TW201030468A - Positive photosensitive composition and permanent resist - Google Patents

Abstract

A positive photosensitive composition which comprises (A) a silicone resin bearing, in one molecule, at least two groups represented by general formula (1) [wherein R1 is a C1-10 alkylene group which may have a substituent hydrocarbon group; R2 is a C1-4 alkyl group; a is a number of 0 or 1 to 4; and b is a number of 1 to 3, with the proviso that the sum of a and b does not exceed 5], (B) a siloxane compound bearing a glycidyl group, (C) a diazonaphthoquinone, and (D) an organic solvent. The permanent resist is produced by applying the positive photosensitive composition to a substrate, exposing the coated substrate to light, and then subjecting the resulting coated substrate to alkali development and then to post-baking at 120 to 350 DEG C.

Description

201030468 6. Technical Field of the Invention The present invention relates to a positive photosensitive composition using a polyoxo compound, and further relates to a permanent resist using the positive photosensitive composition and A method of manufacturing a permanent resist. [Prior Art] Due to the progress of the information society and the popularity of multimedia systems, liquid crystal display devices and organic EL (Electro-Luminescence) display devices are becoming more and more important. In these display devices, an active matrix substrate having a switching element such as a thin film transistor (TFT) for each pixel is used. A plurality of scanning lines are formed on the active matrix substrate, and a signal wiring, a signal wiring, an insulating film, and the like of the active matrix substrate are connected to the scanning wiring via the insulating medium, and the sputtering method is used. A conductive film or an insulating film formed by a CvD (Chemical Vapor Deposition) method or a coating method is formed by patterning by photolithography (see, for example, Patent Documents 1 and 2). Usually, a photoresist is used in the photolithography method, and a resist (permanent resist) which is used as an insulating film or a protective film after patterning is also being developed, but permanent resist is used on the active matrix substrate. In the case of an etchant, chemical resistance (acid resistance, alkali resistance, and solvent resistance) is required, and high heat resistance and chemical resistance after a high heat history are required. The active matrix substrate has a problem in that a TFT having a polycrystalline germanium film as an active layer is formed on a glass substrate as an insulating substrate, and a polysilicon film is covered by an insulating film 144043.doc 201030468, but it is easy to be inside the polycrystalline silicon, or a crystalline germanium film and an insulating substrate. Or the interface of the insulating film generates a dangling bond as a defect of the 矽 bond, and the characteristics of the transistor are lowered. In order to eliminate the problem of the dangling bonds, it is necessary to carry out a hydrogenation treatment at a temperature of about 300 to 40 Torr in a state in which a film for preventing diffusion of hydrogen such as tantalum nitride (SiNx) is present (for example, see Patent Document 3). The heat resistance of the prior permanent resist refers to heat resistance which can withstand the soldering in the printed wiring board, and can withstand heat resistance at a temperature of 260 〇C for several minutes (for example, refer to Patent Document 4). The heat resistance required for the active matrix substrate and the chemical resistance after the high thermal history are greatly different. On the other hand, the epoxy resin is excellent in transparency, insulation, heat resistance, chemical resistance, etc., and a photoresist which is mainly composed of a ruthenium oxide resin is known. Since the chemical resistance of the agent after the heat resistance and the high heat history is insufficient, only the surface flattening film is applied to the active matrix substrate (see, for example, Patent Document 5). CITATION LIST Patent Literature Patent Literature 1: Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2007-225860. SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION 144043.doc 201030468 Therefore, the object of the present invention is to provide a positive photosensitive composition and use thereof. The permanent anti-money agent of the positive photosensitive composition and the method for producing the same, the positive photosensitive composition can provide a high heat resistance and high heat which is excellent in transparency and can also be used as an insulating film of a ±-moving substrate A chemical resistant permanent resist after the course. Means for Solving the Problems The inventors of the present invention conducted intensive studies and as a result completed the present invention. 0. The present invention provides a positive photosensitive composition comprising: as component (A) having at least two of the following formula (1) [Chemical Formula 1]

(wherein R1 represents an alkylene group which may have a carbon number of a substituted hydrocarbon group, R2 represents an alkyl group having 1 to 4 carbon atoms, a represents a number of hydrazine or 1 to 4, b represents a number of ^, φ but a+b Not more than 5.) the base of the epoxy resin; the component (B) having a glycidyl group; the diazonaphthoquinone as the component (C); and • as the component (D) Organic solvent. Further, the present invention provides a permanent anti-surname agent which is obtained from the above-mentioned positive photosensitive composition. Further, the present invention provides a method for producing a permanent anti-surname agent, which is characterized in that, in the case of I44043.doc 201030468, the positive-type photosensitive composition is applied onto a substrate, and the coated article is exposed to 'after inspection and development'. Post-bake is carried out at a temperature of 12 Torr to 350 ° C. Further, the present invention provides a liquid crystal display device comprising a permanent resist obtained by using the above positive photosensitive composition as an insulating layer. Or planarizing the active matrix substrate of the film. Moreover, the present invention provides an organic EL display device comprising an active matrix substrate using a permanent resist obtained by using the positive photosensitive composition as an insulating layer or a planarizing film. Advantageous Effects of Invention The present invention provides an positive photosensitive composition, a permanent resist using the positive photosensitive composition, and a method for producing the same. The positive photosensitive composition can provide a high transparency Moreover, it can withstand the heat resistance and solvent resistance of the temperature at the time of substrate production, and further, it is an insulating layer which is excellent in resistance to change over time as a permanent anti-surname agent. [Embodiment] Hereinafter, the present invention will be described in detail based on preferred embodiments. First, the epoxy resin which is the component (A) of the present invention will be described. The oxime resin which is the component (A) of the present invention has at least two groups represented by the above formula (1) in one molecule. In the above formula (1), Ri represents an alkylene group having a carbon number of 丨~1〇 which may have a substituted hydrocarbon group. Examples of the alkylene group of the carbon number are methylene, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, thiol and hydrazine Base, in terms of heat resistance, it is preferred that the carbon number is small, 144043.doc 201030468 In terms of the ease of industrial availability, 'better ethyl, propyl and butyl groups' are preferred. It is an ethyl group and a butyl group, and the most preferable one is an ethyl group. Examples of the substituted hydrocarbon group which may be contained in Ri may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group or a t-butylphenyl group, and are preferably in terms of heat resistance. It does not have a substituted hydrocarbon group. R2 represents an alkyl group having 1 to 4 carbon atoms, and examples of the alkyl group having a carbon number of 丨4 to 4 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, and a third group. Butyl and the like. As R2, in terms of heat resistance, an alkyl group having a carbon number of 丨3 to 3 is preferable, and a methyl group and an ethyl group are more preferable, and a methyl group is most preferable. a represents the number of 0*^4, b represents the number of Bu 3, but a+b does not exceed 5. When 3 is a number of 2 to 4, R 2 may be the same alkyl group or a different alkyl group. In terms of heat resistance, a is preferably a number of ruthenium or osmium, and further preferably ruthenium. In terms of the ease of industrial acquisition, 1 is preferably 丨 or 2, and more preferably 1. The position of the carboxyl group of the group represented by the above formula (1) is not particularly limited, and in terms of improvement in heat resistance, it is preferred that i carboxyl groups are positioned opposite to R2. The oxime resin having at least two groups represented by the formula (1) in one molecule of the present invention can be produced, for example, by the following method or the like: an alkoxy group having a group represented by the formula (1) A hydrazine compound (hereinafter referred to as a compound 1AS) or a chlorosilane compound (hereinafter referred to as a compound 1CS) undergoes a hydrolysis/condensation reaction or a carbon-carbon double bond having an reactivity with a Si-H group and an aromatic carboxyl group. The compound (hereinafter referred to as compound DAC) undergoes a hydrogenation reaction with a compound having at least two Si-H groups in one molecule. 144043.doc 201030468 First, a method of subjecting Compound 1 AS or Compound 1CS to hydrolysis and condensation reaction will be described. In the hydrolysis/condensation reaction of the compound 1AS or the compound 1CS, a so-called sol-gel reaction may be carried out, and a method of performing a hydrolysis/condensation reaction using an acid or a catalyst such as a solvent in a solvent may be specifically mentioned. The solvent to be used in this case is not particularly limited, and specific examples thereof include water, decyl alcohol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, acetone, mercaptoethyl ketone, and dioxane. For example, tetrahydrofuran or the like can be used, and two or more kinds can be used in combination. Hydrolysis of alkoxy decane or gas oxime. The condensation reaction is carried out by hydrolyzing a oxydecane or a gas oxime by water to form a nicotinic alcohol group (Si-OH group), and the resulting sterol group Each of them, a sterol group and an alkoxyalkyl group, or a decyl group is condensed with a gas alkyl group. In the hydrolysis/condensation reaction, any one of an alkoxydecane compound and a gas oxane compound may be used, or each compound may be used in combination, since it is easy to control the reaction and remove by-products, it is preferably used as an alkoxydecane. Compound 1AS of the compound. In order to carry out the hydrolysis reaction rapidly, it is preferred to add an appropriate amount of water, or to add the catalyst in water. Further, the hydrolysis reaction can be carried out by water in the air or a trace amount of water contained in a solvent other than water. The hydrolysis or the catalyst used in the condensation reaction may be a hydrolysis reaction or a condensation reaction, and specific examples thereof include inorganic acids such as hydrochloric acid, scalylic acid, and sulfuric acid, such as citric acid, acetic acid, oxalic acid, and citric acid. , methyl acid, benzene 144043.doc 201030468 acid, p-toluene acid, squaric acid mono-^. Organic acid, sodium hydroxide, single L:, oxidation clock, ammonia and other inorganic tests, trimethylamine, three An amine compound (organic test) such as ethylamine, =:, diethanolamine or the like; one of the above-mentioned ones may be used, or two or more kinds may be used in combination. The condensation condensation reversal temperature is the type of the root (four) agent, the type of the catalyst, and the enthalpy, etc., and the better county is better than 0~80C, and then preferably 5~5〇〇c, preferably It is 8~30 °C. In the compound 1AS, R: is a compound having a tetyl group in the exoethyl group, and examples thereof include, for example,

, a=0, b=l, and p-(2-carboxyphenyl)ethyltrimethoxydecaneoxydecane; 2-(4-carboxyphenyl)ethyltriethoxydecane, etc. Alkyl 2-(4-carboxyphenyl)ethyldimethoxymethylnonane, 2-(4-mercaptophenyl)ethyldiethoxymethyl sulphate, 2-(decylphenyl)ethyl Dimethoxyethyl decane, 2-(4-carboxyphenyl)ethyldiethoxyethyl decane, 2-(4-carboxyphenyl)ethyldimethoxypropyl decane, 2_(4_ Carboxyphenyl)ethyldiethoxypropyl decane, 2-(4-carboxyphenyl)ethyldimethoxy

Butyl decane, 2-(4-carboxyphenyl)ethyldiethoxybutyl decane, 2-(4-carboxyphenyl)ethyldimethoxyisobutyl decane, 2(4•carboxyphenyl)B Dioxane such as diethoxybutyl isodecane, 2-(4-carboxyphenyl)ethyldimethoxycyclohexyldecane, 2-(4-carboxyphenyl)ethyldiethoxycyclohexyldecane Oxydecanes; 2-(4-carboxyphenyl)ethyloxydimethoxydecane, 2-(4-carboxyphenyl)ethylethoxydidecyldecane, 2-(4-carboxyphenyl Ethyl nonoxydiethyl decane, 2-(4-carboxyphenyl)ethyl ethoxydiethyl decane, 2-(4-carboxyphenyl)ethyl decyloxydipropyl decane, 2 -(4-carboxyphenyl)ethylethoxydipropylnonane, 2-(4-carboxyphenyl)ethylmethoxydi 144043.doc 201030468 butyl astaxane, 2-(4-reasterylbenzene Ethyl ethoxy dibutyl oxalate, 2 (heart-reactive phenyl) ethyl methoxy diisobutyl sulphate, 2 - (4 phenyl) ethyl ethoxy diisobutyl Decane, 2-(4-carboxyphenyl)ethyl decyloxydicyclohexyldecane, 2-(4-carboxyphenyl)ethylethoxydicyclohexyl Alkoxy and other monoalkoxy > 6 burning evening class. Among these compounds, 2-(4-carboxyphenyl)ethyltrimethoxy decane and 2-(4-carboxybenzene are preferred in terms of good reactivity and good heat resistance. Ethyltriethoxydecane, 2-(4-carboxyphenyl)ethyldimethoxyoxydecane' 2-(4-carboxyphenyl)ethyldiethoxymethyldecane, 2-(4 -carboxyphenyl)ethyldimethoxyethyl decane, 2-(4-carboxyphenyl)ethyldiethoxyethyl decane, 2-(4-carboxyphenyl)ethyltrimethoxy decane, 2-(4-carboxyphenyl)ethyltriethoxydecane, further preferably 2-(4-carboxyphenyl)ethyltrimethoxynonane, 2-(4-carboxyphenyl)ethyl dimethyl Oxydecyl decane, 2-(4-carboxyphenyl)ethyldimethoxyethyl decane, most preferably 2-(4-carboxyphenyl)ethyltrimethoxy decane, 2 (4_ Carboxyl) Ethyldimethoxymethyl. The compound 1AS may be used alone or in combination of two or more. In the compound 1CS, 'as a compound in which R1 is an ethyl group, a=〇, b=l, and a carboxyl group is contained in the para position, for example, three gases such as 2-(4-carboxyphenyl)ethyltrioxane may be mentioned. Hydranes; 2-(4.carboxyphenyl)ethyldioxamethylnonane, 2-(4-carboxyphenyl)ethyldiethyleneethyloxane, 2-(4-carboxyphenyl)ethyldipropane Basestone, 2-(4-carbophenyl)ethyldi-butylbutyl, 2-(4-carboxyphenyl)ethyldichloroisobutylnonane, 2-(4-carboxyphenyl) Dioxanes such as ethyl dicyclohexyldecane; 2-(4-carboxyphenyl)ethyl dimethyl 144043.doc •10· 201030468 decyl, 2-(4-carboxyphenyl)ethyl 2 Ethyl decane, 2-(4-carboxyphenyl)ethyl dipropylene decane, 2-(4-carboxyphenyl)ethyl chlorodibutyl decane, 2-(4-mercaptophenyl)ethyl hexane Monooxane such as isobutyl decane or 2-(4-carboxyphenyl)ethyl dicyclohexyldecane. Among these compounds, in terms of good reactivity and good heat resistance, '(2-carboxyphenyl)ethyltrioxane, 2-(4-carboxyl)ethyl) is preferred. Dioxomethyl decane, 2-(4-carboxyphenyl)ethyldiethyleneethyl decane, more preferably 2-(4-carboxyphenyl)ethyltrioxane, 2-(4-carboxyphenyl) Ethyl dioxomethyl decane. The compound 1CS may be used alone or in combination of two or more. The carboxyl group of the above compound 1AS and compound 1CS may also be protected by a protecting group such as a third butyl group. For example, the compound represented by the formula of the compound 1AS and the compound lcs is represented by the following formula (la) [Chemical 2]

