WO2020080207A1 - Photosensitive insulating film composition - Google Patents

Abstract

The present invention provides: a photosensitive resin composition which enables the achievement of a cured body that has a low dielectric constant and a low dielectric loss tangent; a method for producing a substrate with a cured relief pattern with use of this photosensitive resin composition; and a semiconductor device which is provided with this cured relief pattern. A photosensitive resin composition which contains: (A) a polyimide precursor that has a unit structure represented by general formula (1) (wherein X1 represents a tetravalent organic group; Y1 represents a divalent organic group; and each of R1 and R2 independently represents a monovalent organic group); and (B) an isocyanate compound represented by general formula (20) (wherein R23 represents a hydrogen atom or a methyl group; R24 represents an alkylene group; and R25 represents an isocyanate group or a blocked isocyanate group).

Description

Photosensitive insulating film composition

The present invention relates to a photosensitive resin composition, a photosensitive resin film obtained from the composition, a cured relief pattern using the composition, a method for producing the same, and a semiconductor device having the cured relief pattern.

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

On the other hand, in recent years, the method of mounting semiconductor devices on a printed wiring board has also changed in order to improve the degree of integration and arithmetic functions, and to reduce the chip size. Compared with the conventional mounting method using metal pins and lead-tin eutectic solder, the polyimide coating directly contacts the solder bumps, such as BGA (ball grid array) and CSP (chip size packaging), which enables higher density mounting. Structures are being used. When forming such a bump structure, the coating is required to have high heat resistance and chemical resistance.

Further, with the progress of miniaturization of semiconductor devices, the problem of wiring delay has become apparent. As a means for improving the wiring resistance of a semiconductor device, the gold or aluminum wiring that has been used so far has been changed to copper or copper alloy wiring having a lower resistance. Furthermore, a method of preventing wiring delay by increasing insulation between wirings is also adopted. In recent years, a low-dielectric constant material often constitutes a semiconductor device as this highly insulating material, but on the other hand, a low-dielectric constant material tends to be fragile and easily broken. However, there is a problem that the low dielectric constant material portion is destroyed by the contraction due to the temperature change.
As a means for solving this problem, Patent Document 1 discloses that a photosensitive material containing a polyimide precursor is introduced by introducing an aliphatic group having an ethylene glycol structure and having 5 to 30 carbon atoms into a part of a side chain of the polyimide precursor. Disclosed is a photosensitive resin composition that improves the transparency when a photosensitive resin composition is formed and further improves the Young's modulus of a cured film after thermosetting.

Re-table 2013-168675

The photosensitive resin composition comprising the polyimide precursor described in Patent Document 1 has a high transparency and gives a cured product having a high Young's modulus after heat curing, but when used in the above-mentioned applications, the dielectric constant or There has been a demand for further reduction of the dielectric loss tangent.

Therefore, the present invention provides a photosensitive resin composition that gives a cured product having a further reduced dielectric constant or dielectric loss tangent, a method for producing a substrate with a cured relief pattern using the photosensitive resin composition, and the cured relief. It is an object to provide a semiconductor device having a pattern.

As a result of intensive studies to achieve the above object, the inventors of the present invention give a low dielectric constant and a low dielectric loss tangent when a photosensitive resin composition is formed by adding a specific isocyanate compound to a polyimide precursor. They have found that a photosensitive resin composition can be obtained, and completed the present invention.

［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、Ｒ^１及びＲ^２は、それぞれ独立に、１価の有機基である。］で表される単位構造を有するポリイミド前駆体、及び
（Ｂ）下記一般式（２０）：

［式中、Ｒ^２３は水素原子又はメチル基を表し、Ｒ^２４は、置換基を有してもよく、酸素原子によって中断されていてもよい炭素原子数１乃至５のアルキレン基を表し、Ｒ^２５は、イソシアネート基又はブロックイソシアネート基を表す。］
で表されるイソシアネート化合物、
を含む感光性樹脂組成物。
［２］　前記ブロックイソシアネート基が下記一般式（２１）：

［式中、Ａは、アルコール、アミン、アミド、活性メチレン化合物、窒素含有ヘテロアリール化合物、オキシム、ケトオキシム、及びヒドロキサム酸エステルからなる群より選択されるイソシアネートブロック用化合物の残基を表す。］
で表される、［１］に記載の感光性樹脂組成物。
［３］　前記一般式（２０）において、Ｒ^２４がアクリロイル基又はメタクリロイル基で置換された炭素原子数１乃至５のアルキレン基である、［１］又は［２］に記載の感光性樹脂組成物。
［４］　さらに（Ｃ）下記一般式（３０）：

［式中、Ｚ^１及びＺ^２は、それぞれ独立に、
水素原子、ハロゲン原子、ヒドロキシ基、メルカプト基、カルボキシ基、シアノ基、ホルミル基、ハロホルミル基、スルホ基、ニトロ基、ニトロソ基、オキソ基、チオキシ基、
置換されていてもよい炭素原子数１～１０のアルキル、アルコキシ、もしくはアルキルスルファニル基、
置換されていてもよい炭素原子数２～１０のアルケニル、アルキニル、もしくはアルコキシカルボニル基、又は
置換されていてもよいアミノ、イミノ、もしくはカルバモイル基を表し、
Ｚ^１及びＺ^２は、相互に結合して、ヘテロ原子を含んでもよく、置換基を有していてもよく、縮合していてもよい環を形成してもよく、当該環が芳香族環であるとき、

はＨＯＯＣがＣＯＯＨに対してオルト位にある共役二重結合を示し、当該環が芳香族環であるとき以外の場合、

はＨＯＯＣとＣＯＯＨについてのシス型二重結合を示す。］
で表されるカルボン酸化合物又はその無水物、
を含む、［１］～［３］の何れか１項に記載の感光性樹脂組成物。
［５］　［１］～［４］の何れか１項に記載の感光性樹脂組成物の塗布膜の焼成物であることを特徴とする感光性樹脂膜。
［６］　以下の工程：
　（１）［１］～［４］のいずれか１項に記載の感光性樹脂組成物を基板上に塗布して、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して、硬化レリーフパターンを形成する工程と
を含む硬化レリーフパターン付き基板の製造方法。
［７］　［６］に記載の方法により製造された硬化レリーフパターン付き基板。
［８］　半導体素子と、該半導体素子の上部又は下部に設けられた硬化膜とを備える半導体装置であって、該硬化膜は、［７］に記載の硬化レリーフパターンである、半導体装置。 That is, the present invention includes the following.
[1] (A) The following general formula (1):

[In the formula, X ¹ is a tetravalent organic group, Y ¹ is a divalent organic group, and R ¹ and R ² are each independently a monovalent organic group. ] The polyimide precursor which has a unit structure represented by, and (B) following general formula (20):

[In the formula, R ²³ represents a hydrogen atom or a methyl group, R ²⁴ represents an alkylene group having 1 to 5 carbon atoms, which may have a substituent and may be interrupted by an oxygen atom; ²⁵ represents an isocyanate group or a blocked isocyanate group. ]
Isocyanate compound represented by
A photosensitive resin composition containing.
[2] The blocked isocyanate group has the following general formula (21):

[In the formula, A represents a residue of a compound for isocyanate blocking selected from the group consisting of alcohol, amine, amide, active methylene compound, nitrogen-containing heteroaryl compound, oxime, ketoxime, and hydroxamic acid ester. ]
The photosensitive resin composition according to [1], represented by:
[3] The photosensitive resin composition according to [1] or [2], wherein in the general formula (20), R ²⁴ is an alkylene group having 1 to 5 carbon atoms and substituted with an acryloyl group or a methacryloyl group. .
[4] Further, (C) the following general formula (30):

[In the formula, Z ¹ and Z ² are each independently
Hydrogen atom, halogen atom, hydroxy group, mercapto group, carboxy group, cyano group, formyl group, haloformyl group, sulfo group, nitro group, nitroso group, oxo group, thioxy group,
An optionally substituted alkyl, alkoxy, or alkylsulfanyl group having 1 to 10 carbon atoms,
Represents an optionally substituted alkenyl, alkynyl, or alkoxycarbonyl group having 2 to 10 carbon atoms, or an optionally substituted amino, imino, or carbamoyl group,
Z ¹ and Z ² may be bonded to each other to form a ring which may contain a hetero atom, may have a substituent, or may be condensed, and the ring may be an aromatic ring. When

Is a conjugated double bond in which HOOC is in an ortho position with respect to COOH, and when the ring is an aromatic ring,

Indicates a cis double bond for HOOC and COOH. ]
A carboxylic acid compound or an anhydride thereof,
The photosensitive resin composition according to any one of [1] to [3], which comprises:
[5] A photosensitive resin film, which is a baked product of the coating film of the photosensitive resin composition according to any one of [1] to [4].
[6] The following steps:
(1) A step of applying the photosensitive resin composition according to any one of [1] to [4] onto a substrate to form a photosensitive resin layer on the substrate,
(2) exposing the photosensitive resin layer to light,
(3) a step of developing the photosensitive resin layer after the exposure to form a relief pattern,
(4) A method for producing a substrate with a cured relief pattern, which comprises a step of heating the relief pattern to form a cured relief pattern.
[7] A substrate with a cured relief pattern produced by the method described in [6].
[8] A semiconductor device comprising a semiconductor element and a cured film provided on an upper portion or a lower portion of the semiconductor element, wherein the cured film is the cured relief pattern described in [7].

