JP5479993B2 - Positive photosensitive composition and permanent resist - Google Patents

Description

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

  With the progress of the information society and the spread of multimedia systems, the importance of liquid crystal display devices, organic EL display devices, etc. is increasing more and more. In these display devices, an active matrix substrate provided with a switching element such as a thin film transistor (TFT) for each pixel is used. On the active matrix substrate, a large number of scanning wirings and signal wirings intersecting these scanning wirings through an insulating film are formed. The scanning wiring, signal wiring, insulating film, and the like of the active matrix substrate are formed by repeatedly patterning a conductive film or insulating film formed by sputtering, CVD, coating, or the like in photolithography ( For example, see Patent Documents 1 and 2).

  In general, a photoresist is used for photolithography, and a resist (permanent resist) that is used as an insulating film or a protective film without being peeled after patterning has been developed. However, when a permanent resist is used for an active matrix substrate In addition to chemical resistance (acid resistance, alkali resistance, and solvent resistance), high heat resistance and chemical resistance after a high heat history are required. That is, in an active matrix substrate, a TFT having 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. There is a problem that a dangling bond which is a defect of silicon bond is easily generated at the interface between the insulating substrate and the insulating film and the characteristics of the transistor is deteriorated. In order to solve the problem of dangling bonds, it is necessary to perform a hydrogenation process at a temperature of about 300 to 400 ° C. in the presence of a film that prevents diffusion of hydrogen such as silicon nitride (SiNx) (for example, patents). Reference 3). The heat resistance in the conventional permanent resist is heat resistance that can withstand soldering on a printed wiring board at a temperature of 260 ° C. for several minutes (see, for example, Patent Document 4), and is required for an active matrix substrate. And chemical resistance after high heat history are very different.

  On the other hand, silicone resins are excellent in transparency, insulation, heat resistance, chemical resistance, etc., and photoresists based on silicone resins are also known, but conventional silicone resin photoresists are heat resistant. In addition, since the chemical resistance after the high heat history is insufficient, the active matrix substrate is merely applied as a surface flattening film (see, for example, Patent Document 5).

JP 2004-281506 A JP 2007-225860 A JP-A-6-77484 JP 2007-304543 A JP 2008-116785 A

  Accordingly, an object of the present invention is to provide a positive photosensitive composition that is capable of providing a permanent resist having excellent transparency, high heat resistance that can be used as an insulating film of an active matrix substrate, and chemical resistance after high heat history, An object of the present invention is to provide a permanent resist using the positive photosensitive composition and a method for producing the permanent resist.

（式中、Ｒ¹は同一でも異なっていてもよい炭素数１〜１０のアルキル基又は炭素数６〜１０のアリール基を表わし、Ｘ¹は同一でも異なっていてもよい下記一般式（３）、（４）、（５）又は（６）で表される基を表わす。ｍは１分子あたりの一般式（３）で表される基の数を表わし、ｎは１分子あたりの一般式（４）で表される基の数を表わし、ｐは１分子あたりの一般式（５）で表される基と一般式（６）で表される基の数の合計を表わす。但し、ｍ、ｎ及びｐは、ｍ：ｎ：ｐ＝１：０〜２：１〜３、ｍ＋ｎ＋ｐ＝３〜６となる数である。）

（式中、Ｒ²は炭素数１〜３のアルキル基又は炭素数６〜１０のアリール基を表わし、
Ｒ³は炭素数１〜４のアルキル基を表わし、ａは１又は２の数を表わす。）

（式中、Ｒ⁴は置換アルキル基を有してもよい炭素数１〜１０のアルキレン基を表わし、Ｒ⁵は炭素数１〜４のアルキル基を表わし、ｂは０又は１〜４の数を表わす。）

（式中、Ｒ⁶は置換アルキル基を有してもよい炭素数１〜１０のアルキレン基を表わし、Ｒ⁷は炭素数１〜４のアルキル基を表わし、ｃは０又は１〜４の数を表わす。）

（式中、Ｒ⁸は分子量１０００以下のジビニル化合物又はトリビニル化合物からビニル基を除いた残基を表わし、Ｒ⁹は炭素数１〜４のアルキル基を表わし、Ｒ¹⁰は炭素数１〜４のアルキル基又はフェニル基を表わす。ｄは１〜３の数を表わし、ｅは１又は２の数を表わす。）

（式中、Ｒ¹¹及びＲ¹²は各々独立して同一でも異なっていてもよい炭素数１〜１０のアルキル基又は炭素数６〜１０のアリール基を表わす。ｆは０〜１００の数を表わす。） The present inventors have reached the present invention as a result of intensive studies in view of the above.
That is, in the present invention, as the component (A), a cyclic siloxane compound represented by the following general formula (1) and an alkoxysilane compound represented by the following general formula (2) are hydrolyzed and condensed so that silanol groups remain. A polysiloxane compound obtained by reaction, a compound having at least two epoxy groups as the component (B), a diazonaphthoquinones as the component (C), and a positive photosensitive material containing an organic solvent as the component (D) A composition is provided.

Wherein R ¹ represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms which may be the same or different, and X ¹ may be the same or different; , (4), (5) or (6), m represents the number of groups represented by the general formula (3) per molecule, and n represents the general formula (1) 4) represents the number of groups represented by 4), and p represents the total number of groups represented by general formula (5) and groups represented by general formula (6) per molecule, provided that m, n and p are numbers such that m: n: p = 1: 0 to 2: 1 to 3 and m + n + p = 3 to 6.

(In the formula, R ² represents an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 10 carbon atoms,
R ³ represents an alkyl group having 1 to 4 carbon atoms, and a represents a number of 1 or 2. )

(In the formula, R ⁴ represents an alkylene group having 1 to 10 carbon atoms which may have a substituted alkyl group, R ⁵ represents an alkyl group having 1 to 4 carbon atoms, and b is a number of 0 or 1 to 4). Represents.)

(Wherein R ⁶ represents an alkylene group having 1 to 10 carbon atoms which may have a substituted alkyl group, R ⁷ represents an alkyl group having 1 to 4 carbon atoms, and c is 0 or a number of 1 to 4) Represents.)

(In the formula, R ⁸ represents a residue obtained by removing 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 group having 1 to 4 carbon atoms. And represents an alkyl group or a phenyl group, d represents a number of 1 to 3, and e represents a number of 1 or 2.)

(In the formula, R ¹¹ and R ¹² each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, which may be the same or different. F represents a number of 0 to 100. .)

  The effect of the present invention is not only highly transparent, but also has excellent heat resistance and chemical resistance such as solvent resistance that can withstand the temperature at the time of manufacturing an active matrix substrate, and also has excellent aging resistance as a permanent resist. The present invention provides a positive photosensitive composition capable of providing a film, a permanent resist using the positive photosensitive composition, and a method for producing the permanent resist.

Hereinafter, the present invention will be described in detail based on preferred embodiments.
The component (A) of the present invention is obtained by subjecting the cyclic siloxane compound represented by the general formula (1) and the alkoxysilane compound represented by the general formula (2) to hydrolysis / condensation reaction so that silanol groups remain. It is a polysiloxane compound obtained (hereinafter also referred to as silanol group-containing polysiloxane compound).
First, the cyclic siloxane compound represented by the general formula (1) will be described.

In the general formula (1), R ¹ represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, which may be the same or different. Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, t-butyl, pentyl, isopentyl, neopentyl, secondary pentyl, t-pentyl, hexyl and isohexyl. 2-methylpentyl, secondary hexyl, t-hexyl, heptyl, isoheptyl, t-heptyl, octyl, isooctyl, t-octyl, 2-ethylhexyl, nonyl, isononyl, t-nonyl, decyl, isodecyl, t-decyl, And 2-propylheptyl. Examples of the aryl group having 6 to 10 carbon atoms include phenyl, ethylphenyl, toluyl, cumenyl, xylyl, pseudocumenyl, mesityl, t-butylphenyl, benzyl, phenethyl and the like. R ¹ is preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl and phenyl, more preferably methyl, ethyl and phenyl, and most preferably methyl, from the viewpoint of industrial availability.

X ¹ represents a group represented by the general formulas (3), (4), (5) and (6) which may be the same or different. In the general formula (3), R ⁴ represents an alkylene group having 1 to 10 carbon atoms which may have a substituted alkyl group. Examples of the alkylene group having 1 to 10 carbon atoms include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene and decanylene. R ⁴ preferably has a small number of carbon atoms from the viewpoint of heat resistance, but is preferably ethylene, propylene and butylene, more preferably ethylene and butylene, and most preferably ethylene from the viewpoint of industrial availability. Examples of the substituted alkyl group that may be contained in R ⁴ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, etc., but from the viewpoint of heat resistance, the substituted alkyl group should not have a substituted alkyl group. Is preferred.

In the general formula (3), R ⁵ represents an alkyl group having 1 to 4 carbon atoms, b represents a number of 0 or 1 to 4. 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 ⁵ has good heat resistance. It is preferable not to have R ⁵ , that is, b is 0. In the general formula (3), the carboxyl group (COOH) is preferably in the ortho position or the para position, more preferably in the para position with respect to R ⁴ , since the heat resistance is improved.

In the general formula (4), R ⁶ represents an alkylene group having 1 to 10 carbon atoms which may have a substituted alkyl group. Examples of the alkylene group having 1 to 10 carbon atoms include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene and decanylene. R ⁶ preferably has a small number of carbons from the viewpoint of heat resistance, but is preferably ethylene, propylene and butylene, more preferably ethylene and butylene, and most preferably ethylene from the viewpoint of industrial availability. Examples of the substituted alkyl group that may be contained in R ⁶ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl and the like, but from the viewpoint of heat resistance, the substituted alkyl group should not have a substituted alkyl group. Is preferred.

In the general formula (4), R ⁷ represents an alkyl group having 1 to 4 carbon atoms, c is a number from 0 or 1 to 4. Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, and t-butyl. R ⁷ preferably has no R ⁷ , that is, c is 0 because heat resistance is good. In the general formula (4), the hydroxyl group (OH) is preferably in the ortho position or the para position, more preferably in the para position, with respect to R ⁶ because heat resistance is improved.

（式中、Ｒ⁸及びｅは前記一般式（５）と同義である。） In the general formula (5), R ⁸ represents a residue obtained by removing a vinyl group from a divinyl compound or trivinyl compound having a molecular weight of 1000 or less. Such a divinyl compound or trivinyl compound is a compound represented by the following general formula (7), and examples thereof include compounds represented by the following general formulas (8) to (12).

(In the formula, R ⁸ and e are as defined in the general formula (5).)

（式中、Ｒ¹³及びＲ¹⁴は各々独立して同一でも異なっていてもよい炭素数１〜１０のアルキル基又は炭素数６〜１０のアリール基を表わし、ｇは０〜６の数を表わす。）

(In the formula, R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms which may be the same or different, and g represents a number of 0 to 6). .)

（式中、Ｒ¹⁵〜Ｒ¹⁷は各々独立して同一でも異なっていてもよい炭素数１〜１０のアルキル基又は炭素数６〜１０のアリール基を表わし、ｈは０〜４の数を表わす。）

(Wherein R ^{15 to} R ¹⁷ each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms which may be the same or different, and h represents a number of 0 to 4). .)

（式中、Ｒ¹⁸及びＲ¹⁹は各々独立して同一でも異なっていてもよい炭素数１〜１０のアルキル基又は炭素数６〜１０のアリール基を表わし、ｅは前記一般式（５）と同義である。）

(In the formula, R ¹⁸ and R ¹⁹ each independently represent a C 1-10 alkyl group or a C 6-10 aryl group which may be the same or different, and e represents the formula (5) and Synonymous.)

（式中、ｅは前記一般式（５）と同義である。）

(In the formula, e has the same meaning as the general formula (5).)

（式中、ｅは前記一般式（５）と同義である。）

(In the formula, e has the same meaning as the general formula (5).)

（式中、Ｒ²⁰は炭素数１〜４のアルキル基、炭素数６〜１０のアリール基又はアリル基を表わす。）

(In the formula, R ²⁰ represents an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an allyl group.)

