JP2022050106A - Negative-type photosensitive resin composition, cured film, and compound - Google Patents

Abstract

To provide a negative-type type photosensitive resin composition which is excellent in lithography performance in a short development time, a patterned cured film using the negative-type photosensitive resin composition and a compound.SOLUTION: There is provided a negative-type photosensitive resin composition which comprises the following components: (A) 100 pts.mass of at least one resin selected from the group consisting of a polyamide acid, a polyamide acid ester, a polyamide, a polyamideimide and a polyimide which are a polyimide precursor, (B) 0.01 to 10 pts.mass of at least one compound selected from n=1 to 10 including a compound represented by the chemical formula (b1) (wherein, R1 represents a hydrogen atom or a monovalent organic group of an alkyl group having 1 to 12 carbon atoms and n is an integer of 1 to 10) and (C) 0.5 to 30 pts.mass of a photosensitive agent.SELECTED DRAWING: None

Description

The present invention relates to, for example, an insulating material for electronic components, a negative photosensitive resin composition used for forming a relief pattern such as a passivation film, a buffer coat film, and an interlayer insulating film in a semiconductor device, and a cured film using the same. And compounds.

Conventionally, a polyimide resin having excellent heat resistance, electrical properties, and mechanical properties has been used as an insulating material for electronic components, a passivation film for semiconductor devices, a surface protective film, an interlayer insulating film, and the like. Among these polyimide resins, those provided in the form of a photosensitive polyimide precursor easily form a heat-resistant relief pattern film by coating, exposing, developing, and thermally imidizing the precursor. be able to. Such a photosensitive polyimide precursor has a feature that the process can be significantly shortened as compared with the conventional non-photosensitive polyimide.

As a resin used for the same purpose other than the photosensitive polyimide, polybenzoxazole (hereinafter, also referred to as “PBO”), which becomes a heat-resistant resin after curing, is known. A PBO precursor resin and a photoacid generator such as a photosensitive diazoquinone compound are mixed with a solvent such as γ-butyl lactone (hereinafter referred to as GBL) to prepare a varnish of the PBO precursor composition, and this PBO precursor composition is prepared. A method of using a substance as a positive photosensitive resin composition is disclosed in, for example, Patent Document 1.

Patent Document 2 describes a method for adding a phenol compound to a positive photosensitive resin composition of a PBO precursor composition in order to improve the solubility in an alkaline water developer and shorten the development time. It has been disclosed. Further, in Patent Document 3, the development time is similarly shortened by adding the N-hydroxyimide compound.

Japanese Unexamined Patent Publication No. 63-096162 Japanese Unexamined Patent Publication No. 9-30221 Japanese Unexamined Patent Publication No. 2009-3202

On the other hand, in the negative photosensitive resin composition developed by an organic solvent using a polyimide precursor resin or the like, shortening of the developing time has not been studied much.
Therefore, in the present invention, even in a negative photosensitive resin composition developed by an organic solvent, a pattern is formed by using a negative photosensitive resin composition having excellent lithography performance in a short development time and the negative photosensitive resin composition. It is an object of the present invention to provide a cured film as well as a compound.

The present inventors have found that a negative photosensitive resin composition having excellent lithography performance can be obtained in a short development time by blending a specific compound in the photosensitive resin composition, and complete the present invention. I arrived. That is, the present invention is as follows.

（式中のＲ１は、水素原子、炭素数１～１２のアルキル基の１価の有機基を表し、ｎ＝１～１０の整数である。）で示される化合物を含み、ｎ＝１～１０から選ばれる少なくとも一つの化合物：０．０１～１０質量部、並びに、
（Ｃ）感光剤：０．５～３０質量部、を含むことを特徴とするネガ型感光性樹脂組成物。
［２］
前記（Ａ）樹脂は、下記一般式（１）：

｛式中、Ｘ１は、４価の有機基であり、Ｙ１は、２価の有機基であり、ｎ１は、２～１５０の整数であり、そしてＲ１及びＲ２は、それぞれ独立に、水素原子、又は下記一般式（２）：

（式中、Ｒ３、Ｒ４及びＲ５は、それぞれ独立に、水素原子又は炭素数１～３の有機基であり、そしてｍ１は、２～１０の整数である。）で表される１価の有機基、又は炭素数１～４の飽和脂肪族基である。｝で表される構造を有するポリイミド前駆体、又は、
下記一般式（３）：

（式中、Ｘ２は、炭素数６～１５の３価の有機基であり、Ｙ２は、炭素数６～３５の２価の有機基であり、かつ同一の構造であるか、又は複数の構造を有してよく、Ｒ６は、炭素数３～２０のラジカル重合性の不飽和結合基を少なくとも一つ有する有機基であり、そしてｎ２は、１～１０００の整数である。）
で表される構造を有するポリアミド、から成る群より選ばれる少なくとも一種の樹脂である、［１］に記載のネガ型感光性樹脂組成物。
［３］
（Ｂ）化学式（ｂ１）で示される前記化合物のＲ１が、炭素数１～１２のアルキル基の１価の有機基である、［１］または［２］に記載のネガ型感光性樹脂組成物。
［４］
前記（Ａ）樹脂１００質量部を基準として、（Ｂ）化学式（ｂ１）で示される前記化合物を０．０５～５質量部含む、［１］～［３］のいずれかに記載のネガ型感光性樹脂組成物。
［５］
（Ｄ）溶剤を含み、該（Ｄ）溶剤が、γ－ブチロラクトン、γ－バレロラクトン、３―メトキシ－Ｎ，Ｎ－ジメチルプロピオンアミド、および３―ブトキシ－Ｎ，Ｎ－ジメチルプロピオンアミドから成る群から選ばれる少なくとも１種を含む、［１］～［４］のいずれかに記載のネガ型感光性樹脂組成物。
［６］
前記（Ｄ）溶剤が、炭素数１～１２のアルコール化合物を含む、［５］に記載のネガ型感光性樹脂組成物。
［７］
（１）［１］～［６］のいずれかに記載の感光性樹脂組成物を基板上に塗布することによって感光性樹脂層を該基板上に形成する工程と、
（２）該感光性樹脂層を露光する工程と、
（３）該露光後の感光性樹脂層を現像してレリーフパターンを形成する工程と、
（４）該レリーフパターンを加熱処理することによって硬化レリーフパターンを形成する工程を経て得られた硬化膜。
［８］
（Ｂ）化学式（ｂ１）：

（式中のＲ１は、水素原子、または炭素数１～１２のアルキル基の１価の有機基を表し、ｎ＝１～１０の整数をとる。）で示される化合物。
［９］
前記化学式（ｂ１）において、前記Ｒ１が、メチル基、エチル基、およびイソプロピル基からなる群から選ばれる１種である、［８］に記載の化合物。
［１０］
前記化学式（ｂ１）において、ｎ＝２～５である、［８］または［９］に記載の化合物。
［１１］
［８］～［１０］のいずれかに記載の前記化学式（ｂ１）において、ｎ＝２～５である化合物のすべてを含む組成物。 [1]
The following ingredients;
(A) At least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamide, polyamide-imide, and polyimide, which are polyimide precursors: 100 parts by mass,
(B) Chemical formula (b1):

(R1 in the formula represents a hydrogen atom, a monovalent organic group of an alkyl group having 1 to 12 carbon atoms, and is an integer of n = 1 to 10), and contains a compound represented by n = 1 to 10. At least one compound selected from: 0.01 to 10 parts by mass, as well as
(C) A negative photosensitive resin composition comprising 0.5 to 30 parts by mass of a photosensitive agent.
[2]
The resin (A) has the following general formula (1):

{In the formula, X1 is a tetravalent organic group, Y1 is a divalent organic group, n1 is an integer of 2 to 150, and R1 and R2 are independently hydrogen atoms, respectively. Or the following general formula (2):

(In the formula, R3, R4 and R5 are independently hydrogen atoms or organic groups having 1 to 3 carbon atoms, and m1 is an integer of 2 to 10). A group or a saturated aliphatic group having 1 to 4 carbon atoms. }, A polyimide precursor having a structure represented by
The following general formula (3):

(In the formula, X2 is a trivalent organic group having 6 to 15 carbon atoms, and Y2 is a divalent organic group having 6 to 35 carbon atoms and has the same structure or a plurality of structures. R6 is an organic group having at least one radically polymerizable unsaturated bonding group having 3 to 20 carbon atoms, and n2 is an integer of 1 to 1000.)
The negative photosensitive resin composition according to [1], which is at least one kind of resin selected from the group consisting of polyamide having a structure represented by.
[3]
(B) The negative photosensitive resin composition according to [1] or [2], wherein R1 of the compound represented by the chemical formula (b1) is a monovalent organic group of an alkyl group having 1 to 12 carbon atoms. ..
[4]
The negative type photosensitive according to any one of [1] to [3], which comprises (B) 0.05 to 5 parts by mass of the compound represented by the chemical formula (b1) based on 100 parts by mass of the (A) resin. Negative resin composition.
[5]
A group containing (D) a solvent, wherein the (D) solvent consists of γ-butyrolactone, γ-valerolactone, 3-methoxy-N, N-dimethylpropionamide, and 3-butoxy-N, N-dimethylpropionamide. The negative type photosensitive resin composition according to any one of [1] to [4], which comprises at least one selected from.
[6]
The negative photosensitive resin composition according to [5], wherein the solvent (D) contains an alcohol compound having 1 to 12 carbon atoms.
[7]
(1) A step of forming a photosensitive resin layer on the substrate by applying the photosensitive resin composition according to any one of [1] to [6] on the substrate.
(2) The step of exposing the photosensitive resin layer and
(3) A step of developing the photosensitive resin layer after the exposure to form a relief pattern, and
(4) A cured film obtained through a step of forming a cured relief pattern by heat-treating the relief pattern.
[8]
(B) Chemical formula (b1):

(R1 in the formula represents a hydrogen atom or a monovalent organic group of an alkyl group having 1 to 12 carbon atoms, and takes an integer of n = 1 to 10).
[9]
The compound according to [8], wherein in the chemical formula (b1), the R1 is one selected from the group consisting of a methyl group, an ethyl group, and an isopropyl group.
[10]
The compound according to [8] or [9], wherein n = 2 to 5 in the chemical formula (b1).
[11]
A composition comprising all of the compounds having n = 2 to 5 in the chemical formula (b1) according to any one of [8] to [10].

According to the present invention, by blending a specific compound in a photosensitive resin composition, a negative photosensitive resin composition having excellent lithography performance can be obtained in a short development time, and further, the negative photosensitive resin composition can be obtained. It is possible to provide a cured film in which a pattern is formed using a resin composition, as well as a compound.

The present invention will be specifically described below. It should be noted that throughout the present specification, the structures represented by the same reference numerals in the general formula may be the same or different from each other when a plurality of structures are present in the molecule.

（式中のＲ１はそれぞれ独立して、水素原子、炭素数１～１２のアルキル基の１価の有機基を表し、ｎ＝１～１０の整数をとる。）を必須成分とする。 <Photosensitive resin composition>
The negative photosensitive resin composition of the present invention has the following components; (A) at least one resin selected from the group consisting of a polyimide precursor, polyamic acid, polyamic acid ester, polyamide, polyamideimide, and polyimide: 100. By mass, 0.01 to 10 parts by mass of (B) the compound represented by the chemical formula (b1), and 0.01 to 10 parts by mass of at least one compound selected from n = 1 to 10, and (C) photosensitizer: 0. It is characterized by consisting of 5 to 30 parts by mass.

(R1 in the formula independently represents a hydrogen atom and a monovalent organic group of an alkyl group having 1 to 12 carbon atoms, and takes an integer of n = 1 to 10) as an essential component.

(A) Resin The (A) resin used in the present invention will be described. The resin (A) of the present invention contains at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamide, polyamideimide, and polyimide, which are polyimide precursors, as a main component. Here, the main component means that these resins are contained in an amount of 60% by mass or more of the total resin, and is preferably contained in an amount of 80% by mass or more. Further, other resins may be contained if necessary.

