JP6643824B2 - Photosensitive resin composition, method for producing cured relief pattern, and semiconductor device - Google Patents

Description

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

  2. Description of the Related Art Conventionally, a polyimide resin having excellent heat resistance, electrical properties, and mechanical properties has been used for an insulating material of an electronic component, a passivation film, a surface protection film, an interlayer insulating film, and the like of a semiconductor device. Among the polyimide resins, those provided in the form of a photosensitive polyimide precursor are easily coated with the precursor, exposed to light, developed, and thermally imidized by curing to easily form a heat-resistant relief pattern film. be able to. Such a photosensitive polyimide precursor has a feature that the process can be significantly shortened as compared with a conventional non-photosensitive polyimide.

  On the other hand, in recent years, the method of mounting a semiconductor device on a printed wiring board has also changed from the viewpoint of improving the degree of integration and functions and reducing the chip size. From the conventional mounting method using metal pins and lead-tin eutectic solder, polyimide coating directly contacts solder bumps, such as BGA (ball gripped array) and CSP (chip size packaging), which allow higher density mounting. The use of such a structure has been increasing. When forming such a bump structure, the coating is required to have high heat resistance and chemical resistance. A method of improving the heat resistance of a polyimide coating or a polybenzoxazole coating by adding a thermal crosslinking agent to a composition containing a polyimide precursor or a polybenzoxazole precursor is disclosed (for example, see Patent Document 1). .

JP 2003-287889 A

  However, with the sophistication of functions required for semiconductor chips, the number of input / output terminals mounted on a semiconductor package has increased, and there has been a problem that all terminals cannot be mounted on a small-area CSP. To address this problem, a fan-out CSP has been proposed. This fan-out CSP has a necessary terminal by providing an extended portion around the semiconductor chip with a material such as epoxy resin, performing rewiring from the electrode on the semiconductor chip to the extended portion, and mounting a solder ball on the extended portion. This is a semiconductor package with a sufficient number. As for the substrate used in the fan-out CSP, a technique using a large-sized square panel substrate has been spread from the viewpoint of cost. Since the substrate size of this substrate is much larger than that of a conventional Si wafer, the spin coating method of rotating and applying the substrate has been difficult.

  The present invention has been devised in view of such conventional circumstances, a non-spin (bar coating, slit coating, etc.) photosensitive resin composition suitable for coating method, polyimide using the photosensitive resin composition An object of the present invention is to provide a method for manufacturing a cured relief pattern for forming a pattern and a semiconductor device.

｛式中、Ｘ_１は、４価の有機基であり、Ｙ_１は、２価の有機基であり、ｎは、２〜１５０の整数であり、Ｒ_１及びＲ_２は、それぞれ独立に、水素原子、下記一般式（２）：

（式中、Ｒ_３、Ｒ_４及びＲ_５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ｍ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。但し、Ｒ_１及びＲ_２は、同時に水素原子であることはない。｝で表される繰り返し単位を有するポリイミド前駆体：１００質量部、
（Ｂ）光重合開始剤：該（Ａ）ポリイミド前駆体１００質量部を基準として１質量部以上２０質量部以下、
（Ｃ）大気圧下における沸点が１８０℃以上である有機溶媒、並びに、
（Ｄ）大気圧下における沸点が１３０℃以上１６０℃以下である有機溶媒：該（Ａ）ポリイミド前駆体１００質量部を基準として有機溶媒全量が３００〜６００質量部、を含み、
前記溶媒は、(Ｃ)成分の含有量が有機溶媒全量に対して６０重量%以上９０重量％以下であり、（Ｄ）成分の含有量が有機溶媒全量に対して１０重量%以上４０%重量以下であり、
２３℃における粘度が０．５Ｐ以上４０Ｐ以下であることを特徴とする、ノンスピンコート用の感光性樹脂組成物。
［２］
（Ａ）下記一般式（１）：

｛式中、Ｘ _１ は、４価の有機基であり、Ｙ _１ は、２価の有機基であり、ｎは、２〜１５０の整数であり、Ｒ _１ 及びＲ _２ は、それぞれ独立に、水素原子、下記一般式（２）：

（式中、Ｒ _３ 、Ｒ _４ 及びＲ _５ 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ｍ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。但し、Ｒ _１ 及びＲ _２ は、同時に水素原子であることはない。｝で表される繰り返し単位を有するポリイミド前駆体：１００質量部、
（Ｂ）光重合開始剤：該（Ａ）ポリイミド前駆体１００質量部を基準として１質量部以上２０質量部以下、
（Ｃ）大気圧下における沸点が１８０℃以上である有機溶媒、並びに、
（Ｄ）大気圧下における沸点が１３０℃以上１６０℃以下である有機溶媒：該（Ａ）ポリイミド前駆体１００質量部を基準として有機溶媒全量が３００〜６００質量部、を含み、
前記溶媒は、(Ｃ)成分の含有量が有機溶媒全量に対して６０重量%以上９０重量％以下であり、（Ｄ）成分の含有量が有機溶媒全量に対して１０重量%以上４０%重量以下であり、
２３℃における粘度が０．５Ｐ以上２０Ｐ未満であることを特徴とする、ノンスピンコート用の感光性樹脂組成物。
［３］
前記溶媒は、(Ｃ)成分がＮ−メチル−２−ピロリドンまたはγ−ブチロラクトンであり、（Ｄ）成分が乳酸エチルである、［１］または［２］に記載の感光性樹脂組成物。
［４］
（Ａ）下記一般式（１）：

｛式中、Ｘ _１ は、４価の有機基であり、Ｙ _１ は、２価の有機基であり、ｎは、２〜１５０の整数であり、Ｒ _１ 及びＲ _２ は、それぞれ独立に、水素原子、下記一般式（２）：

（式中、Ｒ _３ 、Ｒ _４ 及びＲ _５ 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ｍ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。但し、Ｒ _１ 及びＲ _２ は、同時に水素原子であることはない。｝で表される繰り返し単位を有するポリイミド前駆体：１００質量部、
（Ｂ）光重合開始剤：該（Ａ）ポリイミド前駆体１００質量部を基準として１質量部以上２０質量部以下、
（Ｃ）大気圧下における沸点が１８０℃以上である有機溶媒、並びに、
（Ｄ）大気圧下における沸点が１３０℃以上１６０℃以下である有機溶媒：該（Ａ）ポリイミド前駆体１００質量部を基準として有機溶媒全量が３００〜６００質量部、を含み、
前記溶媒は、(Ｃ)成分の含有量が有機溶媒全量に対して６０重量%以上９０重量％以下であり、（Ｄ）成分の含有量が有機溶媒全量に対して１０重量%以上４０%重量以下であり、
２３℃における粘度が０．５Ｐ以上４０Ｐ以下である、ノンスピンコート用の感光性樹脂組成物を、ノンスピン塗布を用いて基板に塗布し、塗布膜を形成する工程、および、
前記塗布膜を乾燥する工程を含むことを特徴とする、感光性樹脂膜の製造方法。
［５］
以下の：
（１）［１］〜［３］のいずれかに記載の感光性樹脂組成物を基板上にノンスピン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と、
を含むことを特徴とする、硬化レリーフパターンの製造方法。
［６］
［５］に記載の硬化レリーフパターンの製造方法を有することを特徴とする、半導体装置の製造方法。
The present inventors have optimized a combination of organic solvents having specific characteristics and a solvent content to form a cured film having a uniform film thickness in non-spin coating, having no defects in the film, and having no coating unevenness like citron skin. It was found that a photosensitive resin composition giving the following was obtained, and the present invention was completed. That is, the present invention is as follows.
[1]
(A) The following general formula (1):

