TWI437369B - A positive type photosensitive composition and a permanent resist - Google Patents

Description

Positive photosensitive composition and permanent resist

The present invention relates to a positive photosensitive composition using a polyoxyalkylene compound, and further to a method for producing a permanent resist and a permanent resist using the positive photosensitive composition.

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 each having a switching element such as a thin film transistor (TFT) is used.

A plurality of scanning wirings and signal wirings crossing the scanning wirings via the insulating film are formed on the active matrix substrate. The scanning wiring, the signal wiring, the insulating film, and the like of the active matrix substrate are made of a conductive film or an insulating film formed by a sputtering method, a CVD (Chemical Vapor Deposition) method, a coating method, or the like. The lithography method is formed by repeating patterning (for example, refer to 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 the polysilicon film is covered with an insulating film, but is easily formed inside the polycrystalline silicon or the interface between the crystalline germanium film and the insulating substrate or the insulating film. The dangling bond, which is a defect of the 矽 bond, is generated, and the characteristics of the transistor are lowered.

In order to eliminate the problem of the dangling bonds, it is necessary to carry out hydrogenation treatment at a temperature of about 300 to 400 ° C in a state in which a film for preventing hydrogen diffusion such as tantalum nitride (SiN _x ) is present (for example, see Patent Document 3). The heat resistance of the conventional permanent resist refers to heat resistance which can withstand the soldering in the printed wiring board, and can withstand heat resistance at 260 ° C for several minutes (for example, refer to Patent Document 4), and 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, insulating properties, heat resistance, chemical resistance, and the like, and a photoresist which is mainly composed of a phthalocyanine resin is known, but the conventional oxirane-based photoresist is Since the chemical resistance after heat resistance and high heat history is insufficient, only a flattening film for the surface is applied to the active matrix substrate (see, for example, Patent Document 5).

Prior technical literature Patent literature

Patent Document 1: Japanese Patent Laid-Open Publication No. 2004-281506

Patent Document 2: Japanese Patent Laid-Open Publication No. 2007-225860

Patent Document 3: Japanese Patent Laid-Open No. Hei 6-77484

Patent Document 4: Japanese Patent Laid-Open Publication No. 2007-304543

Patent Document 5: Japanese Patent Laid-Open Publication No. 2008-116785

Accordingly, an object of the present invention is to provide a positive photosensitive composition and a permanent resist using the positive photosensitive composition, and a method for producing the same, wherein the positive photosensitive composition can provide an excellent transparency and can also provide A permanent resist which is used as an insulating film of an active matrix substrate and has high heat resistance and chemical resistance after a high thermal history.

The inventors of the present invention conducted intensive studies and as a result completed the present invention.

That is, the present invention provides a positive photosensitive composition comprising, as component (A), at least two of the following formula (1)

[Chemical 1]

(wherein R ¹ represents an alkylene group having 1 to 10 carbon atoms which may have a substituted hydrocarbon group, R ² represents an alkyl group having 1 to 4 carbon atoms, a represents 0 or 1 to 4, and b represents 1 to 3 Number, but a+b does not exceed 5.)

An oxygen-containing resin of the group represented; a fluorinated alkane compound having a glycidyl group as the component (B); a diazonaphthoquinone as the component (C); and an organic solvent as the component (D).

Further, the present invention provides a permanent resist which is obtained from the above positive photosensitive composition.

Moreover, the present invention provides a method for producing a permanent resist, which comprises applying the positive photosensitive composition to a substrate, exposing the coated article, and performing alkaline development at 120 to 350 ° C. Post-bake at the temperature.

Moreover, the present invention provides a liquid crystal 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.

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.

An effect of the present invention is to provide a positive photosensitive composition, a permanent resist using the positive photosensitive composition, and a method for producing the same, which can provide not only high transparency but also high transparency It is resistant to the heat resistance at the time of substrate production, solvent resistance, and further excellent as a permanent resist.

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), R ¹ represents an alkylene group having 1 to 10 carbon atoms which may have a substituted hydrocarbon group. Examples of the alkylene group having a carbon number of 1 to 10 include a methylene group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, a decyl group, a hydrazine group, and a stretching group. In the case of heat resistance, it is preferred that the carbon number is small, and in terms of ease of industrial availability, it is preferred to extend ethyl, propyl and butyl, and more preferably Base and butyl, the best is extended ethyl. Examples of the substituted hydrocarbon group which may be contained in R ¹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a phenyl group, and the like, and in terms of heat resistance, Preferably, it does not have a substituted hydrocarbon group.

R ² represents an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms 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 butyl group. R ² is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group, and most preferably a methyl group.

a represents 0 or 1~4, b represents 1~3, but a+b does not exceed 5. When a is a number from 2 to 4, R ² may be the same alkyl group or a different alkyl group. In terms of heat resistance, a is preferably 0 or 1, and more preferably 0. In terms of the ease of industrial availability, b is preferably 1 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 from the viewpoint of improving heat resistance, it is preferred that one carboxyl group is located in the para position with respect to R ² .

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) The decane compound (hereinafter referred to as the compound 1AS) or the chlorosilane compound (hereinafter referred to as the compound 1CS) undergoes a hydrolysis ‧ condensation reaction; or a carbon-carbon double bond having an reactivity with the Si—H group and an aromatic carboxyl group The compound (hereinafter referred to as compound DAC) is subjected to a hydrazine 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 hydrolysis and condensation reaction will be described.

The hydrolysis/densation reaction of the compound 1AS or the compound 1CS may be carried out by a so-called sol-gel reaction, and specific examples thereof include a method of performing a hydrolysis and a condensation reaction using a catalyst such as an acid or a base in a solvent.

The solvent to be used in this case is not particularly limited, and specific examples thereof include water, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, acetone, methyl ethyl ketone, and One type of these may be used for the alkane, tetrahydrofuran or the like, or two or more types may be used in combination.

The hydrolysis/condensation reaction of alkoxydecane or chlorodecane is carried out by hydrolyzing alkoxydecane or chlorodecane by water to form a sterol group (Si-OH group), and the resulting sterol groups are mutually The sterol group is condensed with an alkoxyalkyl group or a decyl group with a chloroalkyl group.

In the hydrolysis/condensation reaction, any one of an alkoxydecane compound and a chlorodecane compound may be used, or each compound may be used in combination, and since it is easy to control the reaction and remove by-products, it is preferably used as an alkoxy group. Compound 1AS of a decane 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 catalyst such as an acid or a base used in the hydrolysis/condensation reaction may be a catalyst for promoting hydrolysis and condensation, and specific examples thereof include inorganic acids such as hydrochloric acid, phosphoric acid, and sulfuric acid, formic acid, acetic acid, oxalic acid, citric acid, and methanesulfonic acid. Organic acids such as acid, benzenesulfonic acid, p-toluenesulfonic acid, monoisopropyl phosphate, inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia, trimethylamine, triethylamine, monoethanolamine, diethanolamine An amine compound (organic base) or the like may be used, and one type of these may be used, or two or more types may be used in combination.

The temperature of the hydrolysis and the condensation reaction varies depending on the kind of the solvent, the kind and amount of the catalyst, and the like, and is preferably 0 to 80 ° C, more preferably 5 to 50 ° C, and most preferably 8 to 30 ° C.

In the compound 1AS, examples of the compound in which R ¹ is an exoethyl group, a=0, b=1, and a carboxyl group in the para position include 2-(4-carboxyphenyl)ethyltrimethoxynonane. Trialkoxy decanes such as 2-(4-carboxyphenyl)ethyltriethoxydecane; 2-(4-carboxyphenyl)ethyldimethoxymethylnonane, 2-(4-carboxybenzene Ethyl diethoxymethyl decane, 2-(4-carboxyphenyl)ethyldimethoxyethyl decane, 2-(4-carboxyphenyl)ethyldiethoxyethyl decane, 2-(4-carboxyphenyl)ethyldimethoxypropyl decane, 2-(4-carboxyphenyl)ethyldiethoxypropyl decane, 2-(4-carboxyphenyl)ethyldi Methoxybutyl decane, 2-(4-carboxyphenyl)ethyldiethoxybutyl decane, 2-(4-carboxyphenyl)ethyldimethoxyisobutyl decane, 2-(4 -carboxyphenyl)ethyldiethoxyisobutyldecane, 2-(4-carboxyphenyl)ethyldimethoxycyclohexyldecane, 2-(4-carboxyphenyl)ethyldiethoxy a dialkoxy decane such as cyclohexyldecane; 2-(4-carboxyphenyl)ethyl methoxy dimethyl decane, 2-(4-carboxyphenyl)ethyl ethoxy dimethyl decane, 2 -(4-carboxyphenyl)B Methoxy diethyl decane, 2-(4-carboxyphenyl)ethyl ethoxydiethyl decane, 2-(4-carboxyphenyl)ethyl methoxydipropyl decane, 2-(4 -carboxyphenyl)ethylethoxydipropylnonane, 2-(4-carboxyphenyl)ethylmethoxydibutylnonane, 2-(4-carboxyphenyl)ethylethoxydibutyl Base decane, 2-(4-carboxyphenyl)ethyl methoxy diisobutyl decane, 2-(4-carboxyphenyl)ethyl ethoxy diisobutyl decane, 2-(4-carboxybenzene Monoalkoxy decane such as ethyl methoxy dicyclohexyl decane or 2-(4-carboxyphenyl)ethyl ethoxy dicyclohexyl decane.

Among these compounds, 2-(4-carboxyphenyl)ethyltrimethoxydecane and 2-(4-carboxyphenyl group are preferred in terms of good reactivity and good heat resistance. Ethyltriethoxydecane, 2-(4-carboxyphenyl)ethyldimethoxymethylnonane, 2-(4-carboxyphenyl)ethyldiethoxymethyldecane, 2-( 4-carboxyphenyl)ethyldimethoxyethyl decane, 2-(4-carboxyphenyl)ethyldiethoxyethyl decane, 2-(4-carboxyphenyl)ethyltrimethoxydecane 2-(4-carboxyphenyl)ethyltriethoxydecane, further preferably 2-(4-carboxyphenyl)ethyltrimethoxydecane, 2-(4-carboxyphenyl)ethyl Dimethoxymethyldecane, 2-(4-carboxyphenyl)ethyldimethoxyethyl decane, most preferably 2-(4-carboxyphenyl)ethyltrimethoxydecane, 2-( 4-carboxyphenyl)ethyldimethoxymethylnonane. The compound 1AS may be used alone or in combination of two or more.