According to the present invention, a photosensitive resin composition giving a cured product having a low dielectric constant and a low dielectric loss tangent, a method for producing a cured relief pattern using the photosensitive resin composition, and a semiconductor device having the cured relief pattern Can be provided.

[Photosensitive resin composition]
The photosensitive resin composition of the present invention contains (A) a polyimide precursor, (B) an isocyanate compound, optionally (C) a carboxylic acid compound or an anhydride thereof, and optionally other components. Each component will be described below in order.

[(A) Polyimide precursor]
The (A) polyimide precursor is a resin component contained in the photosensitive resin composition and has a unit structure represented by the following general formula (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、Ｒ^１及びＲ^２は、それぞれ独立に、１価の有機基である。］

[In the formula, X ¹ is a tetravalent organic group, Y ¹ is a divalent organic group, and R ¹ and R ² are each independently a monovalent organic group. ]

In the general formula (1), X ¹ is not particularly limited as long as it is a tetravalent organic group, but from the viewpoint of achieving both heat resistance and photosensitivity, it is preferably a tetravalent group having 6 to 40 carbon atoms. And more preferably an aromatic group in which the —COOR ¹ group, the —COOR ² group and the —CONH— group are in the ortho position to each other, or an alicyclic aliphatic group. The tetravalent organic group represented by X ¹ is more preferably an organic group containing an aromatic ring and having 6 to 40 carbon atoms.

More preferably, X ¹ is a tetravalent organic group represented by the following formula (5) or the following formulas (5-1) to (5-7).

The structure of X ¹ may be one kind or a combination of two or more kinds.

In the general formula (1), Y ¹ is not limited as long as it is a divalent organic group having 6 to 40 carbon atoms, but Y ¹ may be substituted from the viewpoint of achieving both heat resistance and photosensitivity. A cyclic organic group having 1 to 4 aromatic rings or aliphatic rings, or an aliphatic group having no cyclic structure or a siloxane group is preferable. More preferably, Y ¹ is a structure represented by the following general formula (6), the following general formula (7) or the following formula (8).

(In the formula, each A independently represents 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 ). .}

The structure of Y ¹ may be one kind or a combination of two or more kinds.

In the general formula (1), R ¹ and R ² are not particularly limited as long as they are independently monovalent organic groups. For example, R ¹ and R ² are each independently a monovalent aliphatic group having 1 to 30 carbon atoms or 5 to 22 carbon atoms, a cycloaliphatic group, an aromatic group and an aliphatic group bonded to each other. Or a group in which these groups are substituted with a halogen atom, a nitro group, an amino group, a cyano group, a methoxy group, an acetoxy group or the like. Typical halogen atoms are F, Cl, Br and I.

Preferably, R ¹ and R ² are each independently the following general formula (2):

(In the formula, R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m is an integer of 1 to 10. * is , Which is a binding site for the carboxylic acid present in the polyamic acid main chain of the general formula (1).)
It is preferable that

R ¹ and R ² are each independently the following general formula (3):

(In the formula, R ⁶ is a monovalent group selected from an alkyl group having 1 to 30 carbon atoms. * Is the same as the above.)
A monovalent organic group represented by may be included.

Each of R ¹ and R ² in the general formula (1) may be one kind or a combination of two or more kinds, but is preferably a combination of three kinds or less, preferably a combination of two kinds, and most preferably 1 It is a seed.

In the general formula (1), the monovalent organic group represented by the general formula (2) with respect to all of R ¹ and R ² and the general formula from the viewpoints of the photosensitivity and mechanical properties of the photosensitive resin composition. The total proportion of monovalent organic groups represented by (3) is preferably 80 mol% or more, preferably 90 mol% or more, and preferably 100 mol%.

In the above general formula (1), the ratio of the total of the monovalent organic groups represented by the above general formula (2) to all R ¹ and R ² from the viewpoint of the photosensitive properties and mechanical properties of the photosensitive resin composition. Is preferably 80 mol% or more, preferably 90 mol% or more, and preferably 100 mol%.

R ³ in the above general formula (2) is not limited as long as it is a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, but from the viewpoint of the photosensitive characteristics of the photosensitive resin composition, R ³ is a hydrogen atom or methyl. It is preferably a group.

R ⁴ and R ⁵ in the above general formula (2) are not limited as long as they are independently hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms. From the viewpoint, it is preferably a hydrogen atom.

M in the general formula (2) is an integer of 1 or more and 10 or less, preferably 2 or more and 4 or less from the viewpoint of photosensitivity.

R ⁶ in the general formula (3) is not limited as long as it is a monovalent organic group selected from alkyl groups having 1 to 30 carbon atoms. An alkyl group having 5 to 30 carbon atoms is preferable, an alkyl group having 8 to 30 carbon atoms is preferable, an alkyl group having 9 to 30 carbon atoms is preferable, and an alkyl group having 10 to 30 carbon atoms is preferable. Preferably, an alkyl group having 11 to 30 carbon atoms is more preferable, and an alkyl group having 17 to 30 carbon atoms is further preferable. It may have a branched structure or a cyclic structure as well as a linear structure.

Specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group (amyl group), hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group (lauryl group), tridecyl group Group, tetradecyl group (myristyl group), pentadecyl group, hexadecyl group (palmityl group), heptadecyl group (margalyl group), octadecyl group (stearyl group), nonadecyl group, icosyl group (arachil group), henicosyl group, docosyl group (behenyl) Group), tricosyl group, tetracosyl group (lignoceryl group), pentacosyl group, hexacosyl group, heptacosyl group, and other linear alkyl groups; isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group , Tert-pentyl group, sec-isoa Group, isohexyl group, neohexyl group, 4-methylhexyl group, 5-methylhexyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 4-ethylhexyl group, 2-ethylpentyl group, heptane -3-yl group, heptan-4-yl group, 4-methylhexan-2-yl group, 3-methylhexan-3-yl group, 2,3-dimethylpentan-2-yl group, 2,4-dimethyl Pentan-2-yl group, 4,4-dimethylpentan-2-yl group, 6-methylheptyl group, 2-ethylhexyl group, octan-2-yl group, 6-methylheptan-2-yl group, 6-methyl Octyl group, 3,5,5-trimethylhexyl group, nonan-4-yl group, 2,6-dimethylheptan-3-yl group, 3,6-dimethylheptan-3-yl group, -Ethylheptan-3-yl group, 3,7-dimethyloctyl group, 8-methylnonyl group, 3-methylnonan-3-yl group, 4-ethyloctane-4-yl group, 9-methyldecyl group, undecane-5- -Yl group, 3-ethylnonan-3-yl group, 5-ethylnonan-5-yl group, 2,2,4,5,5-pentamethylhexane-4-yl group, 10-methylundecyl group, 11-methyl Dodecyl group, tridecan-6-yl group, tridecan-7-yl group, 7-ethylundecane-2-yl group, 3-ethylundecane-3-yl group, 5-ethylundecane-5-yl group, 12-methyl Tridecyl group, 13-methyltetradecyl group, pentadecane-7-yl group, pentadecane-8-yl group, 14-methylpentadecyl group, 15-methylhexadecyl group, hepta Decan-8-yl group, heptadecane-9-yl group, 3,13-dimethylpentadecan-7-yl group, 2,2,4,8,10,10-hexamethylundecane-5-yl group, 16-methyl Heptadecyl group, 17-methyloctadecyl group, nonadecane-9-yl group, nonadecane-10-yl group, 2,6,10,14-tetramethylpentadecane-7-yl group, 18-methylnonadecyl group, 19-methylicosyl group , Henicosan-10-yl group, 20-methylhenicosyl group, 21-methyldocosyl group, tricosane-11-yl group, 22-methyltricosyl group, 23-methyltetracosyl group, pentacosane-12-yl group, Pentacosan-13-yl group, 2,22-Dimethyltricosane-11-yl group, 3,21-Dimethyltricosane-11-a Group, 9,15-dimethyltricosane-11-yl group, branched-chain alkyl group such as 24-methylpentacosyl group, 25-methylhexacosyl group, heptacosan-13-yl group; cyclopropyl group, cyclobutyl Group, cyclopentyl group, cyclohexyl group, 4-tert-butylcyclohexyl group, 1,6-dimethylcyclohexyl group, menthyl group, cycloheptyl group, cyclooctyl group, bicyclo [2.2.1] heptan-2-yl Group, bornyl group, isobornyl group, 1-adamantyl group, 2-adamantyl group, tricyclo [5.2.1.0 ^2,6 ] decan-4-yl group, tricyclo [5.2.1.0 ^2,6 Examples thereof include alicyclic alkyl groups such as a decan-8-yl group and a cyclododecyl group.

