted at room temperature to 80 ° C. for 1 to 8 hours, A method of obtaining a diester by carboxylic dianhydride and alcohol, adding a diamine, and then adding a condensing agent such as dicyclohexylcarbodiimide and reacting at -30 ° C. to room temperature for 1 to 8 hours, tetracarboxylic dianhydride A diester is obtained with a product and an alcohol, and then the remaining dicarboxylic acid is acid chlorided, added with a diamine, and synthesized using a known method such as a method of reacting at -30 ° C to room temperature for 1 to 8 hours. Can do. Examples of the reaction solvent used in these known methods include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, and γ-butyrolactone.

R ³ and R ^{4 in the} general formulas (1) to (5) may be the same or different and are represented by hydrogen or general formulas (6) to (7), which have 1 to 20 carbon atoms. Represents an alkyl group.

  α is an integer from 0 to 19, preferably 0 to 3. β is an integer from 0 to 16, preferably 0-2.

R ³ and R ⁴ are preferably alkyl groups from the viewpoint of the stability of the resulting positive photosensitive resin solution, but hydrogen is preferred from the viewpoint of the solubility in an aqueous alkali solution. In the present invention, a hydrogen atom and an alkyl group can be mixed. By controlling the amounts of hydrogen and alkyl groups in R ³ and R ^4, the dissolution rate with respect to the aqueous alkali solution is changed, so that a positive photosensitive resin composition having an appropriate dissolution rate can be obtained by this adjustment. it can. A preferred range is that 10% to 90% of R ³ and R ⁴ are hydrogen atoms. When R ³ and R ^{4 have} more than 20 carbon atoms, they will not dissolve in the alkaline aqueous solution. From the above, R ³ and R ⁴ preferably contain one or more hydrocarbon groups having 1 to 16 carbon atoms, and the others are hydrogen atoms.

-NH- (R ⁵ ) m-X, which is a structural component in the general formula (2) and the general formula (3), is represented by the following general formula (8), and these are the first class which is a terminal blocking agent. It is a component derived from monoamine.

In addition, —CO— (R ⁵ ) mY, which is a structural component in the general formula (4) and the general formula (5), is represented by the following general formula (9) and / or the following general formula (10). These are components derived from those selected from an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, and a monoactive ester compound, which are end-capping agents.

R ^{5 in the} general formulas (8) to (10) represents a divalent organic group, and —CR ¹¹ R ¹² —, —CH ² O—, and —CH ² SO ² — are preferable. R ¹¹ and R ¹² each represent a monovalent group selected from a hydrogen atom, a hydroxyl group, and a hydrocarbon group having 1 to 10 carbon atoms. R ⁹ and R ¹⁰ are a hydrogen atom, a hydroxyl group, a carboxyl group, a monovalent group selected from hydrocarbon groups having 1 to 10 carbon atoms, or a zero-valent group indicating that R ⁹ and R ¹⁰ are directly bonded. Show. R ⁸ represents a monovalent group selected from a hydrogen atom and a hydrocarbon group having 1 to 10 carbon atoms. Of these, a hydrogen atom and a hydrocarbon group having 1 to 4 carbon atoms are preferable, and a hydrogen atom, a methyl group, and a t-butyl group are particularly preferable. R ⁶ and R ⁷ are each a hydrogen atom, a hydroxyl group, a carboxyl group, a sulfonic acid group, a thiol group, an unsaturated hydrocarbon group having 1 to 10 carbon atoms, a nitro group, or a methylol group. , An ester group, a hydroxyalkynyl group, or a hydrocarbon group having 1 to 10 carbon atoms. A ^{1 to} A ³ are each a carbon atom or a nitrogen atom. m is an integer from 0 to 10, preferably an integer from 0 to 4. l is 0 or 1, preferably 0. i is 0 or 1, preferably 0. j is an integer from 1 to 3, preferably 1 and 2. k, t, and u are 0 or 1.

  Primary monoamines which are end-capping agents represented by the general formula (8) are 5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline, 1-hydroxy-8-aminonaphthalene, 1-hydroxy- 7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 1-hydroxy-3-aminonaphthalene, 1-hydroxy-2-aminonaphthalene, 1-amino-7-hydroxynaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 2-hydroxy-4-aminonaphthalene, 2-hydroxy-3 -Aminonaphthalene, 1-amino-2-hydroxynaphthalene, 1-carboxyl Boxy-8-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 1-carboxy-4-aminonaphthalene, 1-carboxy-3-amino Naphthalene, 1-carboxy-2-aminonaphthalene, 1-amino-7-carboxynaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-carboxy -4-aminonaphthalene, 2-carboxy-3-aminonaphthalene, 1-amino-2-carboxynaphthalene, 2-aminonicotinic acid, 4-aminonicotinic acid, 5-aminonicotinic acid, 6-aminonicotinic acid, 4- Aminosalicylic acid, 5-aminosalicylic acid, 6-amino Salicylic acid, 3-amino-O-toluic acid, amelide, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfone Acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 5-amino-8-mercaptoquinoline, 4-amino-8-mercaptoquinoline, 1-mercapto- 8-aminonaphthalene, 1-mercapto-7-aminonaphthalene, 1-mercapto-6-aminonaphthalene, 1-mercapto-5-aminonaphthalene, 1-mercapto-4-aminonaphthalene, 1-mercapto-3-aminonaphthalene, 1-mercapto-2-aminonaphthalene, 1-amino-7 -Mercaptonaphthalene, 2-mercapto-7-aminonaphthalene, 2-mercapto-6-aminonaphthalene, 2-mercapto-5-aminonaphthalene, 2-mercapto-4-aminonaphthalene, 2-mercapto-3-aminonaphthalene, 1 -Amino-2-mercaptonaphthalene, 3-amino-4,6-dimercaptopyrimidine, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, 2-ethynylaniline, 3-ethynylaniline, 4- Ethynylaniline, 2,4-diethynylaniline, 2,5-diethynylaniline, 2,6-diethynylaniline, 3,4-diethynylaniline, 3,5-diethynylaniline, 1-ethynyl-2-amino Naphthalene, 1-ethynyl-3-aminonaphthalene, 1-ethynyl- -Aminonaphthalene, 1-ethynyl-5-aminonaphthalene, 1-ethynyl-6-aminonaphthalene, 1-ethynyl-7-aminonaphthalene, 1-ethynyl-8-aminonaphthalene, 2-ethynyl-1-aminonaphthalene, 2 -Ethynyl-3-aminonaphthalene, 2-ethynyl-4-aminonaphthalene, 2-ethynyl-5-aminonaphthalene, 2-ethynyl-6-aminonaphthalene, 2-ethynyl-7-aminonaphthalene, 2-ethynyl-8- Aminonaphthalene, 3,5-diethynyl-1-aminonaphthalene, 3,5-diethynyl-2-aminonaphthalene, 3,6-diethynyl-1-aminonaphthalene, 3,6-diethynyl-2-aminonaphthalene, 3,7 -Diethynyl-1-aminonaphthalene, 3,7-diethynyl-2-aminonaphthalene , 4,8-diethynyl-1-aminonaphthalene, 4,8-diethynyl-2-amino-naphthalene, and the like, but is not limited thereto.

  Of these, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2 -Hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5 Aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4- Aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2- Aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, 3-ethynylaniline, 4-ethynylaniline, 3,4-diethynylaniline, 3,5-diethynylaniline and the like are preferable.

  Compounds selected from acid anhydrides, monocarboxylic acids, monoacid chloride compounds and monoactive ester compounds which are end-capping agents represented by general formula (9) and general formula (10) are phthalic anhydride and maleic anhydride. , Nadic acid, cyclohexanedicarboxylic anhydride, acid anhydrides such as 3-hydroxyphthalic anhydride, 2-carboxyphenol, 3-carboxyphenol, 4-carboxyphenol, 2-carboxythiophenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-8-carboxynaphthalene, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-hydroxy-4-carboxynaphthalene 1-hydroxy-3-ca Boxynaphthalene, 1-hydroxy-2-carboxynaphthalene, 1-mercapto-8-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 1 -Mercapto-4-carboxynaphthalene, 1-mercapto-3-carboxynaphthalene, 1-mercapto-2-carboxynaphthalene, 2-carboxybenzenesulfonic acid, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, 2-ethynyl Benzoic acid, 3-ethynylbenzoic acid, 4-ethynylbenzoic acid, 2,4-diethynylbenzoic acid, 2,5-diethynylbenzoic acid, 2,6-diethynylbenzoic acid, 3,4-diethynylbenzoic acid, 3,5 -Diethynylbenzoic acid, 2 Ethynyl-1-naphthoic acid, 3-ethynyl-1-naphthoic acid, 4-ethynyl-1-naphthoic acid, 5-ethynyl-1-naphthoic acid, 6-ethynyl-1-naphthoic acid, 7-ethynyl-1-naphthoic acid Acid, 8-ethynyl-1-naphthoic acid, 2-ethynyl-2-naphthoic acid, 3-ethynyl-2-naphthoic acid, 4-ethynyl-2-naphthoic acid, 5-ethynyl-2-naphthoic acid, 6-ethynyl Monocarboxylic acids such as 2-naphthoic acid, 7-ethynyl-2-naphthoic acid, 8-ethynyl-2-naphthoic acid and the like, and monoacid chloride compounds in which these carboxyl groups are acid chloride, terephthalic acid, phthalic acid, Maleic acid, cyclohexanedicarboxylic acid, 3-hydroxyphthalic acid, 5-norbornene-2,3-dicarboxylic acid, 1,2-dicarboxynaphthalene, 1 , 3-dicarboxynaphthalene, 1,4-dicarboxynaphthalene, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 1,8-dicarboxynaphthalene, 2,3 A monoacid chloride compound in which only the monocarboxyl group of dicarboxylic acids such as dicarboxynaphthalene, 2,6-dicarboxynaphthalene and 2,7-dicarboxynaphthalene is acid chloride, monoacid chloride compound and N-hydroxybenzotriazole, And an active ester compound obtained by reaction with N-hydroxy-5-norbornene-2,3-dicarboximide.

  Among these, phthalic anhydride, maleic anhydride, nadic acid, cyclohexanedicarboxylic anhydride, acid anhydrides such as 3-hydroxyphthalic anhydride, 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, 3-ethynylbenzoic acid, 4-ethynylbenzoic acid, 3,4-diethynylbenzoic acid, 3,5-diethynylbenzoic acid Acid etc. Nocarboxylic acids and monoacid chloride compounds in which these carboxyl groups are converted to an acid chloride, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7- Monoacid chloride compounds in which only the monocarboxyl group of dicarboxylic acids such as dicarboxynaphthalene and 2,6-dicarboxynaphthalene is acid chloride, monoacid chloride compounds and N-hydroxybenzotriazole and N-hydroxy-5-norbornene-2 An active ester compound obtained by reaction with 1,3-dicarboximide is preferred.