In the formula, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n is an integer of _{2 to} 150, and R ₁ and R ₂ are each independently Hydrogen atom, 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 is an integer of 2 to 10). A valent organic group or a saturated aliphatic group having 1 to 4 carbon atoms. However, R ₁ and R ₂ are not hydrogen atoms at the same time. Polyimide precursor having a repeating unit represented by｝: 100 parts by mass,
(B) a photopolymerization initiator: 1 to 20 parts by mass based on 100 parts by mass of the (A) polyimide precursor;
(C) an organic solvent having a boiling point of 180 ° C. or higher under atmospheric pressure, and
(D) an organic solvent having a boiling point of 130 ° C. or more and 160 ° C. or less at atmospheric pressure: (A) a total amount of 300 to 600 parts by mass of the organic solvent based on 100 parts by mass of the polyimide precursor;
In the solvent, the content of the component (C) is 60% by weight or more and 90% by weight or less based on the total amount of the organic solvent, and the content of the component (D) is 10% by weight or more and 40% by weight based on the total amount of the organic solvent. Is the following,
A photosensitive resin composition for non-spin coating, wherein the viscosity at 23 ° C. is 0.5 P or more and 40 P or less.
[2]
(A) The following general formula (1):

In the formula, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n is an integer of _{2 to} 150, and R ₁ and R ₂ are each independently Hydrogen atom, 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 is an integer of 2 to 10). A valent organic group or a saturated aliphatic group having 1 to 4 carbon atoms. However, R ₁ and R ₂ are not hydrogen atoms at the same time. Polyimide precursor having a repeating unit represented by｝: 100 parts by mass,
(B) a photopolymerization initiator: 1 to 20 parts by mass based on 100 parts by mass of the (A) polyimide precursor;
(C) an organic solvent having a boiling point of 180 ° C. or higher under atmospheric pressure, and
(D) an organic solvent having a boiling point under atmospheric pressure of 130 ° C. or more and 160 ° C. or less: (A) a total amount of 300 to 600 parts by mass of the organic solvent based on 100 parts by mass of the polyimide precursor,
In the solvent, the content of the component (C) is 60% by weight or more and 90% by weight or less based on the total amount of the organic solvent, and the content of the component (D) is 10% by weight or more and 40% by weight based on the total amount of the organic solvent. Is the following,
A photosensitive resin composition for non-spin coating, wherein the viscosity at 23 ° C. is 0.5 P or more and less than 20 P.
[3]
The photosensitive resin composition according to [1] or [2], wherein the component (C) is N-methyl-2-pyrrolidone or γ-butyrolactone, and the component (D) is ethyl lactate.
[4]
(A) The following general formula (1):

In the formula, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n is an integer of _{2 to} 150, and R ₁ and R ₂ are each independently Hydrogen atom, 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 is an integer of 2 to 10). A valent organic group or a saturated aliphatic group having 1 to 4 carbon atoms. However, R ₁ and R ₂ are not hydrogen atoms at the same time. Polyimide precursor having a repeating unit represented by｝: 100 parts by mass,
(B) a photopolymerization initiator: 1 to 20 parts by mass based on 100 parts by mass of the (A) polyimide precursor;
(C) an organic solvent having a boiling point of 180 ° C. or higher under atmospheric pressure, and
(D) an organic solvent having a boiling point under atmospheric pressure of 130 ° C. or more and 160 ° C. or less: (A) a total amount of 300 to 600 parts by mass of the organic solvent based on 100 parts by mass of the polyimide precursor,
In the solvent, the content of the component (C) is 60% by weight or more and 90% by weight or less based on the total amount of the organic solvent, and the content of the component (D) is 10% by weight or more and 40% by weight based on the total amount of the organic solvent. Is the following,
A step of applying a photosensitive resin composition for non-spin coating having a viscosity at 23 ° C. of 0.5 P or more and 40 P or less to a substrate using non-spin coating to form a coating film; and
A method for producing a photosensitive resin film, comprising a step of drying the coating film.
[5]
below:
(1) a step of forming the photosensitive resin layer on the substrate by applying the photosensitive resin composition according to any one of [1] to [3] on the substrate by non-spin coating;
(2) exposing the photosensitive resin layer to light;
(3) developing the photosensitive resin layer after the exposure to form a relief pattern;
(4) a step of forming a cured relief pattern by heat-treating the relief pattern;
A method for producing a cured relief pattern, comprising:
[6]
[5] and having a method for manufacturing a cured relief pattern according to method of manufacturing a semiconductor device.

  According to the present invention, in the photosensitive resin composition, by optimizing the combination and the solvent content of an organic solvent having specific characteristics, the film thickness is uniform and non-defective in non-spin coating, and it has a yuzu texture. It is possible to obtain a photosensitive resin composition that provides a cured film without coating unevenness, and to provide a method for producing a cured relief pattern for forming a polyimide pattern using the photosensitive resin composition and a semiconductor device. it can.

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

｛式中、Ｘ₁は、４価の有機基であり、Ｙ₁は、２価の有機基であり、ｎ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、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ｍ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。但し、Ｒ₁及びＲ₂の両者が同時に水素原子であることはない。｝で表される構造を有するポリイミド前駆体（以下、（Ａ）ポリイミド前駆体ともいう）：１００質量部、（Ｂ）光重合開始剤：１〜２０質量部、（Ｃ）大気圧下における沸点が１８０℃以上の有機溶媒、並びに（Ｄ）大気圧下における沸点が１３０℃以上１６０℃以下の有機溶媒：１８５〜６００質量部を必須成分とする。 <Photosensitive resin composition>
The present invention provides (A) the following general formula (1):

In the formula, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n is an integer of _{2 to} 150, and R ₁ and R ₂ are each independently: Hydrogen atom, 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 is an integer of 2 to 10). A valent organic group or a saturated aliphatic group having 1 to 4 carbon atoms. However, R ₁ and R ₂ are not both hydrogen atoms at the same time. Polyimide precursor having the structure represented by｝ (hereinafter also referred to as (A) polyimide precursor): 100 parts by mass, (B) photopolymerization initiator: 1 to 20 parts by mass, (C) boiling point under atmospheric pressure And 185 to 600 parts by mass of an organic solvent having a boiling point of 130 ° C. or more and 160 ° C. or less under atmospheric pressure.

(A) Polyimide precursor (A) The polyimide precursor used in the present invention will be described. (A) The polyimide precursor is a resin component in the photosensitive resin composition of the present invention, and is a polyamide having a structure represented by the general formula (1). (A) The polyimide precursor is converted to polyimide by subjecting it to a cyclization treatment (for example, 200 ° C. or higher).

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（５）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好ましい。 In the general formula (1), the tetravalent organic group represented by X ₁ is preferably an organic group having 6 to 40 carbon atoms, more preferably from the viewpoint of achieving both heat resistance and photosensitive characteristics. , A —COOR ₁ group, a —COOR ₂ group, and a —CONH— group are an aromatic group or an alicyclic aliphatic group which are ortho to each other. As the tetravalent organic group represented by X ₁ , more preferably, the following formula (5):

However, the present invention is not limited thereto. The structure of X ₁ may be one type or a combination of two or more types. The X ₁ group having the structure represented by the above formula (5) is preferable in terms of achieving both heat resistance and photosensitive characteristics.