In the compound 1CS, examples of the compound in which R ¹ is an exoethyl group, a=0, b=1, and a carboxyl group is contained in the para position include, for example, 2-(4-carboxyphenyl)ethyltrichlorodecane. Chlorodecane; 2-(4-carboxyphenyl)ethyldichloromethylnonane, 2-(4-carboxyphenyl)ethyldichloroethyldecane, 2-(4-carboxyphenyl)ethyldi Chloropropyl decane, 2-(4-carboxyphenyl)ethyldichlorobutyl decane, 2-(4-carboxyphenyl)ethyldichloroisobutyl decane, 2-(4-carboxyphenyl) Dichlorodecanes such as dichlorocyclohexyldecane; 2-(4-carboxyphenyl)ethyl chlorodimethyl decane, 2-(4-carboxyphenyl)ethyl chlorodiethyl decane, 2-(4 -carboxyphenyl)ethyl chlorodipropyl decane, 2-(4-carboxyphenyl)ethyl chlorodibutyl decane, 2-(4-carboxyphenyl)ethyl chlorodiisobutyl decane, 2- Monochlorodecanes such as (4-carboxyphenyl)ethylchlorodicyclohexyldecane.

Among these compounds, 2-(4-carboxyphenyl)ethyltrichlorodecane and 2-(4-carboxyphenyl) are preferred in terms of good reactivity and good heat resistance. Ethyl dichloromethyl decane, 2-(4-carboxyphenyl)ethyl dichloroethyl decane, more preferably 2-(4-carboxyphenyl)ethyl trichloro decane, 2-(4- Carboxyphenyl)ethyldichloromethylnonane. 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 (1) of the compound 1AS and the compound 1CS is represented by the following formula (1a).

[Chemical 2]

(wherein R ¹ , R ² , a and b have the same meanings as in the above formula (1).)

As shown, the carboxyl group can be protected by a third butyl ester group.

The above protected compound can be subjected to hydrolysis and condensation reaction in the same manner as the unprotected compound. In the case where the protecting group is a third butyl group, the third butyl group may be detached after the above hydrolysis/densation reaction, if necessary, using a catalyst in a solvent.

As a catalyst in this case, a boron trifluoride diethyl ether complex is preferred.

Further, as the solvent, an organic solvent capable of dissolving 1% by mass or more of water at 25 ° C is preferred. Examples of the organic solvent include alcohols such as methanol, ethanol, propanol, and isopropanol; 1-methoxy-ethanol, 1-ethoxy-ethanol, 1-propoxy-ethanol, and 1-iso Propoxy-ethanol, 1-butoxy-ethanol, 1-methoxy-2-propanol, 3-methoxy-1-butanol, 3-methoxy-3-methyl-1-butene Ether alcohols such as alcohol; 1-methoxy-ethyl acetate, 1-ethoxy-ethyl acetate, 1-methoxy-2-propyl acetate, 3-methoxy-1-butyl acetate, Acetate of ether alcohols such as 3-methoxy-3-methyl-1-butyl acetate; ketones such as acetone and methyl ethyl ketone; 4-hydroxy-2-butanone, 3-hydroxy-3- Keto alcohols such as methyl-2-butanone and 4-hydroxy-2-methyl-2-pentanone (diacetone alcohol); 1,4-two An ether such as an alkane, tetrahydrofuran or 1,2-dimethoxyethane. Among these solvents, preferred are methanol, ethanol, propanol, methyl ethyl ketone, and 1,4-two. Alkane, tetrahydrofuran.

In the case where a protected compound is used as a raw material of the above component (A), a step of removing the protective group is required, and the production step becomes complicated, but it is difficult to cause a side reaction, and the heat resistance and resistance of the permanent resist of the present invention are resistant. The advantages of improved chemical properties.

Then, a compound (compound DAC) containing a carbon-carbon double bond and an aromatic carboxyl group having reactivity with an Si-H group is subjected to a hydrazine hydrogenation reaction with a compound having at least two Si-H groups in one molecule. The method is explained.

The compound having at least two Si—H groups in one molecule may, for example, be represented by the following formula (5).

[Chemical 3]

(wherein, X represents a hydrogen atom or a methyl group, R ¹⁴ represents a methyl group or a phenyl group which may be the same or different, and R ¹⁵ , R ¹⁶ and R ¹⁷ represent an alkyl group which may be the same or different and have a carbon number of 1 to 6 , a cycloalkyl group having a carbon number of 5 to 6 or a phenyl group, q represents a number from 0 to 1000, and r represents a number from 0 to 1000. Wherein, when q is 0 or 1, X represents a hydrogen atom.

The linear compound represented by the following formula (6)

[Chemical 4]

(wherein R ¹⁸ , R ¹⁹ and R ²⁰ 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 S represents a number of 2 to 6, t Indicates that s+t becomes the number of 0~4 of 3~6.)

The cyclic compound represented by the above formula (6) is preferably a cyclic compound represented by the above formula (6) in terms of improvement in heat resistance.

In the above formula (5), X represents a hydrogen atom or a methyl group, R ¹⁴ represents a methyl group or a phenyl group which may be the same or different, and R ¹⁵ , R ¹⁶ and R ¹⁷ represent a carbon number which may be the same or different. ~6 alkyl, 5 to 6 cycloalkyl or phenyl. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, a third butyl group, a pentyl group, and an isopentyl group. And a second pentyl group, a third pentyl group, a hexyl group, a second hexyl group, etc., and a cycloalkyl group having 5 to 6 carbon atoms, for example, a cyclopentyl group, a cyclohexyl group, a cyclopentylmethyl group, a methylcyclopentane Base.

R ^{14 is} preferably a methyl group in terms of industrially readily available. In the aspect which has less influence on the hydrogenation reaction, R ^{15 is} preferably a methyl group and an ethyl group, and more preferably a methyl group. In terms of heat resistance of the permanent resist of the present invention, R ¹⁶ and R ^{17 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 methyl group. .

X represents a hydrogen atom or a methyl group, q represents a number from 0 to 1000, r represents a number from 0 to 1000, and when r is 0, X represents a hydrogen atom.

In the above formula (6), R ¹⁸ , R ¹⁹ and R ²⁰ 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. 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 as R ¹⁵ , R ¹⁶ and R ¹⁷ .

R ^{18 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, R ¹⁹ and R ^{20 are} preferably a methyl group, an ethyl group and a phenyl group, more preferably a methyl group and a phenyl group, and most preferably methyl.

s represents the number of 2~6, and t represents the number of 0~4 where s+t becomes 3~6. In terms of industrially readily available aspects, s+t is preferably 4-6, and more preferably 4-5, and most preferably 4. Also, t is preferably 0.

Specific examples of the cyclic oxirane compound represented by the above formula (6) include 2,4,6-trimethylcyclotrioxane and 2,4,6-triethylcyclohexane. Oxane, 2,4,6-triphenylcyclotrioxane, 2,4,6,8-tetramethylcyclotetraoxane, 2,2,4,6,8-pentamethylcyclo Tetraoxane, 2,2,4,4,6,8-hexamethylcyclotetraoxane, 2,4,6,8-tetraethylcyclotetraoxane, 2,4,6,8 - tetraphenylcyclotetraoxane, 2-ethyl-4,6,8-trimethylcyclotetraoxane, 2-phenyl-4,6,8-trimethylcyclotetraoxane, 2,4,6,8,10-pentamethylcyclopentaoxane, 2,4,6,8,10-pentaethylcyclopentaoxane, 2,4,6,8,10-pentabenzene Base ring pentaoxane, 2,4,6,8,10,12-hexamethylcyclohexaoxane, 2,4,6,8,10,12-hexaethylcyclohexaoxane, 2 , 4,6,8,10,12-hexaphenylcyclohexaoxane, etc., in terms of industrially readily available, 2,4,6,8-tetramethylcyclotetrazepine is preferred. Alkane and 2,4,6,8,10-pentamethylcyclopentaoxane, and more preferably 2,4,6,8-tetramethylcyclotetraoxane.

Next, the compound DAC will be described. Examples of the compound DAC include 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid, 4-(1-phenylvinyl)benzoic acid, and 2-methyl-4-ethene. Benzoic acid, 2-allylbenzoic acid, 3-allylbenzoic acid, 4-allylbenzoic acid, 2-isopropenylbenzoic acid, 3-isopropenylbenzoic acid, 4-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-phthalic acid, 5 - Vinyl-1,3-phthalic acid, and the like.

Among these compound DACs, 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-ethylene are preferred in terms of industrially readily available aspects and heat resistance of the permanent resist of the present invention. Benzoic acid, 2-allylbenzoic acid, 4-allylbenzoic acid, 2-isopropenylbenzoic acid, 4-isopropenylbenzoic acid, further preferably 2-vinylbenzoic acid, 4- Vinylbenzoic acid, the most preferred being 4-vinylbenzoic acid. The compound DAC may be used alone or in combination of two or more.

The aromatic carboxyl group of the compound DAC may 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 third butyl group can be removed by the above method.

The conditions for subjecting the compound DAC to a hydrazine hydrogenation reaction with a compound having at least two Si-H groups in one molecule can be carried out under known conditions. For example, it can be used in toluene, isopropanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, 1,2-dimethoxyethane, 1,4-two In a solvent such as an alkane or 1-methoxy-2-propanol acetate, chloroplatinic acid, a platinum-olefin complex, a platinum-carbonylvinylmethyl complex (Ossko catalyst), or platinum may be used as needed. a platinum-based catalyst such as a divinyltetramethyldioxane complex (Karstedt catalyst) is used as a catalyst, and the reaction is carried out at a reaction temperature of 20 to 130 ° C, preferably 50 to 80 ° C, and the reaction is completed. Thereafter, the solvent was subjected to distillation under reduced pressure to obtain a target product from the reaction liquid.

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 (1a). Further, the compound protected by the protecting group can be subjected to a 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 1AS and the compound 1CS.

When the mass average molecular weight of the component (A) of the present invention is too small, the film forming property when the permanent photosensitive composition is formed by using the positive photosensitive composition becomes poor, and when it is too large, the alkaline developing solution is dissolved. The property or the dispersibility is lowered, the resist residue on the surface of the substrate after the alkali development is increased, and the mass average molecular weight of the component (A) of the present invention is higher in terms of industrial suitability such as workability and efficiency. The good is 600~50000, and then the better is 800~20000, and the best is 1000~10000. In the present invention, the mass average molecular weight refers to polystyrene in the case of GPC (Gel Permeation Chromatography) analysis using tetrahydrofuran (hereinafter referred to as THF (tetrahydrofuran)) as a solvent. The mass average molecular weight converted.

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. 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:

[Chemical 5]

(wherein R ³ represents an alkylene group having 1 to 10 carbon atoms which may have a substituted hydrocarbon group, R ⁴ represents an alkyl group having 1 to 4 carbon atoms, c represents 0 or 1 to 4, and d represents 1 to 3; Number, but c+d does not exceed 5).

In the above formula (2), R ³ represents an alkylene group having 1 to 10 carbon atoms which may have a substituted hydrocarbon group. The alkylene group having a carbon number of 1 to 10 may, for example, be an alkylene group exemplified as R ¹ , and in terms of ease of industrial availability, it is preferably 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 R ³ may, for example, be a hydrocarbon group exemplified as R ¹ , but it is preferred to have no substituted hydrocarbon group in terms of heat resistance. R ¹ and R ³ may be the same or different.

