JP2010174195A - Polyimide polyamide copolymer and photosensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer which has a low coefficient of thermal expansion (a low CTE), a low residual stress and a strong tenacity (a high elongat), and is excellent in solubility in organic solvents and aqueous alkaline solutions. <P>SOLUTION: The polyimide polyamide copolymer includes a repeating unit represented by formula (1) and another repeating unit represented by formula -[-NHCOZCONHY(OH)<SB>2</SB>-]- (wherein X is a divalent organic group directly coupled by one or more benzene rings or naphthalene rings which may have substituent groups, and Y is a tetravalent organic group directly coupled by two or more benzene rings which may have substituent groups). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polyimide polyamide copolymer suitably used for an insulating material of an electronic component or a passivation film, a buffer coat film, an interlayer insulating film, an α-ray shielding film or the like in a semiconductor device, and a photosensitive material containing the polyimide polyamide copolymer. The present invention relates to a functional resin composition.

  In recent years, polyimide resins and polybenzoxazole resins having excellent heat resistance, electrical characteristics, mechanical characteristics, and the like have been used in applications such as surface protective films and interlayer insulating films of semiconductor elements.

  As a material used for such applications, a photosensitive polyimide resin and a photosensitive polybenzoxazole resin are often used because the pattern creation process can be simplified and complicated manufacturing processes can be shortened. It has been. Conventional photosensitive polyimides that use organic solvents as the developer have been the mainstream, but organic solvent waste liquids are usually incinerated, so from the viewpoint of environmental harmony and the cost of incineration, alkaline aqueous solutions Therefore, there is an increasing demand for photosensitive resin compositions that can be developed.

  As a conventional technique, for example, a positive photosensitive resin composition that can be developed with an alkaline developer, in which an orthoquinonediazide compound is blended as a photosensitive agent with a polyimide resin having a phenolic hydroxyl group has been proposed (for example, the following) Patent Document 1). A positive photosensitive resin composition in which a diazonaphthoquinone compound is blended with a polybenzoxazole precursor has also been proposed (see, for example, Patent Document 2 below). These compositions exhibit relatively good developability, but use a diazoquinone compound containing a large number of aromatic rings as a photosensitizer, so the sensitivity is low, and it is necessary to increase the amount of photosensitizer added. There is a problem that the mechanical properties of the later machine are remarkably lowered. Further, since it is a positive type, there is a problem that it is difficult to take a difference in solubility between an exposed portion and an unexposed portion, and the film thickness of the pattern portion is large.

  Therefore, (a) an aqueous alkali-soluble polymer having a terminal phenolic hydroxyl group, (b) a compound that generates an acid upon irradiation with actinic rays, and (c) a compound that can be crosslinked or polymerized by the generation of an acid. The negative photosensitive resin composition characterized by the above has been proposed as a composition that is excellent in sensitivity, resolution, and heat resistance and that can provide good cured film properties (see Patent Document 3 below).

  By the way, due to the difference in the material of the photosensitive material and the silicon wafer as the surface protective film, there is a difference in the coefficient of thermal expansion (CTE) between the two materials, but in recent years, as the diameter of the silicon wafer serving as the substrate becomes larger, The warpage of the silicon wafer due to the difference in thermal expansion coefficient (CTE) is larger than before. Further, there are problems that the adhesion between the formed photosensitive material film and the silicon wafer is lowered, the photosensitive material film is peeled off from the base material, or the base material is destroyed. This warpage of the silicon wafer is not preferable in view of defective products in the manufacturing process, conveyance failure, cracking factors, influence on device characteristics, and the like. Therefore, development of a low residual stress photosensitive material that can reduce the warpage of the wafer is strongly desired.

  Generally, low residual stress can be achieved by making the molecular structure rigid and lowering the coefficient of thermal expansion (CTE). However, when the rigid structure is introduced, the toughness of the photosensitive resin film as a surface protective film necessary for the device processing process Property is lost (refer to Non-Patent Document 1 below), cracks are generated in the protective film, and the final physical properties of the product are greatly damaged. Moreover, the solubility with respect to an organic solvent and alkaline aqueous solution falls remarkably, gelatinization at the time of varnish preparation, and white turbidity at the time of coating film formation generate | occur | produce, development time with an alkaline developing solution becomes long, and becomes impractical.

  On the other hand, in order to impart physical properties such as heat resistance, long-term environmental stability, organic solvent solubility, and flame retardancy to the polyimide resin, a specific acid dianhydride and a specific diamine are reacted as essential components to synthesize a polyimide resin. A technique is disclosed (see Patent Document 4 below).

Japanese Patent No. 2906737 Japanese Examined Patent Publication No. 1-46862 JP 2006-189788 A JP 2007-099842 A

“Latest Polyimide: Fundamentals and Applications,” issued by NTS, p. 114 (2002)

  The problem to be solved by the present invention is to provide a polymer having low thermal expansion coefficient (low CTE), low residual stress, and toughness (high elongation), and excellent solubility in organic solvents and aqueous alkali solutions. is there. Also, by using the above-mentioned polymer, low thermal expansion coefficient (low CTE), low residual stress, used for insulating materials of electronic components and passivation films in semiconductor devices, buffer coat films, interlayer insulating films, α-ray shielding films, etc. And a photosensitive resin composition for forming a thin film pattern having high toughness (high elongation).

  As a result of repeated studies to solve the above problems, the present inventors have both a rigid structure in which an ester structure and a plurality of benzene rings are directly connected, and a polyimide having a phenolic hydroxyl group on the benzene ring, Polyimide polyamide copolymer obtained by copolymerizing with polyamide has unexpectedly good organic solvent and aqueous alkali solubility, low thermal expansion coefficient (low CTE), low residual stress, and toughness (high elongation) As a result, the present invention has been completed.

｛式中、Ｘは、置換基を有していてもよいベンゼン環又はナフタレン環が１つ以上直接連結した２価の有機基であり、そしてＹは、置換基を有していてもよいベンゼン環が２つ以上直接連結した４価の有機基である。｝で表される繰り返し単位、及び下記式（２）：

｛式中、Ｚは、芳香環を１つ以上含む２価の有機基であり、そしてＹは、置換基を有していてもよいベンゼン環が２つ以上直接連結した４価の有機基である。｝で表される繰り返し単位を有するポリイミドポリアミド共重合体。 That is, the present invention is as follows [1] to [5].
[1] The following formula (1):

{Wherein X is a divalent organic group in which one or more benzene rings or naphthalene rings which may have a substituent are directly connected, and Y is an optionally substituted benzene It is a tetravalent organic group in which two or more rings are directly connected. } And the following formula (2):

{Wherein Z is a divalent organic group containing one or more aromatic rings, and Y is a tetravalent organic group in which two or more benzene rings which may have a substituent are directly connected. is there. } The polyimide polyamide copolymer which has a repeating unit represented by these.