で表される構造、及び下記式（７）：

｛式中、Ａは、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（６）及び（７）で表される構造を有するＹ₁基は、耐熱性と感光特性とを両立するという点で好ましい。 In the general formula (1), the divalent organic group represented by Y ₁ is preferably an aromatic group having 6 to 40 carbon atoms from the viewpoint of achieving both heat resistance and photosensitive characteristics. The following equation (6):

And the following formula (7):

{Wherein, A represents a methyl group (-CH _3), ethyl group (-C ₂ H _5), propyl (-C ₃ H ₇₎ or butyl group (-C ₄ H _9). ｝
However, the present invention is not limited thereto. The structure of Y ₁ may be one type or a combination of two or more types. The Y ₁ group having a structure represented by the above formulas (6) and (7) is preferable in terms of achieving both heat resistance and photosensitive characteristics.

Regarding R ₁ and R ₂ , R ₃ in the above general formula (2) is preferably a hydrogen atom or a methyl group, and R ₄ and R ₅ are preferably hydrogen atoms from the viewpoint of photosensitive characteristics. M is 2 or more and 10 or less, preferably 2 or more and 4 or less from the viewpoint of photosensitive characteristics.

[(A) Preparation method of polyimide precursor]
(A) In the polyimide precursor, the structure represented by the general formula (1) may be, for example, first, a tetracarboxylic dianhydride containing the tetravalent organic group X ₁ and a photopolymerizable unsaturated An alcohol having a double bond and optionally a saturated aliphatic alcohol having 1 to 4 carbon atoms are reacted to prepare a partially esterified tetracarboxylic acid (hereinafter also referred to as acid / ester). Thereafter, the obtained acid / ester compound and the diamine containing the above-mentioned divalent organic group Y ₁ are subjected to amide polycondensation.

(Preparation of acid / ester)
In the present invention, examples of the tetracarboxylic dianhydride containing a tetravalent organic group X ₁ which is preferably used for preparing the polyimide precursor (A) include, for example, pyromellitic anhydride, diphenyl ether-3,3 ', 4,4'-tetracarboxylic dianhydride, benzophenone-3,3', 4,4'-tetracarboxylic dianhydride, biphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride Product, 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, and the like, but are not limited thereto. Not something. These can be used alone, or two or more of them may be used in combination.

In the present invention, (A) alcohols having a photopolymerizable unsaturated double bond suitably used for preparing a polyimide precursor include, for example, 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-cyclohexyloxypropyl acrylate, 2-methacryloyloxyethyl alcohol , 1-methacryloyloxy-3-propyl alcohol, 2-methacrylamidoethyl alcohol, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2- Examples thereof include hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, and 2-hydroxy-3-cyclohexyloxypropyl methacrylate.
For example, methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol and the like may be partially mixed and used as the above-mentioned alcohols as a saturated aliphatic alcohol having 1 to 4 carbon atoms.

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

As the reaction solvent, those which completely dissolve the acid / ester compound and the polyimide precursor which is an amide polycondensation product of the acid / ester compound and the diamine component are preferable. For example, N-methyl-2-pyrrolidone, N, N -Dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, tetramethylurea, gamma-butyrolactone and the like.
Other reaction solvents include ketones, esters, lactones, ethers, halogenated hydrocarbons, and hydrocarbons such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, and butyl acetate. , Diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene, xylene and the like. These may be used alone or as a mixture of two or more, if necessary.

(Preparation of polyimide precursor)
The above acid / ester (typically a solution in the above reaction solvent) is added to a suitable dehydration condensing agent such as dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline under ice-cooling. 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N, N′-disuccinimidyl carbonate and the like were added and mixed to convert the acid / ester into a polyanhydride. A diamine containing a divalent organic group Y ₁ suitably used in the present invention is separately added to a solvent by dissolving or dispersing the diamine in a solvent, and the desired polyimide precursor can be obtained by polycondensation with amide. it can.
Examples of the diamine containing a divalent organic group Y ₁ preferably used in the present invention include, for example, p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3'-diaminodiphenylether, 4,4'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone 3,3′-diaminodiphenylsulfone, 4,4′-diaminobiphenyl, 3,4′-diaminobiphenyl, 3,3′-diaminobiphenyl, 4,4′-diaminobenzophenone, 3,4′-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenyl Methane, 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-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 these In which a part of the hydrogen atoms on the benzene ring has been substituted with a methyl group, an ethyl group, a hydroxymethyl group, a hydroxyethyl group, a halogen or the like, for example, 3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-di Butyl-4,4′-diaminodiphenylmethane, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 3,3′-dichloro-4,4′-diaminobiphenyl, and mixtures thereof. However, the present invention is not limited to this.

  In addition, for the purpose of improving the adhesion between the photosensitive resin layer formed on the substrate and the various types of substrates by applying the photosensitive resin composition of the present invention onto the substrate, (A) the preparation of the polyimide precursor And diaminosiloxanes such as 1,3-bis (3-aminopropyl) tetramethyldisiloxane and 1,3-bis (3-aminopropyl) tetraphenyldisiloxane.

  After completion of the amide polycondensation reaction, the water-absorbing by-product of the dehydration condensing agent coexisting in the reaction solution is filtered off as necessary, and then a poor solvent such as water, an aliphatic lower alcohol, or a mixture thereof is removed. , Into the obtained polymer component, to precipitate the polymer component, further, by re-dissolving, repeating the re-precipitation precipitation operation, etc., to purify the polymer, vacuum-dried, the desired polyimide precursor Isolate. To improve the degree of purification, the solution of the polymer may be passed through a column packed by swelling an anion and / or cation exchange resin with a suitable organic solvent to remove ionic impurities.

  (A) The molecular weight of the polyimide precursor is preferably from 8,000 to 150,000, and more preferably from 9,000 to 50,000, as measured by weight average molecular weight in terms of polystyrene by gel permeation chromatography. Is more preferred. When the weight average molecular weight is 8,000 or more, mechanical properties are good, and when it is 150,000 or less, dispersibility in a developing solution is good, and the resolution performance of a relief pattern is good. Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as developing solvents for gel permeation chromatography. The molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. It is recommended that the standard monodisperse polystyrene be selected from STANDARD SM-105, an organic solvent-based standard sample manufactured by Showa Denko KK.

(B) Photopolymerization initiator (B) The photopolymerization initiator used in the present invention will be described. As the photopolymerization initiator (B), a compound conventionally used as a photopolymerization initiator for UV curing can be arbitrarily selected. (B) Compounds that can be suitably used as a photopolymerization initiator include, for example, benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenylketone, dibenzylketone, and fluorenone; 2′-Diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, acetophenone derivatives such as 1-hydroxycyclohexylphenyl ketone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, thioxanthone derivatives such as diethylthioxanthone, benzyl, Benzyl derivatives such as benzyldimethyl ketal and benzyl-β-methoxyethyl acetal, benzoin derivatives such as benzoin and benzoin methyl ether, 1-phenyl-1,2-butanedione- 2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) Oxime, 1-phenyl-1,2-propanedione-2- (o-benzoyl) oxime, 1,3-diphenylpropanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrione- Preferred examples include oximes such as 2- (o-benzoyl) oxime, N-arylglycines such as N-phenylglycine, peroxides such as benzoyl perchloride, and aromatic biimidazoles, but are not limited thereto. It is not something to be done. In using these, one kind or a mixture of two or more kinds may be used. Among the above photopolymerization initiators, oximes are more preferable, particularly from the viewpoint of photosensitivity.

  The compounding amount of the photopolymerization initiator (B) is 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the polyimide precursor (A), and 2 parts by mass or more and 15 parts by mass or less from the viewpoint of photosensitivity characteristics. preferable. By blending the photopolymerization initiator in an amount of 1 part by mass or more with respect to 100 parts by mass of the polyimide precursor (A), excellent photosensitivity is obtained.

