KR20140006855A - Positive-acting photosensitive composition and hardened material thereof - Google Patents

Abstract

R¹은 C1∼4 알킬기 등, R²는 C2∼10의 2가 탄화수소기, R³는 C2∼10의 2가 포화지방족 탄화수소기, X는 일반식(3)∼(5)로 표시되는 기(상세한 내용은 명세서 참조)를 각각 나타낸다. m, n 및 p는 m:n:p=1:2.1∼12:1∼6 및 m+n+p=3∼6을 만족하는 수를 나타낸다. R⁴는 C1∼4의 알킬기 등, R⁵는 탄소수 C1∼4의 알킬기, a는 1∼2를 각각 나타낸다.(A) A silanol group containing polysiloxane compound which consists of a structure obtained by hydrolyzing and condensing the compound represented by Formula (1) and the compound represented by Formula (2), (B) The compound which has at least two epoxy-containing organic groups, Positive type photosensitive composition containing (C) diazonaphthoquinones and (D) organic solvent.

R ¹ is a C1-4 alkyl group, R ² is a C2-10 divalent hydrocarbon group, R ³ is a C2-10 divalent saturated aliphatic hydrocarbon group, X is a group represented by general formulas (3) to (5) (For details, refer to the specification), respectively. m, n, and p represent the numbers which satisfy m: n: p = 1: 2.1-12: 1-6 and m + n + p = 3-6. R <^4> is a C1-C4 alkyl group, R <^5> is a C1-C4 alkyl group, and a represents 1-2.

Description

Positive type photosensitive composition and its hardened | cured material {POSITIVE-ACTING PHOTOSENSITIVE COMPOSITION AND HARDENED MATERIAL THEREOF}

The present invention relates to a positive photosensitive composition using a polysiloxane compound, and to a cured product using the positive photosensitive composition and a method of producing a permanent resist using the positive photosensitive composition.

With the progress of the information society and the spread of multimedia systems, the importance of liquid crystal displays and organic EL displays is increasing. In these display devices, an active matrix substrate including switching elements such as a thin film transistor (TFT) is used for each pixel. On the active matrix substrate, a plurality of scan wirings and signal wirings intersecting the scan wirings through an insulating film are formed. Scanning wirings, signal wirings, insulating films and the like of an active matrix substrate are formed by repeating patterning by photolithography on a conductive film or insulating film formed by a sputtering method, a CVD method, a coating method, or the like (see Patent Documents 1 and 2, for example). .

In general, photoresist is used for photolithography, and resists (permanent resists) used as insulating films or protective films without peeling even after patterning have also been developed. When a permanent resist is used for an active matrix substrate, not only chemical resistance (acid resistance, alkali resistance, solvent resistance) but also high heat resistance and chemical resistance after high heat history are required. This is based on the following reasons.

That is, in an active matrix substrate, a TFT including a polycrystalline silicon thin film as an active layer is formed on a glass substrate, which is an insulating substrate, and the polycrystalline silicon thin film is covered with an insulating film, which is inside the polycrystalline silicon or at the interface between the polycrystalline silicon thin film and the insulating substrate or insulating film. Dangling bonds, which are defects in bonding, are liable to occur, resulting in a problem of deterioration of transistor characteristics. In order to solve the problem of a dangling bond, it is necessary to hydrogenate at the temperature of about 300-400 degreeC in the state in which the film | membrane which prevents the diffusion of hydrogen, such as silicon nitride (SiNx), exists (refer patent document 3, for example). ). The heat resistance in the conventional permanent resist is the heat resistance (for example, refer patent document 4) to the point which can endure for several minutes at 260 degreeC which can endure the soldering in a printed wiring board, and is It is very different from the heat resistance required for permanent resist and the chemical resistance after high heat history.

On the other hand, silicone resins are excellent in transparency, insulation, heat resistance, chemical resistance, and the like, and photoresists using silicone resins as base resins have also been developed. In recent years, the photoresist (for example, refer patent document 5, 6) based on the silicone resin which introduce | transduced the phenolic hydroxyl group and the cyclic siloxane structure as a thing of the structure which improved heat resistance and chemical-resistance is also examined. However, the conventionally known photoresist using a silicone resin having a phenolic hydroxyl group or a cyclic siloxane structure as a base resin has excellent heat resistance and chemical resistance after high temperature heat history, but has a large film reduction during development and forms a fine pattern. In addition, since the developing margin in the developing step (the width of the time for which the developing time is optimal) is narrow, even when the developing time is excessively excessive, the developer penetrates between the pattern and the substrate and peels off. Since it became easy, it was necessary to strictly control developing time, and there existed a problem in the yield of a product.

Japanese Patent Laid-Open No. 2004-281506 Japanese Unexamined Patent Publication No. 2007-225860 Japanese Patent Laid-Open No. Hei 6-77484 Japanese Unexamined Patent Publication No. 2007-304543 Japanese Patent Laid-Open No. 2010-101957 International Publication No. 2009/063887

Accordingly, an object of the present invention is a positive photosensitive composition having excellent heat resistance and chemical resistance after a high temperature heat history, a small film reduction during development, and a large development margin in a developing step, and a permanent resist using the positive photosensitive composition. And a method for producing the permanent resist.

According to the present invention,

The silanol group containing polysiloxane compound which consists of a structure obtained by hydrolyzing and condensation reaction of the cyclic siloxane compound represented by following General formula (1) and the alkoxysilane compound represented by following General formula (2) as (A) component,

A compound having at least two epoxy-containing organic groups as the component (B),

(C) diazonaphthoquinones as a component, and

The said objective was achieved by providing the positive photosensitive composition characterized by containing the organic solvent as (D) component.

In the formula, R ¹ represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, R ² represents a divalent hydrocarbon group having 2 to 10 carbon atoms, and R ³ represents a divalent saturated aliphatic hydrocarbon having 2 to 10 carbon atoms. Group is represented, X represents a group represented by the following general formula (3), a group represented by the following general formula (4), or a group represented by the following general formula (5): m, n and p each represent an average of one molecule As the number, m: n: p = 1: 2.1 to 12: 1 to 6 and m + n + p = 3 to 6 are satisfied.)

(In formula, R <^4> represents a C1-C4 alkyl group or a C6-C10 aryl group, R <^5> represents a C1-C4 alkyl group and a represents the number of 1-2. "

(In formula, R <^6> represents a C1-C4 alkyl group, R <^7> represents a C1-C4 alkyl group or a C6-C10 aryl group, and b shows the number of 1-3.)

(Wherein R ⁸ represents a residue obtained by subtracting a vinyl group from a divinyl compound or trivinyl compound having a molecular weight of 1000 or less, R ⁹ represents an alkyl group having 1 to 4 carbon atoms, and R ¹⁰ represents an alkyl or phenyl group having 1 to 4 carbon atoms) C represents a number from 1 to 3, and d represents a number from 1 or 2.

(In formula, R <^11> and R <^12> respectively independently represents a C1-C4 alkyl group or a C6-C10 aryl group, and e shows the number of 1-10.)

Moreover, this invention achieves the said objective by providing the hardened | cured material formed by hardening | curing the said positive photosensitive composition.

Moreover, after this positive photosensitive composition is apply | coated to the target material, it is prebaked, it exposes, alkali develops, and then bleaches and exposes, it post-bakes at the temperature of 120-400 degreeC, It is characterized by the above-mentioned. The above object is achieved by providing a method for producing a permanent resist.

Moreover, this invention provides the liquid crystal display device and organic electroluminescence display which have an active-matrix board | substrate which makes a permanent resist obtained using the said positive photosensitive composition into an insulating layer or a planarization film.

Advantageous Effects of Invention According to the present invention, a positive photosensitive composition having excellent heat resistance and chemical resistance after high temperature heat history, a small film reduction during development, and a large development margin in a developing step, and a permanent resist using the positive photosensitive composition It may provide a method. The permanent resist which consists of hardened | cured material of the said positive photosensitive composition is suitable as insulating layers or planarization films, such as a liquid crystal display device and an organic electroluminescence display which have an active-matrix board | substrate.

The (A) component which concerns on this invention contains the silanol group which consists of a structure obtained by hydrolyzing and condensing a cyclic siloxane compound represented by the said General formula (1), and the aryl alkoxysilane compound represented by the said General formula (2). Polysiloxane compound.

First, the cyclic siloxane compound represented by General formula (1) is demonstrated. In addition, in the cyclic siloxane compound represented by General formula (1), two or more R <^1> may mutually be same or different, and when ^two or more R <^2> , R <^3> and X may respectively be same or different.

In General formula (1), R <^1> represents a C1-C4 alkyl group or a C6-C10 aryl group. Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, t-butyl and the like. Examples of the aryl group having 6 to 10 carbon atoms include phenyl, ethylphenyl, tolyl, cumenyl, xylyl, pseudocumenyl, mesityl, t-butylphenyl, benzyl and phenethyl.

As R ¹ , methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, phenyl are preferable, methyl, ethyl and phenyl are more preferable, and methyl is most preferable.

R <^2> represents a C2-C10 bivalent hydrocarbon group. Examples of the divalent hydrocarbon group having 2 to 10 carbon atoms include ethylene, propylene, 1-methylethylene, 2-methylethylene, tetramethylene, pentamethylene, 3-methylpentamethylene, hexamethylene, octamethylene, decamethylene, cyclohexane-1, 4-diyl, 2-phenylethane-1,2'-diyl, 2-phenylethane-1,4'-diyl, 2-phenylpropane-1,4'-diyl, etc. are mentioned, and industrial availability is easy. In terms of heat resistance and heat resistance, ethylene, 2-methylethylene, 2-phenylethane-1,4'-diyl are preferred, ethylene and 2-methylethylene are more preferred, and ethylene is most preferred.

R <^3> represents a C2-C10 divalent saturated aliphatic hydrocarbon group. Examples of the divalent saturated aliphatic hydrocarbon group having 2 to 10 carbon atoms include ethylene, propylene, 1-methylethylene, 2-methylethylene, tetramethylene, pentamethylene, 3-methylpentamethylene, hexamethylene, octamethylene, and decamethylene. In view of industrial availability and heat resistance, R ³ is preferably ethylene, 2-methylethylene or propylene, and more preferably ethylene.

Position of the benzene ring of the phenolic hydroxyl groups bonded to the R ³ is in o-position with respect to R ^3, the meta position, which is, but even in the para position, the R ³ in the point higher than the heat resistance, is easy industrial availability of raw materials It is preferred to be in the ortho position or the para position relative to the para position, and more preferably in the para position.

In General formula (1), X represents group represented by the said General formula (3), group represented by the said General formula (4), or group represented by the said General formula (5).

In General formula (3), R <^6> represents a C1-C4 alkyl group. Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl and t-butyl, and R ⁶ is an alkoxysilane compound represented by the general formula (2); Methyl and ethyl are preferable and methyl is more preferable at the point that reaction of is good. R ⁷ represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms include the groups exemplified in R ^{1. As} R ⁷ , heat resistance is further improved, and methyl and phenyl are preferable, and methyl is more preferable. b shows the number of 1-3, since the reaction with the alkoxysilane compound represented by General formula (2) is favorable, the number of 2-3 is preferable, and 3 is more preferable.

