JP5625549B2 - Photosensitive polymer composition, pattern manufacturing method, and electronic component - Google Patents

Description

  The present invention relates to a photosensitive polymer composition, a method for producing a pattern, and an electronic component. More specifically, a positive photosensitive polymer composition capable of improving adhesion with a substrate while maintaining a good shape pattern without deteriorating sensitivity, resolution, heat resistance and chemical resistance, The present invention relates to a method for producing a patterned cured film using a polymer composition and an electronic component.

  Conventionally, polyimide resins having excellent heat resistance, electrical characteristics, mechanical characteristics, and the like have been used for surface protection films and interlayer insulating films of semiconductor elements. This polyimide resin film is generally made by reacting tetracarboxylic dianhydride and diamine in a polar solvent at room temperature and normal pressure, and thinning a polyimide precursor (polyamic acid) solution (so-called varnish) by spin coating or the like. It is formed by dehydrating and ring-closing (curing) (for example, Non-Patent Document 1).

  In recent years, a photosensitive polyimide obtained by imparting photosensitive characteristics to a polyimide resin itself has been used. When this photosensitive polyimide is used, the pattern forming process can be simplified, and the complicated pattern manufacturing process can be shortened (see, for example, Patent Documents 1 to 3).

Conventionally, an organic solvent such as N-methylpyrrolidone has been used for developing the photosensitive polyimide. Recently, however, a positive photosensitive resin that can be developed with an alkaline aqueous solution has been proposed from the viewpoint of environment and cost. ing. As a method for obtaining such an alkali developable positive photosensitive resin, a method of introducing an o-nitrobenzyl group into a polyimide precursor via an ester bond (for example, Non-Patent Document 2), soluble hydroxylimide or poly There are methods (for example, Patent Documents 4 and 5) of mixing a naphthoquinonediazide compound with a benzoxazole precursor.
Resins obtained by such a method can be expected to have a low dielectric constant, and photosensitive polybenzoxazole is attracting attention together with photosensitive polyimide from such a viewpoint.

  With the change in package form, photosensitive polyimide or photosensitive polybenzoxazole is increasingly used as an interlayer insulating film such as a rewiring layer. As a result, resistance to chemicals is required more than conventional materials. However, conventional polyimide and polybenzoxazole-based materials have a problem that a chemical resistance and a photosensitive property or film property are not yet obtained.

  In addition, studies have been made to use aluminum complexes in positive photosensitive resin compositions, but all use compounds having an epoxy group or oxetane group as a crosslinking agent, and aluminum complexes promote the ring opening of the crosslinking agent. (For example, Patent Documents 6 to 9).

JP-A-49-115541 JP 59-108031 A JP 59-219330 A JP-A 64-60630 U.S. Pat. No. 4,395,482 JP 2008-107512 A JP 2008-139328 A JP 2008-145579 A No. 2008-063721

Japan Polyimide Study Group "Latest Polyimides-Fundamentals and Applications" (2002) J. et al. Macromol. Sci. , Chem. , Vol. A24, 12, 1407 (1987)

An object of the present invention is to provide a photosensitive polymer composition which is excellent in sensitivity, resolution, substrate adhesion, heat resistance and chemical resistance and can produce a pattern having a good shape.
The objective of this invention is providing the reliable electronic component which reduced the damage to the device in a heat processing process by using the photosensitive polymer composition of this invention which can be hardened | cured by a low-temperature process.

  As a result of diligent research, the inventors of the present invention have improved chemical resistance and substrate adhesion in addition to high heat resistance and mechanical properties by using an alkali-developable polymer together with an aluminum complex compound as an adhesion aid. I found that I can do it. Furthermore, it discovered that it could be set as the photosensitive resin composition which can be hardened | cured by a low-temperature process by using the polymer of a specific structure.

（式中、Ｕは４価の有機基であり、Ｖは２価の有機基である。）
３．前記（ｃ）成分が、アルミニウムキレート接着助剤である１又は２記載の感光性重合体組成物。
４．前記（ｃ）成分が、下記式（II）で表されるアルミニウムキレートである１〜３のいずれかに記載の感光性重合体組成物。

（式中、Ｒ_１，Ｒ_２，Ｒ_３，Ｒ_４，Ｒ_５及びＲ_６は、各々独立に水素原子又は１価の有機基である。）
５．（ｄ）アルコキシシラン接着剤をさらに含有する１〜４のいずれかに記載の感光性重合体組成物。
６．（ｅ）架橋剤をさらに含有する１〜５のいずれかに記載の感光性重合体組成物。
７．前記（ｅ）成分が、下記式（III）で表される化合物である６に記載の感光性重合体組成物。

（式中、複数のＲ^７は、各々独立に水素原子又は１価の有機基である。
複数のＲ^８は、各々独立に水素原子又は１価の有機基であり、互いが結合して置換基を有してもよい環構造を形成してもよい。）
８．（ａ）成分１００重量部に対して、（ｂ）成分５〜１００重量部、（ｃ）成分０．１〜５０重量、（ｅ）成分１〜３０重量部を含有する６又は７に記載の感光性重合体組成物。
９．（ａ）成分１００重量部に対して、（ｂ）成分５〜１００重量部、（ｃ）成分０．１〜５０重量、（ｄ）成分０．１〜２０重量部、（ｅ）成分１〜３０重量部を含有する６又は７に記載の感光性重合体組成物。
１０．１〜９のいずれかに記載の感光性重合体組成物を支持基板上に塗布し乾燥する工程、露光する工程、現像する工程及び加熱処理する工程を含むパターンの製造方法。
１１．前記露光する工程において使用する光源が、ｉ線である１０記載のパターンの製造方法。
１２．１〜９のいずれかに記載の感光性重合体組成物を硬化してなる硬化物。
１３．１２に記載の硬化物を表面保護膜又は層間絶縁膜として有してなる電子部品。 According to the present invention, the following photosensitive polymer composition and the like are provided.
1. A photosensitive polymer composition comprising the following components (a) to (c).
(A) Polymer soluble in alkaline aqueous solution (b) Compound that generates acid by light (c) Aluminum complex adhesion assistant 2. The photosensitive polymer composition according to 1, wherein the component (a) is an alkaline aqueous solution-soluble polyamide having a structural unit represented by the following formula (I).

(In the formula, U is a tetravalent organic group, and V is a divalent organic group.)
3. 3. The photosensitive polymer composition according to 1 or 2, wherein the component (c) is an aluminum chelate adhesion aid.
4). The photosensitive polymer composition in any one of 1-3 whose said (c) component is the aluminum chelate represented by following formula (II).