(wherein, R1, R2, a and b have the same meanings as in the above formula (1).) As shown, the carboxyl group can be protected by the third butyl ester group. The above protected compound can be hydrolyzed or condensed in the same manner as the unprotected compound. In the case where the protecting group is a tert-butyl group, the third butyl group may be detached after the above hydrolysis or condensation reaction, using a catalyst as needed. 144043.doc -11 - 201030468 As a catalyst in this case, it is preferable that the three gasification collars are inconsistent with each other, and that the solvent is the organic solvent of the water in the water. As Α μ + can solve 1 quality. /. The above-mentioned organic solvent alcohol, ethanol, and propanol are both exemplified by methyl-ethanol, 1-propoxy rt w-rolling base, ethanol, ethoxylated-ethanol, and isopropoxy. Base_ethanol, 1-methyl gas, which is set to fresh butoxy-B

Ether alcohols such as oxy '2-propanol, 3-methoxybutanol' 3m G-based 1-butyryl carboxymethoxy-3-carbamyl alcohol; acetic acid br acetamidine, 7 silk 1st, 1-ethoxyxy T-oxy-2-propyl acetate, acetic acid 3-methoxy-3-methoxy-3-carboxamidine, butyl butyl sulfonate S 曰, acetate acetate 1 Acetate and vinegar. Fine ethyl net etc. _ class., methyl spear 頬 4-, 4-cool base 2_ butanone, 3_ carbyl _3_ 4 - haiqitian hang · 2-τ ketone, soil - soil Ketone alcohols such as 1-2~pentanone (diacetone alcohol); ethers such as 14-dione oxime tetrahydrofuran and 1,2-dimethoxyethane; methanol, ethanol, propanol, mercapto In the case of using a protected compound as a raw material of the above (Α) component, a step of removing the protective group is required, the manufacturing step becomes complicated, but it is difficult to generate a side reaction, and the permanent resist of the present invention The advantages of heat resistance, chemical resistance, etc. are improved. Then, the compound (compound DAC) containing a carbon-carbon double bond and an aromatic sulfhydryl group having reactivity with the Si-H group is subjected to hydrazine hydrogenation reaction with a compound having at least two Si-H groups in one molecule. The method is explained. As the compound having at least two Si-H groups in one molecule, for example, the following formula (5) 144043.doc • 12-(5) 201030468 [Chemical 3] can be cited.

(In the formula, X, 7F, fluorenyl or fluorenyl group, R14, which may be the same or different methyl or phenyl group] R15, R16 and R17 represent the same or different carbon number of 1 to 6 5 to 6 of a cycloalkyl group or a phenyl group 'q represents a number of 〇~, and r represents a number of 0 to 1000. Wherein, when q is 〇 or 1, X represents a hydrogen atom.) The linear compound represented, And the following general formula (6) [Chemical 4]

(6)

(wherein, Ru, R19&R2〇 represents an alkyl group having the same or different carbon number, a cycloalkyl group having a carbon number of 5 to 6 or a phenyl group, and s represents a number of 2 to 6, and t represents a state. The number of 〇~4 of 3 to 6. The cyclic compound represented by the above formula (6) is preferably a cyclic compound in terms of improvement in heat resistance. It is called π 砍 γ γ Lane, κ 衣 同 can also be different methyl or phenyl '~1R17 represents the same = carbon number 1~6 of the alkyl group, carbon number of the ring alkyl or phenyl. Examples of the alkyl group of the bamboo 6 include methyl ethyl propyl group, 144043.doc -13·201030468 group, butyl group, isobutyl group, second butyl group, tert-butyl group, pentyl group, isopentyl group, a second pentyl group, a third pentyl group, a hexyl group, a second hexyl group, etc., as a cycloalkyl group having a carbon number of 5 to 6, for example, can be listed as a reneg, a ruthenium, a cyclopentyl group, a cyclohexyl group, a cyclopentyl group. Base, methylcyclopentyl and the like. R14 is preferably a methyl group in terms of industrially readily available. In the case where the influence of the hydrogenation reaction is less, t15 is preferably a methyl group and an ethyl group, and more preferably a methyl group. With respect to the thermal resistance of the permanent resist of the present invention, R16 and Rl7 are preferably a methyl group, an ethyl group and a phenyl group, more preferably a methyl group and a phenyl group, and most preferably a mercapto group. X represents a hydrogen atom or a methyl group, q represents the number of Q~1G(10), and "is a number of 〇~1〇〇〇. When r is 0, χ represents a hydrogen atom. In the above formula (6), Ru, Rl9 & R2〇 represent a carbon group having 1 to 6 carbon atoms which may be the same or different, a cycloalkyl group having 5 to 6 carbon atoms or a phenyl group. Examples of the alkyl group having 1 to 6 carbon atoms and the cycloalkyl group having 5 to 6 carbon atoms include an alkyl group and a cycloalkyl group exemplified by Rls, R16 and a ruler. Rls is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group and an ethyl group, and most preferably a methyl group.

Further, in terms of heat resistance of the permanent resist of the present invention, r1 9 and rM are preferably a methyl group, an ethyl group and a phenyl group, and more preferably a methyl group and a stupid group, and most preferably a type A base. s represents the number of 2 to 6, and t represents the number of 〇~4 where s+t becomes 3 to 6. In terms of industrially readily available, s+t is preferably 4 to 6, and more preferably 4 to 5' is preferably 4. Also, t is better. Specific examples of the cyclic siloxane compound represented by the above formula (6) are 144043.doc -14· 201030468, which may be exemplified by 2,4,6-trimethylcyclotrioxane, 2,4. 6-triethylcyclotricarbazone, 2,4,6-triphenylcyclotricarbazone, 2,4,6,8 tetramethylcyclotetrazepine, 2,2,4,6 , 8-penta-based ring four-stone oxy-oxygen, 2,2,4,4,6,8-hexamethyl ring. Four stone ritual burning, 2,4,6,8-tetraethyl ring Oxygen, 2,4,6,8-tetraphenylcyclotetrazepine, 2-ethyl-4,6,8-trimethylcyclotetraoxane, 2-phenyl_ 4.6.8- Triterpene ring tetraoxane, 2,4,6,8,10-pentamethylcyclopentaoxane, 2,4,6,8,10-pentaethylcyclopentaoxane, 2,46 , 81〇_pentaphenylcyclopentaoxane φ alkane, 2,4,6,8,10,12-hexamethylcyclohexaoxane, 2,4,6,8,10,12-hexaethyl Cyclohexaoxane, 2,4,6,8,10,12-hexaphenylcyclohexaoxane, etc., in terms of industrially readily available, 2, 4, 6, 8- Tetramethylcyclotetraoxane and 2,4,6,8,1〇-pentamethylcyclopentaoxane, and more preferably 2.4.6.8-tetradecylcyclotetrazepine. Next, the compound DAC will be described. Examples of the compound DAC include 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid, 4-(1·phenylidenevinyl)benzoic acid, and 2-methyl-4-tetraethylene. Benzoic acid, 2-allenylbenzoic acid, allyl benzoic acid, 4-aldolylbenzoic acid, 2·isopropenylbenzoic acid, 3-isopropenylbenzoic acid, n-isopropenylbenzene Formic acid, 4-(3-butenyl)benzoic acid, 4-(4-pentenyl)benzoic acid, 4-(5-hexenyl) benzoic acid, 4-(6-heptenyl)benzoic acid, 4_(7_ Octenyl)benzoic acid, 4-(8-decenyl)benzoic acid, 4-(9-nonenyl)benzoic acid, 2-vinyl-1,4-1,4--F-acid, 5-ethylene - ΐ, 3·phthalic acid, etc. Among these compound DACs, 2 -vinylbenzoic acid, 3-vinylbenzoic acid, 'vinyl group' are preferred in terms of industrially readily available aspects and heat resistance of the permanent resist of the present invention. Benzene f acid, 2·allylbenzyl I44043.doc ltr 201030468 acid, 4-allylbenzoic acid, 2-isopropenylbenzoic acid, 4-isopropenylbenzoic acid, and more preferably 2- Vinylbenzoic acid '4-vinylbenzoic acid, the most preferred is 4-ethylenebenzoic acid. The compound j) may be used alone or in combination of two or more. The aromatic carboxyl group of the compound DAC may optionally be protected by a protecting group such as a third butyl group. For example, when the aromatic carboxyl group is protected by the third butyl group, it becomes a third butyl ester, and after the hydrogenation reaction, the tributyl group can be removed by the above method. The conditions for subjecting the compound DAC to the compound φ having at least two groups of seven groups in one molecule can be carried out under known conditions. For example, it can be used in toluene, isopropanol, acetone, methyl ethyl ketone, decyl isobutyl ketone, 12-dimethoxy ethane, 1,4-dioxane, 丨 曱 曱 oxy 2 _ In a solvent such as an alcohol acetate, if necessary, gas platinum acid, platinum-olefin complex, platinum-carbonyl vinyl methyl complex (Ossko catalyst), platinum-divinyl tetradecyldioxane A platinum-based catalyst such as a complex (Kamedt catalyst) is used as a catalyst, and the reaction is carried out at a reaction temperature of 2 Torr to 130 ° C, preferably 5 Torr to 8 Torr, and after the reaction is completed, the solvent is subjected to a solvent. Steam (4) under reduced pressure, and obtain the target from the reaction solution. The carboxyl group of the compound DAC can be protected by a protecting group such as a third butyl group as in the case of the compound 1AS and the compound 1CS, as shown in the above formula (la). Further, the compound protected by the protecting group can be subjected to the hydrazine hydrogenation reaction in the same manner as the unprotected compound, and the protective group can be removed by the same method as in the case of the compound ias and the compound 1CS. When the mass average molecular weight of the component (A) of the present invention is too small, there is a case where the film forming property is poor when a positive resist is formed by using a positive photosensitive composition of 144043.doc •16·201030468, and when it is too large, it exists. The solubility or dispersibility of the alkaline developing solution is lowered, and the anti-caries agent residue on the surface of the substrate after the in-situ development is increased, and the industrial applicability such as workability and efficiency is the present invention. The mass average molecular weight of the component A) is preferably from 600 to 50,000, more preferably from 800 to 20,000, most preferably from 1,000 to 10,000. In the present invention, the mass average molecular weight refers to polyphenylene when GPC (Gel Permeation Chromatography) analysis is carried out using tetrahydrofuran (hereinafter referred to as THF (tetrahydrofuran)) as a solvent.质量 Converted mass average molecular weight. The number of the groups represented by the formula (1) contained in the component (A) of the present invention is preferably from 2 to 300, more preferably from 4 to 250, per molecule. It is 6~200. Further, the amount of the group represented by the formula (1) contained in the component (A) of the present invention is preferably from 1 to 60% by mass, more preferably from 3 to 55% by mass, most preferably 5 to 50% by mass. In the aspect of improving the adhesion of the permanent resist of the present invention, the component (A) of the present invention preferably further has at least one group represented by the following formula (2) in one molecule: (wherein R3 represents an alkylene group having 1 to 10 carbon atoms which may have a substituted hydrocarbon group, and R4 144043.doc -17- 201030468 represents a burning group of carbon number 1 to 4 'c represents 0 or 1 to 4 The number, d represents the number of 1 to 3, but c + d does not exceed 5). In the above formula (2), R3 represents an alkylene group which may have a carbon number of the substituted hydrocarbon group. The alkylene group having a carbon number of 1 to 1 Å may, for example, be an alkylene group exemplified by Ri. In terms of ease of industrial availability, it is preferred to extend an ethyl group, a propyl group and a butyl group. Preferred are ethyl and butyl groups, and the most preferred ones are ethyl groups. The substituted hydrocarbon group which may be contained in R3 may, for example, be a hydrocarbon group exemplified as R1. However, in terms of heat resistance, it is preferred to have no substituted hydrocarbon group. R1 and R3 may be the same or different. Spring R4 represents an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having a carbon number of 丨4 include an alkyl group exemplified by R2. R4 is preferably an alkyl group having 1 to 3 carbon atoms in terms of heat resistance, more preferably a methyl group and an ethyl group, and most preferably a methyl group. R2 and R4 may be the same or different. c represents 0 or 1 to 4, and d represents the number of Bu 3, but c + d does not exceed 5. When 〇 is a number of 2 to 4, R4 may be the same alkyl group or a different alkyl group. In terms of heat resistance, what is good is the number of... and then the better. In terms of the ease of industrial acquisition, 'd is preferably the number of Μ 2, and φ is preferably 1. The position of the divalent radical group represented by the above formula (2) is not particularly limited. The preferred phenolic hydroxyl group is located in the para position with respect to R4 in terms of improvement in heat resistance. The component (4) having a group represented by the above formula (2) can be produced by the following method or the like: a compound 1AS or a compound core and an alkoxylated compound having a group represented by the above formula (7) (below The compound 144043.doc -18-201030468 2AS) or the gas stone compound (hereinafter referred to as the compound 2cs) is subjected to hydrolysis and condensation reaction; or the compound DAC and the carbon-carbon double having reactivity with the Si_H group are contained. A compound having a bond and a phenolic hydroxyl group (hereinafter referred to as a compound DAH) is subjected to a hydrogenation reaction with a compound having at least two Si-H groups in one molecule. First, a method of subjecting the compound 1AS or the compound 1CS to the compound 2AS or the compound 2CS to carry out a hydrolysis/condensation reaction will be described. In the compound 2AS, R3 is an ethyl group, c=〇, d=l, and a hydroxyl group is contained in the para position. For example, 2-(4-hydroxyphenyl)ethyltrimethoxysulfonate is exemplified, a trialkoxynonane such as -(4-hydroxyphenyl)ethyltriethoxydecane; 2-(4•hydroxyphenyl)ethyldimethoxymethylnonane, 2_(4-hydroxyphenyl) Ethyldiethoxymethyl sinter, 2-(4-phenylphenyl)ethyldimethoxyethyl decane, 2-(4-hydroxyphenyl)ethyldiethoxyethyl decane , 2-(4-hydroxyphenyl)ethyldimethoxypropyl decane, 2-(4-hydroxyphenyl)ethyldiethoxypropyl decane, 2-(4-hydroxyphenyl)ethyl Methoxybutyl oxime, 2-(4-hydroxyphenyl)ethyldiethoxybutyl decane, 2-(4-hydroxyphenyl)ethyldimethoxyisobutyl sulphate, 2-( 4-Phenylphenyl)ethyldiethoxyisobutylnonane, 2-(4-hydroxyphenyl)ethyldimethoxycyclohexyldecane, 2-(4-hydroxyphenyl)ethyldiethyl a dialkoxy decane such as oxycyclohexyldecane; 2-(4-hydroxyphenyl)ethylmethoxydimethyl decane, 2-(4-hydroxyphenyl)ethyl B Dimethyldecane, 2-(4-hydroxyphenyl)ethylmethoxydiethyldecane, 2-(4-hydroxyphenyl)ethylethoxydiethyldecane, 2-(4-hydroxyl Phenyl)ethylmethoxydipropylnonane, 2-(4-hydroxyphenyl)ethylethoxydipropylnonane, 2-(4-hydroxyphenyl)ethylmethoxydibutyl 144043 .doc •19- 201030468 decane, 2-(4-hydroxyphenyl)ethylethoxydibutylnonane, 2-(4-diphenylphenyl)ethylmethoxydiisobutylnonane, 2-( 4-hydroxyphenyl)ethylethoxydiisobutyl decane, 2-(4-hydroxyphenyl)ethyl decyloxybicyclohexyl pulverization, 2-(4-phenylphenyl)ethyl b A single-burning oxygen-alkali burning type such as oxydicyclohexyl sulphate. Among these compounds, 2-(4-hydroxyphenyl)ethyltrimethoxydecane, 2-(4-pyridylphenyl) is preferred in terms of good reactivity and also good heat. Ethyl triethoxy zeoxime, 2-(4-phenylphenyl)ethyldimethoxymethyl decane, 2-(4-hydroxyphenyl)ethyldiethoxymethyl zeshi '2-(4-Hydroxyphenyl)ethyldimethoxyethyl decane, 2-(4-hydroxyphenyl)ethyldiethoxyethyl decane, 2-(4.hydroxyphenyl)ethyl three曱 石 夕 、, 2-(4-amino group-based) ethyl triethoxy oxy-burning, and further preferably 2-(4-pyridylphenyl)ethyl ruthenium oxylate, 2- (4-Phenylphenyl)ethyldimethoxyoxydecyl '' 2-(4-hydroxyphenyl)ethyldimethoxyethyl oxime 'The best is 2-(4-hydroxyphenyl) Ethyltrimethoxy decane, 2-(4-diphenylphenyl)ethyldimethoxydecyldecane. The compound 2AS may be used alone or in combination of two or more. In the compound 2CS, 'when R3 is an exoethyl group, c=〇, d=l', and a hydroxyl group is contained in the para position, for example, 2-(4-hydroxyphenyl)ethyl trioxane or the like may be mentioned. Hydranes; 2-(4-hydroxyphenyl)ethylbis gas decane, 2-(4-hydroxyphenyl)ethyldioxaethyl decane, 2-(4-hydroxyphenyl)ethyldichloropropyl Wonderful burning, 2-(4-hydroxyphenyl)ethyldicyclobutyl decane, 2·(4-hydroxyphenyl)ethyldiisobutylene, 2-(4-pyridylphenyl) Dioxanes such as dicyclohexyl ketone; 2-(4-hydroxyphenyl)ethyl dimethyl hydrazine 144043.doc -20- 201030468 alkane 2 (4 light base) ethyl urethane Ethyl; ^, 2-(4-phenylphenyl)ethyl chloride: hydroxy, 2, (tetra)phenyl) ethyl dibutyl, 2 (4 & phenyl) ethyl Diisobutyl ketone, 2_(4-hydroxyphenyl)ethyl, dicyclohexyl sulphate, etc.