R ⁶ in the above general formula (3) is preferably an alkyl group having 5 to 30 carbon atoms, an alkyl group having 8 to 30 carbon atoms, and an alkyl group having 9 to 30 carbon atoms, An alkyl group having 10 to 30 carbon atoms is preferable, an alkyl group having 11 to 30 carbon atoms is more preferable, and an alkyl group having 17 to 30 carbon atoms is further preferable.

Preferably, R ⁶ is represented by the following formula (4):

(Z ¹ is hydrogen or an alkyl group having 1 to 14 carbon atoms,
Z ² is an alkyl group having 1 to 14 carbon atoms,
Z ³ is an alkyl group having 1 to 14 carbon atoms,
However, Z ¹ , Z ² and Z ³ may be the same or different from each other,
The total number of carbon atoms of Z ¹ , Z ² and Z ³ is 4 or more. ) Is preferable.

It is preferred that Z ¹ is hydrogen.
Z ¹ , Z ² and Z ³ are preferably alkyl groups having 2 to 12 carbon atoms, and more preferably alkyl groups having 2 to 10 carbon atoms.
The total number of carbon atoms of Z ¹ , Z ² and Z ³ is preferably 5 or more, more preferably 6 or more, preferably 10 or more, preferably 12 or more, and 14 or more. Preferably, it is preferably 15 or more, more preferably 16 or more.
The total number of carbon atoms of Z ¹ , Z ² and Z ³ is preferably 6 or more and 20 or less.
The upper limit of the total number of carbon atoms of Z ¹ , Z ² and Z ³ is preferably 28.

Further, R ⁶ may be selected from the following formulas (3-1) to (3-7).

R ⁶ is preferably selected from the above formulas (3-1) to (3-7).

The polyimide precursor (A) is converted into polyimide by subjecting it to a heat cyclization treatment.
[(A) Method for Preparing Polyimide Precursor]
The polyimide precursor represented by the general formula (1) in the present embodiment includes, for example, a tetracarboxylic dianhydride containing a tetravalent organic group X ¹ having 6 to 40 carbon atoms, and (a) the above. An alcohol in which a monovalent organic group represented by the general formula (2) and a hydroxyl group are bonded, and (b) a monovalent organic group represented by the general formula (3) and a hydroxyl group are bonded. A partially esterified tetracarboxylic acid (hereinafter, also referred to as an acid / ester form) is prepared by reacting the resulting alcohols, and then the above-mentioned divalent organic group Y ¹ having 6 to 40 carbon atoms is added. It is obtained by polycondensation with the diamines containing it.

(Preparation of acid / ester form)
In the present embodiment, examples of the tetracarboxylic acid dianhydride containing a tetravalent organic group X ¹ having 6 to 40 carbon atoms include pyromellitic dianhydride, diphenyl ether-3,3 ′, 4,4′-tetracarboxylic acid. Acid dianhydride (= 4,4'-oxydiphthalic dianhydride), benzophenone-3,3 ', 4,4'-tetracarboxylic dianhydride, biphenyl-3,3', 4,4'-tetra Carboxylic dianhydride, diphenylsulfone-3,3 ', 4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3', 4,4'-tetracarboxylic dianhydride, 2,2-bis Examples thereof include (3,4-phthalic anhydride) propane and 2,2-bis (3,4-phthalic anhydride) -1,1,1,3,3,3-hexafluoropropane.
Further, tetracarboxylic dianhydrides represented by the following formulas (5-1-a) to (5-7-a) are also exemplified.

These can be used alone or in combination of two or more.

In the present embodiment, (a) alcohols having a structure represented by the general formula (2) include, for example, 2-acryloyloxyethyl alcohol, 1-acryloyloxy-3-propyl alcohol, methylol vinyl ketone, and 2 -Hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3- Propyl alcohol, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxyethylmethac Mention may be made of the rate, and the like.

(B) As the aliphatic alcohol having 1 to 30 carbon atoms having the structure represented by the general formula (3), for example, the hydrogen atom of the alkyl group having 1 to 30 carbon atoms is substituted with a hydroxy group. Examples thereof include alcohols.

Further, alcohols having the structures of the above formulas (3-1) to (3-6) may be used.
The following commercial products may be used.
Alcohols containing the structure of formula (3-1): Fineoxochol (registered trademark) 180 (manufactured by Nissan Chemical Co., Ltd.),
Alcohols containing the structure of formula (3-2): Fineoxochol (registered trademark) 2000 (manufactured by Nissan Chemical Co., Ltd.),
Alcohols having the structure of formula (3-3): Fineoxochol (registered trademark) 180N (manufactured by Nissan Chemical Co., Ltd.),
Alcohols containing the structure of formula (3-4) or formula (3-5): Fineoxochol (registered trademark) 180T (manufactured by Nissan Chemical Co., Ltd.),
Alcohols containing the structure of formula (3-6): Fineoxochol (registered trademark) 1600K (manufactured by Nissan Chemical Co., Ltd.).
As these alcohols, it is preferable to use alcohols having the structures of the above formulas (3-1) to (3-6).

The total content of the component (a) and the component (b) in the photosensitive resin composition is preferably 80 mol% or more based on the total content of R ¹ and R ² in the general formula (1). In order to reduce the dielectric constant and the dielectric loss tangent, the content of the component (b) is preferably 1 mol% to 90 mol% with respect to the total content of R ¹ and R ² .

The above tetracarboxylic dianhydride and the above alcohols are stirred, dissolved and mixed in the reaction solvent at a reaction temperature of 0 to 100 ° C. for 10 to 40 hours in the presence of a basic catalyst such as pyridine. As a result, the half-esterification reaction of the acid dianhydride proceeds, and the desired acid / ester form can be obtained.

The reaction solvent is preferably one that dissolves the acid / ester form and a polyimide precursor which is a polycondensation product of the acid / ester form and diamines. For example, N-methyl-2-pyrrolidone, N , N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, tetramethylurea, gammabutyrolactone, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, acetone, methylethylketone, 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 Emissions, 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)
A known dehydration-condensation agent such as dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, to the above acid / ester (typically a solution in the above reaction solvent) under ice cooling. 1,1-Carbonyldioxy-di-1,2,3-benzotriazole, N, N'-disuccinimidyl carbonate, N, N'-diisopropylcarbodiimide, etc. are added and mixed to form an acid / ester compound as a polyacid. After the anhydride is prepared, a diamine containing a divalent organic group Y ¹ having 6 to 40 carbon atoms, which is separately dissolved or dispersed in a solvent, is added dropwise to the mixture, and polycondensation is carried out. It is possible to obtain a polyimide precursor that can be used in.