(In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom or a monovalent organic group.)
5. (D) The photosensitive polymer composition in any one of 1-4 which further contains an alkoxysilane adhesive.
6). (E) The photosensitive polymer composition in any one of 1-5 which further contains a crosslinking agent.
7). 7. The photosensitive polymer composition according to 6, wherein the component (e) is a compound represented by the following formula (III).

(In the formula, a plurality of R ⁷ are each independently a hydrogen atom or a monovalent organic group.
A plurality of R ⁸ are each independently a hydrogen atom or a monovalent organic group, and may be bonded to each other to form a ring structure that may have a substituent. )
8). (A) 5 or 100 parts by weight of (b) component, 0.1 to 50 parts by weight of component (c), or 6 to 7 containing 1 to 30 parts by weight of component (e) with respect to 100 parts by weight of component (a) Photosensitive polymer composition.
9. (A) 100 parts by weight of component (b) 5 to 100 parts by weight of component, (c) 0.1 to 50 parts by weight of component, (d) 0.1 to 20 parts by weight of component, (e) 1 to 1 part of component The photosensitive polymer composition of 6 or 7 containing 30 parts by weight.
The manufacturing method of the pattern including the process of apply | coating the photosensitive polymer composition in any one of 10.1-9 on a support substrate, drying, the process of exposing, the process of developing, and the process of heat-processing.
11. 11. The method for producing a pattern according to 10, wherein the light source used in the exposing step is i-line.
12. Hardened | cured material formed by hardening | curing the photosensitive polymer composition in any one of 12.1-9.
An electronic component comprising the cured product according to 13.12 as a surface protective film or an interlayer insulating film.

ADVANTAGE OF THE INVENTION According to this invention, the photosensitive polymer composition which is excellent in a sensitivity, resolution, board | substrate adhesiveness, heat resistance, and chemical resistance and can manufacture the pattern which has a favorable shape can be provided.
ADVANTAGE OF THE INVENTION According to this invention, the highly reliable electronic component which reduced the damage to the device in a heat processing process can be provided by using the photosensitive polymer composition of this invention which can be hardened | cured by a low-temperature process.

It is a schematic sectional drawing explaining the manufacturing process of the semiconductor device which has a multilayer wiring structure concerning one Embodiment of this invention, Comprising: It is a figure which shows a 1st process. It is a schematic sectional drawing explaining the manufacturing process of the semiconductor device which has a multilayer wiring structure concerning one Embodiment of this invention, Comprising: It is a figure which shows a 2nd process. It is a schematic sectional drawing explaining the manufacturing process of the semiconductor device which has a multilayer wiring structure concerning one Embodiment of this invention, Comprising: It is a figure which shows a 3rd process. It is a schematic sectional drawing explaining the manufacturing process of the semiconductor device which has a multilayer wiring structure concerning one Embodiment of this invention, Comprising: It is a figure which shows a 4th process. It is a schematic sectional drawing explaining the manufacturing process of the semiconductor device which has a multilayer wiring structure concerning one Embodiment of this invention, Comprising: It is a figure which shows a 5th process.

  The photosensitive polymer composition of the present invention contains the components (a) to (c) described later, and increases the dissolution rate difference (dissolution contrast) between the pattern exposed portion and the unexposed portion of the developer. , Excellent sensitivity and resolution.

From the viewpoint of processability and heat resistance, the polymer soluble in the alkaline aqueous solution as component (a) is preferably a polyimide-based polymer or a polyoxazole-based polymer, and specifically preferred are: It is at least one polymer compound selected from polyimide, polyamideimide, polyoxazole, polyamide, and precursors thereof (for example, polyamic acid, polyamic acid ester, polyhydroxyamide, etc.).
The component (a) may be a copolymer having two or more main chain skeletons described above, or a mixture of two or more of the above polymers.

  From the viewpoint of solubility in alkaline aqueous solution, (a) the polymer soluble in alkaline aqueous solution is preferably a polymer having a plurality of phenolic hydroxyl groups, a plurality of carboxyl groups, or both groups.

（式中、Ｕは４価の有機基であり、Ｖは２価の有機基である。） The component (a) is more preferably an aqueous alkaline solution-soluble polyamide having a structural unit represented by the following formula (I) that functions as a precursor of polybenzoxazole and has good photosensitivity and film properties.

(In the formula, U is a tetravalent organic group, and V is a divalent organic group.)

The amide unit containing a hydroxy group represented by the formula (I) is finally converted into an oxazole having excellent heat resistance, mechanical properties and electrical properties by dehydration and ring closure at the time of curing.
The alkaline aqueous solution is an alkaline solution such as a tetramethylammonium hydroxide aqueous solution, a metal hydroxide aqueous solution, or an organic amine aqueous solution.

The tetravalent organic group of U in formula (I) is generally a residue derived from dihydroxydiamine that reacts with a dicarboxylic acid to form a polyamide structure, preferably a tetravalent aromatic group, and its carbon atom. The number is preferably 6 to 40, more preferably a tetravalent aromatic group having 6 to 40 carbon atoms.
As the tetravalent aromatic group, a diamine having a structure in which all four bonding sites are present on the aromatic ring and the two hydroxy groups are each located at the ortho position of the amine bonded to U. Residues are preferred.

Such diamines include 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, bis (3-amino-4-hydroxyphenyl) propane. Bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 2,2-bis (3-amino-) 4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-amino-3-hydroxyphenyl) -1,1,1,3,3,3- Examples include hexafluoropropane.
The residue of diamine is not limited to these, You may combine the residue of these compounds individually or in combination of 2 or more types.

The divalent organic group of V in formula (I) is generally a residue derived from a dicarboxylic acid that reacts with a diamine to form a polyamide structure, preferably a divalent aromatic group, and has a carbon atom number. Is preferably a divalent aromatic group having 6 to 40 carbon atoms, more preferably 6 to 40.
As the divalent aromatic group, those in which two bonding sites are both present on the aromatic ring are preferred.

Examples of such dicarboxylic acids include isophthalic acid, terephthalic acid, 2,2-bis (4-carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane, and 4,4′-dicarboxybiphenyl. 4,4′-dicarboxydiphenyl ether, 4,4′-dicarboxytetraphenylsilane, bis (4-carboxyphenyl) sulfone, 2,2-bis (p-carboxyphenyl) propane, 5-tert-butylisophthalic acid Aromatic dicarboxylic acids such as 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, Aliphatic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid, oxalic acid, malonic acid and succinic acid Although Bonn acid and the like are not limited thereto.
The residue of these compounds can be used individually or in combination of 2 or more types.

  The alkaline aqueous solution-soluble polyamide having the structural unit represented by the formula (I) may have a structure other than the structural unit represented by the formula (I).

