JP7693296B2 - Photosensitive resin composition and method for producing cured film - Google Patents

Description

The present invention relates to a photosensitive resin composition used, for example, in forming an insulating material for electronic components, and relief patterns for passivation films, buffer coat films, and interlayer insulating films in semiconductor devices, and a method for producing a cured film using the same.

Conventionally, polyimide resins, which have excellent heat resistance, electrical properties, and mechanical properties, have been used for insulating materials in electronic components, passivation films, surface protective films, interlayer insulating films, etc. in semiconductor devices. Among these polyimide resins, those provided in the form of photosensitive polyimide precursors can easily form heat-resistant relief pattern coatings by applying the precursor, exposing it to light, developing it, and subjecting it to a thermal imidization treatment by curing. Such photosensitive polyimide precursors have the characteristic of enabling a significant reduction in process times compared to conventional non-photosensitive polyimides.

Such photosensitive polyimides are provided as a varnish-like resin composition in which a resin, a photosensitizer, and other additives are dissolved in a solvent, and are applied to a substrate by a spin coating method (Patent Document 1) or a slit coating method (Patent Document 2). The color of this varnish is due to the light absorption of the resin, and after preparation, the varnish exhibits a unique color tone ranging from light yellow to red.

JP 2014-71373 A JP 2017-21113 A

In varnishes of a specific composition, there has been a phenomenon in which the color tone of the varnish changes over time, and the color tone of the coating film also changes. Because the color tone changes, there has been a problem in that erroneous recognition of the pattern image occurs when managing the relief pattern by image recognition. The present invention aims to identify a substance that can change the color tone of the varnish over time, and to provide a photosensitive resin composition that does not change the color tone of the varnish, and a method for producing a cured film that forms a pattern using the photosensitive resin composition.

The inventors discovered that a specific compound in a photosensitive resin composition decomposes over time, leading to a change in the color of the varnish, and discovered that by reducing the remaining amount of that compound, a photosensitive resin composition can be obtained in which the color of the varnish does not change over time, leading to the completion of the present invention. That is, the present invention is as follows.

（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＝１～５の整数をとる。）で示される化合物
（Ｃ）感光剤：０．５～３０質量部、および
（Ｄ）溶剤、を含み、
前記（Ｂ）化学式（ｂ１）で示される化合物において、ｎ＝１～５の化合物の合計が、０．０１質量部未満である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、または、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］
前記（Ｂ）化学式（ｂ１）で示される化合物において、前記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（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より選ばれる少なくとも一種である、［１］～［３］のいずれかに記載のネガ型感光性樹脂組成物。
［５］
前記（Ｄ）溶剤は、炭素数１～１２のアルコール化合物を含む、［１］～［４］のいずれかに記載のネガ型感光性樹脂組成物。
［６］
（１）［１］～［５］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含む、硬化膜の製造方法。
［７］
（１）［１］～［５］のいずれかに記載の感光性樹脂組成物のワニス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含み、
前記感光性樹脂組成物のワニスの色調が黄色乃至は赤色に準ずる範囲である、硬化膜の製造方法。 [1]
Ingredients below:
(A) 100 parts by mass of at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamide, polyamideimide, and polyimide, which is a polyimide precursor;
(B) Chemical formula (b1):

(wherein R1's each independently represent 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 5); (C) 0.5 to 30 parts by mass of a photosensitizer; and (D) a solvent,
A negative photosensitive resin composition, characterized in that, in the compound (B) represented by chemical formula (b1), the total amount of compounds where n=1 to 5 is less than 0.01 parts by mass.
[2]
The resin (A) is represented by the following general formula (1):

In the formula, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer from 2 to 150, and R ₁ and R ₂ are each independently a hydrogen atom or a group represented by the following general formula (2):

(wherein R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m ₁ is an integer from 2 to 10), or a saturated aliphatic group having 1 to 4 carbon atoms.}; or 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, _Y2 is a divalent organic group having 6 to 35 carbon atoms, and may have the same structure or multiple 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 1,000.}
and a polyamide having a structure represented by the formula (1):
[3]
The negative type photosensitive resin composition according to [1] or [2], wherein in the compound (B) represented by chemical formula (b1), the R1 is a monovalent organic group of an alkyl group having 1 to 12 carbon atoms.
[4]
The negative type photosensitive resin composition according to any one of [1] to [3], wherein the solvent (D) is at least one selected from the group consisting of γ-butyrolactone, γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide, and 3-butoxy-N,N-dimethylpropionamide.
[5]
The negative type photosensitive resin composition according to any one of [1] to [4], wherein the (D) solvent contains an alcohol compound having 1 to 12 carbon atoms.
[6]
(1) A step of forming a photosensitive resin layer on a substrate by applying the photosensitive resin composition according to any one of items [1] to [5] onto the substrate;
(2) exposing the photosensitive resin layer to light;
(3) developing the exposed photosensitive resin layer to form a relief pattern;
(4) A method for producing a cured film, comprising the step of heat-treating the relief pattern to form a cured relief pattern.
[7]
(1) A step of forming a photosensitive resin layer on a substrate by applying a varnish of the photosensitive resin composition according to any one of [1] to [5] onto the substrate;
(2) exposing the photosensitive resin layer to light;
(3) developing the exposed photosensitive resin layer to form a relief pattern;
(4) forming a hardened relief pattern by heat treating the relief pattern;
The method for producing a cured film, wherein the color tone of the varnish of the photosensitive resin composition is in the range from yellow to red.

According to the present invention, by reducing the amount of a specific compound in a photosensitive resin composition to a certain level, it is possible to obtain a photosensitive resin composition having fewer voids on the film surface, and further to provide a method for producing a cured film that forms a pattern using the photosensitive resin composition.

The present invention will be described in detail below. Throughout this specification, structures represented by the same symbols in general formulas may be the same or different when multiple structures are present in a 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。）。
そして本発明のネガ型感光性樹脂組成物は、（Ｂ）化学式（ｂ１）で示される化合物において、ｎ＝１～５の化合物の合計が、０．０１質量部未満であることを特徴とする。
本発明では、（Ｂ）化学式（ｂ１）で示される化合物を０．０１質量部未満まで減少させる事により、膜表面上にボイドが少ない感光性樹脂組成物を得ることができる。 <Photosensitive resin composition>
The negative type photosensitive resin composition of the present invention contains (A) 100 parts by mass of at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamide, polyamideimide, and polyimide, which is a polyimide precursor, (B) a compound represented by chemical formula (b1), (C) 0.5 to 30 parts by mass of a photosensitizer, and (D) a solvent.

(In the formula, each R1 independently represents a hydrogen atom or a monovalent organic group such as an alkyl group having 1 to 12 carbon atoms, and n is an integer of 1 to 10.)
The negative type photosensitive resin composition of the present invention is characterized in that the total amount of the compounds (B) represented by chemical formula (b1), where n=1 to 5, is less than 0.01 parts by mass.
In the present invention, by reducing the amount of the compound (B) represented by the chemical formula (b1) to less than 0.01 parts by mass, it is possible to obtain a photosensitive resin composition having few voids on the film surface.

