TWI490649B - Positive photosensitive composition, hardened film formed from the same and element having hardened film - Google Patents

Description

Positive photosensitive composition, cured film formed therefrom, and component having a cured film

The present invention relates to a flat film for a thin film transistor (TFT) substrate for forming a liquid crystal display element or an organic electroluminescence (EL) display element, a protective film for a touch panel, or an insulating film. An interlayer insulating film of a film or a semiconductor element, a planarizing film for a solid-state imaging device or a microlens array pattern, a photosensitive composition of a core portion or a coating material of an optical waveguide, a cured film formed therefrom, and a cured film having the cured film element.

In recent years, in liquid crystal displays, organic EL displays, and the like, it is required to achieve further high definition and high resolution.

In addition, in recent years, in liquid crystal displays and the like, a touch panel has been actively used, and in particular, a capacitive touch panel has been attracting attention. In order to improve the transparency or functionality of the touch panel, indium tin oxide is required as a transparent electrode member. (Indium Tin Oxide, ITO) has high transparency, and also requires a high conductive protective film or insulating film to have heat resistance for high temperature processing.

Prior technical literature

Patent literature

For example, Patent Document 1 describes a method of improving the aperture ratio of a display device as a method for realizing further high definition and high resolution in a liquid crystal display or an organic EL display. This method is a method in which a transparent planarizing film is provided as a protective film on the upper portion of the TFT substrate, whereby the data line and the pixel electrode are overlapped, and the aperture ratio is improved as compared with the prior art.

As a material of the flattening film for a TFT substrate, it is necessary to have high heat resistance and high transparency, and a hole pattern of about several μm to 50 μm is formed in order to connect the TFT substrate electrode and the ITO electrode. A positive photosensitive material is usually used.

Patent Document 2, Patent Document 3, and Patent Document 4 describe a material obtained by combining an acrylic resin and a quinone diazide compound as a representative positive photosensitive material.

On the other hand, as a material having high heat resistance and high transparency, a polyoxyalkylene is known, and Patent Document 5 and Patent Document 6 disclose that a positive photosensitive property is added thereto. The material of the quinone diazide compound has high heat resistance, and even if it is treated by high temperature, it does not cause cracks and the like, and a highly transparent cured film can be obtained.

Patent Document 7 discloses a method of adding a metal chelating agent to polyoxyalkylene as a method for improving the moist heat resistance. It is believed that the mechanism is that the titanium or zirconium chelating agent promotes the crosslinking of the decane, thereby improving the heat and humidity resistance.

Further, in Patent Document 8, a negative photosensitive material containing an organic metal chelate compound is reported.

Further, Patent Document 9 discloses a positive photosensitive material obtained by adding metal particles to a siloxane.

Further, in Patent Document 10, improvement in coating unevenness of a decane composition containing a specific solvent has been reported. Among them, an example in which naphthoquinonediazide is added as a positive photosensitive material and an example in which a chelate compound is added as a positive photosensitive property are individually described.

Patent Document 1: Japanese Patent Laid-Open No. Hei 9-152625 (Application) Patent area 1)

Patent Document 2: Japanese Patent Laid-Open Publication No. 2001-281853 (Patent Application No. 1)

Patent Document 3: Japanese Patent Laid-Open No. Hei 5-165214 (Patent No. 1 of the Patent Application)

Patent Document 4: Japanese Patent Laid-Open Publication No. 2002-341521 (Application No. 1)

Patent Document 5: Japanese Patent Laid-Open No. 2006-178436 (Patent No. 1 of the Patent Application)

Patent Document 6: Japanese Patent Laid-Open Publication No. 2009-211033 (Patent Application No. 1)

Patent Document 7: Japanese Patent Laid-Open No. Hei 07-331173 (Patent Application No. 1)

Patent Document 8: Japanese Patent Laid-Open Publication No. 2007-308688 (Application No. 1)

Patent Document 9: Japanese Patent Laid-Open No. 2007-246877 (Application No. 1 of the Patent Application No. 6 of the Patent Application Area)

Patent Document 10: WO2007-049440 (paragraph number 0040~paragraph number 0041 and paragraph number 0054)

However, since the transparent planarizing film of the patent document 1 uses an acrylic resin material, heat resistance is inadequate.

In addition, the acrylic resin which is a material described in Patent Document 2, Patent Document 3, and Patent Document 4 has a problem that heat resistance or chemical resistance is insufficient, and high temperature processing of a substrate or high temperature of a transparent electrode is required. The film and various etching chemicals are treated to cause the cured film to be colored, and the transparency is lowered, or the electrical conductivity of the electrode is lowered due to degassing in the high-temperature film formation. In addition, these acrylic materials generally have low sensitivity, so productivity is low, and a material having higher sensitivity is required. Further, the size of the opening of the hole pattern or the like is also refinement year by year, and it is required to form a fine pattern of 3 μm or less. However, the resolution of the acrylic material is not sufficient.

The polysiloxane raw materials described in Patent Document 5 and Patent Document 6 have high heat resistance and high transparency, but in this material, the adhesion between the film on which the pattern is formed during development and the substrate (hereinafter referred to as The development adhesiveness is not sufficient, and in particular, the fine pattern is peeled off together with the developer or the eluent. Therefore, a good positive photosensitive material having better development adhesion is strongly required.

Usually, in order to make the development adhesiveness favorable, the pre-baking temperature after coating is raised. However, since the sensitizer is deactivated by increasing the pre-baking temperature, the sensitivity is lowered. On the other hand, when the pre-bake temperature is set to be low, there is a trade-off between the residual solvent in the film and the deterioration of the development adhesiveness, and it is extremely difficult to coexist both.

Further, the heat and humidity resistance cannot be said to be sufficient, and a positive photosensitive material having a better heat and humidity resistance is strongly required.

Regarding the photosensitive composition described in Patent Document 7, there is no mention of how much chelating agent should be added.

In Patent Document 8, in order to form a conductive film and perform baking, an insulating organic film does not remain.

In Patent Document 9, there is no mention of heat and humidity resistance.

In Patent Document 10, there is no description about the simultaneous use of naphthoquinonediazide and a chelate compound, and there is no such thing as to be able to easily introduce a positive photosensitive property by using these compounds at the same time. And the description of coexistence of moist heat resistance and development adhesion.

As described above, although a positive photosensitive material having high transparency and high heat and humidity resistance and having good development adhesion has been sought, the technology has not been established so far.

The present invention has been made in view of the above-described circumstances, and an object of the invention is to provide a photosensitive composition which is excellent in heat resistance and high transparency, and which is excellent in development adhesiveness and moist heat resistance. Further, another object of the present invention is to provide a flattening film for a TFT substrate, an interlayer insulating film, a protective film or an insulating film for a touch panel, a core or a covering material, and a lens which are formed of the photosensitive composition. A cured film of a material, and a display element, a semiconductor element, a solid-state imaging element, an optical waveguide, or the like having the cured film.

In order to solve the above problems, the positive photosensitive composition of the present invention has the following constitution. That is, a positive photosensitive composition comprising (A) an alkali-soluble polyoxyalkylene oxide and/or an alkali-soluble acrylic resin, (B) a naphthoquinonediazide compound, (C) a solvent, and (D) a metal The chelating compound, the (D) metal chelating compound has a structure represented by the following formula (1), and is related to (A) an alkali-soluble polyoxyalkylene oxide and/or an alkali-soluble acrylic resin (hereinafter referred to as The "base-soluble resin") is contained in an amount of 0.1 part by weight to 5 parts by weight based on 100 parts by weight of the (D) metal chelate compound.

(In the metal chelate compound represented by the formula (1), M is a metal atom. R ¹ may be the same or different and each represents a hydrogen, an alkyl group, an aryl group, an alkenyl group, and a substituent thereof. ² , R ³ may be the same or different, and each represents hydrogen, an alkyl group, an aryl group, an alkenyl group, an alkoxy group, and the substituents thereof. j represents the valence of the metal atom M, and k represents an integer of 0 to j. ).

Further, the cured film of the present invention has any one of the following (1) and (2). That is, (1) a cured film formed of the above-mentioned positive photosensitive composition, and having a light transmittance of 85% or more per 3 μm at a wavelength of 400 nm, or (2) a cured film The positive photosensitive composition is formed, and is selected from the group consisting of titanium, zirconium, aluminum, zinc, cobalt, molybdenum, niobium, tantalum, and 100 parts by weight of the alkali-soluble polyoxyalkylene oxide and/or alkali-soluble acrylic resin composition. The metal content of one or more of cerium, magnesium, and calcium is from 0.005 parts by weight to 1 part by weight.

The element of the present invention has the following constitution. That is, an element comprising the above cured film.

The positive photosensitive composition of the present invention has high heat resistance and high transparency, and is excellent in development adhesiveness and moist heat resistance. In addition, the obtained cured film can be preferably used as a flat film or interlayer insulating film for a TFT substrate, and a protective film for a touch panel. Insulation film, the core of the optical waveguide. Coating material.

The positive photosensitive composition of the present invention comprises (A) an alkali-soluble resin, (B) a naphthoquinonediazide compound, (C) a solvent, and (D) a metal chelate compound, and (D) a metal chelate compound has In the structure represented by the following formula (1), the content of the (D) metal chelate compound is from 0.1 part by weight to 5 parts by weight based on 100 parts by weight of the (A) alkali-soluble resin.

(In the metal chelate compound represented by the formula (1), M is a metal atom. R ¹ may be the same or different and each represents a hydrogen, an alkyl group, an aryl group, an alkenyl group, and a substituent thereof. ² , R ³ may be the same or different, and each represents hydrogen, an alkyl group, an aryl group, an alkenyl group, an alkoxy group, and the substituents thereof. j represents the valence of the metal atom M, and k represents an integer of 0 to j. ).

The (A) alkali-soluble resin used in the present invention is polyoxyalkylene and/or Or an acrylic resin, and is a resin which is dissolved in an alkaline aqueous solution having a pH of 8 or more. In order to exhibit alkali solubility, the resin has an acidic functional group such as at least one of a decyl group, a carboxylic acid group, and a phenol group. Preferred examples of the resin include an acrylic resin having the above acidic functional group and polyoxyalkylene oxide. From the viewpoint of heat resistance, polyoxyalkylene is preferred.

The alkali-soluble acrylic resin used in the present invention may further contain a polymerization unit of the unsaturated carboxylic acid (a-1), and optionally other radical polymerizable copolymerizable with the above unsaturated carboxylic acid (a-1). The polymer unit of the compound (hereinafter referred to as "other radical polymerizable compound") (a-2) is used as a copolymerization component.

The unsaturated carboxylic acid (a-1) used in the present invention is preferably an unsaturated carboxylic acid having an ethylenically unsaturated double bond.

Specific examples of such an unsaturated carboxylic acid (a-1) include monocarboxylic acids such as methacrylic acid, acrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, and p-vinylbenzoic acid; Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 1,4-cyclohexene dicarboxylic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid Dicarboxylic acid, methyl-5-norbornene-2,3-dicarboxylic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, Dicarboxylic acid such as dimethyltetrahydrophthalic acid. Among these, methacrylic acid, acrylic acid, itaconic acid, and the like can be preferably used.

Further, in the present invention, as the unsaturated carboxylic acid (a-1), a partial esterified product or a partial amide derivative of the above unsaturated carboxylic acid remaining in a free state may be used, for example, an unsaturated carboxylic acid (a-1). A half ester of a carboxylic acid or a hemiamine. As a half ester or a half amide of such an unsaturated carboxylic acid, it is preferred to Use itaconic acid monomethyl ester, itaconic acid monobutyl ester and the like. These unsaturated carboxylic acids may be used singly or in combination of two or more.

Specific examples of the other radical polymerizable compound (a-2) used in the present invention include glycidyl (meth)acrylate, glycidyl α-ethyl (meth)acrylate, and α-positive Glycidyl propyl (meth)acrylate, glycidyl α-n-butyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 3,4-cyclo(meth)acrylate Alkyl heptyl ester, α-ethyl-6,7-epoxyheptyl (meth)acrylate, allyl glycidyl ether, vinyl glycidyl ether, o-vinylbenzyl glycidyl ether, meta-vinyl An epoxy group-containing radical polymerizable compound such as benzyl glycidyl ether, p-vinylbenzyl glycidyl ether or 3-vinylcyclohexene oxide; methyl (meth)acrylate or ethyl (meth)acrylate , (meth)acrylic acid-n-propyl ester, isopropyl (meth)acrylate, (meth)acrylic acid-n-butyl ester, (meth)acrylic acid-secondary butyl ester, (meth)acrylic acid-third Ester, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, dicyclopentanyl (meth)acrylate, isobornyl (meth)acrylate (A Cyclohexyl acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclohexyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, (methyl) Acetylene propyl acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, decyl (meth) acrylate, cyclopentyl (meth) acrylate, furyl (meth) acrylate, (methyl) ) tetrahydrofuran acrylate, pyryl (meth) acrylate, benzyl (meth) acrylate, phenethyl (meth) acrylate, cresyl (meth) acrylate, (meth) acrylate-1, 1, 1-trifluoroethyl ester, perfluoroethyl (meth)acrylate, perfluoro-n-propyl (meth)acrylate, perfluoroisopropyl (meth)acrylate, triphenylmethyl (meth)acrylate , cumyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylic acid-decylamine, (meth)acrylic acid- N,N-dimethyl decylamine, (meth)acrylic acid-N,N-dipropyl decylamine, (meth) acrylamide benzene, (meth) acrylonitrile, methacrylic acid tricyclo [5.2. radical polymerizable 1.0 ^2,6] dec-8-yl ester-containing (meth) Bing Xixi group Acrolein, vinyl chloride, vinylidene chloride, N-vinylpyrrolidone, vinyl acetate, styrene, α-methylstyrene, o-methylstyrene, m-methylbenzene Ethylene, p-methylstyrene, p-methoxystyrene, p-methoxymethylstyrene, p-tert-butoxystyrene, chloromethylstyrene, butadiene, 2,3-dimethyl Butadiene, isoprene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinyl benzyl ether, m-vinyl benzyl ether, vinyl A vinyl group-containing radical polymerizable compound such as benzyl ether; an unsaturated dicarboxylic acid diester such as diethyl maleate, diethyl fumarate or diethyl itaconate.