（式中、Ｒ²¹〜Ｒ²³は各々独立して同一でも異なっていてもよい炭素数１〜１０のアルキル基又は炭素数６〜１０のアリール基を表わし、ｊは２又は３の数を表わし、ｋはｊ＋ｋが３〜６となる０〜４の数を表わす。）

(In the formula, R ^{21 to} R ²³ each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms which may be the same or different, and j represents a number of 2 or 3). , K represents a number from 0 to 4 where j + k is 3 to 6.)

In the general formula (8), R ¹³ and R ¹⁴ each independently represent an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, which may be the same or different. Examples of the alkyl group having 1 to 10 carbon atoms or the aryl group having 6 to 10 carbon atoms include the groups exemplified in the description of R ¹ . R ¹³ and R ¹⁴ are preferably methyl, ethyl, propyl and phenyl, more preferably methyl, ethyl and phenyl, and most preferably methyl because of good heat resistance. g represents a number of 0 to 6 and is easily available industrially, so that a number of 0 to 2 is preferable, and a number of 0 or 1 is more preferable.

  Among the compounds represented by the general formula (8), 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- Examples include divinyltrisiloxane, 1,1,3,3,5,5,7,7-octamethyl-1,7-divinyltetrasiloxane, and among these, 1,1,3,3-tetramethyl 1,1,3,3-tetraethyl-1,3-divinyldisiloxane, and 1,1,3,3,5,5-hexamethyl-1,5-divinyltrisiloxane Are preferred, and 1,1,3,3-tetramethyl-1,3-divinyldisiloxane is more preferred.

In the general formula (9), R ^{15 to} R ¹⁷ each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, which may be the same or different. Examples of the alkyl group having 1 to 10 carbon atoms or the aryl group having 6 to 10 carbon atoms include the groups exemplified in the description of R ¹ . R ^{15 to} R ¹⁷ are preferably methyl, ethyl, propyl and phenyl, more preferably methyl, ethyl and phenyl, and most preferably methyl because of good heat resistance. h represents a number of 0 to 4 and is easily available industrially, and is preferably a number of 0 to 2, and more preferably 0 or 1.

  Among the compounds represented by the general formula (9), preferable compounds include trivinylmethylsilane tris (dimethylvinylsiloxy) methylsilane, tris (dimethylvinylsiloxy) phenylsilane, tris {(dimethylvinylsiloxy) dimethylsiloxy}. Examples include methylsilane, and among these, tris (dimethylvinylsiloxy) methylsilane is preferable.

In the general formula (10), R ¹⁸ and R ¹⁹ each independently represent an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, which may be the same or different, and e represents the general formula It is synonymous with (5). Examples of the alkyl group having 1 to 10 carbon atoms or the aryl group having 6 to 10 carbon atoms include the groups exemplified in the description of R ¹ . R ¹⁸ and R ¹⁹ are preferably methyl and ethyl, and more preferably methyl, because of good heat resistance.

  Among the compounds represented by the general formula (10), preferred compounds are 1,2-bis (dimethylvinylsilyl) benzene, 1,3-bis (dimethylvinylsilyl) benzene, and 1,4-bis (dimethyl). Vinylsilyl) benzene, 1,2-bis (diethylvinylsilyl) benzene, 1,3-bis (diethylvinylsilyl) benzene, 1,4-bis (diethylvinylsilyl) benzene, 1,3,5-tris (dimethyl) Vinylsilyl) benzene), 1,3,5-tris (diethylvinylsilyl) benzene) and the like. Among these, since it is easily available industrially and has good heat resistance, 1,2 -Bis (dimethylvinylsilyl) benzene and 1,4-bis (dimethylvinylsilyl) benzene are preferred, 1,4-bis (dimethylvinyl Lil) benzene is more preferred.

  In the said General formula (11), e is synonymous with the said General formula (5). Examples of the compound represented by the general formula (11) include 1,2-divinylbenzene, 1,3-divinylbenzene, 1,4-divinylbenzene, 1,2,4-trivinylbenzene, 1,3,3, 5-Trivinylbenzene and the like can be mentioned, and among these, 1,4-divinylbenzene is preferred because it is easily available industrially and has good heat resistance.

  In the said General formula (12), e is synonymous with the said General formula (5). Examples of the compound represented by the general formula (12) include 1,2-divinylcyclohexane, 1,3-divinylcyclohexane, 1,4-divinylcyclohexane, 1,2,4-trivinylcyclohexane, 1,3, 5-trivinylcyclohexane and the like can be mentioned. Among them, 1,2,4-trivinylcyclohexane and 1,4-divinylcyclohexane are preferable because they are easily available industrially and have good heat resistance. .

In the general formula (13), R ²⁰ represents an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an allyl group. Examples of the alkyl group having 1 to 4 carbon atoms or the aryl group having 6 to 10 carbon atoms include the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms exemplified in the description of R ^1. . R ²⁰ is preferably methyl, ethyl and allyl, more preferably methyl and allyl, because of good heat resistance.

  Among the compounds represented by the general formula (13), preferred compounds include diallyl methyl isocyanurate, diallyl ethyl isocyanurate, triallyl isocyanurate, and among these, triallyl isocyanurate is more preferred.

In the compound represented by the general formula (14), R ^{21 to} R ²³ each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, which may be the same or different. Examples of the alkyl group having 1 to 10 carbon atoms or the aryl group having 6 to 10 carbon atoms include the groups exemplified in the description of R ¹ . R ^{21 to} R ²³ are preferably methyl, ethyl, propyl and phenyl, more preferably methyl, ethyl and phenyl, and most preferably methyl because of good heat resistance. j represents a number of 2 or 3, and k represents a number of 0 to 4 where j + k is 3 to 6. From the viewpoint of easy industrial availability, j + k is preferably a number of 4 or 5, and more preferably a number of 4.

  Among the compounds represented by the general formula (14), preferred compounds 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-divinylsilopentasiloxane, 2,4,6-trimethyl-2,4 , 6-trivinylcyclotrisiloxane, 2,2,4,6,8-pentamethyl-4,6,8-trivinylcyclotetrasiloxane, and the like.

  Among the divinyl compounds or trivinyl compounds having a molecular weight of 1000 or less, preferred compounds are those represented by the general formulas (11), (12) and (13) from the viewpoint of industrial availability and the heat resistance of the resulting cured product. Are preferred, 1,4-divinylbenzene, 1,2,4-trivinylcyclohexane and triallyl isocyanurate are more preferred, and 1,4-divinylbenzene is most preferred.

In the general formula (5), R ⁹ represents an alkyl group having 1 to 4 carbon atoms, and R ¹⁰ represents an alkyl group having 1 to 4 carbon atoms or a phenyl group. The alkyl group having 1 to 4 carbon atoms, for example, alkyl groups exemplified in the description of R ^5. R ⁹ is preferably methyl and ethyl, more preferably methyl, because of good reactivity with the alkoxysilane compound represented by the general formula (2). R ¹⁰ is preferably methyl, ethyl, or phenyl, more preferably methyl, because of improved heat resistance. d represents a number of 1 to 3, and is preferably 2 or 3, more preferably 3 because heat resistance is improved. e represents a number of 1 or 2, and when R ⁸ represents a residue obtained by removing a vinyl group from a divinyl compound having a molecular weight of 1000 or less, e is a number of 1 and R ¹⁰ is from a trivinyl compound having a molecular weight of 1000 or less to vinyl. In the case of representing a residue excluding a group, e is a number of 2.

In the general formula (6), R ¹¹ and R ¹² 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 the description of R ¹ , and R ¹¹ and R ¹² have a carbon number because they are easy to produce. 6-10 aryl groups are preferred, and of these, phenyl is preferred. f represents a number of 0 to 100, and is preferably a number of 0 to 10, more preferably a number of 0 to 5, and most preferably a number of 0 to 1 because of easy production.

  In the general formula (1), m represents the number of groups represented by the general formula (3) per molecule, n represents the number of groups represented by the general formula (4) per molecule, p represents the total of the number of groups represented by the general formula (5) and the group represented by the general formula (5) per molecule. However, m, n, and p are numbers which become m: n: p = 1: 0 to 2: 1 to 3, and m + n + p = 3 to 6. The cyclic siloxane compound represented by the general formula (1) may be used alone or in combination of two or more, but when two or more are used in combination, m, n And the number of p is an average number. For example, an equimolar mixture of a compound where m = 1, n = 0 and p = 3 and a compound where m = 1, n = 1 and p = 2 is m: n: p = 1: 0.5: 2.5. The ratio of n to m is preferably 0 to 1, more preferably 0.01 to 0.7, and most preferably 0.02 to 0.5.

  The cyclic siloxane compound represented by the general formula (1) includes, for example, a cyclic siloxane compound represented by the following general formula (1h), an aromatic carboxylic acid compound represented by the following general formula (3v), and the following general formula ( The phenol compound represented by 4v) is subjected to a hydrosilylation reaction to obtain an intermediate represented by the following general formula (1a), and the intermediate represented by the above general formula (5) and / or the general formula (5) It can be obtained by introducing the group represented by 6).

（式中、ｍ、ｎ及びｐは、ｍ＋ｎ＋ｐ＝３〜６となる数を表わし、Ｒ¹は前記一般式（１）と同義である。）

(In the formula, m, n and p represent a number such that m + n + p = 3 to 6, and R ¹ has the same meaning as in the general formula (1).)

（式中、Ｒ²⁴はＳｉＨ基と反応してＲ⁴となる基を表わし、Ｒ⁵及びｂは前記一般式（３）と同義である。）

(In the formula, R ²⁴ represents a group which reacts with the SiH group to become R ^4, and R ⁵ and b have the same meanings as in the general formula (3).)

（式中、Ｒ²⁵はＳｉＨ基と反応してＲ⁶となる基を表わし、Ｒ⁷及びｃは前記一般式（４）と同義である。）

(In the formula, R ²⁵ represents a group which reacts with the SiH group to become R ^6, and R ⁷ and c have the same meanings as in the general formula (4).)

（式中、Ｒ¹、ｍ、ｎ及びｐは前記一般式（１）と同義であり、Ｒ⁴、Ｒ⁵及びｂは前記一般式（３）と同義であり、Ｒ⁶、Ｒ⁷及びｃは前記一般式（４）と同義である。）

(In the formula, R ¹ , m, n and p are as defined in the general formula (1), R ⁴ , R ⁵ and b are as defined in the general formula (3), R ⁶ , R ⁷ and c. Is synonymous with the general formula (4).)

  Specific examples of preferable compounds among the cyclic siloxane compounds represented by the general formula (1h) include 2,4,6-trimethylcyclotrisiloxane, 2,4,6-triethylcyclotrisiloxane, 2,4,6. -Triphenylcyclotrisiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, 2,2,4,6,8-pentamethylcyclotetrasiloxane, 2,2,4,4,6,8-hexa Methylcyclotetrasiloxane, 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-pentamethylcyclopentacillo Sun, 2,4,6,8,10-pentaethylcyclopentasiloxane, 2,4,6,8,10-pentaphenylcyclopentasiloxane, 2,4,6,8,10,12-hexamethylcyclohexa Examples include siloxane, 2,4,6,8,10,12-hexaethylcyclohexasiloxane, 2,4,6,8,10,12-hexaphenylcyclohexasiloxane, among these, 6,8-tetramethylcyclotetrasiloxane and 2,4,6,8,10-pentamethylcyclopentasiloxane are more preferred, and 2,4,6,8-tetramethylcyclotetrasiloxane is most preferred.

  Among the aromatic carboxylic acid compounds represented by the general formula (3v), specific examples of preferable compounds include 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid, 4- (1-phenylvinyl). ) Benzoic acid, 2-methyl-4-vinylbenzoic acid, 2-allylbenzoic acid, 3-allylbenzoic acid, 4-allylbenzoic acid, 2-isopropenylbenzoic acid, 3-isopropenylbenzoic acid, 4-isopropenyl Benzoic acid, 4- (3-butenyl) benzoic acid, 4- (4-pentenyl) benzoic acid, 4- (5-hexenyl) benzoic acid, 4- (6-heptenyl) benzoic acid, 4- (7-octenyl) Benzoic acid, 4- (8-nonenyl) benzoic acid, 4- (9-decenyl) benzoic acid, 2-vinyl-1,4-benzenedicarboxylic acid, 5-vinyl-1,3-benzenedicarboxylic acid and the like Among these, industrially easily available, and from the viewpoint of heat resistance of the permanent resist of the present invention, 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid, 2-allylbenzoic acid Acid, 4-allylbenzoic acid, 2-isopropenylbenzoic acid, and 4-isopropenylbenzoic acid are preferred, 2-vinylbenzoic acid and 4-vinylbenzoic acid are more preferred, and 4-vinylbenzoic acid is most preferred. As the aromatic carboxylic acid represented by the general formula (3v), only one type may be used, or two or more types may be used.

