JP7327410B2 - Polyamic acid ester resin composition - Google Patents

Description

The present invention relates to a polyamic acid ester composition, a 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.

BACKGROUND ART Conventionally, polyimide resins, which have excellent heat resistance, electrical properties and mechanical properties, have been used as insulating materials for electronic parts, passivation films, surface protective films, interlayer insulating films, etc. for semiconductor devices. Among these polyimide resins, those provided in the form of a photosensitive polyimide precursor easily form a heat-resistant relief pattern film by thermal imidization treatment by applying, exposing, developing, and curing the precursor. be able to. Such a photosensitive polyimide precursor has the feature of enabling a significant process reduction compared to conventional non-photosensitive polyimide resins.

On the other hand, in recent years, the method of mounting semiconductor devices on printed wiring boards has also changed from the viewpoint of improvements in the degree of integration and arithmetic functions, as well as miniaturization of chip sizes. Polyimide coating directly contacts solder bumps, such as BGA (Ball Grid Array), CSP (Chip Size Packaging), etc. where higher density mounting is possible from the conventional mounting method using metal pins and lead-tin eutectic solder. Structures are coming into use. When forming such a bump structure, the film is required to have high heat resistance and chemical resistance.

Furthermore, the problem of wiring delay has become apparent as the miniaturization of semiconductor devices progresses. As a means of improving the wiring resistance of a semiconductor device, the gold or aluminum wiring that has been used so far is being changed to a copper or copper alloy wiring having a lower resistance. Furthermore, a method of preventing wiring delay by increasing the insulation between wirings is also adopted. In recent years, semiconductor devices are often made of low-dielectric-constant materials as materials with high insulating properties. A problem exists in that shrinkage due to temperature changes destroys the low dielectric constant material portion when mounted in a low dielectric constant material.
As a means for solving this problem, Patent Document 1 discloses that a polyamic containing a polyimide precursor is introduced by introducing an aliphatic group having 5 to 30 carbon atoms and having an ethylene glycol structure into a part of the side chains in the polyimide precursor. Disclosed is a polyamic acid ester composition that improves the transparency when the acid ester composition is formed and further improves the Young's modulus of a cured film after thermal curing.

Table 2013-168675

The polyamic acid ester composition composed of the polyimide precursor described in Patent Document 1 has high transparency and gives a cured product with a high Young's modulus after heat curing, but when used for the above applications, transportation and production There has been a demand for improved storage stability that can flexibly accommodate schedules.

Accordingly, the present invention provides a polyamic acid ester composition having high storage stability, a method for producing a substrate with a cured relief pattern using the polyamic acid ester composition, and a semiconductor device having the cured relief pattern. Make it an issue.

The present inventors have made intensive studies to achieve the above problems, and found that when a polyamic acid ester composition is formed by adding a specific carboxylic acid compound or an anhydride thereof to a polyimide precursor, storage stability is high. The inventors have found that a polyamic acid ester composition can be obtained, and have 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（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
を含み、
任意選択的に（Ｐ）前記ポリイミド前駆体（Ａ）以外の高分子化合物を含み、
前記カルボン酸化合物又はその無水物（Ｂ）はＺ^１又はＺ^２を介して前記ポリイミド前駆体（Ａ）及び／又は前記ポリイミド前駆体（Ａ）以外の高分子化合物（Ｐ）に化学結合していてもよい、
ポリアミック酸エステル樹脂組成物。
［２］ 前記一般式（３０）のＺ^１及びＺ^２が、水素原子又は置換されていてもよい炭素原子数１～１０のアルキル基である、［１］に記載の樹脂組成物。
［３］ 前記カルボン酸化合物又はその無水物（Ｂ）が、下記一般式（３１）：

