JP2012237854A - Positive photosensitive composition and cured product of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive photosensitive composition showing excellent heat resistance and chemical resistance after subjected to high temperature thermal history and having little film reduction during development and a large development margin in a developing process.SOLUTION: The positive photosensitive composition includes: (A) a silanol group-containing polysiloxane compound comprising a structure obtained by a hydrolysis and condensation reaction of a compound expressed by formula (1) with a compound expressed by formula (2); (B) a compound having at least two epoxy-containing organic groups; (C) diazonaphthoquinones; and (D) an organic solvent. In formula (1), Rrepresents an alkyl group having 1 to 4 carbon atoms, or the like; Rrepresents a divalent hydrocarbon group having 2 to 10 carbon atoms; Rrepresents a divalent saturated aliphatic hydrocarbon group having 2 to 10 carbon atoms; and X represents a group expressed by a specified general formula.

Description

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

  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, etc. of the active matrix substrate are formed by repeating patterning by photolithography on a conductive film or insulating film formed by sputtering, CVD, coating, or the like (for example, patents) References 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 also been developed. When a permanent resist is used for an active matrix substrate, not only chemical resistance (acid resistance, alkali resistance, solvent resistance) but also high heat resistance and chemical resistance after a high heat history are required. This is due to the following reasons.
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 thin film and the insulating substrate or the insulating film, and the characteristics of the transistor are 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 a 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). It differs greatly from the heat resistance required for resists and the chemical resistance after high heat history.

  On the other hand, silicone resins are excellent in transparency, insulation, heat resistance, chemical resistance, etc., and photoresists based on silicone resins have been developed. In recent years, as a structure with improved heat resistance and chemical resistance, a photoresist based on a silicone resin into which a phenolic hydroxyl group or a cyclic siloxane structure is introduced (for example, see Patent Documents 5 and 6) has been studied. ing. However, a conventionally known photoresist based on a silicone resin into which a phenolic hydroxyl group or a cyclic siloxane structure is introduced is excellent in heat resistance and chemical resistance after high-temperature heat history, but the film loss during development is large. It is difficult to form a fine pattern, and the development margin in the development process (the width of time for which the development time is optimal) is narrow. Since the developer permeates easily and peels off, it is necessary to strictly control the development time, which is problematic in terms of product yield.

JP 2004-281506 A JP 2007-225860 A JP-A-6-77484 JP 2007-304543 A JP 2010-101957 A International Publication No. 2009/063887

  Accordingly, an object of the present invention is to provide a positive photosensitive composition that is excellent in heat resistance and chemical resistance after high temperature thermal history, has little film loss during development, and has a large development margin in the development process, and this positive photosensitive composition An object of the present invention is to provide a permanent resist using an object and a method for producing the permanent resist.

The present invention
(A) Silanol group-containing polysiloxane having a structure obtained by hydrolyzing and condensing a cyclic siloxane compound represented by the following general formula (1) and an alkoxysilane compound represented by the following general formula (2) as the component (A) Compound,
(B) As a component, a compound having at least two epoxy-containing organic groups,
The object is achieved by providing a positive photosensitive composition characterized by containing diazonaphthoquinones as component (C) and an organic solvent as component (D).

Moreover, this invention achieves the said objective by providing the hardened | cured material characterized by hardening the said positive photosensitive composition.
In the present invention, the positive photosensitive composition is applied to a target material, pre-baked, exposed, developed with alkali, then bleached, and then post-baked at a temperature of 120 to 400 ° C. The above object is achieved by providing a method for producing a permanent resist characterized by the following.
The present invention also provides a liquid crystal display device and an organic EL display device having an active matrix substrate having a permanent resist obtained by using the positive photosensitive composition as an insulating layer or a planarizing film. To do.

  According to the present invention, a positive photosensitive composition having excellent heat resistance and chemical resistance after high-temperature heat history, little film loss during development, and a large development margin in the development process, and the positive photosensitive composition It is possible to provide a method for producing a permanent resist using A permanent resist made of a cured product of the positive-type positive-type photosensitive composition is suitable as an insulating layer or a planarizing film for liquid crystal display devices and organic EL display devices having an active matrix substrate.

The component (A) according to the present invention has a structure obtained by subjecting the cyclic siloxane compound represented by the general formula (1) and the arylalkoxysilane compound represented by the general formula (2) to a hydrolysis / condensation reaction. It is a silanol group-containing polysiloxane compound.
First, the cyclic siloxane compound represented by the general formula (1) will be described. In the cyclic siloxane compound represented by the general formula (1), a plurality of R ^{1 s} may be the same as or different from each other, and R ² , R ³ and X may be the same or different from each other when there are a plurality of R ^{1 s.} May be.

In the general formula (1), R ¹ represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, t-butyl and the like. Examples of the aryl group having 6 to 10 carbon atoms include phenyl, ethylphenyl, toluyl, cumenyl, xylyl, pseudocumenyl, mesityl, t-butylphenyl, benzyl, phenethyl and the like.
R ¹ is preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, or phenyl, more preferably methyl, ethyl, or phenyl, and most preferably methyl because of industrial availability.

R ² represents a divalent hydrocarbon group having 2 to 10 carbon atoms. Examples of the divalent hydrocarbon group having 2 to 10 carbon atoms include ethylene, propylene, 1-methylethylene, 2-methylethylene, tetramethylene, pentamethylene, 3-methylpentamethylene, hexamethylene, octamethylene, decamethylene, and cyclohexane. -1,4-diyl, 2-phenylethane-1,2'-diyl, 2-phenylethane-1,4'-diyl, 2-phenylpropane-1,4'-diyl, etc. From the viewpoint of easy availability and heat resistance, ethylene, 2-methylethylene, and 2-phenylethane-1,4′-diyl are preferable, ethylene and 2-methylethylene are more preferable, and ethylene is most preferable.

R ³ represents a divalent saturated aliphatic hydrocarbon group having 2 to 10 carbon atoms. Examples of the divalent saturated aliphatic hydrocarbon group having 2 to 10 carbon atoms include ethylene, propylene, 1-methylethylene, 2-methylethylene, tetramethylene, pentamethylene, 3-methylpentamethylene, hexamethylene, octamethylene, Decamethylene and the like can be mentioned, and R ³ is preferably ethylene, 2-methylethylene or propylene, more preferably ethylene, from the viewpoint of industrial availability and heat resistance.

Position of the phenolic hydroxyl groups of the benzene ring linked to the R ^3, relative to R ^3, ortho, meta-position may be either para-position, heat resistance higher, easy industrial availability of raw materials For this reason, it is preferably in the ortho or para position relative to R ³ , and more preferably in the para position.

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

In the general formula (3), R ⁶ represents an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, and t-butyl. R ⁶ is an alkoxysilane compound represented by the general formula (2) Methyl and ethyl are preferable, and methyl is more preferable. R ⁷ represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms include the groups exemplified for R ¹ , and R ⁷ is preferably methyl or phenyl because heat resistance is further improved. More preferred is methyl. b represents a number of 1 to 3, and preferably 2 to 3 and more preferably 3 because the reaction with the alkoxysilane compound represented by the general formula (2) is good.