Among these, glycidyl (meth)acrylate, styrene, α -methylstyrene, p-tert-butoxystyrene, dicyclopentanyl methacrylate, and methacrylic acid can be preferably used. Ester, 2-hydroxyethyl methacrylate, benzyl methacrylate, butadiene, isoprene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether , o-vinylbenzyl ether, m-vinylbenzyl ether, p-vinylbenzyl ether, and the like. By using these compounds as a copolymerization component, the alkali solubility, the glass transition temperature, the dielectric constant, and the like of the polymer can be controlled, and as a result, there is a resolution, a residual film ratio, and the like as a resist pattern, or transparency. The heat resistance and the like are improved as the performance of the permanent film. These compounds may be used alone as a copolymerization component or in combination of two or more kinds as a copolymerization component.

The alkali-soluble acrylic resin used in the present invention can be obtained by copolymerizing each of the above compounds. The alkali-soluble acrylic resin is preferably a polymerized unit containing an unsaturated carboxylic acid (a-1) in an amount of from 5 wt% to 50 wt%, particularly preferably from 10 wt% to 40 wt%. Further, the alkali-soluble acrylic resin is preferably a polymerized unit containing 90% by weight or less, particularly preferably 20% by weight to 60% by weight, of the other radical polymerizable compound (a-2).

When the content of the polymer unit of the unsaturated carboxylic acid (a-1) is in the above preferred range in the alkali-soluble acrylic resin, the obtained film has high solubility in developing solution containing an alkaline aqueous solution and developability. Excellent, good sensitivity. On the other hand, the solubility of the obtained film with respect to the alkaline aqueous solution does not become excessive, and the residual film rate of the obtained photoresist pattern does not deteriorate. When the content of the polymerization unit of the other radically polymerizable compound (a-2) is in the above preferred range in the alkali-soluble acrylic resin, the polymer has a good balance of solubility in the developer containing the alkaline aqueous solution. , patterning is easier.

The polystyrene-equivalent weight average molecular weight (hereinafter referred to as "Mw") of the alkali-soluble acrylic resin used in the present invention is preferably 2 × 10 ³ to 1 × 10 ⁵ , more preferably 5 × 10 ³ to 5 ×10 ⁴ . When the Mw is in the above-described preferred range, the developability, residual film ratio, and the like of the obtained film are not lowered, and the pattern shape, heat resistance, and the like are excellent. On the other hand, there is also a case where the sensitivity is lowered or the pattern shape is not good. Further, the acrylic resin used in the present invention is alkali-soluble. The acid value of the acrylic resin is preferably from 50 mgKOH/g to 150 mgKOH/g, more preferably from 70 mgKOH/g to 130 mgKOH/g. When the acid value of the acrylic resin is in the above preferred range, dissolution residue is less likely to occur during development. On the other hand, the film of the unexposed portion at the time of development does not increase.

The acrylic resin used in the present invention as described above can be obtained by copolymerizing the unsaturated carboxylic acid (a-1) with another radical polymerizable compound (a-2) by various polymerization methods, but is preferably A method of copolymerization in a solvent and in the presence of a catalyst (polymerization initiator).

Specific examples of the solvent used for the copolymerization include alcohols such as methanol, ethanol, propanol and butanol; cyclic ethers such as tetrahydrofuran and dioxane; methyl cellosolve acetate and ethyl cellosolve. Solvent esters such as acetate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol Glycol ethers such as alcohol ethyl methyl ether and propylene glycol monomethyl ether; propylene glycol alkyl ether acetate such as propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate, propylene glycol propyl ether acetate; benzene, toluene, xylene Aromatic hydrocarbons; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 4-hydroxy-4-methyl-2-pentanone; ethyl 2-hydroxypropionate, 2-hydroxy- Ethyl 2-methylpropionate, ethyl 2-hydroxy-2-methylpropanoate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl Methyl oxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, ethyl acetate, butyl acetate, etc.; Aprotic amine, N-methyl-2-pyrrolidone and other aprotic polarities Solvent. The solvent is usually 100 parts by weight based on the total of the polymerizable compounds [(a-1) and (a-2)]. It is used in an amount of from 20 parts by weight to 1,000 parts by weight.

Further, as the catalyst, a catalyst which is generally known as a radical polymerization initiator can be widely used, and for example, 2,2'-azobisisobutyronitrile and 2,2'-azo can be used. An azo compound such as bis(2,4-dimethylvaleronitrile) or 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile); benzammonium peroxide, An organic peroxide such as laurel laurel, tributyl butyl peroxypivalate, 1,1'-bis(t-butylperoxy)cyclohexane, or hydrogen peroxide. When a peroxide is used as the radical polymerization initiator, a peroxide can also be used together with a reducing agent as a redox type polymerization initiator. Further, a molecular weight modifier such as an α-methylstyrene dimer may be added to the above copolymerization.

The acrylic resin provides a radiation-sensitive resin composition having moderate solubility in an alkaline aqueous solution, high sensitivity, high residual film ratio, and excellent developability. Further, the photoresist pattern obtained by using the acrylic resin is excellent in various properties such as heat resistance, adhesion to a substrate, transparency in a visible light region, and chemical resistance.

The alkali-soluble polyoxane used in the present invention contains one or more kinds of organodecane represented by the following general formula (2), and/or (a-4) is passed through One or more kinds of organodecane represented by the formula (3) are hydrolyzed and condensed to form a polyoxyalkylene.

In the organodecane represented by the formula (2), R ⁴ represents any of hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an aryl group having 6 to 15 carbon atoms. A plurality of R ^{4 's} may be the same or different from each other. Further, the alkyl group, the alkenyl group, and the aryl group may be either an unsubstituted form or a substituted form, and may be selected depending on the properties of the composition. Specific examples of the alkyl group and the substituent thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a n-hexyl group, a n-decyl group, a trifluoromethyl group, and 3, 3,3-trifluoropropyl, 3-glycidoxypropyl, 2-(3,4-epoxycyclohexyl)ethyl, [(3-ethyl-3-oxetanyl)methyl Oxy]propyl, 1-carboxy-2-carboxypentyl, 3-aminopropyl, 3-mercaptopropyl, 3-isocyanatepropyl. Specific examples of the alkenyl group and the substituent thereof include a vinyl group, a 3-propenyloxypropyl group, and a 3-methylpropenyloxypropyl group. Specific examples of the aryl group and the substituent thereof include a phenyl group, a tolyl group, a p-hydroxyphenyl group, a 1-(p-hydroxyphenyl)ethyl group, a 2-(p-hydroxyphenyl)ethyl group, and a 4-hydroxy group. 5-(p-hydroxyphenylcarbonyloxy)pentyl, naphthyl.

R ^{5 of the} formula (2) represents any one of hydrogen, an alkyl group having 1 to 6 carbon atoms, a fluorenyl group having 2 to 6 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and a plurality of R ² groups are each other. Can be the same or different. Further, the alkyl group, the alkenyl group, and the aryl group may be either an unsubstituted form or a substituted form, and may be selected depending on the properties of the composition. Specific examples of the alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, and an n-butyl group. Specific examples of the mercapto group include an ethyl group. Specific examples of the aryl group include a phenyl group.

n of the formula (2) represents an integer of 1 to 3. When n = 1, the organodecane is a trifunctional decane, and when n = 2, the organodecane is a difunctional decane, and when n = 3, the organodecane is a monofunctional decane.

Specific examples of the organic decane represented by the general formula (2) include: Methyl trimethoxy decane, methyl triethoxy decane, methyl triisopropoxy decane, methyl tri-n-butoxy decane, ethyl trimethoxy decane, ethyl triethoxy decane, ethyl Triisopropoxy decane, ethyl tri-n-butoxy decane, n-propyl trimethoxy decane, n-propyl triethoxy decane, n-butyl trimethoxy decane, n-butyl triethoxy decane, n-Hexyltrimethoxydecane, n-hexyltriethoxydecane,decyltrimethoxydecane,vinyltrimethoxydecane,vinyltriethoxydecane,3-methylpropenyloxypropyltrimethoxy Decane, 3-methacryloxypropyltriethoxydecane, 3-propenyloxypropyltrimethoxydecane, phenyltrimethoxydecane, phenyltriethoxydecane, p-hydroxyphenyl Trimethoxydecane, 1-(p-hydroxyphenyl)ethyltrimethoxydecane, 2-(p-hydroxyphenyl)ethyltrimethoxydecane, 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy) Pentyltrimethoxydecane, trifluoromethyltrimethoxydecane, trifluoromethyltriethoxydecane, 3,3,3-trifluoropropyltrimethoxydecane, 3-aminopropyltrimethyl Baseline, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 2-(3,4-ring Oxycyclohexyl)ethyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, [(3-ethyl-3-oxetanyl)methoxy Propyltrimethoxydecane, [(3-ethyl-3-oxetanyl)methoxy]propyltriethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-trimethoxy Trifunctional decane such as dimethyl succinic acid, 3-mercaptopropyltrimethoxy decane, 3-trimethoxymercaptopropyl succinic anhydride, dimethyl dimethoxy decane, dimethyl di Oxydecane, dimethyldiethoxydecane, di-n-butyldimethoxydecane, diphenyldimethoxydecane, (3-glycidoxypropyl)methyldimethoxydecane , (3- Difunctional decane such as glycidoxypropyl)methyldiethoxy decane, trimethyl methoxy decane, tri-n-butyl ethoxy decane, (3-glycidoxypropyl) dimethyl group A monofunctional decane such as oxydecane or (3-glycidoxypropyl) dimethyl ethoxy decane. Further, the organic decane may be used singly or in combination of two or more. Among these organic decanes, trifunctional decane can be preferably used from the viewpoint of crack resistance or hardness of the cured film.

In the organodecane represented by the formula (3), R ⁶ to R ⁹ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, a fluorenyl group having 2 to 6 carbon atoms, and a carbon number of Any of 6 to 15 aryl groups. Any of the alkyl group, the fluorenyl group and the aryl group may be either an unsubstituted form or a substituted form, and may be selected depending on the properties of the composition. Specific examples of the alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, and an n-butyl group. Specific examples of the mercapto group include an ethyl group. Specific examples of the aryl group include a phenyl group. m of the formula (3) is an integer of 1-8.

By using the organodecane represented by the general formula (3), a positive photosensitive composition which maintains high heat resistance and transparency and is excellent in sensitivity and resolution can be obtained.

The content of the organodecane represented by the formula (3) in the polyoxyalkylene used in the present invention is preferably a molar ratio of Si atoms in terms of the number of moles of Si atoms of the polyoxyalkylene as a whole. It is 50% or less. If the content ratio of the organodecane represented by the formula (3) in the polyoxyalkylene is in the above preferred range with respect to the molar ratio of the Si atom of the number of moles of Si atoms of the polyoxyalkylene as a whole, The polyoxyalkylene has good compatibility with the naphthoquinonediazide compound, and the cured film is excellent in transparency. The content ratio of the organodecane represented by the general formula (3) can be ¹ H-NMR, ¹³ C-NMR, ²⁹ Si-NMR, infrared (IR), and time-of-flight mass spectrometry (Time-Of-Flight Mass Spectroscopy). , TOF-MS), elemental analysis, ash determination, etc. are combined to obtain.

Specific examples of the organodecane represented by the general formula (3) include tetramethoxynonane, tetraethoxydecane, tetra-n-propoxydecane, tetraisopropoxydecane, and tetra-n-butylene. Oxy decane, tetraethoxy decane, methyl decanoate 51 (manufactured by Fuso Chemical Industry Co., Ltd.), M citrate 51, citrate 40, citrate 45 (manufactured by Tama Chemical Industry Co., Ltd.) Methyl decanoate 51, methyl decanoate 53A, ethyl decanoate 40, ethyl decanoate 48 (manufactured by Colcoat Co., Ltd.), and the like.

As a form of the polyoxyalkylene used in the present invention, one or more organic decanes represented by the above formula (2) and/or an organic decane represented by the formula (3) may be used. One or more kinds of polysiloxanes synthesized by reacting cerium oxide particles. The pattern resolution is improved by reacting the cerium oxide particles. This is considered to be because the glass transition temperature of the film is increased and the reflow of the pattern at the time of thermosetting is suppressed by introducing the cerium oxide particles into the polysiloxane.

The number average particle diameter of the cerium oxide particles is preferably from 2 nm to 200 Nm is more preferably 5 nm to 70 nm. When the number average particle diameter of the cerium oxide particles is in the above preferred range, the effect of improving the pattern resolution is sufficient, and on the other hand, the cured film is less likely to cause light scattering and is excellent in transparency. Here, when the number average particle diameter of the cerium oxide particles is converted by a specific surface area method, the cerium oxide particles are dried, calcined, and the specific surface area of the obtained particles is measured, and then the particles are assumed to be spheres. The specific surface area was determined by the specific surface area, and the average particle diameter was determined by the number average. The machine to be used is not particularly limited, and "Asap" 2020 (trade name, manufactured by Micromeritics Co., Ltd.) or the like can be used.