［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。］
で表されるカルボン酸化合物又はその無水物である、［１］に記載の樹脂組成物。
［４］ 前記ポリイミド前駆体（Ａ）１００質量部に対し、前記カルボン酸化合物又はその無水物（Ｂ）を０．１質量部～１０重量部含む、［１］～［３］のいずれか１項に記載の樹脂組成物。
［５］ 前記ポリイミド前駆体（Ａ）１００質量部に対し、更に（Ｃ）架橋性化合物を１質量部～５０質量部含む、［１］～［４］のいずれか１項に記載の樹脂組成物。
［６］ ［１］～［５］の何れか１項に記載のポリアミック酸エステル樹脂組成物の塗布膜の焼成物であることを特徴とする樹脂膜。
［７］ 以下の工程：
（１）［１］～［５］のいずれか１項に記載のポリアミック酸エステル樹脂組成物を基板上に塗布して、ポリアミック酸エステル樹脂層を該基板上に形成する工程と、
（２）該ポリアミック酸エステル樹脂層を露光する工程と、
（３）該露光後のポリアミック酸エステル樹脂層を現像して、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。
［８］ ［７］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。
［９］ 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、［８］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. ] A polyimide precursor having a unit structure represented by;
and (B) the following general formula (30):

[Wherein, 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 that may contain a heteroatom, may have a substituent, or may be condensed, and the ring is an aromatic ring when

indicates a conjugated double bond where HOOC is ortho to COOH, except when the ring is an aromatic ring,

indicates a cis double bond for HOOC and COOH. ]
Including a carboxylic acid compound or its anhydride represented by
Optionally (P) contains a polymer compound other than the polyimide precursor (A),
The carboxylic acid compound or its anhydride (B) is chemically bonded to the polyimide precursor (A) and/or the polymer compound (P) other than the polyimide precursor (A) via ^Z1 or ^Z2 . may be
A polyamic acid ester resin composition.
[2] The resin composition according to [1], wherein Z ¹ and Z ² in the general formula (30) are a hydrogen atom or an optionally substituted alkyl group having 1 to 10 carbon atoms.
[3] The carboxylic acid compound or its anhydride (B) has the following general formula (31):

[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 are bonded to each other and may contain a heteroatom, may have a substituent, or may be condensed. may be formed. ]
The resin composition according to [1], which is a carboxylic acid compound represented by or an anhydride thereof.
[4] Any one of [1] to [3], which contains 0.1 to 10 parts by weight of the carboxylic acid compound or its anhydride (B) with respect to 100 parts by weight of the polyimide precursor (A) The resin composition according to Item.
[5] With respect to 100 parts by mass of the polyimide precursor (A), the resin composition according to any one of [1] to [4], further comprising 1 part by mass to 50 parts by mass of a crosslinkable compound (C). thing.
[6] A resin film characterized by being a baked product of a coating film of the polyamic acid ester resin composition according to any one of [1] to [5].
[7] The following steps:
(1) a step of applying the polyamic acid ester resin composition according to any one of [1] to [5] onto a substrate to form a polyamic acid ester resin layer on the substrate;
(2) exposing the polyamic acid ester resin layer;
(3) developing the exposed polyamic acid ester resin layer to form a relief pattern;
(4) A method for producing a substrate with a hardened relief pattern, comprising the step of heat-treating the relief pattern to form a hardened relief pattern.
[8] A substrate with a cured relief pattern produced by the method described in [7].
[9] A semiconductor device comprising a semiconductor element and a cured film provided on or under the semiconductor element, wherein the cured film is the cured relief pattern according to [8].

According to the present invention, it is possible to provide a polyamic acid ester composition with high storage stability, a method for producing a cured relief pattern using the polyamic acid ester composition, and a semiconductor device provided with the cured relief pattern.

[Polyamic acid ester resin composition]
The polyamic acid ester resin composition of the present invention comprises (A) a polyimide precursor, (B) a carboxylic acid compound or an anhydride thereof, optionally (C) a crosslinkable compound, and (P) the polyimide precursor other than (A). polymer compound, and other ingredients. Each component is described in turn below.

[(A) polyimide precursor]
(A) The polyimide precursor is a resin component contained in the polyamic acid ester 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 above 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 photosensitive properties, it is preferably a tetravalent and more preferably an aromatic group or an alicyclic aliphatic group in which the —COOR ¹ and —COOR ² groups and the —CONH— group are ortho-positioned to each other. Further, the tetravalent organic group represented by X ¹ is more preferably an aromatic ring-containing organic group having 6 to 40 carbon atoms.

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

Moreover, the structure of ^X1 may be one or a combination of two or more.

