KR20120056773A - Positive photosensitive resin composition and permanent resist - Google Patents

Abstract

PURPOSE: A positive type photo-sensitive resin composition and a permanent resist obtained from the same are provided to improve pattern shapes although an optimal developing time for a developing process is passed. CONSTITUTION: A positive type photo-sensitive resin composition includes a polysiloxane compound with a carboxylic group and/or phenolic hydroxide group as a base resin, a photo-sensitive diazoquinone compound as a photo-sensitive component, and an organic solvent. The composition includes an epoxy siloxane compound in which groups represented by chemical formula 1 or a group represented by chemical formula 1 and a group represented by chemical formula 2 are connected by a residual group of a compound with 2 to 4 vinyl groups in one molecule except for vinyl groups. In chemical formula 1, R1 is identical or different and is a C1 to C4 alkyl group or a C6 to C10 aryl group; E is a group with an epoxy group; and a is 2 to 5. In chemical formula 2, b is 2 to 6 to satisfy inequality, 0<a-b+1<4; and R1 and E are the same as R1 and E of chemical formula 1.

Description

Positive photosensitive resin composition and permanent resist {POSITIVE PHOTOSENSITIVE RESIN COMPOSITION AND PERMANENT RESIST}

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.

BACKGROUND ART Electronic components such as thin film transistors (hereinafter referred to as 'TFT') type liquid crystal display elements, magnetic head elements, integrated circuit elements, and solid-state imaging elements are generally provided with an interlayer insulating film for insulating between wirings arranged in layers. As a material which forms an interlayer insulation film, since the number of processes for obtaining the required pattern shape is small, and it is preferable to have sufficient flatness, the radiation sensitive resin composition is used widely (refer patent document 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 a liquid crystal alignment film thereon, so that the interlayer insulating film is subjected to a high temperature condition in the process of forming the transparent electrode film. To be exposed to or exposed to the stripping liquid of the resist used for pattern formation of the electrode, sufficient resistance to these is required. Moreover, depending on a manufacturing process, the formed interlayer insulation film may be exposed to dry etching, and sufficient tolerance to dry etching is needed (refer patent document 2).

In recent years, TFT-type liquid crystal display devices tend to have large screens, high brightness, high definition, high-speed response, and thinning, and as a composition for forming an interlayer insulating film used therein, they have high sensitivity. Further high performance is required in the case of high transmittance and the like. As an interlayer insulating film material having excellent insulation, heat resistance, solvent resistance, dry etching resistance, and the like, and capable of forming a fine pattern, a positive photosensitive composition containing a polysiloxane compound having a carboxyl group and a photosensitive diazoquinone compound (see Patent Document 3) has been developed. Although the composition containing the cyclic siloxane compound containing an epoxy group is also known, since the image development margin (width of the time for which development time becomes optimal) is small in the image development process, when the image development time becomes a little excess, between the formed pattern and a board | substrate, Since the developing solution penetrates easily and peels easily, it is necessary to strictly control the developing time, which has a problem in terms of product yield.

On the other hand, although the compound to which the cyclic siloxane compound which has an epoxy group was connected is known (refer patent document 4), the positive photosensitive resin composition containing such a compound is not known.

JP 2001-354822 A Japanese Laid-Open Patent Publication 2005-345757 Japanese Patent Laid-Open No. 2010-101957 Japanese Patent Publication No. 2001-513117

An object of the present invention is to be suitable for the formation of an interlayer insulating film having high heat resistance, high solvent resistance, high transmittance and low dielectric constant, and having a large development margin, which can still form a good pattern shape even after exceeding the optimum development time in the development process. It is providing a positive photosensitive resin composition.

MEANS TO SOLVE THE PROBLEM This inventor reached | attained this invention as a result of earnestly researching in view of said point.

That is, this invention is a positive photosensitive resin composition containing the polysiloxane compound which has a carboxyl group and / or phenolic hydroxyl group as a base resin, the photosensitive diazoquinone compound, and an organic solvent as a photosensitive component, and is represented by following General formula (1) The groups represented by, or the group represented by the following general formula (1) and the group represented by the following general formula (2) contain an epoxysiloxane compound connected by a residue except the vinyl group in a compound having 2 to 4 vinyl groups in one molecule It is providing the positive photosensitive resin composition characterized by the above-mentioned.

(In formula, R <^1> represents a C1-C4 alkyl group or C6-C10 aryl group which may be same or different, E represents the group which has an epoxy group, and a shows the number of 2-5.)

(In formula, b represents the number of 2-6 which a-b + 1 becomes the number of 0-4, and R <^1> , E and a have the same meaning as the said General formula (1).)

The effects of the present invention are suitable for the formation of an interlayer insulating film of high heat resistance, high solvent resistance, high transmittance and low dielectric constant, and have a large development margin, which can still form a good pattern shape even after exceeding the optimum development time in the development process. It is what provided the positive photosensitive resin composition.

EMBODIMENT OF THE INVENTION Hereinafter, the positive photosensitive resin composition and permanent resist of this invention are demonstrated in detail based on preferable embodiment.

The present invention is directed to a positive photosensitive resin composition containing a polysiloxane compound having a carboxyl group and / or phenolic hydroxyl group as a base resin (hereinafter also referred to as the base resin of the present invention), a photosensitive diazoquinone compound as a photosensitive component, and an organic solvent. , Except that the groups represented by the general formula (1) or the group represented by the general formula (1) and the group represented by the general formula (2) have 2 to 4 vinyl groups in one molecule, except the vinyl group It is characterized by containing the epoxysiloxane compound (henceforth an epoxysiloxane compound of this invention) connected by the residue. First, the epoxysiloxane compound of this invention is demonstrated.

In said general formula (1), R <^1> represents a C1-C4 alkyl group or C6-C10 aryl group which may be same or different. 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. As R ¹ , methyl, ethyl and phenyl are preferable in terms of improving heat resistance, methyl and phenyl are more preferable, and methyl is most preferred.

In the said General formula (1), E represents the group which has an epoxy group. As group which has an epoxy group, aliphatic epoxy groups, such as following formula (5) or (6), alicyclic epoxy groups, such as following formula (7)-(9), aromatic epoxy groups, such as following formula (10) or (11), etc. are mentioned. In view of the storage stability of the positive photosensitive resin composition of the present invention, the aliphatic epoxy group of the following formula (5) or (6) is preferably a partial structure, and 1,2-epoxypropyl of the following formula (5) Group is more preferable, Especially, the group which has glycidyl ether group is further more preferable, and 3-glycidoxy propyl group is the most preferable.

In the general formula (1), a represents a number of 2 to 5, and in view of availability of industrial raw materials, a is preferably 2 to 4, more preferably 2 to 3, and most preferably 3 desirable.

In the said General formula (2), b represents the number of 2-6 which a-b + 1 becomes the number of 0-4, R <^1> , E and a have the same meaning as the said General formula (1).

In the epoxysiloxane compound of this invention, the number of vinyl groups of the compound which has 2-4 vinyl groups in said 1 molecule is preferable from the point which the resist residue to a board | substrate after alkali image development hardly remains. As said compound which has 2-4 vinyl groups in said 1 molecule, the compound represented by following General formula (12)-(18) is mentioned, In the point of heat resistance, it is represented by following General formula (12)-(14). A compound is preferable, and the compound represented by following General formula (16) is preferable at the point of industrial availability.

(In formula, R <^4> -R <^6> represents a C1-C4 alkyl group or C6-C10 aryl group which may be same or different, c shows the number of 1-3, d and e are each independently 0? Indicates the number of 6.)

(In formula, R <^7> -R <^9> represents a C1-C4 alkyl group or C6-C10 aryl group which may be same or different, and f shows the number of 0-10.)