  Specific examples of preferable compounds among the phenol compounds represented by the general formula (4v) include 2-vinylphenol, 3-vinylphenol, 4-vinylphenol, 4- (1-phenylvinyl) phenol, and 2-methyl. -4-vinylphenol, 2-allylphenol, 3-allylphenol, 4-allylphenol, 2-isopropenylphenol, 3-isopropenylphenol, 4-isopropenylphenol, 4- (3-butenyl) phenol, 4- (4-pentenyl) phenol, 4- (5-hexenyl) phenol, 4- (6-heptenyl) phenol, 4- (7-octenyl) phenol, 4- (8-nonenyl) phenol, 4- (9-decenyl) Phenol, 2-vinyl-1,4-dihydroxybenzene, 5-vinyl- , 3-dihydroxylbenzene, and the like. Among them, 2-vinylphenol, 3-vinylphenol, 4-vinyl are industrially easily available and from the viewpoint of heat resistance of the permanent resist of the present invention. Phenol, 2-allylphenol, 4-allylphenol, 2-isopropenylphenol, and 4-isopropenylphenol are preferred, 2-vinylphenol and 4-vinylphenol are more preferred, and 4-vinylphenol is most preferred. Only 1 type may be used for the phenolic compound represented by the said general formula (4v), and 2 or more types may be used for it.

The hydrosilylation reaction between the cyclic siloxane compound represented by the general formula (1h), the aromatic carboxylic acid compound represented by the general formula (3v) and the phenol compound represented by the general formula (4v) is a hydrosilylation catalyst. The hydrosilylation catalyst is preferably a platinum-based catalyst, a palladium-based catalyst, a rhodium-based catalyst, or the like. Examples of platinum-based catalysts include chloroplatinic acid, complexes of chloroplatinic acid and alcohols, aldehydes, ketones, platinum-olefin complexes, platinum-carbonylvinylmethyl complexes (Ossko catalysts), platinum-divinyltetramethyldisiloxane complexes. (KaRstedt catalyst), platinum-cyclovinylmethylsiloxane complex, platinum-octylaldehyde complex, platinum-phosphine complex (for example, 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 ), dicarbonyldichloroplatinum and the like. Examples of the palladium-based catalyst or rhodium-based catalyst include compounds containing a palladium atom or a rhodium atom instead of the platinum atom of the platinum-based catalyst. These may be used alone or in combination of two or more. The hydrosilylation catalyst is preferably a platinum-based catalyst from the viewpoint of reactivity, more preferably a platinum-divinyltetramethyldisiloxane complex and a platinum-carbonylvinylmethyl complex, and most preferably a platinum-carbonylvinylmethyl complex. Further, the amount of the catalyst used is preferably 5% by mass or less, more preferably 0.0001 to 1.0% by mass, most preferably 0.001 to 0.1% by mass of the total amount of each raw material from the viewpoint of reactivity. preferable. The reaction conditions for hydrosilylation are not particularly limited, and may be carried out under the conditions known in the art using the above catalyst. From the viewpoint of the reaction rate, it is preferably carried out at room temperature (25 ° C.) to 130 ° C. A conventionally known solvent such as hexane, methyl isobutyl ketone, cyclopentanone, propylene glycol monomethyl ether acetate may be used.

  When the group represented by the general formula (5) is introduced into the intermediate represented by the general formula (1a), the molecular weight of 1000 or less is added to the SiH group of the intermediate represented by the general formula (1a). The vinyl group of the divinyl compound or trivinyl compound is hydrosilylated to give an intermediate represented by the following general formula (1b), and the vinyl group of the intermediate represented by the general formula (1b) is converted to the following general formula (15) A hydrosilylation reaction may be performed on the alkoxysilane compound represented by the formula:

（式中、Ｒ¹、ｍ、ｎ及びｐは前記一般式（１）と同義であり、Ｒ⁴、Ｒ⁵及びｂは前記一般式（３）と同義であり、Ｒ⁶、Ｒ⁷及びｃは前記一般式（４）と同義であり、Ｒ⁸及びｅは前記一般式（５）と同義である。）

(In the formula, R ¹ , m, n and p are as defined in the general formula (1), R ⁴ , R ⁵ and b are as defined in the general formula (3), R ⁶ , R ⁷ and c. Is synonymous with the general formula (4), and R ⁸ and e are synonymous with the general formula (5).)

（式中、Ｒ⁹、Ｒ¹⁰及びｄは前記一般式（５）と同義である。）

(In the formula, R ⁹ , R ¹⁰ and d are as defined in the general formula (5).)

  Specific examples of preferable compounds among the alkoxysilane compounds represented by the general formula (15) include trimethoxysilane, triethoxysilane, dimethoxymethylsilane, dimethoxyethylsilane, phenyldimethoxysilane, and phenyltrimethoxysilane. Of these, trimethoxysilane, triethoxysilane, and phenyltrimethoxysilane are preferable, trimethoxyvinylsilane and triethoxyvinylsilane are more preferable, and trimethoxyvinylsilane is most preferable because heat resistance and adhesion are improved. The alkoxysilane compound represented by the general formula (15) may be used alone or in combination of two or more.

  Conditions under which the SiH group of the intermediate represented by the general formula (1a) is hydrosilylated with a divinyl compound or trivinyl compound having a molecular weight of 1000 or less, and the intermediate represented by the general formula (1b) include the general formula (15 The conditions for the hydrosilylation reaction of the alkoxysilane compound represented by formula (1) are the same as the cyclic siloxane compound represented by formula (1h), the aromatic carboxylic acid compound represented by formula (3v) and the formula (4v). The same conditions as in the hydrosilylation reaction of the phenol compound represented by formula (1) may be used, and the aromatic carboxylic acid compound represented by formula (3v) and the general siloxane compound represented by formula (1h) After the phenol compound represented by the formula (4v) is hydrosilylated, the above general formula ( The intermediate without isolation represented by a), subsequently reacting the molecular weight of 1,000 or less divinyl compounds or trivinyl compounds, it is preferable to further hydrosilylation reaction alkoxysilane compound represented by the general formula (15).

  When the group represented by the general formula (6) is introduced into the intermediate represented by the general formula (1a), the SiH group of the intermediate represented by the general formula (1a) is substituted with the following general formula ( What is necessary is just to make the silanediol represented by 16) react.

（式中、Ｒ¹¹及びＲ¹²は前記一般式（６）と同義である。）

(In the formula, R ¹¹ and R ¹² have the same meaning as in the general formula (6).)

  Among the silane diols represented by the general formula (16), preferred compounds include dimethyl silane diol, diethyl silane diol, diisopropyl silane diol, dimethyl phenyl silane diol, diphenyl silane diol, and the like. Among these, dimethyl phenyl Silane diol and diphenylsilane diol are preferable, and diphenylsilane diol is more preferable.

  When the silanediol represented by the general formula (16) is reacted with the SiH group of the intermediate represented by the general formula (1a), the reaction may be performed using an organometallic catalyst. Examples of the organometallic catalyst include an organotin catalyst, an organoplatinum catalyst, an organozinc catalyst, and an organoaluminum catalyst, and an organotin catalyst is preferred. Examples of the organotin catalyst include tin octylate, tin naphthenate, tin stearate, tin versatate, dibutyltin laurate, triphenyltin acetate, and tributyltin chloride. Among these, tin octylate and naphthene are exemplified. Tin oxide and tin stearate are preferred, and tin octylate is more preferred. The amount of the organometallic catalyst used is preferably 0.001 to 1% by mass, more preferably 0.002 to 0.1% by mass, based on the total amount of each raw material used.

Next, the alkoxysilane compound represented by the general formula (2) will be described.
In the general formula (2), R ² represents an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R ³ represents an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 3 carbon atoms and the alkyl group having 1 to 4 carbon atoms include the groups exemplified in the description of R ⁵ . R ² is preferably methyl or phenyl, more preferably phenyl, because of improved heat resistance. R ³ is preferably methyl, ethyl and propyl, and more preferably methyl because of its high reactivity. c represents the number of 1 or 2, and since the adhesiveness improves, the number of 1 is preferable.

  Examples of the alkoxysilane compound represented by the general formula (2) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, and phenyltrimethoxysilane. Methoxysilane, phenyltriethoxysilane, toluyltrimethoxysilane, xylyltrimethoxysilane, cumenyltrimethoxysilane, t-butylphenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, phenylmethyldimethoxysilane, Phenylmethyldiethoxysilane, toluylmethyldimethoxysilane, xylylmethyldimethoxysilane, cumenylmethyldimethoxysilane, phenylethyldimethoxysilane , Phenylpropyldimethoxysilane, phenylbutyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, etc. Among these, since heat resistance and adhesion are improved, methyltrimethoxysilane, methyltriethoxysilane, Phenyltrimethoxysilane, phenyltriethoxysilane, phenylmethyldimethoxysilane and phenylmethyldiethoxysilane are preferred, phenyltrimethoxysilane and phenyltriethoxysilane are more preferred, and phenyltrimethoxysilane is most preferred.

  Next, the cyclic siloxane compound represented by the general formula (1) and the alkoxysilane compound represented by the general formula (2) are hydrolyzed and condensed so that silanol groups remain, and the component (A) is obtained. A method for obtaining a silanol group-containing polysiloxane compound will be described.

  The hydrolysis / condensation reaction of the cyclic siloxane compound represented by the general formula (1) and the alkoxysilane compound represented by the general formula (2) may be carried out by a so-called sol-gel reaction. The catalyst may be hydrolyzed and condensed with an alkoxysilyl group using a catalyst such as The solvent used at this time is not particularly limited, and specific examples include water, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, toluene, and the like. These can be used alone or in combination of two or more. In the hydrolysis / condensation reaction of the alkoxysilyl group, the alkoxysilyl group is hydrolyzed with water to form a silanol group (Si-OH group), and the generated silanol groups or between the silanol group and the alkoxysilyl group are condensed. It progresses by. The hydrolysis reaction of alkoxysilyl group proceeds even with moisture in the air or a small amount of water contained in a solvent other than water, but in order to accelerate the reaction, an appropriate amount of water should be added. preferable. Examples of the acid and base catalyst used in the hydrolysis / condensation reaction include inorganic acids such as hydrochloric acid, phosphoric acid and sulfuric acid; formic acid, acetic acid, oxalic acid, citric acid, methanesulfonic acid, benzenesulfonic acid, p- Organic acids such as toluenesulfonic acid and monoisopropyl phosphate; inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonia; amine compounds (organic bases) such as trimethylamine, triethylamine, monoethanolamine and diethanolamine These may be used, and one of these may be used, or two or more may be used in combination. The temperature of the hydrolysis / condensation reaction varies depending on the type of solvent, the type 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 reaction molar ratio of the alkoxysilane compound represented by the general formula (2) to 1 mole of the cyclic siloxane compound represented by the general formula (1) is preferably 1 to 30, and preferably 1.5 to 15. Is more preferable, and 2 to 5 is most preferable.

In general, compared to —Si (OH) _{3 having three} silanol groups and —Si (OH) ₂ having _two silanol groups, the condensation reaction is less likely to occur in —Si—OH having one silanol group. For this reason, when the hydrolysis / condensation reaction of the cyclic siloxane compound represented by the general formula (1) and the alkoxysilane compound represented by the general formula (2) is performed under the above-described conditions, the component (A) contains silanol. One -Si-OH group remains.

The content of the silanol group in the component (A) is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, as the content of OH since the adhesion is improved. Most preferably, it is 20 mass%. As a method for quantifying the silanol group, a method in which the silanol group is trimethylsilylated with trimethylchlorosilane or the like and quantified by a mass increase before and after the reaction (TMS method), a near-infrared spectrophotometer (JP 2001-208683 A, JP 2003 2003 A). 35-66767 and the like) and ²⁹ Si-NMR (see Japanese Patent Application Laid-Open No. 2007-217249 and the like).

