JP2015200819A - Positive photosensitive resin composition, patterned cured film using the same, and production method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive photosensitive resin composition which can provide a cured film realizing inhibited warpage, little residual stress and excellent physical properties with a curing temperature of 300°C or less; a patterned cured film using the same; and a production method thereof.SOLUTION: A positive photosensitive resin composition comprises (A) at least one polymer selected from the group consisting of polyimide, polybenzoxazole and precursors thereof, (B) a compound that generates an acid upon irradiation with light, (C) a thermal crosslinking agent, and (D) an acrylic resin including a structure represented by the general formula (1). (In the general formula (1), Rrepresents hydrogen or a methyl group; and Rrepresents a hydrogen atom, a hydroxyl group, a C1-12 alkyl group, alkoxyl group, or a carboxyl group.)

Description

  The present invention relates to a positive photosensitive resin composition, a patterned cured film using the same, and a method for producing the same.

In recent years, with the miniaturization of semiconductor integrated circuits, an interlayer insulating film called a low-k layer for reducing the dielectric constant is required. Since the low-k layer has a pore structure, the mechanical strength decreases. In order to protect such an interlayer insulating film having low mechanical strength, a cured film formed of photosensitive polyimide or photosensitive polybenzoxazole has a thick film formability (for example, 5 μm or more) and a high elastic modulus ( For example, characteristics such as 4 GPa or more are required.
However, by increasing the film thickness and increasing the elastic modulus, the stress after curing increases, and the warpage of the semiconductor wafer increases, which may cause problems when transporting or fixing the wafer. Surface protection with low stress Development of membranes is desired.
Conventionally, photosensitive polyimide or photosensitive polybenzoxazole having both excellent heat resistance, electrical characteristics, mechanical characteristics, and the like has been used for a surface protective film and an interlayer insulating film of a semiconductor element. Photosensitive polyimide or photosensitive polybenzoxazole is usually coated with these precursor compositions on various substrates, exposed with actinic radiation, followed by patterning by development with an organic solvent or an aqueous alkali solution, and high-temperature heat treatment. Thus, a polyimide film or a polybenzoxazole film is finally obtained. Conventionally, it has been cured at a high temperature of about 350 ° C. However, in recent years, from the viewpoint of heat resistance of the material used for the lower layer, curing at a low temperature is required. Specifically, degassing from the surface protective film is required. From the viewpoint of avoidance, a curing temperature of 250 to 300 ° C. is required.

Conventionally, in order to cope with low-temperature curing, a technique for reducing stress using a polyimide or polybenzoxazole having a flexible skeleton has been advanced. These materials exhibit excellent elongation and low residual stress when cured at a low temperature of 200 ° C. or lower, but decrease in elongation and residual stress increase when cured at 250 ° C., so that the crosslinking density increases when cured at higher temperatures, and the residual There is a possibility that the amount stress further increases (for example, see Non-Patent Document 1). Therefore, applying a conventional low-temperature curing material to a curing process near 300 ° C. has room for improvement from the viewpoint of reducing stress.
On the other hand, although there is a material having an excellent low stress property with a buffer coating material that has been conventionally used at a curing temperature of 350 ° C. or higher (see, for example, Patent Document 1), when used at a curing temperature of 300 ° C. or lower, curing is not possible. There is room for improvement, such as stress does not drop because it does not advance sufficiently.

International Publication No. 2006/008991

Functional Materials, Vol. 33, p. 21 (2013)

  The present invention relates to a positive photosensitive resin composition having excellent cured film properties at a curing temperature of 300 ° C. or less, having a small residual stress in the cured film, and capable of suppressing warpage, and a pattern cured film using the same. An object is to provide a manufacturing method.

According to the present invention, the following positive photosensitive resin composition and the like are provided.
<1> (A) At least one polymer selected from the group consisting of polyimide, polybenzoxazole and precursors thereof, (B) a photoacid generator, (C) a thermal crosslinking agent, and (D) A positive photosensitive resin composition comprising an acrylic resin having a structure represented by the general formula (1).

(一般式（１）中、Ｒ^１は水素又はメチル基を示す。Ｒ^２は水素原子、ヒドロキシル基、炭素数１〜１２のアルキル基、アルコキシル基又はカルボキシル基を表す。)
＜２＞ 前記（Ｄ）アクリル樹脂の含有量が、（Ａ）成分１００質量部に対して０．０１〜３０質量部である＜１＞に記載のポジ型感光性樹脂組成物。
＜３＞ 前記（Ｂ）光酸発生剤が、ｏ−キノンジアジド化合物である、＜１＞又は＜２＞に記載のポジ型感光性樹脂組成物。
＜４＞ 前記（Ｄ）アクリル樹脂の重量平均分子量が、２０００〜１０００００である＜１＞〜＜３＞のいずれかに記載のポジ型感光性樹脂組成物。
＜５＞ 前記（Ｄ）アクリル樹脂が、さらに下記一般式（２）、（３）又は（４）で表される構造単位を少なくとも１つ以上有するアクリル樹脂である、＜１＞〜＜４＞いずれか一項に記載のポジ型感光性樹脂組成物。

(In general formula (1), R ¹ represents hydrogen or a methyl group. R ² represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxyl group, or a carboxyl group.)
<2> The positive photosensitive resin composition according to <1>, wherein the content of the (D) acrylic resin is 0.01 to 30 parts by mass with respect to 100 parts by mass of the component (A).
<3> The positive photosensitive resin composition according to <1> or <2>, wherein the (B) photoacid generator is an o-quinonediazide compound.
<4> The positive photosensitive resin composition according to any one of <1> to <3>, wherein the weight average molecular weight of the (D) acrylic resin is 2000 to 100,000.
<5> The acrylic resin (D) is an acrylic resin having at least one structural unit represented by the following general formula (2), (3), or (4), <1> to <4> The positive photosensitive resin composition as described in any one of Claims.