In the above general formula (1), Y ¹ is not limited as long as it is a divalent organic group having 6 to 40 carbon atoms, but may be substituted from the viewpoint of achieving both heat resistance and photosensitive properties. A cyclic organic group having 1 to 4 aromatic rings or aliphatic rings, or an aliphatic group or siloxane group having no cyclic structure is preferred. More preferably, Y ¹ has 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 ). .}

Moreover, the structure of ^Y1 may be one type or a combination of two or more types.

In general formula (1) above, R ¹ and R ² are not particularly limited as long as they are each independently a monovalent organic group. For example, R ¹ and R ² are each independently a monovalent aliphatic group having 1 to 30 carbon atoms, or a monovalent aliphatic group having 5 to 22 carbon atoms, a cycloaliphatic group, or a bond between an aromatic group and an aliphatic group. or a group 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 each independently represent the following general formula (2):

(wherein 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 , is a bonding site with a carboxylic acid present in the polyamic acid main chain of the general formula (1).)
is preferably represented by

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

(In the formula, R ⁶ is a monovalent group selected from alkyl groups having 1 to 30 carbon atoms. * is the same as 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 type or a combination of two or more types, preferably each is a combination of three or less types, preferably each is a combination of two types, most preferably are each one.

In the above general formula (1), from the viewpoint of the photosensitive properties and mechanical properties of the polyamic acid ester resin composition, the monovalent organic group represented by the above general formula (2) for all of R ¹ and R ² and the above general The total proportion of the monovalent organic groups represented by formula (3) is preferably 80 mol% or more, preferably 90 mol% or more, and preferably 100 mol%.

In the above general formula (1), from the viewpoint of the photosensitive properties and mechanical properties of the polyamic acid ester resin composition, the monovalent organic group represented by the above general formula (2) for all of R ¹ and R ² The total ratio of the monovalent organic groups used is preferably 80 mol % or more, preferably 90 mol % or more, and preferably 100 mol %.

R ³ in the 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. A methyl group is preferred.

R ⁴ and R ⁵ in the general formula (2) are each independently not limited as long as they are a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, but the photosensitive properties of the polyamic acid ester resin composition is preferably a hydrogen atom from the viewpoint of

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

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. Alkyl groups having 5 to 30 carbon atoms are preferred, alkyl groups having 8 to 30 carbon atoms are preferred, alkyl groups having 9 to 30 carbon atoms are preferred, and alkyl groups having 10 to 30 carbon atoms are preferred. An alkyl group having 11 to 30 carbon atoms is preferred, and an alkyl group having 17 to 30 carbon atoms is even more preferred. It may have not only a linear structure but also a branched structure and a cyclic 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, tetradecyl group (myristyl group), pentadecyl group, hexadecyl group (palmityl group), heptadecyl group (margaryl group), octadecyl group (stearyl group), nonadecyl group, icosyl group (arachyl group), heneicosyl group, docosyl group (behenyl linear alkyl groups such as group), tricosyl group, tetracosyl group (lignoceryl group), pentacosyl group, hexacosyl group, heptacosyl 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-methylhexyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 4-ethylhexyl group , 2-ethylpentyl group, heptane-3-yl group, heptane-4-yl group, 4-methylhexan-2-yl group, 3-methylhexan-3-yl group, 2,3-dimethylpentane-2- yl group, 2,4-dimethylpentan-2-yl group, 4,4-dimethylpentan-2-yl group, 6-methylheptyl group, 2-ethylhexyl group, octan-2-yl group, 6-methylheptane- 2-yl group, 6-methyloctyl group, 3,5,5-trimethylhexyl group, nonan-4-yl group, 2,6-dimethylheptan-3-yl group, 3,6-dimethylheptan-3-yl group, 3-ethylheptan-3-yl group, 3,7-dimethyloctyl group, 8-methylnonyl group, 3-methylnonan-3-yl group, 4-ethyloctan-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-pentamethylhexan-4-yl group, 10-methylundecyl group, 11-methyldodecyl group, tridecane-6-yl group, tridecane-7-yl group, 7-ethylundecane-2-yl group, 3-ethylundecane-3-yl group, 5-ethylundecane-5-yl group, 12-methyltridecyl group, 13-methyltetradecyl group, pentadecane-7-yl group, pentadecane-8-yl group, 14-methylpentadecyl group, 15-methylhexadecyl group, heptadecane-8-yl group, heptadecane -9-yl group, 3,13-dimethylpentadecan-7-yl group, 2,2,4,8,10,10-hexamethylundecane-5-yl group, 16-methylheptadecyl group, 17-methyloctadecyl group, nonadecan-9-yl group, nonadecan-10-yl group, 2,6,10,14-tetramethylpentadecan-7-yl group, 18-methylnonadecyl group, 19-methylicosyl group, henicosan-10-yl group, 20-methylhenicosyl group, 21-methyldocosyl group, tricosan-11-yl group, 22-methyltricosyl group, 23-methyltetracosyl group, pentacosan-12-yl group, pentacosan-13-yl group, 2 , 22-dimethyltricosan-11-yl group, 3,21-dimethyltricosan-11-yl group, 9,15-dimethyltricosan-11-yl group, 24-methylpentacosyl group, 25-methylhexa Branched chain alkyl groups such as cosyl group and 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 ]decane-4-yl group, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl group, cyclododecyl group and other alicyclic alkyl groups.

