JP2008268788A - Photosensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition having high sensitivity and excellent in pattern profile after being subjected to heat treatment. <P>SOLUTION: The photosensitive resin composition comprises (a) a resin having a repeating unit represented by general formula (1), (b) a resin other than the resin (a), (c) a photoacid generator and (d) a photoacid generator other than the photoacid generator (c). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition.

  A semiconductor device protective film, rewiring film, display insulating film, and the like are required to have excellent heat resistance and electrical insulation. A polyimide material has been widely used as an organic material suitable for such applications. Recently, photosensitive polyimide, photosensitive polybenzoxazole and the like have been developed. On the other hand, a photosensitive resin composition containing a novolak resin and a naphthoquinone diazide sulfonic acid ester is used as a photoresist for pattern formation of metals and insulating films.

  So far, for the purpose of improving heat resistance, a pattern forming method has been proposed in which a photosensitive composition film containing an alkali-soluble resin, a photosensitive agent, a photoacid generator, a crosslinking agent and a solvent is exposed entirely after exposure and development. (For example, refer to Patent Document 1). However, the improvement in heat resistance by this method is in the temperature range up to 200 ° C., and there is a problem that the pattern is destroyed when the temperature is exceeded. Furthermore, in order to improve heat resistance, a positive photosensitive resin composition containing a phenol resin having a methylol group has been proposed (for example, see Patent Document 2). However, even in these cases, when soldering or the like is performed in air at a temperature of 200 ° C. or higher, oxidative decomposition or the like occurs, resulting in a problem that physical properties are deteriorated. Further, it contains an alkali-soluble resin such as a novolak resin and at least two quinonediazide sulfonic acid ester compounds, and the at least two quinonediazide sulfonic acid esters contain 5% by weight of a component in which all phenolic hydroxyl groups are esterified. The following positive resist compositions are disclosed (for example, see Patent Document 3). However, in such a case, there is a problem that the pattern shape collapses when heat-treated at a high temperature of 200 ° C. or higher.

  On the other hand, a photosensitive resin composition containing polyimide, polybenzoxazole, or a precursor thereof and a naphthoquinonediazide compound has been proposed (see, for example, Patent Documents 4-7). Although the pattern shape obtained from these photosensitive resin compositions does not change even when a heat treatment at 300 ° C. or higher is performed, it is less sensitive than the photosensitive resin composition containing novolac resin and has an in-plane resolution dimension. There was a problem such as an increase in the variation.

For this reason, a photosensitive resin composition containing a novolak resin, polyimide, polybenzoxazole, or a precursor thereof, and a photosensitive material has been proposed (see, for example, Patent Documents 8-10). By this method, a composition with high sensitivity and little film loss can be obtained, but there is a problem in that the pattern shape collapses when high-temperature heat treatment is performed at a rapid temperature increase rate.
JP 2004-177683 A (Claim 1) Japanese Patent Laying-Open No. 2005-62374 (Claim 1) Japanese Patent Laid-Open No. 10-148936 (Claim 1) JP 2006-350262 A (Claim 1) JP 2004-334089 A (Claim 1) JP-A-11-143070 (Claim 1) JP 2003-5369 A (Claim 1) Japanese Patent Laying-Open No. 2005-250160 (Claim 1) Japanese Patent Laying-Open No. 2005-255654 (Claim 1) Japanese Patent Laying-Open No. 2005-352004 (Claim 1)

  An object of this invention is to provide the photosensitive resin composition which is highly sensitive and is excellent in the pattern shape after heat processing.

  In order to solve the above problems, the present invention mainly has the following configuration. That is, (a) a resin having a repeating unit represented by the general formula (1), (b) a resin having a repeating unit represented by the general formula (2), (c) represented by the general formula (3) A photosensitive resin composition containing a photoacid generator and (d) a photoacid generator other than the above (c), wherein the total content of (c) and (d) is the above (a) and It is 1 part by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the total content of (b), and the content ratio (c / d) of the content of (c) and (d) is 0. It is a photosensitive resin composition characterized by being 10 or more and 0.70 or less (weight ratio). The present invention also relates to (e) a resin having at least one selected from the group consisting of an imide ring, an imidazole ring, an oxazole ring, a thiazole ring and an oxadiazole ring, and a hydroxyl group or a carboxyl group, (b) a general formula ( A photosensitive resin composition containing a resin having a repeating unit represented by 2), (c) a photoacid generator represented by the general formula (3), and (d) a photoacid generator other than the above (c) The total content of (c) and (d) is 1 part by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the total content of (b) and (e), and The photosensitive resin composition is characterized in that the content ratio (c / d) of the content (c) and the content (d) is 0.10 or more and 0.70 or less (weight ratio).

In the general formula (1), R ¹ represents a C 2-30 divalent organic group, and R ² represents a C 2-30 bivalent organic group. R ³ and R ⁴ each independently represent a hydrogen atom, NH ₄ , SO ₂ NH ₂ or a monovalent organic group having 1 to 10 carbon atoms. p, q, r, and s each independently represent an integer of 0 to 4. However, p + q + r + s> 0, p + r ≦ 6, and q + s ≦ 6. In the general formula (2), R ⁵ represents a C 1-30 divalent organic group having a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group or a sulfonamide group. X represents —CH ₂ —, —C (CH ₃ ) ₂ —, —COO—, —C (CF ₃ ) ₂ —, —CO— or —SO ₂ —. In the general formula (3), R ⁷ and R ⁸ are each independently a benzene ring, a benzene ring substituted with an alkyl group having 1 to 6 carbon atoms, a benzene ring substituted with an ester group having 1 to 6 carbon atoms, or a naphthalene ring. And a naphthalene ring substituted with an alkyl group having 1 to 6 carbon atoms or a naphthalene ring substituted with an ester group having 1 to 6 carbon atoms. Z represents —CH ₂ —, —C (CH ₃ ) ₂ —, —COO—, —C (CF ₃ ) ₂ —, —CO— or —SO ₂ —. Q represents a 4-naphthoquinonediazidosulfonyl group, a 5-naphthoquinonediazidesulfonyl group, or an o-nitrobenzyl group. u represents 0 or 1; v is in the range of 2.5 to 5, x is in the range of 0 to 2.5, and w and y are in the range of 0 to 5. However, 3 ≦ v + x ≦ 5 and 0 ≦ w + y ≦ 5.

  According to the present invention, a photosensitive resin composition having high sensitivity and excellent pattern shape after heat treatment can be obtained.

  1st form of the photosensitive resin composition of this invention is (a) resin which has a repeating unit represented by General formula (1), (b) resin which has a repeating unit represented by General formula (2) (C) a photoacid generator represented by the general formula (3) and (d) a photoacid generator other than the above (c), a photosensitive resin composition comprising the above (c) and (d The total content of (a) and (b) is from 1 part by weight to 50 parts by weight with respect to 100 parts by weight of the total content of (a) and (b), and the content of (c) and the above (d ) Content ratio (c / d) is 0.10 or more and 0.70 or less (weight ratio). In addition, the second form of the photosensitive resin composition of the present invention is (e) at least one selected from the group consisting of an imide ring, an imidazole ring, an oxazole ring, a thiazole ring and an oxadiazole ring, and a hydroxyl group or a carboxyl group. (B) a resin having a repeating unit represented by the general formula (2), (c) a photoacid generator represented by the general formula (3), and (d) a light other than the above (c) A photosensitive resin composition containing an acid generator, wherein the total content of (c) and (d) is 1 wt. Per 100 parts by weight of the total content of (b) and (e). The content ratio of (c) and the content of (d) (c / d) is 0.10 or more and 0.70 or less (weight ratio). And Hereinafter, each component will be described.