［一般式（２）中、Ｒ^３は水素原子又はメチル基を示し、Ｒ^４は１級、２級又は３級アミノ基を有する１価の有機基を示す。］

[In General Formula (2), R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a monovalent organic group having a primary, secondary, or tertiary amino group. ]

［一般式（３）中、Ｒ^５は水素原子又はメチル基を示し、Ｒ^６は炭素数４〜２０のアルキル基を示す。］

[In General Formula (3), R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents an alkyl group having 4 to 20 carbon atoms. ]

［一般式（４）中、Ｒ^７は水素原子又はメチル基を示す。］
＜６＞ ＜１＞〜＜５＞のいずれか一項に記載の感光性樹脂組成物から得られる硬化膜。
＜７＞ ＜１＞〜＜５＞のいずれか一項に記載の感光性樹脂組成物を基板上に塗布し乾燥して感光性樹脂膜を形成する工程と、前記感光性樹脂膜を所定のパターンに露光する工程と、前記露光後の感光性樹脂膜を現像してパターン樹脂膜を得る現像工程と、前記パターン樹脂膜を加熱処理してパターン硬化膜を得る加熱処理工程とを含む、パターン硬化膜の製造方法。
＜８＞ 前記加熱処理工程における加熱処理温度が３００℃以下である＜７＞に記載のパターン硬化膜の製造方法。

[In General Formula (4), R ⁷ represents a hydrogen atom or a methyl group. ]
<6> A cured film obtained from the photosensitive resin composition according to any one of <1> to <5>.
<7> A step of applying the photosensitive resin composition according to any one of <1> to <5> onto a substrate and drying to form a photosensitive resin film; and A pattern including a step of exposing the pattern, a development step of developing the exposed photosensitive resin film to obtain a pattern resin film, and a heat treatment step of heating the pattern resin film to obtain a pattern cured film A method for producing a cured film.
<8> The method for producing a cured pattern film according to <7>, wherein the heat treatment temperature in the heat treatment step is 300 ° C. or lower.

According to the present invention, it is possible to provide a positive photosensitive resin composition capable of reducing the stress of a cured film, suppressing warpage, and forming a cured film having excellent cured film properties. Moreover, the pattern cured film which consists of a positive photosensitive resin composition of this invention has a favorable photosensitive characteristic (sensitivity and resolution), and has sufficient mechanical characteristics (breaking elongation). In addition, since the photosensitive resin composition of the present invention can be cured at a low temperature, it is possible to prevent damage to the electronic component due to heat and to provide a highly reliable electronic component with a high yield.
The present inventors speculate that the effect is that the addition of a specific acrylic resin induces phase separation in the cured film and reduces the stress remaining in the cured film.

  Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In this specification, “(meth) acrylate” means “acrylate” or “methacrylate” corresponding thereto. Similarly, “(meth) acryl” means “acryl” or “methacryl”.

[Positive photosensitive resin composition]
The positive photosensitive resin composition according to this embodiment (hereinafter sometimes referred to as a photosensitive resin composition) is at least one selected from the group consisting of (A) polyimide, polybenzoxazole, and precursors thereof. And (B) a photoacid generator, (C) a thermal crosslinking agent, and (D) an acrylic resin having a structure represented by the general formula (1).

<(A) component: at least one polymer selected from the group consisting of polyimide, polybenzoxazole and their precursors>
The polymer as the component (A) has a main chain skeleton having a structure of polyimide, polyoxazole or a precursor thereof. Specifically, polyimide, polyamideimide, polyoxazole, polyamide, and precursors thereof (for example, polyamic acid, polyamic acid ester, polyhydroxyamide, etc.). Among these, it is preferable to use polyimide, polyoxazole or a precursor thereof from the viewpoint of increasing the solvent resistance of the cured film.

  The component (A) can be synthesized, for example, by the following method. The polyimide can be obtained, for example, by reacting tetracarboxylic dianhydride and diamine and dehydrating and ring-closing. The polyamideimide can be obtained, for example, by reacting tricarboxylic acid and diamine and dehydrating and ring-closing.

  The polyamide can be obtained, for example, by reacting dicarboxylic acid dichloride with diamine. Moreover, the said polyamic acid (polyimide precursor) can be obtained by making tetracarboxylic dianhydride and diamine react, for example.

  The polyamic acid ester (polyimide precursor) can be obtained, for example, by reacting tetracarboxylic acid diester dichloride with a diamine. The polyhydroxyamide (polyoxazole precursor) can be obtained, for example, by reacting dicarboxylic acid dichloride with dihydroxydiamine (usually those in which an amino group and a phenolic hydroxyl group are bonded to the ortho position of the aromatic ring). . Any of the above-described methods for producing a polymer can be a known method. Among these polymers, polyhydroxyamides (polybenzoxazole precursors) that are closed by heating to become polybenzoxazoles are preferable from the viewpoint of excellent heat resistance, mechanical properties, and electrical properties.

  Polyhydroxyamide has a structural unit represented by the following general formula (5). The “amide unit containing a hydroxyl group” represented by the following general formula (5) is finally converted into an oxazole having excellent heat resistance, mechanical properties, and electrical properties by dehydration ring closure at the time of curing.

（一般式（５）中、Ｕは４価の有機基を示し、Ｖは２価の有機基を示す）

(In general formula (5), U represents a tetravalent organic group, and V represents a divalent organic group)

  The polyhydroxyamide that can be used in the present invention preferably has the structural unit represented by the general formula (5). However, since the solubility of the polyhydroxyamide in an alkaline aqueous solution is derived from a phenolic hydroxyl group, It is more preferable that the “amide unit containing a hydroxy group” represented by the formula (5) is contained in a certain ratio or more. As such, polyhydroxyamide represented by the general formula (6) is preferable. Two Vs in the general formula (6) may be the same or different.

（一般式（６）中、Ｕは４価の有機基を示し、ＶとＷは２価の有機基を示す。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０〜４０モル％である。）

(In general formula (6), U represents a tetravalent organic group, V and W represent a divalent organic group, j and k represent mole fractions, and the sum of j and k is 100 mol%. And j is 60 to 100 mol%, and k is 0 to 40 mol%.)

  Here, it is preferable that the molar fraction of j and k in General formula (6) is j = 80-100 mol% and k = 0-20 mol%. The polyhydroxyamide having the structural unit represented by the general formula (6) can generally be synthesized from a dicarboxylic acid derivative, a hydroxy group-containing diamine, and, if necessary, a diamine other than the above. Specifically, it can be synthesized by converting a dicarboxylic acid derivative into a dihalide derivative and then reacting with the diamines. The dihalide derivative is preferably a dichloride derivative. The dichloride derivative can be synthesized by reacting a dicarboxylic acid derivative with a halogenating agent. A known method can be used for these.