In the general formula (4), 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. Examples of the alkyl group having 1 to 4 carbon atoms include the alkyl groups exemplified for R ¹ . R ⁹ is preferably methyl or ethyl, more preferably methyl, because of good reactivity with the alkoxysilane compound represented by the general formula (2). R ¹⁰ is preferably methyl or phenyl, more preferably methyl, because the heat resistance is further improved. c represents a number of 1 to 3, and a number of 2 to 3 is preferable and 3 is more preferable because of good reaction with the alkoxysilane compound represented by the general formula (2). d represents a number of 1 or 2, and when R ¹⁰ represents a residue obtained by removing a vinyl group from a divinyl compound having a molecular weight of 1000 or less, d is 1, and R ¹⁰ represents a vinyl group from a trivinyl compound having a molecular weight of 1000 or less. In the case of representing an excluded residue, d is 2.

In the general formula (4), 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 a trivinyl compound is a compound represented by the following general formula (4a), and examples thereof include compounds represented by the following general formulas (6) to (12).

In General formula (6), R < ¹³ > -R < ¹⁶ > represents a C1-C4 alkyl group or a C6-C10 aryl group each independently. Examples of the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms include the groups exemplified for R ¹ , and methyl, ethyl, propyl, and phenyl are preferable because of better heat resistance. Methyl, ethyl, and phenyl are more preferable, and methyl is most preferable. f 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 to 1 is more preferable. Among the compounds represented by the general formula (6), preferred compounds include dimethyldivinylsilane, diethyldivinylsilane, diphenyldivinylsilane, 1,1,3,3-tetramethyl-1,3-divinyldisiloxane, , 1,3,3-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-divinyl Examples include trisiloxane, 1,1,3,3,5,5,7,7-octamethyl-1,7-divinyltetrasiloxane and the like, 1,1,3,3-tetramethyl-1,3-divinyl Disiloxane, 1,1,3,3-tetraethyl-1,3-divinyldisiloxane, 1,1,3,3,5,5-hexamethyl-1,5-divinyltrisiloxane are more preferred, More preferred is 3,3-tetramethyl-1,3-divinyldisiloxane.

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

In the general formula (8), R ²⁰ and R ²¹ each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and d has the same meaning as in the general formula (4). Examples of the alkyl group having 1 to 10 carbon atoms and the aryl group having 6 to 10 carbon atoms include the groups exemplified for R ¹ , and methyl and ethyl are preferable because the heat resistance is better. preferable. Among the compounds represented by the general formula (8), preferred compounds are 1,2-bis (dimethylvinylsilyl) benzene, 1,3-bis (dimethylvinylsilyl) benzene, 1,4-bis (dimethylvinyl). Silyl) benzene, 1,2-bis (diethylvinylsilyl) benzene, 1,3-bis (diethylvinylsilyl) benzene, 1,4-bis (diethylvinylsilyl) benzene, 1,3,5-tris (dimethylvinyl) Silyl) benzene), 1,3,5-tris (diethylvinylsilyl) benzene) and the like, and are easy to obtain industrially and have better heat resistance. More preferred are vinylsilyl) benzene and 1,4-bis (dimethylvinylsilyl) benzene, and 1,4-bis (dimethylvinylsilyl) benzene. A further preferred.

In General formula (9), d is synonymous with General formula (4). Examples of the compound represented by the general formula (9) include 1,2-divinylbenzene, 1,3-divinylbenzene, 1,4-divinylbenzene, 1,2,4-trivinylbenzene, 1,3,5-tri Vinylbenzene etc. are mentioned, 1,4-divinylbenzene is preferable since it is easily available industrially and has better heat resistance.
In General formula (10), d is synonymous with General formula (4). Examples of the compound represented by the general formula (10) include 1,2-divinylcyclohexane, 1,3-divinylcyclohexane, 1,4-divinylcyclohexane, 1,2,4-trivinylcyclohexane, 1,3,5-trimethyl. Vinylcyclohexane etc. are mentioned, 1,4-divinylcyclohexane is preferable from the viewpoint of easy industrial availability and better heat resistance.

In the general formula (11), R ²² 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 and the aryl group having 6 to 10 carbon atoms include the groups exemplified for R ¹ . R ²² is preferably methyl, ethyl, or allyl, more preferably methyl or allyl, because of better heat resistance. Among the compounds represented by the general formula (11), preferable compounds include diallyl methyl isocyanurate, diallyl ethyl isocyanurate, triallyl isocyanurate, and triallyl isocyanurate is more preferable.

In the compound represented by the general formula (12), R ^{23 to} R ²⁵ each independently represents 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 for R ¹ , and methyl, ethyl, propyl, and phenyl are preferable because of better heat resistance. Methyl, ethyl, and phenyl are more preferable, and methyl is most preferable. d is synonymous with General formula (4), and i represents the number of 0-4 from which d + i becomes 3-6. Since industrial acquisition is easy, d + i is preferably a number of 4 to 5, and more preferably 4. Among the compounds represented by the general formula (12), 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 Examples include 6-trivinylcyclotrisiloxane and 2,2,4,6,8-pentamethyl-4,6,8-trivinylcyclotetrasiloxane.

The divinyl compound or trivinyl compound having a molecular weight of 1000 or less capable of providing the group represented by R ⁸ in the general formula (4) has been described in detail above. Among these compounds, industrial availability and curing From the heat resistance of the product, compounds represented by the general formulas (9) to (11) are preferable, 1,4-divinylbenzene, 1,2,4-trivinylcyclohexane, triallyl isocyanurate are more preferable, and 1,4 -Divinylbenzene is most preferred.

In General formula (5), R < ¹¹ >, R < ¹² > represents a C1-C4 alkyl group or a C6-C10 aryl group. Examples of the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms include the groups exemplified for R ¹ in the general formula (1), and the aryl having 6 to 10 carbon atoms is easy to produce. Group is preferred, with phenyl being preferred. e represents a number of 1 to 10, and the number of 1 to 5 is preferable and the number of 1 to 3 is more preferable because of easy production.

  In general formula (1), X is preferably a group represented by general formula (3) because it is easy to produce and has good heat resistance.

  In the general formula (1), m, n and p are average numbers per molecule, respectively, and m: n: p = 1: 2.1 to 12: 1 to 6 and m + n + p = 3 to 6 Represents a number satisfying. The cyclic siloxane compound represented by the general formula (1) may be used alone or in combination of two or more. If the ratio of n to m is too small, the film loss during development is large and the development margin in the development process is small. If it is too large, the resist residue during development increases. Is preferably 10 to 10, more preferably 2.8 to 9, and most preferably 3 to 8.

  The cyclic siloxane compound represented by the general formula (1) includes, for example, a cyclic siloxane compound represented by the following general formula (1a), a carboxylic acid compound represented by the following general formula (13), and the following general formula (14). The phenol compound represented is hydrosilylated to obtain an intermediate represented by the general formula (1b), and the intermediate represented by the above general formulas (3) to (5) is further introduced into this intermediate. be able to.

  Among the cyclic siloxane compounds represented by the general formula (1a), specific examples of preferable compounds include 2,4,6-trimethylcyclotrisiloxane, 2,4,6-triethylcyclotrisiloxane, 2,4, 6-triphenylcyclotrisiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, 2,2,4,6,8-pentamethylcyclotetrasiloxane, 2,2,2,4,4,6,6 8-hexamethylcyclotetrasiloxane ", 2,4,6,8-tetraethylcyclotetrasiloxane, 2,4,6,8-tetraphenylcyclotetrasiloxane, 2-ethyl-4,6,8-trimethylcyclotetrasiloxane 2-phenyl-4,6,8-trimethylcyclotetrasiloxane, 2,4,6,8,10-pentamethylcyclo Ntasiloxane, 2,4,6,8,10-pentaethylcyclopentasiloxane, 2,4,6,8,10-pentaphenylcyclopentasiloxane, 2,4,6,8,10,12-hexamethylcyclohexane Examples include sasiloxane, 2,4,6,8,10,12-hexaethylcyclohexasiloxane, 2,4,6,8,10,12-hexaphenylcyclohexasiloxane, and the like. -Tetramethylcyclotetrasiloxane and 2,4,6,8,10-pentamethylcyclopentasiloxane are more preferred, and 2,4,6,8-tetramethylcyclotetrasiloxane is most preferred.