The weight average molecular weight of these resins is preferably 1,000 or more, more preferably 5,000 or more, in terms of polystyrene by gel permeation chromatography, from the viewpoint of heat resistance after heat treatment and mechanical properties. The upper limit is preferably 100,000 or less, and in the case of a photosensitive resin composition, 50,000 or less is more preferable from the viewpoint of solubility in a developing solution.

In the present invention, the resin (A) is preferably a photosensitive resin in order to form a relief pattern. The photosensitive resin is a resin that is used together with the (C) photosensitive agent described later to form a photosensitive resin composition, which causes a phenomenon of dissolution or undissolution in the subsequent development step.

As the photosensitive resin, among the polyimide precursors polyamic acid, polyamic acid ester, polyamide, polyamideimide, and polyimide, the polyimide precursor, polyamide, and polyimide are preferable because the resin after heat treatment has excellent heat resistance and mechanical properties. Used. Further, these photosensitive resins can be selected according to a desired application, such as whether to prepare a negative type photosensitive resin composition together with the (C) photosensitive agent described later.

｛式中、Ｘ１は、４価の有機基であり、Ｙ１は、２価の有機基であり、ｎ１は、２～１５０の整数であり、Ｒ１及びＲ２は、それぞれ独立に、水素原子、又は下記一般式（２）：

（式中、Ｒ３、Ｒ４及びＲ５は、それぞれ独立に、水素原子又は炭素数１～３の有機基であり、そしてｍ１は、２～１０の整数である。）で表される１価の有機基、又は炭素数１～４の飽和脂肪族基である。｝
で表される構造を有するポリイミド前駆体である。ポリイミド前駆体は、加熱（例えば２００℃以上）環化処理を施すことによってポリイミドに変換される。ポリイミド前駆体はネガ型感光性樹脂組成物用として好適である。 [Polyimide precursor]
In the photosensitive resin composition of the present invention, one example of the most preferable resin (A) from the viewpoint of heat resistance and photosensitive characteristics is the following general formula (1) :.

{In the formula, X1 is a tetravalent organic group, Y1 is a divalent organic group, n1 is an integer of 2 to 150, and R1 and R2 are independently hydrogen atoms or, respectively. The following general formula (2):

(In the formula, R3, R4 and R5 are independently hydrogen atoms or organic groups having 1 to 3 carbon atoms, and m1 is an integer of 2 to 10). A group or a saturated aliphatic group having 1 to 4 carbon atoms. }
It is a polyimide precursor having a structure represented by. The polyimide precursor is converted into polyimide by subjecting it to a cyclization treatment (for example, 200 ° C. or higher). The polyimide precursor is suitable for a negative photosensitive resin composition.

で表される構造が挙げられるが、これらに限定されるものではない。また、Ｘ１の構造は１種でも２種以上の組み合わせでも構わない。上記式（１４）で表される構造を有するＸ１基は、耐熱性と感光特性とを両立するという点で特に好ましい。 In the above general formula (1), the tetravalent organic group represented by X1 is preferably an organic group having 6 to 40 carbon atoms, and more preferably, in terms of achieving both heat resistance and photosensitive characteristics. An aromatic group or an alicyclic aliphatic group in which the -COOR1 group, the -COOR2 group and the -CONH- group are in ortho positions with each other. The tetravalent organic group represented by X1 is preferably an organic group having an aromatic ring and having 6 to 40 carbon atoms, and more preferably the following formula (14) :.

The structure represented by is mentioned, but is not limited to these. Further, the structure of X1 may be one kind or a combination of two or more kinds. The X1 group having the structure represented by the above formula (14) is particularly preferable in that it has both heat resistance and photosensitive characteristics.

で表される構造、及び下記式（１６）：

｛式中、Ｒ２３及びＲ２４は、それぞれ独立に、メチル基（－ＣＨ₃）、エチル基（－Ｃ₂Ｈ₅）、プロピル基（－Ｃ₃Ｈ₇）又はブチル基（－Ｃ₄Ｈ₉）を表す。｝
で表される構造が挙げられるが、これらに限定されるものではない。また、Ｙ１の構造は１種でも２種以上の組み合わせでも構わない。上記式（１５）及び（１６）で表される構造を有するＹ１基は、耐熱性及び感光特性を両立するという点で特に好ましい。 In the above general formula (1), the divalent organic group represented by Y1 is preferably an aromatic group having 6 to 40 carbon atoms in terms of achieving both heat resistance and photosensitive characteristics, and is, for example, the following. Equation (15):

The structure represented by the following formula (16):

{In the formula, R23 and R24 are independently methyl group (-CH ₃ ), ethyl group (-C ₂ H ₅ ), propyl group (-C ₃ H ₇ ) or butyl group (-C ₄ H ₉ ). Represents. }
The structure represented by is mentioned, but is not limited to these. Further, the structure of Y1 may be one kind or a combination of two or more kinds. The Y1 group having the structures represented by the above formulas (15) and (16) is particularly preferable in terms of achieving both heat resistance and photosensitive characteristics.

Regarding R1 and R2, R3 in the above general formula (2) is preferably a hydrogen atom or a methyl group, and R4 and R5 are preferably hydrogen atoms from the viewpoint of photosensitive characteristics. Further, m1 is an integer of 2 or more and 10 or less, preferably an integer of 2 or more and 4 or less from the viewpoint of photosensitive characteristics.

When a polyimide precursor is used as the resin (A), examples of the method for imparting photosensitivity to the photosensitive resin composition include an ester bond type and an ion bond type. The former is a method of introducing a photopolymerizable group, that is, a compound having an olefinic double bond into the side chain of the polyimide precursor by an ester bond, and the latter has a carboxyl group and an amino group of the polyimide precursor (). Meta) This is a method of imparting a photopolymerizable group by bonding an amino group of an acrylic compound via an ionic bond.

In the ester-bonded polyimide precursor, first, the tetracarboxylic acid dianhydride containing the above-mentioned tetravalent organic group X1, alcohols having a photopolymerizable unsaturated double bond, and optionally 1 to 1 to carbon atoms are used. After reacting with the saturated aliphatic alcohols of No. 4 to prepare a partially esterified tetracarboxylic acid (hereinafter, also referred to as an acid / ester compound), this and the above-mentioned divalent organic group Y1 are contained. It is obtained by amide polycondensation with diamines.

(Preparation of acid / ester)
In the present invention, tetracarboxylic acid dianhydride containing a tetravalent organic group X1 preferably used for preparing an ester-bonded polyimide precursor includes, for example, pyromellitic anhydride, diphenyl ether-3,3. ', 4,4'-Tetracarboxylic acid dianhydride, benzophenone-3,3', 4,4'-Tetracarboxylic acid dianhydride, Biphenyl-3,3', 4,4'-Tetracarboxylic acid dianhydride , Diphenylsulfone-3,3', 4,4'-tetracarboxylic acid dianhydride, diphenylmethane-3,3', 4,4'-tetracarboxylic acid dianhydride, 2,2-bis (3,4) -Anhydrous phthalic acid) propane, 2,2-bis (3,4-anhydride phthalic acid) -1,1,1,3,3,3-hexafluoropropane and the like can be mentioned, but are limited thereto. It's not a thing. In addition, these can be used alone or in combination of two or more.

Examples of alcohols having a photopolymerizable unsaturated double bond, which are suitably used for preparing an ester-bonded polyimide precursor in the present invention, include 2-acryloyloxyethyl alcohol and 1-acryloyloxy. -3-propyl alcohol, 2-acrylamide ethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxy Propyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-t-butoxypropyl acrylate, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3- Propyl alcohol, 2-methacrylamide ethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate , 2-Hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate and the like.

As saturated fatty alcohols having 1 to 4 carbon atoms, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol and the like can be partially mixed and used with the above alcohols.

The above-mentioned tetracarboxylic acid anhydride suitable for the present invention and the above-mentioned alcohols are dissolved by stirring in a suitable reaction solvent at a temperature of 20 to 50 ° C. for 4 to 10 hours in the presence of a basic catalyst such as pyridine. By mixing, the esterification reaction of the acid anhydride proceeds, and a desired acid / ester compound can be obtained.

The reaction solvent is preferably one in which the acid / ester form and the polyimide precursor which is an amide polycondensation product of the acid / ester component are completely dissolved, and for example, N-methyl-2-pyrrolidone, N, N. -Dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, gamma butyrolactone and the like can be mentioned.

Other reaction solvents include ketones, esters, lactones, ethers, halogenated hydrocarbons, and hydrocarbons include, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, etc. 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 And so on. These may be used alone or in combination of two or more, if necessary.

(Preparation of polyimide precursor)
A suitable dehydration condensing agent, for example, dicyclocarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, is added to the acid / ester compound (typically the solution in the reaction solvent) under ice-cooling. , 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N, N'-discusin imidazole carbonate, etc. are added and mixed to make an acid / ester compound into a polyacid anhydride. In addition, a diamine containing a divalent organic group Y1 preferably used in the present invention is separately dissolved or dispersed in a solvent, and the mixture is added dropwise and amide polycondensed to obtain the desired polyimide precursor. can.

Examples of diamines containing a divalent organic group Y1 preferably used in the present invention include p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3. '-Diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3 , 3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis ( 4-Aminophenoxy) Benzene,

1,3-bis (3-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 4,4-bis (4-amino) Phenoxy) biphenyl, 4,4-bis (3-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether, 1,4-bis (4-Aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 9,10-bis (4-aminophenyl) anthracene, 2,2-bis (4-aminophenyl) propane, 2,2 -Bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl) propane, 2,2-bis [4- (4-aminophenoxy) phenyl) hexafluoropropane, 1,4-Bis (3-aminopropyldimethylsilyl) benzene, ortho-trizine sulfone, 9,9-bis (4-aminophenyl) fluorene, and some of the hydrogen atoms on these benzene rings are methyl groups. Those substituted with ethyl group, hydroxymethyl group, hydroxyethyl group, halogen, etc., for example, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethitoxy-4,4'-diaminobiphenyl, 3,3'- Examples thereof include, but are not limited to, dichloro-4,4'-diaminobiphenyl and a mixture thereof.

Further, in the preparation of the polyimide precursor, 1,3-, for the purpose of improving the adhesion between the resin layer formed on the substrate and various substrates by applying the photosensitive resin composition of the present invention on the substrate. Diaminosiloxanes such as bis (3-aminopropyl) tetramethyldisiloxane and 1,3-bis (3-aminopropyl) tetraphenyldisiloxane can also be copolymerized.

After completion of the amide polycondensation reaction, the water-absorbing by-products of the dehydration condensate coexisting in the reaction solution are filtered out as necessary, and then a poor solvent such as water, an aliphatic lower alcohol, or a mixed solution thereof is added. The polymer is purified by pouring it into the obtained polymer component, precipitating the polymer component, and further repeating redissolution and reprecipitation precipitation operations to purify the polymer, vacuum dry it, and obtain the desired polyimide precursor. Release. In order to improve the degree of purification, a solution of this polymer may be passed through a column filled with anions and / or cation exchange resins swollen with a suitable organic solvent to remove ionic impurities.

On the other hand, the ion-bonded polyimide precursor is typically obtained by reacting a tetracarboxylic dianhydride with a diamine. In this case, at least one of R1 and R2 in the general formula (11) is a hydroxyl group.

The tetracarboxylic dianhydride is preferably an anhydride of a tetracarboxylic acid containing the structure of the above formula (14), and the diamine is preferably a diamine containing the structure of the above formula (15) or (16). By adding a (meth) acrylic compound having an amino group, which will be described later, to the obtained polyamide precursor, a photopolymerizable group is imparted by an ionic bond between the carboxyl group and the amino group.

The molecular weights of the ester-bonded and ionic-bonded polyimide precursors are preferably 8,000 to 150,000, preferably 9,000, as measured by the polystyrene-equivalent weight average molecular weight by gel permeation chromatography. More preferably, it is ~ 50,000. When the weight average molecular weight is 8,000 or more, the mechanical properties are good, and when it is 150,000 or less, the dispersibility in the developing solution is good and the resolution performance of the relief pattern is good. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. The weight average molecular weight is obtained from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from Showa Denko's organic solvent-based standard sample STANDARD SM-105.