In the X-specialized σ, in terms of good reactivity and good thermal properties, 'better is 2·(4-hydroxyphenyl)ethyltrioxane, 2-(4-hydroxybenzene). Ethyldichlorodecyl decane, 2·(4-hydroxyphenyl)ethyldichloroethyl decane, more preferably 2_(4-hydroxyphenyl)ethyltrioxane, 2_(4- The basic base) ethyl dihistyl sulfite is burned. The compound 2CS may be used alone or in combination of two or more. In the hydrolysis/condensation reaction of the compound 2AS or the compound 2CS, it is preferred to use the compound 2AS as an alkoxydecane compound in terms of easy control of the reaction and removal of by-products. The order of the reaction of the compound 2AS or the compound 2CS is not particularly limited, and the compound ASAS or the compound iCS may be reacted, and then the compound 2AS or the compound 2CS may be reacted, or the reverse order may be used, and the compound 1 may also be used. The reaction is carried out by mixing AS or Compound 1CS with Compound 2AS or Compound 2CS. The phenolic hydroxyl group of the compound 2AS or the compound 2CS can be visually required as shown in the following formula (2a) [Chemical 6]

(2β) 144043.doc • 21- 201030468 (wherein R3, R4, and c^d have the same meanings as in the above formula (7).) As shown, it is protected by a third butyl ether group as a protective group. The protected sigma can be subjected to a fragmentation hydrogenation reaction in the same manner as the unprotected compound, and the protective group can be removed by the same method as in the case of the compound 1AS and the compound iCS. Next, a method of subjecting the compound DAC and the compound DAH to a hydrazine hydrogenation reaction with a compound having at least two Si-H groups in one molecule will be described. Examples of the compound DAH include 2-vinyl phenol, 3·vinyl phenol, 4-ethylene phenol, 4-(1-phenylvinyl) phenol, and 2 fluorenyl 4-vinyl phenol. , 2-allylphenol, 3-allylphenol, 4-dipropyl propyl, 2-isopropylisoben, 3-isopropylthiophene, 4-isopropenylphenol, 4-( 3-butenyl)phenol, 4-(4-pentenyl)benzene, 4-(5-hexenyl)phenol, 4-(6-heptenyl)phenol, 4-(7-octyl) Phenol, 4_(8-decenyl)benzene, 4-(9-fluorenyl)benzene, 2-ethylene-1,4-dipyridyl, 5-vinyl-1,3- Dihydroxybenzene and the like. Among these compounds, in terms of industrially readily available aspects and heat resistance of the permanent anti-surplus agent of the present invention, 2-ethylene benzene is inspected, 3-ethene benzene is expected, and 4- Vinyl benzene, 2-propyl benzene, 4- propyl phenyl, 2-isopropyl benzophenone, 4-isopropyl benzophenone, and more preferably 2-ethenyl benzene Hope, 4-vinyl benzene, the best is 4-vinyl benzene. The compound DAH may be used alone or in combination of two or more. Further, the order of the hydrazine hydrogenation reaction of the compound DAC and the compound DAH with a compound having at least two Si-H groups in one molecule is not particularly limited, and 144043.doc •22· 201030468 can be carried out in the order of the compound DAC-compound DAH. The reaction may be carried out in the reverse order, and the compound DAC may be mixed with the compound DAH to carry out a reaction. Further, the phenolic hydroxyl group of the compound DAH may be protected by a third butyl ether group as a protective group as shown in the above formula (2a). The compound protected by the protecting group can be subjected to a hydrogenation reaction in the same manner as the unprotected compound, and the protecting group can be removed by the same method as in the case of the compound 1AS and the compound 1CS. The content of the base represented by the above formula (2) is preferably from 0 to 80, more preferably from 1 to 10, based on the molar ratio of the group represented by the above formula (1). 70, the best is 2~60. In the aspect of improving the thermal crosslinkability of the positive photosensitive composition of the present invention, the component (A) of the present invention preferably further has a decyl group. As a method of introducing a sterol group, for example, a method of introducing a trialkoxy sulfonium alkyl compound or a trihaloalkylene compound into a hydrolysis/condensation reaction can be mentioned. The sterol group is liable to cause a condensation reaction, and the content of the sterol group decreases as the operation proceeds. Therefore, when the hydrolysis/condensation reaction is carried out in a solvent, it is preferred that the product is not isolated and the solvent is concentrated. Or use it as needed to replace it with other solvents. • Hereinafter, a method of introducing a sterol group or a method of increasing the content of a sterol group will be described based on each production method of the component (A). In the case of producing the component (A) by a method of subjecting the compound 1AS or the compound 1CS to a hydrolysis/condensation reaction, a method of introducing a sterol group can be carried out by using a trialkoxydecane as the compound 1 AS and using three gases. The decane compound is introduced as a compound 1CS to a sterol group. In the trialkoxy decane 144043.doc -23· 201030468, two alkoxyfluorenyl groups are hydrolyzed. The condensation reaction forms a bond of si-〇-Si, and one alkoxyalkyl group becomes a sterol. base. Similarly, in the trichloromethane compound, two gas alkyl groups undergo hydrolysis and condensation reaction to form a bond of Si_O-Si, and one gas alkyl group becomes a sterol group. If the compound having a large content of the alcoholic group is isolated, the dehydration reaction of the lyophilized substrate is liable to form a bond of Si-0-Si, and the content of the sterol group is lowered. Therefore, after the reaction, the product is not isolated, but The solvent is concentrated or the solvent is replaced with a solvent thereof, whereby the sterol group content can be increased. Even if a dialkoxyzepine compound is used as the compound 1 AS and a dioxane compound is used as the compound 1CS, the number of sterol groups cannot be increased, but the volatile component can be reduced by increasing the molecular weight of the component (A). Further, when the compound 1AS or the compound 1CS is subjected to a hydrolysis/condensation reaction, the content of the sterol group can be increased by using another trialkoxysulfonyl group compound, and the molecular weight of the component (A) is increased, and the volatile component is decreased. it is good. In this case, although the dialkoxydecane compound does not increase the sterol group, the volatile component is reduced by the increase in the molecular weight of the component (A), so that it can be used in combination. Examples of the other trialkoxy decane or dialkoxy decane include an alkyl alkoxy decane compound, a cycloalkyl alkoxy decane compound, an aryl alkoxy decane compound, and an arylalkyl alkoxy decane. In the aspect of improving the heat resistance and the adhesion of the permanent resist of the present invention, the aryloxyalkyl oxalate compound is further preferably represented by the following formula (4). Alkoxy alkane compound···················· R12 represents an alkyl group of carbon number 3, Rn represents an alkyl group of 1 to 4 carbon atoms which may be the same or different, f represents a number of 2 to 3, and g represents a number of ruthenium or ruthenium.