（式中、Ｕは４価の有機基であり、Ｖ及びＷは２価の有機基である。
ｊとｋは、モル分率を示し、ｊとｋの和は１００モル％であり、ｊが６０〜１００モル％、ｋが４０〜０モル％である。） Since the solubility of polyamide in an alkaline aqueous solution is derived from a phenolic hydroxyl group, it is preferable that an amide unit containing a hydroxy group is contained in a certain ratio or more.
The alkaline aqueous solution-soluble polyamide having the structural unit represented by the formula (I) is preferably a polyamide represented by the following formula. In the polyamide, j is an amide unit containing a hydroxy group, and the molar fraction of j and k is more preferably j = 80 to 100 mol% and k = 20 to 0 mol%.

(In the formula, U is a tetravalent organic group, and V and W are divalent organic groups.
j and k represent mole fractions, and the sum of j and k is 100 mol%, j is 60 to 100 mol%, and k is 40 to 0 mol%. )

  The divalent organic group represented by W is generally a residue of a diamine that reacts with a dicarboxylic acid to form a polyamide structure, and is a residue other than the diamine that forms the U, preferably a divalent group. The number of carbon atoms is preferably 4 to 40, and more preferably a divalent aromatic group having 4 to 40 carbon atoms.

Such diamines include 4,4′-diaminodiphenyl ether, 4,4′-
Diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenyl sulfide, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4 -Aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4
Aromatic diamine compounds such as aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, 1,4-bis (4-aminophenoxy) benzene; LP-7100 which is a diamine containing a silicone group , X-22-161AS, X-22-161A, X-22-161B, X-22-161C and X-22-161E (all manufactured by Shin-Etsu Chemical Co., Ltd.), etc., but are not limited thereto. It is not a thing.
These compounds can be used alone or in combination of two or more.

The terminal group of the aromatic polyamide represented by the formula (I) becomes an amine having a carboxylic acid or a phenol group depending on the charging ratio of U and V.
If necessary, the polymer end alone or two kinds of end capping agents are reacted, and one end or both ends are saturated aliphatic group, unsaturated aliphatic group, carboxyl group, phenol hydroxyl group, sulfonic acid group, or thiol, respectively. It is good as a basis.
At that time, the end cap rate is preferably 30 to 100%.

The molecular weight of the component (a) is preferably 3,000 to 200,000, more preferably 5,000 to 100,000 in terms of weight average molecular weight.
Here, the molecular weight is a value obtained by measuring by a gel permeation chromatography method and converting from a standard polystyrene calibration curve.

In the present invention, the polyamide having the structural unit represented by the formula (I) can be generally synthesized from a dicarboxylic acid derivative and a hydroxy group-containing diamine.
Specifically, it can be synthesized by converting a dicarboxylic acid derivative into a dihalide derivative and then reacting with the diamine. As the dihalide derivative, a dichloride derivative is preferable.

The dichloride derivative can be synthesized by reacting a dicarboxylic acid derivative with a halogenating agent.
As the halogenating agent, thionyl chloride, phosphoryl chloride, phosphorus oxychloride, phosphorus pentachloride, etc., which are used in the usual acid chlorination reaction of carboxylic acid can be used.

  As a method of synthesizing the dichloride derivative, it can be synthesized by reacting the dicarboxylic acid derivative and the halogenating agent in a solvent, or reacting in an excess halogenating agent and then distilling off the excess. As the reaction solvent, N-methyl-2-pyrrolidone, N-methyl-2-pyridone, N, N-dimethylacetamide, N, N-dimethylformamide, toluene, benzene and the like can be used.

The amount of these halogenating agents to be used in a solvent is preferably 1.5 to 3.0 mol, more preferably 1.7 to 2.5 mol relative to the dicarboxylic acid derivative. When making it react in an agent, 4.0-50 mol is preferable and 5.0-20 mol is more preferable.
The reaction temperature is preferably -10 to 70 ° C, more preferably 0 to 20 ° C.

The reaction between the dichloride derivative and the diamine is preferably performed in an organic solvent in the presence of a dehydrohalogenating agent.
As the dehydrohalogenating agent, organic bases such as pyridine and triethylamine are usually used. As the organic solvent, N-methyl-2-pyrrolidone, N-methyl-2-pyridone, N, N-dimethylacetamide, N, N-dimethylformamide and the like can be used.
The reaction temperature is preferably −10 to 30 ° C., more preferably 0 to 20 ° C.

The compound (b), which generates an acid by light, is a photosensitive agent, and is a compound having a function of generating an acid by light and increasing the solubility of the light irradiated portion in an alkaline aqueous solution.
Examples of the component (b) include o-quinonediazide compounds, aryldiazonium salts, diaryliodonium salts, and triarylsulfonium salts, and o-quinonediazide compounds are preferred because of their high sensitivity.

The o-quinonediazide compound can be obtained, for example, by subjecting o-quinonediazidesulfonyl chlorides to a hydroxy compound, an amino compound or the like in the presence of a dehydrochlorinating agent.
Examples of o-quinonediazidosulfonyl chlorides include benzoquinone-1,2-diazide-4-sulfonyl chloride, naphthoquinone-1,2-diazide-5-sulfonyl chloride, naphthoquinone-1,2-diazide-4-sulfonyl chloride, and the like. Can be used.

  Examples of the hydroxy compound include hydroquinone, resorcinol, pyrogallol, bisphenol A, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, and 2,3,4-trihydroxybenzophenone. 2,3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,2 ′, 3′-pentahydroxybenzophenone, 2,3,4, 3 ′, 4 ′, 5′-hexahydroxybenzophenone, bis (2,3,4-trihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) propane, 4b, 5,9b, 10-tetrahydro -1,3,6,8-tetrahydroxy-5,10-dimethylindeno [2, -a] indene, tris (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) ethane and the like can be used.

  Examples of amino compounds include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 4,4′-diaminodiphenyl sulfide. , O-aminophenol, m-aminophenol, p-aminophenol, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, bis (3- Amino-4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, bis ( 3-amino-4-hydroxyphenyl) hexafluo Propane, bis (4-amino-3-hydroxyphenyl) hexafluoropropane and the like can be used.

The blending ratio of o-quinonediazide sulfonyl chloride and hydroxy compound and / or amino compound is blended so that the total of hydroxy group and amino group is 0.5 to 1 equivalent per mole of o-quinonediazide sulfonyl chloride. It is preferable.
A preferred ratio of the dehydrochlorinating agent and o-quinonediazide sulfonyl chloride is in the range of 0.95 / 1 to 1 / 0.95.
A preferable reaction temperature is 0 to 40 ° C., and a preferable reaction time is 1 to 10 hours.

As the reaction solvent, solvents such as dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, diethyl ether, N-methylpyrrolidone and the like are used.
Examples of the dehydrochlorination agent include sodium carbonate, sodium hydroxide, sodium hydrogen carbonate, potassium carbonate, potassium hydroxide, trimethylamine, triethylamine, pyridine and the like.