（式中、Ｘ２は、炭素数６～１５の３価の有機基であり、Ｙ２は、炭素数６～３５の２価の有機基であり、かつ同一の構造であるか、又は複数の構造を有してもよく、Ｒ６は、炭素数３～２０のラジカル重合性の不飽和結合基を少なくとも一つ有する有機基であり、そしてｎ２は、１～１０００の整数である。）
で表される構造を有するポリアミドである。このポリアミドはネガ型感光性樹脂組成物用として好適である。 [polyamide]
A further example of the preferred resin (A) in the photosensitive resin composition of the present invention is the following general formula (3) :.

(In the formula, X2 is a trivalent organic group having 6 to 15 carbon atoms, and Y2 is a divalent organic group having 6 to 35 carbon atoms and has the same structure or a plurality of structures. R6 is an organic group having at least one radically polymerizable unsaturated bond group having 3 to 20 carbon atoms, and n2 is an integer of 1 to 1000.)
It is a polyamide having a structure represented by. This polyamide is suitable for negative photosensitive resin compositions.

（式中、Ｒ２５は、炭素数２～１９のラジカル重合性の不飽和結合基を少なくとも一つ有する有機基である。）
で表される基であることが好ましい。 In the above general formula (3), the group represented by R6 is the following general formula (17), in that both photosensitive characteristics and chemical resistance are compatible.

(In the formula, R25 is an organic group having at least one radically polymerizable unsaturated bond group having 2 to 19 carbon atoms.)
It is preferably a group represented by.

で表される基の中から選ばれる芳香族基であることが好ましく、そしてアミノ基置換イソフタル酸構造からカルボキシル基及びアミノ基を除いた芳香族基であることがより好ましい。 In the above general formula (3), the trivalent organic group represented by X2 is preferably a trivalent organic group having 6 to 15 carbon atoms, for example, the following formula (18) :.

It is preferably an aromatic group selected from the groups represented by, and more preferably an aromatic group obtained by removing the carboxyl group and the amino group from the amino group-substituted isophthalic acid structure.

（式中、Ｒ２６及びＲ２７は、それぞれ独立に、水酸基、メチル基（－ＣＨ₃）、エチル基（－Ｃ₂Ｈ₅）、プロピル基（－Ｃ₃Ｈ₇）又はブチル基（－Ｃ₄Ｈ₉）から成る群から選ばれる一つの基であり、そして該プロピル基及びブチル基は、各種異性体を含む。）

｛式中、ｍ４は、０～８の整数であり、ｍ５及びｍ６は、それぞれ独立に、０～３の整数であり、ｍ７及びｍ８は、それぞれ独立に、０～１０の整数であり、そしてＲ２８及びＲ２９は、メチル基（－ＣＨ₃）、エチル基（－Ｃ₂Ｈ₅）、プロピル基（－Ｃ₃Ｈ₇）、ブチル基（－Ｃ₄Ｈ₉）又はこれらの異性体である。｝が挙げられる。 In the above general formula (3), the divalent organic group represented by Y2 is preferably an organic group having 6 to 35 carbon atoms, and may be substituted with an aromatic ring or an aliphatic ring. It is more preferably a cyclic organic group having 1 to 4 or an aliphatic group or a siloxane group having no cyclic structure. Examples of the divalent organic group represented by Y2 include the following general formula (15) and the following general formulas (19) and (20):

(In the formula, R26 and R27 are independently hydroxyl groups, methyl groups (-CH ₃ ), ethyl groups (-C ₂ H ₅ ), propyl groups (-C ₃ H ₇ ) or butyl groups (-C ₄ H). It is one group selected from the group consisting of ₉ ), and the propyl group and butyl group include various isomers.)

{In the equation, m4 is an integer of 0-8, m5 and m6 are independently integers of 0-3, m7 and m8 are independently integers of 0-10, and R28 and R29 are a methyl group (-CH ₃ ), an ethyl group (-C ₂ H ₅ ), a propyl group (-C ₃ H ₇ ), a butyl group (-C ₄ H ₉ ) or isomers thereof. }.

｛式中、ｍ９は、２～１２の整数であり、ｍ１０は、１～３の整数であり、ｍ１１は、１～２０の整数であり、そしてＲ３０、Ｒ３１、Ｒ３２及びＲ３３は、それぞれ独立に、炭素数１～３のアルキル基又は置換されていてもよいフェニル基である。｝が好ましいものとして挙げられる。 Examples of the aliphatic group or siloxane group having no cyclic structure include the following general formula (21):

{In the formula, m9 is an integer of 2 to 12, m10 is an integer of 1 to 3, m11 is an integer of 1 to 20, and R30, R31, R32 and R33 are independent of each other. , An alkyl group having 1 to 3 carbon atoms or a optionally substituted phenyl group. } Is mentioned as preferable.

The polyamide resin of the present invention can be synthesized, for example, as follows.
(Synthesis of phthalic acid compound encapsulant)
First, it is selected from the group consisting of compounds having a trivalent aromatic group X2, such as amino group substituted phthalic acid, amino group substituted isophthalic acid, and amino group substituted terephthalic acid. In addition, 1 mol of at least one compound (hereinafter referred to as “phthalic acid compound”) is reacted with 1 mol of a compound that reacts with an amino group, and the amino group of the phthalic acid compound is not radically polymerizable, which will be described later. A compound modified and sealed with a group containing a saturated bond (hereinafter referred to as "phthalic acid compound encapsulant") is synthesized. These may be used alone or in combination.

When the phthalic acid compound is sealed with a group containing the radically polymerizable unsaturated bond, the polyamide resin can be imparted with negative-type photosensitive (photocurability).

The group containing a radically polymerizable unsaturated bond is preferably an organic group having a radically polymerizable unsaturated bond group having 3 to 20 carbon atoms, and a group containing a methacryloyl group or an acryloyl group is particularly preferable.

In the above-mentioned phthalic acid compound encapsulant, the amino group of the phthalic acid compound is reacted with an acid chloride, isocyanate, an epoxy compound or the like having at least one radically polymerizable unsaturated bond group having 3 to 20 carbon atoms. Can be obtained at.

Suitable acid chlorides include (meth) acryloyl chloride, 2-[(meth) acryloyloxy] acetyl chloride, 3-[(meth) acryloyloxy] propionyl chloride, 2-[(meth) acryloyloxy] ethylchloroformate. , 3-[(Meta) acryloyloxypropyl] chloroformate and the like. Suitable isocyanates include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxymethyl] ethyl isocyanate, 2- [2- (meth) acryloyloxyethoxy] ethyl isocyanate and the like. .. Suitable epoxy compounds include glycidyl (meth) acrylate and the like. These may be used alone or in admixture, but it is particularly preferable to use methacryloyl chloride and / or 2- (methacryloyloxy) ethyl isocyanate.

Further, as these phthalic acid compound encapsulants, those in which the phthalic acid compound is 5-aminoisophthalic acid are excellent in photosensitive characteristics and at the same time, a polyamide having excellent film characteristics after heat curing can be obtained. Is preferable.

The sealing reaction is carried out by stirring, dissolving and mixing the phthalic acid compound and the sealing agent in a solvent in the presence of a basic catalyst such as pyridine or a tin catalyst such as di-n-butyltin dilaurate. Can be done.

The reaction solvent is preferably one that completely dissolves the product phthalic acid compound encapsulant, for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide. , Tetramethylurea, gamma butyrolactone and the like.

Other reaction solvents include ketones, esters, lactones, ethers, halogenated hydrocarbons, and hydrocarbons include, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, etc. 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, and Examples include xylene. If necessary, these solvents can be used alone or in combination.

Depending on the type of encapsulant, such as acid chloride, hydrogen chloride may be produced as a by-product in the process of encapsulation reaction. In this case, from the viewpoint of preventing contamination in the subsequent steps, it is preferable to perform appropriate purification such as once re-settling with water and washing and drying, or removing and reducing the ionic components through a column filled with an ion exchange resin. ..

(Synthesis of polyamide)
The above-mentioned phthalic acid compound encapsulant and a diamine compound having a divalent organic group Y2 are mixed in a suitable solvent in the presence of a basic catalyst such as pyridine or triethylamine and amide polycondensed to obtain the present invention. Polyamide can be obtained.

As the amide polycondensation method, a phthalic acid compound encapsulant is made into a symmetric polyacid anhydride using a dehydration condensing agent and then mixed with a diamine compound, or the phthalic acid compound encapsulant is acid chloride by a known method. Examples thereof include a method of mixing with a diamine compound after conversion, a method of reacting a dicarboxylic acid component with an active esterifying agent in the presence of a dehydration condensing agent to form an active ester, and then mixing with the diamine compound.

Examples of the dehydration condensing agent include dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1′-carbonyldioxy-di-1,2,3-benzotriazole, N, N. '-Discusin imidyl carbonate and the like are preferred.

Examples of the chlorolytic agent include thionyl chloride and the like.

Examples of the active esterifying agent include N-hydroxysuccinimide or 1-hydroxybenzotriazole, N-hydroxy-5-norbornen-2,3-dicarboxylic acidimide, 2-hydroxyimino-2-cyanoacetate ethyl, and 2-hydroxyimino-. Examples include 2-cyanoacetic acid amide.

The diamine compound having an organic group Y2 is at least one diamine compound selected from the group consisting of an aromatic diamine compound, an aromatic bisaminophenol compound, an alicyclic diamine compound, a linear aliphatic diamine compound, and a siloxane diamine compound. It is preferable that a plurality of compounds are used in combination, if desired.

Examples of the aromatic diamine compound include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, and the like. 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'- Diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane , 3,4'-diaminodiphenylmethane,

3,3'-Diaminodiphenylmethane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, bis [4 -(4-Aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) ) Biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether, 1,4-bis (4-aminophenyl) benzene, 1,3-bis ( 4-Aminophenyl) benzene, 9,10-bis (4-aminophenyl) anthracene, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2, 2-Bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 1,4-bis (3-aminopropyldimethylsilyl) benzene , Ortho-trizine sulfone, 9,9-bis (4-aminophenyl) fluorene, and some of the hydrogen atoms on these benzene rings are methyl, ethyl, hydroxymethyl, hydroxyethyl, and halogen atoms. Included are diamine compounds substituted with one or more groups selected from the group consisting of.

Examples of the diamine compound in which the hydrogen atom on the benzene ring is substituted are 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3, 3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethitoxy-4,4'-diaminobiphenyl, 3,3'-dichloro- Examples include 4,4'-diaminobiphenyl.

Examples of the aromatic bisaminophenol compound include 3,3'-dihydroxybenzidine, 3,3'-diamino-4,4'-dihydroxybiphenyl, 3,3'-dihydroxy-4,4'-diaminodiphenylsulfone, and bis-. (3-Amino-4-hydroxyphenyl) methane, 2,2-bis- (3-amino-4-hydroxyphenyl) propane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis- (3-hydroxy-4-aminophenyl) hexafluoropropane, bis- (3-hydroxy-4-aminophenyl) methane, 2,2-bis- (3-hydroxy-4-aminophenyl) Propane, 3,3'-dihydroxy-4,4'-diaminobenzophenone, 3,3'-dihydroxy-4,4'-diaminodiphenyl ether, 4,4'-dihydroxy-3,3'-diaminodiphenyl ether, 2,5 -Dihydroxy-1,4-diaminobenzene, 4,6-diaminoresorcinol, 1,1-bis (3-amino-4-hydroxyphenyl) cyclohexane, 4,4- (α-methylbenzylidene) -bis (2-amino Penyl) and the like.