  [2] (A) 100 parts by mass of a polymer containing the polyimide polyamide copolymer according to [1], (B) 0.5 to 20 parts by mass of a compound that generates an acid by light irradiation, and (C) an acid. A photosensitive resin composition comprising 3 to 50 parts by mass of a compound that can be crosslinked by action.

  [3] (1) A step of forming a layer made of the photosensitive resin composition according to [2] on a substrate, (2) a step of exposing, (3) a step of performing a heat treatment, (4) developing A method of forming a cured relief pattern, comprising a step, and (5) a step of heating the obtained relief pattern.

  [4] A method for manufacturing a semiconductor device, including the method for forming a cured relief pattern according to [3].

  [5] A semiconductor device manufactured by the method according to [4].

  By using the polyimide polyamide copolymer of the present invention, a photosensitive resin composition that can be developed with an alkali developer is obtained, and further heat-cured, thereby having a low coefficient of thermal expansion (low CTE), low residual stress, and toughness. A cured resin film having high properties (high elongation) is obtained.

It is IR spectrum in the powder of the copolymer P-1. It is a 1H-NMR spectrum in the deuterated dimethyl sulfoxide solution of copolymer P-1. It is IR spectrum in the powder of copolymer P-2. It is a 1H-NMR spectrum in the deuterated dimethyl sulfoxide solution of copolymer P-2.

｛式中、Ｘは、置換基を有していてもよいベンゼン環又はナフタレン環が１つ以上直接連結した２価の有機基であり、そしてＹは、置換基を有していてもよいベンゼン環が２つ以上直接連結した４価の有機基である。｝で表される繰り返し単位、及び下記式（２）：

｛式中、Ｚは、芳香環を１つ以上含む２価の有機基であり、そしてＹは、置換基を有していてもよいベンゼン環が２つ以上直接連結した４価の有機基である。｝で表される繰り返し単位を有することを特徴とする。 The polyimide polyamide copolymer of the present invention will be described in detail below.
The polyimide polyamide copolymer of the present invention has the following formula (1):

{Wherein X is a divalent organic group in which one or more benzene rings or naphthalene rings which may have a substituent are directly connected, and Y is an optionally substituted benzene It is a tetravalent organic group in which two or more rings are directly connected. } And the following formula (2):

{Wherein Z is a divalent organic group containing one or more aromatic rings, and Y is a tetravalent organic group in which two or more benzene rings which may have a substituent are directly connected. is there. } It has the repeating unit represented by this.

｛式中、Ｒは、ハロゲン基、炭素数が１〜３のアルキル基、炭素数が１〜３のハロゲン化アルキル基又は炭素数が１〜３のアルコキシ基であり、ｎは、０〜２の整数であり、Ｒが複数存在する場合、Ｒは、同一でも異なっていてもよい。｝などを挙げることができる。 X in the above formula (1) is a divalent linking of one or more benzene rings or naphthalene rings from the viewpoint of stiffening the polymer main chain and lowering the thermal expansion coefficient (CTE) to reduce residual stress. An organic group is preferred. The upper limit of the number of linked benzene rings or naphthalene rings is 3 from the viewpoint of ensuring solubility in organic solvents. Moreover, you may have a substituent on an aromatic ring from a viewpoint of improving the solubility with respect to the organic solvent. Examples of such X are as follows:

{In the formula, R is a halogen group, an alkyl group having 1 to 3 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and n is 0 to 2 And when there are a plurality of R, they may be the same or different. } Etc. can be mentioned.

｛式中、Ｒは、ハロゲン基、炭素数が１〜３のアルキル基、炭素数が１〜３のハロゲン化アルキル基又は炭素数が１〜３のアルコキシ基であり、ｎは０〜２の整数であり、Ｒが複数存在する場合、Ｒは、同一でも異なっていてもよい。｝などを挙げることができる。 Y in the above formula (1) or (2) is a group in which two or more benzene rings are directly connected from the viewpoint of stiffening the polymer main chain and lowering the thermal expansion coefficient (CTE) to reduce the residual stress. A valent organic group is preferred. Moreover, you may have a substituent on a benzene ring from a viewpoint of improving the solubility with respect to the organic solvent. Examples of such Y are as follows:

{In the formula, R is a halogen group, an alkyl group having 1 to 3 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and n is 0 to 2 When it is an integer and a plurality of Rs are present, they may be the same or different. } Etc. can be mentioned.

｛式中、Ｒは、ハロゲン基、炭素数が１〜３のアルキル基、炭素数が１〜３のハロゲン化アルキル基又は炭素数が１〜３のアルコキシ基であり、Ｒが複数存在する場合、Ｒは、同一でも異なっていてもよい。｝などを挙げることができる。これらの構造の中で、コート膜の強靭性（高伸度）、有機溶剤及びアルカリ水溶液に対する溶解性、及び基板密着性などを向上させるという観点から、２つの芳香環が１つ以上の原子を介して連結した構造がより好ましい。
ポリイミドポリアミド共重合体におけるＸ、Ｙ及びＺは、各々複数存在する場合は、同一であっても異なっていてもよい。 Z in the formula (2) is preferably a divalent organic group containing one or more aromatic rings from the viewpoint of heat resistance. Examples of such Z are as follows:

{In the formula, R is a halogen group, an alkyl group having 1 to 3 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and a plurality of R's are present. , R may be the same or different. } Etc. can be mentioned. In these structures, two aromatic rings contain one or more atoms from the viewpoint of improving the toughness (high elongation) of the coating film, solubility in organic solvents and aqueous alkali solutions, and substrate adhesion. A structure connected via each other is more preferable.
When a plurality of X, Y, and Z are present in the polyimide polyamide copolymer, they may be the same or different.

  The copolymer of the present invention has a polyimide unit having a rigid structure in which aromatic rings are directly bonded, so that a polymer having a low coefficient of thermal expansion (CTE) and a low residual stress when a cured resin film is produced. Further, by copolymerizing the polyamide unit, the polymer is excellent in toughness (high elongation), solubility in organic solvents and aqueous alkali solutions, and substrate adhesion. At this time, the copolymerization ratio (molar ratio) of the polyamide unit (2) to the polyimide unit (1) is preferably 0.1 to 10, more preferably 0.3 to 3, and still more preferably. 0.7-1.5.