  In addition, since the silanol group in the component (A) is likely to undergo a condensation reaction, after the hydrolysis / condensation reaction, the component (A) is not isolated from the reaction solution, and if necessary, decatalytic treatment, solvent replacement The solution is preferably used in the form of a solution containing the component (A) of the present invention after solvent concentration or the like.

  When the molecular weight of the silanol group-containing polysiloxane compound as component (A) is too small, the film formability when a permanent resist is formed using a positive photosensitive composition becomes poor. The weight average molecular weight of the silanol group-containing polysiloxane compound is preferably from 600 to 50,000 because the solubility or dispersibility in an alkali developer is reduced and the resist residue on the substrate surface after alkali development is increased. It is more preferable that it is ˜25000, and it is most preferable that it is 3000-15000. In the present invention, the mass average molecular weight refers to a polystyrene equivalent mass average molecular weight when GPC analysis is performed using tetrahydrofuran (hereinafter referred to as THF) as a solvent.

（式中、Ｘ²は前記の一般式（５）で表される基又は一般式（６）で表される基を表わし、Ｐｇは保護基を表わし、Ｒ¹、ｍ、ｎ及びｐは前記一般式（１）と同義であり、Ｒ⁴、Ｒ⁵及びｂは前記一般式（３）と同義であり、Ｒ⁶、Ｒ⁷及びｃは前記一般式（４）と同義である。） The silanol group-containing polysiloxane compound as the component (A) of the present invention hydrolyzes the cyclic siloxane compound represented by the general formula (1) and the alkoxysilane compound represented by the general formula (2). Although it is a compound obtained by condensation reaction, the silanol group-containing polysiloxane compound (A) is masked with a protective group on the carboxyl group or phenol group of the cyclic siloxane compound represented by the general formula (1). It is a mask after reacting the compound represented by the following general formula (1p) with the alkoxysilane compound represented by the general formula (2) to obtain a precursor of the alkoxysilane compound. A silanol group-containing polysiloxane compound obtained by removing a protecting group is also included.

(In the formula, X ² represents a group represented by the general formula (5) or a group represented by the general formula (6), Pg represents a protecting group, and R ¹ , m, n and p represent the above-mentioned groups. have the same meanings as defined in formula ^{(1), R 4, R} 5 and b are as defined in the general formula ^{(3), R 6, R} 7 and c are as defined in the general formula (4).)

  When a compound masked with a protecting group is used, a process for removing the protecting group is required and the production process becomes complicated, but side reactions are unlikely to occur, and the heat resistance and chemical resistance of the permanent resist of the present invention are reduced. There is an advantage that the property and the like are improved.

  Examples of the protective group for the carboxyl group or phenol group of the cyclic siloxane compound represented by the general formula (1) include t-butyl group and 1-ethoxyethyl group, and t-butyl group is preferable. Such protecting groups can be removed under acidic conditions, and it is preferable to use hydrochloric acid, trifluoroacetic acid, boron trifluoride or the like as a catalyst.

  As the solvent for removing the protecting group, an organic solvent capable of dissolving 1% by mass or more of water at 25 ° C. is preferable. Examples of such an organic solvent include methanol, ethanol, propanol, isopropanol and the like. Alcohols: 1-methoxy-ethanol, 1-ethoxy-ethanol, 1-propoxy-ethanol, 1-isopropoxy-ethanol, 1-butoxy-ethanol, 1-methoxy-2-propanol, 3-methoxy-1-butanol, Ether alcohols such as 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. Acetic esters of ether alcohol; ketones such as acetone and methyl ethyl ketone; 4-hydroxy-2-butanone, 3-hydroxy-3methyl-2-butanone, 4-hydroxy-2-methyl-2-pentanone (diacetone alcohol) And keto alcohols such as 1,4-dioxane, tetrahydrofuran, ethers such as 1,2-dimethoxyethane and the like. Among these, methanol, ethanol, propanol, methyl ethyl ketone, 1,4-dioxane, tetrahydrofuran, and 1-methoxy-2-propanol acetate are preferable.

  In the compound represented by the general formula (1p), the compound represented by the following general formula (3vp) and the compound represented by the following general formula (4vp) are hydrosilylated with the cyclic siloxane compound represented by the general formula (1h). The intermediate represented by the following general formula (1ap) is converted into the intermediate represented by the general formula (1ap) in the same manner as the intermediate represented by the general formula (1a). A group represented by the general formula (5) and / or a group represented by the general formula (6) may be introduced.

（式中、Ｐｇは保護基を表わし、Ｒ⁵、Ｒ²⁴及びｂは前記一般式（３ｖ）と同義である。）

(In the formula, Pg represents a protecting group, and R ⁵ , R ²⁴ and b have the same meanings as in the general formula (3v).)

（式中、Ｐｇは保護基を表わし、Ｒ⁷、Ｒ²⁵及びｃは前記一般式（４ｖ）と同義である。）

(In the formula, Pg represents a protecting group, and R ⁷ , R ²⁵ and c have the same meaning as in the general formula (4v).)

（式中、Ｐｇは保護基を表わし、Ｒ¹、Ｒ⁴〜Ｒ⁷、ｂ、ｃ、ｍ、ｎ及びｐは前記一般式（１ａ）と同義である。）

(In the formula, Pg represents a protecting group, and R ¹ , R ^{4 to} R ⁷ , b, c, m, n, and p have the same meaning as in the general formula (1a).)

Next, the compound having at least two epoxy groups as the component (B) of the present invention will be described.
As the epoxy group of the compound having at least two epoxy groups as the component (B) of the present invention, an aliphatic epoxy group represented by the following formula (17) or (18) or the like, or the following formulas (19) to (21) Alicyclic epoxy groups represented by the following formulas, aliphatic epoxy groups represented by the following formula (22) or (23), and the like, and the storage stability of the positive photosensitive composition of the present invention is improved. Accordingly, an aliphatic epoxy group is preferable, and a 1,2-epoxypropyl group of the following formula (17) is more preferable, and among them, a glycidyl ether group is preferable.

  Examples of the compound having at least two glycidyl ether groups include a glycidyl ether of a polyhydric phenol compound, a glycidyl ether of a polyhydric alcohol compound, and a siloxane compound having a glycidyl ether group. Among these, heat resistance is good. Because of this, a siloxane compound having a glycidyl ether group is preferred. Examples of the siloxane compound having at least two glycidyl ether groups include linear siloxane compounds represented by the following general formula (24), cyclic siloxane compounds represented by the following general formula (25), and alkoxysilanes having a glycidyl ether group. Examples include hydrolysis / condensation products.

（式中、Ｙはグリシジルエーテル基を有する基又はメチル基を表わし、Ｇはグリシジルエーテル基を有する基を表わし、Ｒ²⁶〜Ｒ³⁰は同一でも異なってもよい炭素数１〜６のアルキル基又はフェニル基を表わし、ｑは０〜１０００の数を表わし、ｒは０〜１０００の数を表わす。但し、ｑが０又は１の場合には、Ｙはグリシジルエーテル基を有する基を表わす。）

(In the formula, Y represents a group having a glycidyl ether group or a methyl group, G represents a group having a glycidyl ether group, and R ^{26 to} R ³⁰ are the same or different alkyl groups having 1 to 6 carbon atoms, or Represents a phenyl group, q represents a number from 0 to 1000, and r represents a number from 0 to 1000. However, when q is 0 or 1, Y represents a group having a glycidyl ether group.

（式中、Ｒ³¹〜Ｒ³³は同一でも異なっていてもよい炭素数１〜６のアルキル基又はフェニル基を表わし、Ｇはグリシジルエーテル基を有する基を表わし、ｓは２〜６の数を表わし、ｔはｓ＋ｔが３〜６となる０〜４の数を表わす。）

(In the formula, R ^{31 to} R ³³ represent the same or different alkyl group having 1 to 6 carbon atoms or phenyl group, G represents a group having a glycidyl ether group, and s represents a number of 2 to 6). T represents a number from 0 to 4 where s + t is 3 to 6.)

First, the linear siloxane compound represented by the general formula (24) will be described.
In the general formula (24), G represents a group having a glycidyl ether group, and R ^{26 to} R ³⁰ represent a C 1-6 alkyl group or phenyl group which may be the same or different. Examples of the alkyl group having 1 to 6 carbon atoms include the groups exemplified in the description of R ¹ . R ^{26 to} R ³⁰ are preferably methyl, ethyl and phenyl, more preferably methyl and phenyl, and most preferably methyl because of good heat resistance. Y represents a group having a glycidyl ether group or a methyl group, q represents a number of 0 to 1000, and r represents a number of 0 to 1000. However, when q is 0 or 1, Y represents a group having a glycidyl ether group.

  The linear siloxane compound represented by the general formula (24) is a compound having a carbon-carbon double bond and a glycidyl ether group having reactivity with the SiH group in the linear compound represented by the following general formula (24h). Can be produced by hydrosilylation reaction. Examples of the compound having a carbon-carbon double bond having reactivity with the SiH group and a glycidyl ether group include vinyl glycidyl ether, allyl glycidyl ether, 5-glycidoxypropyl-2-norbornene, and the like. Among these, allyl glycidyl ether is preferable from the viewpoint of industrial availability and hydrosilylation reactivity.

（式中、Ｚは水素原子又はメチル基を表わし、Ｒ²⁶〜Ｒ³⁰、ｑ、ｒ及びＹは前記一般式（２４）と同義である。但し、ｑが０又は１の場合には、Ｚは水素原子を表わす。）

(In the formula, Z represents a hydrogen atom or a methyl group, and R ^{26 to} R ³⁰ , q, r, and Y have the same meanings as in the general formula (24). However, when q is 0 or 1, Represents a hydrogen atom.)

  The hydrosilylation reaction between the linear compound represented by the general formula (24h) and the compound having a carbon-carbon double bond having reactivity with the SiH group and a glycidyl ether group is performed using a hydrosilylation catalyst. The hydrosilylation catalyst is preferably represented by the cyclic siloxane compound represented by the general formula (1h), the aromatic carboxylic acid compound represented by the general formula (3v), and the general formula (4v). Examples of the hydrosilylation catalyst exemplified in the description of the hydrosilylation reaction with a phenol compound include platinum-based catalysts from the viewpoint of reactivity, and platinum-divinyltetramethyldisiloxane complexes and platinum-carbonylvinyl. More preferred are methyl complexes, most preferred are platinum-carbonylvinylmethyl complexes.Further, the amount of the catalyst used is preferably 5% by mass or less, more preferably 0.0001 to 1.0% by mass, most preferably 0.001 to 0.1% by mass of the total amount of each raw material from the viewpoint of reactivity. preferable. The reaction conditions for hydrosilylation are not particularly limited, and may be carried out under the conditions known in the art using the above catalyst. From the viewpoint of the reaction rate, it is preferably carried out at room temperature (25 ° C.) to 130 ° C. A conventionally known solvent such as hexane, methyl isobutyl ketone, cyclopentanone, propylene glycol monomethyl ether acetate may be used.

  When the proportion of the epoxy group in the molecule of the linear siloxane compound represented by the general formula (24) is too small, the crosslinking effect is reduced and the physical properties of the permanent resist of the present invention are lowered. The epoxy equivalent of the linear siloxane compound represented by (24) is preferably 1000 or less, more preferably 700 or less, and most preferably 350 or less. The epoxy equivalent means a value obtained by dividing the molecular weight by the number of epoxy groups, that is, the molecular weight per epoxy group.

  The molecular weight of the linear siloxane compound represented by the general formula (24) is not particularly limited. However, when the molecular weight is too large, the solubility or dispersibility in an alkali developer is lowered, and a resist residue is formed on the substrate surface after alkali development. May remain, the mass average molecular weight is preferably 20000 or less, more preferably 15000 or less, and most preferably 10,000 or less.

Next, the cyclic siloxane compound represented by the general formula (25) will be described.
In the general formula (25) represents an alkyl group or a phenyl group R ³¹ to R ³³ is 1 to 6 carbon atoms which may be the same or different. Examples of the alkyl group having 1 to 6 carbon atoms include the groups exemplified in the description of R ¹ . R ^{31 to} R ³³ are preferably methyl, ethyl and phenyl, more preferably methyl and phenyl, and most preferably methyl because of good heat resistance. s represents a number from 2 to 6, and t represents a number from 0 to 4 where s + t is 3 to 6. As s + t, since it is easily available industrially, a number of 4 to 6 is preferable, a number of 4 or 5 is more preferable, and a number of 4 is most preferable. T is preferably a number of 0.