Examples of diamines containing a divalent organic group Y ¹ having 6 to 40 carbon atoms 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'-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 their benzene rings Some of the above hydrogen atoms are 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'-dimethyl 4,4'-diaminodiphenylmethane, 3,3'Jimechitokishi-4,4'-diaminobiphenyl,3,3'-dichloro-4,4'-diamino biphenyl, and mixtures thereof, and the like.
Further, diamines represented by the following formula (8-1) are also included.

The diamines used in the present application are not limited to these.

In the embodiment, in order to improve the adhesion between the photosensitive resin layer formed on the substrate and various substrates by applying the photosensitive resin composition onto the substrate, (A) Preparation of polyimide precursor At times, diaminosiloxanes such as 1,3-bis (3-aminopropyl) tetramethyldisiloxane and 1,3-bis (3-aminopropyl) tetraphenyldisiloxane can also be copolymerized.

After the completion of the polycondensation reaction, the water-absorbing by-product of the dehydration condensation agent coexisting in the reaction solution is filtered off as necessary, and then water, an aliphatic lower alcohol, or a poor solvent such as a mixed solution thereof is used. , A polymer precursor that can be used in the embodiment by pouring into a reaction solution to precipitate a polymer component, and further repeating redissolution and reprecipitation precipitation operations to purify the polymer and perform vacuum drying. Isolate the body. In order to improve the degree of purification, a solution of this 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.

The molecular weight of the (A) polyimide precursor is preferably 5,000 to 150,000, and more preferably 7,000 to 50,000, as measured by polystyrene conversion weight average molecular weight by gel permeation chromatography. Is more preferable. When the weight average molecular weight is 5,000 or more, mechanical properties are good, which is preferable. On the other hand, when the weight average molecular weight is 150,000 or less, dispersibility in a developing solution and resolution performance of a relief pattern are good. It is preferable because it is good.

[(B) Isocyanate compound]
The (B) isocyanate compound is represented by the following general formula (20).

［式中、Ｒ^２３は水素原子又はメチル基を表し、Ｒ^２４は、置換基を有してもよく、酸素原子によって中断されていてもよい炭素原子数１乃至５のアルキレン基を表し、Ｒ^２５は、イソシアネート基又はブロックイソシアネート基を表す。］

[In the formula, R ²³ represents a hydrogen atom or a methyl group, R ²⁴ represents an alkylene group having 1 to 5 carbon atoms, which may have a substituent and may be interrupted by an oxygen atom; ²⁵ represents an isocyanate group or a blocked isocyanate group. ]

R ²⁴ is not particularly limited as long as it has a substituent and is an alkylene group having 1 to 5 carbon atoms which may be interrupted by an oxygen atom. Examples of the alkylene group having 1 to 5 carbon atoms include a substituted or unsubstituted methylene group, ethylene group, propylene group, butylene group and the like. Examples of the alkylene group interrupted by an oxygen atom include —CH ₂ —O—CH ₂ —, —C ₂ H ₄ —O—CH ₂ —, —CH ₂ —O—C ₂ H ₄ — and the like. . Examples of the substituent include a halogen atom, an acryloyl group, a methacryloyl group, a nitro group, an amino group, a cyano group, a methoxy group and an acetoxy group, and an acryloyl group and a methacryloyl group are preferable.

R ²⁵ represents an isocyanate group or a blocked isocyanate group. The isocyanate group means a group represented by —NCO, and the blocked isocyanate group means a group in which an isocyanate group is blocked by a heat-eliminating protective group, that is, an isocyanate blocking compound (blocking agent) is added to the isocyanate group. The reacted group.

An isocyanate group blocking agent generally reacts with an isocyanate group to prevent a reaction with a functional group in another molecule (for example, an acid functional group) at room temperature, but desorbs at a high temperature to release an isocyanate group. Regenerate and allow subsequent reactions (eg with acid functional groups).
Examples of the blocking agent include alcohols such as methanol, ethanol, isopropanol, n-butanol, 2-ethoxyhexanol, 2-N, N-dimethylaminoethanol, 2-ethoxyethanol, cyclohexanol, phenol and o-nitrophenol. , Phenols such as p-chlorophenol, o-cresol, m-cresol, p-cresol, lactams such as ε-caprolactam, acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, cyclohexanone oxime, acetophenone oxime, benzophenone oxime, etc. -Containing heteroaryl compounds such as oximes, amines, amides, pyrazole, 3,5-dimethylpyrazole, 3-methylpyrazole, dodecanethiol, benzene Thiols such as thiol, malonic acid diester, acetoacetic acid ester, malonic acid dinitrile, acetylacetone, methylenedisulfone, dibenzoylmethane, dipivaloylmethane, active methylene compounds such as acetonedicarboxylic acid diester, and hydroxamic acid ester. To be
The blocking agent is volatile and advantageously evaporates from the composition after desorption.

［式中、Ａは、アルコール、アミン、アミド、活性メチレン化合物、窒素含有ヘテロアリール化合物、オキシム、ケトオキシム、及びヒドロキサム酸エステルからなる群より選択されるイソシアネートブロック用化合物の残基を表す。］
で表される。 Blocked isocyanate groups, for example,

[In the formula, A represents a residue of a compound for isocyanate blocking selected from the group consisting of alcohol, amine, amide, active methylene compound, nitrogen-containing heteroaryl compound, oxime, ketoxime, and hydroxamic acid ester. ]
It is represented by.

Specific examples of the isocyanate compound represented by the above formula (20) include isocyanate-containing (meth) acrylates such as 2-isocyanate ethyl methacrylate and 2-isocyanate ethyl acrylate, and methyl ethyl ketone oxime, ε-caprolactam, γ-caprolactam. Examples include compounds to which a blocking agent such as 3,5-dimethylpyrazole, diethyl malonate, ethanol, isopropanol, n-butanol, and 1-methoxy-2-propanol is added. In addition, these compounds may be used individually or may be used in combination of 2 or more type.

The (B) isocyanate compound can be synthesized by a known method, or the following commercially available products can be used.
Karens AOI (2-Isocyanatoethyl acrylate, a registered trademark of Showa Denko KK),
Karenz AOI-BM (2- (O- [1'-methylpropylideneamino] carboxamino) ethyl acrylate, registered trademark manufactured by Showa Denko KK)
Karenz AOI-VM (2-Isocyanatoethyl acrylate, a registered trademark of Showa Denko KK),
Karens MOI (2-Isocyanatoethyl methacrylate, a registered trademark of Showa Denko KK),
Karenz MOI-BM (2- (O- [1′-methylpropylideneamino] carboxyamino) ethyl methacrylate, a registered trademark of Showa Denko KK),
Karenz MOI-BP (2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate, a registered trademark of Showa Denko KK),
Karens MOI-EG (registered trademark of Showa Denko KK),
Karens BEI (Showa Denko KK 1,1- (bisacryloyloxymethyl) ethyl isocyanate, registered trademark),
Karenz AOI-BM (2- (O- [1′-methylpropylideneamino] carboxyamino) ethyl acrylate, registered trademark, manufactured by Showa Denko KK).
Among these, 2- (O- [1′-methylpropylideneamino] carboxyamino) ethyl acrylate (eg Karenz AOI-BM) and 1,1- (bisacryloyloxymethyl) ethylisocyanate (eg Karenz) Preference is given to using BEI).

Further, an isocyanate compound having a blocked isocyanate group having the following structure can be used.

The amount of the (B) isocyanate compound in the photosensitive resin composition according to the present invention is usually 1 part by mass to 50 parts by mass with respect to 100 parts by mass of the polyimide precursor (A).

[(C) Carboxylic acid compound or anhydride thereof]
The photosensitive resin composition of the present invention may further contain (C) a carboxylic acid compound represented by the following general formula (30) or an anhydride thereof, if desired.