In General formula (4), R <^9> represents a C1-C4 alkyl group and R <^10> represents a C1-C4 alkyl group or a phenyl group. As a C1-C4 alkyl group, the alkyl group illustrated by R <^1> is mentioned, for example. As R <^9> , methyl and ethyl are preferable at the point with the favorable reactivity with the alkoxysilane compound represented by General formula (2), and methyl is more preferable. As R ¹⁰ , methyl and phenyl are preferable, and methyl is more preferable because the heat resistance is further improved. c represents the number of 1-3, since the reaction with the alkoxysilane compound represented by General formula (2) is favorable, the number of 2-3 is preferable, and 3 is more preferable. d represents the number of 1 or 2, and when R <^10> represents the residue except the vinyl group in the divinyl compound of molecular weight 1000 or less, d becomes 1 and R <^10> is the residue except the vinyl group in the trivinyl compound of molecular weight 1000 or less In the case of d, d is 2.

In General formula (4), R <^8> represents the residue remove | excluding the vinyl group from the divinyl compound or trivinyl compound of molecular weight 1000 or less. Such a divinyl compound or a trivinyl compound is a compound represented by the following general formula (4a), and the compound etc. which are represented by following general formula (6)-(12) are mentioned, for example.

(In formula, R <^8> and d are synonymous with general formula (4).)

(In formula, R <^13> -R <^16> represents a C1-C4 alkyl group or a C6-C10 aryl group each independently, and f represents the number of 0-6.)

(In formula, R <^17> -R <^19> represents a C1-C4 alkyl group or C6-C10 aryl group each independently, g shows the number of 1-4, h shows the number of 0-4.)

(In formula, R <^20> , R <^21> represents a C1-C10 alkyl group or a C6-C10 aryl group each independently, and d is synonymous with general formula (4).)

(In formula, d is the same as general formula (4).)

(In formula, d is the same as general formula (4).)

(In formula, R <^22> represents a C1-C4 alkyl group, a C6-C10 aryl group, or an allyl group.)

(In formula, R <^23> -R <^25> represents a C1-C10 alkyl group or a C6-C10 aryl group each independently, d is the same meaning as General formula (4), and i is d <i> i. It shows the number of 0-4 to become.)

In General formula (6), R <^13> -R <^16> respectively independently represents a C1-C4 alkyl group or a C6-C10 aryl group. Examples of the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms include the groups exemplified in R ¹ , and methyl, ethyl, propyl and phenyl are preferable in terms of better heat resistance, and methyl, ethyl and phenyl More preferred is methyl. f represents the number of 0-6, the number of 0-2 is preferable at the point of industrial availability, and the number of 0-1 is more preferable. Among the compounds represented by the general formula (6), preferred compounds include dimethyldivinylsilane, diethyldivinylsilane, diphenyldivinylsilane, 1,1,3,3-tetramethyl-1,3-divinyldisiloxane , 1,1,3,3-tetraethyl-1,3-divinyldisiloxane, 1,1,3,3-tetraphenyl-1,3-divinyldisiloxane, 1,1,3,3,5 , 5-hexamethyl-1,5-divinyltrisiloxane, 1,1,3,3,5,5-hexaethyl-1,5-divinyltrisiloxane, 1,1,3,3,5,5 -Hexaphenyl-1,5-divinyltrisiloxane, 1,1,3,3,5,5,7,7-octamethyl-1,7-divinyltetrasiloxane, and the like, and 1,1, 3,3-tetramethyl-1,3-divinyldisiloxane, 1,1,3,3-tetraethyl-1,3-divinyldisiloxane, 1,1,3,3,5,5-hexamethyl -1,5-divinyltrisiloxane is more preferable, and 1,1,3, 3-tetramethyl-1,3-divinyldisiloxane is more preferable.

In General formula (7), R <^17> -R <^19> represents a C1-C4 alkyl group or a C6-C10 aryl group each independently. Examples of the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms include the groups exemplified in R ¹ , and methyl, ethyl, propyl and phenyl are preferable in terms of better heat resistance, and methyl, ethyl and phenyl More preferred is methyl. g represents the number of 1-4, h represents the number of 0-4. It is preferable that g is the number of 1-2 and h is the number of 0-2 from the point of industrial availability, and g is 1 and the number of h of 0-1 is more preferable. Among the compounds represented by the general formula (7), preferred compounds include tris (dimethylvinylsiloxy) methylsilane, tris (dimethylvinylsiloxy) phenylsilane, tris {(dimethylvinylsiloxy) dimethylsiloxy} methylsilane and the like. Tris (dimethylvinylsiloxy) methylsilane is more preferable.

In General formula (8), R <^20> , R <^21> represents a C1-C10 alkyl group or a C6-C10 aryl group each independently, and d is synonymous with General formula (4). Examples of the alkyl group having 1 to 10 carbon atoms and the aryl group having 6 to 10 carbon atoms include the groups exemplified in R ¹ , and methyl and ethyl are preferred, and methyl is more preferable because of better heat resistance. Among the compounds represented by the general formula (8), preferred compounds include 1,2-bis (dimethylvinylsilyl) benzene, 1,3-bis (dimethylvinylsilyl) benzene, 1,4-bis (dimethylvinylsilyl) benzene, 1,2-bis (diethylvinylsilyl) benzene, 1,3-bis (diethylvinylsilyl) benzene, 1,4-bis (diethylvinylsilyl) benzene, 1,3,5-tris (dimethylvinylsilyl Benzene), 1,3,5-tris (diethylvinylsilyl) benzene) and the like, and 1,2-bis (dimethylvinylsilyl) benzene in view of easy industrial availability and better heat resistance. 1,4-bis (dimethylvinylsilyl) benzene is more preferable, and 1,4-bis (dimethylvinylsilyl) benzene is more preferable.

In General formula (9), d is synonymous with General formula (4). Examples of the compound represented by the general formula (9) include 1,2-divinylbenzene, 1,3-divinylbenzene, 1,4-divinylbenzene, 1,2,4-trivinylbenzene, 1,3,5 -Trivinyl benzene etc. are mentioned, 1, 4- divinylbenzene is preferable at the point which industrial acquisition is easy and heat resistance is more favorable.

In General formula (10), d is synonymous with General formula (4). Examples of the compound represented by the general formula (10) include 1,2-divinylcyclohexane, 1,3-divinylcyclohexane, 1,4-divinylcyclohexane, 1,2,4-trivinylcyclohexane, 1 1,4-divinylcyclohexane is preferable at the point which can obtain a 3, 5- trivinyl cyclohexane etc., industrial acquisition is easy, and heat resistance is more favorable.

In General formula (11), R <^22> represents a C1-C4 alkyl group, a C6-C10 aryl group, or an allyl group. Examples of the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms include the groups exemplified for R ¹ . R ²² is preferably methyl, ethyl or allyl, and more preferably methyl or allyl from the viewpoint of better heat resistance. Preferred compounds among the compounds represented by the general formula (11) include diallyl methyl isocyanurate, diallyl ethyl isocyanurate, triallyl isocyanurate, and the like. desirable.

In the compound represented by the general formula (12), R ²³ to R ²⁵ each independently represent an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms and the aryl group having 6 to 10 carbon atoms include the groups exemplified in R ¹ , and methyl, ethyl, propyl and phenyl are preferable in terms of better heat resistance, and methyl, ethyl and phenyl More preferred is methyl. d is the same meaning as General formula (4), and i shows the number of 0-4 which d + i becomes 3-6. From the point of industrial availability, d + i has the preferable number of 4-5, and 4 is more preferable. Preferred compounds among the compounds represented by the general formula (12) include 2,2,4,6-tetramethyl-4,6-divinylcyclotrisiloxane, 2,2,4,4,6,8-hexamethyl- 6,8-divinylcyclotetrasiloxane, 2,2,4,4,6,6,8,10-octamethyl-8,10-divinylcyclopentasiloxane, 2,4,6-trimethyl-2,4 , 6-trivinylcyclotrisiloxane, 2,2,4,6,8-pentamethyl-4,6,8-trivinylcyclotetrasiloxane and the like.

As mentioned above, although the divinyl compound or trivinyl compound of the molecular weight 1000 or less which can provide the group represented by R <^8> in General formula (4) was mentioned above, general formula (from the ease of industrial acquisition and the heat resistance of hardened | cured material) was mentioned. The compounds represented by 9)-(11) are preferable, 1, 4- divinylbenzene, 1,2, 4- trivinyl cyclohexane, a triallyl isocyanurate is more preferable, 1, 4- divinyl Benzene is most preferred.

In General formula (5), R <^11> , R <^12> represents a C1-C4 alkyl group or a C6-C10 aryl group. Examples of the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms include the groups exemplified by R ¹ of the general formula (1). An aryl group having 6 to 10 carbon atoms is preferable in view of ease of manufacture, and among these, phenyl This is preferred. e represents the number of 1-10, from the point which manufacture is easy, the number of 1-5 is preferable, and the number of 1-3 is more preferable.

In General formula (1), since X is easy to manufacture and heat resistance is also favorable, group represented by General formula (3) is preferable.

In General formula (1), m, n, and p are the average number per molecule, respectively, and represent the number which satisfy | fills m: n: p = 1: 2.1-12: 1-6 and m + n + p = 3-6 . Only 1 type may be used for the cyclic siloxane compound represented by General formula (1), and may be used for it in combination of 2 or more type. In addition, when the ratio of n to m is too small, the film reduction during development is large, and the development margin in the development process is small. When the ratio is too large, the resist residue during development is 2.4 to 10. It is preferable, it is more preferable that it is 2.8-9, and it is most preferable that it is 3-8.

The cyclic siloxane compound represented by the general formula (1) is represented by, for example, a carboxylic acid compound represented by the following general formula (13) to the cyclic siloxane compound represented by the following general formula (1a) and the following general formula (14) The phenol compound is subjected to hydrosilylation reaction to obtain an intermediate represented by the general formula (1b), and further obtained by introducing a group represented by the general formulas (3) to (5) above into the intermediate.

(In formula, m, n, and p represent the number which satisfy | fills m + n + p = 3-6, R <^1> has the same meaning as General formula (1).)

(Wherein, R ²⁶ represents a group R ² is reacted SiH group, R ² is the same meaning as the general formula (1).)

(Wherein, R ²⁷ represents a group R ³ is reacted SiH group, R ³ is the same meaning as the general formula (1).)

(In formula, R <^1> -R <^3> , m, n, and p have the same meaning as General formula (1).)

As a specific example of a preferable compound, the cyclic siloxane compound represented by General formula (1a), for example, 2,4,6-trimethylcyclotrisiloxane, 2,4,6-triethylcyclotrisiloxane, 2,4, 6-triphenylcyclotrisiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, 2,2,4,6,8-pentamethylcyclotetrasiloxane, 2,2,2,4,4,6, 8-hexamethylcyclotetrasiloxane, 2,4,6,8-tetraethylcyclotetrasiloxane, 2,4,6,8-tetraphenylcyclotetrasiloxane, 2-ethyl-4,6,8-trimethylcyclotetrasiloxane , 2-phenyl-4,6,8-trimethylcyclotetrasiloxane, 2,4,6,8,10-pentamethylcyclopentasiloxane, 2,4,6,8,10-pentaethylcyclopentasiloxane, 2, 4,6,8,10-pentaphenylcyclopentasiloxane, 2,4,6,8,10,12-hexamethylcyclohexasiloxane, 2,4,6,8,10,12-hexaethylcyclohexasiloxane, 2,4,6,8,10,12-hexaphenylcyclohexasiloxane etc. are mentioned, 2,4,6,8- tetramethylcyclo tetrasiloxane And 2,4,6,8,10-pentamethylcyclopentasiloxane are more preferred, and 2,4,6,8-tetramethylcyclotetrasiloxane is most preferred.