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

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,
provided that Z ¹ , Z ² and Z ³ may be the same or different,
The total number of carbon atoms of Z ¹ , Z ² and Z ³ is 4 or more. ) is preferably represented by

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, 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, preferably 6 or more, preferably 10 or more, preferably 12 or more, and 14 or more. It is preferably 15 or 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.

Also, 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).

(A) A polyimide precursor is converted into a polyimide by subjecting it to a heat cyclization treatment.
[(A) Preparation method of polyimide precursor]
The polyimide precursor represented by the general formula (1) in the present embodiment includes, for example, the above-mentioned tetracarboxylic dianhydride containing a tetravalent organic group X ¹ having 6 to 40 carbon atoms, and (a) the above (b) alcohols formed by bonding a monovalent organic group and a hydroxyl group represented by the general formula (2); and (b) a monovalent organic group represented by the general formula (3) and a hydroxyl group A partially esterified tetracarboxylic acid (hereinafter also referred to as an acid/ester form) is prepared by reacting an alcohol comprising the above-mentioned divalent organic group Y ¹ having 6 to 40 carbon atoms. It is obtained by polycondensation with diamines contained.

(Preparation of acid/ester form)
In the present embodiment, examples of the tetracarboxylic dianhydride containing a tetravalent organic group X ¹ having 6 to 40 carbon atoms include pyromellitic anhydride, diphenyl ether-3,3′,4,4′-tetracarboxylic 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 (3,4-phthalic anhydride) propane, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane and the like can be mentioned.
Further, tetracarboxylic dianhydrides represented by the following formulas (5-1-a) to (5-7-a) are also exemplified.

These can be used singly 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, 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-hydroxyethyl methacrylate and the like can be mentioned.

(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 Alcohols etc. can be mentioned.

Alcohols having the structures of formulas (3-1) to (3-6) may also be used.
The following commercial products may be used.
Alcohols containing the structure of formula (3-1): Fine Oxocol (registered trademark) 180 (manufactured by Nissan Chemical Industries, Ltd.),
Alcohols containing the structure of formula (3-2): Fine Oxocol (registered trademark) 2000 (manufactured by Nissan Chemical Industries, Ltd.),
Alcohols containing the structure of formula (3-3): Fine Oxocol (registered trademark) 180N (manufactured by Nissan Chemical Industries, Ltd.),
Alcohols containing the structure of formula (3-4) or formula (3-5): Fine Oxocol (registered trademark) 180T (manufactured by Nissan Chemical Industries, Ltd.),
Alcohols containing the structure of formula (3-6): Fine Oxocol (registered trademark) 1600K (manufactured by Nissan Chemical Industries, 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 components (a) and (b) in the polyamic acid ester resin composition is 80 mol% or more of the total content of R ¹ and R ² in the general formula (1). Preferably, the content of component (b) is 1 mol % to 90 mol % of the total content of R ¹ and R ² in order to lower the dielectric constant and the dielectric loss tangent.