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

From the viewpoint of heat resistance and mechanical properties after heat treatment, the weight average molecular weight of these resins is preferably 1,000 or more, more preferably 5,000 or more, calculated as polystyrene by gel permeation chromatography. The upper limit is preferably 100,000 or less, and when used as a photosensitive resin composition, from the viewpoint of solubility in a developer, it is more preferably 50,000 or less.

In the present invention, the (A) resin is preferably a photosensitive resin in order to form a relief pattern. The photosensitive resin is used together with the (C) photosensitizer described below to form a photosensitive resin composition, and is a resin that causes a phenomenon of dissolving or remaining undissolved in the subsequent development process.

As photosensitive resins, polyimide precursors such as polyamic acid, polyamic acid ester, polyamide, polyamideimide, and polyimide are preferably used, since the resins obtained after heat treatment have excellent heat resistance and mechanical properties. These photosensitive resins can be selected according to the desired application, such as whether to prepare a negative photosensitive resin composition together with the photosensitizer (C) described below.

｛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、又は前記一般式（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 (A) resin from the viewpoint of heat resistance and photosensitive properties is a resin represented by the general formula (1):

In the formula, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer of 2 to 150, and R ₁ and R ₂ are each independently a hydrogen atom or a group represented by the general formula (2):

(wherein R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m ₁ is an integer from 2 to 10), or a saturated aliphatic group having 1 to 4 carbon atoms.)
The polyimide precursor has a structure represented by the following formula: The polyimide precursor is converted into a polyimide by heating (e.g., at 200° C. or higher) for cyclization. The polyimide precursor is suitable for use in a negative-type 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, more preferably an aromatic group in which the _-COOR1 group and the _-COOR2 group are in the ortho position relative to the -CONH- group, or an alicyclic aliphatic group, in order to achieve both heat resistance and photosensitive properties. The tetravalent organic group represented by _X1 is preferably an organic group having 6 to 40 carbon atoms containing an aromatic ring, more preferably an organic group represented by the following formula (14):

Examples of the structure represented by the formula (14) include, but are not limited to, the structure represented by X _1. The structure represented by the formula (14) may be one type or a combination of two or more types. The structure represented by the formula ( ₁₄ ) is particularly preferred in that it provides both heat resistance and photosensitive properties.

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 properties, and is, for example, a group represented by the following formula (15):

and the following formula (16):

{In the formula, R ₂₃ and R ₂₄ each independently represent a methyl group (-CH ₃ ), an ethyl group (-C ₂ H ₅ ), a propyl group (-C ₃ H ₇ ), or a butyl group (-C ₄ H ₉ ).}
Examples of the structures represented by the formulae (15) and (16) include, but are not limited to, the structures represented by Y1. The structures represented by _Y1 may be one type or a combination of two or more types. The _Y1 groups having the structures represented by the formulae (15) and (16) are particularly preferred in that they provide both heat resistance and photosensitive properties.

With respect to _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 properties. Also, _m1 is an integer of 2 to 10, preferably an integer of 2 to 4, from the viewpoint of photosensitive properties.

When a polyimide precursor is used as the (A) resin, methods for imparting photosensitivity to a photosensitive resin composition include an ester bond type and an ionic bond type. The former is a method in which a photopolymerizable group, i.e., a compound having an olefinic double bond, is introduced to the side chain of a polyimide precursor via an ester bond, and the latter is a method in which a carboxyl group of a polyimide precursor and an amino group of a (meth)acrylic compound having an amino group are bonded via an ionic bond to impart a photopolymerizable group.

The ester bond-type polyimide precursor can be obtained by first reacting a tetracarboxylic dianhydride containing the above-mentioned tetravalent organic group _X1 with an alcohol having a photopolymerizable unsaturated double bond and, optionally, a saturated aliphatic alcohol having 1 to 4 carbon atoms to prepare a partially esterified tetracarboxylic acid (hereinafter, also referred to as an acid/ester body), and then subjecting this to amide polycondensation with a diamine containing the above-mentioned divalent organic group _Y1 .

(Preparation of Acid/Ester Forms)
In the present invention, examples of tetracarboxylic dianhydrides containing a tetravalent organic group X ₁ that are preferably used to prepare an ester bond type polyimide precursor include, but are not limited to, pyromellitic anhydride, diphenylether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, diphenylsulfone-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, etc. In addition, these can be used alone, or two or more of them can be mixed and used.

In the present invention, examples of alcohols having a photopolymerizable unsaturated double bond that are preferably used to prepare an ester-bond type polyimide precursor include 2-acryloyloxyethyl alcohol, 1-acryloyloxy-3-propyl alcohol, 2-acrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-t-butoxypropyl acrylate, 2-hydroxy-3-t-butoxypropyl acrylate, and 2-hydroxy-3-t-butoxypropyl acrylate. Examples of the methacryloyloxypropyl acrylate include 1-3-cyclohexyloxypropyl acrylate, 2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3-propyl alcohol, 2-methacrylamidoethyl 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, and 2-hydroxy-3-cyclohexyloxypropyl methacrylate.

The above alcohols can also be mixed with saturated aliphatic alcohols having 1 to 4 carbon atoms, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and tert-butanol.

The tetracarboxylic dianhydride suitable for the present invention and the alcohols described above are stirred, dissolved, and mixed in a suitable reaction solvent in the presence of a basic catalyst such as pyridine at a temperature of 20 to 50°C for 4 to 10 hours, whereby the esterification reaction of the acid anhydride proceeds and the desired acid/ester can be obtained.

The reaction solvent is preferably one that completely dissolves the acid/ester and the polyimide precursor, which is an amide polycondensation product of the acid/ester and the diamine component, such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, tetramethylurea, and γ-butyrolactone.

Other reaction solvents include ketones, esters, lactones, ethers, and halogenated hydrocarbons, and examples of hydrocarbons include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene, and xylene. These may be used alone or in combination as needed.

(Preparation of polyimide precursor)
A suitable dehydration condensation agent, for example, dicyclocarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, or the like is added to and mixed with the above acid/ester body (typically a solution in the above reaction solvent) under ice cooling to convert the acid/ester body into a polyacid anhydride, and then a diamine containing a divalent organic group _Y1 preferably used in the present invention, dissolved or dispersed in a separate solvent, is added dropwise to the above acid/ester body to carry out amide polycondensation, thereby obtaining the target polyimide precursor.

Diamines containing a divalent organic group _Y1 that are preferably used in the present invention include, for example, 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'-diamino diphenyl 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-aminof Examples of such compounds include, but are not limited to, 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'-dimethyloxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and mixtures thereof.

In addition, in order to improve the adhesion between various substrates and the resin layer formed on a substrate by applying the photosensitive resin composition of the present invention to the substrate, diaminosiloxanes such as 1,3-bis(3-aminopropyl)tetramethyldisiloxane and 1,3-bis(3-aminopropyl)tetraphenyldisiloxane can also be copolymerized when preparing the polyimide precursor.

After the amide polycondensation reaction is completed, the water-absorbing by-product of the dehydrating condensing agent coexisting in the reaction solution is filtered off as necessary, and then a poor solvent such as water, aliphatic lower alcohol, or a mixture thereof is added to the resulting polymer component to precipitate the polymer component. The polymer is purified by repeating redissolution and reprecipitation operations, and is vacuum dried to isolate the desired polyimide precursor. To improve the degree of purification, the polymer solution may be passed through a column packed with an anion and/or cation exchange resin swollen with an appropriate organic solvent to remove ionic impurities.