(C) Organic solvent having a boiling point of 180 ° C. or more under atmospheric pressure The (C) organic solvent having a boiling point of 180 ° C. or more under atmospheric pressure used in the present invention will be described.
(C) By using an organic solvent having a boiling point of 180 ° C. or more under atmospheric pressure, it is possible to obtain a cured film having a uniform film thickness after drying and having no yuzu-skin-like coating unevenness. When an organic solvent having a boiling point of 180 ° C. or more at atmospheric pressure is used, the solvent can be volatilized after sufficient leveling and formation of a film, so that the film thickness is excellent in uniformity. In addition, since the drying speed is slow, it is possible to suppress coating unevenness such as citron skin.
As the solvent, it is preferable to use a polar organic solvent from the viewpoint of solubility in the polyimide precursor (A). Specific examples include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylsulfoxide, γ-butyrolactone, 1,3-dimethyl-2-imidazolinone, and the like, alone or in combination of two or more. Can be used in combination. From the viewpoint of storage stability of the photosensitive resin composition, N-methyl-2-pyrrolidone or γ-butyrolactone is preferred.

  In the present invention, the content of the component (C) is from 60% by weight to 90% by weight based on the total amount of the organic solvent. Preferably it is 70% by weight or more and 85% by weight. When the content is 60% by weight or more with respect to the total amount of the organic solvent, a cured film having uniform film thickness and uniform coating can be obtained. On the other hand, when the content of the component (C) is 90% by weight or less, since the content of the component (D) described later is relatively 10% by weight or more, a cured film having no film defect may be obtained. I can do it.

(D) Organic solvent having a boiling point of 130 ° C. or more and 160 ° C. or less under atmospheric pressure The (D) organic solvent having a boiling point of 130 ° C. or more and 160 ° C. or less under atmospheric pressure used in the invention will be described.
(C) In addition to an organic solvent having a boiling point under atmospheric pressure of 180 ° C. or higher and (D) an organic solvent having a boiling point of 130 ° C. or higher and 160 ° C. or lower under atmospheric pressure, a cured film having no film defects can be obtained. You can get it. When an organic solvent having a boiling point of 130 ° C. or more and 160 ° C. or less under atmospheric pressure is used, the solvent is easily volatilized after application, so that repelling of the base can be suppressed, and a cured film having no film defects after drying can be obtained. Can be done. On the other hand, when an organic solvent having a boiling point of 130 ° C. or less under atmospheric pressure is used, the solubility of the component (A) is reduced, and the component may be precipitated.

  In the present invention, the content of the component (D) is from 10% by weight to 40% by weight based on the total amount of the organic solvent. Preferably it is 15% by weight or more and 30% by weight. When the content is 10% by weight or more with respect to the total amount of the organic solvent, a cured film without film defects can be obtained. On the other hand, when the content of the component (D) is 40% by weight or less, it is possible to obtain a cured film having a uniform film thickness and having no yuzu-skin-like coating unevenness.

  As the solvent, a solvent containing an alcohol is preferable from the viewpoint of improving the storage stability of the photosensitive resin composition. Specific examples include lactic acid esters such as ethyl lactate, propylene glycol monoalkyl ethers such as propylene glycol monoethyl ether, and monoalcohols such as ethylene glycol ethyl ether and ethylene glycol-n-propyl ether. Particularly, ethyl lactate is more preferable.

  The total amount of the organic solvents of the components (C) and (D) is 185 parts by mass or more and 600 parts by mass or less based on 100 parts by mass of the polyimide precursor (A). Preferably it is 300 parts by mass or more and 450 parts by mass or less. When the amount of the organic solvent is 185 parts by mass or more and the viscosity is 40 P or less, the photosensitive resin composition can be applied thickly, so that the film thickness is excellent in uniformity. On the other hand, when the content is 600 parts by mass or less and the viscosity is 0.5 P or more, the photosensitive resin composition can be applied thinly, so that the flow inside the coating film hardly occurs, and the coating unevenness like citron skin is generated. Does not occur.

  The photosensitive resin composition of the present invention may further contain a resin component other than the (A) polyimide precursor described above. Examples of the resin component that can be contained include polyimide, polyoxazole, polyoxazole precursor, phenol resin, polyamide, epoxy resin, siloxane resin, and acrylic resin. The compounding amount of these resin components is preferably in the range of 0.01 to 20 parts by mass based on 100 parts by mass of the polyimide precursor (A).

In addition, a sensitizer can be optionally added to the photosensitive resin composition of the present invention in order to improve photosensitivity. Examples of the sensitizer 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-dimethylaminocinna Mylidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylbiphenylene) -benzothiazole, 2- (p-dimethylaminophenylvinylene) benzothiazole, 2- (p-dimethylaminophenylvinylene) Isonaphthothiazole, 1,3-bis (4′-dimethyl Aminobenzal) acetone, 1,3-bis (4'-diethylaminobenzal) acetone, 3,3'-carbonyl-bis (7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7 -Dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N- Phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-f Nyl-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 combination of, for example, 2 to 5 types.
When the photosensitive resin composition contains a sensitizer for improving photosensitivity, the compounding amount is preferably 0.1 to 25 parts by mass based on 100 parts by mass of the polyimide precursor (A).

Further, in the photosensitive resin composition of the present invention, a monomer having a photopolymerizable unsaturated bond can be arbitrarily compounded in order to improve the resolution of the relief pattern. As such a monomer, a (meth) acrylic compound which undergoes a radical polymerization reaction by a photopolymerization initiator is preferable, and is not particularly limited to, but ethylene glycol such as diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate may be used. Or mono or diacrylate and methacrylate of polyethylene glycol, mono or diacrylate and methacrylate of propylene glycol or polypropylene glycol, mono, di or triacrylate and methacrylate of glycerol, cyclohexane diacrylate and dimethacrylate, di of 1,4-butanediol Acrylate and dimethacrylate, diacrylate and dimethacrylate of 1,6-hexanediol, and neopentyl glycol Acrylate and dimethacrylate, bisphenol A mono or diacrylate and methacrylate, benzenetrimethacrylate, isobornyl acrylate and methacrylate, acrylamide and its derivatives, methacrylamide and its derivatives, trimethylolpropane triacrylate and methacrylate, glycerol di or tri Acrylates and methacrylates, pentaerythritol di, tri, or tetraacrylates and methacrylates, and compounds such as ethylene oxide or propylene oxide adducts of these compounds may be mentioned.
When the photosensitive resin composition contains the above-mentioned monomer having a photopolymerizable unsaturated bond for improving the resolution of the relief pattern, the compounding amount is (A) 100 parts by mass of the polyimide precursor. Preferably it is 1 to 50 parts by mass.

Further, an adhesion aid can be arbitrarily compounded for improving the adhesion between a film formed using the photosensitive resin composition of the present invention and a substrate. Examples of the adhesion assistant include γ-aminopropyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, Methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N- (3-diethoxymethylsilylpropyl) succinimide , N- [3- (triethoxysilyl) propyl] phthalamic acid, benzophenone-3,3'-bis (N- [3-triethoxysilyl] propylamide) -4,4'-dicarboxylic acid, benzene-1, 4-bis (N- [3-triet Silicyl] propylamido) -2,5-dicarboxylic acid, 3- (triethoxysilyl) propylsuccinic anhydride, a silane coupling agent such as N-phenylaminopropyltrimethoxysilane, and aluminum tris (ethylacetoacetate); Aluminum-based adhesion aids such as aluminum tris (acetylacetonate) and ethyl acetoacetate aluminum diisopropylate are exemplified.
Among these adhesion assistants, it is more preferable to use a silane coupling agent from the viewpoint of adhesive strength. When the photosensitive resin composition contains the adhesion aid, the compounding amount is preferably in the range of 0.5 to 25 parts by mass based on 100 parts by mass of the polyimide precursor (A).