  Specific examples of the carboxylic acid compound represented by the general formula (13) include acrylic acid, methacrylic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, 8- Nonenic acid, 9-decenoic acid, 10-undecenoic acid, 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid, 2-allylbenzoic acid, 3-allylbenzoic acid, 4-allylbenzoic acid, 2 -Isopropenyl benzoic acid, 3-isopropenyl benzoic acid, 4-isopropenyl benzoic acid and the like can be mentioned, which are easily available industrially, from the viewpoint of film resistance of the positive photosensitive composition of the present invention. Acrylic acid, methacrylic acid and 4-vinylbenzoic acid are preferred, and acrylic acid and methacrylic acid are more preferred. Only 1 type may be used for the carboxylic acid compound represented by General formula (13), and 2 or more types may be used for it.

  Specific examples of the phenol compound represented by the general formula (14) include 2-vinylphenol, 3-vinylphenol, 4-vinylphenol, 2-allylphenol, 3-allylphenol, 4-allylphenol, 2-isopropenyl. Phenol, 3-isopropenylphenol, 4-isopropenylphenol and the like are listed, and since they are easily available industrially, 2-vinylphenol, 3-vinylphenol, 4-vinylphenol, 4-isopropenylphenol are 2-vinylphenol and 4-vinylphenol are more preferable, and 4-vinylphenol is most preferable. Only 1 type may be used for the phenol compound represented by General formula (14), and 2 or more types may be used for it.

The hydrosilylation reaction between the cyclic siloxane compound represented by the general formula (1a), the carboxylic acid compound represented by the general formula (13), and the phenol compound represented by the general formula (14) is preferably performed using a catalyst. Examples of the hydrosilylation catalyst include a platinum-based catalyst, a palladium-based catalyst, and a rhodium-based catalyst. 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 complex (for example, Pt [P (OC ₆ H ₅ ) ₃ ] ₄ ), Pt [P (OC ₄ H ₉ ) ₃ ] ₄ ), Dicarbonyldichloroplatinum and the like. Examples of the palladium catalyst or rhodium catalyst include compounds containing a palladium atom or a rhodium atom instead of the platinum atom of the platinum 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 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, a method for introducing the groups represented by the above general formulas (3) to (5) into the intermediate represented by the general formula (1b) will be described. When the group represented by the general formula (3) is introduced into the intermediate represented by the general formula (1b), the intermediate SiH group represented by the general formula (1b) and the following general formula (3a) What is necessary is just to carry out hydrosilylation reaction with the vinyl group of the alkoxylsilane compound represented. The conditions for the hydrosilylation reaction may be the same as those for obtaining the intermediate represented by the general formula (1b).

  Specific examples of preferable compounds among the alkoxysilane compounds represented by the general formula (3a) include vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinylethyldimethoxysilane, vinylphenyldimethoxysilane and the like. In view of further improving heat resistance and adhesion, vinyltrimethoxysilane, vinyltriethoxysilane, and vinylmethyldimethoxysilane are preferable, and vinyltrimethoxysilane is more preferable. Only 1 type may be used for the alkoxysilane compound represented by General formula (3a), and 2 or more types may be used for it.

  When the group represented by the general formula (4) is introduced into the intermediate represented by the general formula (1b), the intermediate SiH group represented by the general formula (1b) and the general formula (4a) Hydrosilylation reaction with one vinyl group of the divinyl compound or trivinyl compound represented to give an intermediate represented by the following general formula (1c), the vinyl group of the intermediate represented by the general formula (1c) and the following general What is necessary is just to carry out hydrosilylation reaction with the SiH group of the alkoxylsilane compound represented by Formula (4b). The conditions for these hydrosilylation reactions may be the same as the conditions for obtaining the intermediate represented by the general formula (1b).

  Specific examples of preferable compounds among the alkoxysilane compounds represented by the general formula (4b) include, for example, trimethoxysilane, triethoxysilane, dimethoxymethylsilane, dimethoxyethylsilane, dimethoxyphenylsilane, and the like. Therefore, trimethoxysilane, triethoxysilane, methyldimethoxysilane, ethyldimethoxysilane, and phenyldimethoxysilane are preferable, trimethoxysilane and triethoxysilane are more preferable, and trimethoxysilane is most preferable. Only 1 type may be used for the alkoxysilane compound represented by General formula (4b), and 2 or more types may be used for it.

  When the group represented by the general formula (5) is introduced into the intermediate represented by the general formula (1b), the SiH group of the intermediate represented by the general formula (1b) is represented by the following general formula (5a). What is necessary is just to make the silanediol represented to react.

  Among the silane diols represented by the general formula (5a), preferable examples include dimethyl silane diol, diethyl silane diol, diisopropyl silane diol, methyl phenyl silane diol, diphenyl silane diol, and the like. Diol and diphenylsilane diol are preferable, and diphenylsilane diol is more preferable.

  When the silanediol represented by the general formula (5a) is reacted with the SiH group of the intermediate represented by the general formula (1b), 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 organic tin catalyst include tin octylate, tin naphthenate, tin stearate, tin versatate, dibutyltin laurate, triphenyltin acetate, and tributyltin chloride. Tin octylate, tin naphthenate, and tin stearate are preferable. Further, tin octylate is more preferable. The amount of the organometallic catalyst used is preferably 0.001 to 1% by mass, and more preferably 0.002 to 0.1% by mass of the amount of each raw material used.

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

  Examples of the alkoxysilane compound represented by the general formula (2) include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, and phenyltrimethoxy. Silane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, ethylphenyldimethoxysilane, ethylphenyldiethoxysilane, diphenyldimethoxysilane Diphenyldiethoxysilane and the like, and the heat resistance and adhesion are further improved, so that phenyltrimethoxysilane, phenyltriethoxysilane Emissions, phenylmethyl dimethoxysilane and phenyl methyl diethoxy silane are preferable, phenyl trimethoxysilane and phenyl triethoxysilane are more preferable, phenyl trimethoxysilane is most preferred. In addition, the alkoxysilane compound represented by the general formula (2) may be used alone or in combination of two or more.

  Next, a method for hydrolyzing and condensing the cyclic siloxane compound represented by the general formula (1) and the alkoxysilane compound represented by the general formula (2) to obtain (A) 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 arylalkoxysilane compound represented by the general formula (2) may be carried out by a so-called sol-gel reaction. And an alkoxysilyl group may be hydrolyzed and condensed. 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.

  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 Etc. These catalysts may be used alone or in combination of two or more. 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.

All of the silanol groups produced by hydrolysis of the alkoxysilyl group do not cause a condensation reaction, and a part remains without reacting. The silanol group-containing polysiloxane compound which is the component (A) according to the present invention is characterized by having a silanol group. 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) 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, without removing the component (A) from the reaction solution, a decatalytic treatment or a solvent replacement is performed as necessary. The solution is preferably used in the form of a solution containing the component (A) 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 forming a permanent resist using a positive photosensitive composition becomes poor. The weight average molecular weight of the silanol group-containing polysiloxane compound is preferably 1000 to 50000 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-reduced mass average molecular weight when GPC analysis is performed using tetrahydrofuran (hereinafter referred to as THF) as a solvent.