Examples of the alicyclic diamine compound include 1,3-diaminocyclopentane, 1,3-diaminocyclohexane, 1,3-diamino-1-methylcyclohexane, 3,5-diamino-1,1-dimethylcyclohexane, and 1,5. -Diamino-1,3-dimethylcyclohexane, 1,3-diamino-1-methyl-4-isopropylcyclohexane, 1,2-diamino-4-methylcyclohexane, 1,4-diaminocyclohexane, 1,4-diamino-2 , 5-diethylcyclohexane, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 2- (3-aminocyclopentyl) -2-propylamine, mensendiamine, isophoronediamine, norbornan Diamine, 1-Cycloheptene-3,7-diamine, 4,4'-methylenebis (cyclohexylamine), 4,4'-methylenebis (2-methylcyclohexylamine), 1,4-bis (3-aminopropyl) piperazine, Examples thereof include 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro- [5,5] -undecane.

Examples of the linear aliphatic diamine compound include 1,2-diaminoethane, 1,4-diaminobutane, 1,6-diaminohexane, 1,8-diaminooctane, 1,10-diaminodecane, and 1,12-diaminododecane. Hydrocarbon-type diamines such as 2- (2-aminoethoxy) ethylamine, 2,2'-(ethylenedioxy) diethylamine, alkylene oxide-type diamines such as bis [2- (2-aminoethoxy) ethyl] ether, etc. Can be mentioned.

Examples of the siloxane diamine compound include dimethyl (poly) siloxane diamine, for example, manufactured by Shin-Etsu Chemical Co., Ltd., trade names PAM-E, KF-8010, X-22-161A and the like.

The reaction solvent is preferably a solvent that completely dissolves the produced polymer, for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, gamma-butyrolactone. And so on.

In addition, in some cases, ketones, esters, lactones, ethers, hydrocarbons, and halogenated hydrocarbons may be used as the reaction solvent. Specifically, 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-dichloro. Examples thereof include butane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene, xylene and the like.

After the completion of the amide polycondensation reaction, the precipitate derived from the dehydration condensate agent and the like precipitated in the reaction solution are filtered out as necessary. Next, a poor solvent for the polyamide such as water or an aliphatic lower alcohol or a mixture thereof is added to the reaction solution to precipitate the polyamide. Further, the precipitated polyamide is redissolved in a solvent, purified by repeating the reprecipitation and precipitation operation, and vacuum dried to isolate the desired polyamide. In addition, in order to further improve the degree of purification, the solution of this polyamide may be passed through a column filled with an ion exchange resin to remove ionic impurities.

The polystyrene-equivalent weight average molecular weight of the polyamide by gel permeation chromatography (hereinafter referred to as “GPC”) is preferably 7,000 to 70,000, and more preferably 10,000 to 50,000. When the polystyrene-equivalent weight average molecular weight is 7,000 or more, the basic physical properties of the cured relief pattern are ensured. Further, when the polystyrene-equivalent weight average molecular weight is 70,000 or less, the develop solubility at the time of forming the relief pattern is ensured.

Tetrahydrofuran or N-methyl-2-pyrrolidone is recommended as the eluent for GPC. The weight average molecular weight value is obtained from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from Showa Denko's organic solvent-based standard sample STANDARD SM-105.

（式中のＲ１は、水素原子、炭素数１～１２のアルキル基の１価の有機基を表し、ｎ＝１～１０の整数である。）で示される化合物を含み、ｎ＝１～１０から選ばれる少なくとも一つの化合物。 (B) The compound represented by the chemical formula (b1)

(R1 in the formula represents a hydrogen atom, a monovalent organic group of an alkyl group having 1 to 12 carbon atoms, and is an integer of n = 1 to 10), and contains a compound represented by n = 1 to 10. At least one compound selected from.

The compound represented by (B) chemical formula (b1) used in the present invention will be described. (B) By using the compound represented by the chemical formula (b1), the coating film formed by the negative photosensitive resin composition can be rapidly dissolved in the developing solution of the organic solvent, and an excellent relief pattern can be obtained. Can be formed. Although the mechanism is not clear, the compound represented by (B) chemical formula (b1) is the general formula (2) or 1,3-bis (3-aminopropyl) tetramethyl used in the resin of the negative photosensitive resin composition. Since it has a structure similar to that of disiloxane and 1,3-bis (3-aminopropyl) tetraphenyldisiloxane, it is considered to be highly compatible with the resin, and the chemical formula (b) (b1) between the resins is considered to be high. ) Is presumed to be dispersed. Therefore, it is considered that the developer of the organic solvent easily permeates the coating film formed of the negative photosensitive resin composition, so that the developer quickly dissolves and an excellent relief pattern is formed. Further, when (B) the compound represented by the chemical formula (b1) is n ≧ 2, or when a mixture of a plurality of n numbers is used, the bulkier compound represented by the chemical formula (b1) is placed between the resins. It is presumed that the organic solvent will enter and the solubility of the organic solvent in the developer will be further enhanced.
(B) The compound represented by the chemical formula (b1) preferably has n = 2 to 5. Further, the negative photosensitive resin composition may contain any of the compounds having n = 2 to 5 in the chemical formula (b1), or the compound having n = 2 to 5 in the chemical formula (b1). May include all of.

Further, the compound represented by (B) the chemical formula (b1) has an effect of accelerating photocuring, and (B) the compound represented by the chemical formula (b1) has an effect of easily entering between the resins, and the light between the resins is combined. It is presumed that it promotes curing and improves adhesion and resolution during development in the lithography process.

(B) Specific examples of the compound represented by the chemical formula (b1) include 4-hydroxybutyric acid, methyl 4-hydroxybutyric acid, ethyl 4-hydroxybutyric acid, propyl 4-hydroxybutyric acid, isopropyl 4-hydroxybutyric acid and 4-hydroxybutyric acid. Examples thereof include butyl, pentyl 4-hydroxybutyrate, hexyl 4-hydroxybutyrate, heptyl 4-hydroxybutyrate, octyl 4-hydroxybutyrate, nonyl 4-hydroxybutyrate, decyl 4-hydroxybutyrate and derivatives thereof.

Further, when water or an alkyl alcohol and γ-butyrolactone are subjected to a ring-opening reaction under an acid catalyst, a compound represented by the chemical formula (b1) of (B) of n ≧ 2 can be obtained.
As alkyl alcohols, methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, neopentyl alcohol, 1-heptanol, 2-heptanol, 3 -Heptanol, 1-octanol, 2-octanol, 3-octanol, 1-nonanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, benzyl alcohol, etc. However, from the viewpoint of compatibility with the resin, tanol, ethanol, n-propanol, isopropanol, n-butanol, and tert-butanol are desirable.
Examples of the acid catalyst include hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid, ethanesulfonic acid, n-propanesulfonic acid, benzenesulfonic acid, para-toluenesulfonic acid, oxalic acid, malonic acid and the like, and the acidity of the acid catalyst is high. Higher is desirable from the viewpoint of reaction rate.

(B) The compounding amount of the compound represented by the chemical formula (b1) is 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the resin (A). When the blending amount is 0.01 parts by mass or more, the development time is shortened, while when it is 10 parts by mass or less, the resolution is excellent.

(C) Photosensitizer The (C) photosensitive agent used in the present invention will be described.
Examples of the photosensitizer include benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenylketone, dibenzylketone, and fluorenone, 2,2'-diethoxyacetophenone, and 2-hydroxy-. Acetphenone derivatives such as 2-methylpropiophenone and 1-hydroxycyclohexylphenyl ketone, thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone and diethylthioxanthone, benzyl, benzyldimethylketal, benzyl-β-methoxyethylacetal Benzyl derivatives such as, benzoin, benzoin derivatives such as benzoin methyl ether, 1-phenyl-1,2-butandion-2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o). -Methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-benzoyl) oxime, 1,3 -Oximes such as diphenylpropantrion-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrion-2- (o-benzoyl) oxime, N-arylglycines such as N-phenylglycine, Peroxides such as benzoyl parkollides, aromatic biimidazoles and the like are preferable, but the present invention is not limited thereto. In addition, these may be used alone or as a mixture of two or more kinds.

｛式（２９）中、Ｚはイオウ又は酸素原子であり、そしてＲ１２ａはメチル基、フェニル基または２価の有機基を表し、Ｒ１３ａ～Ｒ１５ａは、それぞれ独立に、水素原子または１価の有機基を表す。｝
で表されるオキシム系化合物がより好ましく用いられる。中でも特に好ましくは、下記式（６３）：

、式（６４）：

、式（６５）：

、または式（６６）：

で表される化合物、もしくはこれらの混合物である。式（６３）は、常州強力新電子材料有限公司製ＴＲ－ＰＢＧ－３０５、式（６４）は常州強力新電子材料有限公司製ＴＲ－ＰＢＧ－３０５７、式（６５）はＢＡＳＦ社製Ｉｒｇａｃｕｒｅ ＯＸＥ－０１として商用的に入手可能である。 Among the above photosensitive agents, the following general formula (29):

{In formula (29), Z is a sulfur or oxygen atom, R12a represents a methyl group, a phenyl group or a divalent organic group, and R13a to R15a are independently hydrogen atoms or monovalent organic groups, respectively. Represents. }
The oxime-based compound represented by is more preferably used. Particularly preferably, the following formula (63):

, Equation (64):

, Equation (65):

, Or formula (66):

It is a compound represented by, or a mixture thereof. Formula (63) is TR-PBG-305 manufactured by Changzhou Powerful New Electronic Materials Co., Ltd., formula (64) is TR-PBG-3057 manufactured by Changzhou Powerful New Electronic Materials Co., Ltd., and formula (65) is Irgacure OXE-manufactured by BASF. It is commercially available as 01.

The blending amount of the (C) photosensitive agent in the resin composition is 0.5 to 30 parts by mass with respect to 100 parts by mass of the (A) resin. It is preferably 1 part by mass to 20 parts by mass, more preferably 2 to 10 parts by mass, and when the blending amount is 0.5 parts by mass or more, the resolution of the relief pattern is excellent, and 30 parts by mass or less. If there is, there is little residue in the pattern opening.

(D) Solvent The photosensitive resin composition of the present invention is used as a resin composition in which any component used is dissolved in a solvent to form a varnish. As the solvent, it is preferable to use a polar organic solvent from the viewpoint of solubility in the resin (A). Specifically, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, 3-methoxy-N, N-dimethylpropionamide, 3-butoxy. -N, N-dimethylpropionamide dimethyl sulfoxide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, γ-valerolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, Examples thereof include N-cyclohexyl-2-pyrrolidone, which can be used alone or in combination of two or more.
In particular, γ-butyrolactone, γ-valerolactone, 3-methoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide are represented by (A) resin and B) chemical formula (b1). It is presumed that it has moderate solubility in both compounds, and it is excellent in improving the solubility of the coating film in a developing solution.

The solvent is, for example, in the range of 30 to 1500 parts by mass, preferably 100 to 1000 parts by mass with respect to 100 parts by mass of the resin (A), depending on the desired coating film thickness and viscosity of the photosensitive resin composition. Can be used.

Further, from the viewpoint of improving the storage stability of the photosensitive resin composition, a solvent containing alcohols is preferable, and an alcohol having 1 to 12 carbon atoms is more preferable. Alcohols that can be suitably used are typically alcohols that have an alcoholic hydroxyl group in the molecule and do not have an olefin-based double bond, and specific examples thereof include methyl alcohol, ethyl alcohol, and n-. Alcohol alcohols such as propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, lactic acid esters such as ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-2-methyl ether, propylene glycol Propropylene glycol monoalkyl ethers such as -1-ethyl ether, propylene glycol-2-ethyl ether, propylene glycol-1- (n-propyl) ether, propylene glycol-2- (n-propyl) ether, ethylene glycol methyl ether , Monoalcohols such as ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, 2-hydroxyisobutyric acid esters, ethylene glycol, and dialcohols such as propylene glycol. Among these, lactic acid esters, propylene glycol monoalkyl ethers, 2-hydroxyisobutyric acid esters, and ethyl alcohol are preferable, and in particular, ethyl lactate, propylene glycol-1-methyl ether, and propylene glycol-1-ethyl ether, And propylene glycol-1- (n-propyl) ether are more preferred.