In addition, the photosensitive resin composition of the present invention may optionally include a thermal polymerization inhibitor to improve the stability of the viscosity and photosensitivity of the photosensitive resin composition particularly when stored in a solution containing a solvent. Can be blended. Examples of the thermal polymerization inhibitor 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, N-nitroso-N (1-naphthyl) hydroxylamine ammonium salt and the like are used.
The blending amount of the thermal polymerization inhibitor when blended in the photosensitive resin composition is preferably in the range of 0.005 to 12 parts by mass based on 100 parts by mass of the polyimide precursor (A).

  Further, the photosensitive resin composition of the present invention may optionally contain a crosslinking agent. The cross-linking agent can crosslink the polyimide precursor (A) when the relief pattern formed using the photosensitive resin composition of the present invention is heated and cured, or the cross-linking agent itself can form a cross-linked network. Can be an agent. The crosslinking agent can further enhance the heat resistance and chemical resistance of the cured film formed from the photosensitive resin composition. As the cross-linking agent, amino resins and derivatives thereof are preferably used. Among them, urea resins, glycol urea resins, hydroxyethylene urea resins, melamine resins, benzoguanamine resins, and derivatives thereof are preferably used. Particularly preferred are an alkoxymethylated urea compound and an alkoxymethylated melamine compound. ).

  In consideration of various properties other than heat resistance and chemical resistance, the amount of the photosensitive resin composition when the photosensitive resin composition contains a crosslinking agent is 0.5 to 20 parts by mass based on 100 parts by mass of the polyimide precursor (A). Parts, more preferably 2 to 10 parts by mass. When the amount is 0.5 part by mass or more, good heat resistance and chemical resistance are exhibited, and when the amount is 20 parts by mass or less, storage stability is excellent.

  Further, the photosensitive resin composition of the present invention may contain an organic titanium compound as a compound for improving chemical resistance. The organic titanium compound that can be used here is not particularly limited as long as an organic chemical substance is bonded to a titanium atom through a covalent bond or an ionic bond.

Specific examples of the organic titanium compound are shown in the following I) to VII):
I) Titanium chelate compound: Above all, a titanium chelate having two or more alkoxy groups is more preferable because the stability of the composition and a good pattern can be obtained. Specifically, titanium bis (triethanolamine) diisopro Oxide, titanium di (n-butoxide) bis (2,4-pentanedionate), titanium diisopropoxide bis (2,4-pentanedionate), titanium diisopropoxide bis (tetramethylheptane dionate), Titanium diisopropoxide bis (ethyl acetoacetate).

  II) Tetraalkoxytitanium compound: 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-noniloxide), titanium tetra (n-propoxide), titanium tetrastearyloxide, titanium tetrakis [bis 2,2- (allyloxymethyl) Butoxide｝] and the like.

III) Titanocene compounds: for example, pentamethylcyclopentadienyltitanium trimethoxide, bis (η ⁵ -2,4-cyclopentadien-1-yl) bis (2,6-difluorophenyl) titanium, bis (η ^5- 2,4-cyclopentadien-1-yl) bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium and the like.
IV) Monoalkoxy titanium compound: For example, titanium tris (dioctyl phosphate) isopropoxide, titanium tris (dodecylbenzenesulfonate) isopropoxide and the like.

V) Titanium oxide compound: For example, titanium oxide bis (pentanedionate), titanium oxide bis (tetramethylheptanedionate), phthalocyanine titanium oxide and the like.
VI) Titanium tetraacetylacetonate compound: For example, titanium tetraacetylacetonate and the like.
VII) Titanate coupling agent: for example, isopropyl tridodecylbenzenesulfonyl titanate.

Among them, at least one compound selected from the group consisting of the above-mentioned I) titanium chelate compound, II) tetraalkoxytitanium compound, and III) titanocene compound is preferable from the viewpoint of exhibiting more chemical resistance.
The addition amount of these organic titanium compounds is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the polyimide precursor (A). If the addition amount is 0.05 parts by weight or more, desired heat resistance or chemical resistance is exhibited, while if it is 10 parts by weight or less, storage stability is excellent.

When a substrate made of copper or a copper alloy is used, for example, an azole compound or a purine derivative can be arbitrarily compounded in order to suppress discoloration on copper. As the azole compound, 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, hydroxyphenyl Triazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5- Bis (α, α-dimethylben (Zyl) phenyl] -benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -benzotriazole , 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 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-tetrazo Le, 1-methyl -1H- tetrazole, and the like. Particularly preferred are tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole.
Purine derivatives include purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-methyl Adenine, N-methyladenine, N, N-dimethyladenine, 2-fluoroadenine, 9- (2-hydroxyethyl) adenine, guanine oxime, N- (2-hydroxyethyl) adenine, 8-aminoadenine, 6-amino -8-phenyl-9H-purine, 1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine, N-methylguanine, 7- (2-hydroxyethyl) guanine, N- (3-chlorophenyl) guanine, N -(3-ethylphenyl) guanine, 2-azaadenine, 5-azaadenine, 8-azaadenine, 8- Azaguanine, 8-azapurine, 8-azaxanthine, 8-azahypoxanthine and the like can be mentioned. Particularly preferred are 8-azaadenine and 8-azaguanine.

  These azole compounds or purine derivatives may be used alone or in a mixture of two or more. When the photosensitive resin composition contains the azole compound, the compounding amount is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the polyimide precursor (A). 0.5-5 mass parts is more preferred. When the compounding amount of the azole compound or the purine derivative with respect to 100 parts by mass of the polyimide precursor (A) is 0.1 part by mass or more, when the photosensitive resin composition of the present invention is formed on copper or a copper alloy, Discoloration of the surface of the copper or copper alloy is suppressed. On the other hand, when the amount is 10 parts by mass or less, the photosensitivity is excellent.

  Further, a hindered phenol compound can be arbitrarily compounded to suppress discoloration on copper. 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-tert-butyl-4-hydroxyphenyl) propionate, 4,4′-methylenebis (2,6-di-tert-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-tert-butyl-4-hydroxyphene) L) 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) -isocyanate Nurate, 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-ethyl Propyl) -3-hydroxy-2,6-dimethylbenzyl] -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris [4-triethyl Methyl-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) -tri 1,3,5-tris (4-tert-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-tert-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) - but trione, etc., but is 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 and the like are particularly preferred.

  The compounding amount of the hindered phenol compound is preferably 0.1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the polyimide precursor (A), and is 0.5 part by mass or more and 10 parts by mass or less from the viewpoint of photosensitivity characteristics. More preferably, the amount is not more than part by mass. When the amount of the hindered phenol compound is 0.1 parts by mass or more based on 100 parts by mass of the polyimide precursor (A), for example, when the photosensitive resin composition of the present invention is formed on copper or a copper alloy, Discoloration / corrosion of copper or copper alloy is prevented. On the other hand, when the amount is 20 parts by mass or less, excellent light sensitivity is obtained.

