JP5734629B2 - Positive photosensitive resin composition and permanent resist - Google Patents

Description

  The present invention relates to a positive photosensitive resin composition containing a specific epoxysiloxane compound, and a permanent resist using the positive photosensitive resin composition.

  In an electronic component such as a thin film transistor (hereinafter referred to as “TFT”) type liquid crystal display element, magnetic head element, integrated circuit element, solid-state image sensor, etc., an interlayer insulation is generally used to insulate between wirings arranged in layers. A membrane is provided. As a material for forming an interlayer insulating film, a material having a small number of steps for obtaining a required pattern shape and having sufficient flatness is preferable, and thus a radiation sensitive resin composition is widely used (patents) Reference 1). Among the electronic components, for example, a TFT type liquid crystal display element is manufactured through a process of forming a transparent electrode film on the interlayer insulating film and further forming a liquid crystal alignment film on the interlayer insulating film. The film is exposed to high temperature conditions in the process of forming the transparent electrode film or exposed to a resist stripping solution used for electrode pattern formation, so that sufficient resistance to these is required. Further, depending on the manufacturing process, the formed interlayer insulating film may be exposed to dry etching, and sufficient resistance to dry etching is required (see Patent Document 2).

In recent years, TFT-type liquid crystal display devices have been in the trend of larger screens, higher brightness, higher definition, higher speed response, thinner thickness, etc. The composition for forming an interlayer insulating film used therefor has high sensitivity. Therefore, the formed interlayer insulating film is required to have higher performance than the conventional one in terms of low dielectric constant, high transmittance, and the like. A positive photosensitive material containing a polysiloxane compound having a carboxyl group and a photosensitive diazoquinone compound as an interlayer insulating film material that is excellent in insulation, heat resistance, solvent resistance, dry etching resistance, etc. and can form a fine pattern. A composition (see Patent Document 3) has been developed, and a composition containing an epoxy group-containing cyclic siloxane compound is also known, but the development margin in the development process (the width of time for which development time is optimal) is small. In addition, if the development time is excessive even slightly, the developer tends to permeate between the formed pattern and the substrate and the peeling tends to occur. Therefore, it is necessary to strictly control the development time, and the yield of the product There was a problem.
On the other hand, a compound in which a cyclic siloxane compound having an epoxy group is linked is known (see Patent Document 4), but a positive photosensitive resin composition containing such a compound is not known.

JP 2001-354822 A JP 2005-345757 A JP 2010-101957 A JP-T-2001-513117

  The object of the present invention is suitable for forming an interlayer insulating film having high heat resistance, high solvent resistance, high transmittance and low dielectric constant, and still forms a good pattern shape even if the optimum development time is exceeded in the development process. An object of the present invention is to provide a positive photosensitive resin composition having such a large development margin as possible.

（式中、Ｒ¹は同一でも異なっていてもよい炭素数１〜４のアルキル基又は炭素数６〜１０のアリール基を表わし、Ｅはエポキシ基を有する基を表わし、ａは２〜５の数を表わす。）

（式中、ｂはａ−ｂ＋１が０〜４の数となる２〜６の数を表わし、Ｒ¹、Ｅ及びａは上記一般式（１）と同義である。） The present inventors have reached the present invention as a result of intensive studies in view of the above.
That is, the present invention relates to a positive photosensitive resin composition containing a polysiloxane compound having a carboxyl group and / or a phenolic hydroxyl group as a base resin, a photosensitive diazoquinone compound as a photosensitive component, and an organic solvent. A group represented by (1) or a group represented by the following general formula (1) and a group represented by the following general formula (2) is a compound having 2 to 4 vinyl groups in one molecule. The present invention provides a positive photosensitive resin composition comprising an epoxysiloxane compound linked by a residue excluding a vinyl group.

Wherein R ¹ represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms which may be the same or different, E represents a group having an epoxy group, and a represents 2 to 5 Represents a number.)

(In the formula, b represents a number of 2 to 6 in which ab + 1 is a number of 0 to 4, and R ¹ , E and a have the same meaning as in the general formula (1).)

  The effect of the present invention is suitable for forming an interlayer insulating film having high heat resistance, high solvent resistance, high transmittance and low dielectric constant, and still forms a good pattern shape even if the optimum development time is exceeded in the development process. The present invention provides a positive photosensitive resin composition having such a large development margin as possible.

  Hereinafter, the positive photosensitive resin composition and the permanent resist of the present invention will be described in detail based on preferred embodiments.

  The present invention relates to a positive photosensitive resin containing a polysiloxane compound having a carboxyl group and / or a phenolic hydroxyl group as a base resin (hereinafter also referred to as a base resin of the present invention), a photosensitive diazoquinone compound as a photosensitive component, and an organic solvent. Group represented by the general formula (1), or the group represented by the general formula (1) and the group represented by the general formula (2) are 2 to 2 in one molecule. It is characterized by containing an epoxy siloxane compound (hereinafter also referred to as an epoxy siloxane compound of the present invention) linked by a residue obtained by removing a vinyl group from a compound having four vinyl groups. First, the epoxy siloxane compound of the present invention will be described.

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, secondary butyl, isobutyl, 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, phenethyl and the like. R ¹ is preferably methyl, ethyl and phenyl, more preferably methyl and phenyl, and most preferably methyl since heat resistance is improved.

  In the general formula (1), E represents a group having an epoxy group. Examples of the group having an epoxy group include an aliphatic epoxy group such as the following formula (5) or (6), an alicyclic epoxy group such as the following formula (7) to (9), the following formula (10) or (11). In view of the storage stability of the positive photosensitive resin composition of the present invention, an aliphatic epoxy group represented by the following formula (5) or (6) is used as a partial structure. The group is preferable, the 1,2-epoxypropyl group of the following formula (5) is more preferable, the group having a glycidyl ether group is more preferable, and the 3-glycidoxypropyl group is most preferable.

  In the above general formula (1), a represents a number of 2 to 5, and since it is easy to obtain industrial raw materials, a is preferably a number of 2 to 4, more preferably a number of 2 to 3. The number of 3 is most preferred.

In the general formula (2), b represents a number of 2 to 6 a-b + 1 is the number of 0 to 4, R ^1, E and a are as defined in the above general formula (1).

  In the epoxy siloxane compound of the present invention, the number of vinyl groups in the compound having 2 to 4 vinyl groups in one molecule described above is such that the resist residue on the substrate after alkali development hardly remains. preferable. Examples of the compound having 2 to 4 vinyl groups in one molecule include compounds represented by the following general formulas (12) to (18). From the viewpoint of heat resistance, the following general formula (12) The compound represented by-(14) is preferable, and the compound represented by the following general formula (16) is preferable from the viewpoint of industrial availability.

（式中、Ｒ⁴〜Ｒ⁶は同一でも異なっていてもよい炭素数１〜４のアルキル基又は炭素数６〜１０のアリール基を表わし、ｃは１〜３の数を表わし、ｄ及びｅは各々独立して０〜６の数を表わす。）

(Wherein R ^{4 to} R ⁶ represent the same or different alkyl group having 1 to 4 carbon atoms or aryl group having 6 to 10 carbon atoms, c represents a number of 1 to 3, d and e) Each independently represents a number from 0 to 6.)

（式中、Ｒ⁷〜Ｒ⁹は同一でも異なっていてもよい炭素数１〜４のアルキル基又は炭素数６〜１０のアリール基を表わし、ｆは０〜１０の数を表わす。）

(Wherein, R ⁷ to R ⁹ represents an alkyl group or an aryl group having 6 to 10 carbon atoms of 1 to 4 carbon atoms which may be the same or different, f represents a number from 0 to 10.)