  The first form of the photosensitive resin composition of the present invention contains (a) a resin having a repeating unit represented by the following general formula (1). Such a resin exhibits excellent heat resistance.

In the general formula (1), R ¹ represents a C 2-30 divalent organic group, and R ² represents a C 2-30 bivalent organic group. R ³ and R ⁴ each independently represent a hydrogen atom, NH ₄ , SO ₂ NH ₂ or a monovalent organic group having 1 to 10 carbon atoms. p, q, r, and s each independently represent an integer of 0 to 4. However, p + q + r + s> 0, p + r ≦ 6, and q + s ≦ 6.

In the general formula (1), R ¹ and R ² preferably have an aromatic ring. You may have heterocyclic rings, such as an imide ring, an oxazole ring, an imidazole ring, a thiazole ring, and an oxazine ring. Moreover, in order to improve adhesiveness, siloxane diamine residues such as 1,3-bis (3-aminopropyl) dimethylsiloxane and α, ω-bis (4-phenyl) permethylpolysiloxane are used as R ^1. Also good. Such a siloxane diamine residue is preferably 0.1 to 70 mol% in R ¹ . Examples of R ³ and R ⁴ include hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, trimethylsilyl group, phenyl group, hydroxyphenyl group, carboxylphenyl group, methylcarboxylphenyl Groups and the like. From the viewpoint of solubility in an alkali developer, a hydrogen atom, a hydroxyphenyl group or a carboxylphenyl group is preferred.

  (A) The resin having the repeating unit represented by the general formula (1) has a suitable solubility in an alkali developer by having a carboxyl group or a hydroxyl group, preferably a phenolic hydroxyl group. The dissolution rate in the alkali developer is preferably 4 nm / second or more, more preferably 10 nm / second or more. Moreover, 10,000 nm / second or less is preferable and 5,000 nm / second or less is more preferable.

  In the present invention, (a) the resin having the repeating unit represented by the general formula (1) preferably has 70% by weight or more of the repeating unit represented by the general formula (1). More preferably, it is 90 weight% or more.

  (A) The resin having a repeating unit represented by the general formula (1) preferably has a number average molecular weight of 1,000 or more, more preferably 5,000 or more, and still more preferably 8,000 or more. On the other hand, 500,000 or less is preferable, 100,000 or less is more preferable, and 70,000 or less is more preferable.

  (A) Among resins having a repeating unit represented by the general formula (1), a polyimide precursor or a polybenzoxazole precursor is more preferable. In the state of the precursor, these resins are highly transparent to mercury lamp g-line, h-line and i-line, which are wavelengths mainly used for exposure, and highly soluble in alkaline aqueous solution. This is because the heat resistance and chemical resistance of the resin are greatly improved by ring closure.

  (A) The resin having a repeating unit represented by the general formula (1) is an acid compound such as dicarboxylic acid, tricarboxylic acid or tetracarboxylic acid or a derivative thereof, and diamine, triamine, tetraamine or a derivative thereof, for example, N-methylpyrrolidone, gamma butyrolactone, dimethyl sulfoxide, dimethylacetamide, dimethylformamide, dimethylimidazoline, propylene carbonate, phosphoric acid, polyphosphoric acid, phenol, metacresol, paracresol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, butyl cellosolve, It can be obtained by dissolving in a solvent such as ethyl cellosolve or ethylene glycol dimethyl ether and reacting in a range of -30 ° C to 300 ° C.

  Moreover, in the 2nd form of the photosensitive resin composition of this invention, it replaces with (a) resin which has a repeating unit represented by General formula (1), or is represented by (a) General formula (1). (E) a resin having at least one selected from the group consisting of an imide ring, an imidazole ring, an oxazole ring, a thiazole ring and an oxadiazole ring, and a hydroxyl group or a carboxyl group. . When such a resin is used, a ring-closing reaction such as imidization or oxazolation is unnecessary after pattern processing. Therefore, a pattern having good heat resistance can be obtained simply by removing the solvent. (E) As a resin having at least one selected from the group consisting of an imide ring, an imidazole ring, an oxazole ring, a thiazole ring and an oxadiazole ring and a hydroxyl group or a carboxyl group, for example, hydroxypolyimide, hydroxypolybenzimidazole, Examples include hydroxypolybenzoxazole and hydroxypolybenzothiazole.

  The polyhydroxyimide can be obtained by reacting tetracarboxylic acid and diamine, and it is sufficient that at least one of tetracarboxylic acid or diamine is substituted with a hydroxyl group. Specifically, tetracarboxylic acid or a derivative thereof, and diamine or a derivative thereof are reacted in a polar solvent such as N-methylpyrrolidone, dimethyl sulfoxide, dimethylacetamide, dimethylformamide, gamma butyrolactone. If necessary, the reaction is generally performed at a temperature of 70 ° C. or higher in the presence of a dehydration ring-closing catalyst such as triethylamine, isoquinoline, pyridine, 1,8-diazabicyclo [5,4,0] undec-7-ene, dicyclohexylcarbodiimide. It can be obtained by removing the generated water. Moreover, tetracarboxylic acid and diamine which do not have a hydroxyl group may be copolymerized, and the amount is preferably 70 mol% or less.

  Polyhydroxybenzoxazole can be obtained by reacting dicarboxylic acid and bis (aminophenol), and it is sufficient that at least one of dicarboxylic acid and bis (aminophenol) is substituted with a hydroxyl group. Specifically, the corresponding bisaminophenol compound and dicarboxylic acid are generally reacted at a temperature of 150 ° C. or higher in polyphosphoric acid or the like. Further, dicarboxylic acid or bis (aminophenol) not substituted with a hydroxyl group may be copolymerized, and the amount is preferably 70 mol% or less of the whole. Moreover, after obtaining the above-mentioned polybenzoxazole precursor, polybenzoxazole can also be obtained by setting the temperature of the system to 200 ° C. or higher. Moreover, you may use together polyphosphoric acid, paratoluenesulfonic acid, etc. as a ring-closing catalyst.

  The polyhydroxybenzimidar can be obtained by reacting a dicarboxylic acid with a tetraamine, and it is sufficient that at least one of the dicarboxylic acid or the tetraamine is substituted with a hydroxyl group. Specifically, the corresponding tetraamine and dicarboxylic acid are generally reacted at temperatures of 150 ° C. or higher in N-methylpyrrolidone, gamma butyrolactone, dimethylformamide, dimethylacetamide, polyphosphoric acid and the like. Further, dicarboxylic acid or tetraamine not substituted with a hydroxyl group may be copolymerized, and the amount is preferably 70 mol% or less of the whole.

  Polybenzothiazole can be obtained by reacting bis (aminothiophenol) and dicarboxylic acid, and at least one of bis (aminothiophenol) or dicarboxylic acid may be substituted with a hydroxyl group. Specifically, the corresponding bis (aminothiophenol) and dicarboxylic acid are generally reacted at a temperature of 150 ° C. or higher in polyphosphoric acid or the like. Further, dicarboxylic acid or bis (aminothiophenol) not substituted with a hydroxyl group may be copolymerized, and the amount is preferably 70 mol% or less of the whole. Moreover, after obtaining the above-mentioned polybenzoxazole precursor, polybenzoxazole can also be obtained by setting the temperature of the system to 200 ° C. or higher. Moreover, you may use together polyphosphoric acid, paratoluenesulfonic acid, etc. as a ring-closing catalyst.