(In formula, R <^10> represents a C1-C4 alkyl group or C6-C10 aryl group which may be same or different, and g shows the number of 3-4.)

(In formula, R <^11> and R <^12> represents a C1-C4 alkyl group or C6-C10 aryl group which may be same or different. "

(Wherein h represents a number of 1 to 2.)

(Wherein j represents a number of 1 to 3).

(In formula, R <^13> represents a C1-C4 alkyl group, a C6-C10 aryl group, glycidyl group, or allyl group.)

The compound represented by the said General formula (12) is a compound which has 2-4 vinyl groups in 1 molecule. In the said General formula (12), R <^4> -R <^6> represents a C1-C4 alkyl group or C6-C10 aryl group which may be 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). As R ^{4 to} R ⁶ , methyl and ethyl have good heat resistance. , 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 represent a number of 0 to 6;

As a preferable compound among the compound represented by the said General formula (12) whose c is a number of 1, 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 can be given. , Dimethyldivinylsilane, diethyldivinylsilane and diphenyldivinylsilane are preferable, and 1,1,3,3-tetramethyl-1,3-divinyldisiloxane is more preferable. As a preferable compound among the compound represented by the said General formula (12) whose c is a number of 2, methyl trivinyl silane, ethyl trivinyl silane, phenyl trivinyl silane, 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, etc. are mentioned. As a preferable compound among the compound represented by the said General formula (12) whose number is 3, tetravinyl silane, tetrakis (dimethylvinyl siloxy) silane, etc. are mentioned.

The compound represented by the said General formula (13) is a compound which has four vinyl groups in 1 molecule. In said general formula (13), R <^7> -R <^9> represents a C1-C4 alkyl group or C6-C10 aryl group which may be same or different. C 1? 4 alkyl group and a C 6? 10 aryl groups as can be exemplified by a group such as exemplified in the explanation of R ¹ in the formula ^{(1), R 7? R} 9 as methyl, ethyl, the preferred heat resistant point , Propyl and phenyl are preferred, methyl, ethyl and phenyl are more preferred, and methyl is most preferred. f represents the number of 0-10. Preferred compounds among the compounds represented by the general formula (13) include 1,3-dimethyl-1,1,3,3-tetravinyldisiloxane, 1,3,3,5-tetramethyl-1,1,5, 5-tetravinyltrisiloxane, 1,5-dimethyl-3,3-diphenyl-1,1,5,5-tetravinyltrisiloxane, etc. are mentioned.

The compound represented by the said General formula (14) is a compound which has 3-4 vinyl groups in 1 molecule. In the said General formula (14), R <^10> represents a C1-C4 alkyl group or C6-C10 aryl group which may be 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 General Formula (1), and R ¹⁰ is methyl, ethyl, propyl, Phenyl is preferred, methyl, ethyl and phenyl are more preferred, and methyl is most preferred. g represents the number of 3-4, and since g is easy to obtain industrially, the number of 4 is preferable. As a preferable compound in the compound represented by the said General formula (14) whose g is the number of 3, 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-2,4,6-trivinylcyclo Trisiloxane etc. are mentioned. As a preferable compound among the compound represented by the said General formula (14) whose g is the number of 4, 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotrisiloxane, 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, etc. are mentioned. .

The compound represented by the said General formula (15) is a compound which has two vinyl groups in 1 molecule. In the said General formula (15), R <^11> and R <^12> represents a C1-C4 alkyl group or C6-C10 aryl group which may be 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 ¹¹ and R ¹² are methyl and ethyl in terms of good heat resistance. , 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 (diethyl vinyl silyl) benzene, etc. are mentioned, 1,2-bis (dimethyl vinyl silyl) benzene and 1, 4-bis (dimethyl vinyl silyl) benzene are preferable, and 1, 4-bis More preferred is (dimethylvinylsilyl) benzene.

The compound represented by the said General formula (16) is a compound which has 2-3 vinyl groups in 1 molecule. In the formula (16), h represents a number of 1-2. As a compound represented by the said General formula (16) whose h is a number, 1, 2- divinylbenzene, 1, 3- divinylbenzene, and 1, 4- divinylbenzene are mentioned. 1,2,4-trivinylbenzene and 1,3,5-trivinylbenzene are mentioned as a compound represented by the said General formula (16) whose h is a number of 2.

The compound represented by the said General formula (17) is a compound which has 2-4 vinyl groups in 1 molecule. In the general formula (17), j represents a number of 1 to 3. As a compound represented by the said General formula (17) whose j is a number, 1, 2- divinyl cyclohexane, 1, 3- divinyl cyclohexane, and 1, 4- divinyl cyclohexane are mentioned. 1,2,4-trivinylcyclohexane and 1,3,5-trivinylcyclohexane are mentioned as a compound represented by the said General formula (17) whose h is a number of 2. 1,2,4,5-tetravinylcyclohexane is mentioned as a compound represented by the said General formula (17) whose h is a number of 3.

The compound represented by the said General formula (18) is a compound which has 2-3 vinyl groups in 1 molecule. R <^13> in the said General formula (18) represents a C1-C4 alkyl group, a C6-C10 aryl group, glycidyl group, or allyl group. As R ¹³ , methyl, ethyl, glycidyl and allyl are preferable in terms of heat resistance. Preferred compounds among the compounds represented by the general formula (18) include 1,3-diallyl-5-methylisocyanurate, 1,3-diallyl-5-ethylisocyanurate and 1,3-diallyl -5-glycidyl isocyanurate, 1,3,5-triallyl isocyanurate, etc. are mentioned.

When the ratio of the epoxy group in the epoxysiloxane compound of this invention is too small, since the mechanical property of the hardened | cured material obtained falls, it is preferable that it is 1000 or less in epoxy equivalent, It is more preferable that it is 700 or less, It is most preferable that it is 350 or less. On the other hand, an epoxy equivalent means the molecular weight divided by the number of epoxy groups, ie, the molecular weight per epoxy group.

When the molecular weight of the epoxysiloxane compound of this invention is too small, the improvement effect of image development margin is small, and when too large, since the resist residue may remain on a board | substrate after alkali image development, it is preferable that it is 1000-10000 by mass average molecular weight. It is more preferable that it is 1500-7000, and it is most preferable that it is 2000-5000. In the present invention, the mass average molecular weight refers to the polystyrene reduced mass average molecular weight 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 improvement effect of the development margin is small, and when too large, the alkali developability and the physical properties of the resist are adversely affected. Since a resist residue may remain on a board | substrate after image development, 1-30 mass parts is preferable with respect to 100 mass parts of base resin of this invention, 2-25 mass parts is more preferable, and 3-20 mass parts ê €€ is the most preferable.

The epoxysiloxane compound of the present invention is subjected to hydrosilylation reaction of a vinyl group of a compound having 2 to 4 vinyl groups in one molecule to the SiH group of the cyclic siloxane compound represented by the following general formula (1a), and further reactivity with the SiH group. The branch can be obtained by hydrosilylation of an epoxy compound containing a carbon-carbon double bond.

(In formula, R <^1> and a are the same meaning as the said General formula (1).)