The cyclic siloxane compound represented by the general formula (25) is obtained by hydrolyzing a compound having a carbon-carbon double bond having reactivity with a SiH group and a glycidyl ether group into the cyclic compound represented by the following general formula (25h). It can manufacture by making it react.
Examples of the compound having a carbon-carbon double bond having reactivity with the SiH group and a glycidyl ether group include compounds similar to those exemplified in the description of the linear siloxane compound represented by the general formula (24). .

（式中、Ｒ³¹〜Ｒ³³、ｓ及びｔは前記一般式（２５）と同義である。）

(In the formula, R ^{31 to} R ³³ , s and t have the same meanings as in the general formula (25).)

  The hydrosilylation reaction between the cyclic compound represented by the general formula (25h) and the compound having a carbon-carbon double bond having reactivity with the SiH group and a glycidyl ether group is performed using a hydrosilylation catalyst. Preferably, the hydrosilylation catalyst includes a cyclic siloxane compound represented by the general formula (1h), an aromatic carboxylic acid compound represented by the general formula (3v), and a phenol represented by the general formula (4v). Examples of the hydrosilylation catalyst exemplified in the description of the hydrosilylation reaction with the compound include platinum-based catalysts from the viewpoint of reactivity, and platinum-divinyltetramethyldisiloxane complexes and platinum-carbonylvinylmethyl. Complexes are more preferred, and platinum-carbonylvinylmethyl complexes are most preferred. Further, the amount of the catalyst used is preferably 5% by mass or less, more preferably 0.0001 to 1.0% by mass, most preferably 0.001 to 0.1% by mass of the total amount of each raw material from the viewpoint of reactivity. preferable. The reaction conditions for hydrosilylation are not particularly limited, and may be carried out under the conditions known in the art using the above catalyst. From the viewpoint of the reaction rate, it is preferably carried out at room temperature (25 ° C.) to 130 ° C. A conventionally known solvent such as hexane, methyl isobutyl ketone, cyclopentanone, propylene glycol monomethyl ether acetate may be used.

Next, an alkoxysilane hydrolysis / condensation reaction product having a glycidyl ether group will be described.
The hydrolysis / condensation reaction product of an alkoxysilane having a glycidyl ether group is obtained by subjecting an alkoxysilane having a glycidyl ether group to a known method, for example, the method described in the hydrolysis / condensation reaction in the production method of the component (A). It is a compound obtained by hydrolysis / condensation reaction. Examples of the alkoxysilane having a glycidyl ether group include glycidylalkoxysilane compounds such as glycidyltrimethoxysilane and glycidyltriethoxysilane; glycidyl such as 2-glycidoxyethyltrimethoxysilane and 2-glycidoxyethylmethyldimethoxysilane. Sidoxyethylalkoxysilane compound; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethyldimethoxysilane, 3-glycidoxypropylphenyldimethoxysilane, bis (3 -Glycidoxypropyl) dimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylethyldiethoxysila 3-glycidoxypropylphenyldiethoxysilane, bis (3-glycidoxypropyl) diethoxysilane, etc .; 3-glycidoxypropylalkoxysilane compounds; 2- (4-glycidoxyphenyl) ethyltrimethoxysilane 2- (4-glycidoxyphenyl) ethylalkoxysilane compounds such as 2- (4-glycidoxyphenyl) ethyltriethoxysilane; 5- (glycidoxymethyl) norbornyltrimethoxysilane, 6- (glycidyl Glycidoxymethylnorbornylalkoxysilane compounds such as sidoxymethyl) norbornyltrimethoxysilane and the like. Among them, 3-glycol is preferred due to the reactivity of hydrolysis / condensation reaction and industrial availability. Sidoxypropylalkoxysilane compounds are preferred, and 3-glycidoxypropyla Among the coxisilane compounds, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, bis (3-glycidoxypropyl) dimethoxysilane, and 3-glycidoxypropyltriethoxysilane are preferable, 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane are more preferred, and 3-glycidoxypropyltrimethoxysilane is most preferred.

  When producing a hydrolysis / condensation reaction product of an alkoxysilane having a glycidyl ether group, in addition to an alkoxysilane having a glycidyl ether group, other alkoxysilane compounds having no glycidyl ether group may be used in combination. good. Examples of other alkoxysilane compounds include the alkoxysilane compounds exemplified in the description of the alkoxysilane compound represented by the general formula (2). When the proportion of epoxy groups in the molecule of the alkoxysilane hydrolysis / condensation reaction product having a glycidyl ether group is too small, the crosslinking effect is small and the physical properties of the permanent resist of the present invention may be lowered. The equivalent is preferably 1000 or less, more preferably 700 or less, and most preferably 350 or less.

  The molecular weight of the alkoxysilane hydrolysis / condensation reaction product having the glycidyl ether group is not particularly limited. However, if the molecular weight is too large, the solubility or dispersibility in an alkali developer is lowered, and the substrate after alkali development. Since a resist residue may remain on the surface, the mass average molecular weight is preferably 20000 or less, more preferably 15000 or less, and most preferably 10,000 or less.

  The hydrolysis / condensation reaction product of the alkoxysilane having the glycidyl ether group preferably has a silanol group. The content of silanol groups in the hydrolysis / condensation reaction product of the alkoxysilane having a glycidyl ether group is preferably 1 to 30% by mass, and more preferably 3 to 25% by mass.

  The hydrolysis / condensation reaction product of the alkoxysilane having a glycidyl ether group using a trialkoxysilane compound in the reaction may have a bridged structure due to Si-O-Si bond. In some cases, a ladder shape (ladder shape), a cage shape, a ring shape, or the like is used. A hydrolysis / condensation reaction product of an alkoxysilane having a glycidyl ether group using a trialkoxysilane compound having a glycidyl ether group and another trialkoxysilane compound in the reaction is represented by the following general formula (26), for example. Can do.

（式中、Ｇはグリシジルエーテル基を有する基を表わし、Ｒ³⁴は同一でも異なっていてもよい炭素数１〜１０のアルキル基又は炭素数６〜１０のアリール基を表わし、ｕは０〜２の数を表わし、ｖは０〜２の数を表わし、ｗは２以上の数を表わし、ｘは０又は１以上の数を表わす。）

(In the formula, G represents a group having a glycidyl ether group, R ³⁴ represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms which may be the same or different, and u represents 0 to 2). And v represents a number from 0 to 2, w represents a number of 2 or more, and x represents a number of 0 or 1).

In the general formula (26), G represents a group having a glycidyl ether group, and R ³⁴ represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, which may be the same or different. 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 the description of R ^{1. As} R ³⁴ , methyl, Ethyl and phenyl are preferred, methyl and phenyl are more preferred, and methyl is most preferred. v represents a number from 0 to 2, w represents a number of 2 or more, and x represents a number of 0 or 1 or more.

  The content of the compound having at least two epoxy groups as the component (B) is 1 to 50 parts by mass, preferably 2 to 20 parts by mass with respect to 100 parts by mass of the silanol group-containing polysiloxane compound as the component (A). It is. When the content of the component (B) is less than 1 part by mass, the resolution of the resist pattern is lowered, and when it exceeds 50 parts by mass, the heat resistance of the permanent resist of the present invention becomes insufficient.

Next, the diazonaphthoquinones that are the component (C) of the present invention will be described.
The diazonaphthoquinones that can be used in the present invention are not particularly limited as long as they are diazonaphthoquinones compounds that are known to be usable in photosensitive materials, but among them, hydrogen atoms of compounds having a phenolic hydroxyl group Is preferably a compound substituted with the following formula (27) (4-diazonaphthoquinonesulfonic acid ester) or a compound substituted with the following formula (28) (5-diazonaphthoquinonesulfonic acid ester).

  Preferable specific examples of such diazonaphthoquinones include, for example, compounds represented by the following formulas (29) to (34) and positional isomers thereof. Among these, the compounds represented by the following formulas (29) to (32) are preferable, and the compound represented by the following formula (29) is more preferable because of high exposure sensitivity and improved resolution of the resist pattern. .

（式中、Ｑは前記式（２７）又は（２８）で表わされる基又は水素原子であり、全てが水素原子であることはない。）

(In the formula, Q is a group or a hydrogen atom represented by the formula (27) or (28), and not all are hydrogen atoms.)

（式中、Ｑは前記式（２７）又は（２８）で表わされる基又は水素原子であり、全てが水素原子であることはない。）

(In the formula, Q is a group or a hydrogen atom represented by the formula (27) or (28), and not all are hydrogen atoms.)

（式中、Ｑは前記式（２７）又は（２８）で表わされる基又は水素原子であり、全てが水素原子であることはない。）

(In the formula, Q is a group or a hydrogen atom represented by the formula (27) or (28), and not all are hydrogen atoms.)

（式中、Ｑは前記式（２７）又は（２８）で表わされる基又は水素原子であり、全てが水素原子であることはない。）

(In the formula, Q is a group or a hydrogen atom represented by the formula (27) or (28), and not all are hydrogen atoms.)

（式中、Ｑは前記式（２７）又は（２８）で表わされる基又は水素原子であり、全てが水素原子であることはない。）

(In the formula, Q is a group or a hydrogen atom represented by the formula (27) or (28), and not all are hydrogen atoms.)

（式中、Ｑは前記式（２７）又は（２８）で表わされる基又は水素原子であり、全てが水素原子であることはない。）

(In the formula, Q is a group or a hydrogen atom represented by the formula (27) or (28), and not all are hydrogen atoms.)

  Since the group represented by the formula (27) has absorption in the i-line (wavelength 365 nm) region, it is suitable for i-line exposure, and the group represented by the formula (28) has absorption in a wide wavelength region. Since it is suitable for exposure in a wide range of wavelengths, it is preferable to select either the group represented by the formula (27) or the group represented by the formula (28) depending on the wavelength to be exposed.

The content of diazonaphthoquinones as component (C) is 0.1 to 15 parts by mass, preferably 2 to 7 parts by mass, per 100 parts by mass of the silanol group-containing polysiloxane compound as component (A). However, it is preferable from the viewpoints of developability and fine processability of the permanent resist of the present invention.
Next, the organic solvent which is (D) component of this invention is demonstrated.

  The organic solvent (D) that can be used in the present invention can dissolve or disperse the (A) silanol group-containing polysiloxane compound, (B) a compound having at least two epoxy groups, and (C) diazonaphthoquinones. Although it will not specifically limit if it is an organic solvent, The organic solvent which can melt | dissolve 1 mass% or more of water at 25 degreeC is preferable, and mention | raise | lifts by removal of t-butyl group of a protective group as such an organic solvent. In addition to organic solvents, γ-butyrolactone, γ-valerolactone, δ-valerolactone, ethylene carbonate, propylene carbonate, dimethyl carbonate, and the like, among these, methyl ethyl ketone, 1,4-dioxane, tetrahydrofuran, cyclohexanone, 2-heptanone, γ-butyrolactone, 1-methoxy-2-propano Lumpur acetate are preferred, 1-methoxy-2-propanol acetate is more preferable.

  When 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 elimination reaction of the protecting group is used as it is ( You may utilize as an organic solvent of D) component.

  The content of the organic solvent as the component (D) is 10 to 10000 parts by mass, particularly 100 to 1000 parts by mass with respect to 100 parts by mass of the (A) silanol group-containing polysiloxane compound. From the viewpoints of formability when a permanent resist is formed using a mold type photosensitive composition, physical properties of the obtained permanent resist, and the like.

  The positive photosensitive composition of the present invention comprises (A) a silanol group-containing polysiloxane compound, (B) a compound having at least two epoxy groups, (C) diazonaphthoquinones and (D) an organic solvent. However, if necessary, for example, after filtering with a filter having a pore diameter of about 0.2 μm, it can be used.

  In addition to the above, the positive photosensitive composition of the present invention may optionally be a plasticizer, a thixotropic agent, a photoacid generator, a thermal acid generator, a dispersant, an antifoaming agent, a pigment, a dye, etc. Ingredients can be blended. The compounding amount of these optional components is preferably 5% by mass or less, more preferably 0.01 to 1% by mass in the positive photosensitive composition of the present invention.