  These resins include 1,3-bis (3-aminopropyl) tetramethyldisiloxane, instead of diamine, bisaminophenol, tetraamine, and bis (aminothiophenol) in order to improve adhesion. , 5-bis (3-aminopropyl) hexamethyltrisiloxane, α, ω-bis (3-aminopropyl) permethylpolysiloxane, bis (4-aminophenyl) tetramethylsiloxane, bis (3-aminophenyl) tetra Silicon diamines such as methylsiloxane can be copolymerized in an amount of 1 to 30 mol%.

  The photosensitive resin composition of the present invention contains (b) a resin having a repeating unit represented by the following general formula (2). By containing such a resin, the development characteristics of the resulting photosensitive resin composition can be greatly improved, and high sensitivity and excellent pattern processing accuracy can be exhibited.

In the general formula (2), R ⁵ represents a divalent organic group having 1 to 30 carbon atoms having a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group or a sulfonamido group. X represents —CH ₂ —, —C (CH ₃ ) ₂ —, —COO—, —C (CF ₃ ) ₂ —, —CO— or —SO ₂ —.

In the general formula (2), examples of R ⁵ include those represented by the following general formula.

In the above formula, A represents a COOH, OH, SO ₃ H or SO ₂ NH ₂ group. R ¹⁰ represents a monovalent organic group having 1 to ¹⁰ carbon atoms or NO ₂ . As _the monovalent organic group having 1 to 10 carbon ^{_{atoms, CH 2 OH, CONH 2,}} COOR 11, CN, C 6 H 4 OH, C 5 NH 5, C 6 H 4 COOH, C 6 H 3 ( _{OH) 2,} etc. _{C 6 H 5, C 10 H} 9, C 10 H 8 OH and the like. R ¹¹ is an organic group having 1 to 9 carbon atoms, y is an integer of 0 to 4, z is an integer of 1 to 4, zz is an integer of 1 to 5, and aa represents 0 or 1.

  (B) Examples of the resin having the repeating unit represented by the general formula (2) include a phenol resin, a novolac resin, polyhydroxystyrene, polyacrylic acid, polymethacrylic acid, or a copolymer thereof. it can. Such a resin has moderate solubility in an alkali developer. The dissolution rate in the alkali developer is preferably 10 nm / second or more, and preferably 10,000 nm / second or less. Moreover, in order to adjust the dissolution rate with respect to aqueous alkali solution, the components which are not melt | dissolved in aqueous alkali solution, such as methyl methacrylate, methyl alkrate, styrene, vinylbenzene, can also be copolymerized. As the resin having a repeating unit represented by the general formula (2), a phenol resin, a novolac resin, and hydroxystyrene are preferable from the viewpoint of interaction with the photoacid generator, and film thickness reduction can be reduced. More preferably, it is a phenol resin or a novolac resin.

  In the present invention, (b) the resin having a repeating unit represented by the general formula (2) preferably has 50% by weight or more of the repeating unit represented by the general formula (2). Further, the resin of the component (b) preferably has a number average molecular weight of 1,000 or more, more preferably 2,000 or more, and further preferably 3,000 or more. On the other hand, 1,000,000 or less is preferable, 500,000 or less is more preferable, and 100,000 or less is more preferable.

  (B) Resins having a repeating unit represented by the general formula (2) include, for example, methacrylic acid, acrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, vinyl hydroxybenzene, vinyl carboxybenzene, etc., and azoisobutyronitrile. It can be obtained by radical polymerization in a solvent such as ethanol or isopropanol together with a radical initiator such as benzoyl peroxide. In this case, methyl methacrylate, ethyl methacrylate, styrene or the like can be copolymerized in order to further adjust the solubility. It is also possible to react phenol compounds such as phenol, m-cresol, p-cresol, and xylinol with formaldehyde, acetone, methyl ethyl ketone, etc. under an acid catalyst such as p-toluenesulfonic acid, polyphosphoric acid, sulfuric acid, etc. Obtainable.

  In the photosensitive resin composition of the present invention, the dissolution rate of the resins (a), (b) and (e) as a whole in the alkaline developer is preferably 4 nm / second or more and 10,000 nm / second or less. Other resins can be used as long as they have such a dissolution rate.

  In the photosensitive resin composition of the present invention, (b) the content of the resin having a repeating unit represented by the general formula (2) is 10 with respect to 100 parts by weight of the resin of (a) or (e). Part by weight or more is preferable and 67 parts by weight or more is more preferable. In addition, when both (a) component and (e) component are included, let these total amount be 100 weight part. When the amount of the resin (b) is 10 parts by weight or more, the effect of increasing sensitivity is remarkably obtained. On the other hand, from the viewpoint of heat resistance of the obtained photosensitive resin composition, 1,000 parts by weight or less is preferable, and 900 parts by weight or less is more preferable.

  The photosensitive resin composition of the present invention has high heat resistance and sensitivity by containing the resin (b) in addition to the above (a) or (e). However, a pattern formed from a photosensitive resin composition having such a resin has a problem that the pattern shape is deformed round by heat treatment at a high temperature. The photosensitive resin composition of the present invention contains (c) a photoacid generator represented by the following general formula (3) and (d) a photoacid generator other than the above (c), thereby providing high sensitivity. The deformation of the pattern due to the heat treatment can be suppressed while maintaining the above.

In the general formula (3), R ⁷ and R ⁸ are each independently a benzene ring, a benzene ring substituted with an alkyl group having 1 to 6 carbon atoms, a benzene ring substituted with an ester group having 1 to 6 carbon atoms, or a naphthalene ring. And a naphthalene ring substituted with an alkyl group having 1 to 6 carbon atoms or a naphthalene ring substituted with an ester group having 1 to 6 carbon atoms. Z represents —CH ₂ —, —C (CH ₃ ) ₂ —, —COO—, —C (CF ₃ ) ₂ —, —CO— or —SO ₂ —. Q represents a 4-naphthoquinonediazidosulfonyl group, a 5-naphthoquinonediazidesulfonyl group, or an o-nitrobenzyl group. u represents 0 or 1; v is in the range of 2.5 to 5, x is in the range of 0 to 2.5, and w and y are in the range of 0 to 5. However, 3 ≦ v + x ≦ 5 and 0 ≦ w + y ≦ 5.

  (C) The photoacid generator represented by the general formula (3) is a compound having 2.5 or more naphthoquinonediazidosulfonyl groups or nitrobenzyl groups on one benzene ring or naphthalene ring. Such a compound can be obtained by esterifying a phenol compound having at least three OH groups in one benzene ring or naphthalene ring and naphthoquinone diazide sulfonic acid or o-nitrobenzyl carboxylic acid. Examples of such phenol compounds include trihydroxybenzene, tetrahydroxybenzene, methyl gallate, ethyl gallate, methyl tetrahydroxybenzenecarboxylate, ethyl tetrahydroxybenzenecarboxylate, 2,3,4-trihydroxybenzophenone, 2,3 , 4,5-tetrahydroxybenzophenone or 2,3,4,4′-tetrahydroxybenzophenone, trihydroxynaphthalene, tetrahydroxynaphthalene.