When the solvent contains an alcohol having no olefin-based double bond, the content of the alcohol having no olefin-based double bond in the total solvent is preferably 5 to 50% by mass, more preferably. It is preferably 10 to 30% by mass. When the content of the alcohol having no olefin double bond is 5% by mass or more, the storage stability of the resin composition is good, and when it is 50% by mass or less, the solubility of the resin (A) is good. Become.

(E) Photopolymerizable Compound The (E) photopolymerizable compound used in the present invention will be described. The photopolymerizable compound is a monomer having a photopolymerizable unsaturated bond, and as such a monomer, a (meth) acrylic compound that undergoes a radical polymerization reaction with a photopolymerization initiator is preferable, and is particularly limited to the following. Diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, etc., ethylene glycol or polyethylene glycol mono or diacrylate and methacrylate, propylene glycol or polypropylene glycol mono or diacrylate and methacrylate, glycerol mono, di or Triacrylates and methacrylates, cyclohexanediacrylates and dimethacrylates, 1,4-butanediol diacrylates and dimethacrylates, 1,6-hexanediol diacrylates and dimethacrylates, neopentyl glycol diacrylates and dimethacrylates, bisphenol A Mono or diacrylates and methacrylates, benzenetrimethacrylates, isobornyl acrylates and methacrylates, acrylamides and derivatives thereof, methacrylicamides and derivatives thereof, trimethylolpropane triacrylates and methacrylates, di or triacrylates and methacrylates of glycerol, pentaerythritol. Examples thereof include di, tri, or tetraacrylates and methacrylates, and compounds such as ethylene oxide or propylene oxide adducts of these compounds.

When the photosensitive resin composition contains the above-mentioned monomer having a photopolymerizable unsaturated bond, the blending amount of the monomer having a photopolymerizable unsaturated bond is 1 to 1 to 100 parts by mass of (A) resin. It is preferably 50 parts by mass. When the blending amount is 1 part by mass or more, the curability of the film in the exposed part is improved and the resolution is excellent, and when it is 50 parts by mass or less, the in-plane uniformity of the coating film is excellent.

(F) Organic Titanium Compound The resin composition of the present invention may contain (F) an organic titanium compound. (F) By containing the organic titanium compound, a photosensitive resin layer having excellent chemical resistance can be formed even when cured at a low temperature of about 250 ° C. or lower.

(F) Examples of the organic titanium compound that can be used as the organic titanium compound include those in which an organic chemical substance is bonded to a titanium atom via a covalent bond or an ionic bond.

(F) Specific examples of the organic titanium compound are shown in I) to VII) below:
I) Titanium chelate compound: Among them, a titanium chelate having two or more alkoxy groups is more preferable because the storage stability of the resin composition and a good pattern can be obtained, and a specific example is titanium bis (triethanolamine). ) Diisopropoxiside, Titanium di (n-butoxiside) bis (2,4-pentangionate, Titanium diisopropoxiside bis (2,4-pentangionate), Titanium diisopropoxiside bis (tetramethylheptangio) Nate), titanium diisopropoxyside bis (ethylacetacetate) and the like.

II) Titanium Alkoxy Titanium Compounds: For example, Titanium Tetra (n-Butoxide), Titanium Tetraethoxide, Titanium Tetra (2-ethylhexoxyside), Titanium Tetraisobutoxide, Titanium Tetraisopropoxyside, Titanium Tetramethoxide , Titanium Tetramethoxypropoxyside, Titanium Tetramethylphenoxide, Titanium Tetra (n-Noniloxide), Titanium Tetra (n-Propoxide), Titanium Tetrasteeryloxyside, Titanium Tetrakiss [Bis {2,2- (Aryloxymethyl) Butokiside}] etc.

III) Titanocene compounds: for example, pentamethylcyclopentadienyl titanium trimethoxide, bis (η5-2,4-cyclopentadiene-1-yl) bis (2,6-difluorophenyl) titanium, bis (η5-2, 2). 4-Cyclopentadiene-1-yl) bis (2,6-difluoro-3- (1H-pyrrole-1-yl) phenyl) titanium and the like.

IV) Monoalkoxytitanium compound: For example, titaniumtris (dioctylphosphate) isopropoxyside, titaniumtris (dodecylbenzenesulfonate) isopropoxyside and the like.

V) Titanium oxide compound: For example, titanium oxide bis (pentangionate), titanium oxide bis (tetramethylheptandionate), phthalocyanine titanium oxide and the like.

VI) Titanium tetraacetylacetonate compound: For example, titanium tetraacetylacetonate and the like.

VII) Titanate Coupling Agent: For example, isopropyltridodecylbenzenesulfonyl titanate and the like.

Among them, it is better that the (F) organic titanium compound is at least one compound selected from the group consisting of the above-mentioned I) titanium chelate compound, II) tetraalkoxytitanium compound, and III) titanocene compound. It is preferable from the viewpoint of playing sex. In particular, titanium diisopropoxyside bis (ethylacetacetate), titanium tetra (n-butoxide), and bis (η5-2,4-cyclopentadiene-1-yl) bis (2,6-difluoro-3- (1H)). -Pyrrole-1-yl) phenyl) titanium is preferred.

When the (F) organic titanium compound is blended, the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the resin (A). .. When the blending amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are exhibited, while when it is 10 parts by mass or less, storage stability is excellent.

(G) Other Components The resin composition of the present invention may further contain components other than the above components (A) to (F).

The resin composition of the present invention may contain a cross-linking agent. The cross-linking agent can be a cross-linking agent capable of cross-linking the resin (A) when the resin composition of the present invention is heat-cured, or the cross-linking agent itself can form a cross-linking network. The cross-linking agent can further enhance the heat resistance and chemical resistance of the cured film formed from the resin composition.

Examples of the cross-linking agent include ML-26X, ML-24X, ML-236TMP, 4-methylol 3M6C, ML-MC, and ML-TBC (hereinafter, trade name, Honshu Chemical Industry Co., Ltd.) as having one heat-crosslinkable group. DM-BI25X-F, 46DMOC, 46DMOIPP, 46DMOEP (above, trade name, Asahi Yu), etc. Equipment Industry Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PC, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP, DML-OC, Dimethyrol- Bis-C, Dimethylol-BisOC-P, DML-BisOC-Z, DML-BisOCHP-Z, DML-PFP, DML-PSBP, DML-MB25, DML-MTrisPC, DML-Bis25X-34XL, DML-Bis25X-PCHP ( Above, product name, manufactured by Honshu Chemical Industry Co., Ltd., Nikalac MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.),

B-a type benzoxazine, Bm type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p- Cresol, 2,6-diacetoxymethyl-p-cresol, etc., TriML-P, TriML-35XL, TriML-TrisCR-HAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), etc., 4 TM-BIP-A (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.), TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP (above, product name, etc.) HML-TPPHBA, HML-TPHAP (above, product) as having six such as Honshu Chemical Industry Co., Ltd.), Nicarac MX-280, Nicarac MX-270 (above, trade name, manufactured by Sanwa Chemical Co., Ltd.), etc. Names include Honshu Chemical Industry Co., Ltd., Nicarac MW-390, and Nicarac MW-100LM (above, trade name, manufactured by Sanwa Chemical Co., Ltd.).

Of these, those containing at least two thermally crosslinkable groups are preferable in the present invention, and 46DMOC, 46DMEEP (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.), DML-MBPC, DML- are particularly preferable. MBOC, DML-OCHP, DML-PC, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (above, Product name, Honshu Chemical Industry Co., Ltd., Nicarac MX-290 (Product name, Sanwa Chemical Co., Ltd.), BA type benzoxazine, Bm type benzoxazine (above, product name, Shikoku Kasei) (Manufactured by Kogyo Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, etc., TriML-P, TriML- 35XL (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.), TML-BP, TML-HQ, TML-pp-BPF, HML-TPPHBA such as TML-BPA, TMOM-BP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), Nicarac MX-280, Nicarac MX-270 (trade name, manufactured by Sanwa Chemical Co., Ltd.), etc. , HML-TPHAP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and the like. Further, more preferably, Nikalac MX-290, Nikalac MX-280, Nikalac MX-270 (above, trade name, manufactured by Sanwa Chemical Co., Ltd.), BA type benzoxazine, Bm type benzoxazine (above). , Product name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), Nicarac MW-390, Nicarac MW-100LM (above, product name, manufactured by Sanwa Chemical Co., Ltd.) and the like.

In consideration of various performances other than heat resistance and chemical resistance, the blending amount when the resin composition contains a cross-linking agent shall be 0.5 to 20 parts by mass with respect to 100 parts by mass of (A) resin. Is preferable, and more preferably 2 to 10 parts by mass. When the blending amount is 0.5 parts by mass or more, good heat resistance and chemical resistance are exhibited, while when it is 20 parts by mass or less, the storage stability is excellent.

The resin composition of the present invention may optionally contain a nitrogen-containing heterocyclic compound such as an azole compound purine derivative in order to suppress discoloration on copper. Examples of the azole compound include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-butyl-. 5-Phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1- (2-dimethylaminoethyl) triazole, 5-benzyl-1H-triazole, hydroxy Phenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5 -Bis (α, α-dimethylbenzyl) phenyl] -benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-t-butyl-5-methyl- 2-Hydroxyphenyl) -benzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, hydroxy Phenylbenzotriazole, triltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl Examples thereof include -1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole and the like. Particularly preferred is one or more selected from triltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. These azole compounds may be used alone or in a mixture of two or more.

Specific examples of the purine derivative include purine, adenine, guanine, hypoxanthin, xanthin, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, and the like. 1-Methyladenine, N-methyladenine, N, N-dimethyladenine, 2-fluoroadenine, 9- (2-hydroxyethyl) adenine, guanine oxime, N- (2-hydroxyethyl) adenine, 8-aminoadenine, 6-Amino-8-Phenyl-9H-Purine, 1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine, N-methylguanine, 7- (2-hydroxyethyl) guanine, N- (3-chlorophenyl) Examples thereof include guanine, N- (3-ethylphenyl) guanine, 2-azaadenine, 5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine, 8-azaxanthin, 8-azahipoxanthin and derivatives thereof.

When the resin composition contains the azole compound or the purine derivative, the blending amount is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the (A) resin, and the storage stability of the resin composition is improved. From the viewpoint, 0.5 to 5 parts by mass is more preferable. When the blending amount of the azole compound (A) with respect to 100 parts by mass of the resin is 0.1 part by mass or more, the surface of the copper or the copper alloy is discolored when the resin composition of the present invention is formed on the copper or the copper alloy. On the other hand, when it is 20 parts by mass or less, the storage stability of the resin composition is excellent.

Particularly preferred are tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. Further, these azole compounds may be used alone or in a mixture of two or more kinds.

Further, a hindered phenol compound can be optionally blended in order to suppress discoloration on the copper surface. Examples of the hindered phenol compound include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, and octadecyl-3- (3,5-di-t-butyl-4). -Hydroxyphenyl) propionate, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 4,4'-methylenebis (2,6-di-t-butylphenol), 4, 4'-thio-bis (3-methyl-6-t-butylphenol), 4,4'-butylidene-bis (3-methyl-6-t-butylphenol), triethylene glycol-bis [3- (3-t) -Butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio -Diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocin) Namamide), 2,2'-methylene-bis (4-methyl-6-t-butylphenol), 2,2'-methylene-bis (4-ethyl-6-t-butylphenol),

Pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], Tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3-hydroxy-2,6-dimethyl) -4-Isopropylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl-3-hydroxy-2) , 6-Dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-s-butyl-3-hydroxy-2) , 6-Dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris [4- (1-ethylpropyl) -3- Hydroxy-2,6-dimethylbenzyl] -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trion,

1,3,5-Tris [4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl] -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trion, 1 , 3,5-Tris (3-hydroxy-2,6-dimethyl-4-phenylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3 , 5-Tris (4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trion, 1 , 3,5-Tris (4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -Trione, 1,3,5-tris (4-t-butyl-6-ethyl-3-hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -Trione, 1,3,5-Tris (4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl) -1,3,5-triazine-2,4,6-( 1H, 3H, 5H) -trion, 1,3,5-tris (4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4 , 6- (1H, 3H, 5H) -trion,

1,3,5-Tris (4-t-butyl-3-hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1, 3,5-Tris (4-t-butyl-3-hydroxy-2,5-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1, 3,5-Tris (4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, etc. However, it is not limited to this. Among these, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) ) -Trione or the like is particularly preferable.