Specific examples of the cerium oxide particles include IPA-ST having a particle diameter of 12 nm using isopropyl alcohol as a dispersion medium, and MIBK-ST having a particle diameter of 12 nm using methyl isobutyl ketone as a dispersion medium. IPA-ST-L having a particle diameter of 45 nm as a dispersing medium, IPA-ST-ZL having a particle diameter of 100 nm using isopropyl alcohol as a dispersing medium, and a particle diameter of 15 nm using propylene glycol monomethyl ether as a dispersing medium PGM-ST (the above is a trade name, manufactured by Nissan Chemical Industries Co., Ltd.), γ-butyrolactone as a dispersion medium, "Oscal" 101 having a particle diameter of 12 nm, and γ-butyrolactone as a dispersion medium. "Oscal" 105 having a diameter of 60 nm, "Oscal" 106 having a particle diameter of 120 nm using diacetone alcohol as a dispersing medium, and "Cataloid"-S having a particle diameter of 5 to 80 nm in water (the above is a trade name, "Quartron" PL-2L-PGME having a particle size of 16 nm and gamma-butyrolactone as a dispersion medium, "Quartron" having a particle diameter of 17 nm using propylene glycol monomethyl ether as a dispersion medium "Quartron" PL-2L-DAA with a particle diameter of 17 nm and a dispersion solution of "PL-L-BL" with a diameter of 18 nm to 20 nm. On"PL-2L, GP-2L (the above is a trade name, manufactured by Fuso Chemical Industry Co., Ltd.), cerium oxide (SiO ₂ ) SG-SO100 having a particle diameter of 100 nm (trade name, manufactured by KCM Corporation) "Reolosil" (trade name, manufactured by Tokuyama Co., Ltd.) having a particle diameter of 5 nm to 50 nm. Further, the cerium oxide particles may be used singly or in combination of two or more.

The mixing ratio when the cerium oxide particles are used is not particularly limited, but is preferably 70% or less based on the molar ratio of Si atoms of the number of moles of Si atoms in the entire polyoxyalkylene. When the mixing ratio when the cerium oxide particles are used is in the above preferred range with respect to the molar ratio of Si atoms of the molar number of Si atoms of the polyoxyalkylene as a whole, the polypyridoxane and the naphthoquinonediazide compound The compatibility is good, and the cured film is excellent in transparency.

In addition, in the polyoxane used in the present invention, sufficient compatibility with a naphthoquinonediazide compound or the like to be described later is ensured, and a uniform cured film is formed without phase separation. The content of the phenyl group in the decane is preferably 5% by mole or more, more preferably 20% by mole or more, still more preferably 30% by mole or more, and particularly preferably 40% by mole or more based on the Si atom. . When the content of the phenyl group is in the above preferred range, the polysiloxane and the naphthoquinonediazide compound are less likely to cause phase separation during coating, drying, thermal curing, etc., so that the film does not become cloudy. The cured film has excellent transmittance. Further, the content of the phenyl group is preferably 70 mol% or less, more preferably 60 mol% or less, still more preferably 50 mol% or less. When the content of the phenyl group is in the above preferred range, crosslinking at the time of thermosetting is sufficiently generated, and the cured film is excellent in chemical resistance. The content of the phenyl group can be determined, for example, by ²⁹ Si-NMR of polysiloxane, and is determined from the ratio of the peak area of Si bonded by the phenyl group to the peak area of Si which is not bonded to the phenyl group.

Further, in the polyoxyalkylene used in the present invention, the content of the epoxy group and/or the vinyl group in the polyoxyalkylene is preferably 1% by mole or more, more preferably 3%, based on the Si atom. More than 摩尔, more preferably 5% or more, and particularly preferably 10% or more. When the content of the epoxy group and/or the vinyl group is in the above preferred range, the photosensitive resin composition is excellent in solvent resistance. Further, the content of the epoxy group and/or the vinyl group is preferably 70% by mole or less, more preferably 50% by mole or less. When the content of the epoxy group and/or the vinyl group is in the above preferred range, the polysiloxane and the naphthoquinone diazide compound are less likely to undergo phase separation during coating, drying, thermal curing, etc., and thus the film It does not cause white turbidity, and the cured film has excellent transmittance. The content of the epoxy group and/or the vinyl group is, for example, ²⁹ Si-NMR of the polyoxyalkylene, and the peak area of the Si bonded by the epoxy group and/or the vinyl group and the epoxy group and/or ethylene. The ratio of the peak area of Si which is not bonded to the base is determined, or ¹ H-NMR and ¹³ C-NMR are measured, and the content of the epoxy group and/or the vinyl group is measured, and combined with the measurement of ²⁹ Si-NMR. Thus, the content of the epoxy group and/or the vinyl group can be determined.

Further, the weight average molecular weight (Mw) of the polyoxyalkylene used in the present invention is not particularly limited, but is preferably determined by gel permeation chromatography (GPC) and is polystyrene. The conversion is 500 to 100,000, more preferably 1,000 to 50,000. When the Mw of the polyoxyalkylene is in the above preferred range, the coating property is good, and on the other hand, the solubility in the developer at the time of pattern formation is also good.

The polyoxyalkylene in the present invention is synthesized by subjecting a monomer such as an organic decane represented by the general formula (2) and/or the general formula (3) to hydrolysis and partial condensation. A general method can be used for the hydrolysis and partial condensation. For example, a solvent, water, and an optional catalyst are added to the mixture, and then heated and stirred at 50 ° C to 150 ° C, preferably at 90 ° C to 130 ° C for about 0.5 to 100 hours. Further, during the stirring, the hydrolysis by-product (alcohol such as methanol) or the condensation by-product (water) may be distilled off by distillation as needed.

The reaction solvent is not particularly limited, and usually the same as the solvent (C) to be described later can be used. The amount of the solvent to be added is preferably from 10 parts by weight to 1,000 parts by weight based on 100 parts by weight of the monomer such as organodecane. Further, the amount of water used for the hydrolysis reaction is preferably from 0.5 mol to 2 mol per mol of the hydrolyzable group.

The catalyst to be added as needed is not particularly limited, and an acid catalyst or an alkali catalyst can be preferably used. Specific examples of the acid catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polycarboxylic acid or anhydride thereof, and ion exchange resin. Specific examples of the base catalyst include triethylamine, tripropylamine, tributylamine, triamylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, diethanolamine, and hydroxide. Sodium, potassium hydroxide, an alkoxysilane containing an amine group, an ion exchange resin. The amount of the catalyst added is preferably from 0.01 part by weight to 10 parts by weight per 100 parts by weight of the monomer such as organodecane.

Further, from the viewpoint of storage stability of the composition, it is preferred that the catalyst is not contained in the polyoxane solution after hydrolysis or partial condensation, and the catalyst can be removed as needed. There is no particular limitation on the method of removing the catalyst. From the viewpoint of ease of handling and removability, it is preferably water washing and/or treatment using an ion exchange resin. The term "water washing" refers to a method in which a polyaluminoxane solution is diluted with an appropriate hydrophobic solvent by an evaporator or the like, and then the organic layer obtained by washing with water several times is concentrated. The treatment by the ion exchange resin refers to a method of bringing the polyoxane solution into contact with an appropriate ion exchange resin.

The positive photosensitive composition of the present invention contains (B) a naphthoquinonediazide compound. The positive photosensitive composition containing a naphthoquinonediazide compound forms a positive pattern in which the exposed portion is removed by the developer. The naphthoquinonediazide compound to be used is not particularly limited, and a compound obtained by ester-bonding a compound having a phenolic hydroxyl group to naphthoquinonediazidesulfonic acid can be preferably used, and The ortho and para positions of the phenolic hydroxyl group of the compound are each independently hydrogen, a hydroxyl group or a substituent represented by the general formula (4) to the general formula (5).

In the formula, R ¹⁰ , R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 10 carbon atoms, a carboxyl group, a phenyl group or a substituted phenyl group. Further, a ring may be formed by R ¹⁰ , R ¹¹ , and R ¹² . The alkyl group may be either an unsubstituted form or a substituted form, and may be selected in accordance with the characteristics of the composition. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-hexyl group, cyclohexyl group, n-heptyl group, and n-octyl group. Trifluoromethyl, 2-carboxyethyl. Further, examples of the substituent on the phenyl group include a hydroxyl group and a methoxy group. Further, specific examples of the case where the ring is formed by R ¹⁰ , R ¹¹ and R ¹² include a cyclopentane ring, a cyclohexane ring, an adamantane ring and an anthracene ring.

When the ortho and para positions of the phenolic hydroxyl group are the above-mentioned preferred substituents, oxidative decomposition is less likely to occur even by thermal hardening, and a conjugated compound represented by a fluorene structure is less likely to be formed, so that the cured film is not easily formed. Coloring and colorless transparency are maintained. Further, the naphthoquinonediazide compound can be synthesized by a known esterification reaction of a compound having a phenolic hydroxyl group with naphthoquinonediazidesulfonium chloride.

Specific examples of the compound having a phenolic hydroxyl group include the following compounds (all manufactured by Honshu Chemical Industry Co., Ltd.).

As the naphthoquinonediazidesulfonium chloride to be used as a raw material, 4-naphthoquinonediazidesulfonium chloride or 5-naphthoquinonediazidesulfonium chloride can be used. The 4-naphthoquinonediazide sulfonate compound has absorption in the region of i-ray (wavelength 365 nm), so Suitable for i-ray exposure. Further, the 5-naphthoquinonediazide sulfonate compound is suitable for exposure at a wide range of wavelengths because it has absorption in a wide range of wavelength regions. It is preferred to select a 4-naphthoquinonediazide sulfonate compound or a 5-naphthoquinonediazide sulfonate compound depending on the wavelength at which exposure is performed. A 4-naphthoquinonediazide sulfonate compound can also be used in combination with a 5-naphthoquinonediazide sulfonate compound.

The naphthoquinonediazide compound which can be preferably used in the present invention is a compound represented by the following formula (6).

In the formula, R ¹³ , R ¹⁴ , R ¹⁵ and R ^{16 each} represent a hydrogen atom, an alkyl group selected from the group consisting of carbon numbers 1 to 8, an alkoxy group, a carboxyl group and an ester group. Each of R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ may be the same or different. R ¹⁷ represents hydrogen or an alkyl group or an aryl group selected from the group consisting of carbon numbers 1 to 8. Q represents any one of a 5-naphthoquinonediazidesulfonyl group and a hydrogen atom, and there is no case where all Qs are hydrogen atoms. a, b, c, d, e, α, β, γ, δ represent integers from 0 to 4. However, α + β + γ + δ ≧ 2 . By using the naphthoquinonediazide compound represented by the general formula (6), the sensitivity or resolution at the time of pattern processing is improved.

The amount of the naphthoquinone diazide compound to be added is not particularly limited, and is preferably from 2 parts by weight to 30 parts by weight, based on 100 parts by weight of the alkali-soluble resin. It is preferably from 3 parts by weight to 15 parts by weight.

When the amount of the naphthoquinone diazide compound to be added is in the above preferred range, the dissolution contrast of the exposed portion and the unexposed portion is sufficiently high, and the photosensitive property which is sufficiently practical to be used can be exhibited. On the other hand, the polysiloxane and the naphthalene are used. The compatibility of the quinonediazide compound is not easily deteriorated, so that the whitening of the coating film does not occur, and the coloring caused by the decomposition of the naphthoquinonediazide compound during thermosetting is less likely to occur, so the colorless transparency of the cured film is obtained. Can be maintained. Further, in order to obtain a better solubility contrast, the amount of the naphthoquinonediazide compound to be added is more preferably 5 parts by weight or more. Further, in order to obtain a film having higher transparency, the amount of the naphthoquinone diazide compound to be added is more preferably 20 parts by weight or less, particularly preferably 15 parts by weight or less, and most preferably 10 parts by weight or less.

The positive photosensitive composition of the present invention contains (C) a solvent. The solvent to be used is not particularly limited, but a compound having an alcoholic hydroxyl group is preferably used. When these solvents are used, the alkali-soluble resin and the naphthoquinone diazide compound are uniformly dissolved, and even if the composition is coated with a film, the film is not whitened, and high transparency can be achieved.

The compound having an alcoholic hydroxyl group is not particularly limited, but is preferably a compound having a boiling point of from 110 ° C to 250 ° C at atmospheric pressure. When the boiling point is in the above preferred range, the drying at the time of coating the film is not excessively fast, the surface of the film is less likely to be rough and the coating property is good, and on the other hand, the amount of residual solvent in the film is small, so that the film shrinkage at the time of curing becomes Small, good flatness can be obtained.

Specific examples of the compound having an alcoholic hydroxyl group include acetol, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-3-methyl-2-butanone, and 5-hydroxy-2. -pentanone, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), lactic acid Ethyl ester, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-tert-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, 3-methoxy-1-butanol, 3-methyl-3-methoxy-1-butanol, and the like. Further, the compounds having an alcoholic hydroxyl group may be used alone or in combination of two or more.

Further, the positive photosensitive composition of the present invention may contain other solvents as long as the effects of the present invention are not impaired. Examples of the other solvent include ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, and 3-methoxy-1-butyl acetate. And esters such as 3-methyl-3-methoxy-1-butyl acetate and ethyl acetate, methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone, acetamidine acetone, etc. Ethers such as ketones, diethyl ether, diisopropyl ether, di-n-butyl ether, diphenyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, γ-butyrolactone, γ-pentane Ester, δ-valerolactone, propylene carbonate, N-methylpyrrolidone, cyclopentanone, cyclohexanone, cycloheptanone, and the like.