  (C) Among the photoacid generators represented by the general formula (3), particularly preferred compounds are trihydroxybenzene, tetrahydroxybenzene, methyl gallate, ethyl gallate, methyl tetrahydroxybenzenecarboxylate or tetrahydroxybenzene. Mention may be made of esters of ethyl carboxylate and naphthoquinone diazide sulfonic acid.

  By containing such a compound, particularly when the pattern is heat-treated at a high temperature of 200 ° C. or higher, (c) a photoacid generator represented by the general formula (3), and (b) the general formula (2) Since the cross-linking reaction of the resin having a repeating unit represented by the above occurs densely and the glass transition temperature of the resin composition before curing becomes high, the resin composition softens during the heat treatment and suppresses pattern collapse. Can do. However, this compound has low photosensitivity and tends to lower the sensitivity of the resulting photosensitive resin composition. For this reason, it is important to contain (d) component mentioned later with (c) component. In the photosensitive resin composition of the present invention, the content of the component (c) is 0.1 parts by weight with respect to 100 parts by weight of the resin of the component (a) or the component (e) and the component (b). The above is preferable, and 0.5 parts by weight or more is more preferable. Moreover, 10 weight part or less is preferable, 5 weight part or less is more preferable, and 4 weight part or less is further more preferable.

  The photosensitive resin composition of the present invention contains (d) a photoacid generator other than (c) above, together with the (c) naphthoquinonediazide compound represented by the general formula (3). Such a photoacid generator is a compound that releases an acid upon irradiation with actinic rays such as ultraviolet rays, far ultraviolet rays, near ultraviolet rays, electron beams, and X-rays used for exposure. Specific examples include naphthoquinone diazide compounds other than the component (c), sulfonium salts, iodonium salts, diazonium salts, and the like. When exposure is performed with a mercury lamp, naphthoquinone diazide sulfonic acid esters and amides other than the component (c) are preferable.

  The quinonediazide sulfonic acid ester is an ester-bonded quinonediazide sulfonic acid to a polyhydroxy compound, a quinonediazide sulfonic acid sulfonated to a polyamino compound, a quinonediazide sulfonic acid ester-bonded to a polyhydroxypolyamino compound, and / or Examples thereof include those having a sulfonamide bond. Although all the functional groups of these polyhydroxy compounds and polyamino compounds may not be substituted with quinonediazide, it is preferable that 50 mol% or more of the entire functional groups are substituted with quinonediazide. If it is less than 50 mol%, the solubility in an alkali developer becomes too high, and a contrast with an unexposed portion cannot be obtained, and a desired pattern may not be obtained. By using such a quinonediazide compound, a positive photosensitive resin precursor composition sensitive to i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp, which is a general ultraviolet ray, is obtained. be able to.

  As the polyhydroxy compound, one having two or less phenolic hydroxyl groups in one aromatic ring is used. Specifically, bisphenol A, methylene bisphenol, sulfone bisphenol, hexafluoropropyl (bisphenol), phenol, naphthol, cresol, 1,1,1-tris (4-hydroxyphenyl) ethane, tris (4-hydroxyphenyl) methane 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol, 2,6-bis [(2-hydroxy-5-methylphenyl) methyl ] -4-methylphenol and the like, but are not limited thereto.

  A polyamino compound can also be used in place of the polyhydroxy compound. As the polyamide compound, one having two or less amino groups in one aromatic ring is used. Specifically, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4′-diamino Examples include, but are not limited to, diphenyl sulfide, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, and 3,3′-dihydroxybenzidine.

  In the present invention, quinonediazide is preferably a 5-naphthoquinonediazidosulfonyl group or a 4-naphthoquinonediazidesulfonyl group. The 4-naphthoquinonediazide sulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. The 5-naphthoquinone diazide sulfonyl ester compound has an absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure. In the present invention, it is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound or a 5-naphthoquinone diazide sulfonyl ester compound depending on the wavelength to be exposed. Further, a naphthoquinone diazide sulfonyl ester compound in which 4-naphthoquinone diazide sulfonyl group and 5-naphthoquinone diazide sulfonyl group are used in the same molecule can be obtained, or 4-naphthoquinone diazide sulfonyl ester compound and 5-naphthoquinone diazide sulfonyl ester compound. Can also be used in combination.

  Further, when the molecular weight of the quinonediazide compound is larger than 5,000, the quinonediazide compound is not sufficiently thermally decomposed in the subsequent heat treatment, so that the heat resistance of the obtained film is lowered, the mechanical properties are lowered, and the adhesiveness is lowered. May cause problems. From this point of view, the molecular weight of the preferred quinonediazide compound is 300 to 3,000. More preferably, it is 350-1500.

  From these facts, preferred compounds include 1,1,1-tris (4-hydroxyphenyl) ethane, tris (4-hydroxyphenyl) methane, 4,4 ′-[1- [4- [1- (4 -Hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol, 2,6-bis [(2-hydroxy-5-methylphenyl) methyl] -4-methylphenol, and the like.

  The quinonediazide compound used in the present invention is synthesized from a specific phenol compound by the following method. For example, there is a method of reacting 5-naphthoquinonediazide sulfonyl chloride and a phenol compound in the presence of triethylamine. Examples of the method for synthesizing a phenol compound include a method in which an α- (hydroxyphenyl) styrene derivative is reacted with a polyhydric phenol compound under an acid catalyst.

  In the photosensitive resin composition of the present invention, the total content of the photoacid generators (c) and (d) is 100 parts by weight of the total content of the resin (a) or (e) and the resin (b). On the other hand, it is important that it is 1 part by weight or more and 50 parts by weight or less. If the amount is less than 1 part by weight, the photosensitivity is greatly deteriorated, the difference in dissolution rate between the exposed part and the unexposed part is not sufficient, and a pattern cannot be obtained. Preferably it is 10 weight part or more, More preferably, it is 15 weight part or more. On the other hand, when the amount is more than 50 parts by weight, the light absorption of the photoacid generator is increased and the sensitivity is lowered. Preferably it is 35 weight part or less, More preferably, it is 30 weight part or less.

  Furthermore, it is important that the content ratio (c / d) of (c) and (d) is 0.10 or more and 0.70 or less (weight ratio). If (c / d) is less than 0.1, pattern plasticization occurs during the curing process performed after development with an alkaline aqueous solution, and pattern collapse occurs. On the other hand, if the ratio is more than 0.7, the absorption of ultraviolet rays used for exposure increases and sensitivity is lowered. A more preferable range of c / d is 0.15 or more and 0.60 or less.

  The photosensitive resin composition of the present invention may contain a thermal crosslinking agent for the purpose of increasing chemical resistance after heat treatment and glass transition temperature. Examples of the thermal crosslinking agent include epoxy compounds, oxetane compounds, methylol compounds, alkoxymethyl compounds, bismaleimide compounds, acrylic compounds, and the like, and epoxy compounds and / or oxetane compounds are preferable. By using an epoxy compound and / or an oxetane compound, curing proceeds even in an ultra-low temperature heat treatment at 80 ° C. to 220 ° C., and the insulation and chemical resistance of the cured film after curing are improved.