As a specific example of the carboxylic acid compound represented by General formula (13), acrylic acid, methacrylic acid, 3-butene acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenic acid, 7-octenic acid, 8-nonenoic acid , 9-decenoic acid, 10-undecenoic acid, 2-vinyl benzoic acid, 3-vinyl benzoic acid, 4-vinyl benzoic acid, 2-allyl benzoic acid, 3-allyl benzoic acid, 4-allyl benzoic acid, 2-isopropenyl benzoic acid, 3- Isopropenyl benzoic acid, 4-isopropenyl benzoic acid, etc. are mentioned, Acrylic acid, methacrylic acid, and 4-vinyl benzoic acid are preferable from the viewpoint of the film reduction property of the positive photosensitive composition of this invention. Acrylic acid and methacrylic acid are more preferable. Only 1 type may be used for the carboxylic acid compound represented by General formula (13), and 2 or more types may be used for it.

Specific examples of the phenol compound represented by the general formula (14) include 2-vinylphenol, 3-vinylphenol, 4-vinylphenol, 2-allylphenol, 3-allylphenol, 4-allylphenol, and 2-isopropenyl. Phenol, 3-isopropenyl phenol, 4-isopropenyl phenol, etc. are mentioned, Since it is industrially easy to obtain, 2-vinyl phenol, 3-vinyl phenol, 4-vinyl phenol, 4-isopropenyl Phenol is preferred, 2-vinylphenol and 4-vinylphenol are more preferred, and 4-vinylphenol is most preferred. Only 1 type may be used for a phenol compound represented by General formula (14), and 2 or more types may be used for it.

The hydrosilylation reaction of the cyclic siloxane compound represented by the general formula (1a), the carboxylic acid compound represented by the general formula (13), and the phenol compound represented by the general formula (14) is preferably carried out using a catalyst. As a silylation catalyst, a platinum type catalyst, a palladium type catalyst, a rhodium type catalyst etc. are mentioned, for example. As the platinum catalyst, for example, a chloroplatinic acid, a complex of chloroplatinic acid and an alcohol, an aldehyde, a ketone, or the like, a platinum-olefin complex, a platinum-carbonylvinylmethyl complex (Ossko catalyst), a platinum-divinyltetramethyldisiloxane complex ( KaRstedt catalyst), platinum-cyclovinylmethylsiloxane complex, platinum-octylaldehyde complex, platinum-phosphine complex (e.g. Pt [P (C ₆ H ₅ ) ₃ ] ₄ , PtCl [P (C ₆ H ₅ ) ₃ ] ₃ , Pt [P (C ₄ H ₉ ) ₃ ) ₄ ], platinum-phosphite complexes (eg Pt [P (OC ₆ H ₅ ) ₃ ] ₄ ), Pt [P (OC ₄ H ₉ ) ₃ ] ₄ ) and dicarbonyl dichloro platinum. As a palladium type catalyst or a rhodium type catalyst, the compound containing a palladium atom or a rhodium atom instead of the platinum atom of the said platinum catalyst is mentioned, for example. These may be used alone or in combination of two or more. As the hydrosilylation catalyst, a platinum-based catalyst is preferable in view of reactivity, platinum-divinyltetramethyldisiloxane complex and platinum-carbonylvinylmethyl complex are more preferable, and platinum-carbonylvinylmethyl complex is most preferred. . In terms of reactivity, the amount of the catalyst used is preferably 5% by mass or less, more preferably 0.0001 to 1.0% by mass, and most preferably 0.001 to 0.1% by mass of the total amount of each raw material. Although the reaction conditions of hydrosilylation are not specifically limited, What is necessary is just to carry out on conventionally well-known conditions using the said catalyst, It is preferable to carry out at room temperature (25 degreeC)-130 degreeC from a viewpoint of reaction rate, and toluene at the time of reaction You may use conventionally well-known solvents, such as hexane, methyl isobutyl ketone, cyclopentanone, and a propylene glycol monomethyl ether acetate.

Next, the method of introducing the group represented by said general formula (3)-(5) to the intermediate body represented by general formula (1b) is demonstrated. When introducing the group represented by the general formula (3) into the intermediate represented by the general formula (1b), the vinyl of the alkoxysilane compound represented by the SiH group of the intermediate represented by the general formula (1b) and the general formula (3a) What is necessary is just to hydrosilylate reaction with group. The conditions of the hydrosilylation reaction may be the same as the conditions when obtaining the intermediate represented by General formula (1b).

(In formula, R <^6> , R <^7> and b are synonymous with general formula (3).)

Among the alkoxysilane compounds represented by the general formula (3a), specific examples of the preferred compounds include vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinylethyldimethoxysilane, vinylphenyldimethoxysilane, and the like. The vinyl trimethoxysilane, vinyl triethoxysilane, and vinyl methyl dimethoxysilane are preferable at the point which heat resistance and adhesiveness improve more, and vinyl trimethoxysilane is more preferable. Only 1 type may be used for the alkoxysilane compound represented by General formula (3a), and 2 or more types may be used for it.

When introducing the group represented by the general formula (4) into the intermediate represented by the general formula (1b), the SiH group of the intermediate represented by the general formula (1b) and the divinyl compound or the tree represented by the general formula (4a) Hydrovinylation of one vinyl group of a vinyl compound to give an intermediate represented by the following general formula (1c), and a vinyl group of the intermediate represented by the general formula (1c) and an alkoxysilane compound represented by the following general formula (4b). The SiH group may be hydrosilylation reaction. The conditions of these hydrosilylation reaction may be the same as the conditions in the case of obtaining the intermediate represented by General formula (1b).

(Wherein, R ¹ ~R ^3, and m, n and p are the same meaning as the general formula (1), d and R ⁸ are the same meaning as the general formula (4).)

(Wherein R ⁹ , R ¹⁰ and c have the same meanings as in general formula (4).)

In the alkoxysilane compound represented by General formula (4b), a specific example of a preferable compound is trimethoxysilane, triethoxysilane, dimethoxymethylsilane, dimethoxyethylsilane, dimethoxyphenylsilane, etc. are mentioned, for example. Trimethoxysilane, triethoxysilane, methyldimethoxysilane, ethyldimethoxysilane, phenyldimethoxysilane are preferred, and trimethoxysilane and triethoxysilane are preferred. More preferred, trimethoxysilane is most preferred. Only 1 type may be used for the alkoxysilane compound represented by General formula (4b), and 2 or more types may be used for it.

When introducing the group represented by the general formula (5) to the intermediate represented by the general formula (1b), reacting the silanediol represented by the following general formula (5a) with the SiH group of the intermediate represented by the general formula (1b) do.

(In formula, R <^11> , R <^12> is synonymous with General formula (5).)

Preferred compounds among the silanediols represented by the general formula (5a) include dimethylsilanediol, diethylsilanediol, diisopropylsilanediol, methylphenylsilanediol, diphenylsilanediol, and the like. Silanediol and diphenylsilanediol are preferable, and diphenylsilanediol is more preferable.

What is necessary is just to react using the organometallic catalyst, when making the silanediol represented by General formula (5a) react with the SiH group of the intermediate represented by General formula (1b). As an organometallic catalyst, an organic tin catalyst, an organic platinum catalyst, an organic zinc catalyst, an organic aluminum catalyst, etc. are mentioned, An organic tin catalyst is preferable. Organic tin catalysts include octylic acid tin, naphthenic acid tin, stearic acid tin, versatic acid tin, dibutyltin laurate, triphenyltin acetate, and tributyltin chloride. Tin stannic acid and tin stearic acid are preferable, and octylic acid tin is more preferable. 0.001-1 mass% of the usage-amount of each raw material is preferable, and, as for the usage-amount of an organometallic catalyst, 0.002-0.1 mass% is more preferable.

Next, the alkoxysilane compound represented by the said General formula (2) is demonstrated.

In general formula (2), 1 represents the number of 1-2, and 1 is preferable at the point which heat resistance improves more. R ⁴ represents an alkyl group having 1 to ⁴ carbon atoms or an aryl group having 6 to 10 carbon atoms, and R ⁵ represents an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms include the groups exemplified for R ¹ of the general formula (1). R ⁴ is preferably methyl, ethyl, or phenyl, more preferably methyl or phenyl, and most preferably phenyl, since the heat resistance is further improved. As R ⁵ , methyl, ethyl and propyl are preferable from the viewpoint of excellent reactivity, and methyl is more preferable.

As an alkoxysilane compound represented by General formula (2), for example, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxy Silane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, ethylphenyldimethoxy Silane, ethyl phenyl diethoxy silane, diphenyl dimethoxy silane, diphenyl diethoxy silane, etc. are mentioned, Phenyl trimethoxy silane, phenyl triethoxy silane, phenyl methyl dimethoxy from a point which improves heat resistance and adhesiveness further Silanes and phenylmethyldiethoxysilanes are preferred, phenyltrimethoxysilane and phenyltriethoxysilane are more preferred, and phenyltrimethoxysilane is most preferred. In addition, only 1 type may be used for the alkoxysilane compound represented by the said General formula (2), and may be used for it in combination of 2 or more type.

Next, the method of hydrolyzing and condensing cyclic siloxane compound represented by General formula (1) and the alkoxysilane compound represented by General formula (2), and obtaining (A) silanol-group containing polysiloxane compound is demonstrated.

The hydrolysis / condensation reaction of the cyclic siloxane compound represented by the general formula (1) and the arylalkoxysilane compound represented by the general formula (2) may be performed by a so-called sol-gel reaction, and a catalyst such as an acid or a base may be used in a solvent. The alkoxysilyl group may be hydrolyzed and condensation reaction. The solvent used at this time is not specifically limited, Specifically, water, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, toluene, etc. are mentioned. These 1 type may be used and 2 or more types may be mixed and used for it. The hydrolysis-condensation reaction of the alkoxysilyl group proceeds by the alkoxysilyl group hydrolyzing with water to produce a silanol group (Si-OH group), and the resulting silanol groups or the silanol group and the alkoxysilyl group are condensed.

As a catalyst, such as an acid and a base used in hydrolysis and condensation reaction, For example, inorganic acids, such as hydrochloric acid, phosphoric acid, a sulfuric acid; Organic acids such as formic acid, acetic acid, oxalic acid, citric acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and phosphoric acid monoisopropyl; Inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonia; Amine compounds (organic bases) such as trimethylamine, triethylamine, monoethanolamine and diethanolamine. These catalysts may be used 1 type, or may use 2 or more types together. The temperature of the hydrolysis-condensation reaction varies depending on the kind of solvent, the kind and amount of the catalyst, etc., but is preferably 30 to 100 ° C, more preferably 40 to 80 ° C, and most preferably 45 to 70 ° C.