  In the general formula (6), the tetravalent organic group represented by U is preferably a tetravalent aromatic group, preferably having 6 to 40 carbon atoms, and tetravalent having 6 to 40 carbon atoms. The aromatic group is more preferable. In addition, since the tetravalent organic group represented by U is a polybenzoxazole precursor, it generally reacts with a dicarboxylic acid to form a polyamide structure “two hydroxy groups and two amino groups, respectively. It is a residue of a diamine having two sets of structures having an hydroxy group and an amino group located in the ortho position on an aromatic ring.

  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- Although hexafluoropropane etc. are mentioned, it is not limited to these. These compounds can be used alone or in combination of two or more.

  In the general formula (6), the divalent organic group represented by W is generally a “diamine residue” that forms a polyamide structure by reacting with a dicarboxylic acid, and other than the diamine that forms the U. It is a residue and is preferably a divalent aromatic group or an aliphatic group. The number of carbon atoms is preferably 4 to 40, and more preferably a divalent aromatic group having 4 to 40 carbon atoms.

  Examples of 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-aminophenoxy) biphenyl, bis [4 And aromatic diamine compounds such as-(4-aminophenoxy) phenyl] ether and 1,4-bis (4-aminophenoxy) benzene. In addition to these, diamines containing silicone groups include LP-7100, X-22-161AS, X-22-161A, X-22-161B, X-22-161C, and X-22-161E ( Any of these include, but are not limited to, Shin-Etsu Chemical Co., Ltd., trade name). These compounds can be used alone or in combination of two or more.

  In the general formula (6), the divalent organic group represented by V is a dicarboxylic acid residue that reacts with diamine to form a polyamide structure, and is preferably a divalent aromatic group, preferably a carbon atom. The number is preferably 6 to 40, and a divalent aromatic group having 6 to 40 carbon atoms is more preferable from the viewpoint of heat resistance of the cured film. In addition, when V is a divalent organic group having an aliphatic straight chain structure having 6 to 30 carbon atoms, it is preferable in that sufficient physical properties can be obtained even if the temperature at the time of thermosetting is lowered to 280 ° C. or lower. .

Examples of the dicarboxylic acid having an aromatic group include isophthalic acid, terephthalic acid, 2,2-bis (4-carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane, and 4,4′-di. Carboxybiphenyl, 4,4′-dicarboxydiphenyl ether, 4,4′-dicarboxytetraphenylsilane, bis (4-carboxyphenyl) sulfone, 2,2-bis (p-carboxyphenylpropane), 5-tert-butyl Aromatic dicarboxylic acids such as isophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid and 2,6-naphthalenedicarboxylic acid; 1,2-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid An acid, 1, 3- cyclopentane dicarboxylic acid etc. are mentioned.
Examples of the dicarboxylic acid having an aliphatic straight chain structure having 6 to 30 carbon atoms include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, and methylsuccinic acid. Acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipine Acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid Hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosandioic acid, heneicosandioic acid, docosandioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid Examples thereof include, but are not limited to, acids, nonacosandioic acid, triacontanesandioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, and dicarboxylic acids represented by the following general formula (7). It is not a thing. These compounds can be used alone or in combination of two or more.

（一般式（７）中、Ｚは炭素数１〜６の炭化水素基、ｎは１〜６の整数である。）

(In general formula (7), Z is a C1-C6 hydrocarbon group, and n is an integer of 1-6.)

  (A) As for the molecular weight of a component, 3000-200000 are preferable at a weight average molecular weight, 5000-100000 are more preferable, 10000-50000 are further more preferable. Here, the molecular weight is a value obtained by measuring by gel permeation chromatography (GPC) and converting from a standard polystyrene calibration curve.

<(B) component: Photoacid generator>
The photoacid generator as component (B) is used as a photosensitizer. The component (B) has a function of generating an acid by light irradiation and increasing the solubility of the light-irradiated portion in the alkaline aqueous solution.

  Specific examples of the component (B) include o-quinonediazide compounds, aryldiazonium salts, diaryliodonium salts, and triarylsulfonium salts. Of these, o-quinonediazide compounds are preferred because of their high sensitivity.

  The o-quinonediazide compound can be obtained, for example, by a known method in which an o-quinonediazidesulfonyl chloride, a hydroxy compound, an amino compound, or the like is subjected to a condensation reaction in the presence of a dehydrochlorinating agent. Among these, 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane and 1-naphthoquinone-2-diazide-5 -Ester compounds obtained by reaction with sulfonyl chlorides are preferred. This is commercially available from AZ Electronic Materials (trade name “TPPA528”).

  The content of the component (B) is preferably 3 to 100 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint that the difference in dissolution rate between the exposed part and the unexposed part increases and the sensitivity becomes better. 5-50 mass parts is more preferable, and 5-30 mass parts is further more preferable.

<(C) component: thermal crosslinking agent>
The thermal crosslinking agent as component (C) reacts (bridges) with the polymer as component (A) in the step of heat treatment after application, exposure, and development of the photosensitive resin composition. Or (C) component itself superposes | polymerizes in the process of heat-processing. As a result, the brittleness of the film, which is a concern at curing at a relatively low temperature, for example, 300 ° C. or less, can be prevented, and the mechanical properties, chemical resistance, and flux resistance can be improved.

  The component (C) is not particularly limited except that it is a compound that is crosslinked or polymerized in the heat treatment step, but is preferably a compound having a methylol group, an alkoxymethyl group, an epoxy group, or a vinyl ether group in the molecule. A compound in which these groups are bonded to a benzene ring, or a melamine resin or urea resin in which the N-position is substituted with a methylol group or an alkoxymethyl group is preferable. In addition, a compound in which these groups are bonded to a benzene ring having a phenolic hydroxyl group is more preferable in that the sensitivity can be improved by increasing the dissolution rate of the exposed area during development. Among them, a compound having two or more methylol groups or alkoxymethyl groups in the molecule is more preferable in terms of sensitivity and varnish stability, and in addition, the film can be prevented from melting when the film is cured after pattern formation. Such a compound can be specifically represented by the following general formulas (I) to (III).