［式中、Ｚ^１及びＺ^２は、それぞれ独立に、
水素原子、ハロゲン原子、ヒドロキシ基、メルカプト基、カルボキシ基、シアノ基、ホルミル基、ハロホルミル基、スルホ基、ニトロ基、ニトロソ基、オキソ基、チオキシ基、
置換されていてもよい炭素原子数１～１０のアルキル、アルコキシ、もしくはアルキルスルファニル基、
置換されていてもよい炭素原子数２～１０のアルケニル、アルキニル、もしくはアルコキシカルボニル基、又は
置換されていてもよいアミノ、イミノ、もしくはカルバモイル基を表し、
Ｚ^１及びＺ^２は、相互に結合して、ヘテロ原子を含んでもよく、置換基を有していてもよく、縮合していてもよい環を形成してもよく、当該環が芳香族環であるとき、

はＨＯＯＣがＣＯＯＨに対してオルト位にある共役二重結合を示し、当該環が芳香族環であるとき以外の場合、

はＨＯＯＣとＣＯＯＨについてのシス型二重結合を示す。］

[In the formula, Z ¹ and Z ² are each independently
Hydrogen atom, halogen atom, hydroxy group, mercapto group, carboxy group, cyano group, formyl group, haloformyl group, sulfo group, nitro group, nitroso group, oxo group, thioxy group,
An optionally substituted alkyl, alkoxy, or alkylsulfanyl group having 1 to 10 carbon atoms,
Represents an optionally substituted alkenyl, alkynyl, or alkoxycarbonyl group having 2 to 10 carbon atoms, or an optionally substituted amino, imino, or carbamoyl group,
Z ¹ and Z ² may be bonded to each other to form a ring which may contain a hetero atom, may have a substituent, or may be condensed, and the ring may be an aromatic ring. When

Is a conjugated double bond in which HOOC is in an ortho position with respect to COOH, and when the ring is an aromatic ring,

Indicates a cis double bond for HOOC and COOH. ]

Preferably, the carboxylic acid compound or its anhydride (C) is a carboxylic acid compound represented by the following general formula (31) or its anhydride.

［式中、Ｒ^３３～Ｒ^３６は、それぞれ独立に、
水素原子、ハロゲン原子、ヒドロキシ基、メルカプト基、カルボキシ基、シアノ基、ホルミル基、ハロホルミル基、
スルホ基、ニトロ基、ニトロソ基、オキソ基、チオキシ基、
置換されていてもよい炭素原子数１～６のアルキル、アルコキシ、もしくはアルキルスルファニル基、
置換されていてもよい炭素原子数２～６のアルケニル、アルキニル、もしくはアルコキシカルボニル基、又は
置換されていてもよいアミノ、イミノ、もしくはカルバモイル基を表し、
Ｒ^３３とＲ^３４、Ｒ^３４とＲ^３５、もしくはＲ^３５とＲ^３６は、相互に結合して、ヘテロ原子を含んでもよく、置換基を有していてもよく、縮合していてもよい環を形成してもよい。］

[In the formula, R ³³ to R ³⁶ are each independently
Hydrogen atom, halogen atom, hydroxy group, mercapto group, carboxy group, cyano group, formyl group, haloformyl group,
Sulfo group, nitro group, nitroso group, oxo group, thioxy group,
An optionally substituted alkyl, alkoxy, or alkylsulfanyl group having 1 to 6 carbon atoms,
Represents an optionally substituted alkenyl, alkynyl, or alkoxycarbonyl group having 2 to 6 carbon atoms, or an optionally substituted amino, imino, or carbamoyl group,
R ³³ and R ³⁴ , R ³⁴ and R ³⁵ , or R ³⁵ and R ³⁶ may be bonded to each other to contain a hetero atom, may have a substituent, or may be a condensed ring. May be formed. ]

Specific examples of the alkyl group include straight-chain alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group (amyl group), hexyl group, heptyl group, octyl group, nonyl group and decyl group. Isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, tert-pentyl group, sec-isoamyl group, isohexyl group, neohexyl group, 4-methylhexyl group, 5-methyl Hexyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 4-ethylhexyl group, 2-ethylpentyl group, heptan-3-yl group, heptan-4-yl group, 4-methylhexane-2- Yl group, 3-methylhexane-3-yl group, 2,3-dimethylpentan-2-yl group, 2,4-dimethyl Tan-2-yl group, 4,4-dimethylpentan-2-yl group, 6-methylheptyl group, 2-ethylhexyl group, octan-2-yl group, 6-methylheptan-2-yl group, 6-methyl Octyl group, 3,5,5-trimethylhexyl group, nonan-4-yl group, 2,6-dimethylheptan-3-yl group, 3,6-dimethylheptan-3-yl group, 3-ethylheptane-3 A branched alkyl group such as -yl group, 3,7-dimethyloctyl group, 8-methylnonyl group, 3-methylnonan-3-yl group, 4-ethyloctane-4-yl group; cyclopropyl group, cyclobutyl group, Cyclopentyl group, cyclohexyl group, 4-tert-butylcyclohexyl group, 1,6-dimethylcyclohexyl group, menthyl group, cycloheptyl group, cyclooctyl group, bi Black [2.2.1] heptan-2-yl group, bornyl group, isobornyl group, 1-adamantyl, 2-adamantyl, tricyclo [5.2.1.0 ^{2, 6]} decan-4-yl group And alicyclic alkyl groups such as tricyclo [5.2.1.0 ^2,6 ] decan-8-yl group.

Specific examples of the alkoxy, alkylsulfanyl group, and alkoxycarbonyl group include groups in which -O-, -S-, and -COO- are respectively bonded to the above alkyl group.

Specific examples of the alkenyl group include ethenyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group and 3- Examples include a pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 1-heptenyl group, 2-heptenyl group, 5-heptenyl group, 1-octenyl group, 3-octenyl group, and 5-octenyl group. .

Specific examples of the alkynyl group include an acetylenyl group, a 1-propynyl group, a 2-propynyl group, a 1-butynyl group, a 2-butynyl group, a 3-butynyl group, a 1-pentethyl group, a 2-pentethyl group, and a 3-pentynyl group. Pentethyl group, 1-hexynyl group, 2-hexynyl group, 3-hexynyl group, 1-heptynyl group, 2-heptynyl group, 5-heptynyl group, 1-octynyl group, 3-octynyl group, 5-octynyl group and the like can be mentioned. .

Specific examples of the ring in which Z ¹ and Z ² are bonded to each other to form a ring which may contain a hetero atom, may have a substituent, and may be condensed, and R ³³ In the case where R ³⁴ , R ³⁴ and R ³⁵ , or R ³⁵ and R ³⁶ are bonded to each other to form a ring which may contain a hetero atom, may have a substituent, or may be condensed. Specific examples of the ring of benzene, naphthalene, anthracene, pyrrole, furan, thiophene, pyrrolidine, tetrahydrofuran, tetrahydrothiophene, pyridine, piperidine, tetrahydropyran, tetrahydrothiopyran, imidazole, pyrazole, oxazole, thiazole, imidazoline, dioxane, Morpholine, thiazine, triazole, dioxolane, pyridazine, pyrimidine, pyrazine And indole, isoindole, benzimidazole, purine, benzotriazole, quinoline, isoquinoline, quinazoline, quinoxaline, cinnoline, pteridine, chromene, isochromene, acridine, xanthene, carbazole and the like.

Examples of the substituent include a halogen atom, hydroxy group, mercapto group, carboxy group, cyano group, formyl group, haloformyl group, sulfo group, amino group, nitro group, nitroso group, oxo group, thioxy group, and 1 carbon atom. And an alkyl or haloalkyl group having 1 to 10 carbon atoms and an alkoxy or haloalkoxy group having 1 to 10 carbon atoms.

Preferably, Z ¹ and Z ^{2 in} the general formula (2) are a hydrogen atom or an optionally substituted alkyl group having 1 to 10 carbon atoms.

Some of the suitable carboxylic acid compounds or their anhydrides (C) are shown below.

　上に例示したカルボン酸化合物は、酸無水物であってもよい。

The carboxylic acid compounds exemplified above may be acid anhydrides.

The amount of the carboxylic acid compound or its anhydride (C) in the photosensitive resin composition according to the present invention is usually 0.1 parts by mass to 10 parts by mass with respect to 100 parts by mass of the polyimide precursor (A). .

[Other ingredients]
In the embodiment, the photosensitive resin composition may further contain components other than the above-mentioned components (A) to (C). Examples of other components include a photopolymerization initiator, a crosslinkable compound, a solvent, a resin component other than the (A) polyimide precursor, a sensitizer, an adhesion aid, a thermal polymerization inhibitor, an azole compound, and a hindered phenol. Examples thereof include compounds and fillers.