  The introduction ratio of the monoamine component represented by the general formula (8) is preferably in the range of 0.1 to 60 mol%, particularly preferably 5 to 50 mol%, based on the total amine components. The introduction ratio of the component selected from the acid anhydrides, monocarboxylic acids, monoacid chloride compounds and monoactive ester compounds represented by the general formula (9) and the general formula (10) is 0.1% with respect to the diamine component. The range of -100 mol% is preferable, Most preferably, it is 5-90 mol%. A plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.

  In the general formulas (1) to (5), n represents the number of repeating structural units of the polymer of the present invention, and is preferably in the range of 10 to 100,000.

Furthermore, in order to improve the adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized with R ¹ and R ² as long as the heat resistance is not lowered. Specific examples of the diamine component include those obtained by copolymerizing 1 to 15 mol% of bis (3-aminopropyl) tetramethyldisiloxane, bis (p-amino-phenyl) octamethylpentasiloxane, and the like.

  In the polymer represented by the general formulas (1) to (5) of the present invention, a part of the diamine is replaced with a terminal blocking agent that is a monoamine, or an acid dianhydride is replaced with a monocarboxylic acid, an acid anhydride, It is synthesized by replacing with a terminal capping agent which is a monoacid chloride compound or a monoactive ester compound. For example, a method of reacting a tetracarboxylic dianhydride and a diamine compound (partially substituted with a terminal blocking agent that is a monoamine) at a low temperature, a tetracarboxylic dianhydride (a part of an acid anhydride or A method of reacting a monoacid chloride compound or a monoactive ester compound with an end-capping agent) and a diamine compound, a diester is obtained by tetracarboxylic dianhydride and an alcohol, and then a diamine (a part of which is a monoamine) A method of reacting in the presence of a condensing agent and substitution with a sealant, a diester is obtained by tetracarboxylic dianhydride and an alcohol, and then the remaining dicarboxylic acid is converted to an acid chloride to form a diamine (a part of which is a monoamine) A method such as a method of reacting with a sealant may be used.

  Moreover, the terminal blocker introduced into the polymer can be easily detected by the following method. For example, a polymer having an end-capping agent introduced therein is dissolved in an acidic solution and decomposed into an amine component and an acid anhydride component that are constituent units of the polymer, and this is measured by gas chromatography (GC) or NMR measurement. The end capping agent can be easily detected. Moreover, it is possible to directly measure a pyrolysis gas chromatograph (PGC), an infrared spectrum, and a C13 NMR spectrum of a polymer component into which a terminal blocking agent has been introduced.

  The alkali-soluble resin used in the present invention is composed only of a phenol resin, a polymer containing a radical polymerizable monomer having an alkali-soluble group, and each structural unit represented by the general formulas (1) to (5). Or a polymer containing a phenol resin, a radical polymerizable monomer having an alkali-soluble group, and one or more polymers selected from the respective structural units represented by the general formulas (1) to (5); Copolymers or blends of these may be used. In the case of a copolymer or blend, 50 mol% or more of each structural unit represented by a phenol resin, a polymer containing a radical polymerizable monomer having an alkali-soluble group, and general formulas (1) to (5) It is preferable to contain. More preferably, it is 70 mol% or more. The type and amount of structural units used for copolymerization or blending are preferably selected within a range that does not impair the heat resistance of the polymer obtained by the final heat treatment.

  An epoxy compound and an epoxy curing agent may be added to the alkali-soluble resin used in the present invention. Epoxy compounds include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, phenol novolac epoxy compounds, cresol novolac epoxy compounds, trishydroxyphenylmethane type epoxy compounds, alicyclic epoxy compounds, glycidyl ester epoxy compounds, glycidyl amines. Epoxy compounds, heterocyclic epoxy compounds, fluorene group-containing epoxy compounds, and the like can be used. On the other hand, as the curing agent, usual ones such as alcohol, phenol, amine, acid anhydride, carboxylic acid, and a compound having active hydrogen can be used. Further, a cationic curing catalyst such as an onium salt may be used.

  The quinonediazide compound (b) is preferably a compound in which a sulfonic acid of naphthoquinonediazide is bonded to a compound having a phenolic hydroxyl group with an ester. Compounds having a phenolic hydroxyl group are Bis-Z, BisP-EZ, TekP-TPA, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-PHBA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP- IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-p-CR, Methylenetetra-p-CR, BisRS-26X, Bis-PFP-PC Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A (above , Trade name, manufactured by Asahi Organic Materials Co., Ltd.), naphthol, tetrahi 4-Naphthoquinone diazide sulfonic acid or 5-naphthoquinone diazide sulfonic acid by ester bond to a compound such as loxybenzophenone, gallic acid methyl ester, bisphenol A, methylene bisphenol, BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) Those introduced are preferred. A sulfonamide compound in which naphthoquinone diazide sulfonic acid is bonded to a compound having an amino group can also be used. Compounds other than these can also be used.

  The structure of a compound having a phenolic hydroxyl group is shown below as a specific example.

  In addition, when the molecular weight of the naphthoquinone diazide compound used in the present invention exceeds 1000, the naphthoquinone diazide compound is not sufficiently thermally decomposed in the subsequent heat treatment, so that the heat resistance of the resulting film is lowered, the mechanical properties are lowered, and the adhesion There is a possibility that problems such as a decrease in performance may occur. Accordingly, the molecular weight of the preferred naphthoquinonediazide compound is 300 to 1000. More preferably, it is 350 to 800. The addition amount of the naphthoquinonediazide compound is preferably 1 to 50 parts by weight with respect to 100 parts by weight of the polymer.

  If necessary, the compound having a phenolic hydroxyl group may be used as it is without being esterified with naphthoquinone diazide for the purpose of supplementing the alkali developability of the photosensitive precursor composition. When this compound having a phenolic hydroxyl group is added, the resin composition hardly dissolves in the alkali developer before exposure, and easily dissolves in the alkali developer upon exposure, so that the film loss due to development is small and short. Development becomes easier in time. In this case, the addition amount of the compound having a phenolic hydroxyl group is preferably 1 to 50 parts by weight, more preferably 3 to 40 parts by weight with respect to 100 parts by weight of the polymer.

  The component (c) is a thermochromic compound that develops color when heated and exhibits an absorption maximum at 350 to 700 nm, and more preferably a thermochromic compound that develops heat and exhibits an absorption maximum at 350 to 500 nm. (C) The thermochromic compound that develops color by heating to a wavelength shorter than 350 nm or longer than 700 nm, and exhibits an absorption maximum, has no absorption in the visible light wavelength region after the final heat treatment performed after pattern processing. It is difficult to blacken.

  The component (c) of the present invention is preferably a compound that develops heat at a temperature higher than 120 ° C, more preferably a thermochromic compound that develops a color at a temperature higher than 180 ° C. The higher the coloring temperature of the thermochromic compound, the better the heat resistance under high temperature conditions, and the less the color fading due to long-time ultraviolet-visible light irradiation, the better the light resistance.