（式中、Ｒ¹⁰は同一でも異なっていてもよい炭素数１〜４のアルキル基又は炭素数６〜１０のアリール基を表わし、ｇは３〜４の数を表わす。）

(In the formula, R ¹⁰ represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms which may be the same or different, and g represents a number of 3 to 4).

（式中、Ｒ¹¹及びＲ¹²は同一でも異なっていてもよい炭素数１〜４のアルキル基又は炭素数６〜１０のアリール基を表わす。）

(In the formula, R ¹¹ and R ¹² represent the same or different alkyl group having 1 to 4 carbon atoms or aryl group having 6 to 10 carbon atoms.)

（式中、ｈは１〜２の数を表わす。）

(In the formula, h represents a number of 1 to 2).

（式中、ｊは１〜３の数を表わす。）

(Where j represents a number from 1 to 3)

（式中、Ｒ¹³は炭素数１〜４のアルキル基、炭素数６〜１０のアリール基、グリシジル基又はアリル基を表わす。）

(In the formula, R ¹³ represents an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, a glycidyl group, or an allyl group.)

The compound represented by the general formula (12) is a compound having 2 to 4 vinyl groups in one molecule. In the general formula (12), R ^{4 to} R ⁶ represent an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, which may be the same or different. Examples of the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms include the groups exemplified in the description of R ^{1 in} the general formula (1), and examples of R ^{4 to} R ⁶ include heat resistance. Are preferred, methyl, ethyl, propyl and phenyl are preferred, methyl, ethyl and phenyl are more preferred, and methyl is most preferred. c represents a number of 1 to 3, and d and e each independently represents a number of 0 to 6.

  Among the compounds represented by the general formula (12) in which c is the number 1, preferred compounds include dimethyldivinylsilane, diethyldivinylsilane, diphenyldivinylsilane, 1,1,3,3-tetramethyl-1 , 3-divinyldisiloxane, 1,1,3,3-tetraethyl-1,3-divinyldisiloxane, 1,1,3,3-tetraphenyl-1,3-divinyldisiloxane, and the like. Vinylsilane, diethyldivinylsilane and diphenyldivinylsilane are preferred, and 1,1,3,3-tetramethyl-1,3-divinyldisiloxane is more preferred. Among the compounds represented by the general formula (12) wherein c is a number of 2, preferred compounds include methyltrivinylsilane, ethyltrivinylsilane, phenyltrivinylsilane, 1,1,3,5,5-pentamethyl- 1,3,5-trivinyltrisiloxane, 1,1,5,5-tetramethyl-3-phenyl-1,3,5-trivinyltrisiloxane, tris (dimethylvinylsiloxy) methylsilane, tris (dimethylvinylsiloxy) ) Phenylsilane and the like. Among the compounds represented by the above general formula (12) in which c is a number of 3, preferred compounds include tetravinylsilane, tetrakis (dimethylvinylsiloxy) silane, and the like.

The compound represented by the general formula (13) is a compound having four vinyl groups in one molecule. In the general formula (13), R ^{7 to} R ⁹ represent an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, which may be the same or different. Examples of the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms include the groups exemplified in the description of R ^{1 in} the general formula (1), and examples of R ^{7 to} R ⁹ include heat resistance. Are preferred, methyl, ethyl, propyl and phenyl are preferred, methyl, ethyl and phenyl are more preferred, and methyl is most preferred. f represents a number from 0 to 10. Among the compounds represented by the general formula (13), preferred compounds include 1,3-dimethyl-1,1,3,3-tetravinyldisiloxane, 1,3,3,5-tetramethyl- Examples include 1,1,5,5-tetravinyltrisiloxane, 1,5-dimethyl-3,3-diphenyl-1,1,5,5-tetravinyltrisiloxane, and the like.

The compound represented by the general formula (14) is a compound having 3 to 4 vinyl groups in one molecule. In the general formula (14), R ¹⁰ represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, which may be the same or different. Examples of the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms include the groups exemplified in the description of R ^{1 in} the general formula (1), and R ¹⁰ has good heat resistance. In view of this, methyl, ethyl, propyl and phenyl are preferred, methyl, ethyl and phenyl are more preferred, and methyl is most preferred. g represents a number of 3 to 4, and from the viewpoint of industrial availability, g is preferably a number of 4. Among the compounds represented by the general formula (14) wherein g is a number of 3, preferred compounds include 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane, 2,4 , 6-triethyl-2,4,6-trivinylcyclotrisiloxane, 2,4,6-triphenyl-2,4,6-trivinylcyclotrisiloxane, 2,4-dimethyl-6-phenyl-2, Examples include 4,6-trivinylcyclotrisiloxane. Among the compounds represented by the general formula (14) wherein g is a number of 4, preferred compounds are 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotrimethyl. Siloxane, 2,4,6,8-tetraethyl-2,4,6,8-tetravinylcyclotrisiloxane, 2,4,6,8-tetraphenyl-2,4,6,8-tetravinylcyclotrisiloxane 2,4,6-trimethyl-8-phenyl-2,4,6,8-tetravinylcyclotrisiloxane, 2,4-dimethyl-6,8-diphenyl-2,4,6,8-tetravinylcyclotrisiloxane Examples thereof include siloxane.

The compound represented by the general formula (15) is a compound having two vinyl groups in one molecule. In the general formula (15), an aryl group of R ¹¹ and R ¹² are an alkyl group or a C 6-10 1-4 carbon atoms which may be the same or different. Examples of the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms include the groups exemplified in the description of R ^{1 in} the general formula (1), and examples of R ¹¹ and R ¹² include heat resistance. Are preferred, methyl, ethyl, propyl and phenyl are preferred, methyl, ethyl and phenyl are more preferred, and methyl is most preferred. Among the compounds represented by the general formula (15), preferred compounds include 1,2-bis (dimethylvinylsilyl) benzene, 1,3-bis (dimethylvinylsilyl) benzene, 1,4-bis ( Dimethylvinylsilyl) benzene, 1,2-bis (diethylvinylsilyl) benzene, 1,3-bis (diethylvinylsilyl) benzene, 1,4-bis (diethylvinylsilyl) benzene and the like. Bis (dimethylvinylsilyl) benzene and 1,4-bis (dimethylvinylsilyl) benzene are preferred, and 1,4-bis (dimethylvinylsilyl) benzene is more preferred.

  The compound represented by the general formula (16) is a compound having 2 to 3 vinyl groups in one molecule. In the said General formula (16), h represents the number of 1-2. Examples of the compound represented by the general formula (16) in which h is the number 1 include 1,2-divinylbenzene, 1,3-divinylbenzene, and 1,4-divinylbenzene. Examples of the compound represented by the general formula (16) in which h is a number of 2 include 1,2,4-trivinylbenzene and 1,3,5-trivinylbenzene.

  The compound represented by the general formula (17) is a compound having 2 to 4 vinyl groups in one molecule. In the said General formula (17), j represents the number of 1-3. Examples of the compound represented by the general formula (17) in which j is a number of 1 include 1,2-divinylcyclohexane, 1,3-divinylcyclohexane, and 1,4-divinylcyclohexane. Examples of the compound represented by the general formula (17) in which h is a number of 2 include 1,2,4-trivinylcyclohexane and 1,3,5-trivinylcyclohexane. Examples of the compound represented by the general formula (17) in which h is a number of 3 include 1,2,4,5-tetravinylcyclohexane.

The compound represented by the general formula (18) is a compound having 2 to 3 vinyl groups in one molecule. In the general formula (18), R ¹³ represents an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, a glycidyl group, or an allyl group. R ¹³ is preferably methyl, ethyl, glycidyl or allyl from the viewpoint of heat resistance. Among the compounds represented by the general formula (18), preferred compounds are 1,3-diallyl-5-methylisocyanurate, 1,3-diallyl-5-ethylisocyanurate, 1,3-diallyl-5. -Glycidyl isocyanurate, 1,3,5-triallyl isocyanurate, etc. are mentioned.