<Method of manufacturing cured relief pattern and semiconductor device>
The present invention also provides (1) a step of forming a photosensitive resin layer on the substrate by applying the above-described photosensitive resin composition of the present invention on the substrate, and (2) exposing the photosensitive resin layer to light. And (3) developing the photosensitive resin layer after the exposure to form a relief pattern, and (4) heat-treating the relief pattern to form a cured relief pattern. Provided is a method for producing a cured relief pattern. Hereinafter, typical aspects of each step will be described.

(1) Step of Forming Photosensitive Resin Layer on Substrate by Applying Photosensitive Resin Composition on Substrate In this step, the photosensitive resin composition of the present invention is applied on a substrate, and Thereafter, drying is performed to form a photosensitive resin layer. The application method is non-spin application. By using the photosensitive resin composition of the present invention, it is possible to form a cured film having a uniform thickness, no defect in the film, and no coating irregularities like citron skin without rotating the substrate. The non-spin coating method is not particularly limited. For example, a bar coat or a slit coat can be used.

  If necessary, the coating film made of the photosensitive resin composition can be dried. As the drying method, a method such as air drying, heat drying using an oven or a hot plate, and vacuum drying is used. The drying of the coating film is desirably performed under such conditions that the imidization of the (A) polyimide precursor (polyamic acid ester) in the photosensitive resin composition does not occur. 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. Thus, a photosensitive resin layer can be formed on the substrate.

(2) Step of exposing the photosensitive resin layer In this step, the photosensitive resin layer formed above is exposed through a photomask or reticle having a pattern using an exposure apparatus such as a contact aligner, a mirror projection, and a stepper. Or, it is directly exposed by an ultraviolet light source or the like.
Thereafter, a post-exposure bake (PEB) and / or a pre-development bake at an arbitrary combination of temperature and time may be performed, if necessary, for the purpose of improving light sensitivity. The range of the baking conditions is preferably a temperature of 40 to 120 ° C. and a time of 10 seconds to 240 seconds, but is not limited to this range as long as various characteristics of the photosensitive resin composition of the present invention are not impaired.

(3) Step of developing a photosensitive resin layer after exposure to form a relief pattern In this step, an unexposed portion of the exposed photosensitive resin layer is developed and removed. As a developing method for developing the photosensitive resin layer after the exposure (irradiation), an arbitrary method is selected from conventionally known methods for developing a photoresist, such as a spray method, a paddle method, and an immersion method. can do. Further, after the development, a post-development bake may be performed at an arbitrary combination of temperature and time, if necessary, for the purpose of adjusting the shape of the relief pattern.

  As a 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. As the good solvent, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, and the like are preferable. As the solvent, toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, water and the like are preferable. When a good solvent and a poor solvent are used as a mixture, 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. Further, each solvent may be used in combination of two or more kinds, for example, several kinds.

(4) Step of Forming a Cured Relief Pattern by Heating the Relief Pattern In this step, the relief pattern obtained by the development is heated to disperse the photosensitive component, and (A) the polyimide precursor is converted to an imide. Thus, the resin is converted into a cured relief pattern made of polyimide. Various methods can be selected for the method of heat curing, such as a method using a hot plate, a method using an oven, and a method using a heating type oven in which a temperature program can be set. Heating can be performed, for example, at 200 ° C. to 400 ° C. for 30 minutes to 5 hours. Air may be used as an atmosphere gas at the time of heat curing, and an inert gas such as nitrogen or argon may be used.

<Semiconductor device>
The present invention also provides a semiconductor device having a cured relief pattern obtained by the above-described method for producing a cured relief pattern of the present invention. The present invention also provides a semiconductor device having a substrate which is a semiconductor element and a cured polyimide relief pattern formed on the substrate by the above-described method for producing a cured relief pattern. The present invention is also applicable to a method of manufacturing a semiconductor device using a semiconductor element as a base material and including the above-described method of manufacturing a cured relief pattern as a part of the process. The semiconductor device according to the present invention is a semiconductor device having a cured relief pattern formed by the method for producing a cured relief pattern, a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip chip device, or a bump structure. And can be manufactured by combining with a known method for manufacturing a semiconductor device.

  The photosensitive resin composition of the present invention is useful for applications such as interlayer insulation of a multilayer circuit, a cover coat of a flexible copper clad board, a solder resist film, and a liquid crystal alignment film, in addition to the application to the semiconductor device as described above. It is.

Hereinafter, the present invention will be described specifically with reference to examples.
In the following description, specific compound names and numerical values will be described, but the present invention is not limited to these.
In Examples, Comparative Examples, and Production Examples, 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 polyimide precursor was measured by gel permeation chromatography (standard polystyrene conversion). The column used for the measurement was Shodex 805M / 806M series manufactured by Showa Denko KK, Shodex STANDARD SM-105 manufactured by Showa Denko KK was selected as the standard monodisperse polystyrene, and the developing solvent was N-methyl-2-pyrrolidone. The detector used was Shodex RI-930 (trade name, manufactured by Showa Denko KK).

(2) Evaluation of Yuzu skin-like coating unevenness The photosensitive resin composition was blade-coated on a glass substrate using an SA-201 Baker-type applicator (manufactured by Tester Sangyo Co., Ltd.), dried, and exposed to a 15 μm thick coating film. It was formed as a conductive resin layer.
The obtained coating film was visually observed under an optical microscope, and the coating unevenness in the form of yuzu skin was evaluated according to the following evaluation criteria.
◎ (best): No yuzu skin-like coating unevenness is observed.
（(Good): Slight skin-like coating unevenness is observed.
X (poor): Yuzu skin-like application unevenness is clearly confirmed.

(3) Evaluation of coating uniformity The coating uniformity was evaluated by measuring the thickness of the obtained coating film with a Nanospec 5100L light interference film thickness measuring device (manufactured by Nanometrics Japan Co., Ltd.), and according to the following evaluation criteria. Therefore, it was evaluated.
◎ (best): good uniformity of film thickness.
（(Good): The film thickness uniformity is slightly inferior.
X (poor): film thickness uniformity is poor.

(4) Evaluation of film defect The evaluation of the film defect was performed by visually observing the obtained coating film under a Na lamp and evaluating the film defect according to the following evaluation criteria.
◎ (best): No film defect is observed.
〇 (good): Film defects are slightly observed.
X (defective): A film defect is clearly confirmed.

<Production Example 1> ((A) Synthesis of First Polymer A1 as Polyimide Precursor)
155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) is placed in a 2-liter separable flask, and 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone are added and stirred at room temperature. Then, with stirring, 81.5 g of pyridine was added to obtain a reaction mixture. After the end of the heat generated by the reaction, the mixture was allowed to cool to room temperature and left for 16 hours.
Next, a solution prepared by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring under ice cooling, and subsequently, 4,4′-diaminodiphenyl ether (DADPE) A suspension of 93.0 g in γ-butyrolactone (350 ml) was added over 60 minutes while stirring. After further stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added and the mixture was stirred for 1 hour, and then 400 ml of γ-butyrolactone was added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution.

  The resulting reaction solution was added to 3 liters of ethyl alcohol to produce a precipitate composed of a crude polymer. The generated crude polymer was separated by filtration and dissolved in 1.5 liter of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 liters of water to precipitate the polymer, and the obtained precipitate was separated by filtration and vacuum-dried to obtain a powdery polymer (first polymer A1). When the molecular weight of the polymer A1 was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 20,000.

<Production Example 2> ((A) Synthesis of second polymer A2 as polyimide precursor)
Production Example 1 except that 147.1 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was used in place of 155.1 g of 4,4′-oxydiphthalic dianhydride in Production Example 1. The reaction was carried out in the same manner as described in Example 1 to obtain a second polymer A2. When the molecular weight of the polymer A2 was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 22,000.