  The component (c) of the present invention may be a general heat-sensitive dye or pressure-sensitive dye, or may be another compound. These thermochromic compounds are those that develop color by changing their chemical structure or charge state due to the action of acidic groups that coexist in the system during heating, or cause thermal oxidation reaction due to the presence of oxygen in the air. Examples are those that develop color. Examples of the skeleton structure of the thermochromic compound include triarylmethane skeleton, diarylmethane skeleton, fluorane skeleton, bislactone skeleton, phthalide skeleton, xanthene skeleton, rhodamine lactam skeleton, fluorene skeleton, phenothiazine skeleton, phenoxazine skeleton, and spiropyran skeleton. It is done. Specifically, 4,4 ′, 4 ″ -tris (dimethylamino) triphenylmethane, 4,4 ′, 4 ″ -tris (diethylamino) -2,2 ′, 2 ″ -trimethyltriphenylmethane, 2, 4 ′, 4 ″ -methylidenetrisphenol, 4,4 ′, 4 ″ -methylidenetrisphenol, 4,4 ′-[(4-hydroxyphenyl) methylene] bis (benzeneamine), 4,4 ′-[ (4-Aminophenyl) methylene] bisphenol, 4,4 ′-[(4-aminophenyl) methylene] bis [3,5-dimethylphenol], 4,4 ′-[(2-hydroxyphenyl) methylene] bis [ 2,3,6-trimethylphenol], 4- [bis (4-hydroxyphenyl) methyl] -2-methoxyphenol, 4,4 '-[(2-hydroxyphenyl) methylene Bis [2-methylphenol], 4,4 ′-[(4-hydroxyphenyl) methylene] bis [2-methylphenol], 4- [bis (4-hydroxyphenyl) methyl] -2-ethoxyphenol, 4, 4 ′-[(3-hydroxyphenyl) methylene] bis [2,6-dimethylphenol], 4,4 ′-[(4-hydroxyphenyl) methylene] bis [2,6-dimethylphenol], 2,2 ′ -[(4-hydroxyphenyl) methylene] bis [3,5-dimethylphenol], 4,4 '-[(4-hydroxy-3-methoxyphenyl) methylene] bis [2,6-dimethylphenol], 2, 2 ′-[(2-hydroxyphenyl) methylene] bis [2,3,5-trimethylphenol], 4,4 ′-[(4-hydroxyphenyl) methylene Bis [2,3,6-trimethylphenol], 4,4 ′-[(2-hydroxyphenyl) methylene] bis [2-cyclohexyl-5-methylphenol], 4,4 ′-[(3-hydroxyphenyl) Methylene] bis [2-cyclohexyl-5-methylphenol], 4,4 ′-[(4-hydroxyphenyl) methylene] bis [2-cyclohexyl-5-methylphenol], 4,4 ′-[(3-methoxy -4-hydroxyphenyl) methylene] bis [2-cyclohexyl-5-methylphenol], 4,4 '-[(3,4-dihydroxyphenyl) methylene] bis [2-methylphenol], 4,4'-[ (3,4-dihydroxyphenyl) methylene] bis [2,6-dimethylphenol], 4,4 ′-[(3,4-dihydroxyphenyl) Methylene] bis [2,3,6-trimethylphenol], 4- [bis (3-cyclohexyl-4-hydroxy-6-methylphenyl) methyl] -1,2-benzenediol, 4,4 ′, 4 ″, 4 "'-(1,2-ethanediylidene) tetrakisphenol, 4,4', 4", 4 "'-(1,2-ethanediylidene) tetrakis [2-methylphenol], 4,4', 4", 4 ""-(1,2-ethanediylidene) tetrakis [2,6-dimethylphenol], 4,4 ', 4 ", 4"'-(1,4-phenylenedimethylidene) tetrakisphenol, 4,4 ', 4 ", 4" '-(1,4-phenylenedimethylidene) tetrakis (2,6-dimethylphenol), 4,4'-[(2-hydroxyphenyl) methylene] bis [3-methylphenol 2,2 ′-[(3-hydroxyphenyl) methylene] bis [3,5-dimethylphenol], 4,4 ′-[(2-hydroxy-3-methoxyphenyl) methylene] bis [2,5-dimethyl Phenol], 4,4 '-[(2-hydroxy-3-methoxyphenyl) methylene] bis [2,6-dimethylphenol], 2,2'-[(2-hydroxy-3-methoxyphenyl) methylene] bis [3,5-dimethylphenol], 2,2 '-[(3-hydroxy-4-methoxyphenyl) methylene] bis [3,5-dimethylphenol], 4,4'-[(2-hydroxyphenyl) methylene ] Bis [2-methylethylphenol], 4,4 ′-[(3-hydroxyphenyl) methylene] bis [2-methylethylphenol], 4,4 ′-[(4- Droxyphenyl) methylene] bis [2-methylethylphenol], 2,2 ′-[(3-hydroxyphenyl) methylene] bis [3,5,6-trimethylphenol], 2,2 ′-[(4- Hydroxyphenyl) methylene] bis [3,5,6-trimethylphenol], 2,2 ′-[(4-hydroxy-3-ethoxyphenyl) methylene] bis [3,5-dimethylphenol], 4,4′- [(2-hydroxy-3-methoxyphenyl) methylene] bis [2- (methylethyl) phenol], 4,4 ′-[(3-hydroxy-4-methoxyphenyl) methylene] bis [2- (methylethyl) Phenol], 4,4 ′-[(4-hydroxy-3-methoxyphenyl) methylene] bis [2- (methylethyl) phenol], 2,2 ′-[(2- Hydroxy-3-methoxyphenyl) methylene] bis [3,5,6-trimethylphenol], 2,2 ′-[(3-hydroxy-4-methoxyphenyl) methylene] bis [3,5,6-trimethylphenol] 2,2 ′-[(4-hydroxy-3-methoxyphenyl) methylene] bis [3,5,6-trimethylphenol], 4,4 ′-[(4-hydroxy-3-ethoxyphenyl) methylene] bis [2- (methylethyl) phenol], 2,2 ′-[(4-hydroxy-3-ethoxyphenyl) methylene] bis [3,5,6-trimethylphenol], 4,4 ′-[(4-hydroxy -3-Ethoxyphenyl) methylene] bis [2,3,6-trimethylphenol], 4,4 ′-[(4-hydroxy-3-methoxyphenyl) methylene] [2- (1,1-dimethylethyl) -5-methylphenol], 4,4 ′-[(2-hydroxyphenyl) methylene] bis [2-cyclohexylphenol], 4,4 ′-[(3- Hydroxyphenyl) methylene] bis [2-cyclohexylphenol], 4,4 ′-[(4-hydroxyphenyl) methylene] bis [2-cyclohexylphenol], 4,4 ′-[(2-hydroxy-3-methoxyphenyl) ) Methylene] bis [2-cyclohexylphenol], 4,4 ′-[(3-hydroxy-4-methoxyphenyl) methylene] bis [2-cyclohexylphenol], 4,4 ′-[(4-hydroxy-3-) Ethoxyphenyl) methylene] bis [2- (1,1-dimethylethyl) -6-methylphenol], 4,4 ′-[(4-hydrido Xyl-3-ethoxyphenyl) methylene] bis [2-cyclohexyl-5-methylphenol], 4,4 ', 4 "-methylidenetris [2-cyclohexyl-5-methylphenol], 2,2'-[(3 4-dihydroxyphenyl) methylene] bis [3,5-dimethylphenol], 4,4 ′-[(3,4-dihydroxyphenyl) methylene] bis [2- (methylethyl) phenol], 2,2 ′-[ (3,4-dihydroxyphenyl) methylene] bis [3,5,6-trimethylphenol], 4,4 ′-[(3,4-dihydroxyphenyl) methylene] bis [2-cyclohexylphenol], 3,3 ′ -[(2-hydroxyphenyl) methylene] bis [5-methylbenzene-1,2-diol], 4,4 '-[4-[[bis (4-hydride) Roxy-2,5-dimethylphenyl) methyl] phenyl] methylene] bis [1,3-benzenediol], 4,4′-methylenebis [2- [di (4-hydroxy-3-methylphenyl)] methyl] phenol 4,4′-methylenebis [2- [di (4-hydroxy-2,5-dimethylphenyl)] methyl] phenol, 4,4′-methylenebis [2- [di (4-hydroxy-3,5-dimethyl) Phenyl)] methyl] phenol, 4,4′-methylenebis [2- [di (3-cyclohexyl-4-hydroxy-6-methylphenyl)] methyl] phenol, 4,4 ′-(3,5-dimethyl-4 -Hydroxyphenylmethylene) -bis (2,6-dimethylphenol), 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide 3,6-bis (dimethylamino) fluorane-γ- (4′-nitro) -aminolactam, 2- (2-chloroanilino) -6-diethylaminofluorane, 2- (2-chloroanilino) -6-dibutylaminofluor Oran, 2-N, N-dibenzylamino-6-diethylaminofluorane, 6-diethylamino-benzo [a] -fluorane, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5 ′ -Tetraphenyl-1,2'-bi (imidazole), 1,3-dimethyl-6-diethylaminofluorane, 2-anilino-3-methyl-6-dibutylaminofluorane, 3,7-bis (dimethylamino) -10-benzoylphenothiazine, 3-diethylamino-6-chloro-7- (β-ethoxyethylamino) fluorane, 3-diethylamino 6-methyl-7-anilinofluoran, 3-triethyl-6-methyl-7-anilinofluoran, 3-cyclohexylamino-6-methyl-7-anilinofluoran, and the like.

  Among these, a hydroxyl group-containing compound having a triarylmethane skeleton represented by general formulas (11) to (12) is preferable.

R ^{13 to} R ²⁸ may be the same or different, and are a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, a cyclic aliphatic group having 3 to 8 carbon atoms, or an aromatic ring having 6 to 15 carbon atoms. And a monovalent group selected from a hydrocarbon group having a carbon number and an alkoxy group having 1 to 4 carbon atoms. l is 0 or 1, preferably 0. γ is an integer of 0 to 3, preferably 1. W1 to W23 are integers from 0 to 4. W1 + W2 + W3> 0 and W10 + W11 + W12 + W13> 0.

  Specifically, 2,4 ′, 4 ″ -methylidenetrisphenol, 4,4 ′, 4 ″ -methylidenetrisphenol, 4,4 ′-[(4-hydroxyphenyl) methylene] bis (benzeneamine), 4,4 ′-[(4-aminophenyl) methylene] bisphenol, 4,4 ′-[(4-aminophenyl) methylene] bis [3,5-dimethylphenol], 4,4 ′-[(2-hydroxy Phenyl) methylene] bis [2,3,6-trimethylphenol], 4- [bis (4-hydroxyphenyl) methyl] -2-methoxyphenol, 4,4 ′-[(2-hydroxyphenyl) methylene] bis [ 2-methylphenol], 4,4 ′-[(4-hydroxyphenyl) methylene] bis [2-methylphenol], 4- [bis (4-hydroxyphenyl) methyl ] -2-ethoxyphenol, 4,4 '-[(4-hydroxyphenyl) methylene] bis [2,6-dimethylphenol], 2,2'-[(4-hydroxyphenyl) methylene] bis [3,5 -Dimethylphenol], 4,4 '-[(4-hydroxy-3-methoxyphenyl) methylene] bis [2,6-dimethylphenol], 2,2'-[(2-hydroxyphenyl) methylene] bis [2 , 3,5-trimethylphenol], 4,4 ′-[(4-hydroxyphenyl) methylene] bis [2,3,6-trimethylphenol], 4,4 ′-[(2-hydroxyphenyl) methylene] bis [2-cyclohexyl-5-methylphenol], 4,4 ′-[(4-hydroxyphenyl) methylene] bis [2-cyclohexyl-5-methylphenone ], 4,4 '-[(3-methoxy-4-hydroxyphenyl) methylene] bis [2-cyclohexyl-5-methylphenol], 4,4'-[(3,4-dihydroxyphenyl) methylene] bis [ 2-methylphenol], 4,4 ′-[(3,4-dihydroxyphenyl) methylene] bis [2,6-dimethylphenol], 4,4 ′-[(3,4-dihydroxyphenyl) methylene] bis [ 2,3,6-trimethylphenol], 4- [bis (3-cyclohexyl-4-hydroxy-6-methylphenyl) methyl] -1,2-benzenediol, 4,4 ', 4 ", 4"'- (1,2-ethanediylidene) tetrakisphenol, 4,4 ′, 4 ″, 4 ″ ′-(1,2-ethanediylidene) tetrakis [2-methylphenol], 4,4 ′, 4 ″ , 4 "'-(1,2-ethanediylidene) tetrakis [2,6-dimethylphenol], 4,4', 4", 4 "'-(1,4-phenylenedimethylidene) tetrakisphenol, 4,4' , 4 ", 4" '-(1,4-phenylenedimethylidene) tetrakis (2,6-dimethylphenol), 4,4'-[(2-hydroxyphenyl) methylene] bis [3-methylphenol], 4 , 4 ′-[(2-hydroxy-3-methoxyphenyl) methylene] bis [2,5-dimethylphenol], 4,4 ′-[(2-hydroxy-3-methoxyphenyl) methylene] bis [2,6 -Dimethylphenol], 2,2 '-[(2-hydroxy-3-methoxyphenyl) methylene] bis [3,5-dimethylphenol], 4,4'-[(2-hydroxypheny ) Methylene] bis [2-methylethylphenol], 4,4 ′-[(4-hydroxyphenyl) methylene] bis [2-methylethylphenol], 2,2 ′-[(4-hydroxyphenyl) methylene] bis [3,5,6-trimethylphenol], 2,2 ′-[(4-hydroxy-3-ethoxyphenyl) methylene] bis [3,5-dimethylphenol], 4,4 ′-[(2-hydroxy- 3-methoxyphenyl) methylene] bis [2- (methylethyl) phenol], 4,4 ′-[(4-hydroxy-3-methoxyphenyl) methylene] bis [2- (methylethyl) phenol], 2,2 '-[(2-hydroxy-3-methoxyphenyl) methylene] bis [3,5,6-trimethylphenol], 2,2'-[(4-hydroxy-3-me Xylphenyl) methylene] bis [3,5,6-trimethylphenol], 4,4 ′-[(4-hydroxy-3-ethoxyphenyl) methylene] bis [2- (methylethyl) phenol], 2,2′- [(4-Hydroxy-3-ethoxyphenyl) methylene] bis [3,5,6-trimethylphenol], 4,4 ′-[(4-hydroxy-3-ethoxyphenyl) methylene] bis [2,3,6 -Trimethylphenol], 4,4 '-[(4-hydroxy-3-methoxyphenyl) methylene] bis [2- (1,1-dimethylethyl) -5-methylphenol], 4,4'-[(2 -Hydroxyphenyl) methylene] bis [2-cyclohexylphenol], 4,4 ′-[(4-hydroxyphenyl) methylene] bis [2-cyclohexylphenol] 4,4 ′-[(2-hydroxy-3-methoxyphenyl) methylene] bis [2-cyclohexylphenol], 4,4 ′-[(4-hydroxy-3-ethoxyphenyl) methylene] bis [2 -(1,1-dimethylethyl) -6-methylphenol], 4,4 '-[(4-hydroxy-3-ethoxyphenyl) methylene] bis [2-cyclohexyl-5-methylphenol], 4,4' , 4 "-methylidenetris [2-cyclohexyl-5-methylphenol], 2,2 '-[(3,4-dihydroxyphenyl) methylene] bis [3,5-dimethylphenol], 4,4'-[(3 , 4-Dihydroxyphenyl) methylene] bis [2- (methylethyl) phenol], 2,2 ′-[(3,4-dihydroxyphenyl) methylene] bis [3 5,6-trimethylphenol], 4,4 ′-[(3,4-dihydroxyphenyl) methylene] bis [2-cyclohexylphenol], 3,3 ′-[(2-hydroxyphenyl) methylene] bis [5- Methylbenzene-1,2-diol], 4,4 ′-[4-[[bis (4-hydroxy-2,5-dimethylphenyl) methyl] phenyl] methylene] bis [1,3-benzenediol], 4 , 4′-methylenebis [2- [di (4-hydroxy-3-methylphenyl)] methyl] phenol, 4,4′-methylenebis [2- [di (4-hydroxy-2,5-dimethylphenyl)] methyl ] Phenol, 4,4'-methylenebis [2- [di (4-hydroxy-3,5-dimethylphenyl)] methyl] phenol, 4,4'-methylenebis [2- Di (3-cyclohexyl-4-hydroxy-6-methylphenyl)] methyl] phenol, 4,4 ′-(3,5-dimethyl-4-hydroxyphenylmethylene) -bis (2,6-dimethylphenol), etc. A hydroxyl group-containing compound having a triarylmethane skeleton is particularly preferred because of its high thermal coloring temperature and excellent heat resistance. These may be used alone or in combination. A hydroxyl group-containing compound having a triarylmethane skeleton may be used as a quinonediazide compound by esterifying a sulfonic acid of naphthoquinonediazide to the compound.