The silanol groups produced by hydrolysis of the alkoxysilyl groups do not all cause a condensation reaction, but some remain unreacted. The silanol group containing polysiloxane compound which is (A) component which concerns on this invention is characterized by having a silanol group. Since the adhesiveness improves content of the silanol group in (A) component, it is preferable that it is 1-30 mass% as content of OH, It is more preferable that it is 3-25 mass%, It is most preferable that it is 5-20 mass%. Do. As a method for quantifying silanol groups, silanol groups are trimethylsilylated with trimethylchlorosilane or the like and quantified by the amount of mass increase before and after the reaction (TMSization method), near-infrared spectrophotometer (Japanese Patent Laid-Open No. 2001-208683, Japan) The method of quantifying by the device analysis using Unexamined-Japanese-Patent No. 2003-35667 etc.) and ²⁹ Si-NMR (refer Unexamined-Japanese-Patent No. 2007-217249 etc.) is mentioned.

In addition, since the silanol group in (A) component is easy to condensate reaction, (A) component is not isolated from a reaction liquid after hydrolysis and condensation reaction, As needed, decatalization process, solvent substitution, solvent concentration, etc. are performed. It is preferable to use in the state of the solution containing (A) component.

In the case where the molecular weight of the silanol group-containing polysiloxane compound as the component (A) is too small, the film formability at the time of forming a permanent resist using the positive photosensitive composition becomes poor, and when too large, the solubility or dispersibility in an alkaline developer In view of the lowering of the resist residue on the surface of the substrate after alkali development, the mass average molecular weight of the silanol group-containing polysiloxane compound is preferably 1000-50000, more preferably 2000-25000, and most preferably 3000-15000. Do. In addition, in this invention, a mass average molecular weight means the mass average molecular weight of polystyrene conversion when GPC analysis is performed using tetrahydrofuran (henceforth THF) as a solvent.

In the hydrolysis-condensation reaction which obtains the silanol group containing polysiloxane compound which is (A) component, the reaction ratio of the cyclic siloxane compound represented by General formula (1) and the alkoxysilane compound represented by General formula (2) is a general formula It is preferable that the alkoxysilane compound represented by General formula (2) with respect to the cyclic siloxane compound represented by (1) is 0.5-10 in molar ratio, 1-7 are more preferable, and 1.5-6 are the most preferable. When this ratio is lower than 0.5, the hardness of hardened | cured material may become inadequate, and when higher than 10, the resist residue on the surface of a board | substrate after alkali image development may increase.

Although the silanol group containing polysiloxane compound which is (A) component is a compound which consists of a structure obtained by hydrolyzing and condensing reaction with the cyclic siloxane compound represented by General formula (1), and the aryl alkoxysilane compound represented by General formula (2), When manufacturing the silanol group containing polysiloxane compound of (A) component, it is not necessary to necessarily use the cyclic siloxane compound represented by General formula (1), and the compound which masked a carboxyl group or a phenol group with an acid dissociable protecting group, ie, the following general formula ( After reacting the compound represented by 1p) with the arylalkoxysilane compound represented by the general formula (2) to obtain a precursor of the arylalkoxysilane compound, the acid dissociable protecting group is removed to obtain a silanol group-containing polysiloxane compound as the component (A). It may be. In addition, about the case where the compound represented by General formula (1p) is used, the description at the time of using the cyclic siloxane compound represented by General formula (1) is applicable suitably about the point which is not specifically demonstrated below.

(In formula, Pg represents an acid dissociable protecting group and R <^1> -R <^3> , m, n, p, and X are synonymous with general formula (1).)

In the case of using a compound masked with an acid dissociable protecting group, a step of removing the acid dissociable protecting group is required, which leads to complicated manufacturing, but a side reaction when preparing an intermediate represented by general formula (1b). This is less likely to occur, and there is an advantage that the heat resistance, chemical resistance, and the like of the permanent resist obtained by using the positive photosensitive composition of the present invention are further improved.

Examples of the acid dissociable protecting group for the carboxyl group and the phenol group include t-butyl group, 1-ethoxyethyl group, acetyl group and t-butoxycarbonyl group, and t-butyl group is preferable. Such an acid dissociable protecting group can be detached under acidic conditions, and hydrochloric acid, trifluoroacetic acid, boron trifluoride, or the like is preferably used as a catalyst.

As a solvent in the case of removing an acid dissociable protecting group, the organic solvent which can melt | dissolve 1 mass% or more of water at 25 degreeC is preferable, As such an organic solvent, For example, alcohol, such as methanol, ethanol, propanol, isopropanol; 1-methoxy-ethanol, 1-ethoxy-ethanol, 1-propoxy-ethanol, 1-isopropoxy-ethanol, 1-butoxy-ethanol, 1-methoxy-2-propanol, 3-methoxy- Ether alcohols such as 1-butanol and 3-methoxy-3-methyl-1-butanol; 1-methoxy-ethyl acetate, 1-ethoxy-ethyl acetate, 1-methoxy-2-propyl acetate, 3-methoxy-1-butyl acetate, 3-methoxy-3-methyl-1-butyl acetate, etc. Acetate esters of ether alcohols; Ketones such as acetone and methyl ethyl ketone; Keto alcohols such as 4-hydroxy-2-butanone, 3-hydroxy-3methyl-2-butanone and 4-hydroxy-2-methyl-2-pentanone (diacetone alcohol); And ethers such as 1,4-dioxane, tetrahydrofuran and 1,2-dimethoxyethane. Among these, methanol, ethanol, propanol, methyl ethyl ketone, 1,4-dioxane, tetrahydrofuran and 1-methoxy-2-propanol acetate are preferable.

The compound represented by the general formula (1p) is a compound represented by the following general formula (13p) in place of the compound represented by the general formula (13) in the cyclic siloxane compound represented by the general formula (1a), the general Instead of the compound represented by the formula (14), the compound represented by the following general formula (14p) was subjected to hydrosilylation reaction to obtain an intermediate represented by the following general formula (1bp), and to the intermediate represented by this general formula (1bp). As in the case of the intermediate represented by General Formula (1b), a group represented by General Formulas (3) to (5) may be introduced.

(In formula, Pg represents an acid dissociable protecting group and R <^26> is synonymous with General formula (13).)

(In formula, Pg represents an acid dissociable protecting group and R <^27> is synonymous with General formula (14).)

(In formula, Pg represents an acid dissociable protecting group and R <^1> -R <^3> , m, n, and p are synonymous with general formula (1).)

Next, the compound which has at least two epoxy containing organic groups which are (B) component which the positive photosensitive composition of this invention contains is demonstrated.

As an epoxy group of the compound which has at least two epoxy-containing organic groups which are (B) component which concerns on this invention, Aliphatic epoxy groups, such as following formula (15)-(16), alicyclic epoxy groups, such as following formula (17)-(19) Although aromatic epoxy groups, such as following formula (20)-(21), etc. are mentioned, An aliphatic epoxy group is preferable at the point which the storage stability of the positive photosensitive composition of this invention becomes favorable, and 1,2- of Formula (15) Epoxy propyl group (glycidyl group) is more preferable.

The epoxy containing organic group which the compound which is (B) component has may contain these epoxy groups, for example, these epoxy groups may be sufficient, and these epoxy groups combine one or more of coupling groups, such as a hydrocarbon group, an ether group, and an ester group, It may be a group formed. Especially, it is preferable that the compound which is (B) component is a compound which has glycidyl ether group as an epoxy containing organic group.

As a compound which has at least two glycidyl ether groups which are preferable (B) components, the glycidyl ether of a polyhydric phenol compound, the glycidyl ether of a polyhydric alcohol compound, the siloxane compound which has a glycidyl ether group, etc. are mentioned, In view of better heat resistance, a siloxane compound having a glycidyl ether group is preferable. Examples of the siloxane compound having at least two glycidyl ether groups include linear siloxane compounds represented by the following general formula (22), cyclic siloxane compounds represented by the following general formula (23), and the following general The cyclic siloxane compound represented by Formula (24), the hydrolysis-condensation reaction product of the alkoxysilane which has glycidyl ether group, etc. are mentioned, Especially, the cyclic siloxane compound represented by General formula (23), and General formula (24) is mentioned. The cyclic siloxane compound represented by is preferable, and it is more preferable that it is a cyclic siloxane compound represented by General formula (24).

(Wherein, Y ¹ represents a group having a glycidyl ether group or an ethyl group, G represents a group having a glycidyl ether group, and R ²⁶ to R ³⁰ are the same or different alkyl or phenyl groups having 1 to 4 carbon atoms). J represents a number from 0 to 1000, and k represents a number from 0 to 1000. However, when j is 0 or 1, Y ¹ represents a grillidyl ether group.)

(In formula, R <^31> -R <^33> represents a C1-C4 alkyl group or a phenyl group which may be same or different, G represents the group which has glycidyl ether group, q represents the number of 2-6, r is q + r represents the number of 0-4 which becomes 3-6.)

(In formula, R <^34> represents a C1-C4 alkyl group or a phenyl group, R <^35> represents the residue remove | excluding a vinyl group from the divinyl compound or trivinyl compound of molecular weight 1000 or less, G represents the group which has glycidyl ether group. , s represents a number from 2 to 5, t represents a number from 1 or 2.

The linear siloxane compound represented by the said General formula (22) is demonstrated.

In General formula (22), G represents the group which has a glycidyl ether group, and R <^26> -R <^30> represents the C1-C4 alkyl group or phenyl group which may be same or different. Examples of the alkyl group having 1 to 4 carbon atoms include alkyl groups exemplified in R ¹ of the general formula (1). Methyl, ethyl and phenyl are preferable in terms of better heat resistance, methyl and phenyl are more preferable, and methyl is Most preferred. Y ¹ represents a group or methyl group having a glycidyl ether group, j represents a number from 0 to 1000, and k represents a number from 0 to 1000. However, when j is 0 or 1, Y <^1> represents the group which has glycidyl ether group.

The linear siloxane compound represented by the general formula (22) hydrosilylates a compound having a carbon-carbon double bond and a glycidyl ether group having a reactivity with the SiH group in the linear compound represented by the following general formula (22a). It can manufacture by making it react. Examples of the compound having a carbon-carbon double bond having a reactivity with the SiH group and a glycidyl ether group include vinylglycidyl ether, allylglycidyl ether, and 5-glycidoxypropyl-2-norbornene. Allylglycidyl ether is preferred from the viewpoint of the industrial availability and the reactivity of hydrosilylation. The conditions of the hydrosilylation reaction may be the same as the conditions when obtaining the intermediate represented by General formula (1b).

(Wherein R ² represents a hydrogen atom or a methyl group, and R ²⁶ to R ³⁰ , j and k have the same meanings as in general formula (22), except that when j is 0 or 1, Y ² represents a hydrogen atom); Indicates.)

When the ratio of the epoxy group in the molecule | numerator of the linear siloxane compound represented by General formula (22) is too small, a crosslinking effect will become small and the physical property of the permanent resist obtained from the positive photosensitive composition of this invention will fall. The epoxy equivalent of the linear siloxane compound represented by 22) is preferably 1000 or less, more preferably 700 or less, and most preferably 350 or less. In addition, an epoxy equivalent means the mass (number of grams) of the epoxy compound containing 1 equivalent of epoxy groups.

Although the molecular weight of the linear siloxane compound represented by General formula (22) is not specifically limited, When too large, the solubility or dispersibility with respect to alkaline developing solution may fall, and the resist residue may remain on the board | substrate surface after alkali image development. The mass average molecular weight is preferably 20000 or less, more preferably 15000 or less, and most preferably 10000 or less.