<Example 1>
A photosensitive resin composition was prepared using the first and second polymers A1 and A2 by the following method, and the prepared composition was evaluated. 50 g of the first polymer A1 and 50 g of the second polymer A2 ((A) polyimide precursor), which are polyimide precursors, were treated with 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl)- 4 g of oxime ((B) photopolymerization initiator), 0.2 g of 8-azaadenine, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5 -Triazine-2,4,6- (1H, 3H, 5H) -trione 1.5 g, N-phenyldiethanolamine 10 g, methoxymethylated urea resin (MX-290) 4 g, tetraethylene glycol dimethacrylate 8 g, N- [ (C) Boiling point at atmospheric pressure together with 1.5 g of 3- (triethoxysilyl) propyl] phthalamic acid and 0.05 g of 2-nitroso-1-naphthole 320 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP; boiling point: 202 ° C.) as an organic solvent at 180 ° C. or higher and 80 g of ethyl lactate as an organic solvent having a boiling point at atmospheric pressure of 130 ° C. to 160 ° C. (Boiling point: 151 to 155 ° C.) to obtain a photosensitive resin composition.
The composition was evaluated according to the method described above. As a result, the evaluation of the coating unevenness in the form of yuzu skin was ◎ (best), the evaluation of coating uniformity was ◎ (best), and the evaluation of film defects was ◎ (best). )Met.

<Example 2>
In Example 1, instead of (C) N-methyl-2-pyrrolidone as an organic solvent having a boiling point of 180 ° C. or more under atmospheric pressure, γ-butyl lactone (boiling point: 204 ° C.) was used in the composition shown in Table 1. And a photosensitive resin composition was prepared, and evaluated in the same manner as in Example 1. The evaluation results were as follows: evaluation of coating unevenness in the form of citron skin was ◎ (best), evaluation of coating uniformity was ◎ (best), and evaluation of film defect was ◎ (best).

<Example 3>
Example 1 wherein (C) N-methyl-2-pyrrolidone as an organic solvent having a boiling point of 180 ° C. or more under atmospheric pressure and (D) an organic solvent having a boiling point of 130 ° C. or more and 160 ° C. or less under atmospheric pressure. A photosensitive resin composition was prepared by changing the mixing ratio of ethyl lactate to the composition shown in Table 1, and the same evaluation as in Example 1 was performed.
The evaluation results were as follows: evaluation of coating unevenness in the form of yuzu skin was ◎ (best), evaluation of coating uniformity was ◎ (best), and evaluation of film defects was ◎ (best).

<Example 4>
Example 1 wherein (C) N-methyl-2-pyrrolidone as an organic solvent having a boiling point of 180 ° C. or more under atmospheric pressure and (D) an organic solvent having a boiling point of 130 ° C. or more and 160 ° C. or less under atmospheric pressure. A photosensitive resin composition was prepared by changing the mixing ratio of ethyl lactate to the composition shown in Table 1, and the same evaluation as in Example 1 was performed.
The evaluation results were as follows: evaluation of coating unevenness in the form of yuzu skin was ◎ (best), evaluation of coating uniformity was ◎ (best), and evaluation of film defects was ◎ (best).

<Example 5>
Example 1 wherein (C) N-methyl-2-pyrrolidone as an organic solvent having a boiling point of 180 ° C. or more under atmospheric pressure and (D) an organic solvent having a boiling point of 130 ° C. or more and 160 ° C. or less under atmospheric pressure. A photosensitive resin composition was prepared by changing the mixing ratio of ethyl lactate to the composition shown in Table 1, and the same evaluation as in Example 1 was performed.
The evaluation result of coating uniformity was Δ (good), and the evaluation of coating unevenness in the form of yuzu skin was ◎ (best), and the evaluation of film defects was そ の 他 (best).

< Reference Example 6>
(C) N-methyl-2-pyrrolidone as an organic solvent having a boiling point of 180 ° C. or more under atmospheric pressure and (D) an organic solvent having a boiling point of 130 to 160 ° C. under atmospheric pressure in Example 1 A photosensitive resin composition was prepared by changing the solvent content of ethyl lactate as a solvent to the composition shown in Table 1, and the same evaluation as in Example 1 was performed.
The evaluation result of coating uniformity was Δ (good), and the evaluation of coating unevenness in the form of yuzu skin was ◎ (best), and the evaluation of film defects was そ の 他 (best).

<Example 7>
(C) N-methyl-2-pyrrolidone as an organic solvent having a boiling point of 180 ° C. or more under atmospheric pressure and (D) an organic solvent having a boiling point of 130 to 160 ° C. under atmospheric pressure in Example 1 A photosensitive resin composition was prepared by changing the solvent content of ethyl lactate as a solvent to the composition shown in Table 1, and the same evaluation as in Example 1 was performed.
Regarding the evaluation results, the evaluation result of the coating unevenness in the form of yuzu skin was （(good), the evaluation result of the coating uniformity was （(good), and the evaluation result of the film defect was ◎ (best).

< Reference Example 8>
(C) N-methyl-2-pyrrolidone as an organic solvent having a boiling point of 180 ° C. or more under atmospheric pressure and (D) an organic solvent having a boiling point of 130 to 160 ° C. under atmospheric pressure in Example 1 A photosensitive resin composition was prepared by changing the mixing ratio of ethyl lactate as a solvent to the composition shown in Table 1, and the same evaluation as in Example 1 was performed. Although the evaluation result of the film defect was （(best), the evaluation result of the coating unevenness in the form of yuzu skin was x (poor), and the evaluation result of coating uniformity was x (poor).

<Comparative Example 1>
A photosensitive resin composition was prepared by removing ethyl lactate as an organic solvent having a boiling point of 130 ° C. or more and 160 ° C. or less at atmospheric pressure (D) of the present invention in Example 1 and using the composition shown in Table 1. Then, the same evaluation as in Example 1 was performed. The evaluation result of the coating unevenness in the form of orange peel was ◎ (best) and the evaluation result of coating uniformity was ◎ (best), but the evaluation result of the film defect was x (poor).

<Comparative Example 2>
After removing N-methyl-2-pyrrolidone as an organic solvent having a boiling point of 180 ° C. or more under atmospheric pressure (C) in the present invention in Example 1 and extracting 320 g of N, N-dimethylacetamide having a boiling point of 165 ° C. Other than the addition, a photosensitive resin composition was prepared in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. Although the evaluation result of the film defect was ◎ (best), the evaluation result of the coating unevenness in the form of yuzu skin was Δ (good), and the evaluation result of the coating uniformity was × (poor).

<Comparative Example 3>
(C) N-methyl-2-pyrrolidone as an organic solvent having a boiling point of 180 ° C. or more under atmospheric pressure and (D) an organic solvent having a boiling point of 130 to 160 ° C. under atmospheric pressure in Example 1 A photosensitive resin composition was prepared by changing the amount of ethyl lactate as a solvent to the composition shown in Table 1, and the same evaluation as in Example 1 was performed. The evaluation result of the film defect was ◎ (best), and the evaluation result of coating unevenness in the form of yuzu skin was ◎ (best), but the evaluation result of coating uniformity was x (poor).

<Comparative Example 4>
(C) N-methyl-2-pyrrolidone as an organic solvent having a boiling point of 180 ° C. or more under atmospheric pressure and (D) an organic solvent having a boiling point of 130 to 160 ° C. under atmospheric pressure in Example 1 A photosensitive resin composition was prepared by changing the solvent content of ethyl lactate as a solvent to the composition shown in Table 1, and the same evaluation as in Example 1 was performed. Although the evaluation result of the film defect was ◎ (best), the evaluation result of the application unevenness in the form of yuzu skin was x (poor), and the evaluation result of the coating uniformity was x (poor).