  In the photosensitive polymer composition of the present invention, the content of the component (b) is based on 100 parts by weight of the component (a) in terms of the difference in dissolution rate between the exposed portion and the unexposed portion and the allowable sensitivity range. 5-100 weight part is preferable and 8-40 weight part is more preferable.

  (C) The aluminum complex adhesion | attachment adjuvant which is a component can improve the adhesiveness of a composition by interaction of the metal surface of a board | substrate, and an aluminum chelate. In particular, the aluminum complex adhesion assistant can greatly improve the adhesion of the composition as compared with a silane coupling agent or the like due to the interaction between polyamide and aluminum chelate.

（式中、Ｒ_１，Ｒ_２，Ｒ_３，Ｒ_４，Ｒ_５及びＲ_６は、各々独立に水素原子又は１価の有機基である。１価の有機基は、エーテル結合、エステル結合等を含んでいてもよい） The aluminum complex of the aluminum complex adhesion assistant is preferably an aluminum chelate complex, and more preferably an aluminum chelate represented by the following formula (II).

(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom or a monovalent organic group. The monovalent organic group includes an ether bond, an ester bond, etc. May be included)

Examples of the monovalent organic group for R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ include an alkyl group having 1 to 20 carbon atoms and an alkoxyl group having 1 to 20 carbon atoms.

Examples of the aluminum complex as component (c) include aluminum ethyl acetoacetate diisopropylate, aluminum tris (ethyl acetoacetate), aluminum tris (acetylacetonate), alkyl acetoacetate aluminum diisopropylate, aluminum bisethyl acetoacetate mono Examples include acetylacetonate, and aluminum tris (acetylacetonate) and aluminum bisethylacetoacetate monoacetylacetonate are preferable.
These may be used alone or in combination of two or more.

In the photosensitive polymer composition of the present invention, the content of the component (c) is 0 with respect to 100 parts by weight of the component (a) from the viewpoint of the difference in dissolution rate between the exposed part and the unexposed part and the allowable sensitivity range. 0.1 to 20 parts by weight is preferable, and 0.5 to 10 parts by weight is more preferable.
When the content of the component (c) is 0.1 parts by weight or more, the effect of improving the adhesion to the substrate is effective, and by setting it to 20 parts by weight or less, problems such as precipitation during frozen storage are reduced. can do.

The photosensitive polymer composition of the present invention may further contain (d) an alkoxysilane adhesive.
(D) Examples of the alkoxysilane compound of the alkoxysilane adhesive include bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, and γ-methacryloxypropyltrimethoxysilane. , Ureapropyltriethoxysilane, methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butylsiphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenyl Silanediol, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol , Isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyl Diphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, phenylsilanetriol, 1,4-bis (trihydroxysilyl) benzene, 1,4-bis (Methyldihydroxysilyl) benzene, 1,4-bis (ethyldihydroxysilyl) benzene 1,4-bis (propyldihydroxysilyl) benzene, 1,4-bis (butyldihydroxysilyl) benzene, 1,4-bis (dimethylhydroxysilyl) benzene, 1,4-bis (diethylhydroxysilyl) benzene, , 4-bis (dipropyldroxysilyl) benzene, 1,4-bis (dibutylhydroxysilyl) benzene and the like.
Of these, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane is preferred. These may be used alone or in combination of two or more.

In the photosensitive polymer composition of the present invention, the content of the component (d) is preferably 0.1 to 50 parts by weight, more preferably 1 to 30 parts by weight with respect to 100 parts by weight of the component (a). It is.
When the content of the component (d) is 0.1% by weight or more, good adhesion to the substrate can be imparted to the composition, and when it is 30 parts by weight or less, good storability is obtained.

The photosensitive polymer composition of the present invention preferably further comprises (e) a crosslinking agent. The component (c) contained in the composition of the present invention can improve the crosslinking function of the component (e), and by including both the component (c) and the component (e), the resistance to the plating solution on the aluminum substrate as a synergistic effect. Can be improved.
(E) The cross-linking agent is a compound that reacts with the polymer to crosslink in the step of heat treatment after the application, exposure and development of the photosensitive polymer composition of the present invention, or polymerizes itself in the step of heat treatment. .

（式中、複数のＲ^７は、各々独立に水素原子又は１価の有機基である。
複数のＲ^８は、各々独立に水素原子又は１価の有機基であり、互いが結合して置換基を有してもよい環構造を形成してもよい。） The component (e) is preferably a compound represented by the following formula (III) from the viewpoint of water absorption and chemical resistance of the resulting cured film.

(In the formula, a plurality of R ⁷ are each independently a hydrogen atom or a monovalent organic group.
A plurality of R ⁸ are each independently a hydrogen atom or a monovalent organic group, and may be bonded to each other to form a ring structure that may have a substituent. )

As the monovalent organic group for R ⁷ , an alkyl group having 1 to 20 carbon atoms is preferable.
The monovalent organic group R ^8, an alkyl group having 1 to 30 carbon atoms, the ring structure in which two R ⁸ are bonded to each other is preferable. The ring structure in which two R ⁸ are bonded to each other may contain an oxygen atom or a nitrogen atom.

（式中、Ｚは炭素数１〜１０のアルキル基である。
Ｒは炭素数１〜２０のアルキル基である。） Specific examples of the compound represented by the formula (III) are shown below.
In addition, (e) component can use these compounds individually or in combination of 2 or more types.

(In the formula, Z is an alkyl group having 1 to 10 carbon atoms.
R is an alkyl group having 1 to 20 carbon atoms. )

  In the photosensitive resin composition of the present invention, the content of the compound represented by the formula (III) as the component (e) depends on the development time, the allowable width of the unexposed portion remaining film ratio, and the cured film properties. Therefore, 50 parts by weight or less is preferable with respect to 100 parts by weight of component (a) (base resin). On the other hand, from the viewpoint of chemical resistance of the cured film, 5 parts by weight or more is particularly preferable.

（式中、Ｘは、単結合又は１〜４価の有機基であり、１〜４価の有機基としては、炭素数１〜１０のアルキル基、エチリデン基等の炭素数２〜１０のアルキリデン基、フェニレン基等の炭素数６〜３０のアリーレン基、これら炭化水素基の水素原子の一部又は全部をフッ素原子等のハロゲン原子で置換した基が挙げられ、これらの基はさらにフェニル基、スルホン基、カルボニル基、エーテル結合、チオエーテル結合、アミド結合等を含んでもよい。
Ｒ^１１及びＲ^１２は、それぞれ独立に水素原子又は１価の有機基であり、Ｒ^１１は好ましくはアルキル基又はアルケニル基である。炭素数は１〜２０が好ましく、Ｒ^１２は好ましくはアルキル基、アルケニル基、アルコキシアルキル基又はメチロール基である。炭素数は１〜２０が好ましい。
ｏは１〜４の整数であり、ａは１〜４の整数であり、ｂは０〜４の整数である。） Moreover, it is also preferable to use the compound represented by the compound represented by following formula (IV) for (e) component.