The amount of the solvent to be added is not particularly limited, and is preferably in the range of 100 parts by weight to 2,000 parts by weight based on 100 parts by weight of the alkali-soluble resin.

The photosensitive resin composition of the present invention contains (D) a metal chelate compound represented by the following formula (1).

In the metal chelate compound represented by the formula (1), M is a metal atom. R ¹ may be the same or different and each represents hydrogen, an alkyl group, an aryl group, an alkenyl group, and a substituent thereof. R ² and R ³ may be the same or different and each represent hydrogen, an alkyl group, an aryl group, an alkenyl group, an alkoxy group, and a substituent thereof. j represents the valence of the metal atom M, and k represents an integer of 0 to j.

By containing the above metal chelate compound used in the present invention, the development adhesiveness or the moist heat resistance of the obtained cured film is improved.

In the general formula (1), M is a metal atom and is not particularly limited, but from the viewpoint of transparency, titanium, zirconium, aluminum, zinc, cobalt, molybdenum, cerium, lanthanum, cerium, magnesium, calcium may be mentioned. Wait for a metal atom. From the viewpoint of developing adhesion and heat and humidity resistance, zirconium or aluminum metal atoms are preferred.

R ¹ may, for example, be methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, octadecyl or phenyl. , vinyl, allyl, oleyl and the like. Among them, in terms of compound stability, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl, n-octadecyl and phenyl are preferred. R ² and R ³ may, for example, be hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, t-butyl, phenyl, vinyl, methoxy or ethoxy. , n-propoxy, isopropoxy, n-butoxy, second butoxy, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl, n-octadecyl, Benzyloxy and the like. Among them, a methyl group, a tert-butyl group, a phenyl group, a methoxy group, an ethoxy group, and an n-octadecyl group are preferred in terms of ease of synthesis and stability of the compound.

The compound represented by the formula (1), for example, as the zirconium compound, may be exemplified by tetra-n-propoxy zirconium, tetra-n-butoxy zirconium, tetra-n-butoxy zirconium, tetraphenoxy zirconium, or tetrakis (tetrazine). Ethylene pyruvate) zirconium, zirconium tetrakis(2,2,6,6-tetramethyl-3,5-pimelic acid), zirconium tetrakis(methylacetamidineacetate), zirconium tetrakis(ethylacetamidineacetate) , zirconium tetrakis(methylmalonate), zirconium tetrakis(ethylmalonate), zirconium tetrakis(benzylidenepyruvate), zirconium tetrakis(dibenzopyrimidine), mono-n-butoxy (acetamidine) Acid) bis(ethylacetamidineacetic acid) zirconium, mono-n-butoxy (ethyl acetoacetate) bis(acetyl acetonate) zirconium, mono-n-butoxy tris(acetylpyruvate) zirconium, mono-n-butyl Oxygen tris(acetylpyruvate)zirconium, zirconium di(n-butoxy)bis(ethylacetamidineacetate), zirconium di(n-butoxy)bis(acetoxypyruvate), di(n-butoxy) Zirconium bis(ethylmalonate), zirconium di(n-butoxy)bis(benzimidpyruvate), zirconium di(n-butoxy)bis(dibenzofurazate), and the like.

Examples of the aluminum compound include aluminum triisopropoxide, aluminum tri-n-propoxide, aluminum tri-butoxide, aluminum tri-n-butoxide, aluminum triphenyloxide, and aluminum tris(acetylacetonate). , tris(2,2,6,6-tetramethyl-3,5-pimelic acid) aluminum, tris(ethylacetamidineacetic acid) aluminum, tris(methylacetamidineacetic acid) aluminum, tris(methyl propyl) Diacid) aluminum, aluminum tris(ethylmalonate), aluminum di(isopropoxy)ethylacetate, di(isopropoxy)aluminum acetylate pyruvate, diacetyl isopropoxide Base, aluminum, octadecylacetate, di(isopropanol) aluminum, monoethylpyruvate bis(ethyl acetamidine) Acetic acid) aluminum and the like.

Examples of the titanium compound include titanium tetra-n-propoxide, titanium tetra-n-butoxide, titanium tetra-butoxide, titanium tetraphenoxide, titanium tetrakis(acetate pyruvate), and tetrakis (2, 2, 6,6-tetramethyl-3,5-pimelic acid) titanium, tetrakis(methylacetamidineacetic acid) titanium, tetrakis(ethylacetamidineacetic acid) titanium, tetrakis(methylmalonate)titanium, four ( Ethylmalonate)Titanium, tetrakis(benzimidate)titanium, tetrakis(dibenzopyrimidinecarboxylic acid)titanium, mono-n-butoxy (acetylacetate)bis(ethylacetamidineacetic acid) titanium, single n-Butoxyethylacetate acetic acid bis(acetyl acetonate) titanium, mono-n-butoxy tris(acetylpyruvate) titanium, mono-n-butoxy tris(acetylpyruvate) titanium, di(n-butyl) Oxy) bis(ethylacetamidineacetic acid) titanium, di(n-butoxy)bis(acetylpyruvyl)titanium, di(n-butoxy)bis(ethylmalonic acid)titanium, di(n-butyl) Oxy) bis(benzimid pyruvate) titanium, di(n-butoxy)bis(dibenzofurazate) titanium, tetrakis(2-ethylhexyloxy)titanium, and the like.

Among them, tetra-n-propoxy zirconium, tetra-n-butoxy zirconium, tetraphenoxy zirconium, and tetrakis(acetylacetonate) are preferred from the viewpoints of solubility of various solvents and/or stability of the compound. Zirconium, zirconium tetrakis(2,2,6,6-tetramethyl-3,5-pimelic acid), zirconium tetrakis(methylmalonate), zirconium tetrakis(ethylmalonate), four (B) Ethylene acetoacetate) zirconium, zirconium di-n-butoxy bis(ethyl acetonitrile) and mono-n-butoxy (acetyl acetonate) bis(ethyl acetonitrile) zirconium, tetra-n-propoxy titanium, Tetra-n-butoxytitanium, tetraphenoxytitanium, tetrakis(acetate pyruvate)titanium, tetrakis(2,2,6,6-tetramethyl-3,5-pimelic acid)titanium, tetrakis (methyl) Malonate, titanium, tetrakis(ethylmalonate)titanium, tetrakis(ethylacetamethyleneacetate)titanium, di-n-butoxybis(ethylethanoacetic acid)titanium and mono-n-butoxy (acetamidine) Acid) bis(ethylacetamidineacetic acid) titanium, tris(acetylpyruvyl)aluminum, tris(2,2,6,6-tetramethyl-3,5-heptane Acid) aluminum, tris(ethylacetamethyleneacetate)aluminum, tris(methylacetamethyleneacetate)aluminum, tris(methylmalonate)aluminum, tris(ethylmalonate)aluminum,ethylacetatedi(di(iso) Propyl)aluminum, bis(isopropoxy)aluminum acetylacetonate, bis(isopropoxy)aluminum methacrylate, octadecylacetate bis(isopropanol)aluminum, monoethyl hydrazine Aluminium bis(ethylacetate)aluminate, more preferably a metal complex.

In the photosensitive resin composition of the present invention, the content of the (D) metal chelate compound is from 0.1 part by weight to 5 parts by weight based on 100 parts by weight of the (A) alkali-soluble resin. When the content of the (D) metal chelating compound is less than 0.1 part by weight based on 100 parts by weight of the (A) alkali-soluble resin, there is a problem that the heat-resistant property and the development-adhesiveness are poor, when (D) the metal chelate compound When the content is more than 5 parts by weight based on 100 parts by weight of the (A) alkali-soluble resin, there is a problem that the unexposed portion to be dissolved in the developer is not dissolved and the photosensitive characteristics are deteriorated.

The content of the (D) metal chelate compound is preferably from 0.3 part by weight to 4 parts by weight per 100 parts by weight of the (A) alkali-soluble resin. However, when the metal having a high catalytic activity, for example, the metal atom (M) is aluminum, it is preferably from 0.1 part by weight to 1.5 parts by weight, more preferably from 0.3 part by weight to 1.0 part by weight.

The content of the metal chelate compound can be quantitatively analyzed by means of fluorescence X-ray analysis, inductively coupled plasma mass spectrometry (ICP-MS) or atomic absorption spectrometry, using gas chromatography. The organic analysis by liquid chromatography, ¹ H-NMR and ¹³ C-NMR was used for identification and quantification. In addition, fluorescent, X-ray analysis, inductively coupled plasma mass spectrometry (ICP-MS) or atomic absorption can be used to carry out titanium, zirconium, aluminum, zinc, cobalt, molybdenum, niobium from a photosensitive resin composition or a cured film. Analysis of metals such as lanthanum, cerium, magnesium and calcium. The metal is contained in an amount of 0.005 parts by weight to 1 part by weight based on 100 parts by weight of the alkali-soluble resin composition.

Further, the positive photosensitive composition of the present invention may further contain a dissolution promoter, a decane coupling agent, a crosslinking agent, a crosslinking accelerator, a sensitizer, a thermal radical generator, a dissolution inhibitor, and a surfactant, as needed. Additives such as stabilizers and defoamers.

In particular, in order to adjust the solubility in an alkaline developing solution, the positive photosensitive composition of the present invention preferably contains a dissolution promoter. The solvate or the N-hydroxy quinone imine compound of [Chem. 7] described in the specific example of the compound having a phenolic hydroxyl group is exemplified as the dissolution promoter. Examples of the N-hydroxyquinone imine compound include N-hydroxy-5-norbornene-2,3-hydroxyquinone.

The phenolic compound is not particularly limited, but from the viewpoint of transparency, a phenol compound used as a raw material of the naphthoquinonediazide compound is preferred. That is, a phenolic compound having two to six benzene rings and two to four phenolic hydroxyl groups in the molecule is preferred. Further, from the viewpoint of heat resistance and moist heat resistance, a phenol compound containing no secondary carbon (-CH ₂ -), tertiary carbon (-CH=) or cycloalkane group is preferred. Examples of preferred phenolic compounds are shown below.

Surprisingly, by adding a phenol compound to the photosensitive resin composition of the present invention, the moist heat resistance is drastically improved. It is presumed that the hydrophobic barrier effect is exhibited by the accumulation of the aromatic rings of the phenol compound. Therefore, the heat and humidity resistance is improved. The content of the phenol compound is preferably from 1 part by weight to 30 parts by weight, more preferably from 3 parts by weight to 15 parts by weight, per 100 parts by weight of the alkali-soluble resin. When the content of the phenol compound is in the above preferred range with respect to 100 parts by weight of the alkali-soluble resin, the effect of moist heat resistance is sufficient, and on the other hand, the dissolution promoting effect is not excessively increased, so that a pattern is easily formed.

It is also preferred that the positive photosensitive composition of the present invention contains a crosslinking agent. The crosslinking agent is a compound which crosslinks the alkali-soluble resin or the dissolution promoter used in the present invention and is introduced into the resin at the time of thermal curing, and the degree of crosslinking of the cured film by containing the crosslinking agent improve. Thereby, the chemical resistance and the moist heat resistance of the cured film are improved, and the decrease in the resolution of the pattern due to the pattern reflow at the time of thermosetting is suppressed.

The crosslinking agent is not particularly limited, and preferably has two or more groups selected from the group consisting of a methylol structure represented by the formula (7), an epoxy group structure, and an oxetane structure. Structure of the compound. The combination of the above structures is not particularly limited, but it is preferred that the selected structures are the same.

In the methylol-based compound having two or more methylol-based structures represented by the formula (7), R ¹⁸ represents any of hydrogen and an alkyl group having 1 to 10 carbon atoms. Further, a plurality of R ¹⁸ in the compound may be the same or different from each other. Specific examples of the alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a tert-butyl group, a n-hexyl group, and a n-decyl group.

Specific examples of the methylol-based compound having two or more methylol-based structures include DM-BI25X-F, 46DMOC, 46DMOIPP, and 46DMOEP as the methylol-based compound having two methylol-based structures. Above, trade name, manufactured by Asahi Organic Materials Co., Ltd., DML-MBPC, DML-MBOC, DML-OCHP, DML-PC, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP , DML-OC, dimethylol-Bis-C, dimethylol-BisOC-P, DML-BisOC-Z, DML-BisOCHP-Z, DML-PFP, DML-PSBP, DML-MB25, DML-MTrisPC , DML-Bis25X-34XL, DML-Bis25X-PCHP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), Nikalac MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxy Methyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diethyloxymethyl-p-cresol, and the like. Examples of the methylol-based compound having a three-hydroxymethyl group structure include TriML-P, TriML-35XL, and TriML-TrisCR-HAP (trade name, manufactured by Honshu Chemical Co., Ltd.). Examples of the methylol-based compound having a four-hydroxymethyl group structure include TM-BIP-A (trade name, manufactured by Asahi Organic Materials Co., Ltd.), TML-BP, TML-HQ, and TML-pp-BPF. TML-BPA, TMOM-BP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), Nikalac MX-280, Nikalac MX-270 (above, trade name, manufactured by Sanwa Chemical Co., Ltd.). Examples of the methylol-based compound having a six-hydroxymethyl group structure include HML-TPPHBA and HML-TPHAP. HMOM-TPPHBA, HMOM-TPHAP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), Nikalac MW-390, Nikalac MW-100LM, Nikalac 30-HM (above, trade name, manufactured by Sanwa Chemical) .