  The amount of the (c) thermochromic compound used in the present invention is preferably 1 to 300 parts by weight, particularly preferably 10 to 200 parts by weight, based on 100 parts by weight of the (a) alkali-soluble resin. (A) When the usage-amount of (c) thermochromic compound with respect to 100 weight part of alkali-soluble resin becomes larger than 300 weight part, a resin ratio will decrease and the adhesive strength of the photosensitive resin film and a board | substrate will fall.

  The component (d) of the present invention is a compound having no absorption maximum at 350 nm or more and less than 500 nm and having an absorption maximum at 500 nm or more and 750 nm or less. The compound preferably uses a dye and / or an organic pigment. The component (d) may be at least one, for example, a method using one kind of dye or organic pigment, a method using two or more kinds of dye or organic pigment in combination, one or more kinds of dye and one or more kinds And a method using an organic pigment in combination with each other. In the present invention, a method having an absorption maximum at 500 to 750 nm is preferably selected.

  The dye used as the component (d) component is preferably one that is soluble in the organic solvent that dissolves the alkali-soluble resin (a) and is compatible with the resin. Examples of preferable dyes include oil-soluble dyes, disperse dyes, reactive dyes, acid dyes, and direct dyes. As the skeleton structure of the dye, anthraquinone series, azo series, phthalocyanine series, methine series, oxazine series, and metal complex complexes of these dyes can be used. Among them, phthalocyanine series and metal complex complexes are available. Excellent in heat resistance and light resistance, and more preferable. Specifically, Sumilan, Lanyl dye (manufactured by Sumitomo Chemical Co., Ltd.), Orasol, Oracet, Filamid, Irgasperse dye (manufactured by Ciba Specialty Chemicals) Zapon, Neozapon, Neptune, Acidol dye (BASF Corporation) )) Kayaset, Kayakalan dye (Nippon Kayaku Co., Ltd.), Valifast colors dye (Orient Chemical Co., Ltd.) Savinyl, Sandoplast, Polysynthren, Lanasyn dye (Clariant Japan Co., Ltd.), Aizen Spilon dye ( Hodogaya Chemical Co., Ltd.). These dyes are used alone or in combination.

  The organic pigment used as the compound of component (d) of the present invention is preferably a pigment having high heat resistance and light resistance.

  Specific examples of the organic pigment used in the present invention are indicated by color index (CI) numbers. Examples of purple pigments include pigment violet 19, 23, 29, 32, 33, 36, 37, 38, and the like. Examples of blue pigments include Pigment Blue 15 (15: 3, 15: 4, 15: 6, etc.), 21, 22, 60, 64, and the like. Examples of the green pigment include Pigment Green 7, 10, 36, 47, and the like. Pigments other than these can also be used.

  The amount of the compound (d) used in the present invention is preferably 1 to 300 parts by weight, particularly preferably 10 to 200 parts by weight, per 100 parts by weight of the (a) alkali-soluble resin. (A) If the usage-amount of (d) compound with respect to 100 weight part of alkali-soluble resin becomes larger than 300 weight part, the resin ratio will decrease and the adhesive strength of the photosensitive resin film and a substrate will fall.

  In the present invention, an organic pigment that has been subjected to a surface treatment such as rosin treatment, acidic group treatment, basic group treatment, or the like may be used as necessary. Moreover, it can be used with a dispersing agent depending on the case. Examples of the dispersant include cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants.

  In order to apply the photosensitive composition of the present invention on a substrate, a liquid composition (varnish) is prepared by dissolving or dispersing each component described above in a solvent. Preferred examples of the solvent used include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, γ-butyrolactone, N-methyl-2-pyrrolidone, 3- The organic solvent which melt | dissolves the alkali-soluble resin which is (a) component of this invention like methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutanol, ethyl lactate, diacetone alcohol, etc. can be mentioned. However, it is not limited to this. An organic solvent may be used independently and may be used in mixture of 2 or more types. Although the solid content concentration in a varnish is not specifically limited, Usually, it is 5 to 50 weight% with respect to the whole quantity of a composition, Preferably it is about 10 to 40 weight%.

  If necessary, for the purpose of improving the wettability between the positive photosensitive resin composition and the substrate, a surfactant, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, 3 -Mix esters such as methyl-3-methoxybutyl acetate, alcohols such as 3-methyl-2-butanol and 3-methyl-3-methoxybutanol, ketones such as cyclohexanone, ethers such as tetrahydrofuran and dioxane. May be used. In addition, inorganic particles such as silicon dioxide and titanium dioxide, or polyimide powder can be added.

Furthermore a silicon wafer or ITO substrate, in order to enhance the adhesion to the underlying substrate, such as SiO _2, a silane coupling agent, may be added from 0.005 to 10 wt% varnish, such as a photosensitive resin composition of titanium chelating agent The base substrate can be pretreated with such a chemical solution.

  When added to the varnish, 0.005 to 10% by weight of a silane coupling agent such as methylmethacryloxydimethoxysilane or 3-aminopropyltrimethoxysilane, a titanium chelating agent or an aluminum chelating agent is added to the polymer in the varnish. To do.

  When the substrate is treated, the coupling agent described above is added to a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate and the like in an amount of 0.5-20. Surface treatment is performed by spin coating, slit die coating, bar coating, dip coating, spray coating, steam processing, and the like for the solution in which the weight% is dissolved. In some cases, the reaction between the substrate and the coupling agent is allowed to proceed by applying a temperature from 50 ° C. to 300 ° C.

  Next, a method for forming a heat resistant resin pattern using the photosensitive resin composition of the present invention will be described.

  A photosensitive resin composition is applied onto a substrate. Examples of the material of the substrate include all materials that can be provided with the electrode metal on the surface, such as metal, glass, semiconductor, metal oxide insulating film, silicon nitride, and polymer film. Preferably glass is used. The material of the glass is not particularly limited, but alkali zinc borosilicate glass, sodium borosilicate glass, soda lime glass, low alkali borosilicate glass, barium borosilicate glass, borosilicate glass, aluminosilicate glass, molten Quartz glass, synthetic quartz glass, and the like are used, and soda-lime glass with a barrier coating such as non-alkali glass or SiO 2 that usually has few ions eluted from the glass is used. Moreover, since the thickness should just have sufficient thickness to maintain mechanical strength, it is 0.1 mm or more, Preferably it is 0.5 mm or more. The coating method includes a slit die coating method, a spin coating method, a spray coating method, a roll coating method, a bar coating method and the like, and these methods may be applied in combination, but the photosensitive resin composition of the present invention may be used. The slit die coating method is most effective. Further, the coating film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, and the like, but is usually applied so that the film thickness after drying becomes 0.1 to 100 μm.

  Next, the substrate coated with the photosensitive resin composition is dried to obtain a photosensitive resin composition film. For drying, a hot plate, an oven, an infrared ray, a vacuum chamber or the like is used.

When using a hot plate, the object to be heated is directly held on the plate, or the object to be heated is held on a jig such as a proxy pin installed on the plate and heated. As a material of the proxy pin, there is a metal material such as aluminum or stellenless, or a synthetic resin such as polyimide resin or Teflon (registered trademark), and any proxy pin may be used. The height of the proxy pin varies depending on the size of the substrate, the type of the resin layer to be heated, the purpose of heating, etc. For example, a resin layer coated on a 300 × 350 × 0.7 mm ³ glass substrate is used. When heating, the height of the proxy pin is preferably about 2 to 12 mm.

  The heating temperature varies depending on the type and purpose of the object to be heated, and it is preferably performed in the range of room temperature to 180 ° C for 1 minute to several hours.

  Next, the photosensitive resin composition film is exposed to actinic radiation through a mask having a desired pattern. As the actinic radiation used for exposure, there are ultraviolet rays, visible rays, electron beams, X-rays and the like. In the present invention, it is preferable to use i-ray (365 nm), h-ray (405 nm), and g-ray (436 nm) of a mercury lamp. .