｛式中、Ｘは、置換基を有していてもよいベンゼン環又はナフタレン環が１つ以上直接連結した２価の有機基である。｝で表されるテトラカルボン酸二無水物１当量に対し、下記式（４）：

｛式中、Ｙは、置換基を有していてもよいベンゼン環が２つ以上直接連結した４価の有機基である。｝で表されるジアミン化合物１．２〜３当量、好ましくは１．８〜２当量を極性有機溶媒中、必要に応じて反応温度−５℃〜２００℃で、２〜２４時間攪拌反応させ、アミン末端のイミドオリゴマーを得る。 The polyimide polyamide copolymer of the present invention can be suitably synthesized as follows.
First, the following formula (3):

{In the formula, X represents a divalent organic group in which one or more benzene rings or naphthalene rings which may have a substituent are directly connected. } With respect to 1 equivalent of tetracarboxylic dianhydride represented by the following formula (4):

{Wherein Y is a tetravalent organic group in which two or more benzene rings which may have a substituent are directly connected. } In a polar organic solvent, 1.2 to 3 equivalents, preferably 1.8 to 2 equivalents of a diamine compound represented by the formula is stirred and reacted at a reaction temperature of −5 ° C. to 200 ° C. for 2 to 24 hours, if necessary. An amine-terminated imide oligomer is obtained.

  Examples of tetracarboxylic dianhydrides having an ester bond represented by the above formula (3) and containing a divalent organic group X that are preferably used in the present invention include p-phenylenebis (trimellitic acid ester) 2 Anhydride, 2-methyl-p-phenylenebis (trimellitic acid ester) dianhydride, 2-methoxy-p-phenylenebis (trimellitic acid ester) dianhydride, 4,4'-biphenylylene bis (trimellitic Acid ester) dianhydride, 2,2′-dimethyl-4,4′-biphenylylene bis (trimellitic acid ester) dianhydride, 4,4 ″ -p-terphenylenebis (trimellitic acid ester) Anhydride, 1,4-naphthalene bis (trimellitic acid ester) dianhydride, etc. are mentioned. These tetracarboxylic dianhydrides having an ester bond and containing a divalent organic group X may be used alone or in combination.

  As the diamine compound suitably used in the present invention and having a phenolic hydroxyl group represented by the above formula (4) and containing a tetravalent organic group Y, 3,3′-diamino-4,4′-dihydroxybiphenyl is used. 4,4′-diamino-3,3′-dihydroxybiphenyl, 2,2′-dihydroxy-4,4′-diaminobiphenyl, 2,2′-dihydroxy-4,4′-diamino-5,5′- Examples thereof include dimethylbiphenyl and 2,2′-dimethyl-4,4′-diamino-5,5′-dihydroxybiphenyl. These diamine compounds having a phenolic hydroxyl group and containing a tetravalent organic group Y may be used alone or as a mixture of a plurality of types of diamine compounds.

  Further, as the above-mentioned solvent, amides, sulfoxides, tetramethylurea, ketones, esters, lactones, ethers, halogenated hydrocarbons, and hydrocarbons are preferable. For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene , O-dichlorobenzene, hexane, heptane, benzene, toluene, xylene, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, gamma butyrolactone, sulfolane, etc. Is mentioned. Among these, those that completely dissolve the imide oligomer are more preferable. Examples include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, gamma butyrolactone, sulfolane and the like. These solvents may be used alone or as a mixture as required.

｛式中、Ｚは、芳香環を１つ以上含む２価の有機基である。｝で表されるジカルボン酸のハロゲン化物、又は活性エステル、又は適当な縮合剤やカルボン酸活性化剤の存在下、ジカルボン酸（以下、上記３つの化合物群を総称して「２価の有機基Ｚを含むジカルボン酸等」という。）を５〜１００部、好ましくは５０〜１００部を、必要に応じて反応温度−２０℃〜５０℃で、２〜２４時間攪拌反応させることによって共重合体を得る。 Secondly, with respect to 100 parts of the amine-terminated imide oligomer obtained by the above method, the following formula (5):

{In the formula, Z is a divalent organic group containing one or more aromatic rings. } In the presence of a suitable dicarboxylic acid halide or active ester, or a suitable condensing agent or carboxylic acid activator (hereinafter, the above three compound groups are collectively referred to as “divalent organic group”). A dicarboxylic acid containing Z and the like ") is copolymerized by stirring and reacting 5 to 100 parts, preferably 50 to 100 parts at a reaction temperature of -20 ° C to 50 ° C for 2 to 24 hours, if necessary. Get.

  Specifically, when dicarboxylic acid dichloride is used, a tertiary amine compound such as pyridine or triethylamine is added as an acid scavenger to the reaction solution of the amine-terminated imide oligomer obtained by the above-described method, and then the reaction is performed. The solution is cooled to a temperature range of −20 ° C. to 10 ° C., and dicarboxylic acid dichloride previously dissolved or dispersed in a solvent is added dropwise. Then, it is made to react with -20 degreeC-50 degreeC which is preferable reaction temperature, and 2-24 hours which is preferable reaction time, and the copolymer of this invention can be obtained.

  For the reaction at this stage, a mixture such as dicarboxylic acid containing a divalent organic group Z may be used. Further, before adding a dicarboxylic acid or the like containing a divalent organic group Z, by adding an additional diamine compound having a phenolic hydroxyl group and containing a tetravalent organic group Y, an arbitrary copolymerization ratio can be obtained. The copolymer which has can be obtained.

  Examples of the dicarboxylic acid having a divalent organic group Z represented by the above formula (5) preferably used in the present invention include 3,3′-biphenyldicarboxylic acid, 4,4′-biphenyldicarboxylic acid, and 4,4. '-Diphenyl ether dicarboxylic acid, 4,4'-diphenyl sulfide dicarboxylic acid, 4,4'-diphenylsulfone dicarboxylic acid, 4,4'-diphenylmethane dicarboxylic acid, 4,4'-(2,2-diphenylpropane) dicarboxylic acid 4,4′-benzophenone dicarboxylic acid, terephthalic acid, and isophthalic acid. As mentioned above, compounds obtained by chlorinating these dicarboxylic acids are used. These compounds may be used alone or in combination.