R ⁴ represents an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include an alkyl group exemplified as R ² . As R ⁴ , in terms of heat resistance, an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group and an ethyl group are more preferable, and a methyl group is most preferable. R ² and R ⁴ may be the same or different.

c means 0 or 1~4, d means 1~3, but c+d does not exceed 5. When c is a number of 2 to 4, R ⁴ may be the same alkyl group or a different alkyl group. In terms of heat resistance, c is preferably 0 or 1, and more preferably 0. In terms of ease of industrial availability, d is preferably 1 or 2, and more preferably 1.

The position of the phenolic hydroxyl group of the group represented by the above formula (2) is not particularly limited, and in terms of improvement in heat resistance, it is preferred that one phenolic hydroxyl group is located in alignment with respect to R ⁴ .

The component (A) having a group represented by the above formula (2) can be produced by subjecting the compound 1AS or the compound 1CS to an alkoxydecane having a group represented by the above formula (2) The compound (hereinafter referred to as compound 2AS) or the chlorodecane compound (hereinafter referred to as compound 2CS) undergoes hydrolysis and condensation reaction; or the compound DAC and the carbon-carbon double bond having reactivity with the Si-H group and phenolic property The hydroxy compound (hereinafter referred to as compound DAH) is subjected to a hydrazine 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 hydrolysis or ‧ condensation reaction of the compound 2AS or the compound 2CS will be described.

In the compound 2AS, as R ³ is an exoethyl group, c=0, d=1, and a hydroxyl group is contained in the para position, for example, 2-(4-hydroxyphenyl)ethyltrimethoxydecane, 2 is exemplified. a trialkoxynonane such as -(4-hydroxyphenyl)ethyltriethoxydecane; 2-(4-hydroxyphenyl)ethyldimethoxymethylnonane, 2-(4-hydroxyphenyl) Ethyldiethoxymethylnonane, 2-(4-hydroxyphenyl)ethyldimethoxyethyl decane, 2-(4-hydroxyphenyl)ethyldiethoxyethyl decane, 2 -(4-hydroxyphenyl)ethyldimethoxypropyl decane, 2-(4-hydroxyphenyl)ethyldiethoxypropyl decane, 2-(4-hydroxyphenyl)ethyl dimethyl Oxybutyl decane, 2-(4-hydroxyphenyl)ethyldiethoxybutyl decane, 2-(4-hydroxyphenyl)ethyldimethoxyisobutyl decane, 2-(4- Hydroxyphenyl)ethyldiethoxyisobutylnonane, 2-(4-hydroxyphenyl)ethyldimethoxycyclohexyldecane, 2-(4-hydroxyphenyl)ethyldiethoxycyclo a dialkoxy decane such as hexyl decane; 2-(4-hydroxyphenyl)ethyl methoxy dimethyl decane, 2-(4-hydroxyphenyl)ethyl ethoxy dimethyl decane, 2- (4-hydroxyphenyl)ethyl methoxy Diethyldecane, 2-(4-hydroxyphenyl)ethylethoxydiethyldecane, 2-(4-hydroxyphenyl)ethylmethoxydipropylnonane, 2-(4-hydroxybenzene Ethyl ethoxy dipropyl decane, 2-(4-hydroxyphenyl)ethyl methoxy dibutyl decane, 2-(4-hydroxyphenyl)ethyl ethoxy dibutyl decane, 2-(4-hydroxyphenyl)ethyl methoxy diisobutyl decane, 2-(4-hydroxyphenyl)ethyl ethoxy diisobutyl decane, 2-(4-hydroxyphenyl) Monoalkoxydecanes such as methoxycyclodicyclohexyldecane and 2-(4-hydroxyphenyl)ethylethoxydicyclohexyldecane.

Among these compounds, 2-(4-hydroxyphenyl)ethyltrimethoxydecane and 2-(4-hydroxyphenyl group are preferred in terms of good reactivity and good heat resistance. Ethyltriethoxydecane, 2-(4-hydroxyphenyl)ethyldimethoxymethylnonane, 2-(4-hydroxyphenyl)ethyldiethoxymethyldecane, 2-( 4-hydroxyphenyl)ethyldimethoxyethyl decane, 2-(4-hydroxyphenyl)ethyldiethoxyethyl decane, 2-(4-hydroxyphenyl)ethyltrimethoxydecane 2-(4-hydroxyphenyl)ethyltriethoxydecane, further preferably 2-(4-hydroxyphenyl)ethyltrimethoxydecane, 2-(4-hydroxyphenyl)ethyl Dimethoxymethyldecane, 2-(4-hydroxyphenyl)ethyldimethoxyethyl decane, most preferably 2-(4-hydroxyphenyl)ethyltrimethoxydecane, 2-( 4-hydroxyphenyl)ethyldimethoxymethylnonane. The compound 2AS may be used alone or in combination of two or more.

In the compound 2CS, as R ³ is an exoethyl group, c=0, d=1, and a hydroxyl group is contained in the para position, for example, trichlorobenzene such as 2-(4-hydroxyphenyl)ethyltrichlorodecane may be mentioned. Hydranes; 2-(4-hydroxyphenyl)ethyldichloromethyl decane, 2-(4-hydroxyphenyl)ethyldichloroethyl decane, 2-(4-hydroxyphenyl)ethyldichloride Propyl decane, 2-(4-hydroxyphenyl)ethyldichlorobutyl decane, 2-(4-hydroxyphenyl)ethyldichloroisobutyl decane, 2-(4-hydroxyphenyl)ethyl Dichlorodecane such as dichlorocyclohexyldecane; 2-(4-hydroxyphenyl)ethyl chlorodimethyl decane, 2-(4-hydroxyphenyl)ethyl chlorodiethyl decane, 2-(4- Hydroxyphenyl)ethyl chlorodipropyl decane, 2-(4-hydroxyphenyl)ethyl chlorodibutyl decane, 2-(4-hydroxyphenyl)ethyl chlorodiisobutyl decane, 2-( Monochlorodecanes such as 4-hydroxyphenyl)ethylchlorodicyclohexyldecane.

Among these compounds, 2-(4-hydroxyphenyl)ethyltrichlorodecane and 2-(4-hydroxyphenyl) are preferred in terms of good reactivity and good heat resistance. Ethyl dichloromethyl decane, 2-(4-hydroxyphenyl)ethyl dichloroethyl decane, more preferably 2-(4-hydroxyphenyl)ethyl trichloro decane, 2-(4- Hydroxyphenyl)ethyldichloromethylnonane. 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, in terms of easy control of the reaction and removal of by-products, it is preferred to use the compound 2AS as an alkoxydecane compound. The order of the reaction of the compound 2AS or the compound 2CS is not particularly limited, and the compound 1AS or the compound 1CS may be reacted, and then the compound 2AS or the compound 2CS may be reacted, or the reverse order may be used, or the compound 1AS or the compound 1AS may be used. Compound 1CS is mixed with Compound 2AS or Compound 2CS to carry out a reaction.

The phenolic hydroxyl group of the compound 2AS or the compound 2CS may be as required in the following formula (2a).

[Chemical 6]

(wherein R ³ , R ⁴ , c and d have the same meanings as in the above formula (2).)

As shown, it is protected by a third butyl ether group as a protecting group. The compound protected by the protecting group can be subjected to a 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 1AS and the compound 1CS.

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-vinylphenol, 3-vinylphenol, 4-vinylphenol, 4-(1-phenylvinyl)phenol, 2-methyl-4-vinylphenol, and 2 -allylphenol, 3-allylphenol, 4-allylphenol, 2-isopropenylphenol, 3-isopropenylphenol, 4-isopropenylphenol, 4-(3-butenyl) Phenol, 4-(4-pentenyl)phenol, 4-(5-hexenyl)phenol, 4-(6-heptenyl)phenol, 4-(7-octenyl)phenol, 4-(8 -nonenyl)phenol, 4-(9-nonenyl)phenol, 2-vinyl-1,4-dihydroxybenzene, 5-vinyl-1,3-dihydroxybenzene, and the like.

Among these compounds, 2-vinylphenol, 3-vinylphenol, 4-vinylphenol, and 2-vinylphenol, 4-vinylphenol, and 4-vinylphenol are preferred in terms of industrially readily available aspects and heat resistance of the permanent resist of the present invention. 2-allylphenol, 4-allylphenol, 2-isopropenylphenol, 4-isopropenylphenol, more preferably 2-vinylphenol, 4-vinylphenol, most preferably 4 -vinylphenol. 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 the reaction may be carried out in the order of the compound DAC-compound DAH. In the reverse order, the compound DAC and the compound DAH may be mixed and reacted. 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 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 1AS and the compound 1CS.

The content of the group represented by the above formula (2) is preferably from 0 to 80, more preferably from 1 to 70, based on the molar ratio of the group represented by the above formula (1). The best is 2~60.

In view 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 trichlorodecane alkyl compound by hydrolysis and ‧ condensation reaction can be mentioned. The sterol group is liable to cause a condensation reaction, and as the content of the sterol group decreases with the operation, when the hydrolysis/densation reaction is carried out in a solvent, it is preferred that the product is not isolated, and the solvent is concentrated or Use as needed to replace 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).

The method of introducing a sterol group 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 can be carried out by using a trialkoxy decane as the compound 1AS and using trichloromethane The compound is introduced as a compound 1CS into a sterol group. In the trialkoxy decane compound, two alkoxyalkylene groups undergo hydrolysis and ‧ condensation reaction to form a bond of Si-O-Si, and one alkoxyalkylene group becomes a sterol group. Similarly, in the trichloromethane compound, two chlorodecyl groups undergo hydrolysis and ‧ condensation reaction to form a bond of Si-O-Si, and one chlorodecyl group becomes a sterol group.

When a compound having a large sterol group content is isolated, a dehydration reaction of a decyl group is likely to occur to form a bond of Si-O-Si, and a sterol group content is lowered. Therefore, after the reaction, the product is not isolated, and the solvent is concentrated. Alternatively, the solvent may be replaced with a solvent thereof, whereby the sterol group content may be increased. Even if a dialkoxy decane compound is used as the compound 1AS and a dichlorosilane 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 hydrolysis and 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 dialkoxy decane 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. The compound is preferably an aryl alkoxydecane compound, and further preferably represented by the following formula (4), in terms of improvement of heat resistance and adhesion of the permanent resist of the present invention. Aryl alkoxy decane compounds:

[Chemistry 7]

(wherein R ¹¹ represents an alkyl group or a cycloalkyl group having 1 to 6 carbon atoms which may be the same or different, R ¹² represents an alkyl group having 1 to 3 carbon atoms, and R ¹³ represents a carbon number which may be the same or different. ~4 alkyl, f represents the number of 2~3, g represents 0 or 1~5).