  Examples of the epoxy compound include those having two epoxy groups, "Epolite" (registered trademark) 40E, "Epolite" (registered trademark) 100E, "Epolite" (registered trademark) 200E, "Epolite" (registered trademark) 400E, "Epolite" (registered trademark) 70P, "Epolite" (registered trademark) 200P, "Epolite" (registered trademark) 400P, "Epolite" (registered trademark) 1500NP, "Epolite" (registered trademark) 80MF, "Epolite" (registered trademark) ) 4000, “Epolite” (registered trademark) 3002 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), “Denacol” (registered trademark) EX-212L, “Denacol” (registered trademark) EX-214L, “Denacol” (Registered trademark) EX-216L, "Denacol" (registered trademark) EX-850L , Manufactured by Nagase ChemteX Co., Ltd.), “GAN” (registered trademark), “GOT” (registered trademark) (trade name, manufactured by Nippon Kayaku Co., Ltd.), “Epicoat” (registered trademark) 828, “ “Epicoat” (registered trademark) 1002, “Epicoat” (registered trademark) 1750, “Epicoat” (registered trademark) 1007, “YX8100-BH30”, “E1256”, “E4250”, “E4275” (above, trade name, Japan) Epoxy Co., Ltd.), "Epiclon" (registered trademark) EXA-9583, "HP4032" (trade name, manufactured by Dainippon Ink & Chemicals, Inc.), and "Tepic" (registered trademark) ) S, “Tepic” (registered trademark) G, “Tepic” (registered trademark) P (above, trade name, manufactured by Nissan Chemical Industries, Ltd.), “Denacol” (registered trademark) EX-321 (Trade name, manufactured by Nagase ChemteX Corporation), “NC6000” (trade name, manufactured by Nippon Kayaku Co., Ltd.), and having four or more, “EPPN502H”, “NC3000” (above, trade name, Japan) Kayaku Co., Ltd.), “Epiclon” (registered trademark) N695, “HP7200” (trade name, manufactured by Dainippon Ink & Chemicals, Inc.), and the like. Two or more of these may be used in combination.

  “Epolite” (registered trademark) M-1230 having one epoxy group, “Epolite” (registered trademark) EHDG-L (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), “PP-101” (trade name, (Tohto Kasei Co., Ltd.), “NK Oligo EA-1010 / ECA” (trade name, Shin-Nakamura Chemical Co., Ltd.), glycidyl methyl ether and the like can be added to adjust the degree of crosslinking.

  Examples of oxetane compounds include “Ethanacol” (registered trademark) EHO, “Ethanacol” (registered trademark) OXBP, “Ethanacol” (registered trademark) OXTP, “Ethanacol” (registered trademark) OXMA (above, trade name, Ube Industries, Ltd.) Manufactured) and oxetaneated phenol novolac. Two or more of these may be used in combination.

  In the present invention, the epoxy compound and / or oxetane compound preferably has two or more epoxy groups or oxetane groups. By having two or more epoxy groups or oxetane groups, a crosslinked structure can be introduced into the resin after thermosetting, and solvent resistance can be further improved.

  The epoxy compound and / or oxetane compound preferably has an epoxy equivalent or oxetane equivalent of 100 to 500. By setting it to 100 or more, the toughness of the cured film after heat treatment can be improved, and by setting it to 500 or less, a high-density stitch structure can be introduced after heat treatment, so that the cured film after heat treatment is made highly insulating. be able to.

  The content of such a thermal crosslinking agent is preferably 1 to 20 parts by weight, more preferably 100 parts by weight of the total content of the resin (a) or (e) and the resin (b). Is in the range of 3 to 15 parts by weight.

  Moreover, it is also preferable to contain the compound which has a thermal crosslinkable group represented by following General formula (4) as a thermal crosslinking agent. By having such a thermally crosslinkable group, the electrical insulation and chemical resistance of the cured film after heat treatment can be improved.

In the general formula (4), E represents an organic group having 3 to 50 carbon atoms, ^{R 9} is a hydrogen atom, an alkyl group or an alkoxyl group having 1 to 10 carbon atoms. k shows the integer of 1-12. From the viewpoint of further improving the chemical resistance of the cured film, k is preferably 3 or more. Further, from the viewpoint of suppressing shrinkage during curing, k is preferably 6 or less.

  (F) Preferred compounds as a thermal crosslinking agent having 3 to 6 thermal crosslinkable groups in one molecule are exemplified below.

  When the photosensitive resin composition of the present invention contains an epoxy compound and / or an oxetane compound, it may further contain a curing accelerator. By combining an epoxy compound and / or oxetane compound and a curing accelerator, curing of the epoxy compound and / or oxetane compound can be promoted, and the solvent resistance can be improved even by heat treatment at 150 ° C. or lower. Examples of the curing accelerator include various imidazoles, imidazole silanes, imidazolines, acid anhydrides, phosphorus compounds such as triphenylphosphine, and the like. As various imidazoles, imidazole, 2-methylimidazole, 2-undecylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2 -Methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole and the like. As imidazole silane, IS-1000, IS-1000D, IM-1000, SP-1000, IA-100A, IA-100P, IA-100F (above, trade name, manufactured by Nikko Materials Co., Ltd.), 1 in addition , 8-diazabicyclo [5,4,0] undec-7-ene. Examples of the acid anhydride include methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, “ADEKA HARDNER” (registered trademark) EH-3326, “ADEKA HARDNER” (registered trademark) EH-703, “ADEKA HARDNER” ( (Registered trademark) EH-705A (trade name, manufactured by Asahi Denka Kogyo Co., Ltd.), "Epicron" (registered trademark) B-570, "Epicron" (registered trademark) B-650 (trade name, Dainippon Ink and Chemicals, Inc.) As a phosphorus compound, triphenylphosphine, quaternary phosphonium salt, and the like can be given. The content of the curing accelerator is preferably in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the total content of the resin (a) or (e) and the resin (b). By setting it as 0.01 weight part or more, hardening of a thermal crosslinking agent can be accelerated | stimulated effectively, and the insulation and heat resistance of hardened | cured material can be improved by setting it as 10 weight part or less.

  The photosensitive resin composition of the present invention is suitably used as a material for semiconductor passivation films, protective films for semiconductor elements, interlayer insulating films for multilayer wiring for high-density mounting, insulating layers for organic electroluminescent elements, and the like.

  Hereinafter, it demonstrates more concretely using an Example. First, an evaluation method of each example will be described.

(1) Sensitivity Using a coating and developing apparatus Mark-7 manufactured by Tokyo Electron Co., Ltd. on an 8-inch mirror silicon wafer, the film thickness after pre-baking at 120 ° C. for 3 minutes is 8 ± 0.5 μm. Varnish was spin coated. Then, the prebaking process for 120 degreeC x 3 minutes was similarly performed using the hot plate of Mark-7.

To the resulting pre-baked film, using a reduction projection exposure apparatus DSW8750 of GCA ^{Corporation, 0mJ / cm 2 ~1000mJ / cm} 2 to 25 mJ / cm ² by varying the exposure amount was exposed process. The exposure wavelength was 365 nm.

  Using a Mark-7 developing device, a 2.38 wt% tetramethylammonium hydroxide aqueous solution (ELM-D manufactured by Mitsubishi Gas Chemical Co., Ltd.) is rotated 50 times on the pre-baked film after exposure using a straight nozzle. Was discharged for 8 seconds, and then stopped for 20 seconds. This development process was repeated until the exposed part was eluted in the developer, and after elution, the same development process was performed once more to obtain a pattern. In the case where the pattern does not become clear even after this development processing is performed for 3 minutes or more, the further processing was stopped.

  The pattern thus obtained was observed, and the minimum exposure amount at which the pattern was resolved was defined as sensitivity.