[Photopolymerization initiator]
The photosensitive resin composition of the present invention may contain a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it is a compound having absorption in the light source used during photocuring, and examples thereof include tert-butylperoxy-iso-butyrate and 2,5-dimethyl-2,5-bis (benzoyl). Dioxy) hexane, 1,4-bis [α- (tert-butyldioxy) -iso-propoxy] benzene, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis (tert-butyldioxy) hexenehydro Peroxide, α- (iso-propylphenyl) -iso-propyl hydroperoxide, tert-butyl hydroperoxide, 1,1-bis (tert-butyldioxy) -3,3,5-trimethylcyclohexane, butyl-4,4-bis (Tert-Butyldioxy) valerate, cyclohexano Peroxide, 2,2 ′, 5,5′-tetra (tert-butylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, 3,3 ′, 4 4'-tetra (tert-amylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra (tert-hexylperoxycarbonyl) benzophenone, 3,3'-bis (tert-butylperoxycarbonyl) -4,4 Organic peroxides such as'-dicarboxybenzophenone, tert-butylperoxybenzoate, di-tert-butyldiperoxyisophthalate; 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, octamethylanthraquinone, 1, 2-Benz anthraquinone, etc. Quinones; benzoin methyl, benzoin ethyl ether, α-methylbenzoin, α-phenylbenzoin and other benzoin derivatives; 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl- Ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one , 2-hydroxy-1- [4- {4- (2-hydroxy-2-methyl-propionyl) benzyl} -phenyl] -2-methyl-propan-1-one, phenylglyoxylic acid methyl ester, 2- Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl- 2-Dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butane-1 -One and other alkylphenone compounds; bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and other acylphosphine oxide compounds; 2- (O -Benzoyl oxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H- Examples include oxime ester compounds such as carbazol-3-yl] ethanone.
The photopolymerization initiator is available as a commercially available product, for example, IRGACURE [registered trademark] 651, 184, 2959, 127, 907, 369, 379EG, 819, 819DW, and 1800, 1870, 784, OXE01, OXE02, 250, 1173, MBF, TPO, 4265, TPO (manufactured by BASF), KAYACURE [registered trademark] DETX, MBP, and the like. DMBI, EPA, OA (all manufactured by Nippon Kayaku Co., Ltd.), VICURE-10, all 55 (all manufactured by STAUFFER Co. LTD), ESACURE KIP150, TZT, 1001, KTO46, KB1 and KB1. KL200, KS300, EB3, triazine-PMS, triazine A, triazine B Or more, Japan Siber Hegner Co., Ltd.), ADEKAOPTOMER N-1717, the same N-1414, the same N-1606 (or more, Co., Ltd. ADEKA), and the like. These photopolymerization initiators may be used alone or in combination of two or more kinds.
The blending amount of the photopolymerization initiator is usually 0.1 parts by mass to 20 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor, and preferably 0.5 parts by mass to 15 parts by mass from the viewpoint of photosensitivity. It is a department. When the photopolymerization initiator is blended in an amount of 0.1 part by mass or more with respect to 100 parts by mass of the (A) polyimide precursor, the photosensitivity of the photosensitive resin composition is likely to be improved, while in the case of blending 20 parts by mass or less. In particular, the thick film curability of the photosensitive resin composition is easily improved.

[Crosslinkable compound]
In the embodiment, in order to improve the resolution of the relief pattern, a monomer (crosslinking compound) other than the (B) isocyanate compound having a photopolymerizable unsaturated bond is optionally mixed with the photosensitive resin composition. be able to. As such a crosslinkable compound, a (meth) acrylic compound that undergoes a radical polymerization reaction with a photopolymerization initiator is preferable, and is not particularly limited to, but includes, for example, diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate. Ethylene glycol or polyethylene glycol mono- or diacrylates and methacrylates, propylene glycol or polypropylene glycol mono- or diacrylates and methacrylates, glycerol mono-, di- or triacrylates and methacrylates, cyclohexane diacrylates and dimethacrylates, 1,4-butanediol Diacrylates and dimethacrylates, diacrylates and dimethacrylates of 1,6-hexanediol, neopentyl glycol Diacrylates and dimethacrylates, bisphenol A mono- or diacrylates and methacrylates, benzene trimethacrylate, isobornyl acrylates and methacrylates, acrylamides and their derivatives, methacrylamides and their derivatives, trimethylolpropane triacrylates and methacrylates, glycerol dimethacrylates. Or compounds such as triacrylate and methacrylate, pentaerythritol di-, tri- or tetraacrylate and methacrylate, and ethylene oxide or propylene oxide adducts of these compounds may be mentioned.

The amount of the cross-linking compound (B) other than the isocyanate compound to be blended is preferably 1 part by mass to 100 parts by mass, more preferably 1 part by mass to 50 parts by mass, relative to 100 parts by mass of the (A) polyimide precursor. is there.

Examples of the thermal crosslinking agent include hexamethoxymethylmelamine, tetramethoxymethylglycoluril, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis (methoxymethyl) glycoluril, 1,3,4,6-tetrakis (butoxymethyl). ) Glycoluril, 1,3,4,6-tetrakis (hydroxymethyl) glycoluril, 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea and 1,1,1. Examples thereof include 3,3-tetrakis (methoxymethyl) urea.
Examples of the filler include inorganic fillers, and specific examples include sol such as silica, aluminum nitride, boron nitride, zirconia, and alumina.

As the solvent, it is preferable to use an organic solvent from the viewpoint of solubility in the (A) polyimide precursor. Specifically, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, cyclopentanone, cyclohexanone, γ-butyrolactone , Α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, etc., which may be used alone or in combination of two or more. .

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

In the embodiment, the photosensitive resin composition may further contain a resin component other than the (A) polyimide precursor. Examples of the resin component that can be contained in the photosensitive resin composition include polyimide, polyoxazole, polyoxazole precursor, phenol resin, polyamide, epoxy resin, siloxane resin, acrylic resin and the like.
The blending amount of these resin components is preferably in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.

In the embodiment, the photosensitive resin composition may optionally contain a sensitizer 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 Millidene indanone, 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-acetyl-7-dimethylaminocoumarin, 3-ethoxy Carbonyl-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, dimethylaminobenzoic acid isoamyl, diethylaminobenzoic acid isoamyl, 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 can be mentioned. These can be used alone or in combination of two or more.

The compounding amount of the sensitizer is preferably 0.1 part by mass to 25 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.

In the embodiment, in order to improve the adhesiveness between the film formed using the photosensitive resin composition and the substrate, an adhesion aid can be optionally added to the photosensitive resin composition. Examples of the adhesion aid include γ-aminopropyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N- (3-diethoxymethylsilylpropyl ) Succinimide, N- [3- (triethoxysilyl) propyl] phthalamic acid, benzophenone-3,3'-bis (N- [3-triethoxysilyl] propylamide) -4,4'-dicarboxylic acid, benzene- 1,4-bis (N- [3 -Triethoxysilyl] propylamide) -2,5-dicarboxylic acid, 3- (triethoxysilyl) propylsuccinic hydride, silane coupling agents such as N-phenylaminopropyltrimethoxysilane, and aluminum tris (ethylaceto) Acetate), aluminum tris (acetylacetonate), ethylacetoacetate aluminum diisopropylate, and other aluminum-based adhesion aids.

Among these adhesion aids, it is more preferable to use a silane coupling agent from the viewpoint of adhesive strength. The amount of the adhesion aid compounded is preferably in the range of 0.5 to 25 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.

In the embodiment, a thermal polymerization inhibitor may be optionally added in order to improve the stability of the viscosity and photosensitivity of the photosensitive resin composition during storage, particularly in the state of a solution containing a solvent. Examples of the thermal polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2 , 6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-) N-sulfopropylamino) phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N (1-naphthyl) hydroxylamine ammonium salt and the like are used.

The blending amount of the thermal polymerization inhibitor is preferably in the range of 0.005 parts by mass to 12 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.

For example, when a substrate made of copper or a copper alloy is used, an azole compound can be optionally added to the photosensitive resin composition in order to suppress discoloration of the substrate. Examples of the azole compound include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole and 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-dim Cylbenzyl) 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 Tetrazole, 1-methyl -1H- tetrazole, and the like. 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.

The compounding amount of the azole compound is preferably 0.1 part by mass to 20 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor, and is 0.5 part by mass to 5 parts by mass from the viewpoint of photosensitivity. More preferably. When the compounding amount of the azole compound with respect to 100 parts by mass of the (A) polyimide precursor is 0.1 parts by mass or more, when the photosensitive resin composition is formed on copper or a copper alloy, copper or the copper alloy is formed. Discoloration of the surface is suppressed, while when it is 20 parts by mass or less, the photosensitivity is excellent, which is preferable.