（一般式（Ｉ）中、Ｘは単結合又は１〜４価の有機基を示し、Ｒ^１１は水素原子又は一価の有機基を示し、Ｒ^１２は一価の有機基を示し、ｎは１〜４の整数であり、ｐは１〜４の整数であり、ｑは０〜３の整数である）

(In general formula (I), X represents a single bond or a monovalent to tetravalent organic group, R ¹¹ represents a hydrogen atom or a monovalent organic group, R ¹² represents a monovalent organic group, and n represents (It is an integer of 1-4, p is an integer of 1-4, q is an integer of 0-3)

（一般式（ＩＩ）中、２つのＹは各々独立に水素原子又は炭素原子数１〜１０のアルキル基、その水素原子の一部又は全部がフッ素原子で置換されたフルオロアルキル基、その水素原子の一部がヒドロキシル基で置換されたヒドロキシアルキル基、炭素原子数１〜１０のアルコキシ基であり、Ｒ^１３及びＲ^１４は一価の有機基を示し、Ｒ^１５及びＲ^１６は水素原子又は一価の有機基を示し、ｍ及びｎは各々独立に１〜３の整数であり、ｐ及びｑは各々独立に０〜４の整数である）

(In the general formula (II), two Y's are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group in which part or all of the hydrogen atoms are substituted with fluorine atoms, and the hydrogen atoms Is a hydroxyalkyl group partially substituted with a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, R ¹³ and R ¹⁴ represent a monovalent organic group, and R ¹⁵ and R ¹⁶ represent a hydrogen atom or And m and n are each independently an integer of 1 to 3, and p and q are each independently an integer of 0 to 4)

（一般式（ＩＩＩ）中、Ｒ^１７及びＲ^１８は各々独立に水素原子又は一価の有機基を示し、互いが結合することで環構造となっていてもよい。）

(In the general formula (III), R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom or a monovalent organic group, and may be bonded to each other to form a ring structure.)

  In the general formulas (I) to (III), the monovalent organic group is an alkyl group, alkoxy group, hydroxyalkyl group, hydroxyalkoxy group, or part of hydrogen atoms having 1 to 10 carbon atoms. Alternatively, those in which all are substituted with halogen atoms are preferred.

  Among the compounds represented by the general formula (III), the following compounds are preferable.

  In the photosensitive resin composition of the present invention, the compounding amount of the component (C) is based on 100 parts by weight of the component (A) from the viewpoints of development time, allowable width of the unexposed part remaining film ratio, and cured film properties. 1 to 50 parts by mass is preferable. On the other hand, from the viewpoint of chemical resistance and flux resistance of the cured film at 230 ° C. or less, 15 parts by mass or more is preferable, and 20 parts by mass or more is more preferable.

<(D) component>
If the photosensitive resin composition which concerns on this embodiment contains the structure represented by following General formula (1), and the acrylic resin of (D) component is resin which is soluble with respect to an alkali developing solution. There is no particular limitation.

(一般式（１）中、Ｒ^１は水素又はメチル基を示す。Ｒ^２は水素原子、ヒドロキシル基、炭素数１〜１２のアルキル基、アルコキシル基又はカルボキシル基を表す。)

(In general formula (1), R ¹ represents hydrogen or a methyl group. R ² represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxyl group, or a carboxyl group.)

  The structure represented by the general formula (1) can be introduced by polymerizing a corresponding polymerizable monomer. Specifically, it can be introduced into an acrylic resin using benzyl (meth) acrylate, 4-hydroxybenzyl (meth) acrylate, 4-methylbenzyl (meth) acrylate, 4-chlorobenzyl (meth) acrylate, or the like. . Among these, benzyl (meth) acrylate is preferable.

  In the acrylic resin as the component (D), the composition ratio of the structural unit represented by the general formula (1) is 1 to 90 from the viewpoint of compatibility and low stress with respect to the total amount of the component (D). It is preferably mol%, more preferably 5 to 87 mol%, further preferably 10 to 85 mol%, particularly preferably 30 to 70 mol%, and 50 to 70 mol%. Very preferably.

  The component (D) is preferably an acrylic resin containing any structure represented by the following general formulas (2) to (4).

［一般式（２）中、Ｒ^３は水素原子又はメチル基を示し、Ｒ^４は１級、２級又は３級アミノ基を有する１価の有機基を示す。］

[In General Formula (2), R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a monovalent organic group having a primary, secondary, or tertiary amino group. ]

［一般式（３）中、Ｒ^５は水素原子又はメチル基を示し、Ｒ^６は炭素数４〜２０のアルキル基を示す。］

[In General Formula (3), R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents an alkyl group having 4 to 20 carbon atoms. ]

［一般式（４）中、Ｒ^７は水素原子又はメチル基を示す。］

[In General Formula (4), R ⁷ represents a hydrogen atom or a methyl group. ]

Examples of the polymerizable monomer that gives the structural unit represented by the general formula (2) include aminoethyl (meth) acrylate, N-methylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N-ethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, aminopropyl (meth) acrylate, N-methylaminopropyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N-ethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, aminoethyl (meth) acrylamide, N-methylaminoethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, N-ethylaminoe (Meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, aminopropyl (meth) acrylamide, N-methylaminopropyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N-ethylamino Propyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, piperidin-4-yl (meth) acrylate, 1-methylpiperidin-4-yl (meth) acrylate, 2,2,6,6-tetramethyl Piperidin-4-yl (meth) acrylate, 1,2,2,6,6-pentamethylpiperidin-4-yl (meth) acrylate, (piperidin-4-yl) methyl (meth) acrylate, 2- (piperidine- 4-yl) ethyl (meth) acrylate And the like. These polymerizable monomers are used alone or in combination of two or more. Among these, from the viewpoint of further improving the adhesion of the resist pattern to the substrate, mechanical properties, and thermal shock resistance, in the general formula (2), R ⁴ is a monovalent group represented by the following general formula (8). An organic group is preferred.

In the general formula (8), X represents an alkylene group having 1 to 5 carbon ^atoms, R 20 ^{to R 24} each independently represent a hydrogen atom or an alkyl group having a carbon number of 1 to 20, m is 0 to an integer of It is.

Examples of the polymerizable monomer that gives the structural unit of the general formula (2) in which R ⁴ is a monovalent organic group represented by the general formula (8) include piperidin-4-yl (meth) acrylate, 1- Methylpiperidin-4-yl (meth) acrylate, 2,2,6,6-tetramethylpiperidin-4-yl (meth) acrylate, 1,2,2,6,6-pentamethylpiperidin-4-yl (meth) ) Acrylate, (piperidin-4-yl) methyl (meth) acrylate, 2- (piperidin-4-yl) ethyl (meth) acrylate, and the like. Among these, 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate is FA-711MM, and 2,2,6,6-tetramethylpiperidin-4-yl methacrylate is FA-712HM. (Both manufactured by Hitachi Chemical Co., Ltd.) are commercially available.
R ⁴ is a polymerizable monomer that gives a structural unit of the general formula (2) that is a monovalent organic group represented by the general formula (8), and thus obtained acrylic resin of component (D) It can have good interaction with at least one polymer selected from the group consisting of (A) component polyimide, polybenzoxazole and precursors thereof.