(2) Film reduction amount The film thickness of the pre-baked film (before development) prepared by the method described in (1) above and the film developed by the method described in (1) above (after development) is determined by Dai Nippon Screen Co., Ltd. The film thickness was measured at a refractive index of 1.629 using a film thickness measuring device (Lambda Ace VM802). The film thickness was obtained by subtracting the film thickness after development from the film thickness before development. The amount of film reduction is preferably 1 μm or less, and more preferably 0.5 μm or less.

(3) Pattern shape after heat treatment The wafer with a pattern produced by the method described in (1) above is put into an inert oven INT-21CD manufactured by Koyo Thermo System Co., Ltd., and the temperature is raised from room temperature to 150 ° C. in 10 minutes. The temperature was raised at 150 ° C. for 15 minutes, then at 7 ° C./minute, and heat-treated at 300 ° C. for 30 minutes in a nitrogen atmosphere with an oxygen concentration of 20 ppm or less. After the heat treatment, it was cooled in an oven until it became 50 ° C. or lower and then taken out. A necessary portion was divided from the taken-out wafer, and the cross-sectional shape of the pattern was observed using a scanning electron microscope S-4800 manufactured by JEOL Ltd. and Hitachi Electronics Co., Ltd. A pattern with a rectangular corner was good, and a pattern with a rounded shape was considered defective.

(4) Mechanical properties A 6-inch silicon wafer was coated with varnish so that the film thickness after pre-baking would be 13 μm, and then using a hot plate (coating and developing apparatus Mark-7 manufactured by Tokyo Electron Ltd.) A prebaked film was obtained by prebaking at 120 ° C. for 3 minutes. Thereafter, development was performed by the method described in (1) above. The obtained resin film was heated using an inert oven INH-21CD manufactured by Koyo Thermo System Co., Ltd. under a nitrogen stream (oxygen concentration 20 ppm or less) at 150 ° C. for 30 minutes and then to 300 ° C. in 1 hour. Heat treatment was performed at 300 ° C. for 30 minutes to produce a heat resistant resin film (cured film).

  The cured film prepared on the silicon wafer was immersed in 47 wt% hydrofluoric acid for 7 minutes at room temperature, washed with water, and carefully peeled from the silicon wafer. The moisture was wiped, and then cut into strips having a width of 1 cm and a length of 10 cm to obtain measurement samples.

  The measurement sample was set at an initial sample length of 50 mm in Orientec Tensilon RTM-100, and a tensile test was performed at a tensile speed of 50 mm / min. The breaking elongation was measured at n = 5, and the largest value was taken as the mechanical property. This value is preferably 15% or more.

Synthesis Example 1: Synthesis of polyimide precursor 16.4 g of 4,4′-diaminodiphenyl ether (Wakayama Seika Kogyo Co., Ltd., DAE, 0.08 mol) was added to 300 g of N-methylpyrrolidone (Mitsubishi Chemical Co., Ltd.) NMP), 31.0 g of oxydiphthalic anhydride (manac Co., Ltd., ODPA, 0.1 mol) was added, and the mixture was stirred at 40 ° C. for 1 hour. Thereafter, 4.36 g of 3-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd., AMP, 0.04 mol) was added, and the mixture was further stirred at 40 ° C. for 2 hours. Then, the obtained solution was thrown into 3000 mL of water, and white solid was obtained. Further, washing was repeated twice with 3 L of water, and then dried with a vacuum dryer at 50 ° C. for 72 hours to obtain a white powder of polyimide precursor 1.

Synthesis Example 2: Synthesis of polyimide resin 29-28 g (3-amino-4-hydroxyphenyl) hexafluoropropane (manufactured by AZ Materials, 6FAP, 0.08 mol) was dissolved in 300 g of NMP. 31.0 g (0.1 mol) of ODPA was added thereto, and after stirring for 1 hour at 40 ° C., 4.36 g (0.04 mol) of AMP was added, 1 hour at 70 ° C., and then 1 g of isoquinoline and 100 mL of toluene were added. The mixture was stirred for 4 hours at 180 ° C. while removing water distilled off with toluene. Thereafter, the solution was naturally cooled and poured into 3 L of water to obtain a white solid. Further, it was washed with 3 L of water three times and filtered to collect a white solid. This solid was dried with a vacuum dryer at 50 ° C. for 72 hours to obtain a polyimide resin 2.

Synthesis Example 3 Synthesis of Polybenzoxazole (PBO) Precursor 36.6 g (0.1 mol) of 6FAP was dissolved in 200 g of NMP and 100 g of glycidyl methyl ether (manufactured by Tokyo Chemical Industry Co., Ltd., 1 mol) and cooled to −10 ° C. did. A solution prepared by dissolving 28.91 diphenyl ether dicarboxylic acid chloride (DEDC, manufactured by Nippon Agricultural Chemicals Co., Ltd., 0.098 mol) in 300 mL of acetone was added dropwise so that the internal temperature did not exceed 10 ° C. After completion of the dropping, the temperature of the solution was kept at −10 ° C. for 2 hours, and then the temperature of the solution was returned to room temperature over 30 minutes. Thereafter, the solution was poured into 3 L of 50% methanol water to collect a white solid. Further, it was washed with methanol water and then with water, and the white solid was collected by filtration and dried with a vacuum dryer at 50 ° C. for 48 hours to obtain polybenzoxazole (PBO) precursor 3.

Synthesis Example 4 Synthesis of acrylic resin Methyl methacrylate 10 g (manufactured by Tokyo Chemical Industry Co., Ltd., 0.1 mol), styrene 5.2 g (manufactured by Tokyo Chemical Industry Co., Ltd., 0.05 mol), hydroxystyrene 12 g (Tokyo Chemical Industry Co., Ltd.) ), 0.1 mol) and 1.72 g of methacrylic acid (Tokyo Kasei Co., Ltd., 0.02 mol) were added to 120 g of isopropyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.). Azoisobutyronitrile 0.5 g (manufactured by Tokyo Chemical Industry Co., Ltd.) was added thereto and stirred at 70 ° C. for 4 hours. Thereafter, the solution was poured into 10 L of water to obtain a white solid. Further, the solid was washed with water three times and then dried with a vacuum dryer at 50 ° C. for 72 hours to obtain an acrylic resin 4.

Synthesis Example 5 Synthesis of Photoacid Generator 1 36.8 g of methyl gallate (manufactured by Tokyo Chemical Industry Co., Ltd., 0.2 mol) was dissolved in 1000 mL of dioxane (manufactured by Wako Pure Chemical Industries, Ltd.), and the solution temperature was 40 ° C. I made it. To this, 161.1 g of 5-naphthoquinone diazide sulfonic acid chloride (Toyo Gosei Co., Ltd., NAC-5, 0.6 mol) was added, and 60.7 g of triethylamine (manufactured by Wako Pure Chemical Industries, Ltd., 0.6 mol). Was added dropwise over 15 minutes so that the internal temperature did not exceed 45 ° C. Thereafter, the mixture was stirred at 40 ° C. for 2 hours to carry out the reaction, and the triethylamine hydrochloride precipitated in the system was removed by filtration. The filtrate was poured into 5 L of water to obtain a yellowish red precipitate. This precipitate was washed with a 1% aqueous hydrochloric acid solution, and further washed with 1 L of water three times. After confirming that the pH of the water was 6-8, the precipitate was collected by filtration, and a vacuum dryer at 50 ° C. And dried for 72 hours to obtain a photoacid generator 1 represented by the following formula.