Examples of the alkyl alkoxydecane compound include methyltrimethoxydecane, methyltriethoxydecane, ethyltrimethoxydecane, ethyltriethoxydecane, propyltrimethoxydecane, and C. Triethoxy decane, isopropyl trimethoxy decane, isopropyl triethoxy decane, butyl trimethoxy decane, butyl triethoxy decane, isobutyl trimethoxy decane, isobutyl An alkyltrialkoxydecane compound such as triethoxydecane, tert-butyltrimethoxydecane or tert-butyltriethoxydecane, dimethyldimethoxydecane, dimethyldiethoxy Decane, diethyldimethoxydecane, diethyldiethoxydecane, dipropyldimethoxydecane, dipropyldiethoxydecane, diisopropyldimethoxydecane, diiso Propyl diethoxy decane, dibutyl dimethoxy decane, dibutyl diethoxy decane, diisobutyl dimethoxy decane, diisobutyl diethoxy decane, two (third a dialkyldialkoxydecane compound such as butyl)dimethoxydecane or di(t-butyl)diethoxydecane; as a cycloalkylalkoxy group; Examples of the decane compound include a cycloalkyltrialkoxydecane compound such as cyclohexyltrimethoxydecane or cyclohexyltriethoxydecane, dicyclohexyldimethoxydecane, dicyclohexyldiethoxydecane, and a ring. a cycloalkyl dialkoxy decane compound such as hexyl (methyl) diethoxy decane; and examples of the arylalkyl alkoxy decane compound include benzyltrimethoxydecane, benzyltriethoxydecane, and the like. Arylalkyltrialkoxydecane compounds, arylalkyldialkoxydecanes such as dibenzyldimethoxydecane, dibenzyldiethoxydecane, benzyl(methyl)dimethoxydecane Compound.

Examples of the aryl alkoxydecane compound represented by the above formula (4) include phenyltrimethoxydecane, phenyltriethoxysilane, tolylmethyltrimethoxydecane, and xylyl group. Trimethoxydecane, cumyltrimethoxydecane, tert-butylphenyltriethoxydecane, phenylmethyldimethoxydecane, phenylmethyldiethoxydecane, tolylmethyl Methyldimethoxydecane, xylylmethyldimethoxydecane, cumylmethyldimethoxydecane, phenylethyldimethoxydecane, phenylpropyldimethoxydecane , phenylbutyl dimethoxy decane, phenylhexyl dimethoxy decane, phenylcyclohexyl dimethoxy decane, phenyl dimethyl methoxy decane, and the like.

Among these compounds, phenyltrimethoxydecane, phenyltriethoxydecane, phenylmethyldimethoxydecane, and phenyl are preferred in terms of heat resistance and adhesion. Methyldiethoxydecane 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 The decyl or dialkoxy decane (preferably, the aryl alkoxy decane compound represented by the above formula (4)) is subjected to hydrolysis and condensation reaction, whereby a component (A) having a decyl group is obtained. 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.

As the compound DS, trimethoxyvinyl decane, trimethoxy allyl decane, trimethoxy isopropenyl decane, trimethoxy-3-butenyl decane, trimethoxy-4-pentenyl may, for example, be mentioned. Decane, trimethoxy-5-hexenyl decane, trimethoxy-6-heptenyl decane, trimethoxy-7-octenyl decane, trimethoxy-8-nonenyl decane, trimethoxy- 9-nonenyl decane, triethoxyvinyl decane, triethoxy allyl decane, triethoxy isopropenyl decane, triethoxy-3-butenyl decane, triethoxy- 4-pentenyl decane, triethoxy-5-hexenyl decane, triethoxy-6-heptenyl decane, triethoxy-7-octenyl decane, triethoxy-8- Decenyl decane, triethoxy-9-nonenyl decane, dimethoxymethylvinyl decane, dimethoxyethyl vinyl decane, dimethoxypropyl vinyl decane, dimethoxy Isopropyl vinyl decane, methoxydimethyl vinyl decane, methoxy diethyl vinyl decane, and the like.

Among these compounds, preferred are trimethoxyvinyl decane, triethoxyvinyl decane, trimethoxyallyl decane, and dimethoxy group in terms of improvement in heat resistance and adhesion. Methyl vinyl decane is further preferably trimethoxyvinyl decane and triethoxy vinyl decane, and most preferably trimethoxy vinyl decane. The compound DS may be used alone or in combination of two or more.

The content of the sterol group in the component (A) is preferably from 1 to 30% by mass, more preferably from 3 to 25% by mass, most preferably from 5 to 20% by mass, based on the OH content.

The method for quantifying the sterol group of the component (A) of the present invention includes a method in which a sterol group is trimethylsulfonated by trimethylchloromethane or the like and quantified by weight increase before and after the reaction ( TMS (trimethylsilyl, trimethylsilyl); by using a near-infrared spectrophotometer (refer to Japanese Patent Laid-Open No. 2001-208683, Japanese Patent Laid-Open No. 2003-35667, etc.) or ²⁹ Si-NMR (Method of quantitative analysis by machine analysis of Japanese Patent Laid-Open Publication No. 2007-217249, etc.).

As the component (A) of the present invention, it is preferred to use the following formula (3)

[化8]

(wherein R ¹ , R ³ and R ⁸ may be the same or different and each represents an alkylene group having 1 to 10 carbon atoms which may have a substituted hydrocarbon group, and R ² and R ⁴ represent a carbon number which may be the same or different. An alkyl group of 4, R ⁵ , R ⁶ and R ⁷ represent an alkyl group or a phenyl group having 1 to 10 carbon atoms which may be the same or different. a represents a number of 0 or 1 to 4, and b represents a number of 1 to 3, However, a+b does not exceed 5. c represents 0 or 1~4, d represents the number of 1~3, but c+d does not exceed 5. R ⁹ represents the same or different carbon number 1~6. Or a cycloalkyl group, R ¹⁰ represents an alkyl group having 1 to 3 carbon atoms, and e represents a number of 1 to 3. m, n and p represent m: n: p = 1: 0 to 2: 0.5 to 3 and m + n+p=3~6.)

An anthracene resin obtained by reacting a cyclic siloxane compound represented by the above-mentioned aryl alkoxy decane 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, R ¹ , R ² , R ³ and R ⁴ and a, b, c and d, are passed. The description of the formula (1) and the formula (2) is suitably applied. R ⁸ 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 R ⁵ , R ⁶ and R ⁷ represent an alkyl group or a phenyl group having 1 to 10 carbon atoms which may be the same or different. . R ⁹ represents an alkyl group or a cycloalkyl group having 1 to 6 carbon atoms which may be the same or different, and R ¹⁰ represents an alkyl group having 1 to 3 carbon atoms.

Examples of the alkylene group having 1 to 10 carbon atoms include an alkylene group exemplified as R ¹ and a substituted hydrocarbon group which may be represented by R ⁸ . The hydrocarbon group exemplified as R ¹ may be mentioned as the carbon number 1 to 10 The alkyl group may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, a third butyl group, a pentyl group, a second pentyl group or a third pentyl group. Hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, trioctyl, decyl, isodecyl, fluorenyl, as alkyl having 1 to 6 carbon atoms, may be exemplified by R ¹⁵ , R R ¹⁷ and ¹⁶ of the embodiment shown an alkyl group, cycloalkyl group, include: cyclopentyl, cyclohexyl, methylcyclopentyl, cyclopentylmethyl, 1 to 3 carbon atoms as the alkyl group include: Methyl, ethyl, propyl, isopropyl.

In terms of ease of industrial availability, R ¹ , R ³ and R ^{8 are} preferably an ethyl group, a propyl group and a butyl group, and more preferably an ethyl group and a butyl group. It is an ethyl group. R ⁵ , R ⁶ and R ^{7 are} preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl and phenyl, in terms of ease of industrial availability. In terms of improvement in heat resistance, R ⁵ , R ⁶ and R ^{7 are} more preferably a methyl group, an ethyl group and a phenyl group, and most preferably a methyl group. In terms of improvement in heat resistance, R ^{9 is} preferably a methyl group or an ethyl group, and more preferably a methyl group. In terms of improvement in heat resistance, R ^{10 is} preferably a methyl group.

e represents the number of 1~3, m, n and p represent the number of m:n:p=1:0~2:0.5~3 and m+n+p=3~6. The cyclic siloxane compound represented by the formula (3) may be used alone or in combination of two or more. When two or more types are used in combination, the number of m, n, and p is an average number. For example, an equimolar mixture of a compound of m=1, n=0, p=3 and a compound of m=1, n=1, p=2 can be expressed as m:n:p=1:0.5:2.5. In terms of improvement in chemical resistance after a high temperature heat history, n is preferably 0 to 1 with respect to m, more preferably 0.01 to 0.7, and most preferably 0.02 to 0.5. Further, in terms of improvement in thermal crosslinkability of the positive photosensitive composition of the present invention, p 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 groups derived from the cyclic siloxane compound represented by the general formula (3) are present in the molecule of the oxirane resin, so that the values of m, n and p of the general formula (3) become The average value in the molecule.

A compound in which a carboxyl group or a phenolic hydroxyl group is protected by a third butyl group or the like can be used, for example, the following formula (3a)

[Chemistry 9]

(wherein R ¹ to R ¹⁰ , a, b, c, d, e, m, n and p have the same meanings as in the above formula (3).)

The cyclic oxoxane compound represented by the above formula (3) is substituted for the cyclic oxirane compound 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, a heptane group having a glycidyl group as a component (B) of the present invention will be described.

The glycidyl group-containing oxirane compound as the component (B) of the present invention has at least one glycidyl group and at least one fluorenylalkyl group (a group represented by Si-O-Si) in one molecule. The number of the glycidyl groups is preferably at least two in one molecule, and examples of the glycidyl group-containing oxirane compound include the following formula (7).

[化10]

(wherein, Y represents a group having a glycidyl group or a methyl group, G represents a group having a glycidyl group, R ²¹ represents a methyl group or a phenyl group which may be the same or different, and R ²² , R ²³ and R ²⁴ represent The same or different carbon number of 1~6 alkyl, carbon number 5~6 cycloalkyl or phenyl, u represents the number of 0~1000, w represents the number of 0~1000. Among them, u is 0 or In the case of 1, Y represents a hydrogen atom.)

The linear siloxane compound represented by the following formula (8)

[11]

(wherein R ²⁵ , R ²⁶ and R ²⁷ 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 group having a glycidyl group, x represents the number of 2~6, and y represents the number of 0~4 where x+y becomes 3~6.)

A cyclic oxirane compound and a hydrolysis condensation reaction product of a glycidyl group-containing alkoxysilane.

First, the linear siloxane compound represented by the above formula (7) will be described.

In the above formula (7), Y represents a group having a glycidyl group or a methyl group, G represents a group having a glycidyl group, and R ²¹ represents a methyl group or a phenyl group which may be the same or different, R ²² and R ²³ And R ²⁴ represents 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.

In terms of ease of manufacture, R ^{21 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 those exemplified as R ¹⁵ , R ¹⁶ and R ¹⁷ . In terms of ease of manufacture, R ^{22 is} preferably a methyl group and an ethyl group, and more preferably a methyl group. In terms of heat resistance of the permanent resist of the present invention, R ²³ and R ^{24 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 methyl group. .