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

(1st process) Coating film formation process A coating film formation process is a process of apply | coating the prepared positive photosensitive composition of this invention to object material, and forming a coating film. The target material is particularly limited as long as the material has chemical resistance to an organic solvent or the like in the positive photosensitive composition, development with an alkaline solution in the fourth step, and heat resistance for processing in the sixth step. The target material can be glass, metal, semiconductor, or the like. In particular, a TFT surface of a liquid crystal display that requires a permanent resist as an insulating layer can be exemplified as a preferable one. The application method is not particularly limited, and various methods such as spin coating, dip coating, knife coating, roll coating, spray coating, and slit coating can be used.

  Thereafter, pre-baking is performed in order to remove the organic solvent as the component (D) from the positive photosensitive composition layer formed from the coating applied to the target material. The pre-baked positive-type photosensitive composition layer is hardly soluble in an alkaline solution, and the portion irradiated with light by irradiating light in the next exposure step (hereinafter sometimes referred to as an exposed portion) is alkaline. It becomes soluble. The pre-baking temperature varies depending on the type of organic solvent used. If the temperature is too low, the residual amount of the organic solvent increases, which may cause a reduction in exposure sensitivity and resolution, and the temperature is too high. Then, the entire curing of the coating proceeds by pre-baking, so that the solubility in the alkali developer of the portion irradiated with light is lowered, and as a result, the exposure sensitivity and resolution may be lowered, so that the temperature is 60 to 140 ° C. Is preferable, and 70-120 degreeC is still more preferable. The pre-baking time varies depending on the type of the organic solvent used and the pre-baking temperature, but is preferably 30 seconds to 10 minutes, and more preferably 1 to 5 minutes.

  Pre-baking may be carried out as it is after the positive photosensitive composition of the present invention is applied to the target material. However, since the physical properties and chemical resistance of the permanent resist of the present invention after high heat history are improved, pre-baking is performed. Before evaporating the organic solvent at a temperature of room temperature to less than 60 ° C. under normal pressure or reduced pressure so that the concentration of the organic solvent in the positive photosensitive composition layer is 5% by mass or less. It is preferable to carry out. The thickness of the positive photosensitive composition layer after pre-baking varies depending on the application in which the permanent resist of the present invention is used, and is not particularly limited, but is usually about 0.1 μm to 100 μm, preferably 0.3 μm to 10 μm. It ’s fine.

(2) Exposure process An exposure process is a process which irradiates the patterned light with respect to the pre-baked positive photosensitive composition layer, and improves the alkali solubility of an exposed part. The pre-baked positive photosensitive composition layer is poorly soluble in alkaline solution, but diazonaphthoquinones in the exposed part are decomposed by light irradiation and converted into indenecarboxylic acid, which is dissolved and dispersed in the alkaline solution. Is possible. Irradiation light is not particularly limited as long as it is light having an energy amount capable of improving alkali solubility of the light irradiated portion of the pre-baked positive photosensitive composition layer, for example, 10 to 1000 mJ / cm ² , 40 to 300 mJ / cm ² is preferable. The wavelength of irradiation light may be visible light or ultraviolet light and is not particularly limited. However, when 4-diazonaphthoquinonesulfonic acid esters are used as the diazonaphthoquinones as component (C), i-line (365 nm) is used. When 5-diazonaphthoquinonesulfonic acid esters are mainly used as light of a narrow wavelength, light of a broad wavelength including i-line (365 nm), h-line (405 nm) and g-line (436 nm) Irradiation may be performed using a high-pressure mercury lamp, an ultra-high pressure mercury lamp, or the like. The patterning method of the irradiation light is not particularly limited, and may be a conventionally known method, for example, a light irradiation method through a photomask or the like, or a selective light irradiation method using laser light. Good.

(3) Development Step The development step is a step of forming a predetermined pattern by removing a portion of the exposure step that has been irradiated with light and improved in alkali solubility using a developer.
As a developing method, for example, any method such as a liquid filling method, a dipping method, a shower method, a spray method, or the like can be used. The development time varies depending on the type and molecular weight of the polysiloxane compound as the component (A) and the compound having at least two epoxy groups as the component (B), the temperature of the developer, and the like, but is usually 30 to 180 seconds. The developer used in the development step is not particularly limited as long as the exposed portion can be removed by dissolving or dispersing in the solution. For example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate Inorganic amines such as 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, 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; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide An aqueous alkali solution such as an aqueous solution of the above can be used, and the concentration thereof may be the alkali concentration of a developer used for removing a conventional positive photosensitive composition layer. These alkaline aqueous solutions may further contain an appropriate amount of a water-soluble organic solvent such as methanol and ethanol and / or a surfactant. After removing an exposed part with a developing solution, it is preferable to rinse with running water or water with a shower, and may be dehydrated and dried within a range of 50 to 120 ° C. if necessary.

(4) Bleaching exposure process In the bleaching exposure process, the entire positive photosensitive composition layer (hereinafter sometimes referred to as a resist layer) remaining after the alkali solution treatment is irradiated with light to make visible light transmission. It is a process to improve. Since the resist layer contains diazonaphthoquinones, the resist layer is colored light yellow to light brown. By irradiating the resist layer with light, the remaining unreacted (C) diazonaphthoquinones are photodegraded to change to indenecarboxylic acid which does not absorb in the visible light region, and the visible light transmittance is improved. This is convenient when used as a permanent resist for an active matrix substrate used in display devices, organic EL display devices, and the like. Irradiation light in the bleaching exposure step is not particularly limited, and for example, light of 10 to 1000 mJ / cm ² , preferably 40 to 600 mJ / cm ² may be irradiated. The wavelength of the irradiation light may be visible light or ultraviolet light, and is not particularly limited. (2) Similar to the exposure step, the wavelength of the irradiation light can be selected according to the (C) diazonaphthoquinones used. preferable.

(5) Post-bake process The resist layer subjected to bleaching exposure has improved visible light transmittance but also improved alkali solubility. In the post-baking process, the bleaching-exposed resist layer is heat-treated at 120 ° C. or more to thermally cross-link the silicone resin in the resist layer, thereby requiring heat resistance and chemical resistance required as a permanent resist. , Imparts aging resistance. In the present invention, it is considered that the compound having at least two epoxy groups as the component (B) of the positive photosensitive composition functions as a cross-linking agent and can obtain chemical resistance after a high heat history that has never been obtained. . The post-bake is preferably performed in an inert gas atmosphere such as nitrogen, helium, or argon at a temperature of 120 to 400 ° C. for 15 minutes to 2 hours, and at a temperature of 200 to 350 ° C. for 15 minutes to 2 hours. More preferably, it is performed.

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

  The permanent resist of the present invention can also be used for an interlayer insulating film of a semiconductor element. It can also be used for wafer coating materials (surface protective film, bump protective film, MCM (multi-chip module) interlayer protective film, junction coating), and package materials (sealing material, die bonding material) for semiconductor devices. .

  The permanent resist of the present invention is also useful as an insulating film for semiconductor elements, multilayer wiring boards and the like. As semiconductor elements, individual semiconductor elements such as diodes, transistors, compound semiconductors, thermistors, varistors, thyristors, DRAM (dynamic random access memory), SRAM (static random access memory), EPROM (erasable programmable)・ Read-only memory (ROM), mask ROM (mask read-only memory), EEPROM (electrically erasable programmable read-only memory), storage elements such as flash memory, microprocessors, DSP, ASIC, etc. Theoretical circuit elements, integrated circuit elements such as compound semiconductors represented by MMIC (monolithic microwave integrated circuit), hybrid integrated circuits (hybrid IC), light emitting diodes Such a photoelectric conversion element such as a charge coupled device and the like. Examples of the multilayer wiring board include a high-density wiring board such as MCM.

EXAMPLES The present invention will be further described with reference to examples below, but the present invention is not limited to these examples. The content of silanol groups was determined by reacting the sample with trimethylchlorosilane in a pyridine solution to change the silanol groups to trimethylsilyl ether groups, and then treating with a tetramethylammonium hydroxide ((CH ₃ ) ₄ NOH) aqueous solution. It was determined by hydrolyzing the —O—Si bond and calculating backward from the rate of weight increase after the reaction.

  The raw materials used for the production of the positive photosensitive composition are as follows.

Production Example 1 Production of Polysiloxane Compound (A1) To 300 g of toluene, 240 g (1 mol) of 2,4,6,8-tetramethylcyclotetrasiloxane as a compound of the above general formula (1h), the above general formula (3 vp ) As a compound of 4-vinylbenzoic acid-t-butyl ester 204 g (1 mol), as a compound of the general formula (4 vp), 264 g (1.5 mol) of 4-t-butoxystyrene, and as a hydrosilylation catalyst Then, 0.0001 g of platinum-divinyltetramethyldisiloxane complex (Karstedt catalyst) was added and reacted at 60 ° C. for 10 hours with stirring to synthesize the intermediate (A1-a) of the above general formula (1ap). Without isolating the intermediate (A1-a), 195 g (1.5 mol) of 1,4-divinylbenzene as a compound of the general formula (11) was added dropwise to the reaction solution at 60 ° C. over 30 minutes. Then, after reacting at 60 ° C. for 10 hours, 328 g (2 mol) of triethoxysilane was added dropwise over 30 minutes as the compound of the general formula (15), and then reacted at 60 ° C. for 10 hours. Then, toluene and excess triethoxysilane were distilled off under reduced pressure at 60 ° C. to obtain 1034 g (yield 90%) of the cyclic siloxane compound (A1-c) of the general formula (1).

  To 500 g (0.44 mol) of the obtained cyclic siloxane compound (A1-c), 400 g of toluene and 201 g (1.02 mol) of phenyltrimethoxysilane as a compound of the above general formula (2) are added. While stirring with ice cooling so that the temperature became 0 ° C., 100 g of 5% oxalic acid aqueous solution was added dropwise over 30 minutes as an acid catalyst, and further stirred at 10 ° C. for 1 hour. Reflux dehydration and dealcoholization treatment under reduced pressure at 50 ° C., and solvent exchange of solvent toluene into 1-methoxy-2-propanol acetate (hereinafter referred to as PGMEA) under reduced pressure at 50 ° C. gave a 25% PGMEA solution. .

In order to remove the t-butyl group, 3 g of boron trifluoride diethyl ether complex was added as a catalyst, and after stirring at 80 ° C. for 3 hours, an adsorbent for acidic substances (trade name: Kyowa Chemical Industry, trade name: Kyo) The solid solution was removed by filtration in the slurry solution which was stirred at 80 ° C. for 1 hour after adding 10 g of the word 500SH. Thereafter, a part of the solvent was distilled off at 80 ° C. to adjust the concentration, and 30% PGMEA of the polysiloxane compound (A1) (m: n: p = 1: 1.5: 1.5) of the present invention. A solution was obtained.
In addition, the mass mean molecular weight by GPC analysis of the polysiloxane compound (A1) was 9000, and the silanol group content was 5.4% by mass.

Production Example 2: Production of polysiloxane compound (A2) In Production Example 1, instead of 195 g (1.5 mol) of 1,4-divinylbenzene as the compound of the general formula (11), the general formula (13) The same procedure as in Production Example 1 except that 374 g (1.5 mol) of triallyl isocyanurate was used as the compound of, and the amount of triethoxysilane was increased from 328 g (2 mol) to 656 g (4 mol). To obtain 1418 g (yield 90%) of a cyclic siloxane compound (A2-c).

Hereinafter, in Production Example 1, 500 g (0.32 mol) of the cyclic siloxane compound (A2-c) is used instead of 500 g of the cyclic siloxane compound (A1-c), and the compounding amount of phenyltrimethoxysilane is 201 g (1. The polysiloxane compound (A2) of the present invention (m: n: p = 1: 1.5: 1) was carried out in the same manner as in Production Example 1, except that the amount was increased from 302 mol) to 302 g (1.52 mol). 5) 30% PGMEA solution was obtained.
In addition, the mass mean molecular weight by GPC analysis of the polysiloxane compound (A2) was 11000, and the silanol group content was 8.0 mass%.

Production Example 3: Production of polysiloxane compound (A3) In Production Example 2, instead of 374 g (1.5 mol) of triallyl isocyanurate as the compound of general formula (13), the compound of general formula (12) As described above, except that 243 g (1.5 mol) of 1,2,4-trivinylcyclohexane was used, the same operation as in Production Example 2 was carried out to obtain 1299 g of cyclic siloxane compound (A3-c) (yield 90%). Obtained.