  When the proportion of the epoxy group in the epoxy siloxane compound of the present invention is too small, the mechanical properties of the resulting cured product are lowered, so that the epoxy equivalent is preferably 1000 or less, and 700 or less. Is more preferable, and is most preferably 350 or less. The epoxy equivalent means a value obtained by dividing the molecular weight by the number of epoxy groups, that is, the molecular weight per epoxy group.

  If the molecular weight of the epoxy siloxane compound of the present invention is too small, the effect of improving the development margin is small, and if it is too large, a resist residue on the substrate after alkali development may remain, so the mass average The molecular weight is preferably 1000 to 10,000, more preferably 1500 to 7000, and most preferably 2000 to 5000. In the present invention, the weight average molecular weight means a weight average molecular weight in terms of polystyrene when GPC (Gel Permeation Chromatography) analysis is performed using tetrahydrofuran as a solvent.

  In the positive photosensitive resin composition of the present invention, when the content of the epoxysiloxane compound of the present invention is too small, the effect of improving the development margin is small, and when it is too large, the alkali developability and the resist resistance are reduced. Since there is an adverse effect on physical properties and resist residues on the substrate after development may remain, 1 to 30 parts by weight is preferable with respect to 100 parts by weight of the base resin of the present invention, and 2 to 25 parts by weight is further Preferably, 3 to 20 parts by mass is most preferable.

  The epoxysiloxane compound of the present invention is obtained by subjecting the SiH group of the cyclic siloxane compound represented by the following general formula (1a) to a hydrosilylation reaction with a vinyl group of a compound having 2 to 4 vinyl groups in one molecule. Furthermore, it can obtain by carrying out the hydrosilylation reaction of the epoxy compound containing the carbon-carbon double bond which has the reactivity with SiH group.

（式中、Ｒ¹及びａは上記一般式（１）と同義である。）

(In the formula, R ¹ and a have the same meaning as in the general formula (1)).

The hydrosilylation reaction between the cyclic siloxane compound represented by the general formula (1a) and the compound having 2 to 4 vinyl groups in one molecule is preferably performed using a catalyst. Platinum-based catalyst, palladium-based catalyst, rhodium-based catalyst, and the like. Examples of platinum-based catalysts include chloroplatinic acid, complexes of chloroplatinic acid and alcohols, aldehydes, ketones, platinum-olefin complexes, platinum-carbonylvinylmethyl complexes (Ossko catalysts), platinum-divinyltetramethyldisiloxane complexes. (KaRstedt catalyst), platinum-cyclovinylmethylsiloxane complex, platinum-octylaldehyde complex, platinum-phosphine complex (for example, Pt [P (C ₆ H ₅ ) ₃ ] ₄ , PtCl [P (C ₆ H ₅ ) ₃ ]) ₃ , Pt [P (C ₄ H ₉ ) ₃ ) ₄ ], platinum-phosphite 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. The amount of the catalyst used is preferably 5% by mass or less, more preferably 0.0001 to 1.0% by mass, and 0.001 to 0.1% by mass of the total amount of each raw material from the viewpoint of reactivity. Most preferred. 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.

  Contains a reaction product of the cyclic siloxane compound represented by the general formula (1a) and a compound having 2 to 4 vinyl groups in one molecule, and a carbon-carbon double bond having reactivity with SiH groups. The hydrosilylation reaction with the epoxy compound may be performed under the same conditions as the hydrosilylation reaction between the cyclic siloxane compound represented by the general formula (1a) and a compound having 2 to 4 vinyl groups in one molecule. After the hydrosilylation reaction, it is preferable to continue the reaction without isolating / purifying the reaction product.

  As an epoxy compound containing a carbon-carbon double bond having reactivity with the SiH group, 5,6-epoxyhexene, 7,8-epoxyoctene, allyl glycidyl ether, glycidyl methacrylate and the like can be used. 5) aliphatic epoxy group; if 3,4-epoxy-3-methylbutene or the like is used, the aliphatic epoxy group of the above formula (6); 1,2-epoxy-4-vinylcyclohexane, (3,4-epoxy If cyclohexyl) methyl methacrylate or the like is used, an alicyclic epoxy group of the above formula (7); if 1,2-epoxy limonene or the like is used, an alicyclic epoxy group of the above formula (8); 3-vinyl-5 , 6-epoxy-norpinane and the like, the alicyclic epoxy group of the above formula (9); and 4-epoxyethylstyrene and the like of the above formula (10) Aromatic epoxy group: aromatic epoxy group 4- (1-methyl-epoxy ethyl) Using the styrene above formula (11) can be introduced, respectively.

Next, the base resin of the present invention will be described. The base resin of the present invention is a polysiloxane compound having a carboxyl group and / or a phenolic hydroxyl group. In a positive photosensitive resin composition containing a photosensitive diazoquinone compound as a photosensitive component, the base resin is originally soluble in a developer, but in an unexposed portion, the photosensitive diazoquinone is insoluble or hardly soluble in the developer. While the compound inhibits dissolution of the base resin in the developer, in the exposed area, the photosensitive diazoquinone compound is decomposed by irradiation with ultraviolet rays, etc., so that the base resin can be dissolved in the developer. Utilizing it, a pattern is formed.
In a positive photosensitive resin composition based on a polysiloxane compound having a carboxyl group and / or a phenolic hydroxyl group, the alkali development is performed by the carboxyl group or the phenolic hydroxyl group of the polysiloxane compound having a carboxyl group and / or a phenolic hydroxyl group. However, the positive photosensitive resin composition of the present invention may increase the development margin by containing the epoxysilane compound of the present invention. it can.

  In the base resin of the present invention, if the content of the carboxyl group and the phenolic hydroxyl group is too small, the alkali developability is poor, and if it is too large, if the film reduction is large, the total amount is 0.1. It is preferably ˜5 mmol / g, more preferably 0.5 to 4 mmol / g, and most preferably 1 to 3 mmol / g.

  Further, when the molecular weight of the base resin of the present invention is too small, film loss is large, and when the molecular weight is too large, a resist residue on the substrate surface after alkali development is likely to be generated. It is preferably ˜20000, more preferably 2000-16000, and most preferably 4000-13000.

  The base resin of the present invention preferably contains a silanol group because the thermal crosslinkability of the positive photosensitive resin composition is improved and the mechanical strength and chemical resistance of the resulting cured product are improved. The content of silanol groups in the base resin of the present invention is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and 5 to 20% by mass as the OH content. Most preferred.

  As the base resin of the present invention, since the effect of improving the development margin by the additive of the present invention is great, a cyclic siloxane compound represented by the following general formula (19) and a siloxane represented by the following general formula (20) Hydrolysis condensates with compounds (see Patent Document 3 above) are particularly preferred.