Next, the cyclic siloxane compound represented by the said General formula (23) is demonstrated.

In General formula (23), R <^31> -R <^33> represents a C1-C4 alkyl group or phenyl group which may be same or different. Examples of the alkyl group having 1 to 4 carbon atoms include the alkyl group exemplified for R ¹ . R ³¹ to R ³³ are preferably methyl, ethyl and phenyl from the viewpoint of better heat resistance, more preferably methyl and phenyl, and most preferably methyl. q represents the number of 2-6, r represents the number of 0-4 which q + r turns into 3-6. 4-6 are preferable, as for q + r from the point of industrial availability, 4-5 are more preferable, and 4 is the most preferable. Moreover, it is preferable that r is zero.

The cyclic siloxane compound represented by the general formula (23) is subjected to hydrosilylation reaction of a cyclic compound represented by the following general formula (23a) to a compound having a carbon-carbon double bond having a reactivity with the SiH group and a glycidyl ether group. It can manufacture. The conditions of the hydrosilylation reaction may be the same as the conditions when obtaining the intermediate represented by General formula (1b).

(In formula, R <^31> -R <^33> , q and r are synonymous with General formula (23).)

As a cyclic compound represented by General formula (23a), 2,2,4,6- tetramethylcyclotrisiloxane, 2,2,4,4,6 other than the compound illustrated by the cyclic compound represented by General formula (1a) , 8-hexamethylcyclotetrasiloxane, 2,2,4,4,6,6,8,10-octamethylcyclopentasiloxane, 2,4,6-trimethylcyclotrisiloxane, 2,2,4,6, 8-pentamethyl cyclotetrasiloxane etc. are mentioned.

Next, the cyclic siloxane compound represented by the said General formula (24) is demonstrated.

In General formula (24), R <^34> represents a C1-C4 alkyl group or a phenyl group. Examples of the alkyl group having 1 to 4 carbon atoms include the alkyl group exemplified for R ¹ . R ³⁴ is preferably methyl, ethyl and phenyl in view of better heat resistance, more preferably methyl and phenyl, and most preferably methyl. R ³⁵ represents a moiety excluding a vinyl group from a divinyl compound or trivinyl compound having a molecular weight of 1,000 or less, and a divinyl compound having a molecular weight of 1000 or less illustrated in General Formula (4) as a divinyl compound or trivinyl compound having a molecular weight of 1000 or less. Or a trivinyl compound. As a divinyl compound or trivinyl compound which provides the group represented by R <^35> , the compound represented by said General formula (9)-(11) from the ease of industrial acquisition and the heat resistance of hardened | cured material is preferable, 1, 4- di More preferred are vinylbenzene, 1,2,4-divinylcyclohexane, triallyl isocyanurate, and most preferred is 1,4-divinylbenzene. G represents a group having a glycidyl ether group, and s represents a number from 2 to 5. As s, the number of 2-4 is preferable at the point which an industrial raw material is easy to obtain, and 3 is more preferable. t represents the number of 1 or 2, t is 1 when R ³⁵ is a residue except a vinyl group in a divinyl compound having a molecular weight of 1000 or less, and t is a residue except a vinyl group in a trivinyl compound having a molecular weight of 1,000 or less. 2

The cyclic siloxane compound represented by General Formula (24) is represented by the following General Formula (24b) by hydrosilylation of a divinyl compound or trivinyl compound having a molecular weight of 1,000 or less to a cyclic compound represented by the following General Formula (24a). It can be manufactured by making the intermediate | middle intermediate | mold into which the compound which has the carbon-carbon double bond which has the reactivity with SiH group, and the glycidyl ether group by the SiH group of the intermediate represented by General formula (24b) by hydrosilylation reaction. The conditions of the hydrosilylation reaction may be the same as the conditions when obtaining the intermediate represented by General formula (1b).

(Of (24a) and (24b), R ³⁴ , R ³⁵ , s and t have the same meaning as in general formula (24).)

As a cyclic compound represented by General formula (24a), the compound etc. which were illustrated by the cyclic compound represented by General formula (1a) are mentioned, As a divinyl compound or trivinyl compound with a molecular weight of 1000 or less, General formula (4) And the compounds exemplified for R ⁸ may be mentioned.

Next, the hydrolysis-condensation reaction product of the alkoxysilane which has said glycidyl ether group is demonstrated.

The hydrolysis and condensation reaction of the alkoxysilane having a glycidyl ether group is hydrolyzed and alkoxysilane having a glycidyl ether group by a known method, for example, the method described in the hydrolysis and condensation reaction described in (A) component. It is a compound obtained by condensation reaction. As an alkoxysilane which has a glycidyl ether group, For example, glycidyl alkoxysilane compounds, such as glycidyl trimethoxysilane and glycidyl triethoxysilane; Glycidoxy ethylalkoxysilane compounds such as 2-glycidoxyethyltrimethoxysilane and 2-glycidoxyethylmethyldimethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethyldimethoxysilane, 3-glycidoxypropylphenyldimethoxysilane, bis (3-glycidyl Doxypropyl) dimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylethyldiethoxysilane, 3-glycidoxypropylphenyldiethoxysilane 3-glycidoxy propyl alkoxysilane compounds, such as bis (3-glycidoxy propyl) diethoxysilane; 2- (4-glycidoxyphenyl) ethylalkoxysilane compounds such as 2- (4-glycidoxyphenyl) ethyltrimethoxysilane and 2- (4-glycidoxyphenyl) ethyltriethoxysilane; Glycidoxy methyl norbornyl alkoxysilane compounds, such as 5- (glycidoxy methyl) norbornyl trimethoxysilane and 6- (glycidoxy methyl) norbornyl trimethoxysilane, etc. are mentioned, A hydrolysis and condensation are mentioned. 3-glycidoxypropylalkoxysilane compounds are preferred from the reactivity of the reaction and the ease of industrial availability. Among the 3-glycidoxypropyl alkoxysilane compounds, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, bis (3-glycidoxypropyl) dimethoxysilane, 3-glycidoxy More preferred is propyltriethoxysilane, more preferably 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and most preferred 3-glycidoxypropyltrimethoxysilane Do.

When manufacturing the hydrolysis-condensation reaction product of the alkoxysilane which has glycidyl ether group, you may use together the other alkoxysilane compound which does not have glycidyl ether group in addition to the alkoxysilane which has glycidyl ether group.

When the ratio of the epoxy group in the molecule | numerator of the hydrolysis and condensation reaction product of the alkoxysilane which has glycidyl ether group is too small, the crosslinking effect is small and the physical property of the permanent resist obtained from the positive photosensitive composition of this invention may fall. It is preferable that epoxy equivalent is 1000 or less, It is more preferable that it is 700 or less, It is most preferable that it is 350 or less.

Although the molecular weight of the hydrolysis-condensation reaction product of the alkoxysilane which has glycidyl ether group is not specifically limited, When too large, the solubility or dispersibility with respect to alkaline developing solution will fall, and the resist residue may remain on the surface of the board | substrate after alkali developing. It is preferable that the mass mean molecular weight is 20000 or less in it, it is more preferable that it is 15000 or less, and it is most preferable that it is 10000 or less.

It is preferable that the hydrolysis-condensation reaction product of the alkoxysilane which has glycidyl ether group has a silanol group. It is preferable that it is 1-30 mass%, and, as for content of the silanol group in the hydrolysis-condensation reaction product of the alkoxysilane which has glycidyl ether group, it is more preferable that it is 3-25 mass%.

The hydrolysis-condensation reaction product of the alkoxysilane which has the glycidyl ether group which used the trialkoxysilane compound for reaction may have a crosslinked structure by Si-O-Si bond, and the crosslinked structure, for example, has a ladder shape ( Ladder shape, basket shape, annular shape, etc. may be used.

Hydrolysis and condensation reaction product of the alkoxysilane which has glycidyl ether group is reaction conditions like hydrolysis and condensation reaction of the cyclic siloxane compound represented by General formula (1), and the alkoxysilane compound represented by General formula (2). It can manufacture by.

In the positive photosensitive composition of the present invention, the content of the compound having at least two epoxy-containing organic groups as the component (B) is preferably 1 to 50 parts by mass, and 2 to 40 parts by mass based on 100 parts by mass of the component (A). It is more preferable, and it is most preferable that it is 5-30 mass parts.

Next, the diazonaphthoquinone which is (C) component of this invention is demonstrated.

The diazonaphthoquinones usable in the present invention are not particularly limited as long as they are known to be used for photosensitive materials. Among them, the hydrogen atom of the compound having a phenolic hydroxyl group is represented by the following formula (25): Preferred is a compound (4-diazonaphthoquinone sulfonic acid ester) substituted with a compound or a compound (5-diazonaphthoquinone sulfonic acid ester) substituted with the following formula (26).

As a preferable specific example of such diazonaphthoquinones, the compound represented by following formula (27)-(32), their positional isomers, etc. can be illustrated, for example.

(In Formulas (27) to (32), Q is a group or a hydrogen atom represented by Formula (25) or Formula (26). However, in each formula, not all of the plurality of Q are hydrogen atoms. .)

In addition, since the group represented by the formula (25) has absorption in the i-line (wavelength 365 nm) region, it is suitable for i-line exposure, and the group represented by the formula (26) has a wide range of absorption because the absorption exists in the broad wavelength region. It is preferable to select either the group represented by Formula (25) or the group represented by Formula (26) according to the wavelength exposed at the point suitable for exposure at a wavelength.

Positive type photosensitive composition of this invention that content of diazonaptoquinones which is (C) component is 0.1-20 mass parts with respect to 100 mass parts of silanol group containing polysiloxane compounds of (A) component, Preferably it is 2-10 mass parts. It is preferable at the point of the developability and the fine workability of the permanent resist obtained from.

Next, the organic solvent which is (D) component of this invention is demonstrated.

The (D) organic solvent which can be used for this invention can melt | dissolve or disperse the said (A) silanol-group containing polysiloxane compound, the (B) compound which has at least two epoxy-containing organic groups, and (C) diazonaptoquinones. Although there is no particular limitation as long as it is an organic solvent, an organic solvent capable of dissolving 1 mass% or more of water at 25 ° C. is preferred. Valerolactone, delta-valerolactone, ethylene carbonate, propylene carbonate, dimethyl carbonate and the like.

In the case where the component (A) is a compound obtained from a compound in which a carboxyl group or a phenolic hydroxyl group is masked with a protecting group, the organic solvent used in the detachment reaction of the protecting group may be used as an organic solvent of the component (D).

Content of the organic solvent which is (D) component is 10-10000 mass parts with respect to 100 mass parts of (A) silanol-group containing polysiloxane compounds, More preferably, it is 100-1000 mass parts permanently using the positive photosensitive composition of this invention. It is preferable at the point of the formability at the time of forming a resist, the physical property of the obtained permanent resist, etc.

The positive photosensitive composition of the present invention is obtained by dissolving or dispersing (A) a silanol group-containing polysiloxane compound, (B) a compound having at least two epoxy-containing organic groups, (C) diazonaphthoquinones and (D) an organic solvent. If necessary, after filtration with a filter having, for example, a pore diameter of about 0.2 μm, it may be used for use.