On the other hand, the ionic bond type 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.

As the tetracarboxylic dianhydride, a tetracarboxylic anhydride having the structure of the above formula (14) is preferred, and as the diamine, a diamine having the structure of the above formula (15) or (16) is preferred. 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 weight of the ester-bonded and ion-bonded polyimide precursors is preferably 8,000 to 150,000, more preferably 9,000 to 50,000, when measured by gel permeation chromatography in terms of polystyrene equivalent weight average molecular weight. 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 developer is good, and the resolution performance of the relief pattern is good. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as the developing solvent for gel permeation chromatography. The weight average molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from the organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko KK.

｛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]
Another example of a preferable resin (A) in the photosensitive resin composition of the present invention is a resin represented by the following general formula (3):

{In the formula, _X2 is a trivalent organic group having 6 to 15 carbon atoms, _Y2 is a divalent organic group having 6 to 35 carbon atoms, and may have the same structure or multiple 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 1,000.}
The polyamide has a structure represented by the following formula: This polyamide is suitable for use in a negative-type photosensitive resin composition.

｛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 preferably a group represented by the following general formula (17):

{In the formula, R ₂₅ is an organic group having at least one radically polymerizable unsaturated bond group having 2 to 19 carbon atoms.}
It is preferable that the group is represented by the following formula:

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, a trivalent organic group represented by the following formula (18):

and more preferably an aromatic group obtained by removing a carboxyl group and an amino group from an amino-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 more preferably a cyclic organic group having 1 to 4 aromatic or aliphatic rings which may be substituted, or an aliphatic group or siloxane group having no cyclic structure. The divalent organic group represented by _Y2 includes the following general formula (15) and the following general formulas (19) and (20):

In the formula, R ₂₆ and R ₂₇ are each independently one group selected from the group consisting of a hydroxyl group, a methyl group (-CH ₃ ), an ethyl group (-C ₂ H ₅ ), a propyl group (-C ₃ H ₇ ) or a butyl group (-C ₄ H ₉ ), and the propyl group and the butyl group include various isomers.

{In the formula, _m4 is an integer from 0 to 8, _m5 and _m6 are each independently an integer from 0 to 3, _m7 and _m8 are each independently an integer from 0 to 10, and _R28 and _R29 are a _methyl group ( _-CH3 ), an ethyl _{group (-C2H5 )} , a _propyl group ( _-C3H7 ), a butyl group ( _-C4H9 ) or an isomer 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。 The aliphatic group or siloxane group having no cyclic structure may be a group represented by 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 each independently represent an alkyl group having 1 to 3 carbon atoms or a phenyl group which may be substituted.} is mentioned as a preferred example.

The polyamide resin of the present invention can be synthesized, for example, as follows.
(Synthesis of phthalic acid compound-terminated product)
First, a compound having a trivalent aromatic group _X2 , for example, at least one compound selected from the group consisting of phthalic acid substituted with an amino group, isophthalic acid substituted with an amino group, and terephthalic acid substituted with an amino group (hereinafter referred to as a "phthalic acid compound") is reacted with 1 mole of a compound that reacts with an amino group to synthesize a compound in which the amino group of the phthalic acid compound is modified and blocked with a group containing a radically polymerizable unsaturated bond as described below (hereinafter referred to as a "blocked phthalic acid compound"). These may be used alone or in combination.

By capping a phthalic acid compound with a group containing the above-mentioned radically polymerizable unsaturated bond, it is possible to impart negative photosensitivity (photocurability) to the polyamide resin.

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

The above-mentioned phthalic acid compound-sealed product can be obtained by reacting the amino group of the phthalic acid compound with an acid chloride, isocyanate, epoxy compound, or the like having at least one radically polymerizable unsaturated bond group having 3 to 20 carbon atoms.

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

Furthermore, among these phthalic acid compound-sealed products, those in which the phthalic acid compound is 5-aminoisophthalic acid are preferred, as they have excellent photosensitive properties and can produce polyamides with excellent film properties after heat curing.

The above sealing reaction can be 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-based catalyst such as di-n-butyltin dilaurate.

The reaction solvent is preferably one that completely dissolves the product, the sealed phthalic acid compound, and examples of such solvents include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, tetramethylurea, and γ-butyrolactone.

Other reaction solvents include ketones, esters, lactones, ethers, and halogenated hydrocarbons, and examples of hydrocarbons include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene, and xylene. These solvents can be used alone or in combination as needed.

Some types of sealing agents, such as acid chlorides, produce hydrogen chloride as a by-product during the sealing reaction. In this case, in order to prevent contamination of subsequent processes, it is preferable to purify the product appropriately, such as by reprecipitation in water, rinsing with water and drying, or by passing the product through a column filled with ion exchange resin to remove and reduce ionic components.

(Synthesis of Polyamide)
The polyamide of the present invention can be obtained by mixing the above-mentioned phthalic acid compound-blocked product and a diamine compound having a divalent organic group _Y2 in a suitable solvent in the presence of a basic catalyst such as pyridine or triethylamine, and carrying out amide polycondensation.

Examples of the amide polycondensation method include a method in which a phthalic acid compound-sealed product is converted into a symmetric polyacid anhydride using a dehydrating condensing agent and then mixed with a diamine compound, a method in which a phthalic acid compound-sealed product is converted into an acid chloride by a known method and then mixed with a diamine compound, and a method in which a dicarboxylic acid component is reacted with an active esterifying agent in the presence of a dehydrating condensing agent to convert it into an active ester and then mixed with a diamine compound.

Preferred examples of dehydration condensation agents include dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1'-carbonyldioxy-di-1,2,3-benzotriazole, and N,N'-disuccinimidyl carbonate.

Chlorinating agents include thionyl chloride.

Examples of active esterification agents include N-hydroxysuccinimide or 1-hydroxybenzotriazole, N-hydroxy-5-norbornene-2,3-dicarboxylic acid imide, 2-hydroxyimino-2-cyanoethyl acetate, and 2-hydroxyimino-2-cyanoacetic acid amide.

The diamine compound having the organic group _Y2 is preferably 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, and a plurality of diamine compounds may be used in combination as desired.

Aromatic diamine compounds 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'-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-tolidine sulfone, 9,9-bis(4-aminophenyl)fluorene, and diamine compounds in which some of the hydrogen atoms on the benzene ring are substituted with one or more groups selected from the group consisting of methyl groups, ethyl groups, hydroxymethyl groups, hydroxyethyl groups, and halogen atoms.

Examples of diamine compounds in which the hydrogen atoms on the benzene ring are substituted include 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'-dimethytoxy-4,4'-diaminobiphenyl, and 3,3'-dichloro-4,4'-diaminobiphenyl.

Aromatic bisaminophenol compounds include 3,3'-dihydroxybenzidine, 3,3'-diamino-4,4'-dihydroxybiphenyl, 3,3'-dihydroxy-4,4'-diaminodiphenyl sulfone, 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)hexafluoropropane, nophenyl)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-aminophenol), etc.