X represents a hydrogen atom or a methyl group, u represents a number from 0 to 1000, w represents a number from 0 to 1000, and when u is 0 or 1, X represents a hydrogen atom.

The linear siloxane compound represented by the above formula (7) can be obtained by the above formula (5) by using a compound having a carbon-carbon double bond and a glycidyl group having reactivity with a Si-H group. The linear compound shown is produced by a hydrazine hydrogenation reaction.

Examples of the compound containing a carbon-carbon double bond and a glycidyl group having reactivity with a Si-H group include vinyl glycidyl ether, allyl glycidyl ether, and 5-glycidoxypropyl group. 2-norbornurethane or the like is preferably an allyl glycidyl ether in terms of ease of industrial availability and reactivity with hydrazine hydrogenation.

When the ratio of the epoxy group in the molecule of the linear siloxane compound represented by the above formula (7) is too small, the crosslinking effect is small, and the physical properties of the permanent resist of the present invention are lowered, so 7) The epoxy equivalent of the linear azide compound represented by the catalyst is preferably 1,000 or less, more preferably 700 or less, and most preferably 350 or less. Further, the epoxy equivalent means a value obtained by dividing the molecular weight by the number of epoxy groups, that is, a molecular weight corresponding to one epoxy group.

The molecular weight of the linear siloxane compound represented by the above formula (7) is not particularly limited. However, when it is too large, the solubility or dispersibility of the alkaline developer is lowered, and after alkaline development. When the resist residue remains on the surface of the substrate, the mass average molecular weight is preferably 20,000 or less, more preferably 15,000 or less, and most preferably 10,000 or less.

Next, the cyclic siloxane compound represented by the above formula (8) will be described.

In the above formula (8), R ²⁵ , R ²⁶ and R ²⁷ represent an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 5 to 6 carbon atoms which may be the same or different, and G represents a shrinkage. Glyceryl 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 as R ¹⁵ , R ¹⁶ and R ¹⁷ .

In terms of ease of manufacture, R ^{25 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, R ²⁶ and R ^{27 are} preferably a methyl group, an ethyl group and a phenyl group, more preferably a methyl group and a phenyl group, and most preferably methyl.

x represents the number of 2~6, and y represents the number of 0~4 where x+y becomes 3~6. In terms of industrial availability, x+y is preferably 4-6, and more preferably 4-5, and most preferably 4. Also, y is preferably 0.

The cyclic oxirane compound represented by the above formula (8) can be obtained by reacting a compound having a carbon-carbon double bond and a glycidyl group having reactivity with a Si-H group with the above formula (6) The cyclic compound shown is produced by a hydrazine hydrogenation reaction.

Next, the hydrolysis/condensation reaction of the alkoxysilane having a glycidyl group will be described.

Hydrolysis/condensation reaction of a glycidyl group-containing alkoxy decane The hydrolysis of a glycidyl group-containing alkoxy decane is carried out by a known method, for example, the method described in the hydrolysis of the compound 1AS or the compound 1CS, the condensation reaction, and the like. ‧ compounds obtained by condensation reaction.

Examples of the alkoxydecane having a glycidyl group include a glycidyl alkoxydecane compound such as glycidyl trimethoxydecane or glycidyl triethoxysilane; 2-glycidoxyethyltrimethyl a glycidoxyethylalkoxydecane compound such as oxydecane or 2-glycidoxyethylmethyldimethoxydecane; 3-glycidoxypropyltrimethoxydecane, 3-glycidyloxy Propylmethyldimethoxydecane, 3-glycidoxypropylethyldimethoxydecane, 3-glycidoxypropylphenyldimethoxydecane, bis(3-glycidoxy) Propyl)dimethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 3-glycidoxypropylethyl 3-glycidoxypropyl alkoxy groups such as diethoxydecane, 3-glycidoxypropyl phenyl diethoxy decane, bis(3-glycidoxypropyl) diethoxy decane Decane compound; 2-(4-glycidoxyphenyl)ethyltrimethoxydecane, 2-(4-glycidoxyphenyl)ethyltriethyl 2-(4-glycidoxyphenyl)ethylalkoxydecane compound such as decane or the like; 5-(glycidoxymethyl)norbornyltrimethoxydecane, 6-(glycidyloxymethyl) A glycidyloxymethylnorbornyloxy alkane compound such as a thiol trimethoxydecane.

Among these compounds, a 3-glycidoxypropyl alkoxydecane compound is preferred in terms of reactivity of the hydrolysis/condensation reaction and ease of industrial availability. Among the 3-glycidoxypropyl alkoxydecane compounds, more preferred are 3-glycidoxypropyltrimethoxydecane and 3-glycidoxypropylmethyldimethoxydecane. Bis(3-glycidoxypropyl)dimethoxydecane, 3-glycidoxypropyltriethoxydecane, more preferably 3-glycidoxypropyltrimethoxydecane, 3 - Glycidoxypropyltriethoxydecane, most preferably 3-glycidoxypropyltrimethoxydecane.

In the case of producing a hydrolysis/condensation reactant of a glycidyl group-containing alkoxydecane, in addition to the glycidyl group-containing alkoxydecane, other alkoxydecane compounds having no glycidyl group may be used in combination. The other alkoxydecane compound may be exemplified as the other exemplified method of introducing a sterol group or a method of increasing the sterol group content as another trialkoxy decane or dialkoxy decane.

When the ratio of the epoxy group in the molecule of the hydrolysis/densation reactant of the glycidyl group is too small, the crosslinking effect is small, 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 350 or less.

The molecular weight of the hydrolysis/densation reactant of the glycidyl group having a glycidyl group is not particularly limited, but when it is too large, the solubility or dispersibility of the alkaline developer is lowered, and the surface of the substrate after alkali development remains resistant. In the case of the etchant residue, the mass average molecular weight is preferably 20,000 or less, more preferably 15,000 or less, and most preferably 10,000 or less.

The hydrolysis/condensation reactant of the alkoxydecane having a glycidyl group preferably has a decyl group. The content of the sterol group in the hydrolysis/densation reaction of the glycidyl group having a glycidyl group is preferably from 1 to 30% by mass, more preferably from 3 to 25% by mass.

The hydrolysis/densation reactant of a glycidyl group-containing alkoxysilane having a trialkoxy decane compound is used in the presence of a crosslinked structure caused by a Si—O—Si bond, and also due to the crosslinking. The structure is a structure such as a ladder shape, a cage shape, or a ring shape. The hydrolysis/densation reaction product of the glycidyl group-containing alkoxysilane having a glycidyl group-containing trialkoxy decane compound and other trialkoxy decane compound can be represented, for example, by the following formula (9). :

[化12]

(wherein G represents a group having a glycidyl group, R ²⁸ represents an alkyl group or a phenyl group having 1 to 10 carbon atoms which may be the same or different, i represents a number of 2 or more, and k represents a number of 0 or more, h represents the number of 0~2, and j represents the number of 0~2, where h×i+j×k does not exceed h+i+2).

In the above formula (9), G represents a group having a glycidyl group, and R ²⁸ represents an alkyl group or a phenyl group having 1 to 10 carbon atoms which may be the same or different. In terms of heat resistance, R ^{28 is} preferably a methyl group, an ethyl group or a phenyl group, more preferably a methyl group and a phenyl group, and most preferably a methyl group.

i represents a number of 2 or more, k represents a number of 0 or more, and h represents a number of 0 to 2. h×i+j×k 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)

[Chemistry 13]

Is derived from a portion of a trialkoxy decane compound having a glycidyl group, the latter half of the above formula (9)

[Chemistry 14]

It is derived from parts of other trialkoxy decane compounds.

With respect to the improvement of the chemical resistance after the high-temperature heat history, the content of the glycidyl group-containing oxirane compound as the component (B) is preferably 100 parts by mass of the (A) oxime resin. 1 to 100 parts by mass, more preferably 3 to 50 parts by mass, most preferably 5 to 20 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 (10)

[化15]

The substituted compound (4-diazonaphthoquinone sulfonate) or the following formula (11)

[Chemistry 16]

Substituted compound (5-diazonaphthoquinone sulfonate).

Preferred examples of the diazonaphthoquinones include, for example, the compounds represented by the following formulas (12) to (17), and the positional isomers thereof.

[化17]

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

[化18]

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

[Chemistry 19]

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

[Chemistry 20]

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

[Chem. 21]

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

[化22]

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

The base represented by the formula (10) has absorption in the i-line (wavelength: 365 nm) region, so it is suitable for i-line exposure, and the base represented by the formula (11) has absorption in a wide range of wavelength regions, so it is suitable for The exposure at a wide range of wavelengths is preferably selected from the group represented by the formula (10) 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 resist of the present invention, it is preferred that the content of the diazonaphthoquinone as the component (C) is 0.1 part by mass based on 100 parts by mass of the (A) epoxy resin. ~10 parts by mass, preferably 1 to 5 parts by mass.

Next, an organic solvent which is the component (D) of the present invention will be described.

The organic solvent (D) which can be used in the present invention is an organic solvent which can dissolve or disperse the above (A) anthracene resin, (B) a glycidyl ether group-containing oxirane compound, and (C) a diazonaphthoquinone group. Further, it is not particularly limited, and an organic solvent capable of dissolving 1% by mass or more of water at 25 ° C is preferable as the organic solvent, except for the organic solvent exemplified in the description of the removal of the protective group of the third butyl group. Further, γ-butyrolactone, γ-valerolactone, δ-valerolactone, ethylene carbonate, propylene carbonate, dimethyl carbonate, and the like can be also exemplified.

A compound which is protected by a carboxyl group in the group represented by the above formula (1) or a phenolic hydroxyl group in the group represented by the above formula (2), for example, a ring represented by the above formula (3a) In the case of the oxirane compound, the organic solvent used in the desorption reaction of the third butyl group can be directly used as the organic solvent of the component (D) of the present invention.

The formability of the permanent resist formed by using the positive photosensitive composition of the present invention and the physical properties of the obtained permanent resist are preferably 100 parts by mass relative to (A) the epoxy resin. The content of the organic solvent as the component (D) is from 10 to 10,000 parts by mass, more preferably from 100 to 1,000 parts by mass.

The positive photosensitive composition of the present invention dissolves or disperses (A) an oxirane resin, (B) a glycidyl ether group-containing oxirane compound, (C) a diazonaphthoquinone, and (D) an organic solvent. It can also be filtered by a filter having a pore diameter of about 0.2 μm, for example, and then used.

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 dispersant, an antifoaming agent, a pigment, a dye, or the like may be blended as needed.

Next, the permanent resist of the present invention will be described. The permanent resist of the present invention is produced by using the above positive photosensitive composition. Hereinafter, an example of a preferred method for producing a permanent resist of the present invention will be described in order of steps.

(Step 1) 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 chemical resistance to an organic solvent or the like in the positive photosensitive composition, and heat resistance in the fourth step by the development of the alkaline solution and the treatment in the sixth step. The material 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 is not particularly limited, and various methods such as a spin coating method, a dip coating method, a blade coating method, a roll coating method, a spray coating method, and a slit coating method can be used.