Synthesis Example 6 Synthesis of Photoacid Generator 2 2,3,4,4′-Tetrahydroxybenzophenone 23.0 g (manufactured by Tokyo Chemical Industry Co., Ltd., 0.1 mol) was added to dioxane (manufactured by Wako Pure Chemical Industries, Ltd.) 1000 mL. The solution temperature was adjusted to 40 ° C. A solution obtained by adding 80.6 g of 4-naphthoquinonediazidesulfonic acid chloride (manufactured by Toyo Gosei Co., Ltd., NAC-4, 0.3 mol) and diluting 30.3 g (0.3 mol) of triethylamine to 30 mL of dioxane was added. It was added dropwise over 15 minutes so that the internal temperature did not exceed 45 ° C. Thereafter, the mixture was stirred at 40 ° C. for 2 hours to carry out the reaction, and the triethylamine hydrochloride precipitated in the system was removed by filtration. The filtrate was poured into 5 L of water to obtain a yellowish red precipitate. This precipitate was washed with a 1% aqueous hydrochloric acid solution, and further washed with 1 L of water three times. After confirming that the pH of the water was 6-8, the precipitate was collected by filtration, and a vacuum dryer at 50 ° C. And dried for 72 hours to obtain a photoacid generator 2 represented by the following formula.

Synthesis Example 7 Synthesis of Photoacid Generator 3 Pyrogallol 25.2 g (manufactured by Tokyo Chemical Industry Co., Ltd., 0.2 mol) was dissolved in 1000 mL of dioxane (manufactured by Wako Pure Chemical Industries, Ltd.), and the solution temperature was adjusted to 40 ° C. . A solution obtained by adding 155.7 g of 5-naphthoquinone diazide sulfonic acid chloride (Toyo Gosei Co., Ltd., NAC-5, 0.58 mol) and diluting 58.6 g (0.58 mol) of triethylamine in 60 g of dioxane was added thereto. It was added dropwise over 15 minutes so that the internal temperature did not exceed 45 ° C. Thereafter, the mixture was stirred at 40 ° C. for 2 hours to carry out the reaction, and the triethylamine hydrochloride precipitated in the system was removed by filtration. The filtrate was poured into 5 L of water to obtain a yellowish red precipitate. This precipitate was washed with a 1% aqueous hydrochloric acid solution, and further washed with 1 L of water three times. After confirming that the pH of the water was 6-8, the precipitate was collected by filtration, and a vacuum dryer at 50 ° C. And dried for 72 hours to obtain a photoacid generator 3 represented by the following formula.

Synthesis Example 8 Synthesis of Photoacid Generator 4 Resorcinol 22.0 g (manufactured by Tokyo Chemical Industry Co., Ltd., 0.2 mol) was dissolved in 1000 mL of dioxane (manufactured by Wako Pure Chemical Industries, Ltd.), and the solution temperature was adjusted to 40 ° C. . A solution in which 5-naphthoquinone diazide sulfonic acid chloride 107.4 (manufactured by Toyo Gosei Co., Ltd., NAC-5, 0.4 mol) was added and 40.4 g (0.58 mol) of triethylamine was diluted in 60 g of dioxane was added. It was added dropwise over 15 minutes so that the internal temperature did not exceed 45 ° C. Thereafter, the mixture was stirred at 40 ° C. for 2 hours to carry out the reaction, and the triethylamine hydrochloride precipitated in the system was removed by filtration. The filtrate was poured into 5 L of water to obtain a yellowish red precipitate. This precipitate was washed with a 1% aqueous hydrochloric acid solution, and further washed with 1 L of water three times. After confirming that the pH of the water was 6-8, the precipitate was collected by filtration, and a vacuum dryer at 50 ° C. And dried for 72 hours to obtain a photoacid generator 4 represented by the following formula.

Synthesis Example 9 Synthesis of Photoacid Generator 5 4,4 ′-[1- [4- [1- (4-Hydroxyphenyl) -1-methylethyl] phenyl] -ethylidene] bisphenol 42.4 g (Honshu Chemical Co., Ltd.) ) TrisP-PA (0.1 mol) was dissolved in 1000 mL of dioxane (manufactured by Wako Pure Chemical Industries, Ltd.), and the solution temperature was adjusted to 40 ° C. To this, 67.1 g of 4-naphthoquinonediazidesulfonic acid chloride (Toyo Gosei Co., Ltd., NAC-5, 0.25 mol) was added, and 25.3 g of triethylamine (Wako Pure Chemical Industries, Ltd., 0.25 mol) was added. Was added dropwise over 15 minutes so that the internal temperature did not exceed 45 ° C. Thereafter, the mixture was stirred at 40 ° C. for 2 hours to carry out the reaction, and the triethylamine hydrochloride precipitated in the system was removed by filtration. The filtrate was poured into 5 L of water to obtain a yellowish red precipitate. This precipitate was washed with a 1% aqueous hydrochloric acid solution, and further washed with 1 L of water three times. After confirming that the pH of the water was 6-8, the precipitate was collected by filtration, and a vacuum dryer at 50 ° C. And dried for 72 hours to obtain a photoacid generator 5 represented by the following formula.

Synthesis Example 10 Synthesis of Photoacid Generator 6 2,3.0-Trihydroxybenzophenone 23.0 g (manufactured by Sankyo Kasei Kogyo Co., Ltd., 3HBP, 0.1 mol) was added to dioxane (manufactured by Wako Pure Chemical Industries, Ltd.) Dissolved in 1000 mL, the solution temperature was 40 ° C. 4-Naphthoquinonediazide sulfonic acid chloride 53.7g (Toyo Gosei Co., Ltd., NAC-5, 0.2mol) was added here, and triethylamine 20.2g (Wako Pure Chemical Industries, Ltd., 0.2mol). Was added dropwise over 15 minutes so that the internal temperature did not exceed 45 ° C. Thereafter, the mixture was stirred at 40 ° C. for 2 hours to carry out the reaction, and the triethylamine hydrochloride precipitated in the system was removed by filtration. The filtrate was poured into 5 L of water to obtain a yellowish red precipitate. This precipitate was washed with a 1% aqueous hydrochloric acid solution, and further washed with 1 L of water three times. After confirming that the pH of the water was 6-8, the precipitate was collected by filtration, and a vacuum dryer at 50 ° C. And dried for 72 hours to obtain a photoacid generator 6 represented by the following formula.

Synthesis Example 11 Synthesis of Photoacid Generator 7 17.6 g of 2,4-dihydroxybenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd., 0.1 mol) was dissolved in 1000 mL of dioxane (manufactured by Wako Pure Chemical Industries, Ltd.), and the solution temperature Was brought to 40 ° C. 4-Naphthoquinonediazide sulfonic acid chloride 53.7g (Toyo Gosei Co., Ltd., NAC-5, 0.2mol) was added here, and triethylamine 20.2g (Wako Pure Chemical Industries, Ltd., 0.2mol). Was added dropwise over 15 minutes so that the internal temperature did not exceed 45 ° C. Thereafter, the mixture was stirred at 40 ° C. for 2 hours to carry out the reaction, and the triethylamine hydrochloride precipitated in the system was removed by filtration. The filtrate was poured into 5 L of water to obtain a yellowish red precipitate. This precipitate was washed with a 1% aqueous hydrochloric acid solution, and further washed with 1 L of water three times. After confirming that the pH of the water was 6-8, the precipitate was collected by filtration, and a vacuum dryer at 50 ° C. And dried for 72 hours to obtain a photoacid generator 7 represented by the following formula.