Alicyclic diamine compounds include 1,3-diaminocyclopentane, 1,3-diaminocyclohexane, 1,3-diamino-1-methylcyclohexane, 3,5-diamino-1,1-dimethylcyclohexane, 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, and 1,3-bis(aminomethyl)cyclohexa amine, 1,4-bis(aminomethyl)cyclohexane, 2-(3-aminocyclopentyl)-2-propylamine, menthene diamine, isophorone diamine, norbornane diamine, 1-cycloheptene-3,7-diamine, 4,4'-methylenebis(cyclohexylamine), 4,4'-methylenebis(2-methylcyclohexylamine), 1,4-bis(3-aminopropyl)piperazine, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro-[5,5]-undecane, etc.

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

Examples of siloxane diamine compounds include dimethyl (poly)siloxane diamine, such as those manufactured by Shin-Etsu Chemical Co., Ltd. under the trade names PAM-E, KF-8010, and X-22-161A.

The reaction solvent is preferably one that completely dissolves the resulting polymer, such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, tetramethylurea, and γ-butyrolactone.

In some cases, ketones, esters, lactones, ethers, hydrocarbons, and halogenated hydrocarbons may also be used as reaction solvents. Specific examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene, and xylene.

After the amide polycondensation reaction is completed, the precipitates derived from the dehydration condensation agent that have precipitated in the reaction solution are filtered off as necessary. Next, a poor solvent for polyamide, such as water or a lower aliphatic alcohol or a mixture thereof, is added to the reaction solution to precipitate the polyamide. The precipitated polyamide is then redissolved in a solvent and purified by repeating the reprecipitation operation, and vacuum dried to isolate the desired polyamide. In order to further improve the degree of purification, the polyamide solution 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 determined by gel permeation chromatography (hereinafter referred to as "GPC") is preferably 7,000 to 70,000, and more preferably 10,000 to 50,000. If the polystyrene-equivalent weight average molecular weight is 7,000 or more, the basic physical properties of the cured relief pattern are ensured. Furthermore, if the polystyrene-equivalent weight average molecular weight is 70,000 or less, the development solubility when 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 determined from a calibration curve created using standard monodisperse polystyrene. It is recommended that the standard monodisperse polystyrene be selected from Showa Denko's organic solvent-based standard sample STANDARD SM-105.

（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＝１～５の整数をとる。） (B) A compound represented by the chemical formula (b1)

(In the formula, each R1 independently 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 5.)

The compound represented by (B) chemical formula (b1) is explained below. The compound represented by (B) chemical formula (b1) is thought to be produced by a ring-opening reaction of an alkyl alcohol with gamma-butyrolactone activated by an acid catalyst, and the compound represented by (B) chemical formula (b1) where n is greater than or equal to 2 is produced by the alkyl alcohol moiety of the compound represented by (B) chemical formula (b1) reacting with gamma-butyrolactone. On the other hand, the compound represented by (B) chemical formula (b1) is thought to undergo a ring-closing reaction due to its own thermal vibration in the absence of an acid catalyst or in a sufficiently diluted condition, and is presumed to produce gamma-butyrolactone.

The mechanism by which the color tone of the varnish changes over time is still in the realm of speculation, but it is thought that when the compound represented by chemical formula (b1) (B) is present in the varnish of the photosensitive resin composition, the resin that interacts with the compound represented by chemical formula (b1) (B) exhibits a certain color tone (e.g., red). As the varnish ages, the compound represented by chemical formula (b1) (B) decomposes to γ-butyrolactone, and the interaction between the compound represented by chemical formula (b1) (B) and the resin is eliminated, causing the color tone to change.

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

In addition, when water or an alkyl alcohol and γ-butyrolactone are subjected to a ring-opening reaction in the presence of an acid catalyst, a compound represented by (B) chemical formula (b1) where n≧2 is obtained.

Examples of alkyl alcohols include 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, and benzyl alcohol. From the viewpoint of compatibility with the resin, however, methanol, ethanol, n-propanol, isopropanol, n-butanol, and tert-butanol are preferable.

Examples of acid catalysts include hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid, ethanesulfonic acid, n-propanesulfonic acid, benzenesulfonic acid, para-toluenesulfonic acid, oxalic acid, and malonic acid. The higher the acidity of the acid catalyst, the higher the reaction rate and the easier it is to produce the compound represented by (B) chemical formula (b1).

When the amount of the compound (B) represented by chemical formula (b1) is less than 0.01 parts by mass relative to 100 parts by mass of the resin (A), the change in color tone of the varnish over time is small, and preferably when the amount is less than 0.005 parts by mass, the change in color tone is even smaller.

(C) Photosensitizer The (C) photosensitizer used in the present invention will be described.
Examples of photosensitizers include benzophenone derivatives such as benzophenone, o-benzoylmethylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone; acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexylphenyl ketone; thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone; benzyl derivatives such as benzil, benzil dimethyl ketal, and benzyl-β-methoxyethyl acetal; benzoin derivatives such as benzoin methyl ether; and 1-phenyl-1,2-butanedione-2-(o- Preferred examples of the oximes include 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-diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime, N-arylglycines such as N-phenylglycine, peroxides such as benzoyl perchloride, and aromatic biimidazoles, but are not limited to these. These may be used alone or in a mixture of two or more.

｛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。 Among the above photosensitizers, those represented by the following general formula (29):

In formula (29), Z is a sulfur or oxygen atom, R12a is a methyl group, a phenyl group, or a divalent organic group, and R13a to R15a each independently represent a hydrogen atom or a monovalent organic group.
The oxime-based compound represented by the following formula is more preferably used.

、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 them, the following formula (63):

, formula (64):

, formula (65):

, or formula (66):

The compound represented by formula (63) is commercially available as TR-PBG-305 manufactured by Changzhou New Strong Electronic Materials Co., Ltd., the compound represented by formula (64) is commercially available as TR-PBG-3057 manufactured by Changzhou New Strong Electronic Materials Co., Ltd., and the compound represented by formula (65) is commercially available as Irgacure OXE-01 manufactured by BASF.

The amount of the photosensitizer (C) in the resin composition is 0.5 to 30 parts by mass relative to 100 parts by mass of the resin (A). It is preferably 1 to 20 parts by mass, and more preferably 2 to 10 parts by mass. If the amount is 0.5 parts by mass or more, the relief pattern has excellent resolution, and if it is 30 parts by mass or less, there is little residue at the openings of the pattern.

(D) Solvent The photosensitive resin composition of the present invention is used as a resin composition in the form of a varnish obtained by dissolving the optional components in a solvent. As the solvent, it is preferable to use a polar organic solvent in terms of solubility in the (A) resin. Specific examples of the solvent include 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, and N-cyclohexyl-2-pyrrolidone, which can be used alone or in combination of two or more kinds.
In particular, γ-butyrolactone, γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide, and 3-butoxy-N,N-dimethylpropionamide are presumed to have moderate solubility in both the resin (A) and the compound represented by chemical formula (b1) (B), and are excellent in improving the solubility of the coating film in a developer.

The above solvent can be used in an amount ranging from, for example, 30 to 1500 parts by mass, preferably 100 to 1000 parts by mass, per 100 parts by mass of resin (A), depending on the desired coating thickness and viscosity of the photosensitive resin composition.