The tetracarboxylic dianhydride and the alcohol are stirred, dissolved and mixed in a 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. Thereby, the half-esterification reaction of the acid dianhydride proceeds to obtain the desired acid/ester form.

The reaction solvent preferably dissolves the acid/ester and the polycondensation product of the acid/ester and diamines, such as N-methyl-2-pyrrolidone, N , N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, gamma-butyrolactone, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, hexane , heptane, benzene, toluene, xylene and the like. These may be used alone or in combination of two or more as needed.

(Preparation of polyimide precursor)
To the above acid/ester form (typically a solution in the above reaction solvent), under ice-cooling, a known dehydration condensation agent such as dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-Carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate or the like is added and mixed to convert the acid/ester form into a polyanhydride, which is then , A polyimide precursor that can be used in the embodiments by adding dropwise a diamine containing a divalent organic group Y ¹ having 6 to 40 carbon atoms dissolved or dispersed in a separate solvent and polycondensing it. can be obtained.

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-amino phenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-tolysine sulfone, 9,9-bis(4-aminophenyl)fluorene, and hydrogen atoms on their benzene rings is partially substituted with a methyl group, an ethyl group, a hydroxymethyl group, a hydroxyethyl group, a halogen, etc., such as 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl- 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethytoxy-4,4'- diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and mixtures thereof.
Also included are diamines represented by the following formula (8-1).

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 polyamic acid ester resin composition on the substrate, (A) the polyimide precursor Diaminosiloxanes such as 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 1,3-bis(3-aminopropyl)tetraphenyldisiloxane, and the like can also be copolymerized during preparation.

After the completion of the polycondensation reaction, water-absorbing by-products of the dehydration condensation agent coexisting in the reaction solution are filtered off if necessary, and then a poor solvent such as water, lower aliphatic alcohol, or a mixture thereof is added. , Precipitate the polymer component by putting it into the reaction solution, and repeat re-dissolution, re-precipitation, etc. to purify the polymer, vacuum dry, and polyimide precursor that can be used in the embodiment. Isolate the body. In order to improve the degree of purification, the polymer solution may be passed through a column packed with anion and/or cation exchange resins swollen with a suitable organic solvent to remove ionic impurities.

(A) The molecular weight of the polyimide precursor is preferably 5,000 to 150,000, preferably 7,000 to 50,000, when measured by polystyrene equivalent weight average molecular weight by gel permeation chromatography. is more preferred. When the weight-average molecular weight is 5,000 or more, the mechanical properties are favorable. It is preferable because it is good.

[(B) Carboxylic acid compound or its anhydride]
The polyamic acid ester resin composition of the present invention contains (B) a carboxylic acid compound represented by the following general formula (30) or an anhydride thereof.

［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。］

[Wherein, 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 that may contain a heteroatom, may have a substituent, or may be condensed, and the ring is an aromatic ring when

indicates a conjugated double bond where HOOC is ortho to COOH, except when the ring is an aromatic ring,

indicates a cis double bond for HOOC and COOH. ]

Preferably, the carboxylic acid compound or its anhydride (B) 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 are bonded to each other and may contain a heteroatom, may have a substituent, or may be condensed. may be formed. ]

Specific examples of alkyl groups include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl (amyl), hexyl, heptyl, octyl, nonyl, and decyl groups. ; 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, heptane-3-yl group, heptane-4-yl group, 4-methylhexane-2- yl group, 3-methylhexan-3-yl group, 2,3-dimethylpentan-2-yl group, 2,4-dimethylpentan-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-methyloctyl group, 3,5,5-trimethylhexyl group, nonan-4-yl group, 2,6-dimethylheptan-3-yl group, 3,6-dimethylheptan-3-yl group, 3-ethylheptan-3-yl group, 3,7-dimethyloctyl group, 8-methylnonyl group, 3-methylnonane -3-yl group, branched chain alkyl groups such as 4-ethyloctan-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, 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 ]decan-8-yl group and other alicyclic alkyl groups.

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

Examples of alkenyl groups include ethenyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3- 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 alkynyl groups include acetylenyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentyl, 2-pentyl, 3- 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 .