  After completion of the copolycondensation reaction, a poor solvent such as water, an aliphatic lower alcohol or a mixture thereof is added to the reaction solution to precipitate the copolymer. Further, the precipitated copolymer is redissolved in a solvent, purified by repeating the precipitation operation by reprecipitation, vacuum dried, and the desired copolymer is isolated. In order to further improve the degree of purification, the copolymer solution may be passed through a column filled with an ion exchange resin to remove ionic impurities.

  The molecular weight of the polyimide polyamide copolymer obtained by the synthesis method is preferably 4,000 to 150,000, more preferably 5,000 to 100,000 in terms of weight average molecular weight. The weight average molecular weight is preferably 4,000 or more from the viewpoint of securing the mechanical properties and heat resistance of the material, and is preferably 150,000 or less from the viewpoint of ensuring the solubility of the material in an organic solvent and an alkaline aqueous solution.

The photosensitive resin composition of the present invention includes (A) a polymer containing the copolymer, (B) a compound that generates an acid by light irradiation, and (C) a compound that can be crosslinked by the action of the acid.
(A) Polymer containing the copolymer The polymer used in the photosensitive resin composition of the present invention may be a copolymer obtained by the above synthesis method, or may be used in combination with another heat-resistant polymer. May be. When the copolymer of the present invention and other heat-resistant polymer are used in combination, from the viewpoint of sufficiently reducing the residual stress of the cured film, the amount of the copolymer used is 20% by mass or more and 100% by mass of the whole polymer. It is preferable that it is below mass%. Examples of other heat resistant polymers include polyimide, polyoxazole, polyamide, polyamic acid, polyamic acid ester, polyhydroxyamide, and copolymers thereof.

(B) Compound that generates acid by light irradiation Examples of the (B) compound that generates acid by light irradiation used in the present invention include the following compounds.
i) Trichloromethyl-s-triazines:
Tris (2,4,6-trichloromethyl) -s-triazine, 2-phenyl-bis (4,6-trichloromethyl) -s-triazine, 2- (3-chlorophenyl) -bis (4,6-trichloromethyl) ) -S-triazine, 2- (2-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -bis (4,6-trichloromethyl) -s-triazine 2- (3-methoxyphenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (2-methoxyphenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- ( 4-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (3-methylthiophenyl) bis (4,6-trichloromethyl-s-to Azine, 2- (2-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (3-methoxynaphthyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (2-methoxynaphthyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (3,4 , 5-trimethoxy-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methylthio-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2- (3-Methylthio-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2- (2-methylthio-β-styryl) -bis (4,6-trichloromethyl) Chill) -s-triazine and the like.

  Among these compounds, 2- (3-chlorophenyl) -bis (4,6-trichloromethyl) -S-triazine, 2- (4-chlorophenyl) -bis (4,6-trichloromethyl) -S-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl) -S-triazine, 2- (4-methoxy-β-styryl) -bis (4,6-trichloromethyl) -S-triazine, 2 -(4-Methoxynaphthyl) -bis (4,6-trichloromethyl) -S-triazine and the like are preferable.

ii) Diallyl iodonium:
Diphenyliodonium tetrafluoroborate, diphenyliodonium tetrafluorophosphate, diphenyliodonium tetrafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, 4-methoxyphenylphenyliodonium tetrafluoroborate 4-methoxyphenylphenyliodonium hexafluorophosphonate, 4-methoxyphenylphenyliodonium hexafluoroarsenate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, 4-methoxyphenylphenyliodoni Mu-p-toluenesulfonate, bis (4-tert-butylphenyl) iodonium tetrafluoroborate, bis (4-tert-butylphenyl) iodonium hexafluoroarsenate, bis (4-tert-butylphenyl) iodonium trifluoromethanesulfone Nert, bis (4-tert-butylphenyl) iodonium trifluoroacetate, bis (4-tert-butylphenyl) iodonium-p-toluenesulfonate, and the like.

  Of these compounds, diphenyliodonium trifluoroacetate, diphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, and the like are preferable.

iii) Triallylsulfonium salts:
Triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, 4-methoxyphenyl Diphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium methanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-methoxy Phenyldiphenylsulfo Um-p-toluenesulfonate, 4-phenylthiophenyldiphenyltetrafluoroborate, 4-phenylthiophenyldiphenylhexafluorophosphonate, 4-phenylthiophenyldiphenylhexafluoroarsenate, 4-phenylthiophenyldiphenyltrifluoromethanesulfonate, 4-phenylthiophenyl diphenyl trifluoroacetate, 4-phenylthiophenyl diphenyl-p-toluenesulfonate, and the like.

Among these compounds, triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium methanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-phenylthiophenyldiphenyltrifluoromethanesulfonate 4-phenylthiophenyl diphenyl trifluoroacetate and the like are preferable.
In addition, the following compounds can be used.

(1) Diazoketone compound Examples of the diazoketone compound include 1,3-diketo-2-diazo compounds, diazobenzoquinone compounds, diazonaphthoquinone compounds, and the like. Specific examples include 1,2-naphthoquinone diazide of phenols. A 4-sulfonic acid ester compound can be mentioned.

(2) Sulfone compounds Examples of the sulfone compounds include β-ketosulfone compounds, β-sulfonylsulfone compounds and α-diazo compounds of these compounds. Specific examples include 4-trisphenacylsulfone, mesitylphena. Examples include silsulfone and bis (phenacylsulfonyl) methane.

(3) Sulfonic acid compound Examples of the sulfonic acid compound include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates. Preferred examples include benzoin tosylate, pyrogallol tris-trifluoromethane sulfonate, o-nitrobenzyl trifluoromethane sulfonate, o-nitrobenzyl p-toluene sulfonate, and the like.

(4) Sulfonimide compound As specific examples of the sulfonimide compound, for example, N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide and the like can be mentioned.

(5) Oxime ester compound 2- [2- (4-Methylphenylsulfonyloxyimino)]-2,3-dihydrothiophene-3-ylidene] -2- (2-methylphenyl) acetonitrile (trade name of Ciba Specialty Chemicals) “Irgacure PAG121”), [2- (propylsulfonyloxyimino) -2,3-dihydrothiophene-3-ylidene] -2- (2-methylphenyl) acetonitrile (Ciba Specialty Chemicals trade name “Irgacure PAG103”), etc. Can be mentioned.

(6) Diazomethane compound Specific examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, and the like.
In particular, from the viewpoint of sensitivity, the above (5) oxime ester compound is preferable.