Among the hydroxymethyl compounds, in the present invention, a hydroxymethyl compound containing at least two heat crosslinkable groups is preferable, and a hydroxymethyl compound containing two heat crosslinkable groups is particularly preferable. Good can list 46DMOC, 46DMOEP, DML-MBPC, DML-MBOC, DML-OCHP, DML-PC, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylol-BisOC -P, DML-PFP, DML-PSBP, DML-MTrisPC, Nikalac MX-290, Ba-type benzoxazine, Bm-type benzoxazine, 2,6-dimethoxymethyl-4-third Phenolic, 2,6-dimethoxymethyl-p-cresol, 2,6-diethyloxymethyl-p-cresol, etc., as a methylol compound containing three heat crosslinkable groups Particularly preferred examples thereof include TriML-P and TriML-35XL, and examples thereof include a methylol-based compound having four heat-crosslinkable groups, and particularly preferably TM-BIP-A, TML-BP, and TML-HQ. TML-pp-BPF, TML-BPA, TMOM-BP, "Nikalac" MX-280, "Nikala" MX-270, etc., as a methylol-based compound containing six heat crosslinkable groups, particularly preferably HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP, and the like. Further, as a more preferable example, "Nikalac" MX-280, "Nikalac" MX-270, "Nikalac" MW-100LM, "Nikalac" MW-390, "Nikalac" 30HM (trade name, Sanwa Chemical (share) ) Manufacturing) and so on.

Among these (e) crosslinking agents, for example, a compound having a methylol group or a methylol group which replaces a hydrogen atom of an alcoholic hydroxyl group is crosslinked by a reaction mechanism directly added to a benzene ring as follows.

The structure of a representative thermally crosslinkable compound which can be used particularly preferably in the photosensitive resin composition of the present invention is shown below. It is particularly surprising that the heat resistance of the cured film is further drastically improved by combining the methylol compound with the above phenol compound in the positive photosensitive composition of the present invention.

Specific examples of the compound having two or more epoxy group structures or oxetane structures include "Epolight" 40E, "Epolight" 100E, "Epolight" 200E, "Epolight" 400E, and "Epolight" 70P. "Epolight" 200P, "Epolight" 400P, "Epolight" 1500NP, "Epolight" 80MF, "Epolight" 4000, "Epolight" 3002 (above is the trade name, manufactured by Kyoei Chemical Industry Co., Ltd.), "Denacol" EX-212L, "Denacol" EX-214L, "Denacol" EX-216L, "Denacol" EX-850L, "Denacol" EX-321L (above trade name, manufactured by Nagase chemteX (share)), GAN, GOT, EPPN502H, NC3000, NC6000 (above is the product name, manufactured by Nippon Chemical Co., Ltd.), "Epikote" 828, "Epikote" 1002, "Epikote" 1750, "Epikote" 1007, YX8100-BH30, E1256, E4250, E4275 (above) Name, manufactured by Japan Epoxy Resins (share), "Epiclon" EXA-9583, "Epiclon" HP4032, "Epiclon" N695, "Epiclon" HP7200 (above, trade name, manufactured by Dainippon Ink Chemical Industry Co., Ltd.), "Tepic" S, "Tepic" G, "Tepic" P (above is the trade name, manufactured by Nissan Chemical Industries Co., Ltd.), and "Epotohto" YH-434L (trade name, manufactured by Tohto Kasei Co., Ltd.).

Further, the above crosslinking agents may be used singly or in combination of two or more.

The amount of the crosslinking agent to be added is not particularly limited, but is preferably in the range of 0.1 part by weight to 20 parts by weight based on 100 parts by weight of the alkali-soluble resin. When the amount of the crosslinking agent added is in the above preferred range, the crosslinking effect of the resin is sufficient, and on the other hand, the colorless transparency of the cured film is maintained, and the storage stability of the composition is also excellent.

The positive photosensitive composition of the present invention may also contain a decane coupling agent. By containing a decane coupling agent, the adhesion to the substrate is improved.

Specific examples of the decane coupling agent include methyltrimethoxydecane, methyltriethoxydecane, dimethyldimethoxydecane, dimethyldiethoxydecane, and ethyltrimethoxydecane. Ethyltriethoxydecane, positive Propyltrimethoxydecane, n-propyltriethoxydecane, n-butyltrimethoxydecane, n-butyltriethoxydecane,phenyltrimethoxydecane,phenyltriethoxydecane, diphenyl Dimethoxy decane, diphenyl diethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, 3-methyl propylene methoxy propyl trimethoxy decane, 3-methyl Propylene methoxypropyl triethoxy decane, 3-methyl propylene methoxy propyl methyl dimethoxy decane, 3-methyl propylene methoxy propyl methyl diethoxy decane, 3- Propylene methoxy propyl trimethoxy decane, 3-aminopropyl trimethoxy decane, 3-aminopropyl triethoxy decane, 3-triethoxy fluorenyl-N-(1,3- Dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxy Decane, 3-glycidoxypropylmethyldiethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2-(3,4-epoxycyclohexyl Ethyltriethoxydecane, [(3-ethyl-3-oxetanyl) Methoxy]propyltrimethoxydecane, [(3-ethyl-3-oxetanyl)methoxy]propyltriethoxydecane, 3-mercaptopropyltrimethoxydecane, 3- Mercaptopropylmethyldimethoxydecane, 3-ureidopropyltriethoxydecane, 3-isocyanatepropyltriethoxydecane, 3-trimethoxymercaptopropylsuccinic acid, N- Tributyl-3-(3-trimethoxymercaptopropyl)butaneimine, and an organic decane represented by the formula (3).

(In the organodecane represented by the formula (3), R ⁶ to R ⁹ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, a fluorenyl group having 2 to 6 carbon atoms, and a carbon number. Any of the 6 to 15 aryl groups. The alkyl group, the fluorenyl group, and the aryl group may be either an unsubstituted form or a substituted form).

Specific examples of the organodecane represented by the general formula (3) include tetramethoxynonane, tetraethoxydecane, tetra-n-propoxydecane, tetraisopropoxydecane, and tetra-n-butoxy Base decane, tetraethoxy decane, methyl decanoate 51 (manufactured by Fuso Chemical Industry Co., Ltd.), M citrate 51, citrate 40, citrate 45 (manufactured by Tama Chemical Industry Co., Ltd.), Methyl decanoate 51, methyl decanoate 53A, ethyl decanoate 40, ethyl decanoate 48 (manufactured by Colcoat Co., Ltd.), and the like.

Preferred is 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-tert-butyl-3-(3-trimethoxy) Mercaptopropyl) butyl quinone imine, tetramethoxy decane, tetraethoxy decane, tetra-n-propoxy decane, tetraisopropoxy decane, tetra-n-butoxy decane, tetraethylene oxime Base decane, methyl decanoate 51 (manufactured by Fuso Chemical Industry Co., Ltd.), M citrate 51, citrate 40, citrate 45 (manufactured by Tama Chemical Industry Co., Ltd.), methyl decanoate 51, hydrazine Methyl ester 53A, tannic acid Ethyl ester 40, ethyl decanoate 48 (manufactured by Colcoat Co., Ltd.).

The amount of the decane coupling agent to be added is not particularly limited, but is preferably in the range of 0.1 part by weight to 10 parts by weight based on 100 parts by weight of the alkali-soluble resin. When the amount of the decane coupling agent to be added is in the above preferred range, the effect of improving the adhesion is sufficient. On the other hand, the decane coupling agents are difficult to undergo a condensation reaction during storage, and thus the dissolution residue at the time of development does not occur.

The positive photosensitive composition of the present invention may also contain a surfactant. By containing a surfactant, coating unevenness is improved, and a uniform coating film can be obtained. A fluorine-based surfactant or a polyoxynitride surfactant can be preferably used.

Specific examples of the fluorine-based surfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl)ether, 1,1,2,2-tetra. Fluococtyl hexyl ether, octaethylene glycol bis(1,1,2,2-tetrafluorobutyl)ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl)ether , propylene glycol bis(1,1,2,2-tetrafluorobutyl)ether, hexapropylene glycol bis(1,1,2,2,3,3-hexafluoropentyl)ether, perfluorododecyl sulfonic acid Sodium, 1,1,2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, N-[3- (perfluorooctanesulfonamide) propyl]-N,N'-dimethyl-N-carboxymethylene ammonium betaine, perfluoroalkylsulfonamide propyltrimethylammonium salt, perfluoroalkane Base-N-ethylsulfonyl glycinate, bis(N-perfluorooctylsulfonyl-N-ethylaminoethyl phosphate), monoperfluoroalkylethyl phosphate, etc. A fluorine-based surfactant having a compound of a fluoroalkyl group or a fluoroalkyl group in at least any part of the chain and the side chain. In addition, as a commercial item, there are "Megafac" F142D, "Megafac" F172, "Megafac" F173, "Megafac" F183, "Megafac" F444, "Megafac" 445, "Megafac" F475, "Megafac" 477 (above, manufactured by Dainippon Ink Chemical Industry Co., Ltd.), "Eftop" EF301, "Eftop" 303, "Eftop" 352 (made by New Akita Chemicals Co., Ltd.), "Fluorad" FC-430, "Fluorad" FC-431 (manufactured by Sumitomo 3M (share)), "Asahi Guard" AG710, "Surflon" S-382, "Surflon" SC-101, "Surflon" SC-102, "Surflon" SC -103, "Surflon" SC-104, "Surflon" SC-105, "Surflon" SC-106 (made by Asahi Glass Co., Ltd.), BM-1000, BM-1100 (Manufactured by Yushang Co., Ltd.), NBX-15 Fluorine-based surfactants such as FTX-218 and DFX-218 (manufactured by Neos).

Commercial products of the polyoxo-based surfactant include SH28PA, SH7PA, SH21PA, SH30PA, and ST94PA (all manufactured by Dow Corning Toray Silicone Co., Ltd.), and BYK-333 (manufactured by BYK Japan). .

In the photosensitive composition, it is more common and preferable to set the content of the surfactant to 0.0001% by weight to 1% by weight.

The positive photosensitive composition of the present invention may further contain a crosslinking accelerator. The crosslinking accelerator is a compound which promotes crosslinking of an alkali-soluble resin during thermosetting, and a thermal acid generator which generates an acid during thermosetting or a photoacid which generates an acid during bleach exposure before thermosetting can be used. Agent. The presence of an acid in the film by thermal hardening promotes a condensation reaction of an unreacted sterol group or an epoxy group in the alkali-soluble resin, and the degree of crosslinking of the cured film becomes high. Thereby, the chemical resistance of the cured film is improved, and the decrease in the resolution of the pattern due to the pattern reflow at the time of thermosetting is suppressed, or the chemical resistance is improved.

The thermal acid generator which can be preferably used in the present invention is produced during thermal hardening The acid compound preferably does not generate an acid upon pre-baking after coating the composition, or produces only a small amount of acid. Therefore, a compound which generates an acid at a temperature higher than the prebaking temperature, for example, 100 ° C or higher is preferable. In the case of a compound which generates an acid at a pre-bake temperature or higher, cross-linking of the alkali-soluble resin does not occur during pre-baking, so that the sensitivity does not decrease, and no dissolution remains during development.

Specific examples of the thermal acid generator which can be preferably used include "San-Aid" SI-60, SI-80, SI-100, SI-200, SI-110, SI-145, and SI-150. , SI-60L, SI-80L, SI-100L, SI-110L, SI-145L, SI-150L, SI-160L, SI-180L (above is the trade name, manufactured by Sanshin Chemical Industry Co., Ltd.), 4- Hydroxyphenyl dimethyl sulfonium trifluoromethanesulfonate, benzyl-4-hydroxyphenylmethyl fluorene trifluoromethanesulfonate, 2-methylbenzyl-4-hydroxyphenylmethyl fluorene trifluoromethyl Sulfonic acid salt, 4-acetoxyphenyl dimethyl fluorene trifluoromethanesulfonate, 4-ethenyloxyphenylbenzylmethyl fluorene triflate, 4-methoxycarbonyl oxide Phenyl phenyl dimethyl trifluoromethanesulfonate, benzyl-4-methoxycarbonyloxyphenylmethyl fluorene trifluoromethanesulfonate (above, manufactured by Sanshin Chemical Industry Co., Ltd.). Further, these compounds may be used singly or in combination of two or more.

The photoacid generator which can be preferably used in the present invention is a compound which generates an acid upon bleaching exposure, and is exposed by a wavelength of 365 nm (i-ray), 405 nm (h-ray), and 436 nm (g-ray). Or a compound that produces an acid upon irradiation of the mixed lines. Therefore, it is possible to generate an acid even in the pattern exposure using the same light source, but since the exposure amount of the pattern exposure is smaller than the bleach exposure, only a small amount of acid is generated without causing a problem. Further, as the acid to be produced, perfluoroalkylsulfonic acid is preferred. A naphthoquinonediazide compound which produces a carboxylic acid, such as a strong acid such as p-toluenesulfonic acid, does not have the function of the photoacid generator described herein, and does not function as a crosslinking accelerator in the present invention.