  In the hydrolysis / condensation reaction for obtaining the silanol group-containing polysiloxane compound as component (A), the reaction ratio between the cyclic siloxane compound represented by the general formula (1) and the alkoxysilane compound represented by the general formula (2) is: It is preferable that the alkoxysilane compound represented by the general formula (2) is 0.5 to 10 in terms of molar ratio with respect to the cyclic siloxane compound represented by the general formula (1), more preferably 1 to 7. 5 to 6 is most preferable. When this ratio is lower than 0.5, the hardness of the cured product may be insufficient. When it is higher than 10, the resist residue on the substrate surface after alkali development may increase.

  The silanol group-containing polysiloxane compound (A) is subjected to hydrolysis / condensation reaction with the cyclic siloxane compound represented by the general formula (1) and the arylalkoxysilane compound represented by the general formula (2). Although it is a compound consisting of the structure obtained, it is not always necessary to use the cyclic siloxane compound represented by the general formula (1) when producing the silanol group-containing polysiloxane compound of the component (A). A compound in which a group is masked with an acid-dissociable protecting group, that is, a compound represented by the following general formula (1p) and an arylalkoxysilane compound represented by the general formula (2) are reacted to form an arylalkoxysilane compound After obtaining the precursor of (1), the silanol group-containing polysiloxane compound as component (A) is removed by removing the acid-dissociable protecting group. It can also be obtained. In addition, about the point which does not explain in particular about the case where the compound represented by general formula (1p) is used, the description in the case of using the cyclic siloxane compound represented by general formula (1) is applicable suitably. .

  When a compound masked with an acid-dissociable protecting group is used, a step for removing the acid-dissociable protecting group is required and the production becomes complicated. However, side reactions, particularly in the general formula (1b) There is an advantage that the side reaction during the production of the intermediate represented is less likely to occur, and the heat resistance and chemical resistance of the permanent resist obtained using the positive photosensitive composition of the present invention are further improved.

  Examples of the acid-dissociable protecting group for a carboxyl group and a phenol group include a t-butyl group, a 1-ethoxyethyl group, an acetyl group, a t-butoxycarbonyl group, and the like, and a t-butyl group is preferable. Such an acid dissociable protecting group 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 acid-dissociable 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, and propanol. Alcohols such as isopropanol; 1-methoxy-ethanol, 1-ethoxy-ethanol, 1-propoxy-ethanol, 1-isopropoxy-ethanol, 1-butoxy-ethanol, 1-methoxy-2-propanol, 3-methoxy- Ether alcohols such as 1-butanol and 3-methoxy-3-methyl-1-butanol; 1-methoxy-ethyl acetate, 1-ethoxy-ethyl acetate, 1-methoxy-2-propyl acetate, 3-methoxy-1- Butyl acetate, 3-methoxy-3-methyl-1-butyla Acetates of ether alcohols such as tate; ketones such as acetone and methyl ethyl ketone; 4-hydroxy-2-butanone, 3-hydroxy-3methyl-2-butanone, 4-hydroxy-2-methyl-2-pentanone Keto alcohols such as acetone alcohol); ethers such as 1,4-dioxane, tetrahydrofuran and 1,2-dimethoxyethane. Among these, methanol, ethanol, propanol, methyl ethyl ketone, 1,4-dioxane, tetrahydrofuran, and 1-methoxy-2-propanol acetate are preferable.

  The compound represented by the general formula (1p) is a compound represented by the following general formula (13p) instead of the compound represented by the general formula (13), instead of the cyclic siloxane compound represented by the general formula (1a), Instead of the compound represented by the general formula (14), a compound represented by the following general formula (14p) is hydrosilylated to form an intermediate represented by the following general formula (1 bp). The groups represented by the general formulas (3) to (5) may be introduced into the represented intermediate as in the case of the intermediate represented by the general formula (1b).

Next, a compound having at least two epoxy-containing organic groups as the component (B) contained in the positive photosensitive composition of the present invention will be described.
Examples of the epoxy group of the compound having at least two epoxy-containing organic groups as the component (B) according to the present invention include aliphatic epoxy groups such as the following formulas (15) to (16), and the following formulas (17) to (19 ) And the like, and aromatic epoxy groups such as the following formulas (20) to (21), and the like. However, since the storage stability of the positive photosensitive composition of the present invention is improved, the fat A group epoxy group is preferred, and a 1,2-epoxypropyl group (glycidyl group) of the formula (15) is more preferred.
The epoxy-containing organic group which the compound which is (B) component has should just contain these epoxy groups, for example, these epoxy groups themselves may be sufficient, and these epoxy groups are hydrocarbons. It may be a group formed by combining one or more linking groups such as a group, an ether group, and an ester group. Especially, it is preferable that the compound which is (B) component is a compound which has a glycidyl ether group as an epoxy-containing organic group.

  Preferred compounds having at least two glycidyl ether groups as component (B) include glycidyl ethers of polyhydric phenol compounds, glycidyl ethers of polyhydric alcohol compounds, siloxane compounds having glycidyl ether groups, and the like. Is more preferable, a siloxane compound having a glycidyl ether group is preferable. Examples of the siloxane compound having at least two glycidyl ether groups include a linear siloxane compound represented by the following general formula (22), a cyclic siloxane compound represented by the following general formula (23), and the following general formula (24 ), A hydrolyzed / condensed reaction product of an alkoxysilane having a glycidyl ether group, among others, a cyclic siloxane compound represented by the general formula (23) and a cyclic represented by the general formula (24). A siloxane compound is preferable, and a cyclic siloxane compound represented by the general formula (24) is more preferable.

The linear siloxane compound represented by the general formula (22) will be described.
In the general formula (22), G represents a group having a glycidyl ether group, and R ^{26 to} R ³⁰ represent an alkyl group having 1 to 4 carbon atoms or a phenyl group which may be the same or different. Examples of the alkyl group having 1 to 4 carbon atoms include the alkyl groups exemplified for R ¹ in the general formula (1), and since heat resistance is better, methyl, ethyl and phenyl are preferable, and methyl and phenyl are More preferred is methyl. Y ¹ represents a group having a glycidyl ether group or a methyl group, j represents a number of 0 to 1000, and k represents a number of 0 to 1000. However, when j is 0 or 1, Y ¹ represents a group having a glycidyl ether group.

  In the linear siloxane compound represented by the general formula (22), a compound having a carbon-carbon double bond and a glycidyl ether group having reactivity with the SiH group is added to the linear compound represented by the following general formula (22a). It 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. Allyl glycidyl ether is preferred due to industrial availability and hydrosilylation reactivity. The conditions for the hydrosilylation reaction may be the same as those for obtaining the intermediate represented by the general formula (1b).

  When the proportion of the epoxy group in the molecule of the linear siloxane compound represented by the general formula (22) is too small, the crosslinking effect is reduced, and the physical properties of the permanent resist obtained from the positive photosensitive composition of the present invention are reduced. Since it falls, it is preferable that the epoxy equivalent of the linear siloxane compound represented by General formula (22) is 1000 or less, More preferably, it is 700 or less, Most preferably, it is 350 or less. In addition, an epoxy equivalent means the mass (gram number) of the epoxy compound containing 1 equivalent of epoxy groups.