The alkyl alkoxydecane compound may, for example, be mercaptotridecyldecane, methyldiethoxydecane, ethyltrimethoxydecane, ethyltriethoxydecane or propyltrimethoxydecane. , propyl triethoxy decane, isopropyl dimethoxy decane, isopropyl triethoxy decane, butyl trimethoxy decane, butyl triethoxy decane, isobutyl trimethoxy decane , an alkyltrialkoxy decane compound such as isobutyltriethoxy sinter, a second butyl dimethoxy sinter, a third butyl triethoxy decane, or a dimethyl di decyl oxide , Dimercaptodiethoxydecane, diethyldimethoxydecane, diethyldiethoxydecane, dipropyldimethoxydecane, dipropyldiethoxydecane, diisopropyl Dimethoxy decane, diisopropyl diethoxy decane, dibutyl methoxy oxime, monobutyl diethoxy, diisobutyl dimethoxy decane, diisobutyl Dialkyldialkoxyalkylation of diethoxydecane, di(t-butyl)dimethoxy decane, di(t-butyl)diethoxydecane Examples of the cycloalkyl group-containing alkoxylated compound include a cycloalkyltrial alkoxy decane compound such as cyclohexyl group, anthracene oxime or cyclohexyltriethoxydecane, and dicyclohexyl dimethyl hydride. a cycloalkyl azolyl oxide compound such as oxydecane, dicyclohexyldiethoxy sinter, cyclohexyl (methyl) diethoxy sinter; as an arylalkyl alkoxy decane compound, Listed: arylalkyltrialkoxydecanes such as benzyl trimethoxydecane, benzyltriethoxydecane, 144043.doc •25- 201030468 Compound, dibenzyldimethoxy decane, dibenzyldiethoxy An arylalkyldialkoxydecane compound such as a decane or a benzyl (indenyl) dimethoxydecane. Examples of the aryl alkoxydecane compound represented by the above formula (4) include phenyltrimethoxydecane, phenyltriethoxynonane, fluorenyltrimethoxydecane, and diterpene. Phenyl trimethoxy decane, cumyl trimethoxy decane, tert-butylphenyl triethoxy decane, phenyl decyl dimethoxy decane, phenyl methyl diethoxy decane, hydrazine Phenylmethyl dimethyl decyl decane, diphenyl phenyl dimethyl decyl decane, cumyl methyl dimethoxy decane, phenyl ethyl decyl decane, phenyl propyl Dimethoxydecane, phenylbutyldimethoxydecane, phenylhexyldimethoxydecane, phenylcyclohexyldimethoxyoxydecane, phenyldianonylmethoxydecane, and the like. Among these compounds, phenyltrimethoxydecane, phenyltriethoxydecane, phenylmethyldimethoxydecane, and phenyl are preferred in terms of heat resistance and adhesion. Further, decyldiethoxydecane is further preferably phenyltrimethoxydecane and phenyltriethoxydecane, and most preferably phenyltrimethoxydecane. Further, as a method of producing a component (A) by a method in which a compound DAC is subjected to a hydrogenation reaction with a compound having at least two Si-H groups in one molecule, a method of introducing a sterol group is a method of introducing a compound DAC. Part of the substitution is carried out by a hydrazine hydrogenation reaction with another alkoxydecane compound having a carbon-carbon double bond having reactivity with a Si-H group (hereinafter referred to as a compound DS), and the obtained product and the above other trialkoxy A decane or a dialkoxy decane (preferably an aryl alkoxy decane compound represented by the above formula (4)) is subjected to hydrolysis and condensation reaction at 144043.doc -26 to 201030468, whereby a ruthenium is obtained. An alcohol-based component. In order to increase the content of the sterol group, after the hydrolysis and condensation reaction, the product is not isolated, and the solvent is concentrated or the solvent is replaced with another solvent.仃# As the compound DS, there may be mentioned: trimethoxyvinyl decane, trimethoxy allylic decane, trimethoxy isopropenyl decane, trimethoxy + butyl sulphate, trif oxy -4- _ Dilute (tetra), trimethoxy _5_ pentyl decane, dimethoxy-6-heptenyl decane, tridecyloxy-7-octenyl decane, dimethoxy-8-nonenyl decane , trimethoxy-9-nonenyl decane, triethoxy vinyl decane, triethoxy allylic decane, triethoxy isopropenyl decane, triethoxy -3- butylene decane, Triethoxypentenyl decane, triethoxy _5-hexenyl decane, triethoxy -6-heptenyl decane, diethoxy-7-octenyl decane, triethoxy _ 8_decenyl decane, triethoxy-9-nonenyl decane, dimethoxy fluorenyl vinyl decane, dimethoxyethyl vinyl decane, dimethoxy propyl vinyl decane, two Methoxyisopropyl vinyl decane, methoxy dimethyl vinyl decane, methoxy diethyl vinyl decane, and the like. Among these compounds, preferred are trimethoxyvinylnonane, triethoxyvinylnonane, trimethoxyallyldecane and dimethoxy in terms of heat resistance and adhesion. Methyl vinyl decane is further preferably trimethoxy ethane decane and triethoxy vinyl decane, and most preferred is dimethoxy vinyl decane. The compound 〇8 may be used alone or in combination of two or more. The content of the sterol group in the (Α) component is preferably from 1 to 3 % by mass based on the content of oh, and more preferably from 3 to 25 parts by mass. /〇, the best is 5~2 enamel 144043.doc -27- 201030468%. The method for quantifying the sterol group of the component (A) of the present invention is exemplified by a method in which a sterol group is subjected to trimethylsulfanization using trimethyl gas oxime or the like, and the amount of weight increase before and after the reaction is quantified ( TMS (trimethylsilyl, trimethylsilyl) method; by using a near-infrared spectrophotometer (refer to Japanese Patent Laid-Open No. Hei 2 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 2003 2003 2003 2003 2003 2003 2003 2003 2003 2003 2003 2003 2003 2003 2003 2003 2003 2003 2003 2003 The method of quantitative analysis by machine analysis of 29si-NMR (refer to Japanese Patent Laid-Open Publication No. 2007-217249, etc.). The component (A) of the present invention is preferably made by the following formula (3) [Chemical 8]

The carbon number of the base is 1~1〇, and R2 and R4 are the same or different calcined carbon number 1~4, and R5, R6 and R7 are the same or different carbon numbers 1~10. Alkyl or phenyl. a represents 〇 or the number of 1 to 4, and b represents the number of 1 to 3, but a+b does not exceed 5. c represents 0 or 1 to 4, and d represents the number 1 to 3 'but c + d does not exceed 5. R9 represents an alkyl group or a cycloalkyl group having 1 to 6 carbon atoms which may be the same or different. ' R G represents an alkyl group having 1 to 3 carbon atoms, and e represents the number of i to 3. m, n &p represents 111 . 11 . P=1 : 0~2 : 0.5~3&m+n+p=3~6. An anthracene resin obtained by reacting a cyclic oxirane compound represented by the above aryl group 144043.doc -28-201030468 alkoxydecane compound represented by the above formula (4). In the above formula (3), the parts derived from the above formula (1) and formula (2), that is, R1, R2, R3 and R4 and a, b, c and d 'the formula (1) and The description of formula (2) is suitable for application. R8 may be the same or different and represents an alkylene group having 1 to 10 carbon atoms which may have a substituted hydrocarbon group, and R5, R6 and R7 represent an alkyl group or a phenyl group which may be the same or different and have a carbon number of 1 to 10. R9 represents an alkyl group or a cycloalkyl group having 1 to 6 carbon atoms which may be the same or different, and R1Q represents an alkyl group having 1 to 3 carbon atoms.

❹ The alkylene group having a carbon number of 1 to 10 may, for example, be an alkylene group exemplified by R1, and the substituted hydrocarbon group which may be represented by R8, and a hydrocarbon group exemplified by R1 may be mentioned as an alkyl group having 1 to 10 carbon atoms. The base may, for example, be methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, tert-butyl, pentyl, second pentyl, third pentyl, hexyl, Heptyl, octyl, isooctyl, 2-ethylhexyl, second octyl, decyl, isodecyl, fluorenyl, as alkyl having 1 to 6 carbon atoms, exemplified by R15, Ri6 and exemplified The alkyl group may, for example, be a cyclopentyl group, a cyclohexyl group, a methylcyclopentyl group or a cyclopentyl fluorenyl group as the alkyl group having a carbon number of 1 to 3, and examples thereof include a methyl group and an ethyl group. Propyl, isopropyl. In terms of ease of industrial availability, Rl, r3 & rS are preferably ethyl, propyl and butyl, and more preferably ethyl and butyl, most preferably ethyl . In terms of ease of industrial availability, it is preferred that r5, r6 and R7 are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl and phenyl groups in terms of heat resistance. In terms of improvement, t, R5 r6 and f" and preferably thiol, ethyl and phenyl, preferably methyl. In terms of improvement, R9 is preferably a methyl group or an ethyl group, and is preferably a methyl group as compared with 144043.doc -29-201030468. In terms of improvement in heat resistance, R10 is preferably a methyl group. The ruler e represents the number of 1 to 3, and m, η and p represent m : ^ : p = 1: 〇 〜 2 : 〇 5~3 and m + n + p = 3 to 6. The cyclic siloxane compound represented by the formula (3) may be used alone or in combination of two or more. When two or more kinds are used in combination, the number of m, η, and P is an average number. For example, an equimolar mixture of a compound of m=l, n==〇, P=3 and a compound of m=1, n=1, p=2 can be expressed as m : n : p=l : 〇·5 : 2.5 . The η is preferably 0.01 to 0.7, more preferably 〇.02 to 〇·5, in terms of chemical resistance improvement after high temperature heat history. Further, in terms of improvement in thermal crosslinkability of the positive photosensitive composition of the present invention, ρ is preferably at least 2 in number. The cyclic siloxane compound represented by the above formula (3) can be a cyclic oxirane compound represented by the above formula (6), a compound DS, a compound DAC, a compound DS, and the like. The compound DAH was produced by hydrogenation of hydrazine. The cyclic siloxane compound represented by the formula (3) may be the same or a mixture of several kinds. In this case, a plurality of molecules derived from the cyclic siloxane compound represented by the general formula (3) are present in the molecule of the oxime resin, and the values of m, η, and ρ of the general formula (3) become The average value in the molecule. A compound which is protected by a tert-butyl group or a desired hydroxyl group by a third butyl group or the like can be used, for example, the following formula (3a) [Chemical Formula 9] 144043.doc -30- 201030468

The cyclic oxoxane compound represented by the above formula (3) is substituted for the cyclic oxirane compound (3) represented by the above formula (3), and the cyclic oxirane represented by the above formula (3a) is used. After reacting the compound with the arylalkoxydecane compound represented by the above formula (4), the tributyl group is removed, and the oxime resin which is the component (A) of the present invention can be obtained. Next, the oxyhydrogenated compound having a glycidyl group as the component (B) of the present invention will be described.

The meaning is the same. The glycidyl group having a glycidyl group as the component (B) of the present invention has at least one glycidyl group and at least one nonoxylalkyl group in one molecule (the group represented by Si-〇_Sl) ). The number of glycidyl groups is preferably at least 2 in the range of 1 molecule, and the glycidyl group-containing oxirane compound is exemplified by the following formula:

(7) wherein Y represents a group having a glycidyl group or a fluorenyl group, and G represents a fluorenyl group or a phenyl group having a condensed 144043.doc -31 - 201030468,

^Teach, W means 〇~1000 hydroglyceryl base' R21 means the same or no R22, R23 number 5~6 of 3 _. Wherein, when U is 〇 or 1, 'γ represents a linear siloxane compound represented by a hydrogen atom, and has the following general formula (8) [Chem. 11]