Thereafter, the (D) organic solvent is removed from the positive photosensitive composition layer formed by coating the coating material on the substrate, and pre-bake is performed. The pre-baked positive photosensitive composition layer is poorly soluble in an alkaline solution, and in the next exposure step, a portion irradiated with light (hereinafter, sometimes referred to as an exposed portion) becomes a base. Solubility.

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. Further, 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 it is preferably 60 to 140 ° C. Further preferably 70 to 120 ° C. The prebaking time varies depending on the kind of the organic solvent to be used and the prebaking temperature, and is preferably from 30 seconds to 10 minutes, and more preferably from 1 to 5 minutes.

The positive photosensitive composition of the present invention may be directly pre-baked after being applied to a target substrate, but the physical properties and chemical resistance of the permanent resist of the present invention after the high heat history may be used. In terms of improvement, it is preferred to adjust the concentration of the organic solvent in the positive photosensitive composition layer at room temperature to below 60 ° C, at normal pressure or under reduced pressure before prebaking. After the organic solvent is volatilized to be 5% by mass or less, prebaking is performed.

The thickness of the positive photosensitive composition layer after prebaking differs depending on the use of the permanent resist of the present invention, but is not particularly limited and is 0.1 μm to 100 μm, preferably 0.3 μm to 10 μm. Just fine.

(Step 2) Exposure step

The exposing step is a step of irradiating the pre-baked positive photosensitive composition layer with the patterned light to increase the alkali solubility of the exposed portion. The pre-baked positive photosensitive composition layer is poorly soluble in an alkaline solution, but the diazonaphthoquinone in the exposed portion is decomposed by light irradiation to become hydrazinecarboxylic acid, thereby being soluble and dispersible in an alkaline solution. in.

The light to be irradiated is not particularly limited, and may be light having an alkali solubility of the light-irradiated portion of the pre-baked positive photosensitive composition layer, and is preferably, for example, 10 to 1000 mJ/cm ² . 40~300mJ/cm ² .

Further, the wavelength of the irradiation light may be visible light or ultraviolet light, and is not particularly limited, and a high pressure mercury lamp, an ultrahigh pressure mercury lamp, or the like is used, and 4-diazonaphthoquinone sulfonate is used as (C) diazonaphthoquinone. In the case of a class, a narrow-wavelength light mainly composed of an i-line (365 nm) may be irradiated, and when a 5-diazonaphthoquinone sulfonate is used as the (C) diazonaphthoquinone, the irradiation includes an i-line. Light of a wide wavelength (365 nm), h line (405 nm), and g line (436 nm) may be used.

The method of patterning the irradiation light is not particularly limited, and may be a previously known method, for example, a light irradiation method such as a photomask or a selective light irradiation method using laser light.

(Step 3) development step

The developing step is a step of obtaining a specific pattern by removing a portion where the alkali solubility is improved by light irradiation in the exposure step by using a developing solution.

As the developing method, for example, any of a shoal development method, a dipping method, a shower method, a spray method, and the like can be used.

The development time varies depending on the type and molecular weight of the (A) oxirane resin or (B) the glycidyl ether group having a glycidyl ether group, the temperature of the developer, and the like, and is usually 30 to 180 seconds.

The developer to be used in the development step is not particularly limited as long as it can be dissolved or dispersed in the liquid, and can be used, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or citric acid. Inorganic bases such as sodium and ammonia; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-propylamine; trimethylamine, methyldiethylamine, dimethylethylamine, triethylamine, etc. Tertiary amines; tertiary alkanolamines such as dimethylethanolamine, methyldiethanolamine, triethanolamine; pyrrole, piperidine, N-methylpiperidine, N-methylpyrrolidine, 1,8-diaza a cyclic tertiary amine such as heterobicyclo[5.4.0]-7-undecene or 1,5-diazabicyclo[4.3.0]-5-nonene; pyridine, trimethylpyridine, dimethyl An aromatic tertiary amine such as pyridine or 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, the concentration of which is better than the previous positive photosensitive The alkali concentration of the developer used in the removal of the composition layer. The aqueous solution of the base may further contain an appropriate amount of a water-soluble organic solvent such as methanol or ethanol and/or a surfactant.

After the exposed portion is removed by the developer, it is preferred to rinse with water by running water or spraying, and it may be dehydrated and dried in the range of 50 to 120 °C as needed.

(Step 4) Bleach exposure step

The bleaching exposure 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.

Since the resist layer contains diazonaphthoquinone, it is colored yellowish or light brown. 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 A permanent resist for an active matrix substrate used in an EL display device or the like.

The irradiation light in the bleaching exposure step is not particularly limited, and for example, it is preferably irradiated with light of 10 to 1000 mJ/cm ² , preferably 40 to 600 mJ/cm ² . 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.

(Step 5) post-baking step

The bleached exposed resist layer has improved visible light transmittance and improved alkali solubility. In the post-baking step, the above-mentioned bleach-exposed resist layer is subjected to heat treatment at 120 ° C or higher to thermally crosslink the epoxy resin in the resist layer, thereby imparting heat resistance and chemical resistance required for the permanent resist. Sexual and time-changing.

In the present invention, the glycidyl ether group having a glycidyl ether group as the component (B) of the positive photosensitive composition functions as a crosslinking agent to obtain a resistance after the high heat history which has not been hitherto. Chemically. The post-baking is preferably carried out in an inert gas atmosphere such as nitrogen, helium or argon at a temperature of 120 to 400 ° C for 15 minutes to 2 hours, more preferably at a temperature of 120 to 350 ° C for 15 minutes. 2 hours, and further preferably 15 minutes to 2 hours at a temperature of 200 to 350 °C.

The permanent resist of the present invention is excellent not only in transparency, insulation, heat resistance, chemical resistance, but also in heat history (high heat history) at a high temperature of about 300 to 350 ° C, transparency, insulation, and chemical resistance. An interlayer insulating film (layer) or a planarizing film for an active matrix substrate used in a liquid crystal display device, an organic EL display device, or the like, in particular, an active matrix including a TFT having a polycrystalline germanium film as an active layer. It is extremely useful for an interlayer insulating film (layer) for a substrate or a planarizing film.

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 film, bump protection film, MCM (Multi-Chip Module) interlayer protection film, junction coating), and packaging material (sealing material) , bonded crystal).

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 discrete semiconductor elements such as a diode, a transistor, a compound semiconductor, a thermistor, a varistor, and a thyristor: DRAM (Dynamic Random Access Memory) and SRAM (Static Random) Access Memory, Static Random Access Memory, EPROM (Erasable Programmable Read Only Memory), Masked Only Memory (Mask Read Only Memory), Memory components such as EEPROM (Electrical Erasable Programmable Read Only Memory) and flash memory: microprocessor, DSP (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 IC) ), a photoelectric conversion element such as a light-emitting diode or a charge-bonding element. Moreover, as a multilayer wiring board, a high-density wiring board, such as MCM, etc. are mentioned.

Example

The present invention will be further illustrated by the following examples, but the invention is not limited thereto.

Further, the content of the sterol group is determined by reacting the sample with trimethylchlorosilane in a pyridine solution to convert the sterol group into a trimethyldecane ether group, and then using tetramethylammonium hydroxide ((CH ₃ ) ₄ NOH The aqueous solution is treated to hydrolyze the CO-Si bond, and is calculated by recalculating the weight increase rate after the reaction.

[(A) Manufacture of enamel resin (a)]

100 parts by mass of 2,4,6,8-tetramethylcyclotetraoxane, 85 parts by mass of 4-vinylbenzoic acid-t-butyl ester, and 4-tert-butoxy group are added to 300 parts by mass of toluene. 110 parts by mass of styrene, 93 parts by mass of trimethoxyvinyl decane, and 0.0001 parts by mass of a platinum-divinyltetramethyldioxane complex (Karstedt catalyst) were reacted at 60 ° C while stirring. 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 siloxane compound (a-1) was a viscous liquid at 25 ° C, and no peak of 4.3 to 5.0 ppm derived from a hydrogen atom derived from Si-H group was observed by ¹ H-NMR analysis. As a result of analysis by GPC, the mass average molecular weight was 900 (theoretical molecular weight was 933.1), and it was confirmed that the peak area ratio derived from unreacted 4-vinylbenzoic acid-t-butyl ester disappeared to 0.5% or less.

Then, 40 parts by mass of phenyltrimethoxydecane (corresponding to the compound of the above formula (4)) and 200 parts by mass of toluene are added to 100 parts by mass of the above cyclic siloxane compound (a-1). 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 reflux-dehydrated and de-alcoholated at 50 ° C under reduced pressure, and solvent exchange was carried out at 50 ° C under reduced pressure to replace the solvent toluene. -Methoxy-2-propanol acetate (hereinafter referred to as PGMEA), thereby obtaining a 25% PGMEA solution of the intermediate product (a-2).

In order to remove the third butyl group, 400 parts by mass of a PGMEA solution of 25% of the intermediate product (a-2) and 3 parts by mass of a boron trifluoride diethyl ether complex were added, and the mixture was stirred at 80 ° C for 3 hours, followed by decompression. 100 parts by mass of the desolvation treatment was carried out, and after adding 10 parts by mass of an acidic adsorbent (manufactured by Kyowa Chemical Industry Co., Ltd., trade name: Kyowaad 500SH), the mixture was stirred at 80 ° C for 1 hour to obtain a slurry solution. The solution 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) Manufacture of epoxy resin (b)]

To 100 parts by mass of the above-mentioned cyclic siloxane compound (a-1), 8 parts by mass of phenyltrimethoxydecane 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. 50 parts by mass of a 5% aqueous solution of oxalic acid was added dropwise. After stirring for 15 hours while maintaining the temperature in the system at 10 ° C, reflux dehydration and decoholization were carried out under reduced pressure at 50 ° C, and solvent exchange of toluene and PGMEA was carried out at 50 ° C under reduced pressure to obtain an intermediate portion. 25% of the PGMEA solution of product (b-2).

Hereinafter, the same operation as 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 epoxy resin (b) by GPC analysis was 9,500, and the sterol group content was 4.2% by mass.