  The addition amount of the compound that generates an acid upon irradiation with light is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the polymer (A). If this addition amount is 0.5 parts by mass or more, a sufficient amount of acid is generated by light irradiation, and the sensitivity is improved. Moreover, if this addition amount is 20 mass parts or less, the mechanical property after hardening will become favorable.

(C) Compound that can be crosslinked by the action of an acid (C) The compound that can be crosslinked by the action of an acid used in the present invention will be described. By adding a compound that can be cross-linked by the action of the acid (C), when the coating film is heat-cured, the polymer (A) can be cross-linked or can itself form a cross-linked network. Sexuality can be strengthened.

  (C) As a compound which can be bridge | crosslinked by the effect | action of an acid, the melamine resin and urea resin by which N-position was substituted by the methylol group or the alkoxymethyl group are preferable. Examples of these are melamine resin, benzoguanamine resin, glycoluril resin, hydroxyethylene urea resin, urea resin, glycol urea resin, alkoxymethylated melamine resin, alkoxymethylated benzoguanamine resin, alkoxymethylated glycoluril resin, alkoxymethylated A urea resin etc. can be mentioned. Among these, alkoxymethylated melamine resin, alkoxymethylated benzoguanamine resin, alkoxymethylated glycoluril resin, and alkoxymethylated urea resin are the methylol groups of known methylolated melamine resin, methylolated benzoguanamine resin, and methylolated urea resin. Obtained by conversion to an alkoxymethyl group.

Examples of the type of alkoxymethyl group include methoxymethyl group, ethoxymethyl group, propoxymethyl group, butoxymethyl group, and the like, but commercially available Cymel 300, 301, 303, 370, 325. 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (Mitsui Cytec Co., Ltd.), Nikarak MX-270, -280, -290, Nikarak MS-11, Nicalac MW-30, -100, -300, -390, -750 (manufactured by Sanwa Chemical Co., Ltd.) and the like can be preferably used. These compounds can be used alone or in combination.
In addition to the above, a monomer of the resin is also used as a compound that can be cross-linked by the action of an acid, and examples thereof include hexamethoxymethylmelamine and dimethoxymethylurea.

  (C) The addition amount of the compound which can be bridge | crosslinked by the effect | action of an acid becomes like this. Preferably it is 3-50 mass parts with respect to 100 mass parts of said polymers (A), More preferably, it is 5-50 mass parts. If this addition amount is 3 parts by mass or more, crosslinking proceeds sufficiently and the patterning property is improved. Moreover, if this addition amount is 50 parts by mass or less, the mechanical properties after curing are good.

(D) Solvent It is preferable to adjust the viscosity by arbitrarily adding a solvent to the photosensitive resin composition of the present invention. Suitable solvents include N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, pyridine, cyclopentanone Cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, etc. Can be mentioned. These solvents can be used alone or in combination of two or more. Among these, N-methyl-2-pyrrolidone and γ-butyrolactone are particularly preferable.

  These solvents can be appropriately added to the photosensitive resin composition of the present invention in accordance with the coating film thickness and viscosity. When added, the solvent is 10 to 1000 with respect to 100 parts by mass of the polymer (A). It is preferable to use in the range of 100 parts by weight, particularly 100 to 800 parts by weight.

For the purpose of improving coating properties, the above solvents include propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1 , 3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropionate and the like can also be mixed and used. In the case of containing an organic solvent, the addition amount is preferably 2 to 900 parts by mass, more preferably 5 to 600 parts by mass with respect to 100 parts by mass of the polymer (A).
Furthermore, in order to improve the storage stability with time of the photosensitive resin composition of the present invention, alcohols can be used in combination with the above-described solvents.

These alcohols include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, benzyl alcohol, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol. Monoethyl ether, propylene glycol mono (n-propyl) ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono (n-propyl) ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monophenyl Monoalcohols such as ether, diethylene glycol, propylene glycol, etc. Alcohol compounds can be mentioned. Among these, benzyl alcohol and ethylene glycol monophenyl ether are particularly preferable.
If these alcohols are 1-50 mass% in the total amount of the said solvent and alcohol, and especially 3-40 mass%, since the solubility of the said (A) polymer is favorable, it is preferable.

(E) Sensitizer A sensitizer for improving photosensitivity can be added to the photosensitive resin composition of the present invention, if necessary.
Examples of such a sensitizer include Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 2,5-bis (4′-diethylaminobenzylidene) cyclopentanone, and 2,6-bis (4′-diethylamino). Benzylidene) cyclohexanone, 2,6-bis (4′-dimethylaminobenzylidene) -4-methylcyclohexanone, 2,6-bis (4′-diethylaminobenzylidene) -4-methylcyclohexanone, 4,4′-bis (dimethylamino) ) Chalcone, 4,4′-bis (diethylamino) chalcone, 2- (4′-dimethylaminocinnamylidene) indanone, 2- (4′-dimethylaminobenzylidene) indanone, 2- (p-4′-dimethylamino) Biphenyl) benzothiazole, 1,3-bis (4-dimethylaminobenzylide) N) acetone, 1,3-bis (4-diethylaminobenzylidene) acetone, 3,3′-carbonyl-bis (7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethyl Aminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, N, N-bis (2-hydroxyethyl) aniline, 4-morpholinobenzophenone, isoamyl 4-dimethylaminobenzoate, isoamid 4-diethylaminobenzoate , Benztriazole, 2-mercaptobenzimidazole, 1-phenyl-5-mercapto-1,2,3,4-tetrazole, 1-cyclohexyl-5-mercapto-1,2,3,4-tetrazole, 1- ( tert-butyl) -5-mercapto-1,2,3,4-tetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2 -(P-dimethylaminostyryl) naphtho (1,2-p) thiazole, 2- (p-dimethylaminobenzoyl) styrene and the like. Among these, benztriazole, 2-mercaptobenzimidazole, 1-phenyl-5-mercapto-1,2,3,4-tetrazole, 1-cyclohexyl-5-mercapto-1,2,3,4-tetrazole, 1- (tert-butyl) -5-mercapto-1,2,3,4-tetrazole, coumarins having substituents at the 3-position and / or 7-position, flavones, dibenzalacetones, diben Adding one or more sensitizers selected from the group consisting of sarcyclohexanes, chalcones, xanthones, thioxanthones, porphyrins, phthalocyanines, acridines, anthracene having a substituent at the 9-position preferable. These sensitizers can be used alone or as a mixture of two or more.
The addition amount in the case of containing a sensitizer is preferably 0.5 to 15 parts by mass and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the polymer (A).