  The molecular weight of the linear siloxane compound represented by the general formula (22) 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. Since it 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 (23) will be described.
In the general formula (23), R ^{31 to} R ³³ each represents an alkyl group having 1 to 4 carbon atoms or a phenyl group, which may be the same or different. Examples of the alkyl group having 1 to 4 carbon atoms include the alkyl groups exemplified for R ¹ . R ^{31 to} R ³³ are preferably methyl, ethyl and phenyl, more preferably methyl and phenyl, and most preferably methyl because of better heat resistance. q represents a number of 2 to 6, and r represents a number of 0 to 4 where q + r is 3 to 6. In view of industrial availability, q + r is preferably 4-6, more preferably 4-5, and most preferably 4. R is preferably 0.

  The cyclic siloxane compound represented by the general formula (23) is obtained by hydrolyzing a cyclic compound represented by the following general formula (23a) with a compound having a carbon-carbon double bond having reactivity with a SiH group and a glycidyl ether group. It can manufacture by making it react. The conditions for the hydrosilylation reaction may be the same as those for obtaining the intermediate represented by the general formula (1b).

  Examples of the cyclic compound represented by the general formula (23a) include compounds exemplified by the cyclic compound represented by the general formula (1a), 2,2,4,6-tetramethylcyclotrisiloxane, 2,2,4, 4,6,8-hexamethylcyclotetrasiloxane, 2,2,4,4,6,6,8,10-octamethylcyclopentasiloxane, 2,4,6-trimethylcyclotrisiloxane, 2,2,4 , 6,8-pentamethylcyclotetrasiloxane and the like.

Next, the cyclic siloxane compound represented by the general formula (24) will be described.
In the general formula (24), R ³⁴ represents an alkyl group having 1 to 4 carbon atoms or a phenyl group. Examples of the alkyl group having 1 to 4 carbon atoms include the alkyl groups exemplified for R ¹ . R ³⁴ is preferably methyl, ethyl and phenyl, more preferably methyl and phenyl, and most preferably methyl, because of better heat resistance. R ³⁵ represents a residue obtained by removing a vinyl group from a divinyl compound or trivinyl compound having a molecular weight of 1000 or less. As the divinyl compound or trivinyl compound having a molecular weight of 1000 or less, a divinyl compound having a molecular weight of 1000 or less exemplified in the general formula (4) or A trivinyl compound etc. are mentioned. As the divinyl compound or trivinyl compound that provides the group represented by R ³⁵ , the compounds represented by the general formulas (9) to (11) are preferable from the viewpoint of industrial availability and heat resistance of the cured product. 1,4-divinylbenzene, 1,2,4-trivinylcyclohexane and triallyl isocyanurate are more preferred, and 1,4-divinylbenzene is most preferred. G represents a group having a glycidyl ether group, and s represents a number of 2 to 5. As s, since the acquisition of an industrial raw material is easy, the number of 2-4 is preferable, and 3 is still more preferable. t represents a number of 1 or 2, and when R ³⁵ is a residue obtained by removing a vinyl group from a divinyl compound having a molecular weight of 1000 or less, t is 1 and a residue obtained by removing the vinyl group from a trivinyl compound having a molecular weight of 1000 or less. In the case of a radical, t is 2.

  The cyclic siloxane compound represented by the general formula (24) is represented by the following general formula (24b) by subjecting the cyclic compound represented by the following general formula (24a) to a hydrosilylation reaction with a divinyl compound or trivinyl compound having a molecular weight of 1000 or less. Produced by subjecting the SiH group of the intermediate represented by the general formula (24b) to a hydrosilylation reaction with a compound having a carbon-carbon double bond having reactivity with the SiH group and a glycidyl ether group. can do. The conditions for the hydrosilylation reaction may be the same as those for obtaining the intermediate represented by the general formula (1b).

Examples of the cyclic compound represented by the general formula (24a) include compounds exemplified by the cyclic compound represented by the general formula (1a), and examples of the divinyl compound or trivinyl compound having a molecular weight of 1000 or less include those represented by the general formula (4). Examples thereof include the compounds exemplified for R ⁸ .

Next, the hydrolysis / condensation reaction product of the alkoxysilane having the glycidyl ether group will be described.
The hydrolysis / condensation reaction product of the alkoxysilane having a glycidyl ether group is obtained by hydrolyzing the alkoxysilane having a glycidyl ether group by a known method, for example, the method described in the hydrolysis / condensation reaction described in the component (A). It is a compound obtained by decomposition / 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 And glycidoxymethylnorbornylalkoxysilane compounds such as sidoxymethyl) norbornyltrimethoxysilane and the like. From the reactivity of hydrolysis and condensation reaction and industrial availability, 3-glycidoxypropylalkoxy Silane compounds are preferred. Among the 3-glycidoxypropylalkoxysilane compounds, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, bis (3-glycidoxypropyl) dimethoxysilane, 3-glycidoxypropyl Triethoxysilane is more preferable, 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane are still more preferable, and 3-glycidoxypropyltrimethoxysilane is most preferable.

  When producing a hydrolysis / condensation reaction product of an alkoxysilane having a glycidyl ether group, in addition to the alkoxysilane having a glycidyl ether group, another alkoxysilane compound having no glycidyl ether group may be used in combination. .

  When the proportion of the epoxy group in the molecule of the alkoxysilane hydrolysis / condensation reaction product having a glycidyl ether group is too small, there is little crosslinking effect and the physical properties of the permanent resist obtained from the positive photosensitive composition of the present invention are low. Since it may decrease, the epoxy 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 a glycidyl ether group is not particularly limited. However, if the molecular weight is too large, the solubility or dispersibility in an alkali developer decreases, and the substrate surface after alkali development. In view of the fact that a resist residue may remain, 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 alkoxysilane having a 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.

  A hydrolysis / condensation reaction product of an alkoxysilane having a glycidyl ether group using a trialkoxysilane compound in the reaction may have a bridged structure due to Si-O-Si bond. There may be a ladder-like (ladder-like), cage-like or annular structure.

  The hydrolysis / condensation reaction product of the alkoxysilane having a glycidyl ether group is the same reaction as the hydrolysis / condensation reaction between the cyclic siloxane compound represented by the general formula (1) and the alkoxysilane compound represented by the general formula (2). It can be manufactured according to conditions.

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

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 (25) (4-diazonaphthoquinonesulfonic acid ester) or a compound substituted with the following formula (26) (5-diazonaphthoquinonesulfonic acid ester).

  Preferable specific examples of such diazonaphthoquinones include, for example, compounds represented by the following formulas (27) to (32) and their positional isomers.

  Since the group represented by the formula (25) has absorption in the i-line (wavelength 365 nm) region, it is suitable for i-line exposure, and the group represented by the formula (26) has absorption in a wide wavelength range. Therefore, since it is suitable for exposure in a wide range of wavelengths, it is preferable to select either the group represented by the formula (25) or the group represented by the formula (26) depending on the wavelength to be exposed.

  The content of the diazonaphthoquinones as component (C) is 0.1 to 20 parts by mass, preferably 2 to 10 parts by mass with respect to 100 parts by mass of the silanol group-containing polysiloxane compound as component (A). However, it is preferable from the viewpoint of developability and fine processability of a permanent resist obtained from the positive photosensitive composition 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 dissolves or disperses the above (A) silanol group-containing polysiloxane compound, (B) a compound having at least two epoxy-containing organic groups, and (C) diazonaphthoquinones. The organic solvent is not particularly limited as long as the organic solvent can be used, but an organic solvent capable of dissolving 1% by mass or more of water at 25 ° C. is preferable. In addition, γ-butyrolactone, γ-valerolactone, δ-valerolactone, ethylene carbonate, propylene carbonate, dimethyl carbonate, and the like can be given.

  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. It may be used as an organic solvent.