[(A) Manufacture of enamel resin (c)]

40 parts by mass of phenyltrimethoxydecane was added to 200 parts by mass of toluene, and while cooling and stirring in an ice bath at 10 ° C, 50 parts by mass of a 5% aqueous oxalic acid solution was added dropwise thereto for 1 hour, and then stirred at 10 ° C. 3 hours. In the reaction mixture, while cooling and stirring in an ice bath at 10 ° C, 44 parts by mass of 2-(4-t-butoxycarbonylphenyl)ethyltrimethoxydecane was added dropwise thereto over 1 hour. a mixture of 4-tert-butoxyphenyl)ethyltrimethoxydecane in 56 parts by mass, and then stirred at 10 ° C for 15 hours, then subjected to reflux dehydration and de-alcohol treatment at 50 ° C under reduced pressure, at 50 The solvent exchange of toluene and PGMEA was carried out under reduced pressure at ° C 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) Manufacture of enamel resin (d)]

In place of 21 parts by mass of 4-vinylbenzoic acid-t-butyl ester, 85 parts by mass of 4-vinylbenzoic acid-t-butyl ester and 110 parts by mass of 4-t-butoxystyrene were used. The same operation as in the production of the above (A) oxime resin (a) was carried out to obtain a PGMEA solution of 30% of the (A) oxime resin (d) of the present invention. 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) Manufacture of enamel resin (e)]

Using 100 parts by mass of 2-(4-t-butoxycarbonylphenyl)ethyltrimethoxydecane instead of 44 parts by mass of 2-(4-t-butoxycarbonylphenyl)ethyltrimethoxydecane Except for the mixture of 56 parts by mass of 2-(4-t-butoxyphenyl)ethyltrimethoxydecane, the same operation as in the production of the above (A) oxime resin (c) was carried out, thereby obtaining (A) A 30% PGMEA solution of the epoxy resin (e) of the present invention. Further, the mass average molecular weight of the epoxy resin (e) by GPC analysis was 7,200, and the sterol group content was 10.1% by mass.

[(A) Manufacture of oxime resin (f)]

170 parts by mass of 4-vinylbenzoic acid-t-butyl ester and 36.7 parts by mass of p-tert-butoxystyrene were used instead of 4-vinylbenzoic acid-t-butyl ester 85 parts by mass and 4-third Except for 110 parts by mass of oxystyrene, the same operation as in the production of the above (A) oxime resin (a) is carried out to obtain a PGMEA solution of 30% of the (A) oxirane resin (f) of the present invention. . Further, the mass average molecular weight of the epoxy resin (f) by GPC analysis was 7,800, and the sterol group content was 5.1% by mass.

[Comparison of the manufacture of oxime resin (g)]

184 parts by mass of 4-tert-butoxy styrene was used instead of 85 parts by mass of 4-vinylbenzoic acid-t-butyl ester and 110 parts by mass of 4-t-butoxy styrene, and The above (A) oxirane resin (a) was produced in the same manner to obtain a PGMEA solution of 30% of the comparative oxime resin (g) having no group represented by the above formula (1). Further, the mass average molecular weight of the epoxy resin (g) by GPC analysis was 6,700, and the sterol group content was 4.8% by mass.

[Comparison of the manufacture of oxime resin (h)]

Using 100 parts by mass of 2-(4-t-butoxyphenyl)ethyltrimethoxydecane instead of 44 parts by mass of 2-(4-t-butoxycarbonylphenyl)ethyltrimethoxydecane In the same manner as the above-mentioned (A) oxirane resin (c), a mixture of 56 parts by mass of 2-(4-t-butoxyphenyl)ethyltrimethoxy decane was obtained, thereby obtaining no A PGMEA solution having 30% of the comparative oxime resin (h) represented by the above formula (1). Further, the mass average molecular weight of the epoxy resin (h) by GPC analysis was 7,400, and the sterol group content was 10.4% by mass.

[Comparison of the manufacture of oxime resin (i)]

According to Synthesis Example 1 of the example of JP-A-2008-116785, 100 parts by mass of methyltrimethoxydecane and phenyltrimethoxydecane are added to 157 parts by mass of diacetone alcohol (hereinafter referred to as DAA). 78 parts by mass, while stirring at room temperature, 61 parts by mass of a 0.3% aqueous phosphoric acid solution was added dropwise over 10 minutes. Thereafter, the mixture was stirred at 40 ° C for 30 minutes, and then heated to 105 ° C for 30 minutes, and further stirred at 105 ° C for 2 hours, thereby obtaining a comparative DAA solution of the epoxy resin (i). The DAA solution of the epoxy resin (i) had a solid content of 39% by mass, a water content of 1.8% by weight, and a mass average molecular weight of the oxime resin (i) of 6,000.

[(B) Manufacture of a heptane compound (j) having a glycidyl ether group]

100 parts by mass of 2,4,6,8-tetramethylcyclotetraoxane, 190 parts by mass of allyl glycidyl ether, and platinum-divinyltetramethyldioxane are added to 300 parts by mass of toluene. 0.0001 part by mass of the complex compound (Karstedt catalyst) was reacted at 50 to 60 ° C for 15 hours while stirring. The solvent was distilled off under reduced pressure from the reaction mixture at 60 ° C to obtain (b) a glycidyl ether compound (j) having a glycidyl ether group of the present invention. The decane compound (j) was a viscous liquid at 25 ° C, and the epoxy equivalent was 174. No peak derived from a hydrogen atom of the Si-H group was observed in the NMR analysis. Further, the mass average molecular weight obtained by GPC analysis was 700, and the peak derived from unreacted allyl glycidyl ether could not be confirmed.

[(B) Production of a heptane compound (k) having a glycidyl ether group]

100 parts by mass of 1,1,3,3-tetramethyldioxane, 170 parts of allyl glycidyl ether, and platinum-divinyltetramethyldioxane are added to 50 parts by mass of toluene. 0.0005 parts by mass of a substance (Karstedt catalyst) was reacted at 50 to 60 ° C for 15 hours while stirring. The solvent was distilled off under reduced pressure from the reaction mixture at 60 ° C to obtain (b) a glycidyl ether compound (k) having a glycidyl ether group of the present invention. The oxirane compound (k) had an epoxy equivalent of 182, and no peak derived from a hydrogen atom of the Si-H group was observed in the NMR analysis. Further, the mass average molecular weight obtained by GPC analysis was 360, and the peak derived from unreacted allyl glycidyl ether could not be confirmed.

[(B) Manufacture of a phthalic acid compound (1) having a glycidyl ether group]

100 parts by mass of phenyltrimethoxydecane and 40 parts by mass of 3-glycidoxypropyltrimethoxydecane were added to 150 parts by mass of toluene, and the mixture was stirred at 30 ° C for 30 minutes while being cooled in an ice bath. 5 parts by mass of formic acid 50 parts by mass. After stirring for 15 hours while maintaining the temperature in the system at 10 ° C, water was added and washed with water until the water layer became neutral. While refluxing at 50 ° C under reduced pressure, water and methanol formed by the reaction were removed, and then solvent exchange of toluene and PGMEA was carried out at 50 ° C under reduced pressure to obtain (B) glycidol of the present invention. A 40% PGMEA solution of an ether-based oxoxane compound solution (1). In the FT-IR (Fourier Transform Tnfrared) analysis, the glycidyl ether group-containing oxirane compound solution (1) was confirmed to have a broader absorption derived from a sterol group at 3100 to 3700 cm ^-1 . The epoxy equivalent was 560, and the mass average molecular weight obtained by GPC analysis was 4000, and the sterol group content was 11.2% by mass.

[Comparison of Preparation of Oxysiloxane Compound (m) Having Epoxy Group]

The operation similar to the above-mentioned (B) oxirane compound (j) having a glycidyl ether group is carried out, except that 207 parts by mass of propylene oxide cyclohexene is used instead of 190 parts by mass of allyl glycidyl ether. Thus, a comparative oxirane compound (m) having an epoxy group was obtained. The decane compound (m) was a viscous liquid at 25 ° C, and the epoxy equivalent was 183. No peak derived from a hydrogen atom of the Si-H group was observed in the NMR analysis. Further, the mass average molecular weight obtained by GPC analysis was 730, and it was not possible to confirm the peak derived from one of the unreacted oxyethylene cyclohexene.

Comparison of compounds with epoxy groups (n)

Diglycidyl ether of bisphenol A (manufactured by ADEKA, trade name: Adeka Resin EP-4100)

Comparison of compounds with epoxy groups (p)

3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate (manufactured by Daicel Chemical Industry Co., Ltd., trade name: Celloxide 2021P)

(C) Diazonaphthos (DNQ)

All of the compounds of the above formula (12) wherein Q is a group represented by the formula (11) (manufactured by Daito Chemix Co., Ltd., trade name: PA-6)

[Examples 1 to 11 and Comparative Examples 1 to 16] Preparation of Positive Photosensitive Composition

After the preparation was carried out in the ratio shown in [Table 1], the mixture was filtered through a filter having a pore size of 0.2 μm, and then the positive photosensitive compositions of Examples 1 to 11 and Comparative Examples 1 to 16 were prepared. Further, the solvent is added to the value in the table.

The positive photosensitive compositions of Examples 1 to 11 and Comparative Examples 1 to 16 were subjected to the following evaluations. The results are shown in [Table 2].

(Preparation method of test piece)

The positive photosensitive composition is applied to a square glass substrate of 25 mm in length and 25 mm in width or an ITO (Indium Tin Oxide) vapor-deposited glass substrate by a spin coating method to a thickness of 4 to 5 μm. (ITO thick: 100 nm), the solvent was then volatilized and used for the test piece. Further, the positive photosensitive composition was used after being stored in a thermostat at 23 ° C for 1 day (24 hours). Further, for the storage stability test, a test piece of a glass substrate was also prepared for a positive photosensitive composition which was stored for 7 days and 60 days in a thermostat at 23 °C.

In the case of using a test piece of a glass substrate, after heat-treating the test piece at 80 ° C for 2 minutes, a mask having a line width of 5 μm was placed on the upper portion of the glass substrate, and the ultrahigh pressure mercury lamp was 70 mJ/cm ² (wavelength 365 nm). Exposure conversion) Irradiation of ultraviolet rays. Then, the test piece was immersed in an aqueous solution of 2.38 mass% of tetramethylammonium hydroxide at a liquid temperature of 23 ° C for 70 seconds, and then washed and air-dried. The air-dried test piece was irradiated with ultraviolet light by an ultrahigh pressure mercury lamp at 200 mJ/cm ² (wavelength conversion of 365 nm), and then heated at 230 ° C for 60 minutes in an atmospheric environment, or at 350 ° C under a nitrogen atmosphere. A heat treatment was performed for 30 minutes to form a permanent resist film.

In the case of using a test piece in which an ITO vapor-deposited glass substrate was used, the test piece was heat-treated at 80 ° C for 2 minutes, and then irradiated with an ultrahigh pressure mercury lamp at 200 mJ/cm ² (wavelength of 365 nm exposure) without using a photomask. After the ultraviolet ray, it was subjected to heat treatment at 230 ° C for 60 minutes in an atmospheric environment, or heat treatment at 350 ° C for 30 minutes in a nitrogen atmosphere. A wiring of A1 was formed on the upper portion of the permanent resist film by a vapor deposition method to prepare a test piece for measuring a 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 glass substrate from which the alkali-soluble portion was removed was observed using a scanning electron microscope, and evaluated according to the following <Evaluation Criteria>. Save stability. The resist residue is produced by partially reducing the amount of the positive photosensitive composition and reducing the solubility or dispersibility of the alkaline developer. The test piece was carried out for each test piece of the positive photosensitive composition which was stored at 23 ° C for 1 day, 7 days, and 60 days, respectively. Further, in the positive photosensitive composition which was stored for 1 day or 7 days, the test piece of the positive photosensitive composition in which the resist residue was observed was not used in the subsequent test.