(F) Polymerization inhibitor A polymerization inhibitor can be added to the photosensitive resin composition of the present invention, if necessary, in order to improve the viscosity of the composition solution during storage and the stability of photosensitivity.
Examples of such polymerization inhibitors include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid. 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N- Ethyl-N-sulfopropylamino) phenol, N-nitroso-N-phenylhydroxyamine ammonium salt, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N- (1-naphthyl) hydroxylamine ammonium salt ,Screw Or the like can be used 4-hydroxy-3,5-di-tert- butyl) phenyl methane.
The addition amount in the case of containing a polymerization inhibitor is preferably 0.1 to 5 parts by mass, more preferably 0.1 to 1 part by mass with respect to 100 parts by mass of the polymer (A). .

(G) Silane coupling agent A silane coupling agent can be added to the photosensitive resin composition of this invention as needed. Specific examples of the silane coupling agent include 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name KBM803, manufactured by Chisso Corporation: trade name: Sylla Ace S810), 3-mercaptopropyltriethoxysilane (Amax stock) Made by company: trade name SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name LS1375, manufactured by Amax Co., Ltd .: trade name SIM6474.0), mercaptomethyltrimethoxysilane (Amax Co., Ltd.) Manufactured: trade name SIM6473.5C), mercaptomethylmethyldimethoxysilane (manufactured by AMAX Co., Ltd .: trade name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropyle Toxidimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2-mercapto Ethyltrimethoxysilane, 2-mercaptoethyldiethoxymethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercapto Ethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltrimethoxysilane 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane, N- (3-triethoxysilylpropyl) urea (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name LS3610, manufactured by Amax Co., Ltd .: trade name SIU9055.0) N- (3-trimethoxysilylpropyl) urea (manufactured by AMAX Co., Ltd .: trade name SIU9058.0), N- (3-diethoxymethoxysilylpropyl) urea, N- (3-ethoxydimethoxysilylpropyl) urea, N- (3-tripropoxysilylpropyl) urea, N- (3-diethoxypropoxysilylpropyl) urea, N- (3-ethoxydipropoxysilylpropyl) urea, N- (3-dimethoxypropoxysilylpropyl) urea, N- (3-methoxydipropo Sisilylpropyl) urea, N- (3-trimethoxysilylethyl) urea, N- (3-ethoxydimethoxysilylethyl) urea, N- (3-tripropoxysilylethyl) urea, N- (3-tripropoxysilyl) Ethyl) urea, N- (3-ethoxydipropoxysilylethyl) urea, N- (3-dimethoxypropoxysilylethyl) urea, N- (3-methoxydipropoxysilylethyl) urea, N- (3-trimethoxysilyl) Butyl) urea, N- (3-triethoxysilylbutyl) urea, N- (3-tripropoxysilylbutyl) urea, 3- (m-aminophenoxy) propyltrimethoxysilane (manufactured by Amax Co., Ltd .: trade name SLA0598. 0), m-aminophenyltrimethoxysilane (Amax Co., Ltd.) Product name: SLA0599.0), p-aminophenyltrimethoxysilane (manufactured by Amax Co .: product name SLA0599.1), aminophenyltrimethoxysilane (product name: SLA0599.2), 2- (Trimethoxysilylethyl) pyridine (manufactured by Amax Co., Ltd .: trade name SIT83396), 2- (triethoxysilylethyl) pyridine, 2- (dimethoxysilylmethylethyl) pyridine, 2- (diethoxysilylmethylethyl) pyridine N- [3- (triethoxysilyl) propyl] phthalamic acid and the like.
When the silane coupling agent is contained, the addition amount is preferably 1 to 20 parts by mass and more preferably 3 to 15 parts by mass with respect to 100 parts by mass of the polymer (A).

(H) Compound having acryloyl group or methacryloyl group In the photosensitive resin composition of the present invention, if necessary, in order to improve the remaining film rate during heat treatment and the flatness of the obtained cured relief pattern surface A compound having an acryloyl group or a methacryloyl group can be added.
Examples of the compound having an acryloyl group or a methacryloyl group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, Pentaerythritol triacrylate, pentaerythritol trimethacrylate, caprolactone 2- (methacryloyloxy) ethyl ester, dicaprolactone 2- (methacryloyloxy) ethyl ester, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol Dimethacrylate, triethylene glycol dimethacrylate, Tet Ethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, ditrimethylolpropane tetraacrylate, ditrimethylolpropane tetramethacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, Hexyl acrylate, isooctyl acrylate, isobornyl acrylate, isobornyl methacrylate, cyclohexyl methacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, neopentyl glycol diacrylate, 1,4-butanediol Diacrylate, 1,4-butanediol dimethyl Acrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol methacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, pentaerythritol triacrylate, Pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, 1,3-acryloyloxy-2-hydroxypropane, 1,3-methacryloyloxy-2-hydroxypropane, methylenebisacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide, dimethacryloyloxyurea, dipentaerythritol hexaacrylate, dipentaerythritol hex Examples include samethacrylate, isocyanuric acid EO-modified triacrylate, and isocyanuric acid EO-modified trimethacrylate.
The addition amount in the case of adding a compound having an acryloyl group or a methacryloyl group is preferably 5 to 500 parts by mass, more preferably 10 to 200 parts by mass with respect to 100 parts by mass of the polymer (A). Yes, more preferably 10 to 50 parts by mass.

(I) Allyl compound If necessary, an allyl compound can be added to the photosensitive resin composition of the present invention.
Examples of such allyl compounds include triallyl trimelliate, tetraallyl pyromellitic acid, allyl phenyl ether, allyl phenol, diallyl ether, diethylene glycol diallyl ether, diallyl hexahydrophthalate, and allyl glycidyl ether.
When the allyl compound is added, the addition amount is preferably 2 to 100 parts by mass and more preferably 3 to 50 parts by mass with respect to 100 parts by mass of the polymer (A).

(J) Other additives In addition to the above, various additives such as a scattered light absorber and a coating film smoothness-imparting agent are appropriately blended in the photosensitive resin composition of the present invention. be able to.