  Formation of the heat-resistant resin pattern is achieved by removing the exposed portion using a developer after exposure. The developer is an aqueous solution of tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylamino An aqueous solution of a compound exhibiting alkalinity such as ethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine and the like is preferable. The pH range of the developer is usually adjusted to 10 or more and 14 or less. In addition, polar solutions such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolaclone, dimethylacrylamide, methanol, ethanol, isopropanol, etc. Alcohols, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added singly or in combination. After development, rinse with water. Here, alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water for rinsing treatment.

  After development, a temperature of 130 ° C. to 350 ° C. is applied in an air or nitrogen atmosphere to convert it into a heat resistant resin film. The heat treatment atmosphere particularly suitable for the photosensitive resin composition of the present invention is an air atmosphere. In heat treatment in an air atmosphere, an oxidation reaction occurs due to the presence of oxygen, and the color development of the thermochromic compound is often promoted by the oxidation reaction. This heat treatment is carried out for 5 minutes to 5 hours by selecting the temperature and raising the temperature stepwise, or selecting a certain temperature range and continuously raising the temperature. As an example, heat treatment is performed at 130 ° C., 200 ° C., and 350 ° C. for 30 minutes each. Alternatively, a method of linearly increasing the temperature from room temperature to 250 ° C. over 2 hours or 350 ° C. over 2 hours may be used.

  The optical density (OD value) at a thickness of 1.0 μm of the heat resistant resin film obtained by heat-treating the photosensitive resin composition of the present invention is preferably 0.3 or more. More preferably, it is 0.5 or more. When the optical density is less than 0.3, the contrast between the light emitting area and the non-light emitting area of a display manufactured using the optical density is not improved. Therefore, it is difficult to obtain a function as a light-shielding separator or a black matrix of an organic electroluminescence element or a liquid crystal display element.

The heat-resistant resin film obtained by converting the photosensitive resin composition of the present invention by heat treatment has an optical density retention of 50% or more before irradiation after 500 hours of light irradiation using a xenon fade meter. Temporarily, the resin film prepared using only the thermochromic compound (c) has an optical density retention of less than 50%. In that case, the light resistance becomes insufficient, and the optical density of the insulating layer is lowered from its initial optical density after long-term use, so that the deterioration of the display quality tends to be remarkable, and the organic electroluminescence element and the liquid crystal display element It is difficult to obtain a function as a light-shielding separator or black matrix. Therefore, the optical density retention is preferably 50% or more, more preferably 70% or more, and particularly preferably 90% or more. In the present invention, the optical density is determined under the following conditions. The film is irradiated for 500 hours through a polarizing filter with a transmittance of 45% at an illuminance of 72,000 lux under a xenon arc lamp light source. The optical density before and after the irradiation was determined as O.D. D ₁ , O.D. D ₂ and the optical density retention rate as r were determined by the following equation.
r (%) = O. D ₂ / O. D ₁ × 100
In the present invention, as shown in FIG. 1, the cross section of the insulating layer 3 at the exposed boundary of the first electrode 4 formed on the substrate 5 is preferably a forward tapered shape. Here, the taper shape indicates that the angle θ in the figure is less than 90 °. The cross-sectional shape of the insulating layer is preferably 60 ° or less, more preferably 45 ° or less, and further preferably 30 ° or less. When the cross-sectional shape is larger than 60 °, the thin film layer 2 and the second electrode 1 tend to be thin at the boundary portion of the insulating layer, and luminance unevenness easily occurs in the light emitting region. In addition, as the driving time increases, moisture or a small amount of gas enters from the interface between the insulating layer and the second electrode, which tends to cause an increase in the dark area. In addition, electric field concentration is likely to occur at the edge portion of the electrode, and undesirable phenomena such as dielectric breakdown and leakage current are likely to occur.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. In the examples, evaluation of optical density, evaluation of light resistance, cross-sectional shape, and evaluation of light emission characteristics were performed by the following methods.
(1) Evaluation of optical density Optical density (OD) was measured using a microspectroscope ("MCPD2000" manufactured by Otsuka Electronics Co., Ltd.), the incident light intensity in the visible region of wavelength 430 to 640 nm was I0, and the transmitted light intensity. Was determined by the following equation as I.

O. D = log10 (I0 / I)
(2) Evaluation of light resistance About a heat resistant resin film produced on non-alkali glass by heat treatment, using a xenon long life fade meter (manufactured by Suga Test Instruments Co., Ltd.), 72000 under a xenon arc lamp light source. The optical density before and after holding for 500 hours through a polarizing filter having a transmittance of 45% at lux illuminance, respectively. D1, O.D. D2 was obtained, and the optical density retention rate was r, and was obtained by the following equation.
r (%) = O. D2 / O. D1 x 100
(3) Evaluation of cross-sectional shape For the 20 μm pattern line of the heat-resistant resin film obtained by heat treatment, the cross-sectional shape was observed using a scanning electron microscope (Hitachi, Ltd., “S-4800 type”). The θ value in FIG. 1 was measured.
(4) Durability evaluation of light emission A simple matrix organic electroluminescence display device was manufactured, the effective light emitting area area was S1, and the light emitting area area after a durability test held at a humidity of 85% for 250 hours was S2. The effective light emission area ratio after the test was determined as S by the following formula.

S (%) = (S2 / S1) × 100
Synthesis Example 1 Synthesis of hydroxyl group-containing acid anhydride (A) In a dry nitrogen stream, 18.3 g (0.05 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF) and allyl 34.2 g (0.3 mol) of glycidyl ether was dissolved in 100 g of gamma butyrolactone and cooled to −15 ° C. To this, 22.1 g (0.11 mol) of trimellitic anhydride chloride dissolved in 50 g of gamma butyrolactone was added dropwise so that the temperature of the reaction solution did not exceed 0 ° C. After completion of dropping, the reaction was carried out at 0 ° C. for 4 hours. This solution was concentrated by a rotary evaporator and poured into 1 l of toluene to obtain an acid anhydride (A).

Synthesis Example 2 Synthesis of hydroxyl group-containing diamine compound (B) 2-Amino-4-nitrophenol (15.4 g, 0.1 mol) was dissolved in acetone (50 ml) and propylene oxide (30 g, 0.34 mol). Cooled down. A solution prepared by dissolving 17.8 g (0.055 mol) of 2,2-bis (4-benzoyl chloride) propane in 60 ml of acetone was gradually added dropwise thereto. After completion of dropping, the reaction was carried out at −15 ° C. for 4 hours. Thereafter, the precipitate formed by returning to room temperature was collected by filtration.

This precipitate was dissolved in 200 ml of γ-butyrolactone, 3 g of 5% palladium-carbon was added, and the mixture was vigorously stirred. A balloon filled with hydrogen gas was attached thereto, and stirring was continued until the balloon of hydrogen gas did not contract any further at room temperature, and further stirred for 2 hours with the balloon of hydrogen gas attached. After completion of the stirring, the palladium compound was removed by filtration, and the solution was concentrated to half by a rotary evaporator. Ethanol was added thereto and recrystallization was performed to obtain crystals of the target compound.

Synthesis Example 3 Synthesis of hydroxyl group-containing diamine compound (C) 18.3 g (0.05 mol) of BAHF was dissolved in 100 ml of acetone and 17.4 g (0.3 mol) of propylene oxide, and cooled to -15 ° C. A solution prepared by dissolving 20.4 g (0.11 mol) of 4-nitrobenzoyl chloride in 100 ml of acetone was added dropwise thereto. After completion of dropping, the mixture was reacted at −15 ° C. for 4 hours and then returned to room temperature. The precipitated white solid was filtered off and vacuum dried at 50 ° C.

  30 g of the obtained solid was put in a 300 ml stainless steel autoclave, dispersed in 250 ml of methyl cellosolve, and 2 g of 5% palladium-carbon was added. Hydrogen was introduced here with a balloon and the reduction reaction was carried out at room temperature. After about 2 hours, the reaction was terminated by confirming that the balloons did not squeeze any more. After completion of the reaction, the catalyst was filtered to remove the palladium compound as a catalyst, and the mixture was concentrated with a rotary evaporator to obtain a diamine compound (C). The resulting solid was used for the reaction.

Synthesis Example 4 Synthesis of Hydroxyl-Containing Diamine Compound (D) 15.4 g (0.1 mol) of 2-amino-4-nitrophenol was dissolved in 100 ml of acetone and 17.4 g (0.3 mol) of propylene oxide, and −15 Cooled to ° C. A solution prepared by dissolving 20.4 g (0.11 mol) of 4-nitrobenzoyl chloride in 100 ml of acetone was gradually added dropwise thereto. After completion of dropping, the reaction was carried out at −15 ° C. for 4 hours. Thereafter, the precipitate formed by returning to room temperature was collected by filtration. Thereafter, the target compound crystal was obtained in the same manner as in Synthesis Example 2.

Synthesis Example 5 Synthesis of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid di n-butyl ester dichloride solution (E) 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride under a dry nitrogen stream 24.82 g (0.08 mol) of the product and 59.3 g (0.8 mol) of n-butyl alcohol were stirred and reacted at 95 ° C. for 6 hours. Excess n-butyl alcohol was distilled off under reduced pressure to obtain 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid di-n-butyl ester. Next, 95.17 g (0.8 mol) of thionyl chloride and 70 g of tetrahydrofuran (THF) were added and reacted at 40 ° C. for 3 hours. Subsequently, 200 g of N-methylpyrrolidone was added, excess thionyl chloride and THF were removed under reduced pressure, and 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid di-n-butyl ester dichloride solution (E) 239 0.6 g (0.08 mol) was obtained.

Synthesis Example 6 Synthesis of quinonediazide compound (F) 21.23 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 33.58 g of 5-naphthoquinonediazidesulfonyl chloride under a dry nitrogen stream (0.125 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 12.65 g (0.125 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the inside of the reaction system would not be 35 ° C. or higher. It stirred at 30 degreeC after dripping for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration. This precipitate was dried with a vacuum dryer to obtain a quinonediazide compound (F).

Synthesis Example 7 Synthesis of quinonediazide compound (G) In a dry nitrogen stream, 6.81 g (0.05 mol) of 4-isopropylphenol and 13.43 g (0.05 mol) of 5-naphthoquinonediazidesulfonyl acid chloride were added to 1,4- Dissolved in 450 g of dioxane and brought to room temperature. A quinonediazide compound (G) was obtained using 5.06 g of triethylamine mixed with 50 g of 1,4-dioxane in the same manner as in Synthesis Example 6.

Synthesis Example 8 Synthesis of quinonediazide compound (H) Under a dry nitrogen stream, 11.41 g (0.05 mol) of bisphenol A and 26.86 g (0.1 mol) of 5-naphthoquinonediazidesulfonyl acid chloride were added to 450 g of 1,4-dioxane. And brought to room temperature. A quinonediazide compound (H) was obtained in the same manner as in Synthesis Example 6 using 10.12 g of triethylamine mixed with 50 g of 1,4-dioxane.