It is preferable to perform the hydrosilylation reaction of the cyclic siloxane compound represented by the said General formula (1a) with the compound which has 2-4 vinyl groups in 1 molecule using a catalyst, As a hydrosilylation catalyst, for example, platinum And catalysts such as palladium catalysts and rhodium catalysts. Examples of the platinum-based catalyst include complexes of chloroplatinic acid, chloroplatinic acid and alcohols, aldehydes, ketones, and the like, platinum-olefin complexes, platinum-carbonylvinylmethyl complexes (Ossko catalysts) and platinum-divinyltetramethyldisiloxane complexes (KaRstedt Catalyst), platinum-cyclovinylmethylsiloxane complex, platinum-octylaldehyde complex, platinum-phosphine complex (eg 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 (eg Pt [P (OC ₆ H ₅ ) ₃ ] ₄ ), Pt [P (OC ₄ H ₉ ) ₃ ] ₄ ) and dicarbonyl dichloro platinum. As a palladium type catalyst or a rhodium type catalyst, the compound containing a palladium atom or a rhodium atom instead of the platinum atom of the said platinum catalyst is mentioned, for example. These may be used by 1 type and may use 2 or more types together. As a hydrosilylation catalyst, a platinum-type catalyst is preferable at the point of reactivity, a platinum-divinyl tetramethyldisiloxane complex and a platinum-carbonylvinylmethyl complex are more preferable, and a platinum-carbonylvinylmethyl complex is the most preferable. In terms of reactivity, the amount of the catalyst used is preferably 5% by mass or less, more preferably 0.0001 to 1.0% by mass, and most preferably 0.001 to 0.1% by mass of the total amount of each raw material. Although the reaction conditions of hydrosilylation are not specifically limited, What is necessary is just to implement on conventionally well-known conditions using the said catalyst, It is preferable to carry out at room temperature (25 degreeC)-130 degreeC from the point of reaction rate, and toluene at the time of reaction You may use conventionally well-known solvents, such as hexane, methyl isobutyl ketone, cyclopentanone, and a propylene glycol monomethyl ether acetate.

Hydrosilylation reaction of a cyclic siloxane compound represented by the general formula (1a) with a reactant of a compound having 2-4 vinyl groups in one molecule, and an epoxy compound containing a carbon-carbon double bond having reactivity with the SiH group. What is necessary is just to carry out on the same conditions as the hydrosilylation reaction of the cyclic siloxane compound represented by the said General formula (1a), and the compound which has 2-4 vinyl groups in 1 molecule, and isolate and refine | purify a reactant after this hydrosilylation reaction. It is preferable to continue reaction, without doing it.

When 5,6-epoxyhexene, 7,8-epoxyoctene, allyl glycidyl ether, glycidyl methacrylate, or the like is used as an epoxy compound containing a carbon-carbon double bond having reactivity with the SiH group, Aliphatic epoxy group of (5); Aliphatic epoxy groups of the formula (6) when 3,4-epoxy-3-methylbutene is used; Alicyclic epoxy groups of the above formula (7) when 1,2-epoxy-4-vinylcyclohexane, (3,4-epoxycyclohexyl) methyl methacrylate is used; When 1,2-epoxylimonene etc. are used, alicyclic epoxy group of said Formula (8); When 3-vinyl-5, 6- epoxy- norfinan etc. are used, the alicyclic epoxy group of said formula (9); When 4-epoxyethyl styrene is used, the aromatic epoxy group of the said Formula (10); When 4- (1-methylepoxyethyl) styrene etc. are used, the aromatic epoxy groups of said Formula (11) can be introduce | transduced, respectively.

Next, the base resin of this invention is demonstrated. The base resin of this invention is a polysiloxane compound which has a carboxyl group and / or a phenolic hydroxyl group. In a positive photosensitive resin composition containing a photosensitive diazoquinone compound as the photosensitive component, the base resin is soluble in the developer, but in the unexposed part, the photoresist diazoquinone compound is insoluble or poorly soluble in the developer. While dissolution is inhibited, a pattern is formed in the exposed portion by using the point that the photosensitive diazoquinone compound is decomposed by irradiation of ultraviolet rays or the like so that the base resin is dissolved in the developer.

In a positive photosensitive resin composition comprising a polysiloxane compound having a carboxyl group and / or a phenolic hydroxyl group as a base resin, alkali developability is improved by the carboxyl group and / or phenolic hydroxyl group of the polysiloxane compound having a carboxyl group and / or phenolic hydroxyl group, but development margin Although there existed a problem that this became small, in the positive photosensitive resin composition of this invention, developing margin can be enlarged by containing the epoxysiloxane compound of this invention.

In the base resin of the present invention, when the content of the carboxyl group and / or the phenolic hydroxyl group is too small, the alkali developability becomes poor, and when the content of the base resin is too large, the film reduction becomes large, so that the total is 0.1-5 mmol / g. It is preferable, it is more preferable that it is 0.5-4 mmol / g, and it is most preferable that it is 1-3 mmol / g.

In addition, when the molecular weight of the base resin of this invention is too small, a film | membrane decrease is large, and when too large, since the resist residue on the surface of a board | substrate after alkali image development will generate | occur | produce easily, it is preferable that mass mean molecular weights are 1000-20000, 2000 It is more preferable that it is -16000, and it is most preferable that it is 4000-13000.

It is preferable that the base resin of this invention contains a silanol group from the point which the thermal crosslinkability of a positive photosensitive resin composition improves, and the mechanical strength and chemical-resistance of the hardened | cured material obtained improve. It is preferable that content of the silanol group in the base resin of this invention is 1-30 mass% as content of OH, It is more preferable that it is 3-25 mass%, It is most preferable that it is 5-20 mass%.

As a base resin of this invention, since the improvement effect of image development margin by the additive of this invention is large, the valence of the cyclic siloxane compound represented by following General formula (19), and the siloxane compound represented by following General formula (20) Decomposition condensate (refer patent document 3) is especially preferable.

(In formula, R <^14> represents a C1-C4 alkyl group or a C6-C10 aryl group, R <^15> represents a C2-C10 divalent hydrocarbon coupling group, and R <^16> and R <^17> may be same or different. Represents a divalent saturated aliphatic hydrocarbon group of 2 to 10, 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, and m represents a number of 0 to 5; N represents the number of 0-5, p represents the number of 1-5, provided that m, n and p are m + n = 1-5 and m + n + p = 3-6. to be.)

(In formula, R <^20> represents a C6-C10 aryl group, R <^21> and R <^22> represent a C1-C4 alkyl group which may be same or different, and q represents the number of 2-3.)

In 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. As a C1-C4 alkyl group and a C6-C10 aryl group, the group illustrated by description of R <^1> of the said General formula (1) is mentioned. R ¹⁴ is preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl and phenyl, more preferably methyl and phenyl, most preferably methyl in view of heat resistance and industrial availability.

In said general formula (19), R <^15> represents a C2-C10 divalent hydrocarbon coupling group. 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, cyclohexane-1, 4-diyl, 2-phenylethane-1,4'-diyl, 2-phenylpropane-1,4'-diyl, etc. are mentioned, As R <^15> , it is ethylene and 2- in terms of industrial availability and heat resistance. Methylethylene and 2-phenylethane-1,4'-diyl are preferred, 2-methylethylene and 2-phenylethane-1,4'-diyl are more preferred, 2-phenylethane-1,4'-diyl Is most preferred.

In said general formula (19), R <^16> and R <^17> represents the C2-C10 divalent saturated aliphatic hydrocarbon group which may be 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, and decamethylene. As R ¹⁶ and R ¹⁷ , ethylene, 2-methylethylene and propylene are preferable, and ethylene is more preferable in terms of industrial availability and heat resistance.

In said general formula (19), R <^18> and R <^19> represents a C1-C4 alkyl group which may be same or different. 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. As R ¹⁸ and R ¹⁹ , methyl and ethyl are preferable, and methyl is more preferable 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 general formula (19), k represents the number of 1 to 3, m represents the number of 0 to 5, n represents the number of 0 to 5, and p represents 1 to 5. However, m, n, and p are the numbers which become m + n = 1-5, m + n + p = 3-6. Since m + n + p is easy to obtain industrial raw materials, the number of 3-5 is preferable, the number of 3-4 is more preferable, and the number of 4 is the most preferable. The ratio of n to m is preferably 0.5 to 2, more preferably 0.8 to 1.8, and most preferably 1.0 to 1.7 from the viewpoint of good adhesion to the substrate.