Furthermore, from the viewpoint of improving the storage stability of the photosensitive resin composition, a solvent containing an alcohol, particularly an alcohol having 1 to 12 carbon atoms, is preferred. Alcohols that can be suitably used are typically alcohols that have an alcoholic hydroxyl group in the molecule and do not have an olefinic double bond, and specific examples include alkyl alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, and tert-butyl alcohol, lactate esters such as ethyl lactate, propylene glycol monoalkyl ethers such as propylene glycol-1-methyl ether, propylene glycol-2-methyl ether, propylene glycol-1-ethyl ether, propylene glycol-2-ethyl ether, propylene glycol-1-(n-propyl) ether, and propylene glycol-2-(n-propyl) ether, monoalcohols such as ethylene glycol methyl ether, ethylene glycol ethyl ether, and ethylene glycol-n-propyl ether, 2-hydroxyisobutyrate esters, ethylene glycol, and dialcohols such as propylene glycol. Of these, lactate esters, propylene glycol monoalkyl ethers, 2-hydroxyisobutyrate esters, and ethyl alcohol are preferred, with ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-1-ethyl ether, and propylene glycol-1-(n-propyl) ether being particularly preferred.

When the solvent contains an alcohol that does not have an olefinic double bond, the content of the alcohol that does not have an olefinic double bond in the total solvent is preferably 5 to 50 mass %, and more preferably 10 to 30 mass %. When the content of the alcohol that does not have an olefinic double bond is 5 mass % or more, the storage stability of the resin composition is good, and when it is 50 mass % or less, the solubility of the (A) resin is good.

(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 by a photopolymerization initiator is preferable, and examples thereof include, but are not limited to, mono- or diacrylates and methacrylates of ethylene glycol or polyethylene glycol, such as diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate, mono- or diacrylates and methacrylates of propylene glycol or polypropylene glycol, mono-, di- or triacrylates and methacrylates of glycerol, cyclohexane diacrylate and dimethacrylate, diacrylates of 1,4-butanediol and Examples of the monomer include dimethacrylate, diacrylate and dimethacrylate of 1,6-hexanediol, diacrylate and dimethacrylate of neopentyl glycol, mono- or diacrylate and methacrylate of bisphenol A, benzene trimethacrylate, isobornyl acrylate and methacrylate, acrylamide and its derivatives, methacrylamide and its derivatives, trimethylolpropane triacrylate and methacrylate, di- or triacrylate and methacrylate of glycerol, di-, tri-, or tetraacrylate and methacrylate of pentaerythritol, and 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 amount of the monomer having a photopolymerizable unsaturated bond is preferably 1 to 50 parts by mass per 100 parts by mass of the (A) resin. If the amount is 1 part by mass or more, the curing property of the film in the exposed area is improved and the resolution is excellent, and if it is 50 parts by mass or less, the in-plane uniformity of the coating film is excellent.

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

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

Specific examples of the organotitanium compound (F) are shown below in I) to VII):
I) Titanium chelate compounds: Among these, titanium chelates having two or more alkoxy groups are more preferred since they provide a resin composition with good storage stability and a good pattern. Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate, titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate), and the like.

II) Tetraalkoxytitanium compounds: For example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis{2,2-(allyloxymethyl)butoxide}], etc.

III) Titanocene compounds: For example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η ⁵ -2,4-cyclopentadiene-1-yl)bis(2,6-difluorophenyl)titanium, bis(η ⁵ -2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and the like.

IV) Monoalkoxytitanium compounds: For example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc.

V) Titanium oxide compounds: For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, etc.

VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate, etc.

VII) Titanate coupling agents: For example, isopropyl tridodecylbenzenesulfonyl titanate, etc.

Among these, from the viewpoint of exhibiting better chemical resistance, it is preferable that the (F) organic titanium compound is at least one compound selected from the group consisting of the above-mentioned I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds. In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η ⁵ -2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are preferred.

When (F) an organic titanium compound is blended, the blending amount is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, per 100 parts by mass of (A) resin. 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, excellent storage stability is exhibited.

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

Examples of crosslinking agents include those having one thermal crosslinking group such as ML-26X, ML-24X, ML-236TMP, 4-methylol 3M6C, ML-MC, and ML-TBC (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), and P-a type benzoxazine (trade name, manufactured by Shikoku Chemical Industry Co., Ltd.), and those having two such groups such as DM-BI25X-F, 46DMOC, 46DMOIPP, and 46DMOEP (all trade names, manufactured by Asahi Organic Chemicals Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, and DML-P. C, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP, DML-OC, Dimethylol-Bis-C, Dimethylol-BisOC-P, DML-BisOC-Z, DML-BisOCHP-Z, DML-PF P, DML-PSBP, DML-MB25, DML-MTrisPC, DML-Bis25X-34XL, DML-Bis25X-PCHP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), Nikalac MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.),

B-a type benzoxazine, B-m type benzoxazine (all trade names, manufactured by Shikoku Chemical Industry Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, etc.; those having three of these, such as TriML-P, TriML-35XL, TriML-TrisCR-HAP (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.); and those having four of these, such as TM-BIP-A (trade name, manufactured by Asahi Organic Chemicals Co., Ltd.). (Corporation), TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP (all product names, manufactured by Honshu Chemical Industry Co., Ltd.), Nikalac MX-280, Nikalac MX-270 (all product names, manufactured by Sanwa Chemical Co., Ltd.), and those with six are HML-TPPHBA, HML-TPHAP (all product names, manufactured by Honshu Chemical Industry Co., Ltd.), Nikalac MW-390, Nikalac MW-100LM (all product names, manufactured by Sanwa Chemical Co., Ltd.).

Among these, those containing at least two thermally crosslinkable groups are preferred in the present invention, and particularly preferred are 46DMOC, 46DMOEP (all trade names, manufactured by Asahi Organic Chemicals Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PC, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), Nikalac MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), B-a type benzoxazine, B-m type benzoxazine (all trade names, manufactured by Shikoku Chemical Industry Co., Ltd.) Examples of suitable phenols include phenols such as 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, TriML-P, TriML-35XL (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by Asahi Organic Chemicals Co., Ltd.), TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), Nikalac MX-280, Nikalac MX-270 (all trade names, manufactured by Sanwa Chemical Co., Ltd.), HML-TPPHBA, HML-TPHAP (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), and the like. More preferred examples include Nikalac MX-290, Nikalac MX-280, and Nikalac MX-270 (all trade names, manufactured by Sanwa Chemical Co., Ltd.), Ba-type benzoxazine, B-m-type benzoxazine (all trade names, manufactured by Shikoku Kasei Corporation), Nikalac MW-390, and Nikalac MW-100LM (all trade names, manufactured by Sanwa Chemical Co., Ltd.).

In consideration of the balance between various properties other than heat resistance and chemical resistance, when the resin composition contains a crosslinking agent, the blending amount is preferably 0.5 to 20 parts by mass, and more preferably 2 to 10 parts by mass, per 100 parts by mass of the (A) resin. 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, excellent storage stability is achieved.