Positive type photosensitive composition of this invention may contain arbitrary components, such as a plasticizer, a thixotropic agent, a photoacid generator, a thermal acid generator, a dispersing agent, an antifoamer, a pigment, and dye as needed other than (A)-(D) component. Can be. It is preferable to make the total content of arbitrary components into 30 mass parts or less with respect to 100 mass parts of (A) silanol-group containing polysiloxane compounds from a viewpoint which does not impair the effect of this invention.

The positive photosensitive composition of the present invention can be cured in the same manner as a conventionally well-known positive photosensitive composition, and, for example, when cured through the steps (1) to (6) described below, heat resistance and chemical resistance after high temperature heat history, etc. It becomes this outstanding hardened | cured material. The hardened | cured material formed by hardening | curing the positive photosensitive composition of this invention is suitable for a permanent resist. Below, the preferable method of manufacturing a permanent resist using the positive photosensitive composition of this invention is demonstrated.

When forming a layer of a positive photosensitive composition on a target material (substrate), after applying the positive photosensitive composition of this invention to the target material directly, and apply | coating to support films, such as polyethylene terephthalate (PET), There is a method of evaporating the solvent to form a layer of the positive photosensitive composition to form a dry film resist (DFR), and bonding the DFR to the target material.

First, the method of apply | coating directly is demonstrated. This method includes (1) coating film forming step, (2) prebake step, (3) exposure step, (4) developing step, (5) bleaching exposure step, and (6) post bake. (post bake) process.

(1) coating film forming process

In this process, the positive photosensitive composition of this invention is apply | coated to a target material (base material), and a coating film is formed. The target material for forming the coating film by applying the positive photosensitive composition of the present invention is chemical resistance to organic solvents and the like in the positive photosensitive composition, and (4) in the developing treatment with the alkaline solution of the developing step or (6) the post-baking step. It will not specifically limit, if it is a material which has tolerance to the heat processing of etc., Glass, a metal, a semiconductor, etc. can be made into a target material. In particular, the TFT surface etc. of a liquid crystal display which require the permanent resist as an insulating layer can be illustrated as a preferable thing. The method of coating is not specifically limited, For example, various methods, such as a spin coat method, the dip coat method, the knife coat method, the roll coat method, the spray coat method, the slit coat method, can be used.

(2) prebaking process

After the process of said (1), prebaking is performed in order to remove (D) organic solvent from the positive photosensitive composition layer apply | coated to the target material. The prebaked positive photosensitive composition layer is poorly soluble with respect to the alkaline solution, and the portion to which light is irradiated (hereinafter sometimes referred to as an exposure portion) becomes alkali-soluble by irradiating light in the next exposure step. The temperature of the prebaking also varies depending on the type of organic solvent used. However, if the temperature is too low, the residual amount of the organic solvent may increase, which may cause exposure sensitivity or a decrease in resolution. If the temperature is too high, the coating film may be prebaked. 60-140 degreeC is preferable at the point that the whole hardening advances, the solubility with respect to the alkaline developing solution of the part to which light was irradiated falls, and as a result, an exposure sensitivity and a resolution may fall, 70-120 degreeC is more preferable. desirable. Although the prebaking time changes with the kind of organic solvent used and the temperature of a prebaking, 30 second-10 minutes are preferable, and 1-5 minutes are more preferable.

Although prebaking may be performed as it is after applying the positive photosensitive composition of this invention to a target material, since the physical property, chemical-resistance, etc. after the high heat history of a permanent resist improve more, it is the temperature of room temperature-less than 60 degreeC before prebaking. It is preferable to carry out prebaking after volatilizing an organic solvent so that the density | concentration of the organic solvent in a positive photosensitive composition layer may be 5 mass% or less under normal pressure or a reduced pressure. The thickness of the positive photosensitive composition layer after prebaking depends on the use of the permanent resist and is not particularly limited, but is preferably 0.1 µm to 100 µm, more preferably 0.3 µm to 10 µm.

(3) Exposure process

An exposure process is a process of irradiating the patterned light with respect to the prebaked positive photosensitive composition layer, and improving alkali solubility of an exposure part. The prebaked positive photosensitive composition layer is poorly soluble in the alkaline solution, but the diazonaptoquinones in the exposed portion are decomposed by light irradiation to change into indencarboxylic acid, so that it can be dissolved and dispersed in the alkaline solution. Irradiation light is not specifically limited, What is necessary is just light of the amount of energy which can improve the alkali solubility of the light irradiation part of the prebaked positive photosensitive composition layer, for example, 10-1000mJ / cm <2>, Preferably it is 40-300mJ / Cm 2 is good. The wavelength of the irradiated light may be visible light or ultraviolet light, and is not particularly limited. (C) When 4-diazonaphthoquinone sulfonic acid esters are used as the diazonaptoquinones, a narrow i-line (365 nm) is mainly used. When 5-diazonaphthoquinone sulfonic acid ester is used for the light of a wavelength, the light of a wide wavelength including i-line (365 nm), h-line (405 nm), and g-line (436 nm) is made into a high pressure mercury lamp, This can be done by using an ultra-high pressure mercury lamp. The method of patterning the said irradiation light is not specifically limited, A conventionally known method, for example, the light irradiation method through a photomask, etc. may be sufficient, and the selective light irradiation method using a laser beam may be sufficient.

(4) Developing process

A developing process is a process of forming a predetermined pattern by removing the part which light was irradiated in the exposure process and the alkali solubility improved using the developing solution.

As a developing method, any method, such as a puddle method, an immersion method, a shower method, and a spray method, can be used, for example. The developing time varies depending on the kind, molecular weight of the compound having at least two (A) silanol group-containing polysiloxane compounds and (B) epoxy-containing organic groups, the temperature of the developer, and the like, and usually for 30 to 180 seconds. The developing solution used in the developing step is not particularly limited as long as it can dissolve or disperse the exposed portion in the liquid, and is not particularly limited. Examples thereof include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate and ammonia; Primary amines such as ethylamine and n-propylamine; Secondary amines such as diethylamine and di-n-propylamine; Tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine and triethylamine; Tertiary alkanolamines such as dimethylethanolamine, methyldiethanolamine and triethanolamine; Pyrrole, piperidine, N-methylpiperidine, N-methylpyrrolidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] Cyclic tertiary amines such as -5-nonene; Aromatic tertiary amines such as pyridine, collidine, lutidine and quinoline; Aqueous solutions of alkalis, such as aqueous solutions of quaternary ammonium salts, such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, can be used, The density | concentration is the alkali of the developing solution used for removal of the conventional positive photosensitive composition layer. Okay with concentration The aqueous solution of these alkalis may further contain a suitable amount of water-soluble organic solvents and / or surfactants such as methanol and ethanol. After removing an exposure part with a developing solution, it is preferable to rinse with water by running water or a shower, and you may dry-dry in 50-120 degreeC as needed.

(5) bleaching exposure process

The bleaching exposure step is a step of irradiating light to the entirety of the positive photosensitive composition layer (hereinafter sometimes referred to as a resist layer) remaining by alkaline solution treatment to improve visible light transmittance. The resist layer is colored pale yellow to light brown in that it contains (C) diazonaphthoquinones. By irradiating the resist layer with light, the remaining unreacted (C) diazonaphthoquinones are photolyzed and changed into indencarboxylic acid without absorption in the visible region, thereby improving the visible light transmittance, and the like. It is suitable for use as a permanent resist for the active matrix substrate to be used. Irradiation light in a bleaching exposure process is not specifically limited, For example, what is necessary is just to irradiate the light of 10-1000mJ / cm <2>, Preferably it is 40-600mJ / cm <2>. The wavelength of the irradiation light may be visible light or ultraviolet light, and the wavelength of the irradiation light is not particularly limited. However, the wavelength of the irradiation light is preferably selected in accordance with the (C) diazonaphthoquinones used in the same manner as in the exposure step (2).

(6) post-baking process

Although the resist layer exposed to a bleaching exposure improves visible light transmittance, alkali solubility also improves. In the post-baking step, the bleached exposed resist layer is subjected to heat treatment of 120 ° C. or higher, and thermally crosslinks the silicone resin in the resist layer to impart heat resistance, chemical resistance, and change in time resistance required as a permanent resist. In this invention, it is thought that the compound which has at least two epoxy groups which are (B) component of a positive photosensitive composition functions as a crosslinking agent, and obtains chemical-resistance after the high heat history which has never existed. Post-baking is preferably performed in inert gas atmosphere, such as nitrogen, helium, argon. Moreover, it is preferable to perform post-baking for 15 minutes-2 hours at 120-400 degreeC, More preferably, 120-350 degreeC, Most preferably, 200-350 degreeC.

Although the positive photosensitive composition of this invention may be directly apply | coated to a target material, such as a semiconductor substrate, as mentioned above, it may be used, It may apply to a support film, form a coating film, and may use it as a dry film resist. As the support film, for example, polyethylene terephthalate (PET), polyethylene, polypropylene, or the like can be used, but a PET film is preferable in terms of excellent thermal and mechanical properties as a support film. The film thickness of a support film is 1 micrometer-5 mm normally, Preferably they are 10 micrometers-100 micrometers. The thickness of the coating film formed on a support film depends on a use, and although it does not specifically limit, 0.1 micrometer-100 micrometers, Preferably 0.3 micrometer-10 micrometers become a reference | standard. After coating film formation, it is prebaked similarly to said (2) prebaking process, the solvent in a coating film is removed, a protective film is laminated on a coating film surface, and a dry film resist is created. When using the dry film resist obtained from the positive photosensitive composition of this invention, after peeling a protective film from a dry film resist, it is thermocompression-bonded to the target material and joined to an object, If necessary, after peeling a support film, It is good to perform exposure, alkali image development, bleaching exposure, and post-baking similarly to the process of (3)-(6).

The permanent resist obtained from the positive photosensitive composition of the present invention is not only excellent in transparency, insulation, heat resistance, and chemical resistance, but also excellent in transparency, insulation, and chemical resistance after a high heat history (high heat history) of about 300 to 350 ° C. It is very useful as an interlayer insulating film for active matrix substrates having an active matrix substrate insulating film or a planarizing film (especially an interlayer insulating film) used in a display device, an organic EL display device, and the like, and a TFT including polycrystalline silicon thin film as an active layer.

Moreover, the permanent resist obtained from the positive photosensitive composition of this invention can be used also for the interlayer insulation film of a semiconductor element. Moreover, it can also be used for the wafer coating material (surface protective film, bump protective film, MCM (multi-chip module) interlayer protective film, junction coating, and package material (real material, die-bonding material)) of a semiconductor element.

The permanent resist obtained from the positive photosensitive composition of this invention is useful also as insulating films, such as a semiconductor element and a multilayer wiring board. Semiconductor devices include diodes, transistors, compound semiconductors, thermistors, varistors, thyristors, and other semiconductor devices, dynamic random access memory (DRAM), static random access memory (SRAM), erasable programmable read only Memory devices such as memory, mask read only memory (ROM), electrical erasable programmable read only memory (EEPROM), flash memory, theoretical circuit elements such as microprocessor, DSP, ASIC, monolithic microwave integrated circuit Photoelectric conversion elements, such as an integrated circuit element, such as a compound semiconductor, a hybrid integrated circuit (hybrid IC), a light emitting diode, and a charge coupling element, etc. are represented. Moreover, high density wiring boards, such as MCM, etc. are mentioned as a multilayer wiring board.