(wherein R25, R26 and R represent an alkyl group which may be the same or different carbon number, a cycloalkyl group having a carbon number of 5 to 6 or a phenyl group, G represents a group having a glycidyl group, and X represents a group of 2 to 6 The number y represents the number of 〇~4 in which x + y is 3 to 6). The cyclic oxirane compound represented by the above, and the hydrolysis 'condensation reaction product of the alkoxy decane having a glycidyl group. First, the linear oxy-oxygen compound represented by the above formula (7) will be described. In the above formula (7), γ represents a group having a glycidyl group or a fluorenyl group, and G represents a group having a glycidyl group, and represents a fluorenyl group or a phenyl group which may be the same or different, and R, R23 and R24 represent The same or different alkyl groups having 1 to 6 carbon atoms, cycloalkyl groups having 5 to 6 carbon atoms or phenyl groups. In terms of ease of manufacture, R21 is preferably a methyl group. Examples of the alkyl group having 1 to 6 carbon atoms and the cycloalkyl group having 5 to 6 carbon atoms include R15 and the exemplified groups. In terms of ease of manufacture, R22 is preferably fluorenyl and 144043.doc • 32- 201030468 ethyl, and more preferably methyl. With respect to the heat resistance of the permanent resist of the present invention, 5, R 3 and r 24 are preferably a methyl group, an ethyl group and a phenyl group, and further preferably a methyl group and a stupid group, and most preferably a methyl group. X represents no hydrogen atom or sulfhydryl group. U represents the number of bbs. 'W represents the number of 〇~1000'. When u is 0 or 1, X represents a hydrogen atom. The linear oxysulfide compound represented by the general formula (7) can be obtained by the above formula (by using a ruthenium ruthenium containing a carbon-carbon double bond having a reactivity with a Si_H group and a glycidyl group) 5) The linear compound shown is produced by a hydrogenation reaction of 9. 'Compounds containing a carbon-carbon double bond and a glycidyl group having reactivity with a Si_H group' include, for example, vinyl glycidol, propyl glycidyl hydrazide, and 5-glycidoxypropyl _2 (IV) Among the primary olefins and the like, it is preferred that propylene propyl glycidin is used in terms of ease of industrial availability and reactivity with dream hydrogenation. When the ratio of the epoxy group in the molecule of the material is too small, the effect of the cross-linking in the molecule is less, and the physical properties of the permanent resist of the present invention are lowered, so the formula () The epoxy equivalent of the linear siloxane compound is preferably hereinafter preferably more than 700, and most preferably 350 or less. Furthermore, 喟^ "月衣巩篁, refers to the value obtained by dividing the molecular weight by the number of decyl groups, that is, the molecular weight corresponding to one ring rolling base. The molecular weight of the linear peptide-like oxyalkylene compound represented by the above formula (7) is particularly limited, but when it is too large, the solubility or the dispersibility of the alkaline developer is lowered. In the case of in-situ development, the residual resist residue remains on the surface of the substrate after the nozzle is applied. Therefore, the mass average molecular weight is preferably 20,000 or less, and is preferably 144043.doc • 33· 201030468 and preferably 15,000 or less. The best is below 10,000. Then, the cyclic siloxane compound represented by the above formula (8) will be described. In the above formula (8), R25, R26 and R27 represent an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms or a phenyl group which may be the same or different, and G represents a glycidyl group. base. Examples of the alkyl group having a carbon number of 66 and the cycloalkyl group having 5 to 6 carbon atoms include an alkyl group and a cycloalkyl group exemplified by R15, R and 6 and Rn. In terms of ease of manufacture, R25 is preferably an alkyl group having a carbon number of 6, and more preferably a methyl group and an ethyl group, and most preferably a methyl group. Further, in terms of the heat resistance of the permanent resist of the present invention, R26 and R27 are preferably a methyl group, an ethyl group and a phenyl group, and more preferably a mercapto group and a phenyl group, and the most preferable. It is 曱基. The X table does not have a number of 2 to 6, and y indicates that x + y becomes 3 to 6 〇 ~ 4 number. In terms of industrially readily available, x + y is preferably 4 to 6, more preferably 4 to 5, and most preferably 4. Also, y is better. The cyclic oxime oxy-compound compound represented by the above formula (8) can be obtained by the above formula (2) by using a ruthenium complex having a carbon-carbon double bond and a glycidyl group having reactivity with an osmium group. 6) The cyclic compound shown is produced by a hydrogenation reaction. Next, the hydrolysis/condensation reaction of the alkoxylate having a glycidyl group will be described. . The hydrolysis-condensation reaction method of the ethoxylated group of the ethoxylated ethoxylates, for example, the compound described in the hydrolysis/condensation reaction of the compound 1 AS or the compound 1CS, has a glycidyl group. The alkoxy decane is introduced into 144043.doc -34· 201030468. The compound obtained by the hydrolysis/condensation reaction. Examples of the activating oxyalkyl group having a glycidyl group include glycidyl alkoxy decane compounds such as glycidyl trimethoxy decane and glycidyl triethoxy decane; and 2-glycidoxyethyl group; Triglycidyl sulphate, 2-glycidoxyethylmethyldimethoxydecane, etc., glycidyloxyethyl oxalate, compound, 3-glycidoxypropyltrimethoxy oxetane , 3-glycidoxypropylmethyldimethoxydecane, 3-glycolate, oxypropylethyldimethoxyoxydecane, 3-glycidoxypropyl stupyl-methoxyxide Calcined, bis(3-glycidoxypropyl) decyloxycarbazide, 3-glycidoxypropyltriethoxy sulphur, 3-glycidoxypropylmethyldiethoxydecane , 3-glycidoxypropylethyldiethoxylate, 3-glycidoxypropylphenyldiethoxydecane, bis(3-glycidoxypropyl)diethoxydecane 3_glycidoxypropyl alkoxy oxime compound; 2-(4-glycidoxyphenyl)ethyltrimethoxy chopped 2-(4-glycidoxyphenyl)ethyltriethoxy oxalate, etc. 2_(4_glycidyl _ 'from oxyphenyl)ethyl oxalate compound; 5-(glycidol) Oxymethyl) thiol-dimethoxy zeoxime, 6-(glycidyloxy fluorenyl) thiol-dimethoxy decane, etc. glycidyloxymethylnorbornyl alkoxy oxane Wait. Among these compounds, a 3-glycidoxypropyl alkoxydecane compound is preferred in terms of the reactivity of the hydrolysis, the condensation reaction, and the ease of industrial transfer. Among the 3 - glycidoxypropyl alkoxy decane compounds, more preferably 3 · glycidoxypropyl trimethoxy decane, 3 - glycidoxypropyl methyl decyloxy decane, double (3-glycidyloxy 144043.doc -35· 201030468 propyl)dimethoxydecane, 3' glycidoxypropyltriethoxydecane, and more preferably 3-glycidoxypropyl Trimethoxy zeoxime, % glycidoxypropyl triethoxy zeoxime, and most preferred is 3' glycidoxypropyl trimethoxy decane. In the case of producing a glycidyl group having a glycidyl group, hydrolysis or condensation reaction. In the case of the product, in addition to the alkoxy decane having a glycidyl group, other anthracene oxides having no glycidyl group may be used in combination. Compound. The other alkoxydecane compound may be exemplified as the other exemplified by the method of introducing a sterol group or the method of increasing the content of the linalool group, and the other three alkoxylates or a dialkoxy decane. Hydrolysis of glycidyl group-containing alkoxy decane. The proportion of epoxy groups in the molecule of the condensation reactant is too small _ 'There is less crosslinking effect, and the physical properties of the permanent resist of the present invention are lowered, so epoxy The equivalent is preferably 1,000 or less, more preferably 700 or less, and most preferably 35 or less. The molecular group of the hydrolysis-condensation reaction product of the glycidyl group-containing alkoxysilane is not particularly limited, but when it is too large, the dissolution of the alkaline developer is good or the knife-off property is lowered, and the surface of the substrate after the development is inspected. In the case where the resist remains as a slag, the mass average molecular weight is preferably 20,000 or less, more preferably 15,000 or less, and most preferably 10,000 or less. Hydrolysis of a glycidyl group having a glycidyl group. The condensation reactant preferably has a decyl group. The content of the sterol group in the hydrolysis/condensation reaction of the alkoxysilane having a glycidyl group is preferably 丨% by mass, more preferably 3 to 5% by mass. A glycidyl group-containing alkane having a dialkoxy decane compound for use in the reaction 144043.doc • 36- 201030468 Hydrolysis of a oxetium. The condensation reactant is present in a parent-linked structure caused by a Si-0-Si bond. In some cases, there are cases in which, for example, a ladder-like shape, a cage shape, a ring shape, or the like is formed due to the crosslinked structure. The hydrolysis/condensation reaction product of the glycidyl group-containing alkoxysilane having a glycidyl group-containing trialkoxy decane compound and another trialkoxy decane compound can be represented, for example, by the following formula (9). : [Chemical 12] 10 [G-SiOXi 丨 丨 ( (10) 攀 (10) 丄 (8) (wherein G represents a glycidyl group, and R28 represents an alkyl or benzene having the same or different carbon number of 1 to 10 Base, i represents a number of 2 or more, k represents 〇 or a number of 1 or more, h represents the number of 〇~2, and 』 represents the number of 〇~2, where hxi+jxk does not exceed h+i+2). In the above formula (9), G represents a group having a glycidyl group, and R28 represents an alkyl group or a phenyl group which may be the same or different in carbon number i to 1 Å. In terms of heat resistance, R28 is preferably a mercapto group, an ethyl group and a phenyl group, and further preferably a methyl group and a phenyl group are most preferably a methyl group. i represents a number of 2 or more, k represents 〇 or a number of 1 or more, and h represents the number of 〇~2. Hxi+jxk represents the total amount of sterol groups in the molecule, but the number does not exceed h+i+2. The first half of the above formula (9) [Chemical 13] {6_Si0(3>w/2<0H)hj is derived from a moiety having a glycidyl group of a trialkoxy decane compound, 144043.doc -37- 201030468 The latter part of the general formula (9) [Chem. 14] [RLSiO (tetra) contact system is derived from the other trialkyloxydecane compound. With respect to the glycerol group, it is preferred that the chemical resistance after the high temperature heat history is improved (A) 100 parts by mass of the oxime resin, and the content of the reduced siloxane compound as the component (B) Preferably, the dip is (8) parts by mass, and the 疋3 to 50 parts by mass is preferably 5 to 2 parts by mass. Next, the diazonaphthoquinones which are the components (C) of the present invention will be described. . The diazonaphthoquinone which can be used in the present invention is not particularly limited as long as it is a diazonaphthoquinone compound which is known to be used for a photosensitive material, and among them, a hydrogen atom having a phenolic hydroxyl group is preferred. The following formula (1〇) [Chem. 15]

Substituted compound (4-diazonaphthalene styrene) or by the following formula (u) [Chem. 16]

Substituted compound (5-diazonaphthoquinone sulfonate). 144043.doc • 38 - 201030468 As a preferable specific example of the diazonaphthoquinones, for example, the compounds represented by the following formulas (12) to (17), the positional isomers, and the like can be exemplified. [Chem. 17]

0-Q (wherein Q is a group represented by the above formula (10) or formula (11) or a hydrogen atom, and not all of them are hydrogen atoms.) [Chem. 18]

(13) (wherein Q is a formula (10) or a formula (1) and not all of them are a gas atom.) A base or a nitrogen atom

Ub 19]

(1 4) (wherein '(10) is in the above formula (Η)) or a formula (and not all of them are a hydrogen atom). A base or a hydrogen atom, [Chem. 20] 144043.doc -39. 201030468

(1 5 > (wherein Q inflammation, a group or a hydrogen atom is represented by the above formula (10) or formula (U) and not all of them are hydrogen atoms.) [Chem. 21]

(1 6) The base or hydrogen atom 弋 Q is in the above formula (10) or formula (11) and is not all hydrogen atoms. q.0〇-C~^-0-Q (17) QO 〇-〇 (wherein Q is a group represented by the above formula (10) or formula (1)) or a chlorine atom, and All are hydrogen atoms. The base represented by the formula (10) has absorption in the region of the 丨 line (wavelength of 365 nm) and is suitable for 1-line exposure, and the base represented by the formula (11) has absorption in a wide range of wavelength regions, so For exposure at a wide range of wavelengths, it is preferred to select one of the groups represented by the formula (1) and the group represented by the formula (11) depending on the wavelength of the exposure. In terms of developability and fine workability of the permanent anti-surname agent of the present invention, it is preferable that the content of the diazonaphthoquinone as the component (C) is 相对 with respect to 100 parts by mass of the (A) oxime resin. 1 to 1 〇 份 份, preferably 1 to 5 144043.doc 201030468 Next, the organic solvent which is the component (D) of the present invention will be described. The (D) organic solvent which can be used in the present invention is not particularly soluble in the organic solvent which can dissolve or disperse the above-mentioned Oxygen Tree Moon Day (B) having a glycidyl ether group, and the diazo naphthalene brewing type. Limited, it is better to

An organic solvent in which lf 4% or more of water is dissolved at 25 C, and as the solvent exemplified in the description of the removal of the protective group of the third butyl group, the γ-butyrolactone and the γ-pental vinegar may be mentioned. , s_ 戊内酉, ethylene carbonate, propylene carbonate, dimethyl carbonate, and the like. a compound which is protected by a group represented by the above formula (1) or a compound which is protected by a group represented by the above formula (2), for example, a ring represented by the above formula (3a) In the case of a cyclooxyalkylene compound, the organic solvent used in the desorption reaction of the second butyl group can be directly used as the organic solvent of the component (D) of the present invention. With regard to the formability when forming a permanent resist using the positive photosensitive composition of the present invention and the physical properties of the obtained permanent resist, it is preferred that the quality is relative to (A) oxime resin. The content of the organic solvent as the component (D) is 10 to 10,000 parts by mass, more preferably (7) by weight. The positive photosensitive composition of the present invention dissolves or disperses (A) an oxirane resin, (B) a glycidyl group-based oxalyl compound, (c) a diazonaphthoquinone, and (D) an organic solvent. Alternatively, it may be filtered by a filter having a hole diameter of about 2, for example, and then used for use. In addition to the positive photosensitive composition of the present invention, a plasticizer, a thixotropic imparting agent, a photoacid generator, a thermal acid generator, a dispersion 144043.doc 41 201030468, an antifoaming agent, a pigment, a dye may be blended as needed. Wait. Next, the permanent resistance (four) of the present invention will be described. The permanent resist of the present invention is produced by using the above positive photosensitive composition. Hereinafter, the preferred manufacturing method of the permanent anti-(4) j of the present invention will be described in the order of steps. (First Step) Coating Film Forming Step The coating film forming step is a step of applying the prepared positive photosensitive composition of the present invention onto a target substrate to form a coating film. The substrate to be used is a material having chemical resistance to an organic solvent or the like in the positive photosensitive composition, and development of the test solution in the fourth step and treatment of the sixth step (IV) heat and the like. Further, it is not particularly limited, and examples thereof include glass, metal, and semiconductor. In particular, a TFT surface or the like of a liquid crystal display which is required as a permanent resist of an insulating layer is preferable. The method of coating by the method is not particularly limited, and the blade coating method, the coating method, and the coating method may be, for example, a spin coating method, a dip coating method, a slit coating method, or the like, and then, for free application. The (D) organic solvent is removed from the positive photosensitive composition layer formed on the substrate by the coating material, and pre-bake is performed. The pre-baked positive photosensitive composition layer is insoluble in the test solution, and in the lower-exposure step, the portion irradiated with light (hereinafter sometimes referred to as an exposed portion) becomes Alkali soluble. The pre-baking temperature varies depending on the type of the organic solvent to be used. If the temperature is too low, there is a large residual variation of the organic solvent, which causes a decrease in exposure sensitivity or resolution, and if the temperature is too high. , 144043.doc 42- 201030468 The entire coating film is hardened by prebaking, and the solubility of the portion irradiated with light to the alkaline developing solution is lowered, and as a result, the exposure sensitivity or the resolution is lowered, so that Preferably, it is 60 to 14 (rc, and more preferably 7 to 12 〇 1. The pre-bake time varies depending on the type of organic solvent used and the temperature of the pre-boiled, preferably 3 〇 seconds to 1 minute, and more preferably 丨 to 5 minutes. The positive photosensitive composition of the present invention may be directly pre-baked after being applied to a target substrate. The permanent anti-contact agent of the present invention is preferably improved in terms of physical properties, chemical resistance, etc. after the thermal history.