  In the acrylic resin as the component (D), the structural unit represented by the general formula (2) has a structure represented by the general formula (8), whereby the acrylic resin as the component (D) is added in ethyl lactate. The molecular weight can be controlled when synthesizing with. The composition ratio of the structural unit represented by the general formula (2) is preferably 0.01 to 10 mol%, and 0.05 to 8 mol% with respect to the total amount of the component (D). Is more preferable, 0.1 to 7 mol% is further preferable, 0.5 to 5 mol% is particularly preferable, and 0.8 to 3 mol% is extremely preferable.

  Examples of the polymerizable monomer that gives the structural unit represented by the general formula (3) include (meth) acrylic acid alkyl esters. Specifically, (meth) acrylic acid butyl ester, (meth) acrylic acid pentyl ester, (meth) acrylic acid hexyl ester, (meth) acrylic acid heptyl ester, (meth) acrylic acid octyl ester, (meth) acrylic acid Nonyl ester, (meth) acrylic acid decyl ester, (meth) acrylic acid undecyl ester, (meth) acrylic acid dodecyl ester, (meth) acrylic acid tridecyl ester, (meth) acrylic acid tetradecyl ester, (meth) acrylic Acid pentadecyl ester, (meth) acrylic acid hexadecyl ester, (meth) acrylic acid heptadecyl ester, (meth) acrylic acid octadecyl ester, (meth) acrylic acid nonadecyl ester, (meth) acrylic acid eicosyl ester Can be mentioned. These polymerizable monomers are used singly or in combination of two or more.

Among the polymerizable monomers that give the structural unit represented by the general formula (3), from the viewpoint of reducing the Tg of the acrylic resin as the component (D) and making it a flexible resin, the carbon number is 6 or less. The polymerizable monomer is preferred.
On the other hand, when the acrylic resin of the component (D) contains a structure having 7 or more carbon atoms among the polymerizable monomers giving the structural unit represented by the general formula (3), the polyimide of the component (A), It is preferable from the viewpoint that it becomes easy to cause phase separation with at least one polymer selected from the group consisting of polybenzoxazole and precursors thereof and has an effect of reducing stress. Therefore, the polymerizable monomer which gives the structural unit represented by the general formula (3) contained in the acrylic resin of component (D) is a polymerizable monomer having 6 or less carbon atoms and a polymerizable monomer having 7 or more carbon atoms. It is particularly preferable to use a combination of monomers.

In the component (D), the compositional ratio of the structural unit represented by the general formula (3) is preferably 1 to 50 mol%, and 2 to 45 mol% with respect to the total amount of the component (D). More preferably, it is more preferably 5 to 40 mol%, and particularly preferably 6 to 35 mol%.
When the compositional ratio of the structural unit represented by the general formula (3) is 1 to 50 mol%, the compatibility with the component (A) is reduced, and in the cured film of the positive photosensitive resin composition When the acrylic resin has a flexible skeleton and takes a phase separation structure, the stress of the cured film can be further reduced.

(D) A component may contain the structural unit derived from the (meth) acrylic acid shown in General formula (4). (D) The solubility to alkaline aqueous solution improves because a component has the structural unit derived from the (meth) acrylic acid shown in General formula (4).
When the structural unit derived from (meth) acrylic acid is contained, the composition ratio of the structural unit is preferably 5 to 35 mol%, and 10 to 30 mol% with respect to the total amount of the component (D). More preferably, it is more preferably 12 to 25 mol%. When the composition ratio is 5 to 35 mol%, the compatibility with the component (A) and the developability of the photosensitive resin composition can be further improved.

  From the viewpoint of further improving the compatibility with the component (A), the adhesion of the patterned cured film to the substrate, the mechanical properties and the thermal shock resistance, the component (D) is represented by the general formulas (1), (2), ( It is more preferable to contain an acrylic resin having the structural units represented by 3) and (4). When (D) component is the said acrylic resin, interaction with the polymer of (D) component and (A) component becomes favorable, and compatibility and phase-separation structure can be balanced effectively.

  The weight average molecular weight of the component (D) is preferably 2000 to 100,000, more preferably 3000 to 60000, further preferably 4000 to 50000, particularly preferably 5000 to 30000. It is very preferably ˜25000. If the weight average molecular weight is less than 2,000, the thermal shock resistance of the cured film tends to decrease, and if it exceeds 100,000, the compatibility with the component (A) and the developability tend to decrease.

  In the case of containing the component (D), the content is 0.01 to 50 parts by mass with respect to 100 parts by mass of the total amount of the component (A) from the viewpoints of adhesion, mechanical properties, thermal shock resistance, and photosensitive properties. Preferably, 0.01-40 mass parts is more preferable, 0.01-30 mass parts is further more preferable, 0.1-20 mass parts is especially preferable, and 0.2-10 mass parts is very preferable.

<Other ingredients>
The positive photosensitive resin composition of the present invention contains other components such as a silane compound, a solvent, an elastomer, a dissolution accelerator, a dissolution inhibitor, a surfactant or a leveling agent, and a thermal acid generator as necessary. Can do.
<Other components (E) component: Silane compound>
The component (E) in the present invention is not particularly limited as long as it is a silane coupling agent that is a silane compound, but among them, a silane coupling agent having a hydroxy group or a glycidyl group is preferable.

  Examples of the silane coupling compound having a hydroxy group or a glycidyl group include methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butylphenylsilanediol, isobutylphenylsilanediol, tert- Butylphenylsilanediol, diphenylsilanediol, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyl n-propylphenyl Silanol, ethyl isopropyl phenyl silanol, n-butyl ethyl phenyl silanol , Isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, 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, , 4-bis (butyldihydroxysilyl) benzene, 1,4-bis (dimethylhydroxysilyl) benzene, 1,4-bis (diethylhydroxysilane) Le) benzene, 1,4-bis (dipropyl hydroxy silyl) benzene, 1,4-bis (dibutyl hydroxy silyl) benzene and compounds represented by the following formula.