In General Formula (20), R ²⁰ represents an aryl group having 6 to 10 carbon atoms. C 6?, And the like 10 Examples of the aryl group exemplified in the explanation of R ¹ in the formula (1) aryl groups. As R <^20> , phenyl and toluyl are preferable at the point of heat resistance and the industrial availability, and phenyl is more preferable. R <^21> and R <^22> represents a C1-C4 alkyl group which may be same or different. Examples of the alkyl group having 1 to 4 carbon atoms include the alkyl group exemplified in the description of R ¹ in General Formula (1), and as R ²¹ and R ^22, the reactivity of the hydrolysis condensation reaction is good, and the base resin of the present invention. Methyl and ethyl are preferable at the point which the heat resistance of is improved, and methyl is more preferable.

When the molecular weight of the base resin of this invention is too small, the film-forming property at the time of apply | coating the positive photosensitive resin composition of this invention to a target object may become poor, and when too large, the resist residue on the surface of a board | substrate after alkali image development will be bad. Since it may increase, it is preferable that it is 600-50000 in a mass mean molecular weight, It is more preferable that it is 800-20000, It is most preferable that it is 1000-10000.

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

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. Or the method of performing hydrolytic condensation reaction using catalysts, such as a base, is mentioned. The solvent used at this time is not specifically limited, Specifically, water, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, 1-methoxy 2-propanol acetate, 1,2-dimethoxyethane, toluene, etc. are mentioned, One type may be used among these, and 2 or more types may be mixed and used for it. In the hydrolysis condensation reaction, which is a reaction between alkoxylyl compounds, the alkoxysilyl group in the compound is hydrolyzed by water to generate a silanol group (Si-OH group), and the silanol groups generated or silanol groups and alkoxysilyl groups The group proceeds by condensation.

In order to advance this hydrolysis condensation reaction rapidly, it is preferable to add a suitable amount of water, and you may melt | dissolve a catalyst in water and add it. The hydrolysis condensation reaction also proceeds with a small amount of water contained in water in the air or in a solvent other than water. Catalysts, such as an acid and a base used in this hydrolysis condensation reaction, should just promote a hydrolytic condensation reaction, Specifically, Inorganic acids, such as hydrochloric acid, phosphoric acid, a sulfuric acid; Organic acids such as formic acid, acetic acid, oxalic acid, citric acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid and monoisopropyl phosphate; Inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonia; Amine compounds (organic base), such as trimethylamine, triethylamine, monoethanolamine, and diethanolamine, etc. are mentioned, One type may be used and two or more types may be used together. Although the temperature of a hydrolysis condensation reaction changes with kinds of solvent, a kind, quantity of a catalyst, etc., 0-80 degreeC is preferable, 5-50 degreeC is more preferable, 8-30 degreeC is the most preferable.

Not all silanol groups produced by hydrolysis of the alkoxysilyl group cause a condensation reaction, and some remain unreacted. It is preferable that the base resin of this invention contains a silanol group from the point that chemical resistance, adhesiveness to a board | substrate improves, and the like. It is preferable that content of the silanol group in the base resin of this invention is 1-30 mass% as content of OH, It is more preferable that it is 3-25 mass%, It is most preferable that it is 5-20 mass%. As a method for quantifying silanol groups, silanol groups are trimethylsilylated with trimethylchlorosilane or the like and quantified by the amount of mass increase before and after the reaction (TMSization method). The method of quantifying by the apparatus analysis using patent publication 2003-35667 etc. and ²⁹ Si-NMR (refer Japanese Unexamined-Japanese-Patent No. 2007-217249 etc.) is mentioned.

The silanol group is liable to cause a condensation reaction, and the content of the silanol group may decrease depending on the handling. In particular, when the product is isolated after the hydrolytic condensation reaction, dehydration condensation reaction between silanol groups is likely to occur. Thus, when the base resin of the present invention is produced, the product is not isolated after the hydrolytic condensation reaction in a solvent. It is preferable to mix | blend with the other solvent as concentrate or as needed, and to mix | blend with a positive photosensitive resin composition.

Next, the photosensitive diazoquinone compound which is a photosensitive component is demonstrated.

The photosensitive diazoquinone compound which can be used in the present invention is not particularly limited as long as it is a diazoquinone compound known to be usable for a photosensitive material. Among them, the photosensitive diazoquinone compound has a phenolic hydroxyl group because of its good photosensitivity and a fine pattern. Compound (4-diazonaphthoquinone sulfonic acid ester) in which the hydrogen atom of the compound is substituted with a group represented by the following formula (21) or group represented by the following formula (22) desirable.

As a preferable specific example of such a photosensitive diazoquinone compound, the compound represented by the following formula (23)-(28), their positional isomers, etc. can be illustrated, for example.

(In Formulas (23) to (28), Q is a group or a hydrogen atom represented by Formula (21) or Formula (22). However, not all Q in each formula is a hydrogen atom.)

The group represented by the above formula (21) is suitable for i-ray exposure because it has absorption in the i-line (wavelength 365 nm) region. In addition, since the group represented by the above formula (22) has absorption in a wide range of wavelengths, it is suitable for exposure at a wide range of wavelengths. For this reason, it is preferable to select either the group represented by the said Formula (21) or the group represented by the said Formula (22) by the wavelength to expose.

Positive type photosensitive resin composition of this invention WHEREIN: Content of the said photosensitive diazoquinone compound is 0.1-10 mass parts with respect to a total of 100 mass parts of content of the epoxysiloxane compound of this invention and the base resin of this invention. Preferably it is 1-5 mass parts from the point of the developability and the fine workability of the permanent resist of this invention.

Next, the organic solvent is demonstrated.

It does not specifically limit as an organic solvent which can be used for this invention, The epoxy siloxane compound of this invention, the base resin of this invention, the said photosensitive diazoquinone compound, and the alkylsilane compound represented by following General formula (3) mentioned later and the following: 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). Examples of such organic solvents include 1-methoxy-ethanol, 1-ethoxy-ethanol, 1-propoxy-ethanol, 1-isopropoxy-ethanol, 1-butoxy-ethanol, 1-methoxy-2-propanol, 3 Ether alcohols such as methoxy-1-butanol and 3-methoxy-3-methyl-1-butanol; 1-methoxy-ethyl acetate, 1-ethoxy-ethyl acetate, 1-methoxy-2-propyl acetate, 3-methoxy-1-butyl acetate, 3-methoxy-3-methyl-1-butyl acetate, etc. Acetate esters of ether alcohols; Ketones such as acetone and methyl ethyl ketone; Keto alcohols such as 4-hydroxy-2-butanone, 3-hydroxy-3methyl-2-butanone and 4-hydroxy-2-methyl-2-pentanone (diacetone alcohol); Ethers such as 1,4-dioxane, tetrahydrofuran and 1-2-dimethoxyethane; cyclic esters such as γ-butyrolactone, γ-valerolactone, and δ-valerolactone; Carbonates, such as ethylene carbonate, a propylene carbonate, and a dimethyl carbonate, etc. are mentioned, Acetate esters of ether alcohol are preferable at the point which is solubility good and has moderate volatility, and 1-methoxy- 2-propyl acetate is preferable. , 3-methoxy-1-butylacetate, and 3-methoxy-3-methyl-1-butylacetate are more preferred, and 1-methoxy-2-propylacetate is most preferred.

In positive type photosensitive resin composition of this invention, content of the said organic solvent is 10 with respect to a total of 100 mass parts of content with the epoxysiloxane compound of this invention and the base resin of this invention from a handling property or the film-forming property of a coating film. It is preferable that it is 10000 mass parts, especially 100-1000 mass parts.