  (D) Content of the organic solvent which is a component is 10-10000 mass parts with respect to 100 mass parts of (A) silanol group containing polysiloxane compounds, More preferably, it is 100-1000 mass parts. From the viewpoints of formability when a permanent resist is formed using the positive photosensitive composition and physical properties of the obtained permanent resist.

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

  In addition to the components (A) to (D), the positive photosensitive composition of the present invention includes a plasticizer, a thixotropic agent, a photoacid generator, a thermal acid generator, a dispersant, and an antifoaming agent as necessary. And optional components such as pigments and dyes. From the viewpoint of not impairing the effects of the present invention, the total content of arbitrary components is preferably 30 parts by mass or less with respect to 100 parts by mass of the (A) silanol group-containing polysiloxane compound.

  The positive photosensitive composition of the present invention can be cured in the same manner as a conventionally known positive photosensitive composition. For example, if it is cured through the following steps (1) to (6), it has heat resistance. And a cured product having excellent chemical resistance after high-temperature heat history. A cured product obtained by curing the positive photosensitive composition of the present invention is suitable for a permanent resist. Below, the preferable method of manufacturing a permanent resist using the positive photosensitive composition of this invention is demonstrated.

When forming a layer of the positive photosensitive composition on the target material (base material), a method of directly applying the positive photosensitive composition of the present invention to the target material, and a support such as polyethylene terephthalate (PET) After applying to a body film, there is a method in which a solvent is evaporated to form a layer of a positive photosensitive composition to form a dry film resist (DFR), and the DFR is bonded to a target material.
First, a method for direct application will be described. This method includes the following (1) coating film forming step, (2) pre-baking step, (3) exposure step, (4) development step, (5) bleaching exposure step, and (6) post-baking step.

(1) Coating film formation process In this process, the positive photosensitive composition of this invention is apply | coated to a target material (base material), and a coating film is formed. The target material to which the positive photosensitive composition of the present invention is applied to form a coating film has chemical resistance to an organic solvent or the like in the positive photosensitive composition, and (4) development treatment with an alkaline solution in the development step (6) The material is not particularly limited as long as the material has resistance to heat treatment in the post-bake process, and glass, metal, semiconductor, and the like can be used as target materials. 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.

(2) Pre-baking step After the step (1), pre-baking is performed to remove (D) the organic solvent from the positive photosensitive composition layer 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 after the high heat history of the permanent resist are further improved, pre-baking is performed. In addition, the organic solvent is volatilized so that the concentration of the organic solvent in the positive photosensitive composition layer is 5% by mass or less at room temperature to less than 60 ° C. under normal pressure or reduced pressure, and then prebaked. It is preferable. The thickness of the positive photosensitive composition layer after pre-baking varies depending on the application for which the permanent resist is used, and is not particularly limited, but is preferably 0.1 μm to 100 μm, more preferably 0.3 μm to 10 μm.

(3) Exposure process An exposure process is a process of irradiating patterned light with respect to the pre-baked positive photosensitive composition layer, and improving 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 the irradiation light may be visible light or ultraviolet light, and is not particularly limited. However, when 4-diazonaphthoquinonesulfonic acid esters are used as (C) diazonaphthoquinones, they are narrow with i-line (365 nm) as the main component. When 5-diazonaphthoquinonesulfonic acid esters are used, light having a broad wavelength including i-line (365 nm), h-line (405 nm) and g-line (436 nm) is used for high-pressure mercury lamp, Irradiation may be performed using a 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.

(4) 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 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 (A) the silanol group-containing polysiloxane compound and (B) the type and molecular weight of the compound having at least two epoxy-containing organic groups, 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 the 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.

(5) Bleaching exposure process In the bleaching exposure process, the entire positive-type photosensitive composition layer (hereinafter sometimes referred to as a resist layer) remaining after the alkali solution treatment is irradiated with light so as to have visible light transmittance. It is a process to improve. The resist layer is colored light yellow to light brown because it contains (C) diazonaphthoquinones. 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.

(6) 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. The post-baking is preferably performed at a temperature of 120 to 400 ° C., more preferably 120 to 350 ° C., and most preferably 200 to 350 ° C. for 15 minutes to 2 hours.

  The positive photosensitive composition of the present invention may be directly applied to a target material such as a semiconductor substrate as described above. However, the positive photosensitive composition is applied to a support film to form a coating film, and a dry film resist. May be used as As the support film, for example, polyethylene terephthalate (PET), polyethylene, polypropylene, and the like can be used, but a PET film is preferable because of excellent thermal characteristics and mechanical characteristics as the support film. The film thickness of the support film is usually 1 μm to 5 mm, preferably 10 μm to 100 μm. Although the thickness of the coating film formed on a support film changes with uses and is not specifically limited, 0.1 micrometer-100 micrometers, Preferably it is 0.3 micrometer-10 micrometers. After forming the coating film, pre-baking is performed in the same manner as in the above (2) pre-baking step to remove the solvent in the coating film, and a protective film is laminated on the coating film surface to prepare a dry film resist. When using a dry film resist obtained from the positive photosensitive composition of the present invention, after peeling off the protective film from the dry film resist, it is thermocompression bonded to the target material and affixed to the target, if necessary After the support film is peeled off, exposure, alkali development, bleaching exposure, and post-baking may be performed in the same manner as the above steps (3) to (6).

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

  Furthermore, the permanent resist obtained from the positive photosensitive composition 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 packaging materials (sealing materials, die bonding materials) for semiconductor devices. .

  The permanent resist obtained from the positive photosensitive composition 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. The —O—Si bond was hydrolyzed and calculated from the rate of mass increase after the reaction.

Production Example 1: Intermediate a1
In a glass reaction vessel equipped with a thermometer and a stirrer, 300 g of toluene, 240 g (1 mol) of 2,4,6,8-tetramethylcyclotetrasiloxane as a solvent, 64.1 g of acrylic acid-t-butyl ester (0) 0.5 mol), 352 g of 4-t-butoxystyrene (2 mol) and 0.05 g of platinum-divinyltetramethyldisiloxane complex (Karstedt catalyst) as a catalyst were added and reacted at 60 ° C. for 10 hours with stirring. The solvent was distilled off to obtain intermediate a1. The intermediate a1 is a compound corresponding to the general formula (1 bp) (R ¹ = methyl, R ² = R ³ = ethylene, Pg = t-butyl, m = 0.5, n = 2, p = 1. 5, m: n: p = 1: 4: 3).

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

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

Production Example 4: Intermediate a′1
In Production Example 1, 204 g (1 mol) of 4-vinylbenzoic acid-t-butyl ester was used instead of 64.1 g (0.5 mol) of acrylic acid-t-butyl ester, and 4-t-butoxystyrene Except having changed the usage-amount from 352g (2 mol) to 264g (1.5 mol), operation similar to manufacture example 1 was performed and intermediate a'1 was obtained. The intermediate a′1 has R ¹ = methyl, R ² = 2-phenylethane-1,4′-diyl, R ³ = ethylene, Pg = t-butyl, m = 1, n = 1.5, Although p = 1.5, the general formula (1 bp) is not satisfied in that m: n: p = 1: 1.5: 1.5.

Production Example 5: Intermediate a′2
In Production Example 1, the amount of acrylic acid-t-butyl ester used was changed from 64.1 g (0.5 mol) to 19.2 g (0.15 mol), and the amount of 4-t-butoxystyrene used was 352 g (2 Mol) to 414 g (2.35 mol), and the same operation as in Production Example 1 was performed to obtain an intermediate a′2. The intermediate a′2 has R ¹ = methyl, R ² = R ³ = ethylene, Pg = t-butyl, m = 0.15, n = 2.35, and p = 1.5. : N: p = 1: 15.7: 10, and does not satisfy the general formula (1 bp).