The organic solvent in the positive photosensitive composition layer is made 5% by mass or less at room temperature to below 6 Torr, at normal temperature or under reduced ink, before the pre-baking, so that the organic solvent concentration in the positive photosensitive composition layer is 5% by mass or less. After the solvent is volatilized, pre-baking is performed. The thickness of the positive photosensitive composition layer after prebaking differs depending on the use of the permanent anti-(four) of the present invention, but is not particularly limited and is 〇1 μπι to 100 μπι, preferably 〇3. Ιιη~1〇μηι can be. (Second Step) Exposure Step The exposure step is a step of increasing the solubility of the exposed portion by irradiating the patterned photosensitive composition layer with the pre-baked positive photosensitive composition layer. The pre-baked positive-type photosensitive composition layer is insoluble in an alkaline solution, but the diazepam of the exposed portion is decomposed by the light emission to become a methylation, 9 to be dissolved and dispersed in the test solution. _. The irradiation light is not particularly limited, and may be light having an energy for improving the solubility of the light-irradiating portion of the pre-baked positive photosensitive composition layer, and is, for example, 10 to 100 mJ/cm 2 '. 〇~3〇〇mJ/cm2. 144043.doc •43- 201030468 And 'the wavelength of the light can be visible light' can also be ultraviolet light, there is no special limit 'use high pressure mercury lamp, ultra high pressure mercury lamp, etc., use 4_diazoxine acid s In the case of (c) diazonaphthalene awakening, the narrow-wavelength light with i-line (365 nm) as the main body can be used as the (c) diazo. In the case of naphthoquinones, it is sufficient to irradiate light of a wide wavelength including a ray line (365 nm), an h line (4 〇 5 nm), and a g line (436 nm). The method of patterning the above illuminating light is not particularly limited. Limited, can be previously

A known method, for example, a light irradiation method using a mask or the like, may be a selective light irradiation method using laser light. (Step 3) Developing Step The developing step is a step of obtaining a specific pattern by removing the portion of the exposure step which is improved by the light irradiation in the exposure step by using a developing solution. As the developing method, for example, a method such as a shoal development method, a dipping method, a shower method, a spray method, or the like can be used. , shadow time silk according to (4) "resin peak" has a glycidyl ether group

The type and molecular weight of the compound, the temperature of the developer, and the like are usually 30 to 18 seconds. The extracting agent used in the developing step is not particularly limited as long as it can be dissolved or dispersed in the liquid to be removed from the liquid, and for example, sodium hydroquinone or potassium strontium oxide can be used. Carbonic acid*5 . - ^ Sodium, potassium citrate, sodium citrate, ammonia, etc., ethylamine, n-propylamine, etc. - sulphamine-like amines; diethylamine, di-n-propylamine, etc. Amine, methyl diamine; - carbamide, nitrate, dimercaptoethylamine, triethylamine, etc., trisyl alcohol, aziridine diethanolamine, triethanolamine and other tertiary alcohol amines, pyrrole , piperidine t ... methyl piperidine, N-methyl pyrrolidine, 1,8 144043.doc -44- 201030468 azabicyclo[5.4.〇]-7-undecene, 1,5-diazabicyclo [4 3 〇]_5- 壬 roasted Γ and other ring-like secondary amines; pyridine bite, trimethyl pyridine bite, dimethyl 0 ratio. An aromatic tertiary amine such as a quinoline or a quinoline; and an aqueous solution of an alkali such as an aqueous solution of a tetra-ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide b-ammonium; The alkali concentration of the developer used in the removal of the photosensitive composition layer. The aqueous solution of the base may further contain an appropriate amount of a water/gluten organic solvent such as decyl alcohol or ethanol and/or a surfactant. φ After removing the exposed portion by the developing solution, it is preferred to rinse with water by running water or spraying, or it may be dehydrated and dried in the range of 50 to 120 °C as needed. (Step 4) Bleaching and Exposure Step The bleaching and exposing step is a step of irradiating light to the entire positive photosensitive composition layer (hereinafter sometimes referred to as a resist layer) remaining in the alkali solution treatment to improve visible light transmittance. . The anti-surname layer is colored yellowish or light brown because it contains diazonaphthoquinones. By irradiating the resist layer with light, the remaining unreacted (C) diazonaphthoquinones are photodecomposed, and become antimony formic acid which is not absorbed in the visible light region, and has improved visible light transmittance, and is suitable for use as a liquid crystal display device or organic The EL display is used as a permanent resist for active matrix substrates used in mounting and the like. The irradiation light in the bleaching exposure step is not particularly limited, and for example, it is possible to irradiate light of 10 to 1000 mJ/cm2, preferably 40 to 600 mj/cm2. Further, the wavelength of the irradiation light may be visible light or ultraviolet light, and is not particularly limited, but it is preferably the same as the (second step) exposure step, depending on the (C) diazonaphthoquinone used. Select the wavelength of the illumination light. 144043.doc •45· 201030468 (Step 5) Post-baking step ▲The visible light penetration of the bleach-exposed resist layer is improved, and the alkali solubility is also improved. The post-baking step suspends the above-mentioned bleached self-exposure resistant layer to a heat treatment of nc or more to thermally crosslink the anti-(4) dream oxygen resin, thereby imparting heat resistance and chemical resistance required for the permanent anti-surname agent. And the person. In the present invention, it is considered that the compound having a glycidyl group as the component (7)) of the positive photosensitive composition exhibits the function of a crosslinking agent and is resistant to a high heat history which has not been hitherto. Chemically. Post-baking is preferably carried out under an inert gas atmosphere such as nitrogen or argon.

15 minutes to 2 hours at a temperature of 120 to 400 ° C. More preferably, it is carried out at a temperature of 120 to 350 ° C for 15 minutes to 2 hours, and more preferably at a temperature of 200 to 350 ° for 15 minutes. ~2 hours. The permanent resist of the present invention is excellent not only in transparency, insulation, heat resistance, and chemical resistance, but also 〜35 (). (: The heat history (high heat history) at the high temperature is excellent in transparency, insulation, and chemical resistance. Therefore, the active matrix is used as a liquid crystal display device i or an organic EL display device.

An interlayer insulating film (layer) or a planarizing film for a substrate is particularly useful as an interlayer insulating film (layer) or a planarizing film for an active matrix substrate including a TFT in which a polycrystalline germanium film is used as an active layer. The permanent resist of the present invention can also be used for an interlayer insulating film of a semiconductor element. Moreover, it can also be used for wafer coating materials for semiconductor devices (surface protection 貘, bump protection film, MCM (Multi-Chip Module) interlayer protection film 'junction coating), packaging material (sealing material) , bonded crystal). 144043.doc -46· 201030468 The permanent resist of the present invention can also be used as an insulating film for a semiconductor element, a multilayer wiring board or the like. Examples of the semiconductor element include a separate semiconductor element such as a diode, a transistor, a compound semiconductor, a thermistor, a varistor, and a thyristor; a DRAM (Dynamic Random Access Memory), and an SRAM (Static Random) Access Memory, Static Random Access Memory, EPROM (Erasable Programmable Read Only Memory), Masked Only Memory (Mask Read Only Memory) ), EEPROM (Electrical Erasable Programmable Read Only Memory), flash memory (memory memory) and other memory components; microprocessor, DSP (Digital Signal Processor, digital signal processor) Theoretical circuit components such as ASIC (Application Specific Integrated Circuit); integrated circuit components such as compound semiconductors represented by MMIC (Monolithic Microwave Integrated Circuits); hybrid integrated circuits ( Hybrid 1C), light-emitting diode, charge-coupled component, etc. Wait. Further, examples of the multilayer wiring board include a high-density wiring board such as MCM. EXAMPLES Hereinafter, the present invention will be further described by way of Examples, but the present invention is not limited thereto. Further, the content of the sterol group is determined by reacting the sample with trimethyl gas decane in a pyridine solution to convert the sterol group into a trimethyl decane ether group, and then using an aqueous solution of tetradecyl ammonium hydroxide ((CH3)4NOH). The treatment was carried out so that the CO-Si bond water 144043.doc -47· 201030468 solution was calculated by recalculating the weight increase rate after the reaction. [(A) Manufacture of oxime resin (a)] In 300 parts by mass of toluene, 2,4,68-tetradecylcyclotetraoxane 100-mass, 4-ethylene base formic acid-third 85 parts by mass of butyl vinegar, 110 parts by mass of 4-tert-butoxy styrene, 93 parts by mass of trimethoxyvinyl decane, and platinum-divinyltetramethyl dioxane complex (Karstedt catalyst) 0.0001 parts by mass, while stirring, was reacted at 6 Torr for 15 hours. The solvent was distilled off under reduced pressure from the reaction mixture at 60 c to obtain a cyclic oxirane compound (a-1) (corresponding to the compound of the above formula (3a)). The cyclic anthraquinone compound (a-Ι) is at 25. (The following is a viscous liquid. In the analysis by W-NMR, no peak of 4 3 to 5 〇 ppm derived from a hydrogen atom of the Si—H group is detected. As a result of analysis by GPC, the mass average molecular weight is 900 ( The theoretical molecular weight is 933.1), and it is confirmed that the peak area ratio derived from unreacted 4-vinylbenzoic acid-t-butyl ester disappears to 0.5% or less. Then, '100 of the above-mentioned cyclic stone compound (a-1)) In the parts by mass, 40 parts by mass of phenyltrimethoxydecane (corresponding to the compound of the above formula (4)) and 200 parts by mass of toluene were added, and the mixture was stirred and cooled in an ice bath at 10 ° C for 30 minutes. 5 parts by mass of a 5% aqueous solution of oxalic acid was added dropwise, and the mixture was stirred for 15 hours while maintaining the temperature in the system at 1 ° C, and then subjected to reflux dehydration and dealcoholization under reduced pressure at 50 ° Under a reduced pressure, a solvent exchange was carried out to replace the solvent benzene with 1-methoxy-2-propanol acetate (hereinafter referred to as PGMEA) to obtain a 25% PGMEA solution of the intermediate product (a_2). .