Synthesis Example 9 Synthesis of active ester compound (I) In a dry nitrogen stream, 18.5 g (0.1 mol) of 4-carboxybenzoic acid chloride and 13.5 g (0.1 mol) of hydroxybenzotriazole were added to 100 g of tetrahydrofuran (THF). And cooled to -15 ° C. 10 g (0.1 mol) of triethylamine dissolved in 50 g of THF was added dropwise so that the temperature of the reaction solution did not exceed 0 ° C. After completion of the dropwise addition, the mixture was reacted at 25 ° C for 4 hours. This solution was concentrated by a rotary evaporator to obtain an active ester compound (I).

Synthesis Example 10 Synthesis of Alkali-Soluble Polymer (J) Under a dry nitrogen stream, 9.61 g (0.016 mol) of a hydroxyl group-containing acid anhydride (A) was dissolved in 100 g of N-methyl-2-pyrrolidone (NMP). To this was added 12 g (0.02 mol) of hydroxyl group-containing diamine (B) together with 25 g of NMP, and the mixture was reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 2 hours. Next, 0.78 g (0.008 mol) of maleic anhydride was added as a terminal blocking agent and reacted at 50 ° C. for 2 hours. Thereafter, a solution obtained by diluting 7.15 g (0.06 mol) of N, N-dimethylformamide dimethylacetal with 10 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 50 ° C. for 3 hours. After completion of the reaction, the solution was poured into 1 liter of water, and a polymer solid precipitate was collected by filtration. The polymer solid was dried with a vacuum dryer at 80 ° C. for 40 hours to obtain an alkali-soluble polymer (J).

Synthesis Example 11 Synthesis of Alkali-Soluble Polymer (K) Under a dry nitrogen stream, 12.01 g (0.02 mol) of a hydroxyl group-containing acid anhydride (A) was dissolved in 100 g of N-methyl-2-pyrrolidone (NMP). To this, 4.84 g (0.008 mol) of hydroxyl group-containing diamine (C) and 1.94 g (0.008 mol) of hydroxyl group-containing diamine (D) are added together with 25 g of NMP, followed by reaction at 20 ° C. for 1 hour, and then at 50 ° C. For 2 hours. Next, 0.94 g (0.008 mol) of 4-ethynylaniline was added and reacted at 50 ° C. for 2 hours. Thereafter, a solution obtained by diluting 7.15 g (0.06 mol) of N, N-dimethylformamide dimethylacetal with 5 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 50 ° C. for 3 hours. After completion of the reaction, the solution was poured into 1 liter of water, and a polymer solid precipitate was collected by filtration. The polymer solid was dried with a vacuum dryer at 80 ° C. for 40 hours to obtain an alkali-soluble polymer (K).

Synthesis Example 12 Synthesis of Alkali-soluble Polymer (L) Hydroxyl-containing diamine compound (C) 9.67 (0.016 mol), 1,3-bis (3-aminopropyl) tetramethyldisiloxane 86 g (0.0075 mol) and 0.94 g (0.008 mol) of 4-ethynylaniline as an end-capping agent were dissolved in 50 g of N-methyl-2-pyrrolidone (NMP). 6.2 g (0.02 mol) of bis (3,4-dicarboxyphenyl) ether dianhydride was added thereto together with 14 g of NMP, and the mixture was reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 4 hours. Thereafter, a solution obtained by diluting 7.15 g (0.06 mol) of N, N-dimethylformamide dimethylacetal with 5 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 50 ° C. for 3 hours. After completion of the reaction, the solution was poured into 1 liter of water, and a polymer solid precipitate was collected by filtration. The polymer solid was dried with a vacuum dryer at 70 ° C. for 60 hours to obtain an alkali-soluble polymer (L).

Synthesis Example 13 Synthesis of alkali-soluble polymer (M) 6.2 g (0.02 mol) of bis (3,4-dicarboxyphenyl) ether dianhydride was added to N-methyl-2-pyrrolidone (NMP) under a dry nitrogen stream. Dissolved in 50 g. 3-aminophenol 1.09g (0.01 mol) was added here as terminal blocker, and it was made to react at 40 degreeC for 1 hour. Next, 4.23 g (0.007 mol) of the hydroxyl group-containing diamine compound (c) and 0.6 g (0.003 mol) of 4,4′-diaminodiphenyl ether were added with 10 g of NMP, and the mixture was further reacted at 40 ° C. for 2 hours. Thereafter, a solution obtained by diluting 5.96 g (0.05 mol) of N, N-dimethylformamide dimethylacetal with 5 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 50 ° C. for 3 hours. After completion of the reaction, the solution was poured into 1 liter of water, and a polymer solid precipitate was collected by filtration. The polymer solid was dried with a vacuum dryer at 70 ° C. for 60 hours to obtain an alkali-soluble polymer (M).

Synthesis Example 14 Synthesis of Alkali-Soluble Polymer (N) Under a nitrogen stream, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (18.68 g, 0.051 mol), 1,3-bis ( 3-aminopropyl) tetramethyldisiloxane 1.86 g (0.0075 mol), 9.62 g (0.034 mol) active ester compound (I) as end-capping agent 11.93 g (0.151 mol) pyridine It was dissolved in 50 g of N-methyl-2-pyrrolidone (NMP). Here, 239.6 g (0.08 mol) of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid di-n-butyl ester dichloride solution (e) was dropped so that the inside of the reaction system would not exceed 10 ° C. did. After dropping, the mixture was stirred at room temperature for 6 hours. After completion of the reaction, the solution was poured into 2 liters of water, and the polymer solid precipitate was collected by filtration. The polymer solid was dried with a vacuum dryer at 80 ° C. for 20 hours to obtain an alkali-soluble polymer (N).

Synthesis Example 15 Synthesis of alkali-soluble polymer (P) Under a dry nitrogen stream, 7.75 g (0.051 mol) of 3,5-diaminobenzoic acid, 4 g (0.02 mol) of 4,4′-diaminodiphenyl ether, end-capped As stopping agents, 1.96 g (0.018 mol) of 3-aminophenol and 12.66 g (0.16 mol) of pyridine were dissolved in 50 g of N-methyl-2-pyrrolidone (NMP). Here, 239.6 g (0.08 mol) of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid di-n-butyl ester dichloride solution (E) was added dropwise so that the temperature in the reaction system would not exceed 10 ° C. did. After dropping, the mixture was stirred at room temperature for 6 hours. After completion of the reaction, the solution was poured into 2 liters of water, and the polymer solid precipitate was collected by filtration. The polymer solid was dried with a vacuum dryer at 80 ° C. for 20 hours to obtain an alkali-soluble polymer (P).

Example 1
Metacresol 57 g (0.6 mol), paracresol 38 g (0.4 mol), 37 wt% aqueous formaldehyde solution 75.5 g (formaldehyde 0.93 mol), Shusan dihydrate 0.63 g (0.005 mol) Was dissolved in 264 g of methyl isobutyl ketone, and polycondensation was performed for 4 hours with stirring while the reaction solution was refluxed. Then, the temperature was raised over 3 hours, and then the pressure in the flask was reduced to 4000 to 6666 Pa to remove volatile components, and the molten resin was cooled to room temperature and recovered. This resin was dissolved in ethyl acetate so that the resin component would be 30%, then 1.3 times the amount of methanol and 0.9 times the amount of water were added and left to stir. Subsequently, the lower layer separated into two layers was taken out, concentrated and dried to obtain a novolak resin.

  To 100 parts by weight of this novolak resin, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1 mol) and 1,2-naphthoquinonediazide- 30 parts by weight of condensate with 5-sulfonic acid chloride (2 mol), 25 parts by weight of thermochromic compound 4,4 ′, 4 ″ -tris (dimethylamino) triphenylmethane (absorption maximum 600 nm), (d) 35 parts by weight of pigment blue 15: 6 (phthalocyanine blue E, absorption maximum 670 nm), 2 parts by weight of a urethane-based dispersant (trade name Disperbyk-182), and 5 parts by weight of γ-methacryloxypropyltrimethoxysilane are mixed. And dissolved in propylene glycol monomethyl ether acetate so that the solid content concentration is 25% by weight. A resin composition varnish A1 was obtained.

A 300 × 350 × 0.7 mm ³ non-alkali glass (Corning Japan Co., Ltd., # 1737) surface was prepared with a 300 × 350 mm glass substrate having a 130 nm thick ITO transparent electrode film formed by sputtering deposition. . A photoresist was applied onto the ITO substrate by a spinner, and patterning was performed by exposure and development by a normal photolithography method. After removing unnecessary portions of the ITO by etching, the ITO film was patterned into a stripe shape having a length of 90 mm and a width of 80 μm by removing the photoresist. The striped first electrodes have a pitch of 100 μm.

  Varnish A1 was applied on a glass substrate patterned with ITO using a slit die coating method so that the film thickness after soft baking was 1.5 μm. The coating speed was 3 m / min. When the spin coating method was used, the coating was performed by adjusting the rotation speed so that the film thickness after soft baking was 1.5 μm. Then, using a hot plate (EA-4331 manufactured by Chuo Riken Co., Ltd.), the glass substrate is held at a height of 5 mm from the hot plate with a proxy pin and heated at 90 ° C. for 3 minutes to apply a positive photosensitive resin. A membrane was obtained. The varnish A1 coating film was exposed to UV through a photomask, developed by dissolving only the exposed portion with a 2.38% TMAH (tetramethylammonium) aqueous solution, and rinsed with pure water. The obtained resin pattern was cured by heating at 220 ° C. for 60 minutes in an air atmosphere in a clean oven, and an insulating layer was formed so as to cover the edge of the first electrode. The thickness of the insulating layer was about 1 μm. A light-shielding insulating layer made of a photosensitive novolac resin was formed so that the central portion of the first electrode was exposed through an opening having a width of 70 μm and a length of 250 μm, and covering the end of the first electrode. O. of the insulating layer. D was 0.5. The cross section of the boundary portion of the insulating layer has a forward taper shape as shown in FIG. 1, and the taper angle θ is about 60 °.

  Similarly, a light-shielding insulating layer was formed on an alkali-free glass and evaluated for light resistance. As a result, the optical density retention ratio r was 60%.

  Next, an organic electroluminescent device was manufactured using the substrate on which the insulating layer was formed. The thin film layer including the light emitting layer was formed by a vacuum evaporation method using a resistance wire heating method. A hole transport layer was formed by vapor deposition over the entire substrate effective area, and a light emitting layer and aluminum for the second electrode were formed using a shadow mask.