<Evaluation criteria>

◎: Even in the case of the positive photosensitive composition which was stored for 60 days, no resist residue was observed, and the storage stability was extremely excellent.

○: In order to preserve the positive photosensitive composition for 7 days, no resist residue was observed. However, when the positive photosensitive composition was stored for 60 days, the resist residue was observed, and the storage stability was excellent.

△: In the case of the positive photosensitive composition after one day of storage, no resist residue was observed. However, when the positive photosensitive composition was stored for 7 days, the resist residue was observed, and the storage stability was slightly inferior.

X: Even in the case of the positive photosensitive composition after one day of storage, the resist residue was observed, and the storage stability was poor.

(resolution test)

In the test piece cut in the storage stability test, the cross section was observed using a scanning electron microscope, and the resolution was evaluated by the following <evaluation criterion> according to whether the line of 5 μm and the gap pattern were formed to have a width of 1 to 1. Sex.

<Evaluation criteria>

○: The pattern can be formed to have a width of 1 to 1, and is excellent in resolution.

×: The pattern cannot form a width of 1 to 1, and the resolution is poor.

(heat-resistant patterning test)

In the above-described resolution test, a 5 μm line and a gap pattern were formed into a test piece having a width of 1 to 1, and further heated at 350 ° C for 30 minutes in a nitrogen atmosphere, and then the cross section was observed using a scanning electron microscope. <Evaluation Criteria> The heat resistance of the patterning was evaluated.

<Evaluation criteria>

○: The patterned shape of the width of 1 to 1 was maintained, and the heat resistance of the pattern was excellent. X: Since the surface was rough, the film thickness was reduced, and the like, the patterned shape having a width of 1 to 1 was not maintained, and the heat resistance of the pattern was poor.

(transparency test)

The transmittance of light having a wavelength of 400 nm was measured for each test piece using a glass substrate, and transparency and heat resistance were evaluated by the following <Evaluation criteria>. Furthermore, the light transmittance of this test refers to the transmittance of light having a wavelength of 400 nm to a film thickness of 4 μm.

<Evaluation criteria>

○: The light transmittance of the test piece heat-treated at 230 ° C was 96% or more, and the light transmittance of the test piece heat-treated at 350 ° C was 90% or more, and the transparency after the high heat history was excellent.

△: 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 90%, and the transparency was excellent, but the transparency after the high heat history was poor. .

X: The light transmittance of the test piece heat-treated at 230 ° C was less than 96%, and the transparency was poor.

(water resistance test)

For each test piece using a glass substrate, the transmittance of light having a wavelength of 400 nm before and after immersion in ion-exchanged water at 60 ° C for 24 hours was measured, and the film thickness of the resist was measured using a stylus type surface shape measuring device. The water resistance was evaluated by the following <evaluation criteria> based on the rate of change of the light transmittance and the rate of change of the film thickness.

<Evaluation criteria>

○: The rate of change of the light transmittance of the test piece which was heat-treated at 350 ° C was less than 1%, and the rate of change of the film thickness was less than 10%, and the water resistance and the water resistance after the high heat history were excellent.

△: The change rate of the light transmittance of the test piece heat-treated at 230 ° C was less than 1%, and the change rate of the film thickness was less than 10%, but the change of the light transmittance of the test piece heat-treated at 350 ° C The rate is 1% or more, or the rate of change in film thickness is 10% or more, and the water resistance is excellent, but the water resistance after a high heat history is inferior.

X: The rate of change in light transmittance of the test piece heat-treated at 230 ° C was 1% or more, or the rate of change in film thickness was 10% or more, and the water resistance was poor.

(acid resistance test)

For each test piece using a glass substrate, the transmittance of light having a wavelength of 400 nm before and after immersion in a 5 mass % aqueous hydrochloric acid solution at 40 ° C for 1 hour was measured, and the resist was measured using a stylus type surface shape measuring device. The film thickness was evaluated according to the rate of change of the light transmittance and the film thickness, and the acid resistance was evaluated by the following <Evaluation Criteria>.

<Evaluation criteria>

○: The rate of change in light transmittance of the test piece heat-treated at 350 ° C was less than 1%, and the rate of change in film thickness was less than 10%, and the acid resistance after acid resistance and high heat history was excellent.

△: The change rate of the light transmittance of the test piece heat-treated at 230 ° C was less than 1%, and the change rate of the film thickness was less than 10%, but the change of the light transmittance of the test piece heat-treated at 350 ° C The rate 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 in light transmittance of the test piece heat-treated at 230 ° C was 1% or more, or the rate of change in film thickness was 10% or more, and the acid resistance was poor.

(Alkaline resistance test)

For each test piece using a glass substrate, immersing in an alkali solution (monoethanolamine: N-methyl-2-pyrrolidone: diethylene glycol butyl ether = 10:30:60 mass ratio) at 40 ° C for 30 minutes The transmittance of light having a wavelength of 400 nm before and after, and the film thickness of the resist was measured using a stylus type surface shape measuring device, and the rate of change of the light transmittance and the film thickness were determined by the following <evaluation criteria>. To evaluate alkali resistance.

<Evaluation criteria>

○: The rate of change of the light transmittance of the test piece heat-treated at 350 ° C was less than 1%, and the rate of change of the film thickness was less than 10%, and the alkali resistance and the alkali resistance after the high heat history were excellent.

△: The change rate of the light transmittance of the test piece heat-treated at 230 ° C was less than 1%, and the change rate of the film thickness was less than 10%, but the change of the light transmittance of the test piece heat-treated at 350 ° C The rate is 1% or more, or the rate of change in film thickness is 10% or more, and the alkali resistance is excellent, but the alkali resistance after a high heat history is poor.

X: The rate of change in light transmittance of the test piece heat-treated at 230 ° C was 1% or more, or the rate of change in film thickness was 10% or more, and the alkali resistance was poor.

(solvent resistance test)

For each test piece using a glass substrate, the transmittance of light having a wavelength of 400 nm before and after immersion in dimethyl sulfoxide at 80 ° C for 1 hour was measured, and a stylus type surface shape measuring device was used. The film thickness of the resist was measured, and the acid resistance was evaluated by the following <Evaluation Criteria> based on the rate of change of the light transmittance and the rate of change of the film thickness.

<Evaluation criteria>

○: The rate of change of the light transmittance of the test piece heat-treated at 350 ° C was less than 1%, and the rate of change of the film thickness was less than 10%, and the solvent resistance and the solvent resistance after the high heat history were excellent.

△: The change rate of the light transmittance of the test piece heat-treated at 230 ° C was less than 1%, and the change rate of the film thickness was less than 10%, but the change of the light transmittance of the test piece heat-treated at 350 ° C The rate is 1% or more, or the rate of change in film thickness is 10% or more, and the solvent resistance is excellent, but the solvent resistance after a high heat history is inferior.

X: The rate of change in light transmittance of the test piece heat-treated at 230 ° C was 1% or more, or the rate of change in film thickness was 10% or more, and the solvent resistance was poor.

(dielectric constant test)

The dielectric constants of the test pieces using the ITO vapor-deposited glass substrate were measured using an LCR measuring instrument (Inductance Capacitance Resistance Meter), and the low dielectric constant characteristics were evaluated by the following <Evaluation Criteria>.

<Evaluation criteria>

○: The dielectric constant of the test piece heat-treated at 230 ° C was less than 3.2, and the difference between the dielectric constant of the test piece heat-treated at 230 ° C and the test piece heat-treated at 350 ° C was less than 0.2, and the low dielectric It has excellent electrical constant characteristics and low dielectric constant characteristics after a high thermal history.

△: The dielectric constant of the test piece heat-treated at 230 ° C was less than 3.2, but the difference between the dielectric constant of the test piece heat-treated at 230 ° C and the test piece heat-treated at 350 ° C was 0.2 or more, low. The dielectric constant characteristics are excellent, but the low dielectric constant characteristics after a high thermal history are poor.

X: The test piece heat-treated at 230 ° C had a dielectric constant of 3.2 or more and a low dielectric constant characteristic.

Claims (8)

A positive photosensitive composition comprising, as component (A), at least two of the following formulas (1) [Chemical Formula 1] (wherein R ¹ represents an alkylene group having 1 to 10 carbon atoms which may have a substituted hydrocarbon group, R ² represents an alkyl group having 1 to 4 carbon atoms, a represents 0 or 1 to 4, and b represents 1 to 3 a number, but a+b does not exceed 5) the base of the epoxy resin; as the component (B), a glycidyl group-containing alkoxylate compound; as the component (C), a diazonaphthoquinone; D) The organic solvent of the component. The positive photosensitive composition of claim 1, wherein the above-mentioned oxygen-containing resin as the component (A) further has at least one of the following formula (2) [Chemical Formula 2] (wherein R ³ represents an alkylene group having 1 to 10 carbon atoms which may have a substituted hydrocarbon group, R ⁴ represents an alkyl group having 1 to 4 carbon atoms, c represents 0 or 1 to 4, and d represents 1 to 3; Number, but c+d does not exceed 5). The positive photosensitive composition of claim 1, wherein the oxime resin as the component (A) further contains a decyl group. The positive photosensitive composition of claim 1, wherein the above-mentioned oxime resin as the component (A) is represented by the following formula (3) [Chemical 3] (wherein R ¹ , R ³ and R ⁸ may be the same or different and each represents an alkylene group having 1 to 10 carbon atoms which may have a substituted hydrocarbon group, and R ² and R ⁴ represent a carbon number which may be the same or different. An alkyl group of 4, R ⁵ , R ⁶ and R ⁷ represent an alkyl group or a phenyl group having 1 to 10 carbon atoms which may be the same or different; a represents a number of 0 or 1 to 4, and b represents a number of 1 to 3, However, a + b does not exceed 5; c represents a number of 0 or 1 to 4, d represents a number of 1 to 3, c + d but does not exceed 5; R ⁹ represents identical or different alkyl having 1 to 6 carbon atoms the Or a cycloalkyl group, R ¹⁰ represents an alkyl group having 1 to 3 carbon atoms, and e represents a number of 1 to 3; m, n and p represent m: n: p = 1: 0 to 2: 0.5 to 3 and m + a cyclic oxirane compound represented by n+p=3~6) and the following general formula (4) [Chemical 4] (wherein R ¹¹ represents an alkyl group or a cycloalkyl group having 1 to 6 carbon atoms which may be the same or different, R ¹² represents an alkyl group having 1 to 3 carbon atoms, and R ¹³ represents a carbon number which may be the same or different. The alkyl group of ~4, f represents the number of 2 to 3, and g represents the number of aryl alkoxy decane compounds represented by 0 or 1 to 5). A permanent resist obtained by the positive photosensitive composition of claim 1. A method for producing a permanent resist, comprising applying a positive photosensitive composition according to claim 1 to a substrate, exposing the coated article, and performing alkaline development at 120 to 350 ° C Post-baking at temperature. A liquid crystal 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. 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.