（式中、Ｒ¹⁴は炭素数１〜４のアルキル基又は炭素数６〜１０のアリール基を表わし、Ｒ¹⁵は炭素数２〜１０の２価の炭化水素連結基を表わし、Ｒ¹⁶及びＲ¹⁷は同一でも異なっていてもよい炭素数２〜１０の２価の飽和脂肪族炭化水素基を表わし、Ｒ¹⁸及びＲ¹⁹は同一でも異なっていてもよい炭素数１〜４のアルキル基を表わす。ｋは１〜３の数を表わし、ｍは０〜５の数を表わし、ｎは０〜５の数を表わし、ｐは１〜５の数を表わす。但し、ｍ、ｎ及びｐは、ｍ＋ｎ＝１〜５、ｍ＋ｎ＋ｐ＝３〜６となる数である。）

Wherein R ¹⁴ represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, R ¹⁵ represents a divalent hydrocarbon linking group having 2 to 10 carbon atoms, R ¹⁶ and R ¹⁷ represents a divalent saturated aliphatic hydrocarbon group having 2 to 10 carbon atoms which may be the same or different, and R ¹⁸ and R ¹⁹ represent an alkyl group having 1 to 4 carbon atoms which may be the same or different. K represents a number of 1 to 3, m represents a number of 0 to 5, n represents a number of 0 to 5, and p represents a number of 1 to 5, provided that m, n and p are (m + n = 1 to 5 and m + n + p = 3 to 6)

（式中、Ｒ²⁰は炭素数６〜１０のアリール基を表わし、Ｒ²¹及びＲ²²は同一でも異なっていてもよい炭素数１〜４のアルキル基を表わし、ｑは２〜３の数を表わす。）

(In the formula, R ²⁰ represents an aryl group having 6 to 10 carbon atoms, R ²¹ and R ²² represent an alkyl group having 1 to 4 carbon atoms which may be the same or different, and q represents a number of 2 to 3). Represents.)

In the general formula (19), R ¹⁴ represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms include the groups exemplified in the description of R ^{1 in} the general formula (1). R ¹⁴ is preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl and phenyl, more preferably methyl and phenyl, and most preferably methyl from the viewpoint of heat resistance and industrial availability.

In the general formula (19), R ¹⁵ represents a divalent hydrocarbon linking group having 2 to 10 carbon atoms. Examples of the divalent hydrocarbon linking group having 2 to 10 carbon atoms include ethylene, propylene, 1-methylethylene, 2-methylethylene, tetramethylene, pentamethylene, 3-methylpentamethylene, hexamethylene, octamethylene, decamethylene, Examples include cyclohexane-1,4-diyl, 2-phenylethane-1,4′-diyl, 2-phenylpropane-1,4′-diyl and the like, and R ¹⁵ includes industrial availability and heat resistance. In view of the above, ethylene, 2-methylethylene and 2-phenylethane-1,4′-diyl are preferable, 2-methylethylene and 2-phenylethane-1,4′-diyl are more preferable, and 2-phenylethane- 1,4′-diyl is most preferred.

In the general formula (19), R ¹⁶ and R ¹⁷ represent a divalent saturated aliphatic hydrocarbon group having 2 to 10 carbon atoms which may be the same or different. 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 ¹⁶ and R ¹⁷ are preferably ethylene, 2-methylethylene and propylene, more preferably ethylene, from the viewpoint of industrial availability and heat resistance.

In the general formula (19), R ¹⁸ and R ¹⁹ represent the same or different 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, t-butyl and the like. R ¹⁸ and R ¹⁹ are preferably methyl and ethyl, and more preferably methyl, because the reactivity of the hydrolysis condensation reaction is good and the heat resistance of the base resin of the present invention is improved.

  In the said General formula (19), k represents the number of 1-3, m represents the number of 0-5, n represents the number of 0-5, p represents 1-5. However, m, n, and p are numbers which become m + n = 1-5 and m + n + p = 3-6. In view of the availability of industrial raw materials, m + n + p is preferably a number of 3 to 5, more preferably 3 to 4, and most preferably 4. The ratio of n to m is preferably 0.5 to 2, more preferably 0.8 to 1.1.8, since adhesion to the substrate is good, and 1.0 to 1 is preferable. .7 is most preferred.

In the general formula (20), R ²⁰ represents an aryl group having 6 to 10 carbon atoms. Examples of the aryl group having 6 to 10 carbon atoms include the aryl groups exemplified in the description of R ^{1 in} the general formula (1). R ²⁰ is preferably phenyl or toluyl, more preferably phenyl, from the viewpoint of heat resistance and industrial availability. R ²¹ and R ²² represent the same or different alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include the alkyl groups exemplified in the description of R ^{1 in} the general formula (1), and R ²¹ and R ²² have good reactivity of the hydrolysis condensation reaction. In view of improving the heat resistance of the base resin of the present invention, methyl and ethyl are preferable, and methyl is more preferable.

  When the molecular weight of the base resin of the present invention is too small, the film formability may be poor when the positive photosensitive resin composition of the present invention is applied to an object, and when the molecular weight is too large. Since the resist residue on the substrate surface after alkali development may increase, the mass average molecular weight is preferably 600 to 50000, more preferably 800 to 20000, and most preferably 1000 to 10000. preferable.

  In the base resin of the present invention, if the content of carboxyl group and phenolic hydroxyl group is too small, alkali developability becomes poor, and if too large, film loss during development becomes large. When the content is A (unit: mmol / g) and the phenolic hydroxyl group content is B (unit: mmol / g), the value of A + 0.1 × B is preferably 0.01 to 3 mmol / g. 0.05 to 2 mmol / g is more preferable, and 0.1 to 1.5 mmol / g is most preferable.

  The hydrolytic condensation reaction between the cyclic siloxane compound represented by the general formula (19) and the siloxane compound represented by the general formula (20) may be performed by a so-called sol-gel reaction. Examples of the reaction include a method of performing a hydrolytic condensation reaction in a solvent using a catalyst such as an acid or a base. The solvent used at this time is not particularly limited. Specifically, water, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, 1-methoxy-2-propanol Examples thereof include acetate, 1,2-dimethoxyethane, toluene and the like. One of these may be used, or two or more may be mixed and used. In the hydrolysis condensation reaction that is a reaction between alkoxylyl compounds, the alkoxysilyl group in the compound is hydrolyzed with water to form a silanol group (Si-OH group), and the generated silanol groups are or It proceeds by condensation of a silanol group and an alkoxysil group.

  In order to make this hydrolysis-condensation reaction proceed quickly, it is preferable to add an appropriate amount of water, and the catalyst may be dissolved in water. In addition, the hydrolysis and condensation reaction proceeds even with a small amount of water contained in air or in a solvent other than water. The catalyst such as acid and base used in this hydrolysis condensation reaction may be any catalyst that accelerates the hydrolysis condensation reaction. Specifically, inorganic acids such as hydrochloric acid, phosphoric acid, sulfuric acid; formic acid, acetic acid, Organic acids such as acid, citric acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, monoisopropyl phosphate; inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia; trimethylamine, triethylamine And amine compounds (organic bases) such as monoethanolamine and diethanolamine. One of these may be used, or two or more may be used in combination. The temperature of the hydrolysis condensation reaction varies depending on the type of solvent, the type and amount of the catalyst, etc., but is preferably 0 to 80 ° C, more preferably 5 to 50 ° C, and most preferably 8 to 30 ° 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 base resin of the present invention preferably contains a silanol group because chemical resistance, adhesion to a substrate, and the like are improved. The content of silanol groups in the base resin of the present invention is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and 5 to 20% by mass as the OH content. Most preferred. 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).

  Silanol groups tend to undergo condensation reactions, and the content of silanol groups may be reduced by handling. In particular, when the product is isolated after the hydrolysis condensation reaction, a dehydration condensation reaction between silanol groups is likely to occur. Therefore, when producing the base resin of the present invention, the hydrolysis condensation reaction is performed in a solvent. Without isolating the product, the solvent is preferably concentrated or substituted with another solvent as necessary, and blended with the positive photosensitive resin composition.

Next, the photosensitive diazoquinone compound which is a photosensitive component will be described.
The photosensitive diazoquinone compound that can be used in the present invention is not particularly limited as long as it is a diazoquinone compound that is known to be usable for a photosensitive material, but among them, it has good photosensitivity and can form a fine pattern. From the above, the hydrogen atom of the compound having a phenolic hydroxyl group is substituted with a compound (4-diazonaphthoquinonesulfonic acid ester) substituted with a group represented by the following formula (21) or a group represented by the following formula (22). The compound (5-diazonaphthoquinonesulfonic acid ester) is preferred.