  The obtained said board | substrate was taken out from the vapor deposition machine, the board | substrate and the glass plate for sealing were bonded together using the ultraviolet curing epoxy resin, and it sealed. A simple matrix type color organic electroluminescent device in which a patterned light emitting layer was formed on the ITO striped first electrode and the striped second electrode was disposed so as to be orthogonal to the first electrode was produced. When this display device was line-sequentially driven, good display characteristics could be obtained. The thin film layer and the second electrode were formed smoothly at the boundary portion of the insulating layer without being thinned or disconnected. No luminance unevenness was observed in the light emitting region, and stable light emission was obtained. Further, the effective light emitting area ratio S after the durability test was 70%.

Example 2
176 g (0.1 mol) of t-butoxystyrene and 5.8 g (0.04 mol) of azobisisobutyronitrile were dissolved in 250 ml of propylene glycol monomethyl ether, and reacted at 75 ° C. for 4 hours. The poly t-butoxystyrene solution thus obtained was mixed with 50 g of a 5 wt% aqueous sulfuric acid solution, and subjected to a hydrolysis reaction at 100 ° C. for 3 hours. The reaction product was washed 3 times with 1000 ml of deionized water, 500 ml of propylene glycol monomethyl ether acetate was added, and the solvent was replaced to obtain an alkali-soluble resin (polyhydroxystyrene) solution.

  This alkali-soluble resin solution (corresponding to 100 parts by weight of polyhydroxystyrene (solid content)), 30 parts by weight of the quinonediazide compound (H), 4,4 ′, 4 ″, 4 ″ ′-(1, 4-phenylenedimethylidene) tetrakisphenol (absorption maximum 440 nm) 25 parts by weight, pigment blue 60 (indanthrone blue, absorption maximum 570 nm, 720 nm) 30 parts by weight, pigment violet 19 (quinacridone red, absorption maximum 510 nm, 550 nm, 600 nm ) Mix 10 parts by weight and 100 parts by weight of glass beads, dissolve in propylene glycol monomethyl ether acetate so that the solids concentration is 25% by weight, and after 30 minutes dispersion at 7000 rpm using a homogenizer, filter the glass beads Removed by positive type To obtain a varnish B1 of radiation-sensitive resin composition.

  The varnish B1 was applied onto the substrate using a spinner and then pre-baked on a hot plate at 90 ° C. for 3 minutes to form a coating film having a thickness of 2.2 μm. Evaluation was performed in the same manner as in Example 1 except that heating was performed at 220 ° C. for 60 minutes in an air atmosphere in a clean oven, and a display panel was produced.

Example 3
In a solution obtained by dissolving 7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) in 200 parts by weight of propylene glycol monomethyl ether acetate, 10 parts by weight of styrene, 20 parts by weight of methacrylic acid, 20 parts by weight of methacrylic acid, After 45 parts by weight of glycidyl methacrylate and 25 parts by weight of dicyclopentanyl methacrylate were charged and purged with nitrogen, the mixture was gently stirred. The temperature of the solution was maintained for 5 hours to obtain an acrylic resin solution.

  This acrylic resin solution (corresponding to 100 parts by weight of acrylic resin (solid content)), 25 parts by weight of quinonediazide compound (G), 4,4 ′, 4 ″ -methylidenetrisphenol (absorption maximum 460 nm) which is a thermochromic compound ) 25 parts by weight Pigment Blue 15: 6 (phthalocyanine blue E, absorption maximum 670 nm), 15 parts by weight Pigment Blue 60 (Indanthrone blue, absorption maximum 570 nm, 720 nm), urethane dispersant ( 2 parts by weight of the product name Disperbyk-182) and 100 parts by weight of glass beads are mixed, dissolved in propylene glycol monomethyl ether acetate so that the solid concentration is 25% by weight, and dispersed at 7000 rpm for 30 minutes using a homogenizer. Then, the glass beads are removed by filtration, To obtain a varnish C1 type radiation-sensitive resin composition. Using this varnish C1, was prepared display panel evaluated in the same manner as in Example 1.

Example 4
(D) Pigment Blue 15: 6 (phthalocyanine blue E, absorption maximum 670 nm) 2.5 g and Pigment Blue 60 (Indanthrone blue, absorption maximum 570 nm, 720 nm) 1.5 g are added to 36 g of γ-butyrolactone. Using a homogenizer together with 50 g of glass beads, the glass beads were removed by filtration at 7000 rpm for 30 minutes to obtain an organic pigment dispersion having a concentration of 10% by weight. 32 g of dispersion liquid 5 g of alkali-soluble polymer (J), thermochromic compound 4,4 ′, 4 ″ -tris (dimethylamino) triphenylmethane (absorption maximum 600 nm) 1.25 g, quinonediazide compound (H) 2 g, lactic acid A mixed solution of 9.75 g of ethyl was added to obtain a varnish D1 of a positive photosensitive resin composition.

  A varnish D1 was applied on the substrate using a slit die coating method, and prebaked on a hot plate at 120 ° C. for 5 minutes to form a coating film having a thickness of 1.5 μm. Thereafter, an evaluation was performed in the same manner as in Example 1 except that curing was performed at 250 ° C. for 30 minutes in an air atmosphere in a clean oven, and a display device was produced.

Example 5
(D) Pigment Blue 15: 6 (phthalocyanine blue E, absorption maximum 670 nm) 2 g is added to 10 g of alkali-soluble polymer (K), 37 g of γ-butyrolactone, 44 g of 3-methyl-3-methoxybutyl acetate, and glass The glass beads were removed by filtration after a dispersion treatment at 7000 rpm for 30 minutes using a homogenizer together with 50 g of beads. To this, 3 g of quinonediazide compound (H) and 4 g of thermochromic compound 4- [bis (4-hydroxyphenyl) methyl] 2-methoxyphenol (absorption maximum 470 nm) were added, and the varnish of the positive photosensitive resin composition was added. E1 was obtained. Evaluation was performed in the same manner as in Example 4 except that varnish E1 was used, and a display device was prepared.

Example 6
10 g of alkali-soluble polymer (L), 2.2 g of quinonediazide compound (F), 2.4 g of thermochromic compound, 2.4 g of methylidenetrisphenol (absorption maximum 460 nm), 0.05 g of vinylmethoxysilane In addition to a mixed solvent of 39.95 g of γ-butyrolactone and 40 g of ethyl lactate, as the component (d), 3.0 g of azochrome complex-based dye Variifast Black 1807 (absorption maximum 580 nm), phthalocyanine dye Variifast blue 2620 (absorption maximum 680 nm) 2.4 g (produced by Orient Chemical Co., Ltd., described in the catalog 2002.2) was added to obtain a positive photosensitive resin composition varnish F1 using varnish F1 and curing conditions in an air atmosphere in a clean oven. Example 4 with the exception of heating at 230 ° C. for 30 minutes below We have created a display device evaluated as.

Example 7
(D) Component Blue 15: 6 (phthalocyanine blue E, absorption maximum 670 nm) 5 g, Pigment Blue 60 (Indanthrone blue, absorption maximum 570 nm, 720 nm) 5 g, Alkali-soluble polymer (M) 20 g, N- 50 g of methyl-2-pyrrolidone and 110 g of 3-methyl-3-methoxybutyl acetate were dispersed together with 100 g of glass beads using a homogenizer at 7000 rpm for 30 minutes, and then the glass beads were removed by filtration. 7 g of quinonediazide compound (H) and 3 g of 4,4 ′, 4 ″ -methylidenetrisphenol (absorption maximum 460 nm) which is a thermochromic compound were added thereto to obtain a varnish G1 of a positive photosensitive resin composition. Evaluation was performed in the same manner as in Example 4 except that the varnish G1 was used and the curing condition was heated at 280 ° C. for 30 minutes in an air atmosphere in a clean oven, thereby producing a display device.

Example 8
(D) 6 g of pigment blue 60 (indanthrone blue, absorption maximum 570 nm, 720 nm) and 2 g of pigment violet 19 (quinacridone red, absorption maximum 510 nm, 550 nm, 600 nm) as components (20 g of γ-butyrolactone, N-methyl-2) -Using a homogenizer together with 52 g of pyrrolidone and 50 g of glass beads, the glass beads were removed by filtration at 7000 rpm for 30 minutes to obtain an organic pigment dispersion having a concentration of 10% by weight. 40 g of dispersion liquid 4 g of alkali-soluble polymer (N), 1 g of quinonediazide compound (H), 4,4 ′, 4 ″, 4 ″ ′-(1,4-phenylenedimethylidene) tetrakisphenol (absorption) which is a thermochromic compound A mixed solution of 1 g (maximum 440 nm) and 3 g of γ-butyrolactone was added to obtain a varnish H1 of a positive photosensitive resin composition. Evaluation was performed in the same manner as in Example 4 except that the varnish H1 was used, and the curing condition was continuously heated at 170 ° C. for 30 minutes in an air atmosphere in a clean oven, and then heated at 320 ° C. for 60 minutes, thereby producing a display device.

Example 9
(D) Component blue 15: 6 (phthalocyanine blue E, absorption maximum 670 nm) 7 g, thermochromic compound 4,4 ′, 4 ″ -methylidenetrisphenol (absorption maximum 460 nm) 2 g, 4,4 ', 4 ", 4"'-(1,4-phenylenedimethylidene) tetrakisphenol (absorption maximum 440 nm) 3 g alkali-soluble polymer (P) 20 g, quinonediazide compound (G) 6.5 g, N-methyl-2-pyrrolidone 80 g, 73.5 g of 3-methyl-3-methoxybutyl acetate were dispersed together with 100 g of glass beads using a homogenizer at 7000 rpm for 30 minutes, and then the glass beads were removed by filtration, thus the varnish of the positive photosensitive resin composition. J1 was obtained, and varnish J1 was used to cure the air in a clean oven. It was heated for 30 minutes at 170 ° C. under air, but heated followed by 350 ° C. for 30 minutes to create a display device evaluated in the same manner as in Example 4.

Comparative Example 1
Evaluation was performed in the same manner as in Example 1 except that 35 parts by weight of Pigment Blue 15: 6 (phthalocyanine blue E, absorption maximum 670 nm) of Example 1 was not used, and a display device was produced.

Comparative Example 2
Instead of using 30 parts by weight of Pigment Blue 60 (Indanthrone Blue, absorption maximum 570 nm, 720 nm) and 10 parts by weight of Pigment Violet 19 (quinacridone red, absorption maximum 510 nm, 550 nm, 600 nm) of Example 2, “NK-2612 A display device was prepared by evaluating in the same manner as in Example 2 except that 40 parts by weight (manufactured by Hayashibara Biochemical Laboratories, Inc., absorption maximum 790 nm) was used.