Example

Although an Example is given to the following and this invention is further demonstrated, this invention is not limited to these.

In addition, the content of silanol group is reacted with trimethylchlorosilane in a pyridine solution to change the silanol group into trimethylsilyl ether group, and then treated with tetramethylammonium hydroxide ((CH ₃ ) ₄ NOH) aqueous solution to form a CO-Si bond. Was hydrolyzed and inversely determined from the mass increase rate after the reaction.

Preparation Example 1 intermediate a1

300 g of toluene, 240 g (1 mol) of 2,4,6,8-tetramethylcyclotetrasiloxane, 64.1 g (0.5 mol) of acrylic acid-t-butyl ester, 4- as a solvent in a glass reaction container equipped with a thermometer and a stirring device 352 g (2 mol) of t-butoxystyrene and 0.05 g of a platinum-divinyl tetramethyldisiloxane complex (Karstedt catalyst) were added as a catalyst, reacted at 60 degreeC for 10 hours, stirring, the solvent was distilled off, and the intermediate a1 was obtained. Got it. Intermediate a1 is a compound corresponding to the general formula (1 bp) (R ¹ = methyl, R ² = R ³ = ethylene, Pg = t-butyl, m = 0.5, n = 2, p = 1.5, m: n: p = 1: 4: 3).

Preparation Example 2 Intermediate a2

In Production Example 1, an intermediate a2 was obtained in the same manner as in Production Example 1, except that 102 g (0.5 mol) of 4-vinyl benzoic acid-t-butyl ester was used instead of 64.1 g (0.5 mol) of acrylic acid t-butyl ester. . Intermediate a2 is a compound corresponding to formula (1 bp) (R ¹ = methyl, R ² = 2-phenylethane-1,4′-diyl, R ³ = ethylene, Pg = t-butyl, m = 0.5, n = 2, p = 1.5, m: n: p = 1: 4: 3).

Preparation Example 3 intermediate a3

In Preparation Example 1, the amount of acrylic acid-t-butyl ester was used at 64.1 g (0.5 mol) to 38.4 g (0.3 mol), and the amount of 4-t-butoxystyrene was used at 352 g (2 mol) to 387 g (2.2 mol). Except for changing to, the same operation as in Production Example 1 was performed to obtain intermediate a3. Intermediate a3 is a compound corresponding to formula (1 bp) (R ¹ = methyl, R ² = R ³ = ethylene, Pg = t-butyl, m = 0.3, n = 2.2, p = 1.5, m: n: p = 1: 7.3: 5).

Preparation Example 4 Intermediate a'1

In Production Example 1, instead of 64.1 g (0.5 mol) of acrylic acid t-butyl ester, 204 g (1 mol) of 4-vinyl benzoate-t-butyl ester was used, and the amount of 4-t-butoxy styrene was 352 g ( 2 mole) to 264 g (1.5 mole) except that the same procedure as in Production Example 1 was carried out to obtain an intermediate a'1. In addition, intermediate a'1 is R ¹ = methyl, R ² = 2-phenylethane-1,4'-diyl, R ³ = ethylene, Pg = t-butyl, m = 1, n = 1.5, p = 1.5 , m: n: p = 1: 1.5: 1.5, which does not satisfy the general formula (1bp).

Preparation Example 5 Intermediate a'2

In Preparation Example 1, the amount of acrylic acid-t-butyl ester was used at 64.1 g (0.5 mol) to 19.2 g (0.15 mol), and the amount of 4-t-butoxystyrene was used at 352 g (2 mol) at 414 g (2.35 mol). The intermediate a'2 was obtained in the same manner as in Production Example 1 except for changing to). In addition, intermediate a'2 is R ¹ = methyl, R ² = R ³ = ethylene, Pg = t-butyl, m = 0.15, n = 2.35, p = 1.5, but m: n: p = 1: 15.7: 10 In general, it does not satisfy the general formula (1bp).

Preparation Example 6 Polysiloxane Compound A1

In a glass reaction vessel equipped with a thermometer and a stirring device, 200 g of toluene as a solvent, 65.6 g (0.1 mole) of intermediate a1, 22.1 g (0.15 mole) of trimethoxyvinylsilane, and a platinum-divinyl tetramethyldisiloxane complex as a catalyst ( Karstedt catalyst) 0.001g was added, and it reacted at 60 degreeC for 10 hours, stirring, and introduce | transduced the group represented by General formula (3).

Subsequently, 45.6 g (0.23 mol) of phenyltrimethoxysilane is added as a compound represented by General formula (2), and 50 g of 5% oxalic-acid aqueous solution is dripped over 30 minutes, ice-cooling-stirring so that it may become 5-10 degreeC. And it stirred further at 10 degreeC for 15 hours. Reflux dehydration and dealcoholization were performed at 50 degreeC and pressure_reduction | reduced_pressure, Toluene of the solvent was solvent-exchanged by 1-methoxy- 2-propanol acetate (henceforth PGMEA) under 50 degreeC reduced pressure, and it was set as 25% PGMEA solution.

In order to remove the t-butyl group, 3 g of boron trifluoride diethyl ether complex was added and stirred at 80 ° C. for 3 hours, and then 10 g of an acidic adsorbent (Kyowakagaku Co., trade name: Kyoword 500SH) was added to 80 ° C. About the slurry solution stirred for 1 hour at, solids were removed by filtration. Thereafter, a portion of the solvent was distilled off at 80 ° C to adjust the concentration to obtain a 30% PGMEA solution of the polysiloxane compound A1 as the component (A). The mass mean molecular weight by GPC analysis of the polysiloxane compound A1 was 6400, and the silanol group content was 5.4 mass%.

Preparation Example 7: Polysiloxane Compound A2

In Production Example 6, the same operation as in Production Example 6 was performed except that 69.4 g (0.1 mol) of intermediate a2 was used instead of 65.6 g (0.1 mol) of intermediate a1, and 30% of the polysiloxane compound A2 as the component (A). PGMEA solution was obtained. The mass mean molecular weight by GPC analysis of the polysiloxane compound A2 was 6500, and the silanol group content was 5.4 mass%.

Preparation Example 8: Polysiloxane Compound A3

In Production Example 6, the same operation as in Preparation Example 6 was carried out except that 65.4 g (0.1 mol) of intermediate a3 was used instead of 65.6 g (0.1 mol) of intermediate a1, and 30% of the polysiloxane compound A3 as the component (A). PGMEA solution was obtained. The mass mean molecular weight by GPC analysis of the polysiloxane compound A3 was 6300, and the silanol group content was 5.4 mass%.

Preparation Example 9 Polysiloxane Compound A4

As a solvent in a glass reaction vessel equipped with a thermometer and a stirring device, 200 g of toluene, 65.6 g (0.1 mole) of intermediate a1, divinyl compound 39 g (0.3 mole) as a divinyl compound represented by the general formula (4a), and a catalyst 0.001 g of platinum-divinyltetramethyldisiloxane complex (Karstedt catalyst) was added and reacted at 60 ° C for 10 hours with stirring to obtain an intermediate represented by the general formula (1c). The solvent was distilled off, and unreacted divinylbenzene was removed under reduced pressure together with the solvent at 60 ° C., and then 19.5 g (0.16 mol) of trimethoxysilane was added as a compound represented by 200 g of toluene and a compound represented by the general formula (4b) as a solvent. It reacted at 60 degreeC for 10 hours, stirring, and introduce | transduced the group represented by General formula (4).

Subsequently, 45.5 g (0.23 mol) of phenyltrimethoxysilane is added as a compound represented by General formula (2), 50 g of 5% aqueous oxalic acid aqueous solution is dripped over 30 minutes, ice-cooling-stirring so that it may become 5-10 degreeC, and 10 degreeC The mixture was further stirred for 15 hours. Reflux dehydration and dealcoholization were performed at 50 degreeC and pressure_reduction | reduced_pressure, Toluene of the solvent was solvent-exchanged by 1-methoxy- 2-propanol acetate (henceforth PGMEA) under 50 degreeC reduced pressure, and it was set as 25% PGMEA solution.

In order to remove the t-butyl group, 3 g of boron trifluoride diethyl ether complex was added and stirred at 80 ° C. for 3 hours, and then 10 g of an acidic adsorbent (Kyowakagaku Co., trade name: Kyoword 500SH) was added to 80 ° C. Solids were removed by filtration with respect to the slurry solution stirred for 1 hour at. Thereafter, a part of the solvent was distilled off at 80 ° C to adjust the concentration to obtain a 30% PGMEA solution of the polysiloxane compound A4 as the component (A). The mass average molecular weight by GPC analysis of the polysiloxane compound A4 was 8300, and the silanol group content was 6.2 mass%.

Preparation Example 10 Polysiloxane Compound A5

200 g of dioxane as a solvent, 65.6 g (0.1 mole) of intermediate a1, 43.2 g (0.2 mole) of diphenylsilanediol, and 0.025 g of tin octylate as a catalyst were dissolved in a glass reaction vessel equipped with a thermometer and a stirring device. Was reacted at 60 ° C for 10 hours to introduce a group represented by the general formula (5).

45.5 g (0.23 mol) of phenyl trimethoxysilanes are added as a compound represented by General formula (2), 50 g of 5% oxalic-acid aqueous solution is dripped over 30 minutes, stirring by ice-cooling so that it may become 5-10 degreeC, and it is 15 at 10 degreeC. It stirred for further time. Reflux dehydration and dealcoholization under reduced pressure at 50 degreeC, The solvent dioxane was solvent-exchanged by 1-methoxy- 2-propanol acetate (henceforth PGMEA) under 50 degreeC reduced pressure, and it was set as 25% PGMEA solution. .

In order to remove the t-butyl group, 3 g of boron trifluoride diethyl ether complex was added and stirred at 80 ° C. for 3 hours, and then 10 g of an acidic adsorbent (Kyowakagaku Co., trade name: Kyoword 500SH) was added to 80 ° C. Solids were removed by filtration with respect to the slurry solution stirred for 1 hour at. Thereafter, a portion of the solvent was distilled off at 80 ° C to adjust the concentration to obtain a 30% PGMEA solution of the polysiloxane compound A5 as the component (A). The mass mean molecular weight by GPC analysis of the polysiloxane compound A5 was 5900, and the silanol group content was 5.1 mass%.

Preparation Example 11: Polysiloxane Compound A'1

30% of polysiloxane compound A'1 of Comparative Example 6 in the same manner as in Production Example 6, except that 70.8 g (0.1 mole) of intermediate a'1 was used instead of 65.6 g (0.1 mole) of intermediate a1. PGMEA solution was obtained. The mass mean molecular weight by GPC analysis of the polysiloxane compound A'1 was 6500, and the silanol group content was 5.4 mass%.

Preparation Example 12: Polysiloxane Compound A'2

30% of the polysiloxane compound A'2 of Comparative Example 6 was prepared in the same manner as in Preparation Example 6, except that 67.3 g (0.1 mol) of intermediate a'2 was used instead of 65.6 g (0.1 mol) of intermediate a1. PGMEA solution was obtained. The mass mean molecular weight by GPC analysis of the polysiloxane compound A'2 was 6400, and the silanol group content was 5.4 mass%.