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

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

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

In 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. As R ² , the development margin is increased. Propyl, isopropyl, butyl and isobutyl are preferred, methyl and ethyl are more preferred, and methyl is most preferred. X ¹ represents a C1-4 alkoxy group or halogen atom. Examples of the alkoxy group having 1 to 4 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. have. As X <^1> , a methoxy, ethoxy, and a chlorine atom are preferable at the point with the favorable reactivity, and methoxy and an ethoxy are more preferable.

Preferred compounds among the alkylsilane compounds represented by the general formula (3) include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane and ethyltrie. Methoxysilane, ethyltripropoxysilane, ethyltriisopropoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, butyltrimethoxysilane, butyl tree Ethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, methyltrichlorosilane, ethyltrichlorosilane, propyltrichlorosilane, isopropyltrichlorosilane, butyltrichlorosilane, isobutyltrichlorosilane, etc. Can be mentioned.

In General Formula (4), R ³ represents an aryl group having 6 to 10 carbon atoms. 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 as R ³ . Phenyl and toluyl are preferable at the point of heat resistance, and phenyl is more preferable. X ² represents an alkoxy group or halogen atom having 1 to 4 carbon atoms. Examples of the alkoxy group having 1 to 4 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. have. As X ² , methoxy, ethoxy and chlorine atoms are preferable from the viewpoint of good reactivity, and methoxy is more preferable.

Preferred compounds among the arylsilane compounds represented by the general formula (4) include phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltriisopropoxysilane, toluyltrimethoxysilane and toluyl Triethoxysilane, phenyl trichlorosilane, toluyl trichlorosilane, etc. are mentioned.

In the hydrolysis-condensation product of the present invention, when the reaction ratio of the arylsilane compound represented by the general formula (4) to the alkylsilane compound represented by the general formula (3) is too small, the base resin of the present invention If the compatibility with the resin decreases and too much, the mechanical properties (for example, crack resistance) of the cured product to be obtained may be adversely affected, so that the molar ratio is preferably 0.1 to 10, and 0.2 to 4 More preferably, 0.4-2 are the most preferable.

As long as the hydrolysis-condensation product of this invention is a range which does not reduce the function, the tetraalkoxysilane compound is a part of the alkylsilane compound represented by the said General formula (3), and the arylsilane compound represented by following General formula (4). 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), represented by R ³ You may make it react by replacing by the silanediol compound which has group (an aryl group of 6-10 carbon atoms).

As such a compound, Tetra alkoxysilane compounds, such as tetramethoxysilane and tetraethoxysilane;

Dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, dibutyldimethoxysilane, dibutyldiethoxysilane, methylethyldimethoxy Dialkoxysilane compounds or dihalosilane compounds having a group represented by R ² such as silane, methylethyldiethoxysilane, dimethyldichlorosilane, diethyldichlorosilane, dipropyldichlorosilane and dibutyldichlorosilane;

Dialkoxysilane compounds or dihalosilane compounds having a group represented by R ³ such as diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldichlorosilane, and diphenyldichlorosilane;

Phenyl dimethoxysilane, phenyl having diethoxysilane, ethyl phenyl dimethoxysilane, ethyl phenyl diethoxy silane, phenyl dichlorosilane, ethyl phenyl dichlorosilane such R ² group represented by the group and R ³ represented by the dialkoxysilane compound Or dihalosilane compounds;

Silanediol compounds which have groups represented by R <^3> , such as diphenylsilanediol and diphenylsilanediol, are mentioned.

If the molecular weight of the hydrolysis-condensation product of the present invention is too small, the improvement effect of the development margin is not seen. If the molecular weight is too large, the solubility in the alkaline developer is lowered and the resist residue after alkali development may increase, so that the mass average molecular weight. Therefore, it is preferable that it is 600-20000, It is more preferable that it is 800-10000, It is most preferable that it is 1000-5000.

The hydrolysis condensation reaction of the alkylsilane compound represented by the general formula (3) and the arylsilane compound represented by the general formula (4) may be carried out under the same conditions as in the case of the base resin of the present invention. In the hydrolysis condensation reaction, either an alkoxysilane compound or a halosilane compound may be used, or may be used in combination. Each of the alkoxysilane compounds has 1 to 4 carbon atoms in view of easy control of the reaction and removal of by-products. the alkyltrialkoxysilane X ² in the (above-mentioned formula (3) in X ¹ is C 1? alkoxy group the compound of 4), the alkoxysilane compound is a C 6? aryl trialkoxysilane of 10 (the general formula (4) Is a C 1-4 alkoxy group).

It is preferable that the hydrolysis-condensation product of this invention contains a silanol group in the point which can enlarge the image development margin of the positive photosensitive resin composition of this invention, and the content of the silanol group in the hydrolysis-condensation product of this invention is OH It is preferable that it is 1-30 mass% as content, It is more preferable that it is 3-25 mass%, It is most preferable that it is 5-20 mass%.

The silanol group produced by hydrolysis of a compound having a trialkoxysilyl group or a trihalosilyl group tends to cause a condensation reaction, and the content of silanol groups may decrease with handling. In particular, when the product is isolated after the hydrolytic condensation reaction, dehydration condensation reaction between silanol groups is likely to occur. Therefore, when preparing the additive of the present invention, the solvent is not isolated after the hydrolytic condensation reaction in the solvent. It is preferable to mix | blend with a positive solvent photosensitive resin composition, concentrating or substituted by another solvent as needed.

In the positive photosensitive resin composition of the present invention, when the content of the hydrolyzed condensate of the present invention is too small, the development margin is not improved, and when too large, the residue tends to occur during development, and the obtained Since the physical property of hardened | cured material falls, it is preferable that it is 5-100 mass parts with respect to 100 mass parts of base resin of this invention, It is more preferable that it is 10-70 mass parts, It is most preferable that it is 15-50 mass parts.

In addition, the positive photosensitive resin composition of this invention mix | blends arbitrary components, such as a plasticizer, a thixotropic agent, a photoacid generator, a thermal acid generator, a dispersing agent, an antifoamer, a pigment, and dye as needed. can do. Although the compounding quantity of this arbitrary component is not specifically limited, Preferably it is 5 mass parts or less with respect to 100 mass parts of base resins of this invention.

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

(Step 1) Coating Film Formation Step

A coating film formation process is a process of apply | coating the positive photosensitive resin composition of this invention on the target material, and performing prebaking, and forming a coating film. It will not specifically limit, if it is a material which has chemical-resistance with respect to the organic solvent etc. in the positive type photosensitive resin composition, image development by the alkaline solution of a 4th process, heat resistance to the process in a 6th process, etc. as a target material which forms a coating film, , Metals, semiconductors and the like can be used as the target material. Especially the TFT surface etc. of a liquid crystal display which require the permanent resist as an insulating layer can be illustrated as a preferable thing. It does not specifically limit as a coating method, For example, various coating methods, such as a spin coat method, the dip coat method, the knife coat method, the roll coat method, the spray coat method, the slit coat method, can be used.

Prebaking is performed in order to remove the organic solvent from the positive photosensitive resin composition layer apply | coated on the said target material. The prebaked positive photosensitive resin composition layer is poorly soluble with respect to an alkaline solution, and by irradiating light in the exposure process of a 2nd process, the part to which light was irradiated (henceforth an exposure part) becomes alkali-soluble. The temperature of the prebaking also varies depending on the type of organic solvent used. However, if the temperature is too low, the residual amount of the organic solvent may increase, which may cause exposure sensitivity or resolution degradation. If the temperature is too high, the coating film may be prebaked. 60-140 degreeC is preferable and 70-120 degreeC is more preferable because the whole hardening advances and the solubility with respect to the alkaline developing solution of the part to which light was irradiated may fall, as a result, an exposure sensitivity and a resolution may fall. . Although the prebaking time changes with the kind of organic solvent used and the temperature of prebaking, 30 second-10 minutes are preferable, and 1-5 minutes are more preferable.