In order to suppress discoloration on copper, the resin composition of the present invention can be optionally blended with a nitrogen-containing heterocyclic compound such as an azole compound or a purine derivative. Examples of azole compounds 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, hydroxyphenyltriazole, 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, and the like. 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, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, etc. Particularly preferred are at least one selected from tolyltriazole, 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 purine derivatives include purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9-(2-hydroxyethyl)adenine, guanine oxime, N-(2-hydroxyethyl)adenine, 8-aminopurine, These include aminoadenine, 6-amino-8-phenyl-9H-purine, 1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine, N-methylguanine, 7-(2-hydroxyethyl)guanine, N-(3-chlorophenyl)guanine, N-(3-ethylphenyl)guanine, 2-azaadenine, 5-azaadenine, 8-azaadenine, 8-azaguanine, 8-azapurine, 8-azaxanthine, 8-azahypoxanthine, and derivatives thereof.

When the resin composition contains the above-mentioned azole compound or purine derivative, the blending amount is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the (A) resin, and more preferably 0.5 to 5 parts by mass from the viewpoint of the storage stability of the resin composition. When the blending amount of the azole compound relative to 100 parts by mass of the (A) resin is 0.1 part by mass or more, discoloration of the copper or copper alloy surface is suppressed when the resin composition of the present invention is formed on copper or a copper alloy, while when the blending amount 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. These azole compounds may be used alone or in a mixture of two or more.

In addition, a hindered phenol compound can be optionally blended 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, 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-hydrocinnamamide), 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)-trione,

1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 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)-trione, 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)-trione, 1,3,5-tris(4-t-butyl-5,6-diethyl-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-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. are included, but are not limited thereto. 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, etc. are particularly preferred.

The amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass per 100 parts by mass of the (A) resin, and more preferably 0.5 to 10 parts by mass from the viewpoint of the degree of polymerization of the compound having an unsaturated bond. When the amount of the hindered phenol compound per 100 parts by mass of the (A) resin is 0.1 part by mass or more, for example, when the resin composition of the present invention is formed on copper or a copper alloy, discoloration and corrosion of the copper or copper alloy are prevented, while when the amount is 20 parts by mass or less, the degree of polymerization of the compound having an unsaturated bond is excellent.

The resin composition of the present invention can be optionally blended with a sensitizer. Examples of such sensitizers include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamylidene indane, and the like. Non, p-dimethylaminobenzylidene indanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetone ethyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-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-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, and the like. These can be used alone or in combinations of, for example, 2 to 5 types.

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

In addition, an adhesive aid can be optionally blended to improve adhesion between the film formed using the resin composition of the present invention and the substrate. Examples of 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]propyl)propanol, and benzophenone-3,3'-bis(N-[3-triethoxysilyl]propyl)propanol. Examples of suitable silane coupling agents include benzene-1,4-bis(N-[3-triethoxysilyl]propylamido)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamido)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, and 3-(trialkoxysilyl)propyl succinic anhydride, as well as aluminum-based adhesion promoters such as aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

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

In addition, a thermal polymerization inhibitor can be optionally blended to improve the viscosity stability of the resin composition during storage, particularly in the form of a solution containing a solvent. Examples of thermal polymerization inhibitors that can be used include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic 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, and N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt.

When blended into a resin composition, the amount of thermal polymerization inhibitor is preferably in the range of 0.005 to 12 parts by mass per 100 parts by mass of resin (A).

<Method for Producing Cured Relief Pattern and Semiconductor Device>
The present invention also provides a method for producing a cured relief pattern, comprising the steps of: (1) forming a resin layer on a substrate by applying the above-mentioned photosensitive resin composition of the present invention onto the substrate; (2) exposing the resin layer to light; (3) developing the exposed resin layer to form a relief pattern; and (4) subjecting the relief pattern to a heat treatment to form a cured relief pattern. Typical aspects of each step are described below.

(1) Step of forming a resin layer on a substrate by applying a photosensitive resin composition onto the substrate In this step, the photosensitive resin composition of the present invention is applied onto a substrate, and then dried as necessary to form a resin layer.
The photosensitive resin composition of the present invention is used as a resin composition in the form of a varnish obtained by dissolving optional components in a solvent. In particular, the color tone of the varnish of the photosensitive resin composition of the present invention as described above is in the range from yellow to red.
As the coating method, a method that has conventionally been used for coating a photosensitive resin composition, such as a coating method using a spin coater, a bar coater, a blade coater, a curtain coater, a screen printing machine, or the like, or a spray coating method using a spray coater, can be used.

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

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

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

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

As the developer 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 is not soluble in an alkaline aqueous solution, the good solvent is preferably N-methylpyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, etc., and the poor solvent is preferably toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, water, etc. When a good solvent and a poor solvent are used in combination, it is preferable to adjust the ratio of the poor solvent to the good solvent depending on the solubility of the polymer in the photosensitive resin composition. In addition, two or more types of each solvent, for example, several types, can be used in combination.

(4) Step of forming a hardened relief pattern by heat treatment of the relief pattern In this step, the relief pattern obtained by the above development is heated to convert it into a hardened relief pattern. As the heat curing method, various methods can be selected, such as a method using a hot plate, a method using an oven, or a method using a temperature-raising oven in which a temperature program can be set. Heating can be performed, for example, under conditions of 180°C to 400°C for 30 minutes to 5 hours. As the atmospheric gas during heat curing, air may be used, or an inert gas such as nitrogen or argon may also be used.

<Semiconductor Device>
The present invention also provides a semiconductor device comprising a cured relief pattern obtained by the above-mentioned method for producing a cured relief pattern of the present invention. The present invention also provides a semiconductor device comprising a substrate which is a semiconductor element, and a cured relief pattern of a resin formed on the substrate by the above-mentioned method for producing a cured relief pattern. The present invention is also applicable to a method for producing a semiconductor device which uses a semiconductor element as the substrate and includes the above-mentioned method for producing a cured relief pattern as part of its steps. The semiconductor device of the present invention can be produced by forming the cured relief pattern formed by the above-mentioned method for producing a cured relief pattern as a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip chip device, or a protective film for a semiconductor device having a bump structure, and combining the method with a known method for producing a semiconductor device.

In addition to being applicable to the semiconductor devices described above, the photosensitive resin composition of the present invention is also useful for applications such as interlayer insulation in multilayer circuits, cover coats for flexible copper-clad boards, solder resist films, and liquid crystal alignment films.

The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. In the examples, comparative examples, and production examples, the physical properties 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 gel permeation chromatography (standard polystyrene equivalent). The column used in the measurement was a "Shodex 805M/806M series" manufactured by Showa Denko K.K., the standard monodisperse polystyrene was "Shodex STANDARD SM-105" manufactured by Showa Denko K.K., the developing solvent was N-methyl-2-pyrrolidone, and the detector was "Shodex RI-930" manufactured by Showa Denko K.K.

(2) Color change of varnish after time A photosensitive resin composition was prepared, and 5 g was placed in a 10 ml glass vial, which was then sealed and the color was observed under a UV-cut fluorescent lamp. The glass vial was stored in a dark place at 25 degrees for 10 days, and the color was observed again under a UV-cut fluorescent lamp. Those that did not change in color were judged to pass. Those that did change were judged to fail.