Specific examples of the photoacid generator which can be preferably used include SI-100, SI-101, SI-105, SI-106, SI-109, PI-105, PI-106, and PI-109. NAI-100, NAI-1002, NAI-1003, NAI-1004, NAI-101, NAI-105, NAI-106, NAI-109, NDI-101, NDI-105, NDI-106, NDI-109, PAI- 01, PAI-101, PAI-106, PAI-1001 (above is the trade name, manufactured by Midori Kagaku (share)), SP-077, SP-082 (the above is the trade name, manufactured by ADEKA (share)), TPS-PFBS (The above is the trade name, manufactured by Toyo Synthetic Industrial Co., Ltd.), CGI-MDT, CGI-NIT (the above is the trade name, manufactured by Ciba Japan (share)), WPAG-281, WPAG-336, WPAG-339, WPAG- 342, WPAG-344, WPAG-350, WPAG-370, WPAG-372, WPAG-449, WPAG-469, WPAG-505, WPAG-506 (the above is the trade name, and Wako Pure Chemical Industries (stock) manufacturing). Further, these compounds may be used singly or in combination of two or more.

Further, as the crosslinking accelerator, the above thermal acid generator and photoacid generator may be used in combination. The amount of the crosslinking accelerator to be added is not particularly limited, but is preferably in the range of 0.01 part by weight to 5 parts by weight based on 100 parts by weight of the alkali-soluble resin. When the amount added is in the above preferred range, the crosslinking promoting effect is sufficient, and on the other hand, crosslinking of polyoxyalkylene is less likely to occur during prebaking or pattern exposure.

The positive photosensitive composition of the present invention may further contain a sensitizer. By containing A sensitizer that promotes the reaction of a naphthoquinonediazide compound as a sensitizer and enhances sensitivity, and when a photoacid generator is contained as a crosslinking accelerator, promotes a reaction at the time of bleach exposure and enhances the resistance of the cured film. Solvent and pattern resolution.

The sensitizer used in the present invention is not particularly limited, but a sensitizer which is vaporized by heat treatment and/or a sensitizer which is discolored by light irradiation is preferably used. The sensitizer must absorb 365 nm (i-ray), 405 nm (h-ray), and 436 nm (g-ray) as a wavelength of a light source during pattern exposure or bleach exposure, but if such absorption directly remains in the cured film, Since there is absorption in the visible light region, there is a case where colorless transparency is lowered. Therefore, in order to prevent a decrease in colorless transparency caused by the sensitizer, the sensitizer to be used is preferably a compound (sensitizer) which is vaporized by heat treatment such as thermal hardening and/or by bleach exposure or the like. A compound (sensitizer) that is discolored by light irradiation.

Specific examples of the sensitizer vaporized by the heat treatment and/or the sensitizer which is discolored by light irradiation include 3,3'-carbonyl bis(diethylamine coumarin) and the like. Bean, 9,10-fluorene, etc., diphenyl ketone, 4,4'-dimethoxydiphenyl ketone, acetophenone, 4-methoxyacetophenone, benzaldehyde, etc. Ketone, biphenyl, 1,4-dimethylnaphthalene, 9-fluorenone, anthracene, phenanthrene, triphenylene, anthracene, anthracene, 9-phenylanthracene, 9-methoxyanthracene, 9,10-diphenyl Base, 9,10-bis(4-methoxyphenyl)anthracene, 9,10-bis(triphenylphosphonium)fluorene, 9,10-dimethoxyanthracene, 9,10-diethoxy Base, 9,10-dipropoxyindole, 9,10-dibutoxyanthracene, 9,10-dipentyloxyanthracene, 2-tert-butyl-9,10-dibutoxyanthracene, Condensed aromatics such as 9,10-bis(trimethyldecylethynyl)fluorene Wait.

Among the sensitizers, the sensitizer which is vaporized by the heat treatment is preferably a sensitizer which sublimes or evaporates the thermal decomposition product produced by sublimation, evaporation, or thermal decomposition by heat treatment. Further, the vaporization temperature as the sensitizer is preferably from 130 ° C to 400 ° C. If the gasification temperature of the sensitizer is in the above preferred range, the sensitizer is not vaporized during the pre-baking process and is present in the exposure process, so that the sensitivity can be maintained high, and on the other hand, sensitization The agent is vaporized at the time of heat hardening without remaining in the cured film, so that colorless transparency can be maintained. In order to suppress the gasification during the pre-baking as much as possible, the gasification temperature of the sensitizer is more preferably 150 ° C or higher. Further, in order to sufficiently vaporize the sensitizer during heat curing, the vaporization temperature of the sensitizer is more preferably 250 ° C or lower.

On the other hand, from the viewpoint of transparency, the sensitizer which is discolored by light irradiation is preferably a sensitizer which absorbs light in the visible light region and is discolored by light irradiation. Further, a more preferable sensitizer which is discolored by light irradiation is a compound which is dimerized by light irradiation. Since the second polymerization is carried out by light irradiation, the molecular weight is increased and insolubilized, so that the chemical resistance is improved, the heat resistance is improved, and the extract from the transparent cured film is reduced.

Further, in addition to the high sensitivity, the sensitizer is preferably a lanthanide compound, and the 9,10-disubstituted lanthanide compound is used for dimerization and fading by light irradiation. Heat resistant, so better. Furthermore, from the viewpoint of the improvement of the solubility of the sensitizer and the reactivity of the photopolymerization reaction, the 9,10-dialkoxy fluorene-based compound represented by the formula (8) is more preferable.

[Chemistry 16]

R ¹⁹ to R ^{26 in the} formula (8) each independently represent hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an alkenyl group, an aryl group, a fluorenyl group, and the substituted organic groups. Specific examples of the alkyl group include a methyl group, an ethyl group, and a n-propyl group. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentyloxy group. Specific examples of the alkenyl group include a vinyl group, an acryloxypropyl group, and a methacryloxypropyl group. Specific examples of the aryl group include a phenyl group, a tolyl group, and a naphthyl group. Specific examples of the mercapto group include an ethyl group. From the viewpoint of the gasification property of the compound and the reactivity of photodimerization, R ¹⁹ to R ^{26 are} preferably hydrogen or an organic group having 1 to 6 carbon atoms. More preferably, R ¹⁹ , R ²² , R ²³ and R ²⁶ are hydrogen.

R ²⁷ and R ^{28 in the} formula (8) represent an alkoxy group having 1 to 20 carbon atoms and the substituted organic group. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentyloxy group. However, from the viewpoint of solubility of the compound and fading reaction by photodimerization, it is preferred. It is a propoxy group and a butoxy group.

The amount of the sensitizer to be added is not particularly limited, but is preferably added in the range of 0.01 part by weight to 5 parts by weight based on 100 parts by weight of the alkali-soluble resin. If the amount of the sensitizer added is in the above preferred range, there is no transparency A decrease in sex or a decrease in sensitivity.

A method of forming a cured film using the positive photosensitive composition of the present invention will be described. The positive photosensitive composition of the present invention is applied onto a base substrate by a known method such as a spinner or a slit, and then prebaked by a heating means such as a hot plate or an oven. The prebaking is preferably carried out in the range of 50 ° C to 150 ° C for 30 seconds to 30 minutes, and the film thickness after prebaking is preferably set to 0.1 μm to 15 μm.

After pre-baking, use a UV-visible exposure machine such as a stepper, a Mirror Projection Mask Aligner (MPA), or a Parallel Light Mask Aligner (PLA). for 10J / m via the desired mask ² ~ ^4,000J / m ² or so (in terms of the amount of exposure wavelength of 365nm) pattern exposure.

After the exposure, the exposed portion is dissolved by development to obtain a positive pattern. As the developing method, it is preferred to immerse in a developing solution for 5 seconds to 10 minutes by a method such as spraying, dipping, stirring, or the like. As the developer, a known alkaline developer can be used. Specific examples include hydroxides containing one or two or more alkali metals, inorganic bases such as carbonates, phosphates, citrates, and borates, and amines such as 2-diethylaminoethanol, monoethanolamine, and diethanolamine. An aqueous solution of a quaternary ammonium salt such as tetramethylammonium hydroxide or choline. Further, it is preferred to carry out rinsing with water after development, and if necessary, dehydration drying baking can be carried out in a range of 50 ° C to 150 ° C by a heating means such as a hot plate or an oven.

Thereafter, bleach exposure is preferably carried out. By performing bleaching exposure, the unreacted naphthoquinonediazide compound remaining in the film undergoes photodecomposition, and the optical transparency of the film is further improved. As a method of bleaching exposure using an ultraviolet-visible exposure machine PLA, etc., for the entire surface 100J / m ² ~ 20,000J / m ² or so (in terms of the amount of exposure wavelength of 365nm) exposure.

If necessary, the bleached exposed film is soft baked in a range of 50 ° C to 150 ° C for 30 seconds to 30 minutes using a heating device such as a hot plate or an oven, and then heated at 150 ° C using a heating plate or an oven. Hardening is performed for about 1 hour in the range of -450 ° C, thereby forming a planarizing film for a TFT in a display element, an interlayer insulating film in a semiconductor element, or a cured film such as a core or a cladding material in an optical waveguide. .

The cured film produced by using the positive photosensitive composition of the present invention has a light transmittance of 85% or more, more preferably 90% or more, per 3 μm of the film thickness at a wavelength of 400 nm. When the light transmittance is less than 85%, in the case of a flattening film for a TFT substrate used as a liquid crystal display element, a color change occurs when the backlight passes, and a white display has a yellow tinge.

The transmittance per 3 μm of the film thickness at the above-mentioned wavelength of 400 nm can be obtained by the following method. The composition was spin-coated on a Tempax glass plate at a random rotation speed using a spin coater, and then prebaked at 100 ° C for 2 minutes using a hot plate. Thereafter, as a bleaching exposure, the entire surface of the film was exposed to 3,000 J/m ² (wavelength of 365 nm exposure amount) using an ultrahigh pressure mercury lamp using PLA, and then a film was formed by heat-hardening in an air at 220 ° C for 1 hour in an air oven. A cured film having a thickness of 3 μm. The ultraviolet visible absorption spectrum of the obtained cured film was measured using MultiSpec-1500 manufactured by Shimadzu Corporation (share), and the transmittance at a wavelength of 400 nm was determined.

The cured film is suitable for use in a flattening film for a TFT in a display element, and a half Interlayer insulating film in conductor elements, insulating film for touch panel. A core or a cladding material or the like in a protective film or an optical waveguide.

The element in the present invention refers to a display element, a semiconductor element, or an optical waveguide material having a cured film having high heat resistance and high transparency as described above, and is particularly suitable for a liquid crystal display having the cured film as a planarizing film for TFT. Components, and organic EL display elements, display elements with a touch panel function.

[Example]

Hereinafter, the invention will be more specifically described by way of examples, but the invention is not limited to the examples. In addition, the compound which uses abbreviations among the compounds used is shown below.

DAA: Diacetone alcohol

PGMEA: propylene glycol monomethyl ether acetate

GBL: γ-butyrolactone

EDM: diethylene glycol methyl ethyl ether

DPM: dipropylene glycol monomethyl ether.

In addition, the solid content concentration of the polyoxyalkylene solution and the acrylic resin solution, and the weight average molecular weight (Mw) of the polysiloxane and the acrylic resin were determined as follows.

(1) Solid concentration

1 g of a polyoxyalkylene solution or an acrylic resin solution was weighed in an aluminum cup, and then the liquid component was evaporated by heating at 250 ° C for 30 minutes using a hot plate. The solid content remaining in the heated aluminum cup was weighed, and the solid content concentration of the polyoxyalkylene solution or the acrylic resin was determined.

(2) Weight average molecular weight

The weight average molecular weight was determined by GPC (Model 410 RI detector manufactured by Waters Co., Ltd., fluidized bed: tetrahydrofuran) and converted from polystyrene.

(3) Ratio of the organodecane structure represented by the general formula (2) to the general formula (3) in polyoxyalkylene oxide

The measurement of ²⁹ Si-NMR was carried out, and the ratio of the integral value with respect to each organic decane was calculated from the integral value of the whole, and the ratio was calculated.

The sample (liquid) was injected into a Teflon (registered trademark) Nuclear Magnetic Resonance (NMR) sample tube having a diameter of 10 mm for measurement. The ²⁹ Si-NMR measurement conditions are shown below.

Device: JNM GX-270 manufactured by Japan Electronics Co., Ltd., assay: Gated Decoupling

Measuring nuclear frequency: 53.6693MHz ( ²⁹ Si core), spectrum width: 20000Hz

Pulse width: 12μsec (45° pulse), pulse repetition time: 30.0sec

Solvent: Acetone-D6, reference material: tetramethyl decane

Measurement temperature: room temperature, sample rotation speed: 0.0 Hz.

Synthesis Example 1: Synthesis of Polyoxane Solution (A1-a)

To a 500 mL three-necked flask was added 81.72 g (0.60 mol) of methyltrimethoxydecane, 59.49 g (0.30 mol) of phenyltrimethoxydecane, and (2-(3,4-epoxycyclohexyl)ethyltrimethyl). 24.64 g (0.10 mol) of oxoxane and 163.1 g of DAA were added while stirring at room temperature, and 0.54 g of phosphoric acid (0.3 wt% relative to the monomer added) was added over 10 minutes. An aqueous solution of phosphoric acid which was obtained by dissolving 55.8 g of water. Thereafter, the flask was immersed in an oil bath of 40 ° C and stirred for 30 minutes, and then the oil bath was heated to 115 ° C over 30 minutes. The internal temperature of the solution reached 100 ° C after 1 hour from the start of the temperature rise, and then the mixture was heated and stirred for 1.5 hours (the internal temperature was 100 ° C to 110 ° C) to obtain a polyoxyalkylene solution (A1-a). Further, during heating and stirring, nitrogen gas was introduced at 0.05 L (liter) / min. A total of 131 g of methanol and water as by-products were distilled off in the reaction.

The solid concentration of the obtained polyoxyalkylene solution (A1-a) was 43% by weight, and the weight average molecular weight of polyoxyalkylene was 4,200. Further, the content of the phenyl-substituted decane in the polyoxyalkylene was 30% in terms of the molar ratio of Si atoms.