Specific examples of rings in which Z ¹ and Z ² are bonded to each other to form a ring that may contain a heteroatom, may have a substituent, and may be condensed, and R ³³ and When R ³⁴ , R ³⁴ and R ³⁵ , or R ³⁵ and R ³⁶ are mutually bonded to form a ring which may contain a heteroatom, may have a substituent, or may be condensed Specific examples of the ring include 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, indole, isoindole, benzimidazole, purine, benzotriazole, quinoline, isoquinoline, quinazoline, quinoxaline, cinnoline, pteridine, chromene, isochromene, acridine, xanthene, carbazole, etc. mentioned.

Substituents include, for example, a halogen atom, a hydroxy group, a mercapto group, a carboxy group, a cyano group, a formyl group, a haloformyl group, a sulfo group, an amino group, a nitro group, a nitroso group, an oxo group, a thioxy group, and 1 carbon atom. to 10 alkyl or haloalkyl groups, and alkoxy or haloalkoxy groups having 1 to 10 carbon atoms.

Preferably, Z ¹ and Z ² in the general formula (30) are a hydrogen atom or an optionally substituted alkyl group having 1 to 10 carbon atoms.

Some of the suitable carboxylic acid compounds or anhydrides thereof (B) are listed 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 (B) in the polyamic acid ester resin composition according to the present invention is usually 0.1 parts by weight to 10 parts by weight with respect to 100 parts by weight of the polyimide precursor (A). be.

The carboxylic acid compound or its anhydride (B) is chemically bonded via ^Z1 or ^Z2 to the polyimide precursor (A) and/or a polymer compound (P) other than the polyimide precursor (A) (described later). may

[(C) crosslinkable compound]
In the embodiment, a monomer having a photopolymerizable unsaturated bond (crosslinking compound) can optionally be added to the polyamic acid ester resin composition in order to improve the resolution of the relief pattern. Such a crosslinkable compound is preferably a (meth)acrylic compound that undergoes a radical polymerization reaction with a photopolymerization initiator, and is not particularly limited to the following, including diethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate, mono- or di-acrylates and methacrylates of ethylene glycol or polyethylene glycol, mono- or di-acrylates and methacrylates of propylene glycol or polypropylene glycol, mono-, di- or tri-acrylates and methacrylates of glycerol, cyclohexane diacrylate and dimethacrylate, 1,4-butanediol diacrylates and dimethacrylates of 1,6-hexanediol, diacrylates and dimethacrylates of neopentyl glycol, mono- or diacrylates and methacrylates of bisphenol A, benzene trimethacrylate, 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 tetra-acrylates and methacrylates, and ethylene oxide or propylene of these compounds. Compounds such as oxide adducts can be mentioned.

The amount of the crosslinkable compound is preferably 1 part by mass to 50 parts by mass, more preferably 0.5 part by mass to 30 parts by mass, based on 100 parts by mass of the polyimide precursor (A).

In order to obtain a cured product with a lower dielectric constant and a lower dielectric loss tangent, it is preferable to use (C') an isocyanate compound represented by the following general formula (20) as the crosslinkable compound.

［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 optionally substituted alkylene group having 1 to 5 carbon atoms and optionally interrupted by an oxygen atom, and R ²⁵ represents an isocyanate group or a blocked isocyanate group. ]

R ²⁴ is not particularly limited as long as it is an alkylene group having 1 to 5 carbon atoms which may have a substituent and which may be interrupted by an oxygen atom. Examples of the alkylene group having 1 to 5 carbon atoms include substituted or unsubstituted methylene group, ethylene group, propylene group and butylene group. 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 substituents include halogen atoms, acryloyl groups, methacryloyl groups, nitro groups, amino groups, cyano groups, methoxy groups, acetoxy groups, etc. Acryloyl groups and methacryloyl groups are preferred.

^R25 represents an isocyanate group or a blocked isocyanate group. The isocyanate group refers to a group represented by —NCO, and the blocked isocyanate group is a group in which the isocyanate group is blocked with a thermally removable protective group, that is, the isocyanate group is added with an isocyanate blocking compound (blocking agent). A group that has been reacted.