Although prebaking may be performed as it is after apply | coating the positive photosensitive resin composition of this invention on the said target material, since the physical property, chemical-resistance, etc. after high heat history of the permanent resist of this invention improve, it is room temperature? 60 before prebaking. It is preferable to carry out í * rebaking after volatilizing an organic solvent so that the density | concentration of the organic solvent in a positive photosensitive resin composition layer may be 5 mass% or less under normal pressure or pressure_reduction to the temperature below ° C. The thickness of the positive photosensitive resin composition layer after prebaking varies depending on the use of the permanent resist of the present invention, and is not particularly limited, but may be 0.1 µm to 100 µm, preferably 0.3 µm to 10 µm.

(2nd process) Exposure process

An exposure process is a process of irradiating patterned light with respect to the prebaked positive photosensitive resin composition layer, and improving alkali solubility of an exposure part. Although the prebaked positive photosensitive resin composition layer is poorly soluble with respect to an alkaline solution, the photosensitive diazoquinone compound of an exposed part decomposes | disassembles by light irradiation, it changes into an indencarboxylic acid compound, and dissolves and disperses in an alkaline solution. It becomes possible. It does not specifically limit as irradiation light, What is necessary is just the light of the amount of energy which can improve the alkali solubility of the light irradiation part of the prebaked positive photosensitive resin composition layer, For example, the range of energy amount of 10-1000mJ / cm <2>, especially 40 Light in the range of 300 mJ / cm 2 is preferred. In addition, the wavelength of irradiation light may be visible light or ultraviolet light, and although it does not specifically limit, When 4-diazonaphthoquinone sulfonic acid ester is used as said photosensitive diazoquinone compound, narrow wavelength mainly having i-line (365 nm) When 5-diazonaptoquinonesulfonic acid esters were used as the light, light having a broad wavelength including i-ray (365 nm), h-ray (405 nm), and g-ray (436 nm) was obtained from a high pressure mercury lamp and an ultra high pressure mercury lamp. You can do this using the back light. The patterning method of the said irradiation light is not specifically limited, The method known conventionally, for example, the light irradiation method through a photomask, etc. may be sufficient, and the selective light irradiation method using a laser beam may be sufficient.

(3rd step) Developing step

The developing step is a step of forming a predetermined pattern by removing a part (exposure part) in which light is irradiated in the exposure step of the second step and the alkali solubility is improved using a developing solution. After removing an exposed part with a developing solution, it is preferable to rinse with water by running water or a shower, and you may dry-dry in 50-120 degreeC as needed.

As the developing method, any method such as a puddle method, an immersion method, a shower method, or a spray method can be used, for example. The optimum development time varies depending on the type, molecular weight, temperature of the developer, etc. of the polysiloxane compound having a carboxyl group and / or phenolic hydroxyl group as the base resin, but is usually between 30 and 180 seconds. Conventionally, although the positive photosensitive resin composition containing the polysiloxane compound which has a carboxyl group and / or phenolic hydroxyl group as a base resin, the photosensitive diazoquinone compound, and an organic solvent as a photosensitive component, there existed a problem that the image development margin in a developing process is small, By including the additive of the present invention, the development margin is increased, and even if the development time is slightly longer than the optimal development time, peeling due to penetration of the developer between the pattern and the substrate is unlikely to occur, and the yield of the product can be improved.

The developing solution used in the developing step is not particularly limited as long as it can remove or disperse the exposed portion in the liquid, and examples thereof include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate and ammonia; Primary amines such as ethylamine and n-propylamine; Secondary amines such as diethylamine and di-n-propylamine; Tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine and triethylamine; Tertiary alkanolamines such as dimethylethanolamine, methyldiethanolamine and triethanolamine; Pyrrole, piperidine, N-methylpiperidine, N-methylpyrrolidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] Cyclic tertiary amines such as -5-nonene; Aromatic tertiary amines such as pyridine, collidine, lutidine and quinoline; Aqueous solutions of alkalis, such as aqueous solutions of quaternary ammonium salts, such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, can be used, The density | concentration is alkali of the developing solution used for removal of the conventional positive photosensitive resin composition layer. What is necessary is just concentration. The aqueous solution of these alkalis may further contain a suitable amount of water-soluble organic solvents and / or surfactants, such as methanol and ethanol.

(4th step) Bleaching exposure process

The bleaching exposure step is performed by irradiating the entire positive photosensitive resin composition layer (hereinafter also referred to as a resist layer) remaining in the alkaline solution treatment in the developing step of the third step to improve visible light transmittance (bleaching). Exposure) process. Since the resist layer contains the photosensitive diazoquinone compound, it is colored by pale yellow to light brown. When the resist layer is irradiated with light, the remaining unreacted photosensitive diazoquinone compound is photolyzed to change into an indencarboxylic acid compound without absorption in the visible region, thereby improving visible light transmittance. It is especially preferable when used as a permanent resist for active matrix substrates used for a display device, an organic EL display device, and the like. Irradiation light in a bleaching exposure process is not specifically limited, For example, what is necessary is just to irradiate light of the range of energy amount of 10-1000mJ / cm <2>, Preferably it is 40-600mJ / cm <2>. The wavelength of the irradiation light may be visible light or ultraviolet light, and is not particularly limited. However, the wavelength of the irradiation light is preferably selected in accordance with the type of the photosensitive diazoquinone compound used, similarly to the exposure step of the second step.

(Step 5) Post Baking Process

Although the resist layer bleached and exposed by the 4th process improves visible light transmittance, alkali solubility also improves. The post-baking process is subjected to heat treatment at 120 ° C. or higher on the bleached exposed resist layer, and thermally crosslinks the silicone resin in the resist layer, so that the heat resistance, chemical resistance, and change in time resistance required as a permanent resist are required. To provide a permanent resist of the present invention. Post-baking is preferably performed at a temperature of 120 to 400 ° C. for 15 minutes to 2 hours under an inert gas atmosphere such as nitrogen, helium, argon, and 15 minutes to 2 hours at a temperature of 200 to 350 ° C. More preferred.

In the coating film formation process which is a 1st process, although the positive photosensitive resin composition of this invention may be apply | coated directly on target materials, such as a semiconductor substrate, it may be used by apply | coating on a support film, forming a coating film, and using it as a dry film resist. A dry film resist is prebaked after coating film formation, removes the solvent in a coating film, and laminates a protective film on the coating film surface, and is produced. When using the dry film resist obtained from the positive type photosensitive resin composition of this invention, after peeling a protective film from a dry film resist, the said dry film resist is thermocompression-bonded on the said target material, and it adhere | attached, and the said support film was peeled off as needed. After that, exposure, development, bleaching exposure, and postbaking may be performed under the above conditions.

As said support film, polyethylene terephthalate (PET), polyethylene, a polypropylene, etc. can be used, for example, PET film is preferable at the point which is excellent in the thermal characteristic and a mechanical characteristic as a support film. The film thickness of a support film is 1 micrometer-5 mm normally, Preferably they are 10 micrometers-100 micrometers. The thickness of the coating film formed on a support film differs according to a use, and although it does not specifically limit, 0.1 micrometer-100 micrometers, Preferably 0.3 micrometer-10 micrometers become a reference | standard.

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

In addition, the permanent resist obtained from the positive photosensitive resin composition of the present invention is an interlayer insulating film of a semiconductor device, or a wafer coating material (surface protective film, bump protective film, MCM (multi-chip module) interlayer protective film, junction coating) of a semiconductor device. ) And package materials (sealing materials, die-bonding materials).