  Table 1 shows the evaluation results of the cured films obtained in the above Examples and Comparative Examples together with the solvent composition and the viscosity.

As is clear from Table 1, (A) polyimide precursor: 100 parts by mass, (B) photopolymerization initiator: 1 to 20 parts by mass, (C) boiling point at atmospheric pressure of 180 ° C. or more And (D) an organic solvent having a boiling point under atmospheric pressure of from 130 ° C. to 160 ° C .: 300 to 600 parts by mass, and the content of the component (C) is 60 with respect to the total amount of the organic solvent. A photosensitive content of not less than 10% by weight and not more than 40% by weight based on the total amount of the organic solvent, and a viscosity at 23 ° C. of not less than 0.5P and not more than 40P. In the coating films of the examples obtained using the resin composition, excellent results of “good” or more were obtained in any evaluation of coating unevenness, coating uniformity, and film defects. However, reference example and the amount of organic solvent and 185 parts by weight 1, in Reference Example 2 was one by 50 wt% each content of the solvent of the solvent and the component (D) of the component (C), coating uniformity, yuzu Skin-like coating unevenness was not sufficient. Therefore, the content of the component (C) is 60% by weight or more and 90% by weight or less based on the total amount of the organic solvent, and the content of the component (D) is 10% by weight or more and 40% by weight or less. It can be seen that good results are obtained.

  On the other hand, in Comparative Example 1 containing no solvent having a boiling point of 130 to 160 ° C., which is the component (D), a film defect occurred. In Comparative Example 2 (boiling point: 165 ° C.) containing no solvent having a boiling point of 180 ° C. or higher, which is the component (C), the coating uniformity was reduced. In Comparative Example 3 (150 parts by weight) in which the amount of the organic solvent was less than 185 parts by weight based on 100 parts by weight of the polyimide precursor, the coating uniformity was reduced. On the other hand, in Comparative Example 4 (900 parts by weight), which was larger than 600 parts by weight, the coating uniformity was poor, and it was possible to form a yuzu skin-like coating unevenness. In Comparative Example 4 (0.1 P) having a viscosity of less than 0.5 P, the coating uniformity was poor, resulting in a yuzu skin-like coating unevenness. On the other hand, in Comparative Example 3 (100P) having a viscosity larger than 40P, the coating uniformity was reduced.

  From the above results, in the photosensitive resin composition, by optimizing the combination and the solvent content of the organic solvent having specific characteristics, the film thickness is uniform in non-spin coating, there is no defect in the film, and it has a citron texture. It was confirmed that a cured film without coating unevenness could be obtained.

  Although the embodiments of the present invention have been described above, the present invention is not limited to these embodiments, and can be appropriately changed without departing from the spirit of the invention.

  The photosensitive resin composition of the present invention has a uniform film thickness in non-spin coating and has no defects in the film, and gives a cured film without coating unevenness like citron skin. It can be suitably used in the field of photosensitive materials useful for producing electronic materials.

Claims (6)

(A) The following general formula (1):

In the formula, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n is an integer of _{2 to} 150, and R ₁ and R ₂ are each independently Hydrogen atom, 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 is an integer of 2 to 10). A valent organic group or a saturated aliphatic group having 1 to 4 carbon atoms. However, R ₁ and R ₂ are not hydrogen atoms at the same time. Polyimide precursor having a repeating unit represented by｝: 100 parts by mass,
(B) a photopolymerization initiator: 1 to 20 parts by mass based on 100 parts by mass of the (A) polyimide precursor;
(C) an organic solvent having a boiling point of 180 ° C. or higher under atmospheric pressure, and
(D) an organic solvent having a boiling point of 130 ° C. or more and 160 ° C. or less at atmospheric pressure: (A) a total amount of 300 to 600 parts by mass of the organic solvent based on 100 parts by mass of the polyimide precursor;
In the solvent, the content of the component (C) is 60% by weight or more and 90% by weight or less based on the total amount of the organic solvent, and the content of the component (D) is 10% by weight or more and 40% by weight based on the total amount of the organic solvent. Is the following,
A photosensitive resin composition for non-spin coating, wherein the viscosity at 23 ° C. is 0.5 P or more and 40 P or less. (A) The following general formula (1):

In the formula, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n is an integer of _{2 to} 150, and R ₁ and R ₂ are each independently Hydrogen atom, 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 is an integer of 2 to 10). A valent organic group or a saturated aliphatic group having 1 to 4 carbon atoms. However, R ₁ and R ₂ are not hydrogen atoms at the same time. Polyimide precursor having a repeating unit represented by｝: 100 parts by mass,
(B) a photopolymerization initiator: 1 to 20 parts by mass based on 100 parts by mass of the (A) polyimide precursor;
(C) an organic solvent having a boiling point of 180 ° C. or higher under atmospheric pressure, and
(D) an organic solvent having a boiling point under atmospheric pressure of 130 ° C. or more and 160 ° C. or less: (A) a total amount of 300 to 600 parts by mass of the organic solvent based on 100 parts by mass of the polyimide precursor,
In the solvent, the content of the component (C) is 60% by weight or more and 90% by weight or less based on the total amount of the organic solvent, and the content of the component (D) is 10% by weight or more and 40% by weight based on the total amount of the organic solvent. Is the following,
A photosensitive resin composition for non-spin coating, wherein the viscosity at 23 ° C. is 0.5 P or more and less than 20 P.   3. The photosensitive resin composition according to claim 1, wherein in the solvent, the component (C) is N-methyl-2-pyrrolidone or γ-butyrolactone, and the component (D) is ethyl lactate. 4. (A) The following general formula (1):

In the formula, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, n is an integer of _{2 to} 150, and R ₁ and R ₂ are each independently Hydrogen atom, 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 is an integer of 2 to 10). A valent organic group or a saturated aliphatic group having 1 to 4 carbon atoms. However, R ₁ and R ₂ are not hydrogen atoms at the same time. Polyimide precursor having a repeating unit represented by｝: 100 parts by mass,
(B) a photopolymerization initiator: 1 to 20 parts by mass based on 100 parts by mass of the (A) polyimide precursor;
(C) an organic solvent having a boiling point of 180 ° C. or higher under atmospheric pressure, and
(D) an organic solvent having a boiling point under atmospheric pressure of 130 ° C. or more and 160 ° C. or less: (A) a total amount of 300 to 600 parts by mass of the organic solvent based on 100 parts by mass of the polyimide precursor;
In the solvent, the content of the component (C) is 60% by weight or more and 90% by weight or less based on the total amount of the organic solvent, and the content of the component (D) is 10% by weight or more and 40% by weight based on the total amount of the organic solvent. Is the following,
A step of applying a photosensitive resin composition for non-spin coating having a viscosity at 23 ° C. of 0.5 P or more and 40 P or less to a substrate using non-spin coating to form a coating film; and
A method for producing a photosensitive resin film, comprising a step of drying the coating film. below:
(1) a step of forming a photosensitive resin layer on a substrate by applying the photosensitive resin composition according to any one of claims 1 to 3 to the substrate by non-spin coating;
(2) exposing the photosensitive resin layer to light;
(3) developing the photosensitive resin layer after the exposure to form a relief pattern;
(4) a step of forming a cured relief pattern by heat-treating the relief pattern;
A method for producing a cured relief pattern, comprising: Characterized in that it has a method of manufacturing a cured relief pattern according to claim 5, the method of manufacturing a semiconductor device.