  Preferable specific examples of such a photosensitive diazoquinone compound include, for example, compounds represented by the following formulas (23) to (28) and their positional isomers.

（上記式（２３）〜（２８）中、Ｑは上記式（２１）若しくは上記式（２２）で表される基又は水素原子である。但し、それぞれの式において、Ｑの全てが水素原子であることはない。）

(In the above formulas (23) to (28), Q is a group represented by the above formula (21) or the above formula (22) or a hydrogen atom. However, in each formula, all of Q are hydrogen atoms. There is never.)

  Since the group represented by the above formula (21) has absorption in the i-line (wavelength 365 nm) region, it is suitable for i-line exposure. Further, since the group represented by the above formula (22) has absorption in a wide range of wavelengths, it is suitable for exposure in a wide range of wavelengths. For this reason, it is preferable to select either the group represented by the above formula (21) or the group represented by the above formula (22) depending on the wavelength to be exposed.

  In the positive photosensitive resin composition of the present invention, the content of the photosensitive diazoquinone compound is 0.1 with respect to a total of 100 parts by mass of the content of the epoxysiloxane compound of the present invention and the base resin of the present invention. From the viewpoint of developability and fine workability of the permanent resist of the present invention, it is preferably from 10 to 10 parts by mass, and preferably from 1 to 5 parts by mass.

Next, the organic solvent will be described.
The organic solvent that can be used in the present invention is not particularly limited, and the epoxysiloxane compound of the present invention, the base resin of the present invention, the photosensitive diazoquinone compound, and an alkylsilane compound represented by the following general formula (3) described below and Any organic solvent can be used as long as it can dissolve or disperse the hydrolysis condensate with the arylsilane compound represented by the general formula (4). Such organic solvents include 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 Ether acetates of ether alcohols such as butyl acetate and 3-methoxy-3-methyl-1-butyl acetate; ketones such as acetone and methyl ethyl ketone; 4-hydroxy-2-butanone, 3-hydroxy-3methyl-2- Butanone, 4-hydroxy-2-methyl-2-pen Keto alcohols such as non (diacetone alcohol); Ethers such as 1,4-dioxane, tetrahydrofuran and 1,2-dimethoxyethane; Cyclic esters such as γ-butyrolactone, γ-valerolactone and δ-valerolactone; Examples thereof include carbonates such as ethylene carbonate, propylene carbonate, dimethyl carbonate, etc. Among these, since they have good solubility and moderate volatility, acetate esters of ether alcohol are preferable, and 1-methoxy- 2-propyl acetate, 3-methoxy-1-butyl acetate, and 3-methoxy-3-methyl-1-butyl acetate are more preferred, and 1-methoxy-2-propyl acetate is most preferred.

  In the positive photosensitive resin composition of the present invention, the content of the organic solvent is the content of the epoxy siloxane compound of the present invention and the base resin of the present invention in terms of handling properties and film-forming properties of the coating film. It is preferable that it is 10-10000 mass parts with respect to a total of 100 mass parts, especially 100-1000 mass parts.

  Since the positive photosensitive resin composition of the present invention can further increase the development margin, hydrolysis condensation of an alkylsilane compound represented by the following general formula (3) and an arylsilane compound represented by the following general formula (4) It is preferable to contain the thing (henceforth the hydrolysis-condensation product of this invention).

（Ｒ²は炭素数１〜４のアルキル基を表わし、Ｘ¹は炭素数１〜４のアルコキシ基又はハロゲン原子を表わす。）

(R ² represents an alkyl group having 1 to 4 carbon atoms, and X ¹ represents an alkoxy group having 1 to 4 carbon atoms or a halogen atom.)

（Ｒ³は炭素数６〜１０のアリール基を表わし、Ｘ²は炭素数１〜４のアルコキシ基又はハロゲン原子を表わす。）

(R ³ represents an aryl group having 6 to 10 carbon atoms, and X ² represents an alkoxy group having 1 to 4 carbon atoms or a halogen atom.)

In the above general formula (3), R ² 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, secondary butyl, isobutyl, t-butyl and the like, and R ² has a large development margin. Methyl, ethyl, propyl, isopropyl, butyl and isobutyl are preferred, methyl and ethyl are more preferred, and methyl is most preferred. X ¹ represents an alkoxy group having 1 to 4 carbon atoms or a halogen atom. Examples of the alkoxy group having 1 to 4 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy and the like, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. X ¹ is preferably methoxy, ethoxy and chlorine atoms, and more preferably methoxy and ethoxy because of good reactivity.

  Among the alkylsilane compounds represented by the general formula (3), preferred compounds are methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, and ethyltriethoxy. Silane, ethyltripropoxysilane, ethyltriisopropoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, isobutyltrimethoxysilane, isobutyltri Ethoxysilane, methyltrichlorosilane, ethyltrichlorosilane, propyltrichlorosilane, isopropyltrichlorosilane, butyltrichloro Silane, isobutyl trichlorosilane silane, and the like.

In the above general formula (4), R ³ represents an aryl group having 6 to 10 carbon atoms. The aryl group having 6 to 10 carbon atoms, e.g., phenyl, ethyl phenyl, toluyl, cumenyl, xylyl, Pusoidokumeniru, mesityl, t- butyl phenyl, benzyl, phenethyl, and examples of the R ^3, in terms of heat resistance Therefore, phenyl and toluyl are preferable, and phenyl is more preferable. X ² represents an alkoxy group having 1 to 4 carbon atoms or a chlorine atom. Examples of the alkoxy group having 1 to 4 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy and the like, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. X ² is preferably methoxy, ethoxy and a chlorine atom, more preferably methoxy, because of good reactivity.

  Among the arylsilane compounds represented by the general formula (4), preferred compounds include phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltriisopropoxysilane, toluyltrimethoxysilane, and toluyltriethoxy. Examples include silane, phenyltrichlorosilane, toluyltrichlorosilane, and the like.

  When the reaction ratio of the arylsilane compound represented by the general formula (4) to the alkylsilane compound represented by the general formula (3) in the hydrolysis condensate of the present invention is too small, the base resin of the present invention is used. In the case where the compatibility is reduced and the amount is too much, the mechanical properties (for example, crack resistance) of the resulting cured product may be adversely affected. Preferably, 0.2 to 4 is more preferable, and 0.4 to 2 is most preferable.

As long as the hydrolysis condensate of the present invention does not lower the function, a part of the alkylsilane compound represented by the general formula (3) or the arylsilane compound represented by the following general formula (4) may be converted to tetra. An alkoxysilane compound, a dialkoxysilane compound or a dihalosilane compound having a group represented by R ² (an alkyl group having 1 to 4 carbon atoms) and / or a group represented by R ³ (an aryl group having 6 to 10 carbon atoms), R You may make it react by replacing with the silanediol compound which has the group (C6-C10 aryl group) represented by ³ .
Examples of such compounds include tetraalkoxysilane compounds such as tetramethoxysilane and tetraethoxysilane;
Dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, dibutyldimethoxysilane, dibutyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, dimethyl Dialkoxysilane compounds or dihalosilane compounds having a group represented by R ² such as dichlorosilane, diethyldichlorosilane, dipropyldichlorosilane, dibutyldichlorosilane;
Dialkoxysilane compounds or dihalosilane compounds having a group represented by R ³ such as diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldichlorosilane, diphenyldichlorosilane;
Dialkoxy having a group represented by R ² and a group represented by R ³ such as methylphenyldimethoxysilane, methylphenyldiethoxysilane, ethylphenyldimethoxysilane, ethylphenyldiethoxysilane, methylphenyldichlorosilane, ethylphenyldichlorosilane A silane compound or a dihalosilane compound;
Examples thereof include silane diol compounds having a group represented by R ³ such as diphenyl silane diol and diphenyl silane diol.