（式中、ｍは１〜１０の整数、Ｒ^１はヒドロキシ基又はグリシジル基を有する１価の有機基、Ｒ^２及びＲ^３は各々独立の炭素数１〜５のアルキル基、ｐは０〜２の整数を示す。）
前記の化合物のうち、特に前記一般式で示される化合物が、密着性を向上する効果が高く好ましい。

(In the formula, m is an integer of 1 to 10, R ¹ is a monovalent organic group having a hydroxy group or a glycidyl group, R ² and R ³ are each independently an alkyl group having 1 to 5 carbon atoms, and p is 0 to 0. Indicates an integer of 2.)
Among the compounds described above, the compound represented by the general formula is particularly preferable because of its high effect of improving adhesion.

  Such silane coupling agents include hydroxymethyltrimethoxysilane, hydroxymethyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyl. Triethoxysilane, 4-hydroxybutyltrimethoxysilane, 4-hydroxybutyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2-glycid Xylethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 4-glycidoxybutyltrimethoxysilane, 4-glycidoxybuty Triethoxysilane, and the like.

In addition, a silane coupling agent containing a nitrogen atom, specifically an amino group or an amide bond, together with a hydroxy group or a glycidyl group in its structure is also preferable. As such a bis (2-hydroxymethyl) ) -3-Aminopropyltriethoxysilane, bis (2-hydroxymethyl) -3-aminopropyltrimethoxysilane, bis (2-glycidoxymethyl) -3-aminopropyltriethoxysilane, bis (2-hydroxymethyl) ) -3-Silane coupling agent having an amino group such as aminopropyltrimethoxysilane, formula X— (CH ₂ ) _m —CO—NH— (CH ₂ ) _n —Si (OR) ₃
(However, X is a hydroxyl group or a glycidyl group, m and n each independently represents an integer of 1 to 3, and R is a methyl group, an ethyl group, or a propyl group). A silane coupling agent etc. are mentioned.

  The amount of component (E) is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of component (A).

[Method for producing patterned cured film]
Next, the manufacturing method of the pattern cured film which uses the positive photosensitive resin composition of this invention is demonstrated.
A method for producing a patterned cured film includes a photosensitive resin film forming step in which the above-described positive photosensitive resin composition is applied onto a substrate and dried to form a photosensitive resin film, and the photosensitive resin film is formed into a predetermined pattern. An exposure step of exposing, a developing step of developing the exposed photosensitive resin film to obtain a pattern resin film, and a heat treatment step of heating the pattern resin film to obtain a pattern cured film.
Hereinafter, each step will be described.

(Photosensitive resin film forming process)
First, in this step, the positive photosensitive resin composition of the present invention is applied to a spinner or the like on a support substrate such as a glass substrate, a semiconductor, a metal oxide insulator (for example, TiO ₂ , SiO ₂ ), or silicon nitride. After spin coating using, dry using a hot plate, oven or the like. Thereby, the photosensitive resin film which is a film of a positive photosensitive resin composition is obtained.

(Exposure process)
Next, in the exposure step, exposure is performed by irradiating the photosensitive resin film formed as a film on the support substrate with an actinic ray such as ultraviolet ray, visible ray, or radiation via a mask.

(Development process)
In the development step, the patterned resin film is obtained by removing the exposed portion of the photosensitive resin film exposed to actinic rays with a developer. Preferred examples of the developer include aqueous alkali solutions such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, and tetramethylammonium hydroxide. The base concentration of these aqueous solutions is preferably 0.1 to 10% by mass. Furthermore, alcohols and surfactants can be added to the developer and used.

(Heat treatment process)
Next, in the heat treatment step, a cured film pattern can be formed by heat-treating the pattern obtained after development. The heating temperature is preferably 350 ° C. or less, more preferably 120 to 320 ° C., further preferably 160 to 300 ° C., and particularly preferably 250 to 300 ° C.

  The heat treatment is performed using a quartz tube furnace, hot plate, rapid thermal annealing, vertical diffusion furnace, infrared curing furnace, electron beam curing furnace, microwave curing furnace, or the like. Moreover, although it can also select either in air | atmosphere or inert atmosphere, such as nitrogen, since the direction performed by nitrogenation can prevent the oxidation of the photosensitive resin composition, it is preferable. Since the heating temperature range is lower than the conventional heating temperature, damage to the support substrate and the device can be reduced. Therefore, a device can be manufactured with a high yield by using the method for manufacturing a cured pattern film of the present invention. It also leads to energy savings in the process.

  The heating time is the time required for the dehydration ring-closing reaction to sufficiently proceed with the polymer of component (A) in the photosensitive resin composition, for example, the polybenzoxazole precursor, but is approximately 5 hours or less in consideration of work efficiency. . The atmosphere of dehydration ring closure can be selected from the air or an inert atmosphere such as nitrogen.

  Thus, a pattern cured film can be manufactured using the photosensitive resin composition of the present invention.

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto.
First, it shows below about the material used in Examples 1-8 and Comparative Examples 1-5.

[(A) component]
[Synthesis Example 1: Polybenzoxazole precursor]
In a 0.5 liter flask equipped with a stirrer and a thermometer, 15.48 g (60 mmol) of 4,4′-diphenyl ether dicarboxylic acid and 90 g of N-methylpyrrolidone were charged, and after the flask was cooled to 5 ° C., thionyl chloride was added. 23.9 g (120 mmol) was added dropwise and reacted for 30 minutes to obtain a solution of 4,4′-diphenyl ether dicarboxylic 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 (50 mmol) of bis (3-amino-4-hydroxyphenyl) hexafluoropropane and m -After 2.18 g (20 mmol) of aminophenol was stirred and dissolved, 9.48 g (120 mmol) of pyridine was added and the solution of 4,4'-diphenyl ether dicarboxylic acid chloride was added for 30 minutes while maintaining the temperature at 0 to 5 ° C. After dropwise addition, stirring was continued for 30 minutes. Next, the solution was poured into 3 liters of water, and the precipitate was collected, washed with pure water three times, and then dried under reduced pressure to obtain a hydroxyl-terminated polyhydroxyamide (hereinafter referred to as polymer A1). The weight average molecular weight calculated | required by GPC method standard styrene conversion of polymer A1 was 23400, and dispersion degree was 1.8.
A2: Cresol novolak resin (cresol / formaldehyde novolak resin, m-cresol / p-cresol (molar ratio) = 60/40, polystyrene-equivalent weight average molecular weight = 12000, manufactured by Asahi Organic Materials Corporation, trade name “EP4020G”)

[Component (B)]
1-naphthoquinone-2-diazide-5-sulfonic acid ester of 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane ( Esterification rate of about 90%, manufactured by AZ Electronic Materials, trade name “TPPA528”)