<Curing relief pattern and semiconductor device manufacturing method>
Next, an example of a method for forming an image using the photosensitive resin composition will be described. First, this composition is apply | coated on a base material so that the film thickness after drying may be 1-50 micrometers, Preferably it is 5-30 micrometers. At this time, the substrate may be previously treated with an adhesion aid such as a silane coupling agent. After the applied film is dried, it is exposed through a normal photomask, and then heat treatment (PEB) is performed. This PEB process is a process for increasing the sensitivity of the present composition, and is necessary to achieve the object of the present invention.

  The PEB temperature is 90 to 160 ° C., preferably 100 to 150 ° C. in consideration of sensitivity, pattern shape to be obtained, and the like. The substrate that has been heat-treated after the exposure is developed with an aqueous alkali solution having an appropriate concentration, whereby a fine resin pattern can be transferred onto the substrate. The developer used at this time is preferably one that can completely dissolve and remove the exposed film within an appropriate time. An inorganic alkaline aqueous solution such as sodium hydroxide or potassium hydroxide, propylamine, butylamine, monoethanolamine, tetramethylammonium. An organic alkaline aqueous solution such as hydroxide or choline is used alone or in combination of two or more.

  The alkaline aqueous solution may contain an organic solvent such as alcohols and various surfactants as necessary. After development, an image of the heat-resistant material precursor is obtained by washing with a rinse solution. The image thus obtained can be converted into a heat-resistant material excellent in heat resistance, chemical resistance, and mechanical properties by high-temperature heat treatment (about 200 to 400 ° C.). A cured resin having a relief pattern is obtained.

Next, although an Example and a comparative example demonstrate this invention further in detail, the scope of the present invention is not limited by these. The characteristics in each example were measured as follows.
(1) Weight average molecular weight The weight average molecular weight (Mw) of each copolymer was measured by gel permeation chromatography (hereinafter referred to as “GPC”) (manufactured by Tosoh Corporation, converted to TSK standard polystyrene). The analysis conditions for GPC are as follows:
Column: Showa Denko Co., Ltd., trade name: Shodex 805/804/802 in series Separation: N-methyl-2-pyrrolidone, 40 ° C.
Flow rate: 1.0 ml / min Detector: JASCO Corporation, RI-2031

(2) Measurement of proton nuclear magnetic resonance (1H-NMR) spectrum Each copolymer was dissolved in deuterated dimethyl sulfoxide so as to have a concentration of 5 wt%. "1H-NMR spectrum") was measured by integrating 256 times using a JNM-LA400 FT-NMR apparatus manufactured by JEOL Ltd.

(3) Measurement of Infrared Absorption (IR) Spectrum The infrared absorption spectrum (hereinafter referred to as “IR spectrum”) in each copolymer powder was obtained from Thermo Nicolet, AVATAR 360 FT-IR apparatus, and Centaurus microscope spectroscopy. It measured by ATR method using the analyzer.

(4) Measurement of residual stress A 6-inch silicon wafer was spin-coated with the photosensitive resin compositions obtained in Examples and Comparative Examples of the present invention so that the film thickness after curing was about 7 to 12 μm. After pre-baking at 180 ° C. for 180 seconds, full-wavelength exposure at 600 mJ / cm ^{2 in} terms of i-line was performed using a high-pressure mercury lamp, followed by heat treatment at 120 ° C. for 180 seconds. Then, it heated at 300 degreeC for 2 hours, and obtained the resin cured film. Changes in the radius of curvature of the substrate due to the cured resin film were measured using a thin film stress measuring device (FLX-2320, manufactured by KLA-Tencor Corporation) while flowing nitrogen gas at a flow rate of 5.0 mL / min. Then, the residual stress of the cured resin film was obtained from the radius of curvature of the substrate using the following formula (1):
δ = Eh ² / {(1-v) 6RT} (1)
δ: thin film average stress E: Young's modulus v: Poisson's ratio h: substrate thickness R: substrate radius of curvature T: film thickness

(5) Measurement of thermal expansion coefficient (CTE) By immersing a cured resin film obtained in the same manner as in (4) above in hydrochloric acid, except that a 6-inch silicon wafer provided with an aluminum vapor deposition layer on the outermost surface is used. It peeled off from the wafer and produced the tape of the resin cured film of 5 mm width. Using the obtained resin cured film tape, using a thermomechanical tester (manufactured by Shimadzu Corporation, TMA-50), under a nitrogen atmosphere, a load of 200 g / mm ² was applied and the temperature rising rate was 10 ° C. / After heating in minutes, the coefficient of thermal expansion (CTE) was measured.

(6) Measurement of elongation Using a resin cured film tape obtained in the same manner as in (5) above, a tensile test was conducted at a speed of 40 mm / min using ASTM D-882-88, and the tape was broken. The elongation (elongation with respect to the sample length before measurement) at the time of measurement was measured.

Hereinafter, specific embodiments of the present invention will be described based on examples.
[Example 1]
In a 1 liter separable flask equipped with a stirrer, a thermometer, a nitrogen gas introduction tube, a water separator, and a cooling tube, 4,4′-diamino-3,3′-dihydroxybiphenyl (hereinafter referred to as “HAB”). ) 64.9 g (0.3 mol) and 480 g of 1-methyl-2-pyrrolidone (hereinafter referred to as “NMP”) were charged and dissolved with stirring. To this, 68.7 g (0.15 mol) of p-phenylenebis (trimellitic acid ester) dianhydride (hereinafter referred to as “TAHQ”) was added and stirred for 30 minutes at room temperature. 100 g of toluene was added as an azeotropic solvent with the resulting water, heated and refluxed at 180 ° C. for 3 hours using an oil bath, and imidation was performed by appropriately removing water from the flask.

After returning this reaction liquid to room temperature, 19.8 g (0.25 mol) of pyridine was added, and 36.9 g (0) of 4,4′-diphenyl ether dicarboxylic acid dichloride (hereinafter referred to as “DEDC”) dissolved in 70 g of NMP. .125 mol) was added little by little while maintaining the temperature of the reaction solution at -5 to 5 ° C., and the temperature was raised to room temperature after the addition was completed and stirring was continued for 4 hours. The obtained reaction solution was added dropwise to ion-exchanged water while stirring, and the deposited copolymer was filtered and washed, followed by vacuum drying to obtain a copolymer (P-1). The weight average molecular weight (Mw) of the obtained copolymer was 15,000.
An IR spectrum of the powder of copolymer P-1 is shown in FIG. Characteristic absorption of an imide group, 1384,1719, and found in 1780 cm ^-1, characteristic absorption of an amide group from being seen in the 1650 cm ^-1, it was confirmed that the polyimide polyamide copolymer.
Moreover, the 1H-NMR spectrum in a deuterated dimethyl sulfoxide solution is shown in FIG. Polyimide calculated from the integral ratio of 4 protons on the benzene ring derived from TAHQ found at 8.48 and 8.56 ppm and 2 protons on the nitrogen atom of the amide group found at 9.57 ppm The copolymerization ratio (molar ratio) of the polyamide unit (2) to the unit (1) was 0.77.