  When the molecular weight of the hydrolyzed condensate of the present invention is too small, no effect of improving the development margin is observed, and when it is too large, the solubility in an alkali developer is lowered and the resist residue after alkali development is reduced. May increase, the weight average molecular weight is preferably 600 to 20,000, more preferably 800 to 10,000, and most preferably 1,000 to 5,000.

The hydrolysis condensation reaction between the alkylsilane compound represented by the general formula (3) and the arylsilane compound represented by the general formula (4) may be performed under the same conditions as in the base resin of the present invention. In the hydrolysis-condensation reaction, either an alkoxysilane compound or a halosilane compound may be used, and they may be used in combination. However, since the reaction control and removal of byproducts are prepared, it is a silane compound, and an alkyl trialkoxy silane having from 1 to 4 carbon atoms (compounds X ¹ in the general formula (3) is an alkoxy group having 1 to 4 carbon atoms), an alkoxy silane compound, a carbon number 6 To 10 aryltrialkoxysilane (a compound in which X ² in the general formula (4) is an alkoxy group having 1 to 4 carbon atoms) is preferable.

  Since the hydrolysis condensate of the present invention can increase the development margin of the positive photosensitive resin composition of the present invention, it preferably contains a silanol group, and the content of the silanol group in the hydrolysis condensate of the present invention is The OH content is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and most preferably 5 to 20% by mass.

  Silanol groups generated by hydrolysis of a compound having a trialkoxysilyl group or a trihalosilyl group are liable to undergo a condensation reaction, and the content of the silanol group may be reduced by handling. In particular, when the product is isolated after the hydrolysis condensation reaction, a dehydration condensation reaction between silanol groups tends to occur. Therefore, when producing the additive of the present invention, the hydrolysis condensation reaction is performed in a solvent. Without isolating the product, the solvent is preferably concentrated or substituted with another solvent as necessary, and blended with the positive photosensitive resin composition.

  In the positive photosensitive resin composition of the present invention, if the content of the hydrolysis condensate of the present invention is too small, the development margin is not improved, and if it is too large, a residue is generated during development. Since it becomes easy and the physical property of the obtained hardened | cured material falls, it is preferable that it is 5-100 mass parts with respect to 100 mass parts of base resins of this invention, and it is further 10-70 mass parts. Preferably, it is 15-50 mass parts.

  In addition to the positive photosensitive resin composition of the present invention, a plasticizer, a thixotropic agent, a photoacid generator, a thermal acid generator, a dispersant, an antifoaming agent, a pigment, a dye, etc. These optional components can be blended. The blending amount of these optional components is not particularly limited, but is preferably 5 parts by mass or less with respect to 100 parts by mass of the base resin of the present invention.

  Next, the permanent resist of the present invention will be described. The permanent resist of the present invention is produced using the positive photosensitive resin composition of the present invention. Hereinafter, the process of producing the permanent resist of this invention is demonstrated.

(1st process) Coating film formation process A coating film formation process is a process of performing a prebaking after apply | coating the prepared positive photosensitive resin composition of this invention on object material, and forming a coating film. The target material for forming the coating film should be a material having chemical resistance to an organic solvent or the like in the positive photosensitive resin composition, development with an alkaline solution in the fourth step, and heat resistance to processing in the sixth step. If it is not specifically limited, glass, a metal, a semiconductor, etc. can be made into a target material. 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 application methods such as a spin coating method, a dip coating method, a knife coating method, a roll coating method, a spray coating method, and a slit coating method can be used.

  Pre-baking is performed in order to remove the organic solvent from the positive photosensitive resin composition layer applied on the target material. The pre-baked positive-type photosensitive resin composition layer is hardly soluble in an alkaline solution, and is irradiated with light in the exposure step of the second step, so that the portion irradiated with light (hereinafter sometimes referred to as an exposed portion). Is) soluble in alkali. 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 performed as it is after the positive photosensitive resin composition of the present invention is applied to the target material, but the physical properties and chemical resistance after the high heat history of the permanent resist of the present invention are improved. Therefore, before pre-baking, the organic solvent is volatilized so that the concentration of the organic solvent in the positive photosensitive resin composition layer is 5% by mass or less at room temperature to less than 60 ° C. under normal pressure or reduced pressure. After that, it is preferable to perform pre-baking. The thickness of the positive photosensitive resin composition layer after pre-baking varies depending on the application in which the permanent resist of the present invention is used, and is not particularly limited, but is 0.1 μm to 100 μm, preferably 0.3 μm to 10 μm. good.

(2nd process) Exposure process An exposure process is a process of irradiating patterned light with respect to the pre-baked positive photosensitive resin composition layer, and improving the alkali solubility of an exposed part. The pre-baked positive photosensitive resin composition layer is hardly soluble in an alkaline solution, but the photosensitive diazoquinone compound in the exposed portion is decomposed by light irradiation, and is converted into an indenecarboxylic acid compound, thereby forming an alkaline solution. Dissolution / dispersion is possible. The irradiation light is not particularly limited as long as it is light having an energy amount capable of improving the alkali solubility of the light irradiation portion of the pre-baked positive photosensitive resin composition layer. to 1000 mJ / cm ^2, especially in the range 40~300mJ / cm ² in the range of light is preferred. 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 the photosensitive diazoquinone compound, the wavelength is narrow mainly composed of i-line (365 nm). 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.

(Third step) Development step The development step is an exposure step in the second step, and a portion (exposed portion) whose alkali solubility has been improved by irradiation with light is removed using a developer to form a predetermined pattern. It is a process of forming. The exposed portion is preferably removed with a developer and then rinsed with running water or water with a shower. If necessary, the exposed portion may be dehydrated and dried in the range of 50 to 120 ° C.
As the 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 optimum development time varies depending on the type and molecular weight of the polysiloxane compound having a carboxyl group and / or a phenolic hydroxyl group as the base resin, the temperature of the developer, and the like, but is usually 30 to 180 seconds. Conventionally, a positive photosensitive resin composition containing a polysiloxane compound having a carboxyl group and / or a phenolic hydroxyl group as a base resin, a photosensitive diazoquinone compound as a photosensitive component, and an organic solvent has a small development margin in the development process. However, the inclusion of the additive of the present invention increases the development margin, and even if the development time is slightly longer than the optimal development time, the developer solution between the pattern and the substrate Peeling due to permeation hardly occurs, and the yield of products can be improved.

  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 alkaline aqueous 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 resin 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.

(Fourth Step) Bleaching Exposure Step The bleaching exposure step is to irradiate the entire positive photosensitive resin composition layer (hereinafter also referred to as resist layer) remaining in the alkaline solution treatment in the development step of the third step. This is a step of improving visible light transmittance by irradiation (bleaching exposure). Since the resist layer contains a photosensitive diazoquinone compound, the resist layer is colored light yellow to light brown. When the resist layer is irradiated with light, the remaining unreacted photosensitive diazoquinone compound is photodegraded and changed to an indenecarboxylic acid compound having no absorption in the visible light region, so that the visible light transmittance is improved. This is particularly preferable when the permanent resist is used as a permanent resist for an active matrix substrate used in a liquid crystal display device, an organic EL display device or the like. Irradiation light in the bleaching exposure step is not particularly limited, and for example, light having an energy amount in the range of 10 to 1000 mJ / cm ² , preferably in the range of 40 to 600 mJ / cm ² suffices. The wavelength of the irradiation light may be visible light or ultraviolet light, and is not particularly limited, but the wavelength of the irradiation light should be selected according to the type of the photosensitive diazoquinone compound used as in the second exposure step. Is preferred.