(In the formula, X is a single bond or a monovalent to tetravalent organic group, and examples of the monovalent to tetravalent organic group include alkylidene having 2 to 10 carbon atoms such as an alkyl group having 1 to 10 carbon atoms and an ethylidene group. Groups, arylene groups having 6 to 30 carbon atoms such as phenylene groups, groups in which some or all of the hydrogen atoms of these hydrocarbon groups are substituted with halogen atoms such as fluorine atoms, and these groups are further phenyl groups, A sulfone group, a carbonyl group, an ether bond, a thioether bond, an amide bond and the like may be included.
R ¹¹ and R ¹² are each independently a hydrogen atom or a monovalent organic group, and R ¹¹ is preferably an alkyl group or an alkenyl group. The number of carbon atoms is preferably from 1 to 20, R ¹² is preferably an alkyl group, an alkenyl group, an alkoxyalkyl group or a methylol group. As for carbon number, 1-20 are preferred.
o is an integer of 1 to 4, a is an integer of 1 to 4, and b is an integer of 0 to 4. )

（式中、Ｘは、単結合又は２価の有機基であり、２価の有機基としては、メチレン基、エチレン基、プロピレン基等の炭素数１〜１０のアルキレン基、エチリデン基、２，２−プロピリデン基等の炭素数２〜１０のアルキリデン基、フェニレン基等の炭素数６〜３０のアリーレン基、これら炭化水素基の水素原子の一部又は全部をフッ素原子等のハロゲン原子で置換した基が挙げられ、これらの基はさらにスルホン基、カルボニル基、エーテル結合、チオエーテル結合、アミド結合等を含んでもよい。
Ｒは、それぞれ独立に、水素原子、アルキル基又はアルケニル基である。炭素数は１〜２０が好ましい。
Ｒ^１４及びＲ^１５は、それぞれ独立に、アルキル基，アルケニル基、メチロール基又はアルコキシアルキル基であり、これらの基は一部にエーテル結合，エステル結合等を有していてもよい。炭素数は１〜２０が好ましい。
ｅ及びｆは、それぞれ独立に、１又は２の整数であり、ｇ及びｈは、それぞれ独立に、０〜３の整数である。） The compound represented by the formula (IV) is preferably a compound represented by the following formula (V).

(In the formula, X is a single bond or a divalent organic group. Examples of the divalent organic group include an alkylene group having 1 to 10 carbon atoms such as a methylene group, an ethylene group and a propylene group, an ethylidene group, 2, Alkylidene groups having 2 to 10 carbon atoms such as 2-propylidene group, arylene groups having 6 to 30 carbon atoms such as phenylene group, and part or all of hydrogen atoms of these hydrocarbon groups are substituted with halogen atoms such as fluorine atoms. Groups, and these groups may further contain a sulfone group, a carbonyl group, an ether bond, a thioether bond, an amide bond, and the like.
Each R is independently a hydrogen atom, an alkyl group or an alkenyl group. As for carbon number, 1-20 are preferred.
R ¹⁴ and R ¹⁵ are each independently an alkyl group, an alkenyl group, a methylol group, or an alkoxyalkyl group, and these groups may partially have an ether bond, an ester bond, or the like. As for carbon number, 1-20 are preferred.
e and f are each independently an integer of 1 or 2, and g and h are each independently an integer of 0 to 3. )

（式中、Ａは、それぞれ独立に、水素原子、炭素原子数１〜１０のアルキル基、炭素数３〜２０のアリール基、又は酸素原子若しくはフッ素原子を一部に含む基である。） X in the compounds represented by formula (IV) and formula (V) is preferably a linking group represented by formula (VI).

(In the formula, each A is independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 3 to 20 carbon atoms, or a group partially containing an oxygen atom or a fluorine atom.)

  In the linking group represented by (VI), preferably, at least one of A is a group partially containing a fluorine atom or an aryl group having 3 to 20 carbon atoms.

  As for the group containing an oxygen atom or a fluorine atom in part, the group containing an oxygen atom includes an alkyloxy group, and the group containing a fluorine atom includes a perfluoroalkyl group. The number of carbon atoms is preferably 1-20.

Examples of the compound represented by (IV) include 2,2′-methylenebis (4-methyl-6-methoxymethylphenol), 4,4′-methylenebis (2-methyl-6-hydroxymethylphenol), 4 , 4′-methylenebis [2,6-bis (methoxymethyl) phenol], 4,4 ′-(1,1,1,3,3,3-hexafluoroisopropylidene) bis [2,6-bis (methoxy) Methyl) phenol], bis (2-hydroxy-3-methoxymethyl-5-methylphenyl) methane, 4,4 ′-(1-phenylethylidene) bis [2,6-bis (methoxymethyl) phenol], bis ( 2-hydroxy-3-ethoxymethyl-5-methylphenyl) methane, bis (2-hydroxy-3-propoxymethyl-5-methylphenyl) methane, bis (2-hydro Xyl-3-butoxymethyl-5-methylphenyl) methane, bis [2-hydroxy-3- (1-propenyloxy) methyl-5-methylphenyl] methane, bis (2-hydroxy-3-methoxymethyl-5- Methylphenyl) ethane, bis (2-hydroxy-3-ethoxymethyl-5-methylphenyl) ethane, 3,3′-bis (methoxymethyl) -4,4′-dihydroxybiphenyl, 3,3′-bis (ethoxy) Methyl) -4,4′-dihydroxybiphenyl, 4,4′-dihydroxy-3,3 ′, 5,5′-tetrakis (methoxymethyl) biphenyl, 4,4′-dihydroxy-3,3 ′, 5,5 '-Tetrakis (ethoxymethyl) biphenyl, bis (4-hydroxy-3-methoxymethylphenyl) methane, bis (4-hydroxy-3-ethoxymethyl) Ruphenyl) methane, bis [4-hydroxy-3,5-bis (methoxymethyl) phenyl] methane, bis [4-hydroxy-3,5-bis (ethoxymethyl) phenyl] methane, 2,2-bis [3, 5-bis (hydroxymethyl) -4-hydroxyphenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [3,5-bis (methoxymethyl) -4-hydroxyphenyl ] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [3,5-bis (ethoxymethyl) -4-hydroxyphenyl] -1,1,1,3,3 3-hexafluoropropane, 2,2-bis [3,5-bis (propoxymethyl) -4-hydroxyphenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [ 3,5- (Acetoxymethyl) -4-hydroxyphenyl] -1,1,1,3,3,3-hexafluoropropane, 4,4′-isopropylidenebis [2,6-bis (methoxymethyl) phenol], 3 , 3-bis [3,5-bis (hydroxymethyl) -4-hydroxyphenyl] perfluoropentane, 3,3-bis [3,5-bis (methoxymethyl) -4-hydroxyphenyl] perfluoropentane, 3, , 3 ″ -methylenebis (2-hydroxy-5-methylbenzenemethanol), 4,4 ′-(1-methylethylidene) bis [2-methyl-6-hydroxymethylphenol], 3,3 ′, 5,5 ', -Tetrakis (hydroxymethyl) [(1,1'-biphenyl) -4,4'-diol], 4,4'-(1-methylethylidene) bis [2,6-bis ( Droxymethyl) phenol], 2,2′-methylenebis (4,6-bishydroxymethylphenol), 2,6-bis [(2-hydroxy-3-hydroxymethyl-5-methylphenyl) methyl] -4-methylphenol 4,4 ′-(1,1,1,3,3,3-hexafluoroisopropylidene) bis [2,6-bis (hydroxymethyl) phenol] and the like.
These compounds can be used alone or in combination of two or more.