The blending amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the (A) resin, and 0.5 to 10 parts by mass from the viewpoint of the degree of polymerization of the compound having an unsaturated bond. It is more preferable that it is a part. When the blending amount of the hindered phenol compound (A) with respect to 100 parts by mass of the resin is 0.1 parts by mass or more, for example, when the resin composition of the present invention is formed on copper or a copper alloy, the copper or copper alloy is formed. On the other hand, when it is 20 parts by mass or less, the degree of polymerization of the compound having an unsaturated bond is excellent.

A sensitizer can be arbitrarily added to the resin composition of the present invention. Examples of the sensitizer include Michler's ketone, 4,4'-bis (diethylamino) benzophenone, 2,5-bis (4'-diethylaminobenzal) cyclopentane, and 2,6-bis (4'-diethylaminobenzal). ) Cyclohexanone, 2,6-bis (4'-diethylaminobenzal) -4-methylcyclohexanone, 4,4'-bis (dimethylamino) chalcone, 4,4'-bis (diethylamino) chalcone, p-dimethylaminocinna Millidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylbiphenylene) -benzothiazole, 2- (p-dimethylaminophenylbinylene) benzothiazole, 2- (p-dimethylaminophenylbinylene) Isonaphthiazole, 1,3-bis (4'-dimethylaminobenzal) acetone, 1,3-bis (4'-diethylaminobenzal) acetone, 3,3'-carbonyl-bis (7-diethylaminocoumarin), 3-Acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7- Diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2- Mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2- (p-dimethylamino) Examples thereof include styryl) naphtho (1,2-d) thiazole, 2- (p-dimethylaminobenzoyl) styrene and the like. These can be used alone or, for example, in a combination of 2 to 5 types.

When the resin composition contains the sensitizer, the blending amount is preferably 0.1 to 25 parts by mass with respect to 100 parts by mass of the resin (A).

In addition, an adhesive aid can be optionally blended in order to improve the adhesiveness between the film formed by using the resin composition of the present invention and the substrate. Adhesive aids include γ-aminopropyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3- Methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N- (3-diethoxymethylsilylpropyl) succinimide , N- [3- (triethoxysilyl) propyl] phthalamic acid, benzophenone-3,3'-bis (N- [3-triethoxysilyl] propylamide) -4,4'-dicarboxylic acid, benzene-1, 4-Bis (N- [3-triethoxysilyl] propylamide) -2,5-dicarboxylic acid, 3- (triethoxysilyl) propylsuccinic hydride, N-phenyl-3-aminopropyltrimethoxysilane, 3 -Silane coupling agents such as ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3- (trialkoxysilyl) propylsuccinic acid anhydride, and aluminum tris (ethylacetacetate), aluminum tris (acetylacetonate). ), Aluminum-based adhesive aids such as ethylacetacetate aluminum diisopropylate and the like.

Among these adhesive aids, it is more preferable to use a silane coupling agent from the viewpoint of adhesive strength. When the resin composition contains an adhesive aid, the blending amount of the adhesive auxiliary is preferably in the range of 0.5 to 25 parts by mass with respect to 100 parts by mass of the resin (A).

In addition, a thermal polymerization inhibitor can be optionally added in order to improve the viscosity stability of the resin composition when stored in a solution containing a solvent. Examples of the thermal polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol etherdiamine tetraacetic 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-phenylhydroxylamine ammonium salt, N-nitroso-N (1-naphthyl) hydroxylamine ammonium salt and the like are used.

The amount of the thermal polymerization inhibitor to be blended in the resin composition is preferably in the range of 0.005 to 12 parts by mass with respect to 100 parts by mass of the resin (A).

<Manufacturing method of cured relief pattern and semiconductor device>
Further, the present invention comprises (1) a step of forming a resin layer on the substrate by applying the above-mentioned photosensitive resin composition of the present invention onto the substrate, and (2) a step of exposing the resin layer. , (3) A step of developing the resin layer after the exposure to form a relief pattern, and (4) a step of forming a cured relief pattern by heat-treating the relief pattern. Provide a method. Hereinafter, typical embodiments of each step will be described.

(1) Step of forming a resin layer on the substrate by applying the photosensitive resin composition on the substrate In this step, the photosensitive resin composition of the present invention is applied on the substrate, and if necessary. Then, it is dried to form a resin layer. As a coating method, a method conventionally used for coating a photosensitive resin composition, for example, a method of coating with a spin coater, a bar coater, a blade coater, a curtain coater, a screen printing machine, or a spray coater is used for spray coating. A method or the like can be used.

If necessary, the coating film made of the photosensitive resin composition can be dried. As a drying method, a method such as air drying, heat drying using an oven or a hot plate, and vacuum drying is used. Specifically, when air-drying or heat-drying, the drying can be performed at 20 ° C. to 140 ° C. for 1 minute to 1 hour. As described above, the resin layer can be formed on the substrate.

(2) Step of exposing the resin layer In this step, the resin layer formed above is exposed to a photomask or reticle having a pattern using an exposure device such as a contact aligner, a mirror projection, or a stepper, or directly. Expose with an ultraviolet light source or the like.

After that, post-exposure bake (PEB) and / or pre-development bake may be applied at any combination of temperature and time, if necessary, for the purpose of improving light sensitivity and the like. The range of baking conditions is preferably a temperature of 40 to 120 ° C. and a time of 10 to 240 seconds, but this range as long as it does not interfere with the properties of the photosensitive resin composition of the present invention. Not limited to.

(3) Step of developing the exposed resin layer to form a relief pattern In this step, the exposed portion or the unexposed portion of the photosensitive resin layer after exposure is developed and removed. In the negative type photosensitive resin composition, the unexposed portion is developed and removed, and the exposed portion remains on the substrate as a relief pattern. As the developing method, any method can be selected and used from conventionally known photoresist developing methods such as a rotary spray method, a paddle method, and a dipping method accompanied by ultrasonic treatment. Further, after development, post-development baking may be performed at an arbitrary combination of temperature and time, if necessary, for the purpose of adjusting the shape of the relief pattern. The range of post-development baking conditions is preferably a temperature of 40 to 180 ° C. and a time of 10 to 600 seconds, as long as it does not interfere with the properties of the photosensitive resin composition of the present invention. Not limited to this range.

As the developing solution used for development, a good solvent for the photosensitive resin composition or a combination of the good solvent and a poor solvent is preferable. For example, in the case of a photosensitive resin composition that does not dissolve in an alkaline aqueous solution, good solvents include N-methylpyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, and α. -Acetyl-γ-butyrolactone and the like are preferable, and as the poor solvent, toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, water and the like are preferable. When a good solvent and a poor solvent are mixed and used, it is preferable to adjust the ratio of the poor solvent to the good solvent by the solubility of the polymer in the photosensitive resin composition. Further, two or more kinds of each solvent, for example, several kinds can be used in combination.

(4) Step of forming a cured relief pattern by heat-treating the relief pattern In this step, the relief pattern obtained by the above development is heated to be converted into a cured relief pattern. As a method of heat curing, various methods such as a hot plate method, an oven method, and a temperature rise type oven in which a temperature program can be set can be selected. The heating can be performed, for example, at 180 ° C. to 400 ° C. for 30 minutes to 5 hours. Air may be used as the atmospheric gas at the time of heat curing, or an inert gas such as nitrogen or argon may be used.

<Semiconductor device>
The present invention also provides a semiconductor device including a cured relief pattern obtained by the method for producing a cured relief pattern of the present invention described above. The present invention also provides a semiconductor device including a base material which is a semiconductor element and a cured relief pattern of a resin formed on the base material by the above-mentioned cured relief pattern manufacturing method. Further, the present invention can also be applied to a method for manufacturing a semiconductor device, which uses a semiconductor element as a base material and includes the above-mentioned method for manufacturing a cured relief pattern as a part of a process. The semiconductor device of the present invention is a semiconductor having a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip chip device, or a bump structure of a cured relief pattern formed by the above-mentioned method for manufacturing a cured relief pattern. It can be manufactured by forming it as a protective film or the like of a device and combining it with a known manufacturing method of a semiconductor device.

The photosensitive resin composition of the present invention is useful not only for applications to semiconductor devices as described above, but also for applications such as interlayer insulation of multilayer circuits, cover coats for flexible copper-clad plates, solder resist films, and liquid crystal alignment films. Is.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto. In Examples, Comparative Examples and Production Examples, the physical characteristics of the photosensitive resin composition were measured and evaluated according to the following methods.

(1) Weight average molecular weight The weight average molecular weight (Mw) of each resin was measured by a gel permeation chromatography method (standard polystyrene conversion). The column used for the measurement is the brand name "Shodex 805M / 806M series" manufactured by Showa Denko KK, and the standard monodisperse polystyrene is the brand name "Shodex STANDARD SM-105" manufactured by Showa Denko KK. The developing solvent was N-methyl-2-pyrrolidone, and the detector used was the brand name "Shodex RI-930" manufactured by Showa Denko KK.

(2) Adhesiveness after development The photosensitive resin composition is spin-coated on a 6-inch silicon wafer using a spin coater (D-SPIN 636 type, manufactured by Dainippon Screen Mfg. Co., Ltd., Japan), and is applied on a hot plate at 100 ° C. It was dried for 240 seconds to form a coating film having a thickness of 10 μm. This coating film was sequentially irradiated with energy of 100 to 700 mJ / cm ² at specific wafer positions by an i-line stepper NSR1755i7B (manufactured by Nikon Corporation) using a reticle with a test pattern. Next, the coating film formed on the wafer was spray-developed with cyclopentanone using a developing machine (D-SPIN 636 type, manufactured by Dainippon Screen Mfg. Co., Ltd.), rinsed with propylene glycol methyl ether acetate, and subjected to a photosensitive resin. A pattern of the composition was obtained. A wafer having a pattern formed is heat-treated at 300 ° C. for 2 hours in a nitrogen atmosphere using a temperature-increasing programmed curing furnace (VF-2000 type, manufactured by Koyo Lindbergh, Japan) to obtain a polyimide having a thickness of about 6 μm. Pattern was obtained on a silicon wafer. For each of the obtained patterns, the pattern shape and the width of the pattern portion were observed under an optical microscope to determine the post-development adhesiveness at 500 mJ / cm ² exposure.
Multiple patterns of different sizes were formed by the above method by exposure through a reticle with a test pattern, and it was observed whether the cylindrical independent pattern remained on the substrate after development, and evaluated based on the following criteria.
⊚: Residual pattern size is 10 μm or more 〇: Residual pattern size is 14 μm or more Δ: Residual pattern size is 18 μm or more ×: Residual pattern size is 22 μm or more

(3) Resolution (2) Similar to the adhesiveness after development, a via hole pattern having openings having a plurality of different areas was formed by the above method by exposure through a reticle with a test pattern. Then, if the area of the obtained pattern opening is ½ or more of the corresponding pattern mask opening area, it is considered to be resolved, and it corresponds to the one having the minimum area among the resolved openings. The length of the opening side of the mask was taken as the resolution. The resolution was evaluated based on the following criteria.
⊚: Patterns of 12 μm or less are resolved ○: Patterns of 13 to 16 μm are resolved Δ: Patterns of 17 to 20 μm are resolved ×: Patterns of 21 μm or more are resolved

<Production Example 1> ((A) Synthesis of polymer A-1 as a polyimide precursor)
Place 155.1 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) in a 2 liter volume separable flask, add 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone, and stir at room temperature. , 81.5 g of pyridine was added with stirring to obtain a reaction mixture. After the heat generated by the reaction was completed, the mixture was allowed to cool to room temperature and left for 16 hours.