(5th process) Post-baking process In the 4th process, although the bleaching exposure resist layer improves visible light permeability, it improves 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. And a process for imparting aging resistance to the permanent resist of the present invention. The post-bake is preferably performed in an inert gas atmosphere such as nitrogen, helium, or argon at a temperature of 120 to 400 ° C. for 15 minutes to 2 hours, and at a temperature of 200 to 350 ° C. for 15 minutes to 2 hours. More preferably, it is performed.

In the coating film forming process, which is the first process, the positive photosensitive resin composition of the present invention may be used by directly coating on a target material such as a semiconductor substrate, but it may be coated on a support film. A coating film may be formed and used as a dry film resist. The dry film resist is produced by pre-baking after forming a coating film to remove the solvent in the coating film, and laminating a protective film on the coating film surface. When using the dry film resist obtained from the positive photosensitive resin composition of the present invention, after peeling off the protective film from the dry film resist, the dry film resist is bonded to the target material by thermocompression bonding. After the support film is peeled off as necessary, exposure, development, bleaching exposure, and post-baking may be performed under the above conditions.
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.

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

  In addition, the permanent resist obtained from the positive photosensitive resin composition of the present invention includes an interlayer insulating film of a semiconductor element and a wafer coating material (surface protective film, bump protective film, MCM (multi-chip module) layer of a semiconductor element. It can also be used for protective films, junction coatings) and package materials (sealing materials, die bonding materials).

  Furthermore, the permanent resist obtained from the positive photosensitive resin 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 below with reference to examples and comparative examples, but the present invention is not limited to these. The content of silanol groups was determined by reacting the sample with trimethylchlorosilane in a pyridine solution to change the silanol groups to trimethylsilyl ether groups, and then treating with a tetramethylammonium hydroxide ((CH ₃ ) ₄ NOH) aqueous solution. It was determined by hydrolyzing the —O—Si bond and calculating backward from the rate of weight increase after the reaction. Unless otherwise specified, “%” is a mass unit.

[Production Example 1: Production of Epoxysilane Compound A-1 of the Present Invention]
In a glass reaction vessel equipped with a thermometer and a stirrer, 250 g of toluene and 144 g (0.6 mol) of 2,4,6,8-tetramethylcyclotetrasiloxane as a cyclic siloxane compound represented by the above general formula (1a) 52 g (0.4 mol) of 1,4-divinylbenzene as a compound having 2 to 4 vinyl groups in one molecule, and allyl as a compound containing a carbon-carbon double bond having reactivity with SiH group 194 g (1.7 mol) of glycidyl ether 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 A-1 of the present invention which is a siloxane compound having a glycidyl ether group. The obtained epoxy silane compound A-1 of the present invention corresponds to the general formula (1) in which R ¹ is methyl, E is a group having an epoxy group of the above formula (5), and a is a number of 3. A compound having 2 to 4 vinyl groups in one molecule is 1,4-divinylbenzene (a compound in which h in the general formula (16) is a number of 1). Moreover, the mass mean molecular weight by the GPC analysis of the epoxy silane compound A-1 of this invention was 1500, and the analytical value of the epoxy equivalent was 244.

[Production Example 2: Production of Epoxysilane Compound A-2 of the Present Invention]
In a glass reaction vessel equipped with a thermometer and a stirrer, 250 g of toluene and 240 g (1.0 mol) of 2,4,6,8-tetramethylcyclotetrasiloxane as a cyclic siloxane compound represented by the above general formula (1a) As a compound having 2 to 4 vinyl groups in one molecule, 24.9 g (0.1 mol) of 1,3,5-triallyl isocyanurate and 9 mg of a platinum-divinyltetramethyldisiloxane complex (Karstedt catalyst) In addition, the reaction was carried out at 50-60 ° C. for 5 hours with stirring. After the solvent and unreacted 2,4,6,8-tetramethylcyclotetrasiloxane were distilled off from this reaction solution under reduced pressure at 100 ° C., a carbon-carbon double having reactivity between 250 g of toluene and SiH group. 114 g (1.0 mol) of allyl glycidyl ether was added as a compound containing a bond, and the mixture was reacted at 50 to 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 A-2 of the present invention which is a siloxane compound having a glycidyl ether group. The obtained epoxy silane compound A-2 of the present invention corresponds to the general formula (1) in which R ¹ is methyl, E is a group having an epoxy group of the above formula (5), and a is a number of 3. The compound having 2 to 4 vinyl groups in one molecule is 1,3,5-triallyl isocyanurate (a compound in which R ¹³ in the general formula (18) is allyl). Moreover, the mass mean molecular weight by GPC analysis of the epoxy silane compound A-2 of this invention was 2400, and the analytical value of epoxy equivalent was 267.

[Production Example 3: Production of base resin B-1 of the present invention]
A base resin B-1 of the present invention was produced according to the production examples of the silicone resin (a) described in paragraphs [0152] to [0155] of Patent Document 3 above. That is, in a glass reaction vessel equipped with a thermometer and a stirrer, 300 g of toluene, 120 g (0.5 mol) of 2,4,6,8-tetramethylcyclotetrasiloxane, 4-vinylbenzoic acid-t-butyl ester 102 g (0.5 mol), 132 g (0.75 mol) of 4-t-butoxystyrene, 111 g (0.75 mol) of trimethoxyvinylsilane, and 1 mg of platinum-divinyltetramethyldisiloxane complex (Karstedt catalyst) were added. After stirring for 15 hours at 60 ° C. with stirring, the solvent was distilled off under reduced pressure at 60 ° C., and the carboxyl group and phenyl hydroxyl group of the cyclic siloxane compound represented by the general formula (19) were masked with a t-butyl group. The intermediate b-1 which is a compound was obtained. The mass average molecular weight of the intermediate b-1 by GPC analysis is 900 (theoretical molecular weight 933.1).

  To 90 g (0.1 mol) of the intermediate b-1, 91 g (0.46 mol) of phenyltrimethoxysilane and 200 g of toluene are added as a siloxane compound represented by the general formula (20). While stirring with ice cooling, 50 g of a 5% oxalic acid aqueous solution as an organic acid catalyst was added dropwise over 1 hour, and stirring was further continued at 10 ° C. for 15 hours. After washing with 100 g of water twice, reflux dehydration and dealcoholization treatment at 50 ° C. under reduced pressure, and solvent exchange into 1-methoxy-2-propanol acetate (hereinafter referred to as PGMEA) under reduced pressure at 50 ° C. And a 25% PGMEA solution of intermediate b-2 was obtained.

In order to remove the t-butyl group, 3 g of boron trifluoride diethyl ether complex was added to 400 g of 25% PGMEA solution of the intermediate b-2, and the mixture was stirred at 80 ° C. for 3 hours and then 100 g under reduced pressure. The solid solution was removed by filtration with respect to the slurry solution stirred for 10 hours at 80 ° C. after adding 10 g of an acidic substance adsorbent (trade name: Kyoward 500SH, manufactured by Kyowa Chemical Industry Co., Ltd.) A 30% PGMEA solution of the base resin B-1 of the present invention, which is a hydrolysis condensate of the cyclic siloxane compound represented by the general formula (19) and the siloxane compound represented by the general formula (20), was obtained. In the obtained base resin B-1 of the present invention, the groups in the general formula (19) are R ¹⁴ : methyl, R ¹⁵ : ethylene, R ¹⁶ : ethylene, R ¹⁷ : ethylene, R ¹⁸ : methyl, m 1: n: 1.5, p: 1.5, k: 3, and the groups in the general formula (20) are R ²⁰ : phenyl, R ²¹ : methyl, q: 3, respectively. It is a certain compound. Moreover, the mass average molecular weight by GPC analysis of the base resin B-1 of this invention is 6900, the content of a silanol group is 5.4% as a content of OH, and a carboxyl group (A) and / or a phenolic hydroxyl group ( The content of B) (A + 0.1 × B) was 1.17 mmol / g.