Moreover, the permanent resist obtained from the positive photosensitive resin composition of this invention is useful also as insulating films, such as a semiconductor element and a multilayer wiring board. Examples of the semiconductor device include individual semiconductor devices such as diodes, transistors, compound semiconductors, thermistors, varistors, and thyristors, dynamic random access memory (DRAM), static random access memory (SRAM), and erasable programmable read only memory (EPROM). Memory devices such as Mask Read Only Memory (ROM), Electrically Erasable Programmable Read Only Memory (EPEROM), flash memory, theoretical circuit elements such as microprocessors, DSPs, ASICs, and monolithic microwave integrated circuits. Photoelectric conversion elements, such as an integrated circuit element, such as a compound semiconductor, a hybrid integrated circuit (hybrid IC), a light emitting diode, and a charge coupling element, etc. are represented. Moreover, as a multilayer wiring board, high density wiring boards, such as MCM, etc. are mentioned.

<Examples>

Although an Example and a comparative example are shown to the following and this invention is further demonstrated, this invention is not limited to these. On the other hand, the content of the silanol group is reacted with trimethylchlorosilane in a pyridine solution to convert the silanol group into a trimethylsilyl ether group, and then treated with an aqueous tetramethylammonium hydroxide ((CH ₃ ) ₄ NOH) to form a CO-Si bond. Was hydrolyzed and inversely calculated from the weight increase rate after the reaction. In addition, "%" is a unit of mass unless there is particular notice.

Preparation Example 1: Preparation of Epoxysilane Compound A-1 of the Present Invention

250 g of toluene in a glass reaction vessel equipped with a thermometer and a stirring device, 144 g (0.6 mol) of 2,4,6,8-tetramethylcyclotetrasiloxane as the cyclic siloxane compound represented by the general formula (1a), 2 in 1 molecule 52 g (0.4 mol) of 1,4-divinylbenzene as a compound having four vinyl groups, 194 g (1.7 mol) of allyl glycidyl ether as a compound containing a carbon-carbon double bond having reactivity with SiH groups, and platinum -9 mg of divinyl tetramethyl disiloxane complex (Karstedt catalyst) was added, and it was made to react at 50-60 degreeC for 15 hours, stirring. The solution was distilled off under reduced pressure from 60 degreeC from this reaction liquid, and the epoxysilane compound A-1 of this invention which is a siloxane compound which has glycidyl ether group was obtained. Epoxysilane compound A-1 of the obtained this invention is group in which R <^1> is methyl and E has the epoxy group of the said Formula (5) in the said General formula (1), a is equivalent to the number of 3, 2 in 1 molecule The compound having ˜4 vinyl groups is a compound which is 1,4-divinylbenzene (a compound in which h is the number of 1 in General Formula (16)). Moreover, the mass mean molecular weight by GPC analysis of the epoxysilane compound A-1 of this invention was 1500, and the analyzed value of the epoxy equivalent was 244.

Preparation Example 2: Preparation of Epoxysilane Compound A-2 of the Present Invention

250 g of toluene in a glass reaction vessel equipped with a thermometer and a stirring device, 240 g (1.0 mol) of 2,4,6,8-tetramethylcyclotetrasiloxane as a cyclic siloxane compound represented by the general formula (1a), 2 in 1 molecule As a compound having four vinyl groups, 24.9 g (0.1 mol) of 1,3,5-triallyl isocyanurate and 9 mg of platinum-divinyltetramethyldisiloxane complex (Karstedt catalyst) are added, and 50-60 is stirred. It was made to react at 5 degreeC. The solvent and unreacted 2,4,6,8-tetramethylcyclotetrasiloxane were distilled off under reduced pressure from the reaction solution at 100 deg. C, containing 250 g of toluene and a carbon-carbon double bond having reactivity with the SiH group. 114 g (1.0 mol) of allyl glycidyl ether was added as a compound, and it was made to react at 50-60 degreeC for 15 hours, stirring. The solvent was distilled off under reduced pressure at 60 degreeC from this reaction liquid, and the epoxysilane compound A-2 of this invention which is a siloxane compound which has glycidyl ether group was obtained. Epoxysilane compound A-2 of the obtained this invention is group in which R <^1> is methyl and E has the epoxy group of the said Formula (5) in the said General formula (1), a is equivalent to the number of 3, 2 in 1 molecule The compound which has four vinyl groups is 1,3,5-triallyl isocyanurate (the compound whose R <^13> in the said General formula (18) is allyl). Moreover, the mass mean molecular weight by GPC analysis of the epoxysilane compound A-2 of this invention was 2400, and the analyzed value of the epoxy equivalent was 267.

Preparation Example 3: Preparation of Base Resin B-1 of the Present Invention

The base resin B-1 of this invention was manufactured according to the manufacture example of the silicone resin (a) of the said patent document 3 Paragraph [0152]-[0155]. That is, in a glass reaction vessel equipped with a thermometer and a stirring device, 300 g of toluene, 120 g (0.5 mol) of 2,4,6,8-tetramethylcyclotetrasiloxane, 102 g (0.5 mol) of 4-vinyl benzoate-t-butyl ester, 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, and stirred for 15 hours at 60 ° C. After reaction, the solvent was distilled off under reduced pressure at 60 degreeC and the intermediate b-1 which is a compound in which the carboxyl group and phenyl hydroxyl group of the cyclic siloxane compound represented by the said General formula (19) was masked with the t-butyl group was obtained. The mass average molecular weight by GPC analysis of intermediate b-1 is 900 (theoretical molecular weight 933.1).

91 g (0.46 mole) of phenyltrimethoxysilane and 200 g of toluene are added to 90 g (0.1 mole) of the said intermediate b-1 as a siloxane compound represented by the said General formula (20), and an organic acid catalyst is carried out by ice-cooling stirring at 10 degreeC. 50 g of 5% oxalic acid aqueous solution was dripped over 1 hour, and stirring was continued at 10 degreeC for 15 hours. After washing twice with 100 g of water, reflux dehydration and dealcoholization were carried out at 50 ° C. and reduced pressure. Toluene, a solvent, was exchanged with 1-methoxy-2-propanol acetate (hereinafter referred to as PGMEA) at 50 ° C. under reduced pressure. 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 the 25% PGMEA solution of the intermediate b-2, and stirred at 80 ° C. for 3 hours, followed by 100 g of desolvation treatment under reduced pressure, After the addition of 10 g of an acid adsorbent (Kyowa Kagaku Kogyo Co., Ltd., trade name: 500 SH), the solids were removed by filtration for a slurry solution stirred at 80 ° C. for 1 hour. The 30% PGMEA solution of the base resin B-1 of this invention which is a hydrolysis-condensation product of the cyclic siloxane compound represented and the siloxane compound represented by the said General formula (20) was obtained. In the obtained base resin B-1, the groups in the general formula (19) are each R ¹⁴ : methyl, R ¹⁵ : ethylene, R ¹⁶ : ethylene, R ¹⁷ : ethylene, R ¹⁸ : methyl, m: 1, m : 1.5, p: 1.5, k: is the number of 3, the above-mentioned formula (20), each group R ²⁰ from: phenyl, R ^21: a number of compounds 3: methyl, q. In addition, the mass average molecular weight by GPC analysis of the base resin B-1 of the present invention is 6900, the content of silanol groups is 5.4% as the content of OH, the content of carboxyl group (A) and / or phenolic hydroxyl group (B) ( A + 0.1 × B) was 1.17 mmol / g.