  Among the examples of the compound represented by (IV), 4,4 ′-(1,1,1,3,3,3-hexafluoroisopropylidene) bis [2,6- Bis (hydroxymethyl) phenol] is most preferable from the viewpoint of the effect of improving the sensitivity and the solubility of the film after pre-baking.

The content of the compound represented by (IV) is preferably 1 part by weight or more with respect to 100 parts by weight of component (a), from the viewpoints of sensitivity during photosensitivity, resolution, and storage stability.
The content of the compound represented by (IV) is more preferably 1 to 30 parts by weight, and 3 to 25 parts by weight with respect to 100 parts by weight of component (a) in terms of balance with the photosensitive characteristics. More preferably.

  The photosensitive polymer composition of the present invention is preferably a compound selected from the group consisting of (f) an onium salt, a diaryl compound and a tetraalkylammonium salt, and inhibits dissolution of the component (a) in an alkaline aqueous solution. It further contains a compound.

The component (f) is a compound that inhibits the solubility of the component (a) in an alkaline aqueous solution.
Examples of the onium salt include iodonium salts such as diaryl iodonium salts, sulfonium salts such as triarylsulfonium salts, diazonium salts such as phosphonium salts and aryldiazonium salts.
Examples of the diaryl compound include compounds in which two aryl groups such as diaryl urea, diaryl sulfone, diaryl ketone, diaryl ether, diaryl propane, and diaryl hexafluoropropane are bonded via a bonding group. Groups are preferred.
Examples of the tetraalkylammonium salt include tetraalkylammonium halides in which the alkyl group is a methyl group, an ethyl group, or the like.

Examples of the component (f) exhibiting a good dissolution inhibiting effect include diaryliodonium salts, diarylurea compounds, diarylsulfone compounds, tetramethylammonium halide compounds, and the like.
Examples of the diarylurea compound include diphenylurea and dimethyldiphenylurea, and examples of the tetramethylammonium halide compound include tetramethylammonium chloride, tetramethylammonium bromide, and tetramethylammonium iodide.

（式中、Ｘ⁻は対陰イオンである。
Ｒ^８及びＲ^９は、それぞれ独立に、アルキル基又はアルケニル基である。
ｍ及びｎは、それぞれ独立に、０〜５の整数である。） The component (f) is preferably a diaryliodonium salt represented by the following formula (VIII).

(In the formula, X ⁻ represents a counter anion.
R ⁸ and R ⁹ are each independently an alkyl group or an alkenyl group.
m and n are each independently an integer of 0 to 5. )

X ^{− in the} formula (VIII) is a nitrate ion, boron tetrafluoride ion, perchlorate ion, trifluoromethanesulfonate ion, p-toluenesulfonate ion, thiocyanate ion, chlorine ion, bromine ion, iodine ion or the like. Can be mentioned.

Examples of the diaryliodonium salt represented by the formula (VIII) include diphenyliodonium nitrate, bis (p-tert-butylphenyl) iodonium nitrate, diphenyliodonium trifluoromethanesulfonate, and bis (p-tert-butylphenyl). Examples thereof include iodonium trifluoromethanesulfonate, diphenyliodonium bromide, diphenyliodonium chloride, and diphenyliodonium iodide.
Of these, diphenyliodonium nitrate, diphenyliodonium trifluoromethanesulfonate, and diphenyliodonium-8-anilinonanaphthalene-1-sulfonate are preferred because of their high effects.

  The content of the component (f) is preferably 0.01 to 15 parts by weight, more preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the component (a) from the viewpoints of sensitivity and an allowable range of development time. 0.05 to 3 parts by weight is more preferable.

The photosensitive polymer composition of the present invention may contain (a) component, (b) component and (c) component, preferably (a) component, (b) component, (c) component and (e). Contains ingredients.
In addition to these components, the photosensitive polymer composition of the present invention can further contain the following additives and the like as long as the effects of the present invention are not impaired.

  Examples of the solvent for the photosensitive polymer composition of the present invention include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphorylamide, tetramethylene sulfone, Aprotic polar solvents such as γ-butyrolactone are preferred, and these solvents may be used alone or in combination of two or more.

The photosensitive polymer composition of the present invention can contain a suitable surfactant or leveling agent in order to prevent coatability, for example, striation (film thickness unevenness) and improve developability.
Examples of such surfactants or leveling agents include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, and specific commercial products include Megafax F171, F173, R-08 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.), Florard FC430, FC431 (trade name, Sumitomo 3M), organosiloxane polymers KP341, KBM303, KBM403, KBM803 (Shin-Etsu Chemical Co., Ltd.) Company name).

A pattern can be produced by applying the photosensitive polymer composition of the present invention.
In particular, by using the photosensitive polymer composition of the present invention, a polyoxazole pattern having excellent sensitivity, resolution, adhesiveness and heat resistance and having a good shape can be obtained.

  The pattern production method of the present invention includes a step of applying and drying the photosensitive polymer composition of the present invention on a support substrate, a step of exposing, a step of developing, and a step of heat-treating.

Examples of the support substrate to which the composition of the present invention is applied include a glass substrate, an aluminum substrate, a semiconductor, a metal oxide insulator (for example, TiO ₂ , SiO _2, etc.), silicon nitride, and the like.
Examples of the coating method include a coating method such as a spinner, and a photosensitive polymer film can be formed by drying the composition of the present invention using a hot plate, an oven or the like after spin coating.

In the exposure step, the photosensitive polymer composition formed as a film on the support substrate is irradiated with actinic rays such as ultraviolet rays, visible rays, and radiations through a mask.
The actinic ray light source is preferably i-line.