Preparation Example 13: Epoxy Compound B1 (Compound Represented by General Formula (23))

200 g of toluene, 120 g (0.5 mol) of 2,4,6,8-tetramethylcyclotetrasiloxane, 228 g (2 mol) of allyl glycidyl ether, and platinum-divinyl as a solvent in a glass reaction vessel equipped with a thermometer and a stirring device After adding 9 mg of tetramethyldisiloxane complex (Karstedt catalyst) and reacting for 15 hours at 50-60 degreeC, stirring, the solvent was distilled off under reduced pressure at 60 degreeC and the epoxy compound B1 which is (B) component was obtained. The analytical value of the epoxy equivalent of epoxy compound B1 was 174.

Preparation Example 14 Epoxy Compound B2 (Compound Represented by Formula (24))

250 g of toluene, 144 g (0.6 mol) of 2,4,6,8-tetramethylcyclotetrasiloxane, 144 g of divinylbenzene (0.4 mol), allyl glycidyl ether 194 g as a solvent in a glass reaction container equipped with a thermometer and a stirring device (1.7 mol) and 9 mg of platinum-divinyltetramethyldisiloxane complex (Karstedt catalyst) were added and reacted for 15 hours at 50 to 60 DEG C while stirring, and then the solvent was distilled off under reduced pressure at 60 DEG C to obtain (B) component. Epoxy compound B2 was obtained. The mass value molecular weight of the epoxy compound B2 was 1500 and the analysis value of the epoxy equivalent was 244.

Preparation Example 15 Epoxy Compound B3

Toluene 200 g, 1,1,3,3-tetramethyldisiloxane 134 g (1 mol), divinylbenzene 52 g (0.4 mol), allyl glycidyl ether 194 g (1.7 mol) in a glass reaction vessel equipped with a thermometer and a stirring device ) And 9 mg of platinum-divinyltetramethyldisiloxane complex (Karstedt catalyst) were added and reacted at 50 to 60 ° C. for 15 hours while stirring. The solvent was distilled off under reduced pressure from 60 degreeC from this reaction liquid, and the epoxysilane compound B3 which is (B) component was obtained. The mass value molecular weight of the epoxy compound B3 was 1500 and the analysis value of the epoxy equivalent was 244.

Examples 1-10 and Comparative Examples 1-3:

After compounding in the ratio shown in Table 1 using the compound obtained by the above manufacture example, it filtered and prepared the positive photosensitive composition of Examples 1-10 and Comparative Examples 1-4, respectively. In addition, the solvent was added so that it might become a value in a table | surface.

(C) component and (D) component of Table 1 are as follows, respectively.

(C) diazonaphthoquinones (DNQ)

In the formula (27), all the Q is a group represented by the formula (26) (manufactured by Daito Chemical Co., Ltd., trade name: PA-6)

(D) solvent

PGMEA: 1-methoxy-2-propanol acetate

The test piece was prepared in the order of the preparation method of the following test piece using the positive photosensitive composition of Examples 1-10 and Comparative Examples 1-4.

[Preparation Method of Test Piece]

The positive photosensitive composition was applied onto a glass substrate by a spin coat method such that the film thickness was 3 to 4 µm, and then the solvent was volatilized, prebaked at 100 ° C. for 3 minutes, and used as a test piece.

Using the obtained test piece, evaluation of optimum developing time and development margin, alkali resistance evaluation after a high heat history, evaluation of a resist residue, and film | membrane reduction rate were performed by the following methods, respectively. In each of the following evaluations, in the patterning exposure, all of the test pieces were heated at 90 ° C. for 2 minutes, a photomask having a line width of 5 μm was formed on the upper portion of the glass substrate, and 90mJ / cm 2 (wavelength: 365 nm) using an ultra-high pressure mercury lamp. Irradiation of the ultraviolet-ray of exposure conversion) was performed.

[Evaluation of optimal development time and development margin]

The development time was changed from 30 seconds to 5 seconds, and the evaluation of the optimum development time and development margin was evaluated in the following order. That is, after preparing and patterning each of 15 test pieces for each positive photosensitive composition, these test pieces were immersed in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at a liquid temperature of 25 ° C., and immersion was started after 30 seconds. One piece was taken out at 5 second intervals. The removed test piece was immediately washed with running water for 1 minute with ultrapure water and dried in the wind. The test piece dried on the wind was observed, and the shortest developing time required for the line line width to be 5 µm was taken as the optimum developing time, and the time from the optimum developing time to the peeling of the line pattern of 5 µm was taken as the developing margin. The results are shown in Table 2.

[Evaluation of alkali resistance after high temperature history]

After patterning exposure about the test piece of positive type photosensitive composition, it developed by the shower image development method (shower pressure 0.05MPa) using the 2.38 mass% tetramethylammonium hydroxide aqueous solution of 25 degreeC of liquid temperature. In addition, developing time was made into the optimal developing time of each positive photosensitive composition calculated | required by the previous evaluation. Immediately after the development, the water was washed with ultrapure water for 1 minute and dried in the wind. Bleaching exposure was performed on the wind-dried test piece on 200 mJ / cm <2> (wavelength 365nm exposure conversion) conditions using the ultrahigh pressure mercury lamp. After bleaching exposure, post-baking was performed by heating for 60 minutes at 230 degreeC in air | atmosphere atmosphere, the permanent resist film was formed, and heat processing for 30 minutes was further performed at 350 degreeC under nitrogen atmosphere. After measuring the film thickness of a resist with the measurement of the transmittance | permeability of the light of wavelength 400nm, and the stylus type surface shape measuring instrument about the test piece which heat-processed at 350 degreeC, alkaline solution (monoethanolamine: N-methyl-) of 40 degreeC 2-pyrrolidone: butyl diglycol = 10:30:60 mass ratio) was immersed for 30 minutes. For each test piece after immersion, the transmittance of light having a wavelength of 400 nm and the film thickness of the resist were measured, and the alkali resistance after high heat history was evaluated from the rate of change of light transmittance before and after immersion in an alkaline solution and the rate of change of film thickness. did. The results are shown in Table 2.

(Evaluation standard)

(Circle): The change rate of a light transmittance is less than 3%, and the change rate of a film thickness is less than 10%, and is excellent in alkali resistance even after high heat history.

(Triangle | delta): Although the change rate of a light transmittance is less than 5%, and the change rate of a film thickness is less than 20%, the change rate of a light transmittance is less than 3% and the change rate of a film thickness is not less than 10%, and alkali resistance after high heat history is slightly inferior.

X: The change rate of light transmittance is 5% or more, or the change rate of film thickness is 10% or more, and the alkali resistance after high heat history is inferior.

[Evaluation of Resist Residue]

After patterning exposure about each positive type photosensitive composition using each of 3 test pieces, it developed by the shower developing method (shower pressure 0.05MPa) using the 2.38 mass% tetramethylammonium hydroxide aqueous solution of 25 degreeC of liquid temperature. . In addition, developing time was made into the optimal developing time of each positive photosensitive composition calculated | required by the previous evaluation.

Immediately after the development, the water was washed with ultrapure water for 1 minute and dried in the wind. After irradiating 200 mJ / cm <2> (wavelength 365nm exposure conversion) light with the ultrahigh pressure mercury lamp on the wind-dried test piece as a bleaching exposure, it post-baked for 60 minutes at 230 degreeC in air atmosphere, and formed the permanent resist film. Each test piece was cut | disconnected, the cut surface was observed using the scanning electron microscope, the presence or absence of the resist residue in the part by which the glass substrate was exposed by image development was examined, and the resist residue was evaluated by the following evaluation criteria. The results are shown in Table 2.

(Evaluation standard)

(Circle): The resist residue is not seen by all three test pieces.

X: The resist residue is seen by 1-3 sheets among three test pieces.

[Evaluation of Membrane Reduction Rate]

Each positive photosensitive composition was subjected to bleaching exposure and post-baking under the same conditions as the evaluation of the resist residue without patterning exposure and development on each of the three test pieces, to form a permanent resist layer. Each test piece was cut | disconnected, and the thickness of the permanent resist layer was measured using the scanning electron microscope. Moreover, also about the test piece used by evaluation of the resist residue, the thickness of the permanent resist film was measured, and the film reduction rate (%) was calculated | required by the following formula. In addition, the average value of each of three test pieces was used for the thickness of a permanent resist layer. The results are shown in Table 2.

Membrane Reduction (%) = 100 × T _D / T ₀

T _D : thickness of the permanent resist layer of the test piece subjected to exposure and development

T ₀ : thickness of the permanent resist layer of the test piece that is not exposed or developed

Claims (6)

The silanol group containing polysiloxane compound which consists of a structure obtained by hydrolyzing and condensation reaction of the cyclic siloxane compound represented by following General formula (1) and the alkoxysilane compound represented by following General formula (2) as (A) component,
A compound having at least two epoxy-containing organic groups as the component (B),
(C) diazonaphthoquinones as a component, and
The positive photosensitive composition containing the organic solvent as (D) component.
[Chemical Formula 1]

In the formula, R ¹ represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, R ² represents a divalent hydrocarbon group having 2 to 10 carbon atoms, and R ³ represents a divalent saturated aliphatic hydrocarbon having 2 to 10 carbon atoms. Group is represented, X represents a group represented by the following general formula (3), a group represented by the following general formula (4), or a group represented by the following general formula (5): m, n and p each represent an average of one molecule As the number, m: n: p = 1: 2.1 to 12: 1 to 6 and m + n + p = 3 to 6 are satisfied.)
(2)

(In formula, R <^4> represents a C1-C4 alkyl group or a C6-C10 aryl group, R <^5> represents a C1-C4 alkyl group and a represents the number of 1-2. "
(3)

(In formula, R <^6> represents a C1-C4 alkyl group, R <^7> represents a C1-C4 alkyl group or a C6-C10 aryl group, and b shows the number of 1-3. "
[Chemical Formula 4]

(Wherein R ⁸ represents a residue obtained by subtracting a vinyl group from a divinyl compound or trivinyl compound having a molecular weight of 1000 or less, R ⁹ represents an alkyl group having 1 to 4 carbon atoms, and R ¹⁰ represents an alkyl or phenyl group having 1 to 4 carbon atoms) C represents a number from 1 to 3, and d represents a number from 1 or 2.
[Chemical Formula 5]

(In formula, R <^11> and R <^12> respectively independently represents a C1-C4 alkyl group or a C6-C10 aryl group, and e shows the number of 1-10.) The method of claim 1,
Positive type photosensitive composition in which the epoxy containing organic group of the compound which has at least two epoxy containing organic groups as said (B) component contains a glycidyl group. Hardened | cured material formed by hardening | curing the positive photosensitive composition of Claim 1 or 2. After applying the positive photosensitive composition of Claim 1 or 2 to a target material, prebaking, exposing, alkali-developing, and then bleaching exposing, post-baking at the temperature of 120-400 degreeC Method for producing a permanent resist, characterized in that. The liquid crystal display device which has an active-matrix board | substrate which makes a permanent resist obtained using the positive photosensitive composition of Claim 1 or 2 an insulating layer or a planarization film. An organic EL display device comprising an active matrix substrate having a permanent resist obtained by using the positive photosensitive composition according to claim 1 as an insulating layer or a planarization film.