Preparation Example 4 Preparation of Hydrolyzed Condensate C-1 of the Present Invention

178 g (1 mol) of methyltriethoxysilane as an alkylsilane compound represented by the said General formula (3) in the glass reaction container provided with a thermometer and a stirring apparatus, and an aryl silane compound represented by the said General formula (4) 198 g (1 mol) of methoxysilane and 100 g of 1-methoxy-2-propanol acetate (hereinafter referred to as PGMEA) were added as a solvent, followed by ice cooling, and 100 g of an aqueous 5% oxalic acid solution was added dropwise over 1 hour as an organic acid catalyst. The mixture was further stirred for 10 hours. 250 g of toluene was added to the reaction vessel, refluxed and dehydrated at 60 ° C under reduced pressure, and concentrated under reduced pressure. The alcohol and toluene produced in the reaction were removed and filtered to obtain 30% by mass of the hydrolyzed condensate C-1 of the present invention. PGMEA solution was obtained. The mass average molecular weight by GPC analysis of the obtained hydrolysis-condensation product C-1 of this invention was 2000, and content of a silanol group was 7.8% as content of OH.

Preparation Example 5 Preparation of Hydrolysis Condensate C-2 of the Present Invention

In Preparation Example 3, 250 g (1.3 mole) of ethyltriethoxysilane was used instead of 178 g (1 mole) of methyltriethoxysilane, and the amount of phenyltrimethoxysilane was changed from 198 g (1 mole) to 125 g (0.7 mole). Except having changed, operation similar to the manufacture example 1 was performed and the 30 mass% PGMEA solution of the hydrolysis-condensation product C-2 of this invention was obtained. The mass average molecular weight by GPC analysis of the obtained hydrolysis-condensation product C-2 of this invention was 1900, and the content of silanol group was 7.5% as content of OH.

Preparation Example 6 Preparation of Comparative Epoxysiloxane Compound D-1

Epoxysiloxane compound D-1 for comparison was manufactured according to the manufacture example of the siloxane compound (j) which has the glycidyl ether group of the said patent document 3 paragraph. That is, toluene 150g, 2,4,6,8-tetramethylcyclotetrasiloxane 60g (0.25mol), allyl glycidyl ether 114g (1mol), and platinum-di in the glass reaction container equipped with a thermometer and a stirring apparatus 0.5 mg of vinyl tetramethyldisiloxane complex (Karstedt catalyst) was added, and it was made to react at 50-60 degreeC for 15 hours, stirring. The solvent was distilled off under reduced pressure at 60 degreeC from this reaction liquid, and the epoxy siloxane compound D-1 for comparison which was a siloxane compound which has glycidyl ether group was obtained.

[Examples 1 to 6 and Comparative Examples 1 to 3: Preparation and Evaluation of Positive Photosensitive Resin Compositions for the Present Invention and Comparative]

As the epoxysilane compound of the present invention obtained in the above production example, the epoxysilane compound for comparison, the PGMEA solution of the base resin of the present invention, the PGMEA solution of the hydrolysis-condensation product of the present invention, and the photosensitive component, the following photosensitive diazoquinone compounds (Diazonaphthoquinones (DNQ)) were mix | blended in the ratio shown in Table 1, and it filtered, and the positive photosensitive resin composition of Examples 1-6 and Comparative Examples 1-3 was prepared. On the other hand, PGMEA of the organic solvent was added so that the values in the table.

Diazonaphthoquinones (DNQ): The compound (Allo-Kyoto company make, brand name = PA-6) which is group which all Q is represented by said Formula (22) in said Formula (23).

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.

[Preparation Method of Test Piece]

After apply | coating positive type photosensitive resin composition on a glass substrate so that the film thickness of a coating film might be set to 2-3 micrometers, the solvent was volatilized and it was set as the test piece.

On the other hand, in the patterning exposure, after heat-treating a test piece at 90 degreeC for 2 minutes, the photomask in which the line width of 5 micrometers was drawn was installed on the upper part of a glass substrate, and ultraviolet-ray of 90mJ / cm <2> (wavelength 365nm exposure conversion) was made with an ultrahigh pressure mercury lamp. It carried out by examining.

[Evaluation of Optimal Development Time and Development Margin]

The development time was changed from 30 seconds to 5 second intervals, and the optimum development time and development margin were evaluated. That is, about each positive photosensitive resin composition, after preparing each of 15 test pieces and patterning exposure, these test pieces were immersed in 2.38 mass% tetramethylammonium hydroxide aqueous solution of 25 degreeC of liquid temperature, and 30 seconds after the immersion start. Taken out every second. The removed test pieces were immediately washed with ultra pure water for 1 minute and air dried. The air-dried test piece was observed and the time required for the line line width to be 5 µm was defined as the development margin as the time between the optimum development time and the optimum development time until the 5 µm line-pattern was peeled off.

[Alkali Resistance Test]

After air drying the test piece developed at the optimum development time, and irradiating it with 200mJ / cm <2> (wavelength 365nm exposure conversion) with an ultra-high pressure mercury lamp as a bleaching exposure, heat processing for 230 minutes at 230 degreeC in air atmosphere, or 350 degreeC in nitrogen atmosphere. The heat treatment for 30 minutes was performed to form a permanent resist film. The transmittance of light with a wavelength of 400 nm and a tactile surface shape before and after 30 minutes of immersion in an alkali solution (monoethanolamine: N-methyl-2-pyrrolidone: butyl diglycol = 10:30:60 mass ratio) at 40 ° C. The film thickness of the resist was measured using a measuring instrument, and the alkali resistance was evaluated based on the following criteria from the rate of change of the light transmittance and the rate of change of the film thickness.

(Circle): The change rate of the light transmittance of the test piece heat-processed at 350 degreeC is less than 1%, and the change rate of a film thickness is less than 10%, and is excellent in alkali resistance and alkali resistance after high heat history.

(Triangle | delta): Although the change rate of the light transmittance of the test piece heated at 230 degreeC is less than 1%, and the change rate of a film thickness is less than 10%, the change rate of the light transmittance of the test piece heated at 350 degreeC is 1% or more, or the change rate of a film thickness. The alkali resistance is excellent in this 10% or more, but the alkali resistance after high heat history is inferior.

X: The change rate of the light transmittance of the test piece heat-processed at 230 degreeC is 1% or more, or the change rate of a film thickness is 10% or more, and alkali resistance is inferior.

As is apparent from the above results, the problem that the development margin is small in the positive photosensitive resin composition containing a polysiloxane compound having a carboxyl group and / or a phenolic hydroxyl group as the base resin and a photosensitive diazoquinone compound as the photosensitive component However, the inclusion of the epoxysilane compound of the present invention increases the development margin, and even if the development time exceeds the optimum development time, it is still difficult to peel off due to penetration of the developer between the pattern and the substrate, thereby forming a good pattern shape. Confirmed.

Claims (3)

In the positive photosensitive resin composition containing the polysiloxane compound which has a carboxyl group and / or phenolic hydroxyl group as a base resin, the photosensitive diazoquinone compound, and an organic solvent as a photosensitive component,
Residues which excluded the vinyl group from the compound in which 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 Positive type photosensitive resin composition characterized by containing the epoxysiloxane compound connected.

(In formula, R <^1> represents a C1-C4 alkyl group or C6-C10 aryl group which may be same or different, E represents the group which has an epoxy group, and a shows the number of 2-5.)

(In formula, b represents the number of 2-6 which a-b + 1 becomes the number of 0-4, and R <^1> , E and a have the same meaning as the said General formula (1).) The method of claim 1,
Furthermore, the positive type photosensitive resin composition containing the hydrolysis-condensation product of the alkylsilane compound represented by following General formula (3), and the arylsilane compound represented by following General formula (4) is contained.

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

(R ³ represents an aryl group having 6 to 10 carbon atoms, and X ² represents an alkoxy group or halogen atom having 1 to 4 carbon atoms.) It is obtained from the positive photosensitive resin composition of Claim 1 or 2, The permanent resist characterized by the above-mentioned.