In the developing process, the pattern film is obtained by removing the exposed portion with a developer.
As the developer to be used, for example, an alkaline aqueous solution such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide is preferable, and the base concentration of these aqueous solutions is 0.1 to 10% by weight is preferable.
The developer may further contain an alcohol and / or a surfactant, and these are preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the developer. Can be included.

By heat-treating the resulting pattern coating, the pattern coating is thermally cured, and a heat-resistant polyoxazole pattern cured film having an oxazole ring or other functional group is obtained.
The temperature of the heat treatment is preferably 150 to 450 ° C.

A method for manufacturing a pattern according to the present invention will be described with reference to the drawings with an example of a manufacturing process of a semiconductor device having a pattern.
1 to 5 are schematic cross-sectional views for explaining a manufacturing process of a semiconductor device having a multilayer wiring structure, and represent a series of processes from a first process to a fifth process.

  1 to 5, a semiconductor substrate 1 such as a Si substrate having a circuit element (not shown) is covered with a protective film 2 such as a silicon oxide film except for a predetermined portion of the circuit element, and on the exposed circuit element. A first conductor layer 3 is formed. A film made of polyimide resin or the like as the interlayer insulating film layer 4 is formed on the semiconductor substrate 1 by a spin coating method or the like (first step, FIG. 1).

  Next, a photosensitive resin layer 5 such as chlorinated rubber or phenol novolac is formed on the interlayer insulating film layer 4 as a mask by a spin coating method, and a predetermined portion of the interlayer insulating film layer 4 is formed by a known photolithography technique. A window 6A is provided so as to be exposed (second step, FIG. 2). The interlayer insulating film layer 4 exposed to the window 6A is selectively etched by a dry etching means using a gas such as oxygen or carbon tetrafluoride to open the window 6B. Next, the photosensitive resin layer 5 is completely removed using an etching solution that corrodes only the photosensitive resin layer 5 without corroding the first conductor layer 3 exposed from the window 6B (third step, FIG. 3).

  Further, the second conductor layer 7 is formed by using a known photolithography technique, and the electrical connection with the first conductor layer 3 is completely performed (fourth step, FIG. 4). When a multilayer wiring structure having three or more layers is formed, each layer can be formed by repeating the above steps.

Next, the surface protective film 8 is formed. In FIG. 5, the photosensitive polymer composition of the present invention is applied and dried by a spin coating method, irradiated with light from a mask on which a pattern for forming a window 6C is formed at a predetermined portion, and then developed with an alkaline aqueous solution. Then, a pattern film is formed. Then, this pattern film is heated to form a pattern cured film (polyoxazole film) as the surface protective film layer 8 (fifth step, FIG. 5).
This surface protective film layer (polyoxazole film) 8 protects the conductor layer from external stress, α rays, etc., and the resulting semiconductor device is excellent in reliability.
In addition, you may form the said interlayer insulation film using the photosensitive polymer composition of this invention.

The photosensitive polymer composition of the present invention can be used for electronic parts such as semiconductor devices and multilayer wiring boards, and specifically, surface protection films and interlayer insulating films of semiconductor devices, and interlayer insulation of multilayer wiring boards. It can be used for forming a film or the like.
The semiconductor device of the present invention is not particularly limited except that it has a surface protective film or an interlayer insulating film formed using the photosensitive polymer composition of the present invention, and can take various structures.

  Hereinafter, based on an Example and a comparative example, it demonstrates further more concretely about this invention. In addition, this invention is not limited to the following Example.

Synthesis example 1
[Synthesis of Polybenzoxazole Precursor (Component (a))]
In a 0.5 liter flask equipped with a stirrer and a thermometer, 15.48 g of 4,4′-diphenyl ether dicarboxylic acid and 90 g of N-methylpyrrolidone were charged, the flask was cooled to 5 ° C., and then 12.64 g of thionyl chloride. Was added dropwise and reacted for 30 minutes to obtain a solution of 4,4′-diphenyl ether tetracarboxylic acid chloride.
Next, 87.5 g of N-methylpyrrolidone was charged into a 0.5 liter flask equipped with a stirrer and a thermometer, and 18.30 g of bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added and stirred. After dissolution, 8.53 g of pyridine was added, and while maintaining the temperature at 0 to 5 ° C., a solution of 4,4′-diphenyl ether dicarboxylic acid chloride was added dropwise over 30 minutes, and stirring was continued for 30 minutes. The stirred solution was poured into 3 liters of water, and the precipitate was collected, washed three times with pure water, and then dried under reduced pressure to obtain polyhydroxyamide (polybenzoxazole precursor) (hereinafter referred to as polymer I). ).

Synthesis example 2
[Synthesis of polyimide precursor (component (a))
In a 0.2 liter flask equipped with a stirrer and a thermometer, 10 g (32 mmol) of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride (ODPA) and 3.87 g (65 mmol) of isopropyl alcohol were added. Is dissolved in 45 g of N-methylpyrrolidone, and after adding a catalytic amount of 1,8-diazabicycloundecene, heating is performed at 60 ° C. for 2 hours, followed by stirring at room temperature (25 ° C.) for 15 hours. Esterification was performed. Thereafter, 7.61 g (64 mmol) of thionyl chloride was added under ice cooling, and the mixture was returned to room temperature and reacted for 2 hours to obtain an acid chloride solution.

  Next, in a 0.5 liter flask equipped with a stirrer and a thermometer, 40 g of N-methylpyrrolidone was charged, and 10.25 g (28 mmol) of bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added, After stirring and dissolving, 7.62 g (64 mmol) of pyridine was added, and while maintaining the temperature at 0 to 5 ° C., the previously prepared acid chloride solution was added dropwise over 30 minutes, and then stirring was continued for 30 minutes. This reaction solution was added dropwise to distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain a carboxylate terminal polyamic acid ester (hereinafter referred to as polymer II).

The weight average molecular weight of the polymer I determined by GPC standard polystyrene conversion was 14580, and the degree of dispersion was 1.6. Similarly, the polymer II had a weight average molecular weight of 19,400 and a dispersity of 2.2.
In addition, the measurement conditions of the weight average molecular weight by GPC method are as follows, It measured using the solvent [THF / DMF = 1/1 (volume ratio)] 1mL solution with respect to 0.5 mg of polymers.
Measuring device: Detector L4000 UV manufactured by Hitachi, Ltd.
Pump: Hitachi Ltd. L6000
C-R4A Chromatopac made by Shimadzu Corporation
Measurement conditions: Column Gelpack GL-S300MDT-5 x 2 eluent: THF / DMF = 1/1 (volume ratio)
LiBr (0.03 mol / L), H ₃ PO ₄ (0.06 mol / L)
Flow rate: 1.0 mL / min, detector: UV 270 nm

Example 1-12 , Reference Example 1 and Comparative Example 1-4
(A) 100 parts by weight of the polymer I prepared in Synthesis Example 1 as a component, and (b) component, (c) component, (d) component, and (e) component as shown in Table 1, respectively, , Γ-butyrolactone / propylene glycol monomethyl ether acetate were dissolved in a solvent mixed at a weight ratio of 9: 1 to prepare photosensitive polymer compositions, respectively.
In Table 1, the numbers in parentheses in each column of the components (b), (c), (d), and (e) indicate the amount added (parts by weight) relative to 100 parts by weight of the component (a). Moreover, the usage-amount of the solvent was 1.5 times with respect to 100 weight part of (a) component in any case.