Production Example 6: Polysiloxane compound A1
In a glass reaction vessel equipped with a thermometer and a stirrer, 200 g of toluene as a solvent, 65.6 g (0.1 mol) of intermediate a1, 22.1 g (0.15 mol) of trimethoxyvinylsilane, and platinum as a catalyst -0.001 g of divinyltetramethyldisiloxane complex (Karstedt catalyst) was added and reacted at 60 ° C. for 10 hours with stirring to introduce a group represented by the general formula (3).
Next, 45.6 g (0.23 mol) of phenyltrimethoxysilane was added as a compound represented by the general formula (2), and 50 g of 5% oxalic acid aqueous solution was added while stirring with ice cooling to 5 to 10 ° C. The solution was added dropwise over 30 minutes and further stirred at 10 ° C. for 15 hours. 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, 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 the polysiloxane compound A1 as the component (A) was obtained. The polysiloxane compound A1 had a mass average molecular weight of 6,400 and a silanol group content of 5.4% by mass by GPC analysis.

Production Example 7: Polysiloxane compound A2
In Production Example 6, instead of 65.6 g (0.1 mol) of Intermediate a1, the same operation as in Production Example 6 was carried out except that 69.4 g (0.1 mol) of Intermediate a2 was used. A 30% PGMEA solution of polysiloxane compound A2 as component (A) was obtained. The mass average molecular weight of the polysiloxane compound A2 by GPC analysis was 6500, and the silanol group content was 5.4% by mass.

Production Example 8: Polysiloxane compound A3
In Production Example 6, the same procedure as in Production Example 6 was performed, except that 65.4 g (0.1 mol) of intermediate a3 was used instead of 65.6 g (0.1 mol) of intermediate a1. A 30% PGMEA solution of polysiloxane compound A3 as component (A) was obtained. The polysiloxane compound A3 had a mass average molecular weight of 6,300 and a silanol group content of 5.4% by mass by GPC analysis.

Production Example 9: Polysiloxane compound A4
In a glass reaction vessel equipped with a thermometer and a stirrer, 200 g of toluene as a solvent, 65.6 g (0.1 mol) of intermediate a1, and 39 g of divinylbenzene as a divinyl compound represented by the general formula (4a) (0 .3 mol), and 0.001 g of platinum-divinyltetramethyldisiloxane complex (Karstedt catalyst) as a catalyst, and the mixture is reacted at 60 ° C. for 10 hours with stirring to obtain an intermediate represented by the general formula (1c) Got. After distilling off the solvent and removing the unreacted divinylbenzene together with the solvent under reduced pressure at 60 ° C., 200 g of toluene as the solvent and 19.5 g (0.3%) of trimethoxysilane as the compound represented by the general formula (4b) were newly obtained. 16 mol) was added, and the mixture was reacted at 60 ° C. for 10 hours with stirring to introduce a group represented by the general formula (4).
Next, 45.5 g (0.23 mol) of phenyltrimethoxysilane was added as a compound represented by the general formula (2), and 50 g of 5% oxalic acid aqueous solution was added while stirring with ice cooling to 5 to 10 ° C. The solution was added dropwise over 30 minutes and further stirred at 10 ° C. for 15 hours. 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, 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, thereby obtaining a 30% PGMEA solution of polysiloxane compound A4 as component (A). The mass average molecular weight of the polysiloxane compound A4 by GPC analysis was 8300, and the silanol group content was 6.2% by mass.

Production Example 10: Polysiloxane compound A5
In a glass reaction vessel equipped with a thermometer and a stirrer, 200 g of dioxane as a solvent, 65.6 g (0.1 mol) of intermediate a1, 43.2 g (0.2 mol) of diphenylsilanediol, octylic acid as a catalyst After 0.025 g of tin was added and dissolved, the mixture was reacted at 60 ° C. for 10 hours to introduce a group represented by the general formula (5).
As a compound represented by the general formula (2), 45.5 g (0.23 mol) of phenyltrimethoxysilane was added, and 50 g of 5% oxalic acid aqueous solution was added for 30 minutes while stirring with ice cooling to 5 to 10 ° C. The mixture was added dropwise and stirred at 10 ° C. for 15 hours. Reflux dehydration and dealcoholization treatment at 50 ° C. under reduced pressure, and the solvent was changed to 1-methoxy-2-propanol acetate (hereinafter referred to as PGMEA) under reduced pressure at 50 ° C. 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, thereby obtaining a 30% PGMEA solution of polysiloxane compound A5 as component (A). The polysiloxane compound A5 had a mass average molecular weight of 5,900 and a silanol group content of 5.1% by mass by GPC analysis.

Production Example 11: Polysiloxane compound A′1
In Production Example 6, the same procedure as in Production Example 6 was used, except that 70.8 g (0.1 mol) of intermediate a′1 was used instead of 65.6 g (0.1 mol) of intermediate a1. A comparative 30% PGMEA solution of polysiloxane compound A′1 was obtained. The mass average molecular weight of the polysiloxane compound A′1 by GPC analysis was 6500, and the silanol group content was 5.4% by mass.

Production Example 12: Polysiloxane compound A′2
In Production Example 6, the same procedure as in Production Example 6 was used, except that 67.3 g (0.1 mol) of intermediate a′2 was used instead of 65.6 g (0.1 mol) of intermediate a1. A comparative 30% PGMEA solution of polysiloxane compound A′2 was obtained. The mass average molecular weight of the polysiloxane compound A′2 by GPC analysis was 6400, and the silanol group content was 5.4% by mass.

Production Example 13: Epoxy compound B1 (compound represented by formula (23))
In a glass reaction vessel equipped with a thermometer and a stirrer, 200 g of toluene as a solvent, 120 g (0.5 mol) of 2,4,6,8-tetramethylcyclotetrasiloxane, 228 g (2 mol) of allyl glycidyl ether, and After adding 9 mg of platinum-divinyltetramethyldisiloxane complex (Karstedt catalyst) and reacting at 50-60 ° C. for 15 hours with stirring, the solvent is distilled off under reduced pressure at 60 ° C., and the epoxy compound as component (B) B1 was obtained. The analytical value of the epoxy equivalent of the epoxy compound B1 was 174.

Production Example 14: Epoxy compound B2 (compound represented by formula (24))
In a glass reaction vessel equipped with a thermometer and a stirrer, 250 g of toluene as a solvent, 144 g (0.6 mol) of 2,4,6,8-tetramethylcyclotetrasiloxane, 52 g (0.4 mol) of divinylbenzene, After adding 194 g (1.7 mol) of allyl glycidyl ether and 9 mg of platinum-divinyltetramethyldisiloxane complex (Karstedt catalyst), the mixture was reacted at 50-60 ° C. for 15 hours with stirring, and then the solvent was reduced in pressure at 60 ° C. It was distilled off to obtain an epoxy compound B2 as component (B). Epoxy compound B2 had a weight average molecular weight of 1500 and an analysis value of epoxy equivalent of 244.

Production Example 15: Epoxy compound B3
In a glass reaction vessel equipped with a thermometer and a stirrer, 200 g of toluene, 134 g (1 mol) of 1,1,3,3-tetramethyldisiloxane, 52 g (0.4 mol) of divinylbenzene, 194 g of allyl glycidyl ether ( 1.7 mol) and 9 mg of a platinum-divinyltetramethyldisiloxane complex (Karstedt catalyst) were added and 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 an epoxysilane compound B3 as component (B). Epoxy compound B3 had a weight average molecular weight of 1500 and an epoxy equivalent weight of 244.