Next, under ice-cooling, a solution prepared by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring. Subsequently, 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) suspended in 350 ml of γ-butyrolactone was added over 60 minutes with stirring. After further stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added and the mixture was stirred for 1 hour, and then 400 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.

The obtained reaction solution was added to 3 liters of ethyl alcohol to form a precipitate composed of a crude polymer. The produced crude polymer was filtered off and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 liters of water to precipitate the polymer, and the obtained precipitate was filtered off and then vacuum dried to obtain a powdery polymer (polymer A-1). When the molecular weight of the polymer A-1 was measured by gel permeation chromatography (standard polystyrene equivalent), the weight average molecular weight (Mw) was 20,000.

<Production Example 2> ((A) Synthesis of polymer A-2 as a polyimide precursor)
Instead of 155.1 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) of Production Example 1, 147.1 g of 3,3', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) was used. Except for this, the reaction was carried out in the same manner as in the method described in Production Example 1 described above to obtain polymer A-2. When the molecular weight of the polymer A-2 was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 22,000.

<Production Example 3> ((A) Synthesis of polymer A-3 as a polyimide precursor)
As described above, except that 98.6 g of 4,4'-diamino-2,2'-dimethylbiphenyl (m-TB) was used instead of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) of Production Example 1. The reaction was carried out in the same manner as in the method described in Production Example 1 to obtain polymer A-3. When the molecular weight of the polymer A-3 was measured by gel permeation chromatography (standard polystyrene equivalent), the weight average molecular weight (Mw) was 20,000.

<Production Example 4> ((A) Synthesis of polymer A-4 as a polyimide precursor)
The method according to Production Example 3 above, except that 109.1 g of pyromerottic acid dianhydride (PMDA) was used in place of 155.1 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) of Production Example 3. The reaction was carried out in the same manner as in the above to obtain polymer A-4. When the molecular weight of the polymer A-4 was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 24,000.

<Production Example 5> ((A) Synthesis of polymer A-5 as a polyimide precursor)
Instead of 155.1 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) of Production Example 1, 77.5 g, 3,3', 4,4 of 4,4'-oxydiphthalic acid dianhydride (ODPA) The reaction was carried out in the same manner as in Production Example 1 described above except that 73.6 g of'-biphenyltetracarboxylic dianhydride (BPDA) was used to obtain polymer A-5. When the molecular weight of the polymer A-5 was measured by gel permeation chromatography (standard polystyrene equivalent), the weight average molecular weight (Mw) was 21,000.

<Production Example 6> ((A) Synthesis of polymer A-6 as a polyimide precursor)
Instead of 155.1 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) of Production Example 3, 77.5 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) and pyromerottic acid dianhydride (PMDA) The reaction was carried out in the same manner as in the above-mentioned production example 3 except that 54.6 g was used to obtain polymer A-6. When the molecular weight of the polymer A-6 was measured by gel permeation chromatography (standard polystyrene equivalent), the weight average molecular weight (Mw) was 23,000.

<Production Example 7> ((A) Synthesis of polymer A-7 as polyamide)
(Synthesis of phthalic acid compound encapsulant AIPA-MO)
5-Aminoisophthalic acid {hereinafter abbreviated as AIPA in a separable flask with a capacity of 5 liters. } 543.5 g and 1700 g of N-methyl-2-pyrrolidone were added, mixed and stirred, and heated to 50 ° C. in a water bath. 512.0 g (3.3 mol) of 2-methacryloyloxyethyl isocyanate diluted with 500 g of γ-butyrolactone was added dropwise to this with a dropping funnel, and the mixture was stirred as it was at 50 ° C. for about 2 hours.

After confirming the completion of the reaction (disappearance of 5-aminoisophthalic acid) by low molecular weight gel permeation chromatography (hereinafter referred to as low molecular weight GPC), this reaction solution was added to 15 liters of ion-exchanged water, stirred, and stirred. The reaction product was allowed to stand, separated by filtration after waiting for the crystallization precipitate of the reaction product, washed with water as appropriate, and then vacuum dried at 40 ° C. for 48 hours to obtain the amino group of 5-aminoisophthalic acid and 2-methacryloyloxyethyl isocyanate. AIPA-MO on which an isocyanate group acted was obtained. The low molecular weight GPC purity of the obtained AIPA-MO was about 100%.

(Synthesis of Polymer A-7)
100.89 g (0.3 mol) of the obtained AIPA-MO, 71.2 g (0.9 mol) of pyridine, and 400 g of GBL were put into a separable flask having a capacity of 2 liters, mixed, and cooled to 5 ° C. in an ice bath. did. To this, 125.0 g (0.606 mol) of dicyclohexylcarbodiimide (DCC) dissolved and diluted in 125 g of GBL was added dropwise over about 20 minutes under ice-cooling, followed by 4,4'-bis (4-aminophenoxy). ) Biphenyl {Hereafter referred to as BAPB. } 103.16 g (0.28 mol) dissolved in NMP 168 g is added dropwise over about 20 minutes, and the mixture is stirred in an ice bath for 3 hours while maintaining the temperature below 5 ° C, then removed from the ice bath and at room temperature for 5 hours. did. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.

A mixed solution of 840 g of water and 560 g of isopropanol was added dropwise to the obtained reaction solution, and the precipitated polymer was separated and redissolved in 650 g of NMP. The obtained crude polymer solution was added dropwise to 5 liters of water to precipitate the polymer, and the obtained precipitate was filtered off and then vacuum dried to obtain a powdery polymer (polymer A-7). When the molecular weight of the polymer A-7 was measured by gel permeation chromatography (standard polystyrene equivalent), the weight average molecular weight (Mw) was 34,700.

<Production Example 8> ((B) Synthesis of compound B-1 as a compound represented by the chemical formula (b1))
31.4 g (0.36 mol) of GBL and 67.3 g (1.46 mol) of ethanol were put into a 100 ml volumetric flask and mixed. To this, 0.1 g of para-toluenesulfonic acid monohydrate was added, and the mixture was stirred at room temperature for 18 hours. The reaction product was confirmed by 1 HNMR, and a reaction solution of compound B-1 containing 27.5% by weight (27.2 g) of ethyl 4-hydroxybutyrate was obtained. The structure represented by the chemical formula (b1) of n ≧ 2 was not found in 1 HNMR.

<Production Example 9> ((B) Synthesis of compound B-2 as a compound represented by the chemical formula (b1))
The reaction was carried out in the same manner as in Production Example 8 described above, except that 46.8 g (1.46 mol) of methanol was used instead of 46.8 g (1.46 mol) of ethanol in Production Example 8. A reaction solution of compound B-2 containing 29.1% by mass (22.8 g) of methyl 4-hydroxybutyrate was obtained. The structure represented by the chemical formula (b1) of n ≧ 2 was not found in 1 HNMR.

<Production Example 10> ((B) Synthesis of compound B-3 as a compound represented by the chemical formula (b1))
85.0 g (0.99 mol) of GBL and Solmix AP-1 (manufactured by Nippon Alcohol Co., Ltd., ethanol 85.5 mass percent, isopropanol 13.4 mass percent, methanol 1.1 mass percent) in a bite flask with a capacity of 100 ml. 5 g of the mixed solution) was added and mixed. To this, 0.1 g of para-toluenesulfonic acid monohydrate was added, and the mixture was stirred at room temperature for 24 hours. The reaction product was confirmed by 1 HNMR, and a reaction solution of compound B-3 containing 9.2% by weight (8.2 g) of the compound represented by the chemical formula (b1) was obtained. From the mass fragment measured by LC-MS, it was confirmed that R1 was a methyl group, an ethyl group, and an isopropyl group, and was a compound represented by the chemical formula (b1) of n = 1-5.

<Production Example 11> ((B) Synthesis of compound B-4 as the compound represented by the chemical formula (b1))
85.0 g (0.99 mol) of GBL and Solmix AP-1 (manufactured by Nippon Alcohol Co., Ltd., ethanol 85.5 mass percent, isopropanol 13.4 mass percent, methanol 1.1 mass percent) in a bite flask with a capacity of 100 ml. 5 g of the mixed solution) was added and mixed. To this, 0.1 g of para-toluenesulfonic acid monohydrate was added, and the mixture was stirred at 40 ° C. for 24 hours. The reaction product was confirmed by 1 HNMR, and a reaction solution of compound B-4 containing 12.3% by weight (11.1 g) of the compound represented by the chemical formula (b1) was obtained. From the mass fragment measured by LC-MS, it was confirmed that R1 is a methyl group, an ethyl group, and an isopropyl group, and is a compound represented by the chemical formula (b1) of n = 4 to 10.

<Production Example 12> ((B) Synthesis of compound B-5 as the compound represented by the chemical formula (b1))
The reaction was carried out in the same manner as in Production Example 8 described above, except that 26.3 g (1.46 mol) of water was used instead of 46.8 g (1.46 mol) of ethanol in Production Example 8. A reaction solution of compound B-5 containing 24.6% by mass (14.2 g) of 4-hydroxybutyric acid was obtained. The structure represented by the chemical formula (b1) of n ≧ 2 was not found in 1 HNMR.

<Example 1>
A negative photosensitive resin composition was prepared by the following method using the polymer A-1, and the prepared photosensitive resin composition was evaluated. 100 g of polymer A-1, which is a polyimide precursor, 7.3 g of reaction solution containing B-1 (2 g of B-1 component), 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl). ) -Oxime (denoted as "PDO" in Table 1) 4 g, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine -2,4,6- (1H, 3H, 5H) -trione 1.5g, N-phenyldiethanolamine 10g, methoxymethylated urea resin (MX-290) 4g, tetraethylene glycol dimethacrylate 8g, N-phenyl-3 It was dissolved in 100 g of GBL together with 1.5 g of aminopropyltrimethoxysilane and 0.05 g of 2-nitroso-1-naphthol. The viscosity of the obtained solution was adjusted to about 40 poise by further adding a small amount of the mixed solvent to obtain a negative photosensitive resin composition.

As a result of evaluating the negative photosensitive resin composition according to the above-mentioned method, the results shown in Table 1 were obtained.

<Example 2>
100 g of polymer A-1 which is a polyimide precursor of Example 1 is changed to 100 g of polymer A-2 which is a polyimide precursor, and a resin composition is prepared in the same manner as in Example 1, and evaluations are the same as in Example 1. Was done. Table 1 shows the evaluation results.

<Example 3>
100 g of polymer A-1 which is a polyimide precursor of Example 1 is changed to 100 g of polymer A-3 which is a polyimide precursor, and a resin composition is prepared in the same manner as in Example 1, and evaluations are the same as in Example 1. Was done. Table 1 shows the evaluation results.

<Example 4>
100 g of polymer A-1 which is a polyimide precursor of Example 1 is changed to 100 g of polymer A-4 which is a polyimide precursor, and a resin composition is prepared in the same manner as in Example 1, and evaluations are the same as in Example 1. Was done. Table 1 shows the evaluation results.

<Example 5>
100 g of polymer A-1 which is a polyimide precursor of Example 1 is changed to 100 g of polymer A-5 which is a polyimide precursor, and a resin composition is prepared in the same manner as in Example 1, and evaluations are the same as in Example 1. Was done. Table 1 shows the evaluation results.

<Example 6>
100 g of polymer A-1 which is a polyimide precursor of Example 1 is changed to 100 g of polymer A-6 which is a polyimide precursor, and a resin composition is prepared in the same manner as in Example 1, and evaluations are the same as in Example 1. Was done. Table 1 shows the evaluation results.

<Example 7>
100 g of polymer A-1 which is a polyimide precursor of Example 1 is changed to 100 g of polymer A-7 which is a polyamide, a resin composition is prepared in the same manner as in Example 1, and the same evaluation as in Example 1 is performed. rice field. Table 1 shows the evaluation results.