Comparative Example 3
Example 3 was evaluated and displayed in the same manner as in Example 3 except that Pigment Blue 15: 6 (phthalocyanine blue E, absorption maximum 670 nm) and Pigment Blue 60 (Indanthrone blue, absorption maximum 570 nm, 720 nm) were not used. Created a device.

Comparative Example 4
Evaluation was performed in the same manner as in Example 4 except that 1.25 g of 4,4 ′, 4 ″ -tris (dimethylamino) triphenylmethane (absorption maximum 600 nm) of Example 4 was not used, and a display device was prepared.

Comparative Example 5
Evaluation was performed in the same manner as in Example 5 except that 4- [bis (4-hydroxyphenyl) methyl] 2-methoxyphenol (absorption maximum 470 nm) of Example 5 was not used, and a display device was produced.

Comparative Example 6
Instead of using 3 g of Valifast Black 1807 (absorption maximum 580 nm) of the azochrome complex dye of Example 6 and 2.4 g of Variphthal blue 2620 (absorption maximum 680 nm) of phthalocyanine dye (produced by Orient Chemical Co., Ltd., described in the catalog 2002.2) In addition, evaluation was performed in the same manner as in Example 6 except that 5.4 g of Pigment Yellow 12 (Disazo Yellow AAA, absorption maximum 420 nm) was used, and a display device was prepared.

Comparative Example 7
Under a dry nitrogen stream, 10.7 g (0.049 mol) of pyromellitic dianhydride, 16.1 g (0.05 mol) of benzophenonetetracarboxylic dianhydride, 3, γ-butyrolactone (274 g), 6.2 g (0.025 mol) of 3′-diaminodiphenylsulfone, 14 g (0.07 mol) of 4,4′-diaminodiphenyl ether, 1.2 g (0.005 mol) of bis-3- (aminopropyl) tetramethylsiloxane ) At 60 ° C. for 3 hours, and then 0.2 g (0.002 mol) of maleic anhydride is added and further reacted at 60 ° C. for 1 hour, whereby the precursor polyamic acid solution (polymer concentration 15 wt. %).

  4,4 ', 4 ", 4"'-(1,4-phenylenedimethylidene) tetrakisphenol (absorption maximum 440 nm) 2.5 g, pigment pigment blue 60 (indanthrone blue, absorption) 3 g of maximum 570 nm, 720 nm), 1 g of pigment violet 19 (quinacridone red, absorption maximum 510 nm, 550 nm, 600 nm), 60 g of the polyamic acid solution, 14.5 g of N-methyl-2-pyrrolidone together with 100 g of glass beads using a homogenizer, 7000 rpm After 30 minutes of dispersion treatment, the glass beads were removed by filtration to obtain a non-photosensitive resin composition varnish Q1.

  After applying onto the substrate using varnish Q1, pre-baking was performed at 145 ° C. to form a polyimide precursor film. A positive type photoresist was applied on the coating film and dried by heating at 90 ° C. to form a photoresist film. The film was exposed to ultraviolet light through a photomask, then immersed in alkali development, and the photoresist film was developed and the polyimide precursor film was etched simultaneously to form openings. After etching, the photoresist film that became unnecessary was peeled off with methyl cellosolve acetate. The etched polyimide precursor film was heated in an air atmosphere at 290 ° C. for 60 minutes using a clean oven to form a polyimide insulating layer. O. of the obtained light-shielding insulating layer. D was 1.8. The cross section of the boundary portion of the insulating layer was a forward tapered shape, and the taper angle θ was about 85 °.

  As a result of forming a light-shielding insulating layer on alkali-free glass using varnish Q1 and evaluating light resistance, the optical density retention ratio r was 95%.

  Thereafter, a simple matrix type organic electroluminescent device was produced in the same manner as in Example 1. When this display device is driven line-sequentially, the cross section of the insulating layer has a forward taper shape with a taper angle of about 85 °. Brightness unevenness was observed in the area. The effective light emission area ratio S after the durability test was 80%.

Comparative Example 8
100 g of negative photosensitive polyimide precursor varnish (UR-3100, manufactured by Toray Industries, Inc.), 10 g of thermochromic compound 4,4 ′, 4 ″ -methylidenetrisphenol (absorption maximum 460 nm), pigment pigment blue 15 : 6 g (phthalocyanine blue E, absorption maximum 670 nm) and 6 g pigment blue 60 (indanthrone blue, absorption maximum 570 nm, 720 nm) were added to obtain a negative photosensitive resin composition varnish R1. R1 was applied onto the substrate on which the first electrode was formed by spin coating, and prebaked on a hot plate at 80 ° C. for 1 hour.After this coating film was exposed through a photomask, a developer (Toray ( Co., Ltd., DV-505) was developed by dissolving only the non-exposed areas and rinsed with pure water, and then in a clean oven The insulating layer was formed by heating at 180 ° C. for 30 minutes and further at 220 ° C. for 30 minutes under the air atmosphere of the above.The OD of the obtained light-shielding insulating layer was 0.9. The cross section was rectangular, and the taper angle θ was about 90 °.

  Similarly, as a result of forming a light-shielding insulating layer on alkali-free glass and evaluating light resistance, the optical density retention ratio r was 90%.

  Thereafter, a simple matrix type organic electroluminescent device was produced in the same manner as in Example 1. When this display device was driven line-sequentially, since the cross section of the insulating layer was rectangular, the thin film layer and the second electrode layer became thin at the boundary portion of the insulating layer, and luminance unevenness was observed in the light emitting region. The effective light emission area ratio S after the durability test was 70%.

Comparative Example 9
Using heat-sensitive material V259-PA (trade name, manufactured by Nippon Steel Chemical Co., Ltd.), which is an alkali-soluble photoresist, is added in advance to the photocurable resin. A plastic resin containing 20-30% crystal violet lactone (absorption maximum 610 nm) as a color former and 20-30% oil-soluble phenol resin as a developer were used. As the thermoplastic resin used at this time, transparent polyethylene terephthalate was used. The concentration of the heat-sensitive material containing the color former or developer in the photosensitive resin is as follows: photosensitive resin: color developer-containing heat-sensitive material: developer-containing heat-sensitive material = 2: 1: 1. The varnish S1 was adjusted so that various materials were sufficiently dispersed in the photosensitive resin.

  Using this varnish S1, it apply | coated on the board | substrate in which the 1st electrode was formed by the spin coat method, and prebaked on 80 degreeC and 3 minutes on the hotplate. Subsequently, it exposed through the photomask, developed with the sodium carbonate aqueous solution, and rinsed with the pure water. Thereafter, heating is performed at 200 ° C. for 30 minutes using a hot plate, the thermosensitive microcapsules added in the photocurable resin layer are dissolved, and the encapsulated color former and developer are reacted. The photocurable resin was blackened to form a resin black matrix insulating layer. O. of the obtained insulating layer. D was 2.0. The cross section of the boundary portion of the insulating layer was rectangular, and the taper angle θ was about 90 °.

  Similarly, as a result of forming a light-shielding insulating layer on alkali-free glass and evaluating light resistance, the optical density retention ratio r was 20%.

  Thereafter, a simple matrix type organic electroluminescent device was produced in the same manner as in Example 1. When this display device was driven line-sequentially, since the cross section of the insulating layer was rectangular, the thin film layer and the second electrode layer became thin at the boundary portion of the insulating layer, and luminance unevenness was observed in the light emitting region. The effective light emission area ratio S after the durability test was 70%.

  The evaluation results of Examples 1 to 9 and Comparative Examples 1 to 9 are shown in Table 1.

It is sectional drawing which shows the boundary part of an insulating layer.

Explanation of symbols

1 Substrate 2 First electrode 3 Insulating layer

Claims (14)

(A) an alkali-soluble resin, (b) a quinonediazide compound, (c) a thermochromic compound that develops color when heated and exhibits an absorption maximum at 350 nm to 700 nm, and (d) 500 nm or more without an absorption maximum at 350 nm to less than 500 nm. A positive photosensitive resin composition comprising a compound having an absorption maximum at 750 nm or less. The composition according to claim 1, wherein the quinonediazide compound is an esterified quinonediazide compound. The composition according to claim 1 or 2, wherein the component (a) is at least one selected from the following resins.
Phenol resin Polymer containing radical polymerizable monomer having alkali-soluble group The composition according to claim 1 or 2, wherein the component (a) comprises a structural unit represented by the general formula (1) as a main component.

(Wherein R ¹ is a divalent to octavalent organic group having 2 or more carbon atoms, R ² is a divalent to hexavalent organic group having 2 or more carbon atoms, and R ³ and R ⁴ are May be the same or different and represents hydrogen or an organic group having 1 to 20 carbon atoms, n is in the range of 5 to 100,000, p and q are integers of 0 to 4, r and s are Each is an integer from 0 to 2. p + q> 0.) The photosensitive resin composition according to claim 4, wherein component (a) is one or more resins selected from resins having structural units represented by general formulas (2) to (5).

(Wherein R ¹ is a divalent to octavalent organic group having 2 or more carbon atoms, R ² is a divalent to hexavalent organic group having 2 or more carbon atoms, and R ³ and R ⁴ are ^{May be the} same or different, hydrogen or an organic group having 1 to 20 carbon atoms, R ⁵ is a divalent organic group, X and Y are carboxyl groups, phenolic hydroxyl groups, sulfonic acid groups, thiol groups , Hydrocarbon groups having 1 to 10 carbon atoms, one or more organic groups selected from unsaturated hydrocarbon groups, nitro groups, methylol groups, ester groups, hydroxyalkynyl groups, hydrocarbons having 1 to 10 carbon atoms An organic group having one or more substituents selected from the group: n is in the range of 5 to 100,000, m is an integer of 0 to 10, p and q are integers of 0 to 4, r and s Are each an integer from 0 to 2. p + q 0, it is.) The composition according to claim 5, wherein s is 0 in the general formulas (2) to (5). The composition according to any one of claims 1 to 6, wherein the component (c) is a thermochromic compound that develops color when heated and exhibits an absorption maximum at 350 to 500 nm. The photosensitive resin composition according to any one of claims 1 to 6, wherein the component (c) is a hydroxyl group-containing compound having a triarylmethane skeleton. The photosensitive resin composition according to claim 1, wherein the optical density of the cured film obtained after the heat treatment is 0.5 or more. The photosensitive resin composition in any one of Claims 1-9 in which the optical density of the cured film obtained after heat processing is hold | maintained 50% or more after progress for 500 hours under light irradiation. A process for producing a pattern comprising a step of applying the photosensitive resin composition according to claim 1 to a support substrate and drying, a step of exposing, a step of developing using an alkali developer, and a step of heat treatment. . A patterned resin obtained by the method according to claim 11. The organic electroluminescent display which has a pattern obtained from the composition of any one of Claims 1-10. An organic light emitting display device having the pattern according to claim 12.

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