In the embodiment, a hindered phenol compound can be optionally added to the photosensitive resin composition in order 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-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-hydro] Cyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N ′ hexamethylenebis (3,5-di-t) -Butyl-4-hydroxy-hydrocinnamide), 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-hi) Roxy-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-dimethyl) Benzyl) -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-d) -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 is particularly preferred.

The content of the hindered phenol compound is preferably 0.1 part by mass to 20 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor, and 0.5 part by mass to 10 parts by mass from the viewpoint of photosensitivity. It is more preferably part. When the blending amount of the hindered phenol compound with respect to 100 parts by mass of the (A) polyimide precursor is 0.1 parts by mass or more, for example, when the photosensitive resin composition is formed on copper or a copper alloy, copper or copper is used. Discoloration / corrosion of the alloy is prevented, while when it is 20 parts by mass or less, the photosensitivity is excellent, which is preferable.

[Method for producing cured relief pattern]
In the embodiment, the following steps are performed:
(1) a step of applying a photosensitive resin composition according to the present invention onto a substrate to form a photosensitive resin layer on the substrate;
(2) exposing the photosensitive resin layer to light,
(3) a step of developing the photosensitive resin layer after the exposure to form a relief pattern,
(4) It is possible to provide a method for producing a substrate with a cured relief pattern, including the step of forming a cured relief pattern by heating the relief pattern.

The following explains each process.

(1) Step of applying the photosensitive resin composition according to the present invention onto a substrate to form a photosensitive resin layer on the substrate In this step, the photosensitive resin composition according to the present invention is applied onto a substrate. The photosensitive resin layer is formed by applying and then drying it if necessary. As a coating method, a method which has been conventionally used for coating a photosensitive resin composition, for example, a spin coater, a bar coater, a blade coater, a curtain coater, a screen printing machine, or a spray coater is used. The method etc. can be used.

If necessary, the coating film made of the photosensitive resin composition can be dried, and as the drying method, for example, methods such as air drying, heat drying using an oven or a hot plate, and vacuum drying are used. Further, it is desirable that the coating film is dried under the condition that the (A) polyimide precursor in the photosensitive resin composition is not imidized. Specifically, when air drying or heat drying is performed, the drying can be performed at 20 ° C. to 200 ° C. for 1 minute to 1 hour. As described above, the 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 in the step (1) is exposed to a photomask having a pattern by using an exposure device such as a contact aligner, a mirror projection, and a stepper. Alternatively, exposure is performed by an ultraviolet light source or the like via a reticle or directly.
Examples of the light source used for the exposure include g-line, h-line, i-line, ghi-line broadband, and KrF excimer laser. The exposure dose is preferably 25 mJ / cm ² to 1000 mJ / cm ² .

After that, for the purpose of improving the photosensitivity, a post-exposure bake (PEB) and / or a pre-development bake may be performed at an arbitrary combination of temperature and time, if necessary. The baking conditions are preferably such that the temperature is from 50 ° C. to 200 ° C. and the time is preferably from 10 seconds to 600 seconds, as long as the characteristics of the photosensitive resin composition are not impaired. Not limited to

(3) Step of developing the exposed photosensitive resin layer to form a relief pattern In this step, the unexposed portion of the exposed photosensitive resin layer is removed by development. As a developing method for developing the photosensitive resin layer after exposure (irradiation), any of conventionally known photoresist developing methods, for example, a rotary spray method, a paddle method, a dipping method involving ultrasonic treatment, etc. can be selected. The method can be selected and used. In addition, after development, for the purpose of adjusting the shape of the relief pattern, etc., post-development baking may be performed at an arbitrary combination of temperature and time, if necessary. Examples of the developer used in the development include N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ -Butyrolactone and the like are preferred. Further, each solvent may be used in combination of two or more kinds, for example, several kinds.

(4) Step of heating the relief pattern to form a substrate with a cured relief pattern In this step, the relief pattern obtained by the development is heated to volatilize the photosensitive component, and (A) the polyimide precursor. Is converted into a cured relief pattern made of polyimide. As the method for heat curing, various methods such as a method using a hot plate, a method using an oven, and a method using a temperature rising oven capable of setting a temperature program can be selected. The heating can be performed, for example, at 130 ° C. to 250 ° C. for 30 minutes to 5 hours. Air may be used as the atmospheric gas at the time of heat curing, and an inert gas such as nitrogen or argon may be used.

[Semiconductor device]
In the embodiment, there is also provided a semiconductor device having a cured relief pattern obtained by the method for producing a cured relief pattern described above. Therefore, it is possible to provide a semiconductor device having a base material that is a semiconductor element and a cured relief pattern of polyimide formed on the base material by the above-described cured relief pattern manufacturing method. The present invention can also be applied to a method of manufacturing a semiconductor device that uses a semiconductor element as a base material and includes the method of manufacturing a cured relief pattern described above as part of the process. A semiconductor device according to the present invention is a semiconductor device having a cured relief pattern formed by the above-described method for producing a cured relief pattern, having a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip chip device, or a bump structure. Can be manufactured by combining it with a known semiconductor device manufacturing method.

[Display device]
In the embodiment, there is provided a display device including a display element and a cured film provided on the display element, wherein the cured film has the above-mentioned cured relief pattern. Here, the cured relief pattern may be laminated in direct contact with the display element, or may be laminated with another layer interposed therebetween. For example, examples of the cured film include a surface protective film for a TFT liquid crystal display element and a color filter element, an insulating film, and a flattening film, a projection for an MVA type liquid crystal display device, and a partition for an organic EL element cathode. .

INDUSTRIAL APPLICABILITY The photosensitive resin composition of the present invention is useful not only for application to the semiconductor device as described above but also for applications such as interlayer insulation of multilayer circuits, cover coat of flexible copper clad board, solder resist film, and liquid crystal alignment film. Is.

The weight average molecular weights shown in the following synthesis examples of the present specification are results of measurement by gel permeation chromatography (hereinafter abbreviated as GPC in the present specification). A GPC device (HLC-8320GPC) manufactured by Tosoh Corporation was used for the measurement, and the measurement conditions and the like are as follows.
GPC column: KD-803, KD-805 (manufactured by Shodex)
Column temperature: 50 ° C
Solvent: N, N-dimethylformamide (Kanto Chemical, special grade), lithium bromide monohydrate (Kanto Chemical, deer special grade) (30 mM) / phosphoric acid (Aldrich) (30 mM) / tetrahydrofuran (Kanto Chemical, special grade) ( 1%)
Flow rate: 1.0 mL / min Standard sample: Polystyrene (GL Science)

The ¹ H-NMR spectrum was measured by JNM-ECX500 (500 MHz, manufactured by JEOL Ltd.).

<Production Example 1> Synthesis of dicarboxylic acid diester (1) 200.00 g (0.68 mol) of 4,4′-biphthalic acid dianhydride (Tokyo Kasei Kogyo Co., Ltd.) was placed in a 2-liter four-necked flask, and 2 -Hydroxyethyl methacrylate (Aldrich) 176.92 g (1.366 mol), hydroquinone (Tokyo Kasei Kogyo Co., Ltd.) 0.74 g (0.007 mol) and γ-butyrolactone (Kanto Kagaku, Shika Special Grade) 600 g were added at 23 ° C. After stirring and adding 108.63 g (1.36 mol) of pyridine (Kanto Kagaku, dehydration), the temperature was raised to 50 ° C. and the mixture was stirred at 50 ° C. for 2 hours to give a compound represented by the following formula (1). A solution containing was obtained.

<Production Example 2> Synthesis of Polymer (2) as Polyimide Precursor 82.46 g of the solution prepared in Production Example 1 and 19.45 g of γ-butyrolactone were placed in a 500 ml four-necked flask, and N was stored at about 5 ° C. , N'-diisopropylcarbodiimide (DIC, Tokyo Chemical Industry Co., Ltd.) (13.13 g) dissolved in 30 g of γ-butyrolactone was added dropwise to the reaction solution over 0.5 hours with stirring, and 0.5 hours after the addition. It was stirred. Then, a solution prepared by dissolving 19.68 g of 2,2-bis [4- (4-aminophenoxy) phenyl] propane (Tokyo Kasei Kogyo Co., Ltd.) in 30 g of N-methyl-2-pyrrolidinone (Kanto Kagaku, deer grade) was used. The mixture was added dropwise with stirring for 2 hours. Then, the temperature was raised to about 25 ° C., the mixture was stirred for 6 hours, then 4.5 g of ethanol (Kanto Kagaku, special grade) was added, and the mixture was stirred for 1 hour.