<Example 8>
Example 1 is obtained by changing 7.3 g of the reaction solution containing B-1 of Example 1 (2 g of the B-1 component) to 6.9 g of the reaction solution containing B-2 (2 g of the B-2 component). The resin composition was prepared in the same manner as in Example 1, and the same evaluation as in Example 1 was carried out. Table 1 shows the evaluation results.
<Example 9>
GBL in which 7.3 g of the reaction solution containing B-1 of Example 1 (2 g of the B-1 component) is changed to 21.7 g of the reaction solution containing B-3 (2 g of the B-3 component) and dissolved. The resin composition was adjusted to 80 g in the same manner as in Example 1, and the same evaluations as in Example 1 were carried out. Table 1 shows the evaluation results.
<Example 10>
GBL in which 7.3 g of the reaction solution containing B-1 of Example 1 (2 g of the B-1 component) is changed to 16.3 g of the reaction solution containing B-4 (2 g of the B-4 component) and dissolved. The resin composition was adjusted to 90 g in the same manner as in Example 1, and the same evaluations as in Example 1 were carried out. Table 1 shows the evaluation results.
<Example 11>
Example 1 is obtained by changing 7.3 g of the reaction solution containing B-1 of Example 1 (2 g of the B-1 component) to 8.1 g of the reaction solution containing B-5 (2 g of the B-5 component). The resin composition was prepared in the same manner as in Example 1, and the same evaluation as in Example 1 was carried out. Table 1 shows the evaluation results.

<Example 12>
The resin composition in the same manner as in Example 9 by changing 100 g of the polymer A-1 which is the polyimide precursor of Example 9 to 50 g of the polymer A-1 which is a polyimide precursor and 50 g of the polymer A-2 which is a polyimide precursor. Was prepared and evaluated in the same manner as in Example 9. Table 1 shows the evaluation results.

<Example 13>
The resin composition in the same manner as in Example 9 by changing 100 g of the polymer A-1 which is the polyimide precursor of Example 9 to 50 g of the polymer A-3 which is the polyimide precursor and 50 g of the polymer A-4 which is the polyimide precursor. Was prepared and evaluated in the same manner as in Example 9. Table 1 shows the evaluation results.

<Example 14>
100 g of polymer A-1 which is a polyimide precursor of Example 9 is changed to 100 g of polymer A-5 which is a polyimide precursor, and a resin composition is prepared in the same manner as in Example 9, and the same as in Example 9 respectively. Evaluation was performed. Table 1 shows the evaluation results.

<Example 15>
100 g of polymer A-1 which is a polyimide precursor of Example 9 is changed to 100 g of polymer A-6 which is a polyimide precursor, and a resin composition is prepared in the same manner as in Example 9, and the same as in Example 9 respectively. Evaluation was performed. Table 1 shows the evaluation results.

<Example 16>
1-Phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) -oxime 4 g, which is the (C) photosensitizer of Example 9, was added to 1,2-octanedione-1- [4- (phenylthio). Phenyl] -2- (O-benzoyloxime)) (trade name: IRGACURE-OXE-01, referred to as OXE-1 in Table 1 manufactured by BASF) Change to 4 g and prepare a resin composition in the same manner as in Example 9. Then, the same evaluation as in Example 9 was performed. Table 1 shows the evaluation results.

<Example 17>
1-Phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) -oxime 4 g, which is the (C) photosensitizer of Example 1, was added to 1,2-octanedione-1- [4- (phenylthio). Phenyl] -2- (O-benzoyloxime)) (trade name: IRGACURE-OXE-01, referred to as OXE-1 in Table 1 manufactured by BASF) Change to 4 g and prepare a resin composition in the same manner as in Example 1. Then, the same evaluation as in Example 1 was performed. Table 1 shows the evaluation results.

<Example 18>
The reaction solution containing B-1 of Example 1 was changed from 7.3 g (2 g of the B-1 component) to 0.036 g of the reaction solution containing B-1 (0.01 g of the B-1 component). The resin composition was prepared in the same manner as in Example 1, and each was evaluated in the same manner as in Example 1. Table 1 shows the evaluation results.

<Example 19>
The reaction solution containing B-1 of Example 1 was changed from 7.3 g (2 g of the B-1 component) to 0.18 g of the reaction solution containing B-1 (0.05 g of the B-1 component). The resin composition was prepared in the same manner as in Example 1, and each was evaluated in the same manner as in Example 1. Table 1 shows the evaluation results.

<Example 20>
The reaction solution containing B-1 of Example 1 was changed to 7.3 g (2 g of the B-1 component) to 18.2 g of the reaction solution containing B-1 (5 g of the B-1 component), and the GBL was 80 g. The resin composition was prepared in the same manner as in Example 1 and evaluated in the same manner as in Example 1. Table 1 shows the evaluation results.
<Example 21>
The reaction solution containing B-1 of Example 1 was changed to 7.3 g (2 g of B-1 component) to 36.4 g of the reaction solution containing B-1 (10 g of B-1 component), and GBL was 60 g. The resin composition was prepared in the same manner as in Example 1 and evaluated in the same manner as in Example 1. Table 1 shows the evaluation results.

<Comparative Example 1>
A negative photosensitive resin composition was prepared by the following method using the polymer A-1, and the prepared photosensitive resin composition was evaluated. 100 g of polymer A-1, which is a polyimide precursor, 4 g, 1,3 of 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) -oxime (denoted as "PDO" in Table 1). , 5-Tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione 1.5 g, N-Phenyldiethanolamine 10 g, methoxymethylated urea resin (MX-290) 4 g, tetraethylene glycol dimethacrylate 8 g, N-phenyl-3-aminopropyltrimethoxysilane 1.5 g, and 2-nitroso-1-naphthol. It was dissolved in 100 g of GBL together with 0.05 g. The viscosity of the obtained solution was adjusted to about 40 poise by further adding a small amount of the mixed solvent to obtain a negative photosensitive resin composition.
As a result of evaluating the negative photosensitive resin composition according to the above-mentioned method, the results shown in Table 1 were obtained.

<Comparative Example 2>
100 g of polymer A-1 which is a polyimide precursor of Comparative Example 1 is changed to 100 g of polymer A-2 which is a polyimide precursor, and a resin composition is prepared in the same manner as in Example 1, and evaluations are the same as in Example 1. Was done. Table 1 shows the evaluation results.

<Comparative Example 3>
100 g of polymer A-1 which is a polyimide precursor of Comparative Example 1 is changed to 100 g of polymer A-3 which is a polyimide precursor, and a resin composition is prepared in the same manner as in Example 1, and evaluations are the same as in Example 1. Was done. Table 1 shows the evaluation results.

<Comparative Example 4>
100 g of polymer A-1 which is a polyimide precursor of Comparative Example 1 is changed to 100 g of polymer A-4 which is a polyimide precursor, and a resin composition is prepared in the same manner as in Example 1, and evaluations are the same as in Example 1. Was done. Table 1 shows the evaluation results.

<Comparative Example 5>
100 g of polymer A-1 which is a polyimide precursor of Comparative Example 1 is changed to 100 g of polymer A-5 which is a polyimide precursor, and a resin composition is prepared in the same manner as in Example 1, and evaluations are the same as in Example 1. Was done. Table 1 shows the evaluation results.
<Comparative Example 6>

100 g of polymer A-1 which is a polyimide precursor of Comparative Example 1 is changed to 100 g of polymer A-6 which is a polyimide precursor, and a resin composition is prepared in the same manner as in Example 1, and evaluations are the same as in Example 1. Was done. Table 1 shows the evaluation results.

<Comparative Example 7>
100 g of polymer A-1 which is a polyimide precursor of Comparative Example 1 is changed to 100 g of polymer A-7 which is a polyimide precursor, and a resin composition is prepared in the same manner as in Example 1, and evaluations are the same as in Example 1. Was done. Table 1 shows the evaluation results.

<Comparative Example 8>
The reaction solution containing B-1 of Example 1 was changed from 7.3 g (2 g of the B-1 component) to 0.018 g of the reaction solution containing B-1 (0.005 g of the B-1 component). The resin composition was prepared in the same manner as in Example 1, and each was evaluated in the same manner as in Example 1. Table 1 shows the evaluation results.

<Comparative Example 9>
The GBL was changed by changing 7.3 g of the reaction solution containing B-1 of Example 1 (2 g of the B-1 component) to 54.5 g of the reaction solution containing B-1 (15 g of the B-1 component). The weight was changed to 50 g, a resin composition was prepared in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. Table 1 shows the evaluation results.

As is clear from Table 1, in contrast to (B) the comparative example in which the compound represented by the chemical formula (b1) is not contained, the examples in which the compound is contained have a short development time of the photosensitive resin composition and are good. It can be seen that it shows lithography performance.

The resin composition of the present invention can be suitably used as, for example, a semiconductor device having a copper pattern, a surface protective film for a multilayer wiring substrate, an interlayer insulating film, an insulating film for rewiring, a cover coat, and a solder resist film.

Claims (11)

The following ingredients;
(A) At least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamide, polyamide-imide, and polyimide, which are polyimide precursors: 100 parts by mass,
(B) Chemical formula (b1):

(R1 in the formula represents a hydrogen atom, a monovalent organic group of an alkyl group having 1 to 12 carbon atoms, and is an integer of n = 1 to 10), and contains a compound represented by n = 1 to 10. At least one compound selected from: 0.01 to 10 parts by mass, as well as
(C) A negative photosensitive resin composition comprising 0.5 to 30 parts by mass of a photosensitive agent. The resin (A) has the following general formula (1):

{In the formula, X1 is a tetravalent organic group, Y1 is a divalent organic group, n1 is an integer of 2 to 150, and R1 and R2 are independently hydrogen atoms, respectively. Or the following general formula (2):

(In the formula, R3, R4 and R5 are independently hydrogen atoms or organic groups having 1 to 3 carbon atoms, and m1 is an integer of 2 to 10). A group or a saturated aliphatic group having 1 to 4 carbon atoms. }, A polyimide precursor having a structure represented by
The following general formula (3):

(In the formula, X2 is a trivalent organic group having 6 to 15 carbon atoms, and Y2 is a divalent organic group having 6 to 35 carbon atoms and has the same structure or a plurality of structures. R6 is an organic group having at least one radically polymerizable unsaturated bonding group having 3 to 20 carbon atoms, and n2 is an integer of 1 to 1000.)
The negative photosensitive resin composition according to claim 1, which is at least one resin selected from the group consisting of the polyamide having the structure represented by. (B) The negative photosensitive resin composition according to claim 1 or 2, wherein R1 of the compound represented by the chemical formula (b1) is a monovalent organic group of an alkyl group having 1 to 12 carbon atoms. The negative type photosensitive according to any one of claims 1 to 3, which contains 0.05 to 5 parts by mass of the compound represented by (B) the chemical formula (b1) based on 100 parts by mass of the (A) resin. Sex resin composition. A group containing (D) a solvent, wherein the (D) solvent consists of γ-butyrolactone, γ-valerolactone, 3-methoxy-N, N-dimethylpropionamide, and 3-butoxy-N, N-dimethylpropionamide. The negative photosensitive resin composition according to any one of claims 1 to 4, which comprises at least one selected from. The negative photosensitive resin composition according to claim 5, wherein the solvent (D) contains an alcohol compound having 1 to 12 carbon atoms. (1) A step of forming a photosensitive resin layer on a substrate by applying the photosensitive resin composition according to any one of claims 1 to 6 onto the substrate.
(2) The step of exposing the photosensitive resin layer and
(3) A step of developing the photosensitive resin layer after the exposure to form a relief pattern, and
(4) A cured film obtained through a step of forming a cured relief pattern by heat-treating the relief pattern. (B) Chemical formula (b1):

(R1 in the formula represents a hydrogen atom or a monovalent organic group of an alkyl group having 1 to 12 carbon atoms, and takes an integer of n = 1 to 10). The compound according to claim 8, wherein in the chemical formula (b1), the R1 is one selected from the group consisting of a methyl group, an ethyl group, and an isopropyl group. The compound according to claim 8 or 9, wherein in the chemical formula (b1), n = 2 to 5. A composition comprising all of the compounds having n = 2 to 5 in the chemical formula (b1) according to any one of claims 8 to 10.