Example 13
(A) 100 parts by weight of the polymer II prepared in Synthesis Example 2 as a component, and (b) component, (c) component, (d) component, and (e) component as shown in Table 1, respectively, A photopolymer composition was prepared by dissolving in γ-butyrolactone.
In Table 1, the numbers in parentheses in each column of the components (b), (c), (d), and (e) indicate the amount added (parts by weight) relative to 100 parts by weight of the component (a). Moreover, the usage-amount of the solvent was used 1.5 times with respect to 100 weight part of (a) component.

The compounds used in Example 1-13 , Reference Example 1 and Comparative Example 1-4 are shown below.

  The prepared photosensitive polymer composition was evaluated for its storage stability, sensitivity and resolution, and plating solution resistance by the following methods. The results are shown in Table 2.

[Storage stability]
The prepared photosensitive polymer composition is stored in a freezer, and after 2 weeks, the case where no precipitate is confirmed in the composition is evaluated as “◯”, and the precipitate is confirmed in the composition Was evaluated as “×”.

[sensitivity]
The prepared photosensitive polymer composition was spin coated on a silicon wafer to form a coating film having a dry film thickness of 7 to 12 μm. Using an ultra high pressure mercury lamp, i-line exposure of 100 to 1000 mJ / cm ^{2 was performed on} the coating film through an interference filter. After exposure, the film is heated at 120 ° C. for 3 minutes, developed with a 2.38 wt% aqueous solution of tetramethylammonium hydroxide (TMAH) until the exposed silicon wafer is exposed, and then rinsed with water to maintain the remaining film ratio (development The minimum exposure amount (sensitivity) required for pattern formation that can obtain 80% or more (ratio of film thickness before and after) was obtained.

[Plating solution resistance]
The prepared photosensitive polymer composition was spin-coated on a silicon wafer on which aluminum was deposited, and then heated at 120 ° C. for 3 minutes to form a coating film having a thickness of 8 μm. This coating film was exposed and developed to form a pattern. The formed pattern was heated in an inert gas oven at 100 ° C. for 60 minutes in a nitrogen atmosphere, and then heated at 320 ° C. for 1 hour to obtain a cured film.
The cured film patterned on the aluminum substrate was mixed at 23 ° C. with a mixed aqueous solution of Meltex FZ-7350 and FBZ2 made of Meltex electroless nickel plating mainly composed of an alkaline aqueous solution (FZ-7350 / FBZ2 / Water = 200 ml / 10 ml / 790 ml) for 10 minutes.
The presence or absence of the chemical solution permeating into the interface between the substrate and the resin layer from the opening pattern was evaluated by observation with a metal microscope from above. The case where penetration was confirmed with a metal microscope was evaluated as “X”, and the case where penetration was not confirmed at all was evaluated as “◯”.

[resolution]
The minimum value of line-and-space peeling on the Si wafer at an exposure amount 1.2 times the minimum exposure amount capable of pattern opening was defined as the resolution.

From the result of Table 2, it was confirmed that the cured film which consists of the photosensitive polymer composition of Examples 1-13 and Reference Example 1 has favorable adhesiveness with a board | substrate, and is a practical use level. That is, the photosensitive polymer composition of the present invention does not decrease sensitivity, resolution, heat resistance and chemical resistance, and can improve the adhesion to the substrate while maintaining a good shape pattern. It turns out that it is a type photosensitive polymer composition. On the other hand, in Comparative Examples 1 to 4, since the C component was not used, the adhesion was weak, and soaking of the chemical solution into the substrate and the resin interface was observed.

  The photosensitive polymer composition of the present invention can be suitably used as a material for a surface protective film or an interlayer insulating film, and can produce highly reliable electronic components with a high yield.

DESCRIPTION OF SYMBOLS 1 Semiconductor substrate 2 Protective film 3 1st conductor layer 4 Interlayer insulating film layer 5 Photosensitive resin layer 6A, 6B, 6C Window 7 2nd conductor layer 8 Surface protective film layer

Claims (11)

A photosensitive polymer composition comprising the following components (a) to (c) and (e) .
(A) Polymer soluble in alkaline aqueous solution (b) Compound that generates acid by light (c) Aluminum complex adhesion assistant
(E) a crosslinking agent which is a compound represented by the following formula (III)

(In the formula, a plurality of R ⁷ are each independently a hydrogen atom or a monovalent organic group.
A plurality of R ⁸ are each independently a hydrogen atom or a monovalent organic group, and may be bonded to each other to form a ring structure that may have a substituent. ) The photosensitive polymer composition according to claim 1, wherein the component (a) is an aqueous alkali-soluble polyamide having a structural unit represented by the following formula (I).

(In the formula, U is a tetravalent organic group, and V is a divalent organic group.)   The photosensitive polymer composition according to claim 1, wherein the component (c) is an aluminum chelate adhesion aid. The photosensitive polymer composition according to claim 1, wherein the component (c) is an aluminum chelate represented by the following formula (II).

(In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom or a monovalent organic group.)   (D) The photosensitive polymer composition according to any one of claims 1 to 4, further comprising an alkoxysilane adhesive. 5) to 100 parts by weight of (a) component, 100 parts by weight of component (c), 0.1 to 50 parts by weight of component (c), and 1 to 30 parts by weight of component (e) . The photosensitive polymer composition in any one . (A) 100 parts by weight of component (b) 5 to 100 parts by weight of component, (c) 0.1 to 50 parts by weight of component, (d) 0.1 to 20 parts by weight of component, (e) 1 to 1 part of component The photosensitive polymer composition according to claim 5, comprising 30 parts by weight. A step of coating and drying on a support substrate a photosensitive polymer composition according to any one of claims 1 to 7 exposing method of pattern including a step of process and heat treatment developed. The pattern manufacturing method according to claim 8 , wherein a light source used in the exposing step is i-line. A cured product obtained by curing the photosensitive polymer composition according to any one of claims 1-7. An electronic component comprising the cured product according to claim 10 as a surface protective film or an interlayer insulating film.

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