Hereinafter, Production Example 2 and Production Example 2 were used except that 500 g (0.35 mol) of the cyclic siloxane compound (A3-c) was used instead of 500 g (0.32 mol) of the cyclic siloxane compound (A2-c). The same operation was performed to obtain a 30% PGMEA solution of the polysiloxane compound (A3) (m: n: p = 1: 1.5: 1.5) of the present invention.
In addition, the mass mean molecular weight by GPC analysis of the polysiloxane compound (A3) was 10500, and the silanol group content was 8.1% by mass.

Production Example 4: Production of polysiloxane compound (A4) An intermediate (A1-a) was synthesized by the same operation as in Production Example 1, and the solvent toluene was distilled off under reduced pressure at 60 ° C to obtain the intermediate (A1-a). ) Was isolated. Intermediate (A1-a) 500 g (0.71 mol), diphenyldisilanediol 229 g (1.5 mol) as a compound of the general formula (16), dioxane 300 g as a solvent, octylic acid tin 0.025 g as a catalyst And dissolved, and then reacted at 60 ° C. for 10 hours. Thereafter, dioxane as a solvent was distilled off under reduced pressure at 60 ° C. to obtain 618 g (yield 95%) of a cyclic siloxane compound (A4-c).

Hereinafter, the same operation as in Production Example 1 was performed except that the cyclic siloxane compound (A4-c) was used instead of the cyclic siloxane compound (A1-c) in Production Example 1, and the polysiloxane compound (A4) of the present invention was used. A 30% PGMEA solution (m: n: p = 1: 1.5: 1.5) was obtained.
In addition, the mass mean molecular weight by GPC analysis of the polysiloxane compound (A4) was 6300, and the silanol group content was 5.1% by mass.

Production Example 5 Production of Polysiloxane Compound (A5) In Production Example 1, instead of 204 g (1 mol) of 4-vinylbenzoic acid-t-butyl ester and 264 g (1.5 mol) of 4-t-butoxystyrene, The same operation as in Production Example 1 was carried out except that 510 g (2.5 mol) of 4-vinylbenzoic acid-t-butyl ester was used, and the polysiloxane compound (A5) (m: n: p = 2. 5: 0: 1.5) 30% PGMEA solution was obtained.
In addition, the mass average molecular weight by GPC analysis of the polysiloxane compound (A5) was 9200, and the silanol group content was 5.1% by mass.

Production Example 6 Production of Comparative Polysiloxane Compound (A′1) In Production Example 1, 204 g (1 mol) of 4-vinylbenzoic acid-t-butyl ester and 264 g (1.5 mol) of 4-t-butoxystyrene were prepared. A 30% PGMEA solution of a comparative polysiloxane compound (A′1) was obtained in the same manner as in Production Example 1 except that 440 g (2.5 mol) of 4-t-butoxystyrene was used instead of .
In addition, the mass mean molecular weight by GPC analysis of the polysiloxane compound (A′1) was 9000, and the silanol group content was 5.3% by mass.

Production Example 7 Production of Comparative Polysiloxane Compound (A′2) In Production Example 2, 204 g (1 mol) of 4-vinylbenzoic acid-t-butyl ester and 264 g (1.5 mol) of 4-t-butoxystyrene were prepared. A 30% PGMEA solution of a comparative polysiloxane compound (A′2) was obtained in the same manner as in Production Example 2 except that 440 g (2.5 mol) of 4-t-butoxystyrene was used instead of .
The polysiloxane compound (A′2) had a mass average molecular weight of 10,000 by GPC analysis and a silanol group content of 8.3% by mass.

Production Example 8 Production of Comparative Polysiloxane Compound (A′3) In Production Example 4, 204 g (1 mol) of 4-vinylbenzoic acid-t-butyl ester and 264 g (1.5 mol) of 4-t-butoxystyrene were prepared. A 30% PGMEA solution of a comparative polysiloxane compound (A′3) was obtained in the same manner as in Production Example 4 except that 440 g (2.5 mol) of 4-t-butoxystyrene was used instead of .
In addition, the mass mean molecular weight by GPC analysis of the polysiloxane compound (A'3) was 6400, and the silanol group content was 5.0 mass%.

Production Example 9 Production of Comparative Polysiloxane Compound (A′4) To 300 g of toluene, 240 g (1 mol) of 2,4,6,8-tetramethylcyclotetrasiloxane and 326 g of 4-vinylbenzoic acid-t-butyl ester (1.6 mol), 422 g (2.4 mol) of 4-t-butoxystyrene and 0.0001 part by mass of a platinum-divinyltetramethyldisiloxane complex (Karstedt catalyst) were added and stirred at 60 ° C. for 10 hours. The reaction was carried out, and the solvent toluene was distilled off under reduced pressure at 60 ° C. to obtain 889 g of cyclic siloxane compound (A′4-c) (yield 90%). To 500 g (0.51 mol) of the cyclic siloxane compound (A′4-c), 1500 g of PGMEA was added and dissolved to obtain a 25% PGMEA solution.
In order to remove the t-butyl group, 3 g of boron trifluoride diethyl ether complex was added, and the mixture was stirred at 80 ° C. for 3 hours, followed by an acidic substance adsorbent (trade name: Kyoward 500SH, manufactured by Kyowa Chemical Industry). From the slurry solution which was stirred at 80 ° C. for 1 hour after adding 10 g, solids were removed by filtration. Thereafter, a part of the solvent was distilled off at 80 ° C. to adjust the concentration, and a 30% PGMEA solution of a comparative polysiloxane compound (A′4) was obtained.
The polysiloxane compound (A′4) had a mass average molecular weight of 9000 and a silanol group content of 5.4% by mass by GPC analysis.

Production Example 10: Production of Comparative Polysiloxane Compound (A′5) According to Synthesis Example 1 of Examples in Japanese Patent Application Laid-Open No. 2008-116785, 157 g (1.35 mol) of diacetone alcohol (hereinafter referred to as DAA) Then, 100 g (0.74 mol) of methyltrimethoxysilane and 78 g (0.38 mol) of phenyltrimethoxysilane were added, and 61 g of 0.3% phosphoric acid aqueous solution was added dropwise over 10 minutes while stirring at room temperature. Then, after stirring at 40 ° C. for 30 minutes, the temperature was raised to 105 ° C. over 30 minutes and further stirred at 105 ° C. for 2 hours to obtain a DAA solution of a comparative polysiloxane compound (A′5).
The solid content concentration of the polysiloxane compound (A′5) in the DAA solution was 39% by mass, the water content was 1.8% by weight, and the mass average molecular weight of the polysiloxane compound (A′5) was 6000. .

Production Example 11 Production of Epoxy Group-Containing Siloxane Compound (B1) 300 g of toluene, 100 g (0.39 mol) of 2,4,6,8-tetramethylcyclotetrasiloxane as a compound of the general formula (25h), carbon -As a compound having a carbon double bond and a glycidyl ether group, 190 g (1.67 mol) of allyl glycidyl ether and 0.0001 g of a platinum-divinyltetramethyldisiloxane complex (Karstedt catalyst) as a hydrosilylation catalyst were added. The mixture was reacted at 50-60 ° C. for 15 hours with stirring. The solvent was distilled off from this reaction solution under reduced pressure at 60 ° C. to obtain 261 g (yield 90%) of an epoxy group-containing siloxane compound (B1) having a glycidyl ether group.
The epoxy group-containing siloxane compound (B1) was a viscous liquid at 25 ° C., the epoxy equivalent was 174, and no peak derived from the hydrogen atom of the Si—H group was observed in the NMR analysis. Moreover, the mass mean molecular weight by GPC analysis is 700, and the peak derived from unreacted allyl glycidyl ether could not be confirmed.

Production Example 12 Production of Epoxy Group-Containing Siloxane Compound (B2) To 50 g of toluene, 100 g (0.73 mol) of 1,1,3,3-tetramethyldisiloxane as a compound of the general formula (24h), carbon- As a compound having a carbon double bond and a glycidyl ether group, 170 g (1.49 mol) of allyl glycidyl ether and 0.0005 g of platinum-divinyltetramethyldisiloxane complex (Karstedt catalyst) as a hydrosilylation catalyst are added and stirred. The reaction was carried out at 50-60 ° C. for 15 hours. The solvent was distilled off from this reaction solution under reduced pressure at 60 ° C. to obtain 243 g (yield 90%) of an epoxy group-containing siloxane compound (B2).
Note that the epoxy equivalent of the epoxy group-containing siloxane compound (B2) was 182, and no peak derived from the hydrogen atom of the Si—H group was observed in the NMR analysis. Moreover, the mass mean molecular weight by GPC analysis was 360, and the peak originating in unreacted allyl glycidyl ether was not able to be confirmed.

Production Example 13 Production of Epoxy Group-Containing Siloxane Compound (B3) As an alkoxysilane other than glycidyl ether group, 150 g of toluene, 100 g (0.47 mol) of phenyltrimethoxysilane, alkoxy having glycidyl ether group As silane, 40 g (0.17 mol) of 3-glycidoxypropyltrimethoxysilane was added, and 50 g of 5% by mass formic acid was added dropwise over 30 minutes as an acid catalyst while stirring with ice cooling at 10 ° C. After stirring for 15 hours while maintaining the system temperature at 10 ° C., water was added, and washing with water was repeated until the aqueous layer became neutral. After removing water and methanol produced by the reaction while refluxing at 50 ° C. under reduced pressure, the solvent was exchanged between toluene and PGMEA under reduced pressure at 50 ° C. to obtain 40% of the epoxy group-containing siloxane compound (B3) of the present invention. A PGMEA solution was obtained.
In the FT-IR analysis, the epoxy group-containing siloxane compound (B3) was confirmed to have broad absorption derived from silanol groups at 3100 to 3700 cm ⁻¹ , the epoxy equivalent was 560, and the mass average molecular weight by GPC analysis was 4000, The silanol group content was 11.2% by mass.

(C) Diazonaphthoquinones (DNQ)
In the formula (29), a compound in which all Qs are groups represented by the formula (28) (trade name: PA-6, manufactured by Daito Chemix)
(D) Organic solvent PGMEA: 1-methoxy-2-propanol acetate DAA: diacetone alcohol GBL: γ-butyrolactone

Examples 1 to 9 and Comparative Examples 1 to 12: Production and Evaluation of Positive Photosensitive Compositions Using the above polysiloxane compounds, epoxy group-containing siloxane compounds, diazonaphthoquinones (DNQ), and organic solvents, Table 1 After mixing at the ratio shown in the above, filtration was carried out to produce positive photosensitive compositions of Examples 1 to 9 and Comparative Examples 1 to 12. The numbers in the table are all in mass units. Moreover, the solvent was added so that it might become the value in a table | surface.

  About the positive photosensitive composition of Examples 1-9 and Comparative Examples 1-12, the test piece was produced with the following method and the following evaluation was performed. The results are shown in Table 2.

(Test piece preparation method)
After applying the positive photosensitive composition on a square glass substrate having a length of 25 mm and a width of 25 mm or an ITO vapor-deposited glass substrate (ITO thickness: 100 nm) by a spin coating method to a thickness of 4 to 5 μm, a solvent is added. Volatilized and used as a test piece. The positive photosensitive composition was used after preparation for 1 day (24 hours) in a 23 ° C. constant temperature bath.

In the case of a test piece using a glass substrate, after heat-treating the test piece at 80 ° C. for 2 minutes, a photomask having a line width of 5 μm is placed on the glass substrate, and ultraviolet light is emitted by an ultrahigh pressure mercury lamp at 70 mJ / Irradiation was performed with cm ² (wavelength 365 nm exposure conversion). Next, this test piece was immersed in a 2.38 mass% tetramethylammonium hydroxide aqueous solution having a liquid temperature of 23 ° C. for 70 seconds, then washed with water and air-dried. The air-dried test piece was irradiated with ultraviolet rays at 200 mJ / cm ² (converted to a wavelength of 365 nm exposure) with an ultra-high pressure mercury lamp, and then heat-treated to form a permanent resist film. In addition, two types of heat-treated permanent resist films were prepared: one that was heat-treated at 230 ° C. for 60 minutes in an air atmosphere and one that was heat-treated at 350 ° C. for 30 minutes in a nitrogen atmosphere.