Synthesis Example 2: Synthesis of Polyoxane Solution (A1-b)

To a 500 mL three-necked flask was added 54.48 g (0.40 mol) of methyltrimethoxydecane, 99.15 g (0.50 mol) of phenyltrimethoxydecane, and (2-(3,4-epoxycyclohexyl)ethyltrimethyl). 24.64 g (0.1 mol) of oxoxane and 179.5 g of DAA were added while stirring at room temperature, and 0.54 g of phosphoric acid (0.3 wt% based on the monomer to be added) was dissolved in 55.8 g of water while adding for 10 minutes. After the flask was immersed in an oil bath at 40 ° C and stirred for 30 minutes, the oil bath was heated to 115 ° C for 30 minutes. The internal temperature of the solution reached 100 ° C after 1 hour of temperature rise, after which The mixture was heated and stirred for 2 hours (internal temperature was 100 ° C to 110 ° C) to obtain a polyoxane solution (A1-b). Further, during heating and stirring, nitrogen gas was introduced at 0.05 L (liter) / min. The middle distillation totaled 121 g of methanol and water as by-products.

The solid concentration of the obtained polyoxyalkylene solution (A1-b) was 42% by weight, and the weight average molecular weight of polyoxyalkylene was 3,200. Further, the content of the phenyl-substituted decane in the polyoxyalkylene is 50% in terms of the molar ratio of Si atoms.

Synthesis Example 3: Synthesis of Polyoxane Solution (A1-c)

To a 500 mL three-necked flask was added 27.24 g (0.20 mol) of methyltrimethoxydecane, 138.81 g (0.70 mol) of phenyltrimethoxydecane, and (2-(3,4-epoxycyclohexyl)ethyltrimethyl). 24.64 g (0.1 mol) of oxoxane and 195.89 g of DAA were added while stirring at room temperature, and 0.54 g of phosphoric acid (0.3 wt% based on the monomer to be added) was dissolved in 55.8 g of water while adding for 10 minutes. After the flask was immersed in an oil bath at 40 ° C and stirred for 30 minutes, the oil bath was heated to 115 ° C for 30 minutes. The internal temperature of the solution reached 100 ° C after 1 hour of temperature rise, after which The mixture was heated and stirred for 3 hours (internal temperature was 100 ° C to 110 ° C) to obtain a polyoxane solution (A1-c). Further, during heating and stirring, nitrogen gas was introduced at 0.05 L (liter) / min. The middle distillation totaled 125 g of methanol and water as by-products.

The solid concentration of the obtained polyoxyalkylene solution (A1-c) was 41% by weight, and the weight average molecular weight of polyoxyalkylene was 3,000. Further, the content of the phenyl-substituted decane in the polyoxyalkylene is 70% in terms of the molar ratio of Si atoms.

Synthesis Example 4: Synthesis of Polyoxane Solution (A1-d)

To a 500 mL three-necked flask, 40.86 g (0.30 mol) of methyltrimethoxydecane and 99.15 g (0.5 mol) of phenyltrimethoxydecane were added. (2-(3,4-Epoxycyclohexyl)ethyltrimethoxydecane 12.32 g (0.05 mol), M decanoate 51 (manufactured by Tama Chemical Co., Ltd.) 17.63 g (0.15 mol), PGMEA 170.77 g, while stirring at room temperature, an aqueous phosphoric acid solution in which 0.51 g of phosphoric acid (0.3 wt% based on the monomer added) was dissolved in 53.55 g of water was added over 10 minutes. Thereafter, the flask was immersed at 40 ° C. After stirring for 30 minutes in an oil bath, the oil bath was heated to 115 ° C for 30 minutes. The internal temperature of the solution reached 100 ° C after 1 hour of temperature rise, and then heated and stirred for 2 hours (internal temperature was 100 ° C - 110 °C), thereby obtaining a polyoxane solution (A1-d). Further, during heating and stirring, nitrogen gas was introduced at 0.05 L (liter) / min. A total of 125 g of methanol as a by-product was distilled off in the reaction. ,water.

The solid concentration of the obtained polyoxyalkylene solution (A1-d) was 43% by weight, and the weight average molecular weight of polyoxyalkylene was 8,500. Further, the content of the phenyl-substituted decane in the polyoxyalkylene is 50% in terms of the molar ratio of Si atoms.

Synthesis Example 5: Synthesis of Polyoxane Solution (A1-e)

To a 500 mL three-necked flask was added 24.52 g (0.18 mol) of methyltrimethoxydecane, 118.98 g (0.60 mol) of phenyltrimethoxydecane, and (2-(3,4-epoxycyclohexyl)ethyltrimethyl). 14.78 g (0.06 mol) of oxoxane, 42.30 g (0.36 mol) of M decanoate 51 (manufactured by Tama Chemical Co., Ltd.), and 181.89 g of PGMEA, and stirred at room temperature for 10 minutes to add phosphoric acid 0.60 g (0.3 wt% based on the monomer added) was dissolved in 62.64 g of water in an aqueous phosphoric acid solution. Thereafter, the flask was immersed in an oil bath at 40 ° C and stirred for 30 minutes. The oil bath was heated to 115 ° C for 30 minutes. The internal temperature of the solution reached 100 ° C one hour after the start of the temperature rise, and then the mixture was heated and stirred for 2 hours (the internal temperature was 100 ° C to 110 ° C) to obtain a polyoxyalkylene solution (A1-e). Further, during heating and stirring, nitrogen gas was introduced at 0.05 L (liter) / min. A total of 150 g of methanol and water as by-products were distilled off in the reaction.

The solid concentration of the obtained polyoxyalkylene solution (A1-e) was 44% by weight, and the weight average molecular weight of polyoxyalkylene was 11,400. Further, the content of the phenyl-substituted decane in the polyoxyalkylene is 50% in terms of the molar ratio of Si atoms.

Synthesis Example 6: Synthesis of Polyoxane Solution (A1-f)

To a 500 mL three-necked flask was added 40.86 g (0.30 mol) of methyltrimethoxydecane, 99.15 g (0.50 mol) of phenyltrimethoxydecane, and (2-(3,4-epoxycyclohexyl)ethyltrimethyl). 49.28 g (0.20 mol) of oxydecane and 173.02 g of PGMEA were added while stirring at room temperature, and 0.57 g of phosphoric acid (0.3 wt% based on the monomer added) was dissolved in 57.60 g of water while adding for 10 minutes. After the flask was immersed in an oil bath at 40 ° C and stirred for 30 minutes, the oil bath was heated to 115 ° C for 30 minutes. The internal temperature of the solution reached 100 ° C after 1 hour of temperature rise, after which The mixture was heated and stirred for 2 hours (internal temperature was 100 ° C to 110 ° C) to obtain a polyoxane solution (A1-f). Further, during heating and stirring, nitrogen gas was introduced at 0.05 L (liter) / min. The middle distillation totaled 139 g of methanol and water as by-products.

The solid concentration of the obtained polyoxyalkylene solution (A1-f) was 43% by weight, and the weight average molecular weight of polyoxyalkylene was 8,000. Furthermore, the gathering The content of the phenyl-substituted decane in the oxane is 50% in terms of the molar ratio of Si atoms.

Synthesis Example 7: Synthesis of Polyoxane Solution (A1-g)

To a 500 mL three-necked flask was added 20.43 g (0.15 mol) of methyltrimethoxydecane, 99.15 g (0.50 mol) of phenyltrimethoxydecane, and (2-(3,4-epoxycyclohexyl)ethyltrimethyl). 49.28 g (0.20 mol) of oxoxane, 17.63 g (0.15 mol) of M decanoate 51 (manufactured by Tama Chemical Co., Ltd.), and 170.90 g of PGMEA were added while stirring at room temperature, and phosphoric acid was added over 10 minutes. 0.56 g (0.3 wt% with respect to the monomer added) was dissolved in 56.25 g of water in an aqueous phosphoric acid solution. Thereafter, the flask was immersed in an oil bath at 40 ° C and stirred for 30 minutes, and then the oil bath was heated for 30 minutes. The temperature of the solution reached 115 ° C. The internal temperature of the solution reached 100 ° C after 1 hour from the start of the temperature rise, and then the mixture was heated and stirred for 2 hours (the internal temperature was 100 ° C to 110 ° C) to obtain a polyoxane solution (A1-g). Nitrogen gas was introduced at 0.05 L (liter) / min during heating and stirring, and a total of 139 g of methanol and water as by-products were distilled off in the reaction.

The solid concentration of the obtained polyoxyalkylene solution (A1-g) was 43% by weight, and the weight average molecular weight of polyoxyalkylene was 9,500. Further, the content of the phenyl-substituted decane in the polyoxyalkylene is 50% in terms of the molar ratio of Si atoms.

Synthesis Example 8: Synthesis of Polyoxane Solution (A1-h)

To a 500 mL three-necked flask was added 27.24 g (0.20 mol) of methyltrimethoxydecane, 99.15 g (0.50 mol) of phenyltrimethoxydecane, and (2-(3,4-epoxycyclohexyl)ethyltrimethyl). Oxydecane 73.92g (0.30 Mol) and PGMEA 173.02 g were stirred at room temperature, and an aqueous phosphoric acid solution in which 0.60 g of phosphoric acid (0.3 wt% based on the monomer added) was dissolved in 59.40 g of water was added over 10 minutes. Thereafter, the flask was immersed in an oil bath of 40 ° C and stirred for 30 minutes, and then the oil bath was heated to 115 ° C over 30 minutes. The internal temperature of the solution reached 100 ° C after 1 hour from the start of the temperature rise, and then the mixture was heated and stirred for 2 hours (the internal temperature was 100 ° C to 110 ° C) to obtain a polyoxane solution (A1-h). Further, during heating and stirring, nitrogen gas was introduced at 0.05 L (liter) / min. A total of 139 g of methanol and water as by-products were distilled off in the reaction.

The solid concentration of the obtained polyoxyalkylene solution (A1-h) was 43% by weight, and the weight average molecular weight of polyoxyalkylene was 9,500. Further, the content of the phenyl-substituted decane in the polyoxyalkylene is 50% in terms of the molar ratio of Si atoms.

Synthesis Example 9: Synthesis of Polyoxane Solution (A1-i)

To a 500 mL three-necked flask was added 27.24 g (0.20 mol) of methyltrimethoxydecane, 99.15 g (0.50 mol) of phenyltrimethoxydecane, and (2-(3,4-epoxycyclohexyl)ethyltrimethyl). 26.64 g (0.10 mol) of oxydecane, 29.65 g (0.20 mol) of vinyltrimethoxydecane, and 164.40 g of PGMEA were added while stirring at room temperature, and 0.54 g of phosphoric acid was added over 10 minutes (relative to the monomer added). 0.3 wt%) was dissolved in 55.80 g of water in an aqueous phosphoric acid solution. Thereafter, the flask was immersed in an oil bath at 40 ° C and stirred for 30 minutes, and then the oil bath was heated to 115 ° C for 30 minutes. The temperature rises to 100 ° C after 1 hour from the start of the temperature rise, and then the mixture is heated and stirred for 2 hours (the internal temperature is 100 ° C to 110 ° C), thereby obtaining polyfluorene. Oxygenane solution (A1-i). Further, during heating and stirring, nitrogen gas was introduced at 0.05 L (liter) / min. A total of 139 g of methanol and water as by-products were distilled off in the reaction.

The solid concentration of the obtained polyoxyalkylene solution (A1-i) was 43% by weight, and the weight average molecular weight of polyoxyalkylene was 8,800. Further, the content of the phenyl-substituted decane in the polyoxyalkylene is 50% in terms of the molar ratio of Si atoms.

Synthesis Example 10: Synthesis of Polyoxane Solution (A1-j)

To a 500 mL three-necked flask, 68.10 g (0.50 mol) of methyltrimethoxydecane, 99.15 g (0.50 mol) of phenyltrimethoxydecane, and 150.40 g of PGMEA were added, and the mixture was stirred at room temperature for 10 minutes. An aqueous phosphoric acid solution obtained by dissolving 0.50 g of phosphoric acid (0.3 wt% with respect to the monomer added) in 54.00 g of water was used. Thereafter, the flask was immersed in an oil bath of 40 ° C and stirred for 30 minutes, and then the oil bath was heated to 115 ° C over 30 minutes. The internal temperature of the solution reached 100 ° C one hour after the start of the temperature rise, and then the mixture was heated and stirred for 2 hours (the internal temperature was 100 ° C to 110 ° C) to obtain a polyoxyalkylene solution (A1-j). Further, during heating and stirring, nitrogen gas was introduced at 0.05 L (liter) / min. A total of 137 g of methanol and water as by-products were distilled off in the reaction.

The solid concentration of the obtained polyoxyalkylene solution (A1-j) was 43% by weight, and the weight average molecular weight of polyoxyalkylene was 7,000. Further, the content of the phenyl-substituted decane in the polyoxyalkylene is 50% in terms of the molar ratio of Si atoms.

Synthesis Example 11: Synthesis of Acrylic Resin Solution (A2-a)

To a 500 mL flask was placed 5 g of 2,2'-azobis(isobutyronitrile), 5 g of tert-dodecylmercaptan, and 180 g of PGMEA. Thereafter, 40 g of methacrylic acid, 35 g of benzyl methacrylate, 35 g of tricyclo [5.2.1.0 ^2,6 ]decane-8-yl methacrylate were added, and the mixture was stirred at room temperature and nitrogen was placed in the flask. After the replacement, the mixture was stirred under heating at 70 ° C for 5 hours. Then, 15 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, and 0.2 g of p-methoxyphenol were added to the obtained solution, and the mixture was heated and stirred at 90 ° C for 4 hours to obtain an acrylic resin solution (A2). -a).