<Production Example 1> (A) Synthesis of Polymer A-1 as Polyimide Precursor)
155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a 2 L separable flask, 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added and stirred at room temperature, and 81.5 g of pyridine was added while stirring to obtain a reaction mixture. After the heat generation due to the reaction had ceased, the mixture was allowed to cool to room temperature and left to stand for 16 hours.

Next, under ice cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring, followed by the addition of a suspension of 93.0 g of 4,4'-diaminodiphenyl ether (DADPE) suspended in 350 ml of γ-butyrolactone over 60 minutes while stirring. After further stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added and 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 liquid.

The resulting reaction solution was added to 3 liters of ethyl alcohol to produce a precipitate consisting 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 resulting crude polymer solution was dropped into 28 liters of water to precipitate the polymer, and the resulting precipitate was filtered off and then vacuum dried to obtain a powdered polymer (Polymer A-1). The molecular weight of Polymer A-1 was measured by gel permeation chromatography (standard polystyrene equivalent) to find that the weight average molecular weight (Mw) was 20,000.

<Production Example 2> (A) Synthesis of Polymer A-2 as Polyimide Precursor)
Polymer A-2 was obtained by carrying out a reaction in the same manner as in the above-mentioned Production Example 1, except that 147.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was used instead of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) in Production Example 1. The molecular weight of Polymer A-2 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 22,000.

<Production Example 3> (A) Synthesis of Polymer A-3 as Polyimide Precursor)
Polymer A-3 was obtained by carrying out a reaction in the same manner as in the above-mentioned Production Example 1, 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) in Production Example 1. The molecular weight of Polymer A-3 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 20,000.

<Production Example 4> (A) Synthesis of Polymer A-4 as Polyimide Precursor)
Polymer A-4 was obtained by carrying out a reaction in the same manner as in the above-mentioned Production Example 3, except that 109.1 g of pyromelotic dianhydride (PMDA) was used instead of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) in Production Example 3. The molecular weight of Polymer A-4 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 24,000.

<Production Example 5> (A) Synthesis of Polymer A-5 as Polyimide Precursor)
Polymer A-5 was obtained by carrying out a reaction in the same manner as in the above-mentioned Production Example 1, except that 77.5 g of 4,4'-oxydiphthalic dianhydride (ODPA) and 73.6 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) were used instead of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) in Production Example 1. The molecular weight of Polymer A-5 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 21,000.

<Production Example 6> (A) Synthesis of Polymer A-6 as Polyimide Precursor)
Polymer A-6 was obtained by carrying out a reaction in the same manner as in the above-mentioned Production Example 3, except that 77.5 g of 4,4'-oxydiphthalic dianhydride (ODPA) and 54.6 g of pyromelotic dianhydride (PMDA) were used instead of 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) in Production Example 3. The molecular weight of Polymer A-6 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 23,000.

<Production Example 7> (A) Synthesis of Polymer A-7 as Polyamide)
(Synthesis of phthalic acid compound-capped AIPA-MO)
Into a 5-liter separable flask, 543.5 g of 5-aminoisophthalic acid (hereinafter abbreviated as AIPA) and 1,700 g of N-methyl-2-pyrrolidone were placed, 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 using a dropping funnel, and the mixture was stirred 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), the reaction liquid was poured into 15 liters of ion-exchanged water, stirred, and allowed to stand. After waiting for the reaction product to crystallize and precipitate, it was filtered off, washed appropriately with water, and then vacuum dried at 40°C for 48 hours to obtain AIPA-MO in which the amino group of 5-aminoisophthalic acid and the isocyanate group of 2-methacryloyloxyethyl isocyanate had reacted. The low molecular weight GPC purity of the obtained AIPA-MO was approximately 100%.

(Synthesis of Polymer A-7)
In a separable flask with a capacity of 2 L, 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 charged and mixed, and cooled to 5 ° C. in an ice bath. To this, 125.0 g (0.606 mol) of dicyclohexylcarbodiimide (DCC) dissolved and diluted in 125 g of GBL was dropped over about 20 minutes under ice cooling, and then 103.16 g (0.28 mol) of 4,4'-bis(4-aminophenoxy)biphenyl {hereinafter referred to as BAPB.} dissolved in 168 g of NMP was dropped over about 20 minutes, and the mixture was stirred for 3 hours while maintaining the temperature below 5 ° C. in an ice bath, and then the ice bath was removed and the mixture was stirred at room temperature for 5 hours. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.

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

<Production Example 8> ((B) Synthesis of Compound B-1 as a Compound Represented by Chemical Formula (b1))
31.4 g (0.36 mol) of GBL and 67.3 g (1.46 mol) of ethanol were placed in a 100 ml one-neck flask and mixed. 0.1 g of para-toluenesulfonic acid monohydrate was added thereto and stirred at room temperature for 18 hours. The reaction product was confirmed by 1HNMR, and a reaction solution of compound B-1 containing 27.5 weight percent (27.2 g) of ethyl 4-hydroxybutyrate was obtained. The structure represented by chemical formula (b1) where n≧2 was not observed by 1HNMR.

<Production Example 9> ((B) Synthesis of Compound B-2 as a Compound Represented by Chemical Formula (b1))
Into a 100 ml one-neck flask, 85.0 g (0.99 mol) of GBL and 5 g of Solmix AP-1 (manufactured by Japan Alcohol Co., Ltd., a mixture of 85.5 mass percent ethanol, 13.4 mass percent isopropanol, and 1.1 mass percent methanol) were charged and mixed. 0.1 g of para-toluenesulfonic acid monohydrate was added thereto, and the mixture was stirred at room temperature for 24 hours. The reaction product was confirmed by 1HNMR, and a reaction solution of compound B-3 containing 9.2 weight percent (8.2 g) of a compound represented by chemical formula (b1) was obtained. From the mass fragments of the LC-MS measurement, it was confirmed that R1 was a methyl group, an ethyl group, or an isopropyl group, and that the compound was a compound represented by chemical formula (b1) with n=1 to 5.

Example 1
Using the polymer A-1, a negative photosensitive resin composition was prepared by the following method, and the prepared photosensitive resin composition was evaluated. 100 g of polymer A-1, which is a polyimide precursor, was dissolved in 100 g of GBL together with 0.03 g of reaction solution containing B-1 (0.008 g of B-1 component), 4 g of 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)-oxime (referred to as "PDO" in Table 1), 1.5 g of 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 10 g of N-phenyldiethanolamine, 4 g of methoxymethylated urea resin (MX-290), 8 g of tetraethylene glycol dimethacrylate, 1.5 g of N-phenyl-3-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.

The negative photosensitive resin composition was evaluated according to the method described above, and the results are shown in Table 1.

Example 2
Resin compositions were prepared in the same manner as in Example 1, except that 100 g of Polymer A-2, a polyimide precursor, was used in place of 100 g of Polymer A-1, a polyimide precursor in Example 1, and evaluations were performed in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 3
Resin compositions were prepared in the same manner as in Example 1, except that 100 g of Polymer A-1, which is a polyimide precursor in Example 1, was replaced with 100 g of Polymer A-3, which is a polyimide precursor, and evaluations were performed in the same manner as in Example 1. Table 1 shows the evaluation results.