Examples 1-10 and Comparative Examples 1-3:
Using the compounds obtained in the above production examples, the positive photosensitive compositions of Examples 1 to 10 and Comparative Examples 1 to 4 were prepared after blending in the proportions shown in Table 1 and filtering. In addition, the solvent was added so that it might become the value in a table | surface.

(C) component and (D) component of Table 1 are as follows, respectively.
(C) Diazonaphthoquinones (DNQ)
In the above formula (27), a compound in which all Qs are groups represented by formula (26) (trade name: PA-6, manufactured by Daito Chemix Co., Ltd.)
(D) Solvent PGMEA: 1-methoxy-2-propanol acetate

Using the positive photosensitive compositions of Examples 1 to 10 and Comparative Examples 1 to 4, test pieces were prepared by the following procedure for preparing test pieces.
[Method for preparing test piece]
After applying the positive photosensitive composition on a glass substrate by spin coating so that the film thickness of the coating film becomes 3 to 4 μm, the solvent is volatilized and prebaked at 100 ° C. for 3 minutes to obtain a test piece. Using.

Using the obtained test pieces, evaluation of optimum development time and development margin, evaluation of alkali resistance after high heat history, evaluation of resist residue, and evaluation of film reduction rate were performed by the following methods. In each of the following evaluations, in each patterning exposure, after the test piece was heat-treated at 90 ° C. for 2 minutes, a photomask having a line width of 5 μm was placed on the glass substrate, and 90 mJ with an ultrahigh pressure mercury lamp. / Cm ² (wavelength 365 nm exposure conversion).

[Evaluation of optimum development time and development margin]
The development time was changed from 30 seconds to every 5 seconds, and the evaluation of the optimum development time and development margin was evaluated according to the following procedure. That is, for each positive photosensitive composition, 15 test pieces were prepared and subjected to patterning exposure, and then these test pieces were immersed in a 2.38 mass% tetramethylammonium hydroxide aqueous solution at a liquid temperature of 25 ° C. After 30 seconds from the start of immersion, one sheet was taken out every 5 seconds. The taken-out test piece was immediately washed with running ultrapure water for 1 minute and air-dried. The air-dried test piece was observed, and the shortest development time necessary for the line width to be 5 μm was set as the optimal development time, and the time from the optimal development time until the 5 μm line pattern was peeled off was set as the development margin. The results are shown in Table 2.

[Evaluation of alkali resistance after high heat history]
The test piece of the positive photosensitive composition was subjected to patterning exposure, and then developed by a shower development method (shower pressure 0.05 MPa) using a 2.38 mass% tetramethylammonium hydroxide aqueous solution having a liquid temperature of 25 ° C. The development time was the optimum development time for each positive photosensitive composition determined in the previous evaluation. Immediately after the development, it was washed with running ultrapure water for 1 minute and air-dried. The air-dried test piece was subjected to bleaching exposure under the condition of 200 mJ / cm ² (wavelength 365 nm exposure conversion) using an ultrahigh pressure mercury lamp. After bleaching exposure, post-baking was performed by heating at 230 ° C. for 60 minutes in an air atmosphere to form a permanent resist film, and further, heat treatment was performed at 350 ° C. for 30 minutes in a nitrogen atmosphere. About the test piece which heat-processed 350 degreeC, after measuring the transmittance | permeability of the light of wavelength 400nm, and measuring the film thickness of a resist using a stylus type surface shape measuring device, 40 degreeC alkaline solution ( It was immersed in monoethanolamine: N-methyl-2-pyrrolidone: butyl diglycol = 10: 30: 60 mass ratio) for 30 minutes. About each test piece after immersion, the transmittance | permeability of the light of wavelength 400nm and the film thickness of a resist are measured, From the change rate of the light transmittance before and behind immersion in an alkaline solution, and the change rate of a film thickness, it is based on the following evaluation criteria. The alkali resistance after a high heat history was evaluated. The results are shown in Table 2.

(Evaluation criteria)
○: Change rate of light transmittance is less than 3% and change rate of film thickness is less than 10%, and excellent in alkali resistance even after high heat history.
Δ: Change rate of light transmittance is less than 5% and change rate of film thickness is less than 20%, but change rate of light transmittance is less than 3% and change rate of film thickness is not less than 10%. Slightly inferior in alkali resistance after history.
X: Change rate of light transmittance is 5% or more or change rate of film thickness is 10% or more, and is inferior in alkali resistance after a high heat history.

[Evaluation of resist residue]
Each positive photosensitive composition was subjected to patterning exposure using three test pieces each, and then subjected to a shower development method (shower pressure 0. 0) using a 2.38 mass% tetramethylammonium hydroxide aqueous solution having a liquid temperature of 25 ° C. (05 MPa). The development time was the optimum development time for each positive photosensitive composition determined in the previous evaluation.
Immediately after the development, it was washed with running ultrapure water for 1 minute and air-dried. The air-dried test piece was irradiated with 200 mJ / cm ² (wavelength 365 nm exposure equivalent) of light using a super-high pressure mercury lamp as bleaching exposure, and then post-baked at 230 ° C. for 60 minutes in an air atmosphere to form a permanent resist film. Formed. Each test piece was cut, the cut surface was observed using a scanning electron microscope, the presence or absence of a resist residue in a portion where the glass substrate was exposed by development was examined, and the resist residue was evaluated according to the following evaluation criteria. The results are shown in Table 2 (Evaluation criteria)
○: Resist residue is not seen in all three test pieces.
X: A resist residue is seen by 1-3 sheets among three test pieces.

[Evaluation of film reduction rate]
For each positive photosensitive composition, bleaching exposure and post-baking were performed under the same conditions as the evaluation of the resist residue without patterning exposure and development for each of the three test pieces to form a permanent resist layer. It was. Each test piece was cut, and the thickness of the permanent resist layer was measured using a scanning electron microscope. Moreover, the thickness of the permanent resist film was also measured for the test piece used in the evaluation of the resist residue, and the film reduction rate (%) was obtained by the following formula. For the thickness of the permanent resist layer, the average value of three test pieces was used. The results are shown in Table 2. Film reduction rate (%) = 100 × T _D / T ₀
T _D : thickness of the permanent resist layer of the test piece that was exposed and developed T ₀ : thickness of the permanent resist layer of the test piece that was not exposed and developed

Claims (6)

(A) Silanol group-containing polysiloxane having a structure obtained by hydrolyzing and condensing a cyclic siloxane compound represented by the following general formula (1) and an alkoxysilane compound represented by the following general formula (2) as the component (A) Compound,
(B) As a component, a compound having at least two epoxy-containing organic groups,
A positive photosensitive composition comprising a diazonaphthoquinones as component (C) and an organic solvent as component (D).

  The positive photosensitive composition according to claim 1, wherein the epoxy-containing organic group of the compound having at least two epoxy-containing organic groups as the component (B) is a group containing a glycidyl group.   A cured product obtained by curing the positive photosensitive composition according to claim 1.   The positive photosensitive composition according to claim 1 or 2 is applied to a target material, pre-baked, exposed, developed with alkali, then bleached and then post-baked at a temperature of 120 to 400 ° C. A method for producing a permanent resist.   A liquid crystal display device comprising an active matrix substrate having a permanent resist obtained by using the positive photosensitive composition according to claim 1 as an insulating layer or a planarizing film.   An organic EL display device comprising an active matrix substrate having a permanent resist obtained by using the positive photosensitive composition according to claim 1 as an insulating layer or a planarizing film.