The obtained acrylic resin solution (A2-a) had a solid content concentration of 40% by weight, and the acrylic resin had a weight average molecular weight of 12,000 and an acid value of 91 mgKOH/g.

Synthesis Example 12: Synthesis of naphthoquinonediazide compound (B-a)

Under dry nitrogen flow, 21.23 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 37.62 g (0.14 mol) of 5-naphthoquinonediazidesulfonium chloride were dissolved in 1,4- In 450 g of dioxane, it was set to room temperature. 15.58 g (0.154 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise thereto so as not to be 35 ° C or more in the system. After the dropwise addition, the mixture was stirred at 30 ° C for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the precipitated precipitate was collected by filtration. The precipitate was dried by a vacuum dryer to obtain a naphthoquinonediazide compound (B-a) having the following structure.

Synthesis Example 13: Synthesis of naphthoquinonediazide compound (B-b)

Under dry nitrogen flow, 13.32 g (0.05 mol) of TrisP-HAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 26.87 g (0.1 mol) of 5-naphthoquinonediazidesulfonium chloride were dissolved in 1,4- In 450 g of dioxane, it was set to room temperature. 11.13 g (0.11 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise thereto so as not to be 35 ° C or more in the system. After the dropwise addition, the mixture was stirred at 30 ° C for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the precipitated precipitate was collected by filtration. The precipitate was dried by a vacuum dryer to obtain a naphthoquinonediazide compound (B-b) having the following structure.

Synthesis Example 14: Synthesis of naphthoquinonediazide compound (B-c)

15.32 g (0.05 mol) of Ph-cc-AP (trade name, manufactured by Honshu Chemical Co., Ltd.) and 37.62 g (0.14 mol) of 5-naphthoquinonediazidesulfonium chloride were dissolved in 1, under a dry nitrogen stream. In 450 g of 4-dioxane, it was set to room temperature. 15.58 g (0.154 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise thereto so as not to be 35 ° C or more in the system. After the dropwise addition, the mixture was stirred at 30 ° C for 2 hours at 30 ° C. The triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the precipitated precipitate was collected by filtration. The precipitate was dried by a vacuum dryer to obtain a naphthoquinonediazide compound (B-c) having the following structure.

Synthesis Example 15: Synthesis of naphthoquinonediazide compound (B-d)

A naphthoquinonediazide compound (B-d) having the following structure was obtained in the same manner as in Synthesis Example 10 except that the amount of 5-naphthoquinonediazidesulfonyl chloride was changed to 33.59 g (0.125 mol).

(Example 1)

15.43 g of the polyaluminoxane solution (A1-a) obtained in Synthesis Example 1 and the naphthoquinonediazide compound obtained in Synthesis Example 7 under a yellow lamp. (B-a) 0.59 g, 3.73 g of DAA as a solvent, and 9.84 g of PGMEA were mixed and stirred to prepare a homogeneous solution, and then filtered using a 0.45 μm filter to prepare a composition 1.

The composition 1 was spin-coated on a tantalum wafer and an OA-10 glass plate (manufactured by Nippon Electric Glass Co., Ltd.) with a molybdenum sputtering film at a random rotation speed using a spin coater (1H-360S manufactured by Mikasa Co., Ltd.). After the glass substrate was baked, it was prebaked at 90 ° C for 2 minutes using a hot plate (SCW-636, manufactured by Dainippon Screen Co., Ltd.) to prepare a film having a film thickness of 3 μm. Using a parallel light type mask to align the exposure machine (hereinafter, abbreviated as PLA) (PLA-501F manufactured by Canon Co., Ltd.), the film produced by the ultra-high pressure mercury lamp is subjected to pattern exposure through a gray scale mask for sensitivity measurement. After that, an automatic developing device (AD-2000 manufactured by Takizawa Sangyo Co., Ltd.) was used as ELM-D (trade name, manufactured by Mitsubishi Gas Chemical Co., Ltd.) as a 2.38 wt% aqueous solution of tetramethylammonium hydroxide. Spray development in 60 seconds, followed by water for 30 seconds. Thereafter, as a bleaching exposure, PLA (Pan-501F manufactured by Canon Co., Ltd.) was used, and the entire surface of the film was exposed to 3,000 J/m ² (converted by a wavelength of 365 nm) using an ultrahigh pressure mercury lamp.

Thereafter, the mixture was soft-baked at 110 ° C for 2 minutes using a hot plate, and then cured in an air at 230 ° C for 1 hour in an oven (IHPS-222, manufactured by Taji Espec Co., Ltd.) to prepare a cured film.

The evaluation results of the photosensitive characteristics and the cured film characteristics are shown in Table 5. Further, the evaluation of the photosensitive characteristics and the properties of the cured film was carried out by the following method. In addition, the following evaluations of (4) to (8) were performed using a ruthenium wafer substrate, and (9) was evaluated using an OA-10 glass plate, (10) The evaluation of ~(11) was carried out using a glass substrate with a molybdenum sputtering film.

(4) Film thickness measurement

The measurement was carried out using a Lambda Ace STM-602 (trade name, manufactured by Dainippon Screen) at a refractive index of 1.50.

(5) Reduction in film thickness of unexposed portions during development

The decrease in the film thickness of the unexposed portion at the time of development was calculated according to the following formula.

Film thickness reduction in unexposed portions = film thickness before development - film thickness after development of unexposed portions

(6) Calculation of sensitivity

After the exposure and development, an exposure amount (hereinafter, referred to as an optimum exposure amount) in which a line-space pattern of 10 μm is formed in a one-to-one width is set as the sensitivity.

(7) Calculation of resolution

The minimum pattern size after development at the optimum exposure amount is set as the resolution after development, and the minimum pattern size after hardening is set as the post-hardening resolution.

(8) Heat resistance

The cured film produced by the method described in Example 1 was peeled off from the substrate, and about 10 mg was placed in an aluminum electrolytic cell, and then a thermogravimetric measuring device (TGA-50, manufactured by Shimadzu Corporation) was used. In a nitrogen atmosphere, the temperature was raised to 150 ° C at a temperature increase rate of 10 ° C / min, and the temperature was maintained at 150 ° C for 1 hour, and then the temperature was raised to 400 ° C at a temperature increase rate of 10 ° C / min. At this time, the temperature Td1% at which the weight reduction was 1% was measured and compared. The higher the Td1%, the better the heat resistance.

(9) Determination of light transmittance

Using MultiSpec-1500 (trade name, Shimadzu Corporation), first, only the OA-10 glass plate was measured, and its ultraviolet-visible absorption spectrum was used as a reference. Next, a cured film of the composition was formed on the OA-10 glass plate (no pattern exposure), and the sample was measured by a single beam, and the light transmittance per 3 μm at a wavelength of 400 nm was determined, and the difference from the reference was set. It is the light transmittance of the cured film.

(10) Development adhesion

The minimum pattern size remaining on the substrate of the residual pattern of the developed film produced on the glass substrate with the molybdenum sputter film by the method described in the above (1) is the development adhesiveness. The finer the pattern, the easier it is to peel off during development, so the smaller the value, the better the development adhesion.

(11) Heat and humidity resistance

A cured film was formed on a glass substrate with a molybdenum sputter film by the method described in the above (1), and then subjected to a reaction chamber at 121 ° C, a humidity of 100%, and a gas pressure of 2.1 atm (manufactured by Espec Co., Ltd., "HAST CAHMBER The test was carried out for 10 hours or 24 hours in EHS-221MD (trade name)", and then the degree of discoloration of molybdenum was evaluated. Further, the glass substrate having only the molybdenum sputtering film was simultaneously tested as an index of the degree of discoloration before and after the test, and was determined as follows.

5: Molybdenum under the hardened film showed no discoloration before and after the test.

4: Before and after the test, the area of 1% was discolored compared with the case where the molybdenum under the hardened film was not covered by the cured film.

3: Before and after the test, the area of 20% was discolored compared with the case where the molybdenum under the hardened film was not covered by the cured film.

2: Before and after the test, the area of 40% was discolored compared with the case where the molybdenum under the hardened film was not covered by the cured film.

1: Before and after the test, the area of 60% or more was discolored compared with the case where the molybdenum under the cured film was not covered by the cured film.

(Example 2 to Example 40, Comparative Example 1 to Comparative Example 4)

In the same manner as the composition 1, the composition 2 to the composition 35 were prepared in the compositions described in Tables 1 to 4. Further, KBM303 used as a decane coupling agent is (2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane manufactured by Shin-Etsu Chemical Co., Ltd.. The phenol compound Phcc- used as a dissolution promoter. AP, TrisP-PA, BisP-FL (all manufactured by Honshu Chemical Industry Co., Ltd.), and Nikalac MW-390 and Nikalac-MX270 (trade name, manufactured by Sanwa Chemical Co., Ltd.) used as a crosslinking agent are as follows A compound of the structure shown.

In addition, CGI-MDT (trade name, Ciba) used as a crosslinking accelerator Japan (share manufacturing)), WPAG-469 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.) is 4-methylphenyldiphenylphosphonium perfluorobutanesulfonate 20% PGMEA solution for sensitization DPA (trade name, manufactured by Kawasaki Chemical Industry Co., Ltd.) is 9,10-dipropoxy oxime.

Evaluation of each composition was carried out in the same manner as in Example 1 using each of the obtained compositions. However, in the evaluation of the acrylic resin, development was carried out by a 0.4 wt% aqueous solution of tetramethylammonium hydroxide for 60 seconds. The results are shown in Tables 5 and 6. In Comparative Example 4, since the amount of the chelate compound added was too large, no analysis was performed even when the exposure amount of 3,000 J/m ² was irradiated.

[Industrial availability]

The positive photosensitive composition of the present invention can be used for forming a flat film for a thin film transistor (TFT) substrate such as a liquid crystal display device or an organic EL display device, a protective film or an insulating film for a touch panel, and an interlayer insulating film for a semiconductor element. A flattening film or a microlens array pattern for a solid-state imaging element, or a core or a cladding material of an optical waveguide.

Claims (14)

A positive photosensitive composition comprising: (A) an alkali-soluble polyoxyalkylene oxide, (B) a naphthoquinonediazide compound, (C) a solvent, and (D) a metal chelate compound, said (D) The metal chelating compound has a structure represented by the following formula (1), and the content of the (D) metal chelating compound is 0.1% by weight based on 100 parts by weight of the (A) alkali-soluble polysiloxane. The content of the epoxy group and/or the vinyl group of the (A) alkali-soluble polysiloxane is 1% by mole or more and 50% by mole or less with respect to the Si atom. (In the metal chelate compound represented by the above formula (1), M is a metal atom; and R ¹ may be the same or different and each represents hydrogen, an alkyl group, an aryl group, an alkenyl group, and a substituent thereof. R ² and R ³ may be the same or different and each represent hydrogen, an alkyl group, an aryl group, an alkenyl group, an alkoxy group, and the substituents thereof; j represents the valence of the metal atom M, and k represents 0 to j. Integer). The positive photosensitive composition according to claim 1, wherein the metal atom M in the general formula (1) is any one of titanium, zirconium or aluminum metal atoms. The positive photosensitive composition according to claim 1 or 2, wherein the metal atom M in the general formula (1) is aluminum Metal atom. The positive photosensitive composition according to claim 3, wherein the (D) metal chelate compound is contained in an amount of 0.1 part by weight based on 100 parts by weight of the (A) alkali-soluble polyoxysiloxane. ~1.5 parts by weight. The positive photosensitive composition according to claim 1 or 2, wherein M of the formula (1) is a zirconium metal atom and is relative to the (A) alkali-soluble polyoxynitride The content of the (D) metal chelate compound is from 0.3 part by weight to 4 parts by weight per 100 parts by weight. The positive photosensitive composition according to claim 1 or 2, wherein the content of the phenyl group in the (A) alkali-soluble polyaluminoxane is 5% or more with respect to the Si atom. 70% or less. The positive photosensitive composition according to claim 1 or 2, further comprising an organodecane represented by the general formula (3) as a decane coupling agent. (In the organodecane represented by the above formula (3), in the formula, R ⁶ to R ⁹ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, a fluorenyl group having 2 to 6 carbon atoms, Any one of aryl groups having 6 to 15 carbon atoms; the alkyl group, the fluorenyl group, and the aryl group may be either an unsubstituted form or a substituted form, and m represents an integer of 1-8. ). Positive sensitization as described in item 1 or 2 of the patent application scope A sexual composition further comprising a dissolution promoter. The positive photosensitive composition according to claim 8, wherein the dissolution promoter is a phenol compound. The positive photosensitive composition according to claim 1 or 2, further comprising a crosslinking agent. The positive photosensitive composition according to claim 10, wherein the crosslinking agent comprises a methylol compound. A cured film formed of a positive photosensitive composition according to any one of claims 1 to 11, and having a light transmittance of 85% or more per 3 μm at a wavelength of 400 nm. . A hardened film formed of a positive photosensitive composition according to any one of claims 1 to 11, and is selected from the group consisting of titanium and zirconium with respect to 100 parts by weight of the alkali-soluble polyoxyalkylene. The metal content of one or more of aluminum, zinc, cobalt, molybdenum, niobium, tantalum, niobium, magnesium, and calcium is from 0.005 parts by weight to 1 part by weight. An element comprising a cured film as described in claim 12 or claim 13.