[Component (C)]
Tetrakis (methoxymethyl) glycoluril (manufactured by Sanwa Chemical Co., Ltd., trade name “Nicalak MX-270”)

[(D) component]
[Synthesis Example 2: Acrylic resin D1]
In a 0.2 L flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 7.45 g (31 mmol) of acrylic acid dodecyl ester, which is a structural unit of the general formula (3), and a structural unit of the general formula (4) 1.86 g (26 mmol) of acrylic acid, 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate (trade name “LA-82” manufactured by ADEKA) serving as a structural unit of the general formula (2) 0.62 g (2.6 mmol), 19.93 g (113 mmol) of benzyl methacrylate as a structural unit of the general formula (1), and 36 g of ethyl lactate were added, and the temperature was raised to 60 ° C. while stirring. Next, 0.14 g (0.9 mmol) of AIBN (azobisisobutyronitrile) was added, the temperature was raised to 65 ° C., and stirring was continued for 3 hours. Then, after heating up to 80 degreeC, it stirred for 2 hours and cooled to room temperature (25 degreeC), and obtained acrylic resin 1 (D1). The weight average molecular weight calculated | required by GPC method standard styrene conversion of the polymer was 22000. In addition, the molar ratio of the polymerizable monomer in the acrylic resin D1 is as follows.
Acrylic acid dodecyl ester / acrylic acid / LA-82 / benzyl methacrylate = 18/15 / 1.5 / 65 (mol%)

[Synthesis Example 3: Acrylic resin D2]
In a 0.2 L flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 8.59 g (36 mmol) of acrylic acid dodecyl ester, 1.84 g (26 mmol) of acrylic acid, 1,2,2,6,6-pentamethyl -4-piperidinyl methacrylate (made by ADEKA, trade name “LA-82”) 0.61 g (2.6 mmol), benzyl methacrylate 18.81 g (107 mmol) and ethyl lactate 36 g were added, and the mixture was stirred up to 60 ° C. The temperature rose. Next, 0.14 g (0.9 mmol) of AIBN was added, the temperature was raised to 65 ° C., and stirring was continued for 3 hours. Then, after heating up to 80 degreeC, it stirred for 2 hours and cooled to room temperature, and obtained acrylic resin 2 (D2). The weight average molecular weight calculated | required by GPC method standard styrene conversion of the polymer was 22000.
In addition, the molar ratio of the polymerizable monomer in acrylic resin D2 is as follows.
Acrylic acid dodecyl ester / acrylic acid / LA-82 / benzyl methacrylate = 21/15 / 1.5 / 62.5 (mol%)

[Synthesis Example 4: Acrylic resin D3]
In a 0.2 L flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 9.72 g (40 mmol) of acrylic acid dodecyl ester, 1.82 g (25 mmol) of acrylic acid, 1,2,2,6,6-pentamethyl -4-piperidinyl methacrylate (made by ADEKA, trade name “LA-82”) 0.60 g (2.5 mmol), benzyl methacrylate 17.72 g (100 mmol) 36 g of ethyl lactate were added, and the mixture was stirred up to 60 ° C. The temperature rose. Next, 0.14 g (0.9 mmol) of AIBN was added, the temperature was raised to 65 ° C., and stirring was continued for 3 hours. Then, after heating up to 80 degreeC, it stirred for 2 hours and cooled to room temperature, and the acrylic resin 3 (D3) was obtained. The weight average molecular weight calculated | required by GPC method standard styrene conversion of the polymer was 22000.
In addition, the molar ratio of the polymerizable monomer in acrylic resin D3 is as follows.
Acrylic acid dodecyl ester / acrylic acid / LA-82 / benzyl methacrylate = 24/15 / 1.5 / 59.5 (mol%)

[Synthesis Example 5: Acrylic resin D4]
In a 0.2 L flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 11.89 g (50 mmol) of acrylic acid dodecyl ester, 1.78 g (25 mmol) of acrylic acid, 1,2,2,6,6-pentamethyl -4-piperidinyl methacrylate (made by ADEKA, trade name “LA-82”) 0.59 g (2.5 mmol), benzyl methacrylate 15.60 g (88 mmol) 36 g of ethyl lactate were added, and the mixture was stirred up to 60 ° C. The temperature rose. Next, 0.14 g (0.9 mmol) of AIBN was added, the temperature was raised to 65 ° C., and stirring was continued for 3 hours. Then, after heating up to 80 degreeC, it stirred for 2 hours and cooled to room temperature, and the acrylic resin 4 (D4) was obtained. The weight average molecular weight calculated | required by GPC method standard styrene conversion of the polymer was 22000.
In addition, the molar ratio of the polymerizable monomer in acrylic resin D4 is as follows.
Acrylic acid dodecyl ester / acrylic acid / LA-82 / benzyl methacrylate = 30.0 / 15.0 / 1.5 / 53.5 (mol%)

[Synthesis Example 6: Acrylic resin D5]
In a 0.2 L flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 24.40 g (190 mmol) of butyl acrylate, 1.44 g (6.0 mmol) of lauryl acrylate, 2.59 g (36 mmol) of acrylic acid, LA -82: 0.86 g (3.6 mmol), hydroxybutyl acrylate 0.52 g (3.5 mmol), and ethyl lactate 36 g were added, and the temperature was raised to 60 ° C. with stirring. Next, 0.20 g (1.2 mmol) of AIBN was added, the temperature was raised to 65 ° C., and stirring was continued for 3 hours. Then, after heating up to 80 degreeC, it stirred for 2 hours and cooled to room temperature, and the acrylic resin 5 (D5) was obtained. The weight average molecular weight calculated | required by GPC method standard styrene conversion of the polymer was 22000.

(Conditions for measuring weight average molecular weight of polymer (A) by GPC method)
measuring device:
Detector L4000UV manufactured by Hitachi, Ltd.
Pump: Hitachi Ltd. L6000,
Integrator: C-R4A manufactured by Shimadzu Corporation
Measurement condition:
Column Gelpack GL-S300MDT-5 × 2 eluent: THF / DMF = 1/1 (volume ratio),
LiBr (0.03 mol / 1),
H ₃ PO ₄ (0.06 mol / L)
Flow rate: 1.0 mL / min,
Detector: UV270nm
The measurement was performed using a solution of 1 mL of a solvent [THF / DMF = 1/1 (volume ratio)] with respect to 0.5 mg of the polymer.