[Example 2]
Example 1 A mixture of 18.4 g (0.062 mol) of DEDC and 12.7 g (0.063 mol) of isophthalic acid dichloride (hereinafter referred to as “IPC”) was used as the dicarboxylic acid dichloride in Example 1. 1 to obtain a copolymer (P-2). The weight average molecular weight (Mw) of the obtained copolymer was 16,400.
An IR spectrum of the powder of copolymer P-2 is shown in FIG. The characteristic absorption of the imide group was observed at 1384, 1720, and 1780 cm ⁻¹ , and the characteristic absorption of the amide group was observed at 1649 cm ⁻¹ , confirming that it was a polyimide polyamide copolymer.
Moreover, the 1H-NMR spectrum in a deuterated dimethyl sulfoxide solution is shown in FIG. Polyimide calculated from the integral ratio of 4 protons on the benzene ring derived from TAHQ found at 8.50 and 8.57 ppm and 2 protons on the nitrogen atom of the amide group found at 9.57 ppm The copolymerization ratio (molar ratio) of the polyamide unit (2) to the unit (1) was 0.73.

[Comparative Example 1]
In a 1 liter separable flask equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, a water separator, and a cooling tube, 21.6 g (0.1 mol) of HAB and 250 g of NMP were charged and dissolved by stirring. To this, 38.0 g (0.083 mol) of TAHQ was added and stirred at room temperature for 30 minutes, and then 50 g of toluene was added as an azeotropic solvent with water generated during the imidization reaction, and the mixture was heated at 180 ° C. for 2 hours using an oil bath. Imidization was performed by heating to reflux and removing water from the flask as appropriate.
When this reaction solution was returned to room temperature, the polymer precipitated and gelled, and the target polymer was not obtained.

[Comparative Example 2]
In a 1 liter separable flask equipped with a stirrer, a thermometer, and a nitrogen gas inlet tube, 21.6 g (0.1 mol) of HAB, 130 g of NMP, and 13.1 g (0.17 mol) of pyridine were charged and dissolved by stirring. did. To this, 24.5 g (0.083 mol) of DEDC dissolved in 50 g of NMP was added little by little while keeping the temperature of the reaction solution at −5 to 5 ° C. After the addition was completed, the temperature was raised to room temperature and further stirred for 4 hours. Continued. About the obtained reaction liquid, the post-process similar to Example 1 was performed, and polyamide (P-3) was obtained. The weight average molecular weight (Mw) of P-3 was 16,600.

[Comparative Example 3]
Example 1 except that 109.9 g (0.3 mol) of 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane (hereinafter referred to as “6FAP”) was used as the diamine in Example 1. 1 to obtain a copolymer (P-4). The weight average molecular weight (Mw) of P-4 was 7,900.

Example 3
100 parts by mass of copolymer (P-1), 2- [2- (4-methylphenylsulfonyloxyimino) -2,3-dihydrothiophene-3-ylidene] -2 as a compound that generates an acid upon light irradiation -(2-methylphenyl) acetonitrile (Irgacure PAG121, manufactured by Ciba Japan Co., Ltd.), 5 parts by mass, an alkoxymethylated urea resin (product number MX-270, manufactured by Sanwa Chemical Co., Ltd.) as a compound that can be crosslinked by the action of acid 20 parts by mass of name Nicarak, monomer 95% or more), 10 parts by mass of trimethylolpropane trimethacrylate, 2 parts by mass of 3- (triethoxysilyl) -N- (phenylcarbonyl) propylamine (SI) to 150 parts by mass of NMP After dissolution, the mixture was filtered through a 1 μm Teflon (registered trademark) filter to obtain a photosensitive varnish.

Example 4
A photosensitive varnish was obtained in the same manner as in Example 3 except that the copolymer P-2 was used.

[Comparative Example 4]
It was prepared in the same manner as in Example 3 except that polyamide P-3 was used. However, gelation occurred during stirring and dissolution, and the intended photosensitive varnish was not obtained.

[Comparative Example 5]
A photosensitive varnish was obtained by blending in the same manner as in Example 3 except that the copolymer P-4 was used.
Using the photosensitive resin compositions obtained from Examples 3-4 and Comparative Examples 4-5, spin coating was performed on a 6-inch silicon wafer so that the film thickness after curing was about 9-10 μm. The plate was pre-baked at 110 ° C. for 3 minutes, exposed to 600 mJ / cm ² (i-line conversion) full wavelength using a high-pressure mercury lamp, and then heat-treated at 120 ° C. for 180 seconds. Then, it heated at 300 degreeC for 2 hours, and obtained the resin cured film. The obtained resin cured film was evaluated for residual stress and mechanical properties. The results are shown in Table 1 below.

  The photosensitive resin composition of this invention can be utilized suitably in the field | area in an electronic component or a semiconductor device.

Claims (5)

Following formula (1):

{Wherein X is a divalent organic group in which one or more benzene rings or naphthalene rings which may have a substituent are directly connected, and Y is an optionally substituted benzene It is a tetravalent organic group in which two or more rings are directly connected. } And the following formula (2):

{Wherein Z is a divalent organic group containing one or more aromatic rings, and Y is a tetravalent organic group in which two or more benzene rings which may have a substituent are directly connected. is there. } The polyimide polyamide copolymer which has a repeating unit represented by these.   (A) 100 parts by mass of the polymer containing the polyimide polyamide copolymer according to claim 1, (B) 0.5 to 20 parts by mass of a compound that generates an acid by light irradiation, and (C) crosslinking by the action of the acid. A photosensitive resin composition comprising 3 to 50 parts by mass of a compound to be obtained.   (1) A step of forming a layer comprising the photosensitive resin composition according to claim 2 on a substrate, (2) a step of exposing, (3) a step of performing a heat treatment, (4) a step of developing, and ( 5) A method for forming a cured relief pattern, comprising a step of heating the obtained relief pattern.   A method for manufacturing a semiconductor device, comprising the method for forming a cured relief pattern according to claim 3.   A semiconductor device manufactured by the method according to claim 4.

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