Example 4
Resin compositions were prepared in the same manner as in Example 1, except that 100 g of Polymer A-1, which is a polyimide precursor in Example 1, was replaced with 100 g of Polymer A-4, which is a polyimide precursor, and evaluations were performed in the same manner as in Example 1. Table 1 shows the evaluation results.

Example 5
Resin compositions were prepared in the same manner as in Example 1, except that 100 g of Polymer A-1, which is a polyimide precursor in Example 1, was replaced with 100 g of Polymer A-5, which is a polyimide precursor, and evaluations were performed in the same manner as in Example 1. Table 1 shows the evaluation results.

Example 6
Resin compositions were prepared in the same manner as in Example 1, except that 100 g of Polymer A-1, which is a polyimide precursor in Example 1, was replaced with 100 g of Polymer A-6, which is a polyimide precursor, and evaluations were performed in the same manner as in Example 1. Table 1 shows the evaluation results.

Example 7
Resin compositions were prepared in the same manner as in Example 1, except that 100 g of Polymer A-1, which is a polyimide precursor, in Example 1 was replaced with 100 g of Polymer A-7, which is a polyamide, and the compositions were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 8
The 0.03 g (0.008 g B-1 component) of the reaction solution containing B-1 in Example 1 was changed to 0.087 g (0.008 g B-2 component) of the reaction solution containing B-2, and resin compositions were prepared in the same manner as in Example 1, and evaluations were performed in the same manner as in Example 1. The evaluation results are shown in Table 1.

<Example 9>
The 100 g of the polyimide precursor, Polymer A-1, in Example 8 was changed to 100 g of the polyimide precursor, Polymer A-3, and resin compositions were prepared in the same manner as in Example 1, and evaluations were performed in the same manner as in Example 1. Table 1 shows the evaluation results.

Example 10
The 0.03 g (0.008 g B-1 component) of the reaction liquid containing B-1 in Example 1 was changed to 0.018 g (0.005 g B-1 component) of the reaction liquid containing B-1, and resin compositions were prepared in the same manner as in Example 1, and evaluations were performed in the same manner as in Example 1. The evaluation results are shown in Table 1.

<Comparative Example 1>
Using the polymer A-1, a negative photosensitive resin composition was prepared by the following method, and the prepared photosensitive resin composition was evaluated. 100 g of polymer A-1, which is a polyimide precursor, was dissolved in 100 g of GBL together with 0.073 g of reaction solution containing B-1 (0.02 g of B-1 component), 4 g of 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)-oxime (referred to as "PDO" in Table 1), 1.5 g of 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 10 g of N-phenyldiethanolamine, 4 g of methoxymethylated urea resin (MX-290), 8 g of tetraethylene glycol dimethacrylate, 1.5 g of N-phenyl-3-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.
The negative photosensitive resin composition was evaluated according to the above-mentioned method, and the results are shown in Table 1.

<Comparative Example 2>
A resin composition was prepared in the same manner as in Comparative Example 1, except that 100 g of Polymer A-1, which is a polyimide precursor, in Comparative Example 1 was replaced with 100 g of Polymer A-2, which is a polyimide precursor, and each composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

<Comparative Example 3>
A resin composition was prepared in the same manner as in Comparative Example 1, except that 100 g of Polymer A-1, which is a polyimide precursor, in Comparative Example 1 was replaced with 100 g of Polymer A-3, which is a polyimide precursor, and each composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

<Comparative Example 4>
A resin composition was prepared in the same manner as in Comparative Example 1, except that 100 g of Polymer A-1, which is a polyimide precursor, in Comparative Example 1 was replaced with 100 g of Polymer A-4, which is a polyimide precursor, and each composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

<Comparative Example 5>
A resin composition was prepared in the same manner as in Comparative Example 1, except that 100 g of Polymer A-1, which is a polyimide precursor, in Comparative Example 1 was changed to 100 g of Polymer A-5, which is a polyimide precursor, and each composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

<Comparative Example 6>
A resin composition was prepared in the same manner as in Comparative Example 1, except that 100 g of Polymer A-1, which is a polyimide precursor, in Comparative Example 1 was changed to 100 g of Polymer A-6, which is a polyimide precursor, and each composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

<Comparative Example 7>
A resin composition was prepared in the same manner as in Comparative Example 1, except that 100 g of Polymer A-1, which is a polyimide precursor, in Comparative Example 1 was replaced with 100 g of Polymer A-7, which is a polyimide precursor, and each composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

As is clear from Table 1, in comparison with the comparative examples in which the compound (B) represented by chemical formula (b1) is contained in an amount of 0.01 parts by mass or more, the examples in which the compound is contained in an amount of less than 0.01 parts by mass exhibit less change in the color tone of the varnish over time.

The resin composition of the present invention can be suitably used, for example, as a surface protection film for semiconductor devices having copper patterns, multilayer wiring boards, etc., an interlayer insulating film, an insulating film for rewiring, a cover coat, and a solder resist film.

Claims (7)

Ingredients below:
(A) 100 parts by mass of at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamide, polyamideimide, and polyimide, which is a polyimide precursor;
(B) Chemical formula (b1):
(wherein R1's each independently represent 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 5),
(C) a photosensitizer: 0.5 to 30 parts by mass; and (D) a solvent;
The negative type photosensitive resin composition is characterized in that, in the compound (B) represented by chemical formula (b1), the total amount of the compounds where n=1 to 5 is 0.005 parts by mass or more and less than 0.01 parts by mass. The resin (A) is represented by the following general formula (1):
In the formula, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n ₁ is an integer from 2 to 150, and R ₁ and R ₂ are each independently a hydrogen atom or a group represented by the following general formula (2):
(wherein R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and m ₁ is an integer from 2 to 10), or a saturated aliphatic group having 1 to 4 carbon atoms.}; or 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, _Y2 is a divalent organic group having 6 to 35 carbon atoms, and may have the same structure or multiple 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 1,000.}
2. The negative type photosensitive resin composition according to claim 1, wherein the resin is at least one resin selected from the group consisting of polyamides having a structure represented by the following formula: The negative type photosensitive resin composition according to claim 1 or 2, wherein in the compound (B) represented by chemical formula (b1), R1 is a monovalent organic group of an alkyl group having 1 to 12 carbon atoms. The negative photosensitive resin composition according to any one of claims 1 to 3, wherein the (D) solvent is at least one selected from the group consisting 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 claims 1 to 4, wherein the (D) solvent contains an alcohol compound having 1 to 12 carbon atoms. (1) forming a photosensitive resin layer on a substrate by applying the photosensitive resin composition according to any one of claims 1 to 5 onto the substrate;
(2) exposing the photosensitive resin layer to light;
(3) developing the exposed photosensitive resin layer to form a relief pattern;
(4) A method for producing a cured film, comprising the step of heat-treating the relief pattern to form a cured relief pattern. (1) forming a photosensitive resin layer on a substrate by applying a varnish of the photosensitive resin composition according to any one of claims 1 to 5 onto the substrate;
(2) exposing the photosensitive resin layer to light;
(3) developing the exposed photosensitive resin layer to form a relief pattern;
(4) forming a hardened relief pattern by heat treating the relief pattern;
The method for producing a cured film, wherein the color tone of the varnish of the photosensitive resin composition is in the range from yellow to red.