The obtained reaction mixture was added to 1500 g of methanol (Kanto Chemical Co., Inc., special grade) to form a precipitate composed of a crude polymer. The supernatant was decanted to separate the crude polymer, which was dissolved in 150.0 g of N-methyl-2-pyrrolidinone to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 2250 g of water to precipitate a polymer, and the obtained precipitate was separated by filtration, washed twice with 600 g of methanol, and vacuum dried to obtain a powdery polymer (2). Obtained. When the molecular weight of the polymer (2) was measured by GPC (standard polystyrene conversion), the weight average molecular weight (Mw) was 8,016. The yield was 73.6%. This reaction product has a repeating unit structure represented by the following formula (2).

<Example 1>
28.5714 g of the polymer obtained in Preparation Example 2, IRGACURE [registered trademark] OXE01 (manufactured by BASF, photopolymerization initiator) 1.71 g, AOI-BM (manufactured by Showa Denko KK, 2- (O- [1 ' -Methylpropylideneamino] carboxyamino) ethyl acrylate) 8.57 g, KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd., 3-acryloxypropyltrimethoxysilane) 0.43 g, IRGANOX [registered trademark] 3114 (manufactured by BASF) , Hindered phenol-based antioxidant) 0.43 g and phthalic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 0.28 g were dissolved in cyclohexanone 48.00 g and ethyl lactate 12.00 g to prepare a composition. Then, it filtered using the polypropylene micro filter with a hole diameter of 5 micrometers, and prepared the negative photosensitive resin composition.

<Comparative Example 1>
33.8983 g of the polymer obtained in Production Example 2, IRGACURE [registered trademark] OXE01 (manufactured by BASF, photopolymerization initiator) 2.03 g, 4G (manufactured by Shin-Nakamura Chemical Co., Ltd., polyethylene glycol (200) dimethacrylate) 2 0.71 g, KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd., 3-acryloxypropyltrimethoxysilane) 0.51 g, IRGANOX [registered trademark] 3114 (manufactured by BASF, hindered phenolic antioxidant) 0.51 g, Further, 0.34 g of phthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 48.00 g of cyclohexanone and 12.00 g of ethyl lactate to prepare a composition. Then, it filtered using the polypropylene micro filter with a hole diameter of 5 micrometers, and prepared the negative photosensitive resin composition.

<Comparative example 2>
33.8983 g of the polymer obtained in Production Example 2, IRGACURE [registered trademark] OXE01 (manufactured by BASF, photopolymerization initiator) 2.03 g, DOD-N (manufactured by Shin-Nakamura Chemical Co., Ltd., 1,10-decanedioldiene) Acrylate) 2.71 g, KBM-5103 (Shin-Etsu Chemical Co., Ltd., 3-acryloxypropyltrimethoxysilane) 0.51 g, IRGANOX [registered trademark] 3114 (BASF, hindered phenol antioxidant) 0 0.51 g and phthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.34 g were dissolved in cyclohexanone 48.00 g and ethyl lactate 12.00 g to prepare a composition. Then, it filtered using the polypropylene micro filter with a hole diameter of 5 micrometers, and prepared the negative photosensitive resin composition.

[Electrical property test]
The negative photosensitive resin composition prepared in Example 1 and Comparative Examples 1 and 2 was applied on a silicon wafer on which aluminum was laminated using a spin coater, prebaked at 100 ° C., and an aligner (PLA-501, The film was exposed (i-line, exposure amount: 500 mJ / cm ² ) using Canon Inc., further baked at 115 ° C., and further baked at 230 ° C. to form a film having a thickness of 10 μm. Then, it was immersed in 6N hydrochloric acid. A part where the aluminum was melted and the film was lifted was collected and cut into a length of 3 cm and a width of 9 cm to obtain a self-supporting film. Using this free-standing film, the relative permittivity and dielectric loss tangent at 1 GHz were calculated by the perturbation type cavity resonator method (apparatus: TMR-1A, manufactured by Keycom Co., Ltd.). The details of the measuring method are as follows.

(Measuring method)
Perturbation type cavity resonator method (device configuration)
Vector network analyzer: FieldFox N9926A (manufactured by Keysight Technologies, Inc.)
Cavity resonator: Model TMR-1A (manufactured by Keycom Co., Ltd.)
Cavity volume: 1192822mm ³
Measurement frequency: Approximately 1 GHz (depends on the resonance frequency of the sample)
Sample tube: Made of PTFE Inner diameter: 3mm Length: About 30mm

The measurement results are shown in Table 1 below.

Example 1 using the isocyanate compound according to the present invention has a dielectric constant substantially equal to that of Comparative Example 1 using dimethacrylate and Comparative Example 2 using diacrylate, but the dielectric loss tangent is significantly reduced. ing.

The photosensitive resin composition according to the present invention provides a cured product having high transparency, high Young's modulus after heat curing, and reduced dielectric constant and dielectric loss tangent.

Claims (8)

(A) The following general formula (1):

[In the formula, X ¹ is a tetravalent organic group, Y ¹ is a divalent organic group, and R ¹ and R ² are each independently a monovalent organic group. ] The polyimide precursor which has a unit structure represented by, and (B) following general formula (20):

[In the formula, R ²³ represents a hydrogen atom or a methyl group, R ²⁴ represents an alkylene group having 1 to 5 carbon atoms, which may have a substituent and may be interrupted by an oxygen atom; ²⁵ represents an isocyanate group or a blocked isocyanate group. ]
Isocyanate compound represented by
A photosensitive resin composition containing. The blocked isocyanate group has the following general formula (21):

[In the formula, A represents a residue of a compound for isocyanate blocking selected from the group consisting of alcohol, amine, amide, active methylene compound, nitrogen-containing heteroaryl compound, oxime, ketoxime, and hydroxamic acid ester. ]
The photosensitive resin composition according to claim 1, represented by: The photosensitive resin composition according to claim 1 or 2, wherein in the general formula (20), R ²⁴ is an alkylene group having 1 to 5 carbon atoms and substituted with an acryloyl group or a methacryloyl group. Further (C) the following general formula (30):

[In the formula, Z ¹ and Z ² are each independently
Hydrogen atom, halogen atom, hydroxy group, mercapto group, carboxy group, cyano group, formyl group, haloformyl group, sulfo group, nitro group, nitroso group, oxo group, thioxy group,
An optionally substituted alkyl, alkoxy, or alkylsulfanyl group having 1 to 10 carbon atoms,
Represents an optionally substituted alkenyl, alkynyl, or alkoxycarbonyl group having 2 to 10 carbon atoms, or an optionally substituted amino, imino, or carbamoyl group,
Z ¹ and Z ² may be bonded to each other to form a ring which may contain a hetero atom, may have a substituent, or may be condensed, and the ring may be an aromatic ring. When

Is a conjugated double bond in which HOOC is in an ortho position with respect to COOH, and when the ring is an aromatic ring,

Indicates a cis double bond for HOOC and COOH. ]
A carboxylic acid compound or an anhydride thereof,
The photosensitive resin composition according to any one of claims 1 to 3, further comprising: A photosensitive resin film, which is a fired product of the coating film of the photosensitive resin composition according to any one of claims 1 to 4. The following steps:
(1) A step of applying the photosensitive resin composition according to any one of claims 1 to 4 onto a substrate to form a photosensitive resin layer on the substrate,
(2) exposing the photosensitive resin layer to light,
(3) a step of developing the photosensitive resin layer after the exposure to form a relief pattern,
(4) A method for producing a substrate with a cured relief pattern, which comprises a step of heating the relief pattern to form a cured relief pattern. A substrate with a cured relief pattern manufactured by the method according to claim 6. A semiconductor device comprising a semiconductor element and a cured film provided on or below the semiconductor element, wherein the cured film is the cured relief pattern according to claim 7.