In the case of a test piece using an ITO vapor-deposited glass substrate, the test piece was heat-treated at 80 ° C. for 2 minutes, and then UV light was applied at 200 mJ / cm ² (wavelength 365 nm exposure conversion) using an ultrahigh pressure mercury lamp without using a photomask. ), Followed by heat treatment at 230 ° C. for 60 minutes in an air atmosphere or heat treatment at 350 ° C. for 30 minutes in a nitrogen atmosphere. An aluminum wiring was formed on the upper portion of the permanent resist film by vapor deposition to produce a test piece for measuring the dielectric constant.

(Resolution test)
After cutting a glass substrate test piece heated at 230 ° C. for 60 minutes, a cross section is observed using a scanning electron microscope to determine whether a 5 μm line-and-space pattern can be formed in a one-to-one width. The resolution was evaluated according to the following <evaluation criteria>.
<Evaluation criteria>
A: The pattern can be formed in a one-to-one width, and the resolution is excellent.
X: The pattern was not formed in the width | variety of 1: 1, and it is inferior to resolution.

(Heat-resistant patterning test)
In the above-described resolution test, a test piece in which a 5 μm line-and-space pattern can be formed to a width of 1: 1 was further heated at 350 ° C. for 30 minutes in a nitrogen atmosphere, and then observed with a scanning electron microscope. Then, the heat resistance of patterning was evaluated according to the following <Evaluation Criteria>.
<Evaluation criteria>
A: A patterning shape having a width of 1: 1 is maintained, and the heat resistance of patterning is excellent. X: The patterning shape of 1 to 1 width is not maintained due to surface roughness, film thickness reduction, etc., and the heat resistance of patterning is inferior.

(Transparency test)
Using a glass substrate, the transmittance of light having a wavelength of 400 nm was measured for a test piece heat-treated at 230 ° C. and a test piece heat-treated at 350 ° C., and transparency and heat resistance were evaluated by the following <evaluation criteria>. did. The light transmittance in this test refers to the transmittance of light having a wavelength of 400 nm per 4 μm thickness.
<Evaluation criteria>
(Double-circle): The light transmittance of the test piece heat-processed at 230 degreeC is 98% or more, and the light transmittance of the test piece heat-processed at 350 degreeC is 95% or more, and is excellent in transparency and the transparency after a high heat history.
○: The light transmittance of the test piece heat-treated at 230 ° C. is 96% or more, and the light transmittance of the test piece heat-treated at 350 ° C. is 90% or more, which is excellent in transparency and transparency after a high heat history.
Δ: The light transmittance of the test piece heat-treated at 230 ° C. is 96% or more, but the light transmittance of the test piece heat-treated at 350 ° C. is less than 90%, which is excellent in transparency, but after a high heat history Inferior in transparency.
X: The light transmittance of the test piece heat-processed at 230 degreeC is less than 96%, and is inferior to transparency.

(Water resistance test)
About the test piece heat-treated at 230 degreeC using the glass substrate, and the test piece heat-treated at 350 degreeC, the transmittance | permeability of light with a wavelength of 400 nm before and after being immersed in 60 degreeC ion exchange water for 24 hours, and a stylus The resist film thickness was measured using a surface shape measuring instrument, and the water resistance was evaluated according to the following <Evaluation Criteria> from the rate of change in light transmittance and the rate of change in film thickness.
<Evaluation criteria>
○: The test piece heat-treated at 230 ° C. and the test piece heat-treated at 350 ° C. have a light transmittance change rate of less than 1% and a film thickness change rate of less than 10%, after water resistance and high heat history. Excellent water resistance.
Δ: The light transmittance change rate of the test piece heat-treated at 230 ° C. is less than 1% and the film thickness change rate is less than 10%, but the light transmittance of the test piece heat-treated at 350 ° C. The rate of change is 1% or more, or the rate of change in film thickness is 10% or more, which is excellent in water resistance but inferior in water resistance after a high heat history.
X: The test piece heat-treated at 230 ° C. and the test piece heat-treated at 350 ° C. have a light transmittance change rate of 1% or more or a film thickness change rate of 10% or more, which is inferior in water resistance.

(Acid resistance test)
For a test piece heat-treated at 230 ° C. and a test piece heat-treated at 350 ° C. using a glass substrate, the transmittance of light having a wavelength of 400 nm before and after immersion in a 5 mass% hydrochloric acid aqueous solution at 40 ° C. The film thickness of the resist was measured using a needle-type surface shape measuring instrument, and the acid resistance was evaluated according to the following <evaluation criteria> from the rate of change in light transmittance and the rate of change in film thickness.
<Evaluation criteria>
○: The test piece heat-treated at 230 ° C. and the test piece heat-treated at 350 ° C. have a light transmittance change rate of less than 1% and a film thickness change rate of less than 10%, after acid resistance and high heat history. Excellent acid resistance.
Δ: The light transmittance change rate of the test piece heat-treated at 230 ° C. is less than 1% and the film thickness change rate is less than 10%, but the light transmittance of the test piece heat-treated at 350 ° C. The rate of change is 1% or more, or the rate of change in film thickness is 10% or more, which is excellent in acid resistance but inferior in acid resistance after a high heat history.
X: The test piece heat-treated at 230 ° C. and the test piece heat-treated at 350 ° C. have a light transmittance change rate of 1% or more or a film thickness change rate of 10% or more, and are inferior in acid resistance.

(Alkali resistance test)
About a test piece heat-treated at 230 ° C. and a test piece heat-treated at 350 ° C. using a glass substrate, an alkali solution at 40 ° C. (monoethanolamine: N-methyl-2-pyrrolidone: butyl diglycol = 10: 30: The film thickness of the resist was measured by using a stylus type surface shape measuring instrument and the transmittance of light having a wavelength of 400 nm before and after being immersed in 60 mass ratio) for 30 minutes, and the change rate of the light transmittance and the change of the film thickness. From the rate, the alkali resistance was evaluated according to the following <evaluation criteria>.
<Evaluation criteria>
○: The test piece heat-treated at 230 ° C. and the test piece heat-treated at 350 ° C. have a light transmittance change rate of less than 1% and a film thickness change rate of less than 10%, after alkali resistance and high heat history. Excellent alkali resistance.
Δ: The light transmittance change rate of the test piece heat-treated at 230 is less than 1% and the film thickness change rate is less than 10%, but the light transmittance change of the test piece heat-treated at 350 ° C. The rate is 1% or more or the change rate of the film thickness is 10% or more, and the alkali resistance is excellent, but the alkali resistance after the high heat history is inferior.
X: The test piece heat-treated at 230 ° C. and the test piece heat-treated at 350 ° C. have a change rate of light transmittance of 1% or more or a change rate of film thickness of 10% or more, and are inferior in alkali resistance.

(Solvent resistance test)
For a test piece heat-treated at 230 ° C. and a test piece heat-treated at 350 ° C. using a glass substrate, the transmittance of light having a wavelength of 400 nm and the touch before and after being immersed in dimethyl sulfoxide (DMSO) at 80 ° C. for 1 hour. The film thickness of the resist was measured using a needle-type surface shape measuring instrument, and the acid resistance was evaluated according to the following <evaluation criteria> from the rate of change in light transmittance and the rate of change in film thickness.
<Evaluation criteria>
○: The test piece heat-treated at 230 ° C. and the test piece heat-treated at 350 ° C. have a change rate of light transmittance of less than 1% and a change rate of film thickness of less than 10%, solvent resistance and high heat history. Excellent solvent resistance.
Δ: The light transmittance change rate of the test piece heat-treated at 230 ° C. is less than 1% and the film thickness change rate is less than 10%, but the light transmittance of the test piece heat-treated at 350 ° C. The rate of change is 1% or more, or the rate of change in film thickness is 10% or more, which is excellent in solvent resistance, but inferior in solvent resistance after a high heat history.
X: The test piece heat-treated at 230 ° C. and the test piece heat-treated at 350 ° C. have a change rate of light transmittance of 1% or more or a change rate of film thickness of 10% or more, and have poor solvent resistance.

(Dielectric constant test)
Using an ITO vapor-deposited glass substrate, the dielectric constant of each of the test pieces heat-treated at 230 ° C. and those heat-treated at 350 ° C. was measured using an LCR meter. The dielectric constant characteristics were evaluated.
<Evaluation criteria>
○: The dielectric constant of the test piece heat-treated at 230 ° C. and the test piece heat-treated at 350 ° C. is less than 3.2, and the dielectric constant of the test piece heat-treated at 230 ° C. The difference is less than 0.2, and the low dielectric constant characteristics and the low dielectric constant characteristics after a high thermal history are excellent.
Δ: The dielectric constant of the test piece heat-treated at 230 ° C. is less than 3.2, but the difference in dielectric constant between the test piece heat-treated at 230 ° C. and the test piece heat-treated at 350 ° C. is 0.2 or more. Yes, it is excellent in low dielectric constant characteristics, but inferior in low dielectric constant characteristics after a high thermal history.
X: The dielectric constant of the test piece heat-processed at 230 degreeC and the test piece heat-processed at 350 degreeC is 3.2 or more, and is inferior to a low dielectric constant characteristic.

From the results of Table 2 above, the positive photosensitive composition of the present invention not only has excellent transparency, but also has heat resistance that can withstand the temperature at the time of manufacturing the substrate, water resistance after high heat history, acid resistance, It was confirmed that it was excellent in alkali resistance, solvent resistance and resistance to aging as a permanent resist.
Therefore, the permanent resist using the positive photosensitive composition of the present invention is particularly suitable as an insulating film for an active matrix substrate.

Claims (6)

As the component (A), a polysiloxane obtained by subjecting a cyclic siloxane compound represented by the following general formula (1) and an alkoxysilane compound represented by the following general formula (2) to a hydrolysis / condensation reaction so that silanol groups remain. A positive photosensitive composition containing a siloxane compound, a compound having at least two epoxy groups as the component (B), diazonaphthoquinones as the component (C), and an organic solvent as the component (D).

Wherein R ¹ represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms which may be the same or different, and X ¹ may be the same or different; , (4), (5) or (6), m represents the number of groups represented by the general formula (3) per molecule, and n represents the general formula (1) 4) represents the number of groups represented by 4), and p represents the total number of groups represented by general formula (5) and groups represented by general formula (6) per molecule, provided that m, n and p are numbers such that m: n: p = 1: 0 to 2: 1 to 3 and m + n + p = 3 to 6.

(In the formula, R ² represents an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 10 carbon atoms, R ³ represents an alkyl group having 1 to 4 carbon atoms, and a represents a number of 1 to 2) .)

(In the formula, R ⁴ represents an alkylene group having 1 to 10 carbon atoms which may have a substituted alkyl group, R ⁵ represents an alkyl group having 1 to 4 carbon atoms, and b is a number of 0 or 1 to 4). Represents.)

(Wherein R ⁶ represents an alkylene group having 1 to 10 carbon atoms which may have a substituted alkyl group, R ⁷ represents an alkyl group having 1 to 4 carbon atoms, and c is 0 or a number of 1 to 4) Represents.)

(In the formula, R ⁸ represents a residue obtained by removing 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 group having 1 to 4 carbon atoms. And represents an alkyl group or a phenyl group, d represents a number of 1 to 3, and e represents a number of 1 or 2.)

(In the formula, R ¹¹ and R ¹² each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, which may be the same or different. F represents a number of 0 to 100. .)   1 to 50 parts by mass of a compound having at least two epoxy groups as the component (B) and 100 parts by mass of the polysiloxane compound as the component (A), diazonaphthoquinones as the component (C) The positive photosensitive composition of Claim 1 containing 1-15 mass parts and 10-10000 mass parts of organic solvents which are said (D) components.   A permanent resist obtained from the positive photosensitive composition according to claim 1.   A positive resist composition according to claim 1 or 2 is applied to a target material, the coated material is exposed and subjected to alkali development, and then post-baked at a temperature of 120 to 350 ° C. Production method.   A liquid crystal display device having an active matrix substrate using a permanent resist obtained by using the positive photosensitive composition according to claim 1 as an insulating film or a planarizing film.   An organic EL display device having an active matrix substrate using a permanent resist obtained by using the positive photosensitive composition according to claim 1 as an insulating film or a planarizing film.