Synthesis Example 12 Synthesis of Photoacid Generator 8 4,4 ′-[(2-Hydroxy-3-methoxylphenyl) methylene] bis [2,5-dimethylphenol] 18.9 g (manufactured by Honshu Chemical Industry Co., Ltd., Tris 25X -OV, 0.05 mol), 26.8 g (0.1 mol) of 5-naphthoquinonediazidesulfonic acid chloride was dissolved in 274 g of dioxane, and 11.1 g of triethylamine was added dropwise at 20 to 30 ° C. Then, stirring was continued at 20-30 degreeC for 2 hours, and reaction was performed. Thereafter, the precipitated hydrochloride of triethylamine is removed by filtration, and the filtrate is poured into a large amount of dilute aqueous hydrochloric acid solution to precipitate the reaction product. Then, the precipitate is filtered, washed with water, and overnight at 40 ° C. in a vacuum dryer. It dried and the photo-acid generator 8 represented by a following formula was obtained.

Example 1-22 and Comparative Example 1-18
Each component shown in Table 1-2 was placed in a 300 mL round bottom flask with stirring blades and stirred at room temperature for 4 hours. After completion of the stirring, the mixture was filtered through a polytetrafluoroethylene membrane filter (Sumitomo Electric Co., Ltd., PF-020) having a pore size of 2 μm to remove foreign matter, thereby obtaining a varnish. Using this varnish, as described above, the sensitivity, the amount of film reduction, the pattern shape after heat treatment, and the mechanical properties were evaluated. The results are summarized in Table 3.
The abbreviations listed in Table 1 are as follows.
PSF2808: Nomurak resin PSF2803 manufactured by Gunei Chemical Industry Co., Ltd. Novolak resin WPAG314 manufactured by Gunei Chemical Industry Co., Ltd. (4-methylphenyl) diphenylsulfonium perfluorooctylsulfonate MX270: Three manufactured by Wako Pure Chemical Industries, Ltd. NIKALAC MX-270 manufactured by WA Chemical Co., Ltd.
MW100: NIKALAC MW-100 manufactured by Sanwa Chemical Co., Ltd.
DMOM: Honshu Chemical Co., Ltd. 2,6-bis (methoxymethyl) -4-t-butylphenol GBL: Mitsubishi Chemical Co., Ltd. gamma butyrolactone

Claims (5)

(A) Resin having a repeating unit represented by the general formula (1), (b) Resin having a repeating unit represented by the general formula (2), (c) Photoacid represented by the general formula (3) A photosensitive resin composition containing a generator and (d) a photoacid generator other than (c) above, wherein the total content of (c) and (d) is the above (a) and (b) 1) to 50 parts by weight with respect to a total content of 100 parts by weight, and the content ratio (c / d) of (c) to (d) is 0.10 or more. The photosensitive resin composition characterized by being 0.70 or less (weight ratio).

(In the general formula (1), R ¹ represents a 2 to 8 valent organic group having 1 to 30 carbon atoms, and R ² represents a 2 to 8 valent organic group having 2 to 30 carbon atoms. R ³ and R ⁴ Each independently represents a hydrogen atom, NH ₄ , SO ₂ NH ₂ or a monovalent organic group having 1 to 10 carbon atoms, p, q, r and s each independently represent an integer of 0 to 4, provided that p + q + r + s> 0, p + r ≦ 6, and q + s ≦ 6 In the general formula (2), R ⁵ is a divalent C 1-30 having a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, or a sulfonamide group. Represents an organic group, X represents —CH ₂ —, —C (CH ₃ ) ₂ —, —COO—, —C (CF ₃ ) ₂ —, —CO— or —SO ₂ —, wherein the above general formula (3) during), ^{R 7} and ^{R 8} are each independently a benzene ring, an alkyl group having 1 to 6 carbon atoms A substituted benzene ring, a benzene ring substituted with an ester group having 1 to 6 carbon atoms, a naphthalene ring, a naphthalene ring substituted with an alkyl group having 1 to 6 carbon atoms, or a naphthalene ring substituted with an ester group having 1 to 6 carbon atoms Z represents —CH ₂ —, —C (CH ₃ ) ₂ —, —COO—, —C (CF ₃ ) ₂ —, —CO— or —SO ₂ —, Q represents a 4-naphthoquinonediazidesulfonyl group. , 5-naphthoquinonediazidosulfonyl group or o-nitrobenzyl group, u is 0 or 1, v is in the range of 2.5 to 5, x is in the range of 0 to 2.5, w and y are 0 to 0. The range is 5. However, 3 ≦ v + x ≦ 5 and 0 ≦ w + y ≦ 5. The photosensitive resin composition according to claim 1, wherein the resin (a) having a repeating unit represented by the general formula (1) contains a polyimide precursor and / or a polybenzoxazole precursor. (E) a resin having at least one selected from the group consisting of an imide ring, an imidazole ring, an oxazole ring, a thiazole ring and an oxadiazole ring, and a hydroxyl group or a carboxyl group, (b) represented by the general formula (2) A photosensitive resin composition comprising a resin having a repeating unit, (c) a photoacid generator represented by the general formula (3), and (d) a photoacid generator other than the above (c), The total content of c) and (d) is from 1 part by weight to 50 parts by weight with respect to the total of 100 parts by weight of the contents of (b) and (e), and the content of (c) The photosensitive resin composition, wherein the content ratio (c / d) of the amount (d) is from 0.10 to 0.70 (weight ratio).

(In the general formula (2), R ⁵ represents a C 1-30 divalent organic group having a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group or a sulfonamide group. X represents —CH ₂ —, — C (CH ₃ ) ₂ —, —COO—, —C (CF ₃ ) ₂ —, —CO— or —SO ₂ —, wherein R ⁷ and R ⁸ are each independently benzene. Ring, benzene ring substituted with an alkyl group having 1 to 6 carbon atoms, benzene ring substituted with an ester group having 1 to 6 carbon atoms, naphthalene ring, naphthalene ring substituted with an alkyl group having 1 to 6 carbon atoms, or 1 carbon atom Represents a naphthalene ring substituted with an ester group of ˜6, Z represents —CH ₂ —, —C (CH ₃ ) ₂ —, —COO—, —C (CF ₃ ) ₂ —, —CO— or —SO ₂ —. Q represents 4-naphthoquinonediazidosulfur N represents a 5-naphthoquinonediazidosulfonyl group or o-nitrobenzyl group, u represents 0 or 1, v represents a range of 2.5 to 5, x represents a range of 0 to 2.5, w and y represent The range is from 0 to 5, provided that 3 ≦ v + x ≦ 5 and 0 ≦ w + y ≦ 5. The photosensitive resin composition according to any one of claims 1 to 3, further comprising (f) a thermal crosslinking agent having 3 to 6 thermally crosslinkable groups in one molecule. (C) The photoacid generator represented by the general formula (3) is trihydroxybenzene, tetrahydroxybenzene, methyl gallate, ethyl gallate, methyl tetrahydroxybenzenecarboxylate, ethyl tetrahydroxybenzenecarboxylate, 2 , 3,4-trihydroxybenzophenone, 2,3,4,5-tetrahydroxybenzophenone or 2,3,4,4′-tetrahydroxybenzophenone containing a compound obtained by esterifying naphthoquinonediazidesulfonic acid The photosensitive resin composition according to any one of claims 1 to 4.