(Conditions for measuring weight average molecular weight of acrylic resin (D) by GPC method)
Measuring device: RI monitor L-3300 manufactured by Hitachi, Ltd.
Pump: Hitachi Ltd. L6000
Autosampler: Hitachi, Ltd. L-7200
Analysis software: Multi-station GPC-8020 model II
Measurement conditions: Column manufactured by Tosoh Corporation _{TSK guard column, H XL -L,} TSK GEL GMH XL -L × 2 present Eluent: THF
Flow rate: 1.0 mL / min, detector: RI
It measured using the solution of 1 mL of solvent with respect to 1.0 mg of samples.

[Other ingredients]
The following silane compounds E1, E2, and E3 were prepared as other components (component (E)) (Me represents a methyl group, Et represents an ethyl group, and an ethylene group).

[Adjustment of photosensitive resin composition]
The components shown in Table 1 were dissolved in a solvent in which γ-butyrolactone / propylene glycol monomethyl ether acetate was mixed at a mass ratio of 9/1 in the blending amounts shown in Table 1 (blending units are parts by mass), Type photosensitive resin composition was prepared.

<Evaluation of residual stress>
The positive photosensitive resin composition solutions obtained in Examples 1 to 8 and Comparative Examples 1 to 5 were spin-coated on a silicon substrate and heated at 120 ° C. for 3 minutes to form a resin film having a thickness of 12 μm. did. This wafer with a resin film is heat-treated (cured) at 270 ° C. in nitrogen using a vertical diffusion furnace (trade name “μ-TF”, manufactured by Koyo Thermo System Co., Ltd.), and a wafer with a cured film having a thickness of 10 μm. Got. About the obtained wafer with a cured film, the residual stress was measured using the thin film stress measuring apparatus FLX-2320 (made by KLA Tencor). The results are shown in Table 1.
Residual stress evaluation criteria were evaluated as follows.
“◎”: 24 MPa or less “Δ”: more than 24 MPa to less than 28 MPa “×”: 28 MPa or more

<Evaluation of cured film physical properties (elongation at break, thermal decomposition temperature (Td1), glass transition temperature (Tg))>
The positive type photosensitive resin composition solutions obtained in Examples 1 to 8 and Comparative Examples 1 to 5 were spin-coated on a silicon substrate and heated at 120 ° C. for 3 minutes to form a resin film having a thickness of 12 to 14 μm. Formed. This resin film was exposed at all wavelengths through a mask using a proximity exposure machine (trade name “PLA-600FA” manufactured by Canon Inc.). After the exposure, development was performed using a 2.38% by mass aqueous solution of TMAH (tetramethylammonium hydroxide) to obtain a pattern resin film having a 10 mm width cross-sectional rectangle. Thereafter, the pattern cured film is heat-treated (cured) at a predetermined temperature in nitrogen using a vertical diffusion furnace (trade name “μ-TF”, manufactured by Koyo Thermo Systems Co., Ltd.), and the pattern cured film having a thickness of 10 μm. Got. The cured film was peeled from the silicon substrate, and the peeled cured film was used as a sample, and the elongation at break was measured by “Autograph AGS-H100N” manufactured by Shimadzu Corporation. The sample width was 10 mm, the film thickness was 10 μm, and the distance between chucks was 20 mm. The pulling speed was 5 mm / min, and the measurement temperature was about room temperature. The average of the measured values of five or more test pieces obtained from the cured film obtained under the same conditions was defined as elongation at break. The results are shown in Table 1.
The breaking elongation evaluation criteria were evaluated as follows.
“◎”: 20% or more,
“○”: 11-19%,
“×”: 10% or less As for the thermal decomposition temperature (Td1) and the glass transition temperature (Tg), the peeled cured film was cut into a width of 2 mm and a length of 20 mm using a razor, and TG-DTA (Seiko Instruments) The temperature was increased to 420 ° C. at 5 ° C./min. The results are shown in Table 1.
Tg evaluation criteria were evaluated as follows.
“○”: 300 ° C. or higher “×”: 300 ° C. or lower

As shown in Table 1, in Examples 1 to 8, the residual stress in the cured film was reduced by the addition of an acrylic resin containing benzyl methacrylate as the component (D). Compared with Comparative Example 4 containing no component (D), the addition of an acrylic resin containing benzyl methacrylate effectively reduces stress without affecting mechanical properties and heat resistance.
It can be seen that the stress reduction effect is large compared to the case where an acrylic resin not containing benzyl methacrylate is added (Comparative Examples 1 to 4), and the mechanical properties and heat resistance are equivalent. Therefore, the addition of an acrylic resin containing benzyl methacrylate can maintain the properties of the cured film and further reduce the stress.

Claims (8)

(A) at least one polymer selected from the group consisting of polyimide, polybenzoxazole and precursors thereof;
(B) a photoacid generator;
(C) a thermal crosslinking agent;
(D) an acrylic resin containing a structure represented by the following general formula (1);
A positive photosensitive resin composition comprising:

(In general formula (1), R ¹ represents hydrogen or a methyl group. R ² represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxyl group, or a carboxyl group.)   The positive photosensitive resin composition according to claim 1, wherein the content of the (D) acrylic resin is 0.01 to 30 parts by mass with respect to 100 parts by mass of the component (A).   The positive photosensitive resin composition according to claim 1 or 2, wherein the (B) photoacid generator is an o-quinonediazide compound.   The positive photosensitive resin composition according to any one of claims 1 to 3, wherein the (D) acrylic resin has a weight average molecular weight of 2000 to 100,000. The (D) acrylic resin is an acrylic resin further having at least one structural unit represented by the following general formula (2), (3), or (4). The positive photosensitive resin composition described in 1.

[In General Formula (2), R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a monovalent organic group having a primary, secondary, or tertiary amino group. ]

[In General Formula (3), R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents an alkyl group having 4 to 20 carbon atoms. ]

[In General Formula (4), R ⁷ represents a hydrogen atom or a methyl group. ]   The cured film obtained from the positive photosensitive resin composition as described in any one of Claims 1-5. Applying the positive photosensitive resin composition according to any one of claims 1 to 5 on a substrate and drying to form a photosensitive resin film;
Exposing the photosensitive resin film to a predetermined pattern;
A development step of developing the photosensitive resin film after the exposure to obtain a pattern resin film;
And a heat treatment process for obtaining a pattern cured film by heat-treating the pattern resin film.   The manufacturing method of the pattern cured film of Claim 7 whose heat processing temperature in a heat processing process is 300 degrees C or less.