To remove the third butyl group, add 25% of the intermediate product (a-2) PGMEA 144043.doc • 48- 201030468 solution 400 parts by mass, boron trifluoride diethyl ether complex 3 parts by mass, at 80 ° C After stirring for 3 hours, 100 parts by mass of the desolvation treatment was carried out under reduced pressure, and 10 parts by mass of an acidic adsorbent (manufactured by Kyowa Chemical Industry Co., Ltd., trade name: Kyowaad 500SH) was added, and the mixture was stirred at 80 ° C for 1 hour. While a slurry solution was obtained, the solid matter was removed by filtration to obtain a PGMEA solution of 30% of the (A) oxime resin (a) of the present invention. The mass average molecular weight of the epoxy resin (a) by GPC analysis was 6,400, and the sterol group content was 5.4% by mass. [(A) Production of the oxime resin (b)] To 100 parts by mass of the above cyclic siloxane compound (a-fluorene), 8 parts by mass of phenyltrimethoxy decane and 200 parts by mass of toluene are added. After cooling and stirring in an ice bath at 10 ° C, 50 parts by mass of a 5% aqueous oxalic acid solution was added dropwise over 30 minutes. After stirring for 15 hours while maintaining the temperature in the system at 10 ° C, the mixture was subjected to reflux dehydration at 50 ° C under reduced pressure. The dealcoholization treatment was carried out, and solvent exchange of toluene and PGMEA was carried out at 50 ° C under reduced pressure. Thus, a 25% PGMEA solution of the intermediate product (b-2) was obtained. Next, the same operation as in the above (A) oxime resin (a) was carried out to obtain a PGMEA solution of 30% of the (A) oxime resin (b) of the present invention. The mass average molecular weight of the oxime resin (b) by GPC analysis was 9,500, and the sterol group content was 4.2% by mass. [(A) Production of the oxime resin (c)] 40 parts by mass of phenyltrimethoxy decane was added to 200 parts by mass of toluene, and the mixture was cooled and stirred at 10 ° C in an ice bath, and 5% was added dropwise over 1 hour. After 50 parts by mass of the aqueous oxalic acid solution, the mixture was further stirred at 10 ° C for 3 hours. In the reaction solution of 144043.doc -49- 201030468, the mixture was stirred and cooled in an ice bath at 1 ° C, and 2-(4-t-butoxycarbonylphenyl)ethyltriazine was added dropwise over 1 hour. a mixture of 44 parts by mass of oxydecane and 56 parts by mass of 2-(4-t-butoxyphenyl)ethyltrimethoxy oxane, and then stirred at 10 ° C for 15 hours, at 50 ° C, Under reduced pressure, reflux dehydration and dealcoholization were carried out, and solvent exchange of toluene with PGMEA was carried out at 50 ° C under reduced pressure to obtain a 25% PGMEA solution of the intermediate product (c-2). Hereinafter, the same operation as the oxime resin (a) was carried out to obtain a PGMEA solution of 30% of the (A) oxime resin (c) of the present invention. The mass average molecular weight of the epoxy resin (c) by GPC analysis was 6,800, and the sterol group content was 4.1% by mass. [(A) Production of Oxygen Resin (d)] Using 42.5 parts by mass of 4-vinylbenzoic acid-t-butyl ester instead of 4-vinylbenzoic acid-t-butyl ester 85 parts by mass and 4- The operation similar to the production of the above (A) oxime resin (a) is carried out, except that the third butoxy styrene is 11 parts by mass, thereby obtaining the (A) oxirane resin (d) of the present invention. % PGMEA solution. The mass average molecular weight of the epoxy resin (d) by GPC analysis was 6,300, and the sterol group content was 5.1% by mass. [(A) Production of Oxygen Resin (e)] Using 2-(4-tert-butoxycarbonylphenyl)ethyltrimethoxy decane in an amount of 100 parts by mass in place of 2-(4-t-butoxy) a mixture of 44 parts by mass of carbonylcarbonyl)ethyltrimethoxydecane and 56 parts by mass of 2-(4-t-butoxyphenyl)ethyltrimethoxynonane, and the above (A) The same operation was carried out for the production of the oxime resin (c), thereby obtaining a PGMEA solution of 30% of the (A) oxime resin 144043.doc - 50 - 201030468 (e) of the present invention. Further, the mass average molecular weight of the epoxy resin (e) by Gpc analysis was 7200, and the sterol group content was 1〇1 mass 〇/〇. [(A) Production of Oxygen Resin (1)] Using 70 parts by mass of 4-vinylbenzoic acid-t-butyl ester and 36.7 parts by mass of p-tert-butoxystyrene instead of 4-vinylbenzoic acid _ (A) The same operation as the above (A) oxy resin (a) is carried out, except that 85 parts by mass of tributyl acrylate and 110 parts by mass of 4-t-butoxy styrene are used, thereby obtaining (A) of the present invention. A 30% PGMEA solution of the epoxy resin (7). Further, the mass average molecular weight of the ground oxygen resin (f) by GPC analysis was 78 Å, and the sterol group content was 5.1% by mass. [Comparison of oxirane resin (g)] 184 parts by mass of 4-tert-butoxy styrene was used instead of 'vinyl benzoic acid-tert-butyl ester 85 parts by mass and 4_t-butoxybenzene In the same manner as in the production of the above (A) oxime oxy-resin (a), a comparative oxime resin having no base represented by the above formula (1) was obtained. g) 30% of PGMEA solution. Further, the mass average molecular weight of the epoxy resin (g) by GPC analysis was 67 Å, and the sterol group content was 4.8% by mass. [Comparison of the production of the oxime resin (h)] The use of 2 (4,2,2-butoxyphenyl)ethyltrimethoxy sulphide in part to replace 2-(4-t-butoxyphenyl)phenyl Ethyltrimethoxy ketone 44 hydrazine and 2-(4-t-butoxyphenyl)ethyltrimethoxy decane "mass portion of a mixture, except m b" and the above (oxygenated resin (4) 144043.doc -51 - 201030468 The same operation was carried out to obtain a PGMEA solution of 30% of the comparative oxime resin (h) having no base represented by the above formula (1). The mass average molecular weight of the tree (h) obtained by gpc analysis is 74 〇〇, and the sterol group content is 1 (^4 mass. / 〇. [Comparative production of oxime resin (1)] According to Japanese Patent Laid-Open In Synthesis Example 1 of the Example of JP-A-2008-785785, methyl methoxy decane was added in an amount of 1 part by mass, and phenyltrimethoxy decane 78 was added to 157 parts by mass of diacetone alcohol (hereinafter referred to as DAA). In a mass portion, while stirring at room temperature, 61 parts by mass of a 3% aqueous phosphoric acid solution was added dropwise thereto for 1 minute, and then, at 4 Torr. (: stirring for 30 minutes) The temperature was raised to 105 ° C in 30 minutes, and further stirred at 1 〇 5 ((:) for 2 hours, thereby obtaining a comparative DAA solution of the oxirane resin (1). The solid content concentration of the DAA solution of the oxirane resin (1) was 39 ❶. The water content is 5% by weight, and the mass average molecular weight of the oxime resin (1) is 6000. [(B) Manufacture of the oxirane compound (1) having a glycidyl ether group] 2, 4 is added to 300 parts by mass of the present invention , 6,8-tetramethylcyclotetrazepine, 1 part by mass, 190 parts by weight of allyl glycidyl ether, and platinum-divinyltetramethyldioxane complex (Karstedt catalyst) 1) parts by mass, while stirring, on the side of 50 to 60. (: 15 hours under reaction. On 60. (:: The solvent is distilled off under reduced pressure from the reaction liquid, thereby obtaining the present invention A glycidyl ether-based oxane compound. The oxirane compound (1) is a viscous liquid at 25 〇c with an epoxy equivalent of 174, and no peak of a hydrogen atom derived from a Si-fluorenyl group is observed in the NMR analysis. The mass average molecular weight obtained by ope analysis is 700 'cannot be confirmed from unreacted allyl glycidol 1 44043.doc -52- 201030468 The peak of ether. [(B) Manufacture of a heptane compound (k) having a glycidyl ether group]

Adding 1,1,3,3-tetramethyldiazepine mass burn to the 50 parts by mass of toluene, 170 parts of dilute propyl glycidol, and turning-diethylene tetramethyl _ oxa hydride 0.0005 parts by mass of the compound (Karstedt catalyst) was transferred and reacted at 50 to 6 (TC for 15 hours). The solvent was evaporated from the reaction liquid under reduced pressure at 6 Torr to obtain the present invention. (B) an oxy-oxygen compound (k) having a glycidyl group. The epoxy equivalent of the oxalate compound (k) was 182, and no peak derived from a hydrogen atom of the si-H group was observed in the NMR analysis. The mass average molecular weight obtained by GPC analysis was 36 Å, and the peak derived from unreacted allyl glycidyl ether could not be confirmed. [(B) Production of a glycidyl ether group-containing oxane compound (1)] Toluene To 100 parts by mass, 1 part by mass of phenyltrimethoxydecane and 4 parts by mass of 3-glycidoxypropyltrimethoxy oxane were added, and the mixture was stirred and cooled in an ice bath under (7) Torr. 5 parts by mass of 5 parts by mass of formic acid was added dropwise in minutes, and the temperature in the system was maintained at 1 〇χ: After an hour, water was added and the water layer was washed repeatedly until the water layer became neutral. The mixture was refluxed under reduced pressure at 5 ° C, and water was removed from the surface and methanol formed by the reaction was then taken at 50 C under reduced pressure. Performing solvent exchange of toluene with pGMEA to obtain (B) a solution of the glycidyl ether group-containing oxy-oxygen compound solution (1) of 4()%2PGMEA of the present invention. The solution of the oxime compound having a glycidyl group (1) is In the analysis of FT-IR (Fourier Transform ared), it is confirmed at ηcm-i (10) to the wider absorption from the alcohol base, and the epoxy equivalent is repeated. By 144043.doc •53· 201030468 by GPC analysis The mass average molecular weight was 4 Å and the sterol group content was 11.2% by mass. [Comparison of the epoxy group-containing oxirane compound (m)] Using vinyl oxyethylene cyclohexene 2 〇 7 In the same manner as in the above (B) the oxyhydrogenated compound (1) having a glycidyl bond group, the same procedure as in the above (B) is carried out in order to obtain a comparative epoxy group having an epoxy group, in addition to 190 parts by mass of the allyl glycidyl ether. Alkane compound The compound was a viscous liquid with an epoxy equivalent of 183, and no peak derived from a hydrogen atom derived from Si-H group in the NMR analysis. Further, the mass average molecular weight obtained by GPC analysis was 730 'unconfirmed One of the unreacted oxidized vinyl cyclohexane peaks. Comparison of compounds having an epoxy group (n) Bisphenol A diglycidyl ether (manufactured by Adek A, trade name: Adeka Resin EP-4100) Oxygen compound (p) 3,4-epoxycyclohexenylmethyl_3,4,-epoxycyclohexenecarboxylate (manufactured by Daicel Chemical Industry Co., Ltd., trade name: Celloxide 2021P) (C) Diazo naphthalene (DNQ) All of the above formula (12) is a compound represented by the formula (11) (manufactured by Daito Chemix Co., Ltd., trade name: PA-6) [Examples 1 to 11 and comparison Example 1-1 6] Preparation of a positive photosensitive composition After blending in the ratio shown in [Table 1], filtration was carried out using a filter having a pore size of 〇.2 μm, and then Examples 1 to 11 and Comparative Examples were prepared. A positive photosensitive composition of 1 to 16. Further, the solvent is added to the value in the table. 144043.doc -54- 201030468 [Table i] (Α) component (B) component (c) component (D) component Example 1 (8) 100 (m〇DNQ, 7 PGMEA, 240 Example 2 (a) 100 (1) 10 DNQ,7 PGMEA » 240 Example 3 (b) 100 (k) l DNQ, 7 PGMEA, 240 ΪΓ Example 4 (c) 100 0) 10 DNQ, 7 PGMEA, 240 Example 5 (d) 100 ( l) i〇DNQ, 7 PGMEA, 240 Example 6 (d) 100 (m〇DNQ, 7 PGMEA, 240 Example 7 (6) 100 0) 10 DNQ, 7 PGMEA, 240 Example 8 (6) 100 (m〇DNQ, 7 PGMEA , 240 Example 9 (f) 100 (i) i 〇 DNQ, 7 PGMEA, 240 Example 10 (f) 100 〇〇i 〇 DNQ, 7 PGMEA, 240 Example 11 (f) 100 0) 10 DNQ, 7 PGMEA, 240 Comparative Example 1 (8) 100 - DN〇» 7 PGMEA , 240 . Comparative Example 2 (b) 100 - DNQ, 7 PGMEA, 240 Comparative Example 3 (c) 100 - DNQ, 7 PGMEA, 240 Comparative Example 4 (d) 100 — DNQ, 7 PGMEA , 240 Comparative Example 5 (e) 100 — DNQ, 7 PGMEA, 240 Comparative Example 6 (8) 100 (m) 10 DNQ, 7 PGMEA, 240 Comparative Example 7 (8) 100 (n) l〇DNQ, 7 PGMEA, 240 Comparative Example 8 (b) 100 in) 10 DNQ, 7 PGMEA, 240 Comparative Example 9 (6) 100 (p) 1 〇 DNQ, 7 PGMEA, 240 Comparative Example 10 (d) 100 (m) 10 DNQ, 7 PGMEA, 240 Comparative Example 11 (6) 100 (m) 10 DNQ, 7 PGMEA, 240 Comparative Example 12 (g) l 〇〇 (i) i 〇 DNQ, 7 PGMEA, 240 Comparative Example 13 (g) ioo (_ DNQ, 7 PGMEA, 240 Comparative Example 14 (h) 100 (i) l DNQ, 7 PGMEA > 240 Comparative Example 15 (h) 100 _ DNQ, 7 PGMEA, 240 Comparative Example 16 ( i) 100 — DNQ, 7 DAA, 173 GBL, 20 water, 7

Solvent PGMEA: 1-methoxy-2-propanol acetate DAA: diacetone alcohol GBL: γ-butyrolactone The positive photosensitive compositions of Examples 1 to 11 and Comparative Examples 1 to 16 were subjected to the following Evaluation. The results are shown in [Table 2]. (Preparation method of test piece) The positive photosensitive composition was applied to a square glass substrate of 25 mm in length and 25 mm in width by a spin coating method to a thickness of 4 to 5 μm, or ITO (Indium Tin) Oxide, indium tin oxide) was evaporated on a glass substrate (ITO thickness: 100 nm), and then the solvent was volatilized and used for a test piece. Furthermore, the positive photosensitive composition is stored in a thermostat at 23 ° C after preparation. 1 144043.doc -55- 201030468

Use it after 曰 (24 hours). In addition, for the test at 23 ° C for preservation stability,

A test piece of a glass substrate was also prepared.

The tetradecyl ammonium hydroxide aqueous solution was immersed in the aqueous solution for 70 seconds, and then washed and air-dried. The test piece for air drying is irradiated with ultraviolet light by an ultrahigh pressure mercury lamp at 2 〇〇mj/cm 2 (wavelength conversion at 365 nm), and then heated at 230 ° C for 60 minutes in an atmosphere, or under a nitrogen atmosphere. The heat treatment was performed at 350 ° C for 30 minutes to form a permanent resist film. In the case of using a test piece for vapor-depositing a glass substrate using ιτο, after heat-treating the test piece for 2 minutes, the ultraviolet ray is irradiated by an ultrahigh pressure mercury lamp at 200 mJ/cm2 (wavelength conversion at 365 nm) without using a photomask. Thereafter, the mixture was heated at 230 ° C for 60 minutes in an atmospheric environment or at 350 ° C for 30 minutes in a nitrogen atmosphere. A wiring for A1 was formed on the upper portion of the permanent resist film by a steaming method to prepare a test piece for measuring the dielectric constant. (Storage Stability Test) After the test piece of the glass substrate which was heat-treated at 230 ° C for 60 minutes was cut, the presence or absence of the resist residue on the surface of the broken substrate on which the alkali-soluble portion was removed was observed using a scanning electron microscope. The storage stability was evaluated according to the following <Evaluation Criteria>. The anti-synthesis agent is due to the fact that the positive photosensitive composition is partially high 144043.doc -56- 201030468 is quantified as a solution to the alkaline developer. The test was carried out for each of the test pieces [_ 7 曰 and 60 曰 of the positive-type photosensitive sensitization combination = 2 which were respectively low in the production of the optical composition. In addition, the test piece of the positive photosensitive sensitizer which was found to have a resist residue in the middle of the storage of 1 曰 or 7 未 was not used for the subsequent test composition < evaluation criteria > ◎ • Even for preservation 6 days of positive type 1 elementary group & thing, no resist