[Production Example 4: Production of hydrolysis condensate C-1 of the present invention]
In a glass reaction vessel equipped with a thermometer and a stirrer, 178 g (1 mol) of methyltriethoxysilane as an alkylsilane compound represented by the above general formula (3), an arylsilane compound represented by the above general formula (4) As a solution, 198 g (1 mol) of phenyltrimethoxysilane, 100 g of 1-methoxy-2-propanol acetate (hereinafter referred to as PGMEA) as a solvent, and 100 g of 5% oxalic acid aqueous solution as an organic acid catalyst for 1 hour while cooling with ice The mixture was added dropwise, and the mixture was further stirred at 10 ° C. for 10 hours. To the reaction vessel, 250 g of toluene was added, dehydrated at 60 ° C. under reduced pressure, and further concentrated under reduced pressure to remove the alcohol and toluene produced by the reaction, filtered, and the hydrolysis condensate C-1 of the present invention. Of 30 mass% PGMEA solution was obtained. The obtained hydrolysis condensate C-1 of the present invention had a mass average molecular weight of 2,000 by GPC analysis and a silanol group content of 7.8%.

[Production Example 5: Production of hydrolysis condensate C-2 of the present invention]
In Production Example 3, 250 g (1.3 mol) of ethyltriethoxysilane was used instead of 178 g (1 mol) of methyltriethoxysilane, and the amount of phenyltrimethoxysilane was changed from 198 g (1 mol) to 125 g (0.7 mol). Except for changing to (mol), the same operation as in Production Example 1 was performed to obtain a 30% by mass PGMEA solution of the hydrolysis-condensation product C-2 of the present invention. The obtained hydrolysis condensate C-2 of the present invention had a mass average molecular weight of 1900 by GPC analysis and a silanol group content of 7.5% as an OH content.

[Production Example 6: Production of comparative epoxysiloxane compound D-1]
In accordance with the production example of the siloxane compound (j) having a glycidyl ether group described in paragraph [0164] of Patent Document 3, a comparative epoxysiloxane compound D-1 was produced. That is, in a glass reaction vessel equipped with a thermometer and a stirrer, 150 g of toluene, 60 g (0.25 mol) of 2,4,6,8-tetramethylcyclotetrasiloxane, 114 g of allyl glycidyl ether (1 mol), and 0.5 mg of platinum-divinyltetramethyldisiloxane complex (Karstedt catalyst) was 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 a comparative epoxysiloxane compound D-1 which is a siloxane compound having a glycidyl ether group.

[Examples 1 to 6 and Comparative Examples 1 to 3: Preparation and Evaluation of Positive Photosensitive Resin Compositions for Comparison with the Present Invention]
As the epoxy silane compound of the present invention obtained in the above production example, the comparative epoxy silane compound, the PGMEA solution of the base resin of the present invention, the PGMEA solution of the hydrolysis condensate of the present invention, and the photosensitive component, The positive diazoquinone compounds (diazonaphthoquinones (DNQ)) were blended in the proportions shown in Table 1 and filtered to prepare positive photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 to 3. In addition, PGMEA of the organic solvent was added so that it might become the value in a table | surface.
Diazonaphthoquinones (DNQ): a compound in which all Qs are groups represented by the above formula (22) in the above formula (23) (trade name: PA-6, manufactured by Daito Chemix)

The following evaluation was performed about the positive photosensitive resin composition of Examples 1-6 and Comparative Examples 1-3.
The results are shown in Table 2.

[Method for preparing test piece]
The positive photosensitive resin composition was applied on a glass substrate by spin coating so that the film thickness of the coating film became 2 to 3 μm, and then the solvent was evaporated to obtain a test piece.
In each patterning exposure, the test piece was heat-treated at 90 ° C. for 2 minutes, a photomask with a line width of 5 μm was placed on the glass substrate, and 90 mJ / cm ² (wavelength 365 nm) was measured with an ultrahigh pressure mercury lamp. (Exposure conversion).

[Evaluation of optimum development time and development margin]
The development time was changed every 30 seconds from 30 seconds, and the optimum development time and development margin were evaluated. That is, for each positive photosensitive resin 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. Then, 30 seconds after the start of immersion, it 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 time required for the line width to become 5 μm was the optimum development time, and the time from the optimum development time until the 5 μm line pattern was peeled was taken as the development margin.

[Alkali resistance test]
After air-drying the test piece developed with the optimum development time, the sample was irradiated with 200 mJ / cm ² (converted to a wavelength of 365 nm exposure) with an ultra-high pressure mercury lamp as bleaching exposure, and then heat-treated at 230 ° C. for 60 minutes in an air atmosphere. Alternatively, heat treatment was performed at 350 ° C. for 30 minutes in a nitrogen atmosphere to form a permanent resist film. Light transmittance of 400 nm wavelength and stylus type before and after being immersed in an alkali solution (monoethanolamine: N-methyl-2-pyrrolidone: butyl diglycol = 10: 30: 60 mass ratio) at 40 ° C. for 30 minutes The film thickness of the resist was measured using a surface shape measuring instrument, and the alkali resistance was evaluated based on the following criteria from the change rate of the light transmittance and the change rate of the film thickness.

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

  As is clear from the above results, in the positive photosensitive resin composition containing a polysiloxane compound having a carboxyl group and / or a phenolic hydroxyl group as a base resin and a photosensitive diazoquinone compound as a photosensitive component, development in the development step is performed. There was a problem that the margin is small, but by including the epoxysilane compound of the present invention, the development margin becomes large, and even if the development time exceeds the optimal development time, the developer is still between the pattern and the substrate. It was confirmed that peeling due to permeation hardly occurred and a good pattern shape could be formed.

Claims (3)

In a positive photosensitive resin composition containing a polysiloxane compound having a carboxyl group and / or a phenolic hydroxyl group as a base resin, a photosensitive diazoquinone compound as a photosensitive component, and an organic solvent,
The groups represented by the following general formula (1), or the group represented by the following general formula (1) and the group represented by the following general formula (2) have 2 to 4 vinyl groups in one molecule. A positive photosensitive material characterized by containing an epoxysiloxane compound (excluding a polysiloxane compound having a carboxyl group and / or a phenolic hydroxyl group) linked by a residue obtained by removing a vinyl group from a compound having Resin composition.

(Wherein the alkyl group or phenyl R ¹ is from 1 to 4 carbon atoms which may be the same or different, ethylphenyl, tolyl, cumenyl, xylyl, Pusoidokumeniru, mesityl, t- butyl phenyl, also either phenethyl E represents a group having an epoxy group, and a represents a number of 2 to 5.)

(In the formula, b represents a number of 2 to 6 in which ab + 1 is a number of 0 to 4, and R ¹ , E and a have the same meaning as in the general formula (1).) The positive photosensitive resin composition according to claim 1, further comprising a hydrolysis condensate of an alkylsilane compound represented by the following general formula (3) and an arylsilane compound represented by the following general formula (4).

(R ² represents an alkyl group having 1 to 4 carbon atoms, and X ¹ represents an alkoxy group having 1 to 4 carbon atoms or a halogen atom.)

(R ³ represents any of phenyl, ethylphenyl, toluyl, cumenyl, xylyl, pseudocumenyl, mesityl, t-butylphenyl, benzyl or phenethyl, and X ² represents an alkoxy group having 1 to 4 carbon atoms or a halogen atom. ) A permanent resist obtained from the positive photosensitive resin composition according to claim 1.