Residual/checking's storage stability is excellent. In the case of the positive photosensitive composition of the seventh day, the anti-money agent was not found. However, when the positive photosensitive composition was stored for 60 days, the resist residue was found to be excellent in storage stability. △: In the case of the positive photosensitive composition after storage for 1 ,, the imaginary photosensitive residue was not used. However, when the positive photosensitive composition was stored for 7 days, the anti-money residue was observed, and the storage stability was slightly inferior. χ Even in the case of the positive photosensitive composition after one day of storage, the anti-rice residue was observed and the storage stability was poor. (Resolution test) For the test piece cut in the storage stability test described above, the cross section was observed using a scanning electron microscope, and the line of 5 μm and the gap pattern were formed to have a width of 1 to 1, according to the following &lt; Evaluation criteria &gt; to evaluate the resolution. &lt;Evaluation Criteria&gt; 〇: The pattern can be formed to have a width of 1 to 1, and is excellent in resolution. χ : The pattern cannot form a width of 1 to 1 and the resolution is poor. (Heat-resistant patterning test) 144043.doc -57· 201030468 For the above-mentioned resolution test, a 5 μm line and a gap pattern can be formed into a test piece having a width of 1 to 1, and further heated in a nitrogen atmosphere by 3 thieves. After 〇 minutes, the scanning electron micrograph was used to observe the cross-section, and the heat resistance of the pattern was evaluated by the following <Evaluation Criteria>. &lt;Evaluation Criteria&gt; The patterned shape of the width of 〇·1 is maintained, and the heat resistance of the pattern is excellent. X: The patterned shape of the width of the uti is not maintained due to the rough surface crack, the film thickness reduction, etc., and the heat resistance of the pattern is poor. (Transparency test) For each test piece using a glass substrate, the transmittance of light having a wavelength of 400 nm was measured, and transparency and heat resistance were evaluated by the following &lt;Evaluation Criteria&gt;. Furthermore, the transmittance of the test refers to the transmittance of light having a wavelength of 400 nm to a film thickness of 4 μm. &lt;Evaluation Criteria&gt; 〇: The light transmittance of the test piece heat-treated at 23% under TC at 96% or more at 350 C was 9 % or more, transparency, high heat history The film was excellent in transparency. Δ: The light transmittance of the test piece heat-treated at 230 ° C was 96% or more, but the light transmittance of the test piece heat-treated at 350 ° C was less than 9 %, and the transparency was excellent. However, the transparency after the high heat history was poor. X: The light transmittance of the test piece heated at 23 ° C was less than 96%, and the transparency was poor. (Water resistance test) For each test piece using a glass substrate, it was measured at 60°. C ion exchange 144043.doc -58· 201030468 The wavelength before and after the water immersion for 24 hours is 々 (the penetration rate of the light of jo nm, and the film thickness of the resist is measured using a stylus type surface shape measuring device, according to The rate of change of the light transmittance and the rate of change of the film thickness were evaluated by the following <Evaluation Criteria>. <Evaluation Criteria> 〇: Change in light transmittance of the test piece heated at 35 (TC) The rate is less than 1%, and the rate of change of film thickness is less than 1%, water resistance and water resistance after high heat history △: The test piece of the test piece heat-treated at 230 ° C has a rate of change of less than 1%, and the rate of change of the film thickness is less than 1%, but the test piece heat-treated at 35 ° C The rate of change of the light transmittance is 1% or more, or the rate of change of the film thickness is 100%. The above is excellent in water resistance, but the water resistance after the high heat history is poor. X: The test piece heat-treated at 23 0 ° C The rate of change in light transmittance is 1% or more, or the rate of change in film thickness is 1% by weight or more, and the water resistance is poor. (Acid resistance test) For each test piece of the bismuth glass substrate, the mass is measured at 5 〇 ° C The transmittance of light having a wavelength of 4 〇〇ηηη before and after immersion in 0% aqueous solution of hydrochloric acid for 1 hour and measuring the film thickness of the resist using a stylus type surface shape measuring device according to the change in light transmittance The rate of change of the film thickness and the film thickness was evaluated by the following <Evaluation Criteria>. &lt;Evaluation Criteria&gt; 〇: The rate of change of the light transmittance of the test piece heat-treated at 350 ° C was less than 1%. 'And the film thickness change rate is less than 丨〇%, acid resistance and acid resistance after high heat history. 144043.doc -59- 20103046 8 △. The rate of change of the light transmittance of the test piece heated at 230 C is less than 10 / 〇, and the rate of change of the film thickness is less than 1%, but the transmittance of the test piece heat-treated under wc The rate of change is 1% or more, or the rate of change in film thickness is 10% or more, and the acid resistance is excellent, but the acid resistance after the high heat history is poor. X · The rate of change of the light transmittance of the test piece heat-treated at 230 C 1 〇 / 〇 or more ' or the film thickness change rate is 1% or more, and the acidity is poor. (Financial test) For each test piece using a glass substrate, the alkali solution of 4 〇〇c is measured (monoethanolamine· N-methylpyrrolidone: diethylene glycol butyl ether = 1 〇: 3 〇: 60 mass ratio) medium & collapsing rate of light having a wavelength of 4 〇〇 nm before and after 3 minutes of lapse and using The film thickness of the resist was measured by a pin type surface shape measuring device, and the sealing property was evaluated by the following &lt; evaluation criteria&gt; according to the rate of change of the light transmittance and the film thickness. &lt;Evaluation criteria&gt; 〇. at 350. (The rate of change of the light transmittance of the test piece subjected to the heat treatment was less than 1%, and the rate of change of the film thickness was less than 丨〇%, and the alkali resistance and the alkali resistance after the high heat history were excellent. △: at 230° The rate of change of the light transmittance of the test piece heated under C was not reached, and the rate of change of the film thickness was less than 1%, but the rate of change of the light transmittance of the test piece heat-treated at 35 〇^ was 1%. The above or the film thickness change rate is 1 〇 0 / or more, and the alkali resistance is excellent, but the alkali resistance after the high heat history is poor. χ : The rate of change of the light transmittance of the test piece heat-treated at 230 ° C ι% or more ' or the film thickness change rate is 1% or more, and the alkali resistance is poor. (Solvent resistance test) 144043.doc 201030468 For each test piece using a glass substrate, the dimethyl hydrazine at 80 〇 c is measured. (DMSO, dimethyl sulfoxide) The transmittance of light having a wavelength of 400 nm before and after the immersion hour, and using a stylus type surface shape measuring device to measure the film thickness of the anti-surname agent, according to the rate of change of light transmittance The rate of change in film thickness was evaluated by the following &lt;Evaluation Criteria&gt;. &lt;Evaluation Criteria&gt; 〇· at 350 C Rate of change of the light transmittance of the test piece heat treatment less than

1% ′ and the rate of change in film thickness is less than 1 G%, and the solvent resistance after the solvent and high heat history is excellent. △. The rate of change of the light transmittance of the test piece heated at 230 C was less than 1%, and the rate of change of the film thickness was less than 1%, but the change of the light transmittance of the test piece heat-treated at 3 Torr The rate is 1% or more, or the rate of change in film thickness is 10% or more. The solvent resistance is excellent, but the solvent resistance after a high heat history is inferior. X: The rate of change of light transmittance of the test piece heat-treated at 23 (TC) was 1% or more, or the rate of change of m-thickness was 10% or more, and the solvent resistance was poor. (Dielectric constant test) Measurement using LCR, inductance Capacitance Electricity The dielectric constant and the electric constant characteristics were measured for each test piece using an ITO vapor-deposited glass substrate, and the instrument (Inductance Capacitance Resistance Meter) was evaluated by the following <Evaluation Criteria>. &lt;Evaluation Criteria&gt; 〇: The dielectric constant of the test piece after the heat treatment was reduced to less than 3.2, and the difference between the dielectric constant of the test piece heat-treated under the 23rd generation and the test piece heat-treated at 3耽 was less than G.2, Low dielectric constant characteristics and high thermal history 144043.doc -61- 201030468 Excellent low dielectric constant characteristics △: The dielectric constant of the test piece heat treated at 230 ° C is less than 3.2, but at 230 ° C The heat-treated test piece and the test piece heat-treated at 35 (the test piece under TC have a difference of 0.2 or more, and have excellent low dielectric constant characteristics, but have poor low dielectric constant characteristics after a high heat history. X: at 23 0 The dielectric constant of the test piece heated at °C is 3 .2 or more, low dielectric constant characteristics are poor. [Table 2]

Storage stability, resolution, patterning, heat, transparency, water resistance, acid resistance, alkalinity, solvent, low dielectric constant, Example 1, ◎ 〇〇〇〇〇〇〇〇 Example 2 ◎ 〇〇〇〇〇〇〇 〇Example 3 ◎ 〇〇〇〇〇〇〇〇 Example 4 ◎ 〇〇〇〇〇〇〇〇 Example 5 ◎ 〇〇〇〇〇〇〇〇 Example 6 ◎ 〇〇〇〇〇〇〇〇 Implementation Example 7 ◎ 〇〇〇〇〇〇〇〇 Example 8 ◎ 〇〇〇〇〇〇〇〇 Example 9 ◎ 〇〇〇〇〇〇〇〇 Example 10 ◎ 〇〇〇〇〇〇〇〇 Example 11 ◎ 〇〇〇〇〇〇〇〇Comparative Example 1 ◎ 〇X 〇Δ Δ Δ Δ Δ Comparative Example 2 ◎ 〇X Δ Δ Δ Δ Δ Δ Comparative Example 3 ◎ 〇X Δ Δ Δ Δ Δ Δ Comparative Example 4 ◎ 〇 X Δ Δ Δ Δ Δ Δ Comparative Example 5 ◎ 〇X Δ Δ X Δ Δ Δ Comparative Example 6 Δ 〇〇 Δ Δ Δ Δ Δ X Comparative Example 7 ◎ 〇X Δ X Δ Δ Δ Δ Comparative Example 8 ◎ 〇X Δ Δ Δ Δ Δ Δ Comparative Example 9 X 〇 Δ Δ Δ Δ Δ Δ Comparative Example 10 〇〇 XX Δ X Δ Δ X Comparative Example 11 〇〇X Δ XX Δ Δ X Comparative Example 12 ◎ 〇X Δ Δ Δ Δ Δ X Comparative Example 13 ◎ 〇X Δ Δ Δ Δ Δ △ Comparative Example 14 ◎ 〇X Δ Δ Δ Δ Δ Δ Comparative Example 15 ◎ 〇X Δ Δ Δ Δ Δ Δ Comparative Example 16 ◎ 〇XXX Δ XXX -62- 144043.doc

Claims (1)

201030468 VII. Patent application scope: 1 - a positive photosensitive composition comprising: as component (A) having at least two in one molecule of the following formula (1) [Chemical Formula 1] (1) (wherein R1 represents an alkylene group which may have a carbon number of a substituted hydrocarbon group, R2 represents an alkyl group having 1 to 4 carbon atoms, a represents a number of hydrazine or 1 to 4, and b represents a 1-3. a number, but a+b does not exceed 5) the base of the oxy-oxygen resin; a glycidyl group-containing oxirane compound as the component (B); and a diazo naphthalene as the component (C); An organic solvent as the component (D). The positive photosensitive composition of claim 1, wherein the above-mentioned oxime resin as the component (A) further has at least one of the following formula (2). (wherein R3 represents a carbon number of 取代~1〇 which may have a substituted hydrocarbon group, and 院 represents a non-carbon number of 1 to 4 of the hospital base 'c represents 〇 or 1 to 4, d car jumps 'cl The table is not 1 to 3 of the 144043.doc 201030468 number, but c+d does not exceed 5). 3. The positive photosensitive composition of claim 1, wherein the above-mentioned component (A) further contains a linaloyl group. 4. The positive photosensitive composition of claim 1, wherein the above-mentioned component is a compound of the following formula (3) [Chemical 3] The alkyl group having a carbon number of 1 to 10, R 2 and R 4 are alkyl groups having the same or different carbon number of 1 to 4, and R 5 , ... and the size 7 are the same or different carbon numbers 1 to 10 Alkyl or phenyl; a represents 〇 or a number from 1 to 4, b represents a number from 1 to 3, but a+b does not exceed 5; c represents 〇 or a number from 1 to 4, and d represents the number of ^, but c +d does not exceed 5; R9 represents a carbon group or a ring-burning group which may be the same or different carbon number, R1G represents a carbon number of 1 to 3: base, and e represents a number of ^; m, η, and P represent m: n : p = 1 ·' 〇~2 : 0.5~3 and m+n+p=3~6) The cyclic siloxane compound represented by the following formula (4) 144043.doc -2 - 201030468 [Chem. 4] (4) at (where R11 represents the same or different carbon number of the hospital or ring group, R12 represents the carbon number 3, and R^3 means the same or different carbon number 1~ 4 alkyl, f represents the number of 2~3, g represents the number of 〇 or 丨~5) The aryl alkoxy decane compound represented by the reaction is obtained. A permanent resist which is obtained from a positive photosensitive composition as claimed in the claims. A method for producing a permanent resist, which comprises applying a positive photosensitive composition according to claim 1 to a substrate, exposing the coated article, and performing alkaline development at 120 to 350 Post-baking at a temperature of °C. A liquid crystal display device comprising an active matrix substrate using a permanent resist obtained by using a positive photosensitive composition of claim i as an insulating layer or a planarizing film. An organic EL display device comprising an active matrix substrate using a permanent resist obtained by using the positive photosensitive composition of claim 1 as an insulating layer or a planarizing film. 144043.doc 201030468 IV. Designation of representative drawings: (1) The representative representative of the case is: (none) (2) The symbol of the symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: 144043.doc