Blocking agents for isocyanate groups generally react with isocyanate groups to prevent reaction with functional groups in other molecules (such as acid functional groups) at room temperature, but desorb at high temperatures to remove isocyanate groups. Regenerate and allow subsequent reaction (eg with acid functional groups).
Examples of blocking agents include alcohols such as methanol, ethanol, isopropanol, n-butanol, 2-ethoxyhexanol, 2-N,N-dimethylaminoethanol, 2-ethoxyethanol and cyclohexanol, phenol, and o-nitrophenol. , p-chlorophenol, o-cresol, m-cresol, phenols such as p-cresol, lactams such as ε-caprolactam, acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, cyclohexanone oxime, acetophenone oxime, benzophenone oxime, etc. Nitrogen-containing heteroaryl compounds such as oximes, amines, amides, pyrazole, 3,5-dimethylpyrazole, and 3-methylpyrazole, thiols such as dodecanethiol and benzenethiol, malonic acid diesters, acetoacetic esters, malon Acid dinitrile, acetylacetone, methylenedisulfone, dibenzoylmethane, dipivaloylmethane, active methylene compounds such as acetonedicarboxylic acid diester, and hydroxamic acid ester.
Advantageously, the blocking agent is volatile and 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 are, for example,

[In the formula, A represents a residue of an isocyanate blocking compound selected from the group consisting of alcohols, amines, amides, active methylene compounds, nitrogen-containing heteroaryl compounds, oximes, ketoximes, and hydroxamic acid esters. ]
is represented by

Specific examples of the isocyanate compound represented by the general 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, 3, Compounds to which blocking agents such as 5-dimethylpyrazole and diethyl malonate are added can be mentioned. In addition, these compounds may be used individually or may be used in combination of 2 or more type.

(C') The isocyanate compound can be synthesized by a known method, and the following commercially available products can be used.
Karenz AOI (2-isocyanatoethyl acrylate, registered trademark, manufactured by Showa Denko K.K.),
Karenz AOI-VM (2-isocyanatoethyl acrylate, registered trademark manufactured by Showa Denko K.K.),
Karenz MOI (2-isocyanatoethyl methacrylate, registered trademark, manufactured by Showa Denko K.K.),
Karenz MOI-BM (2-(O-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate manufactured by Showa Denko Co., Ltd., registered trademark),
Karenz MOI-BP (manufactured by Showa Denko KK, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate, registered trademark),
Karenz MOI-EG (manufactured by Showa Denko K.K., registered trademark),
Karenz BEI (manufactured by 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 are 2-(O-[1′-methylpropylideneamino]carboxyamino)ethyl acrylate (for example the Karenz AOI-BM) and 1,1-(bisacryloyloxymethyl)ethyl isocyanate (for example the Karenz BEI) is preferably used.

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

The amount of the (C') isocyanate compound in the polyamic acid ester resin composition according to the present invention is usually 1 to 50 parts by mass with respect to 100 parts by mass of the polyimide precursor (A).

[(P) Polymer compound other than polyimide precursor (A)]
In an embodiment, the polyamic acid ester resin composition may further contain a resin component other than the polyimide precursor (A). Examples of resin components that can be contained in the polyamic acid ester resin composition include polyimides, polyoxazoles, polyoxazole precursors, phenol resins, polyamides, epoxy resins, siloxane resins, and acrylic resins.
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 polyimide precursor (A).

[Other ingredients]
In embodiments, the polyamic acid ester resin composition may further contain components other than the components (A), (B), (C), and (P). Other components include, for example, photopolymerization initiators, solvents, sensitizers, adhesion aids, thermal polymerization inhibitors, azole compounds, hindered phenol compounds, fillers, and the like.

Thermal crosslinking agents 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, 3,3-tetrakis(methoxymethyl)urea and the like.
Examples of fillers include inorganic fillers, and specific examples include sols of silica, aluminum nitride, boron nitride, zirconia, alumina, and the like.

The polyamic acid ester resin composition of the present invention can contain a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it is a compound that absorbs the light source used for photocuring. dioxy)hexane, 1,4-bis[α-(tert-butyldioxy)-iso-propoxy]benzene, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis(tert-butyldioxy)hexene hydro 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, cyclohexanone 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-butyl peroxycarbonyl)-4,4′-dicarboxybenzophenone, tert-butyl peroxybenzoate, di-tert-butyl diperoxyisophthalate and other organic peroxides; 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone , octamethylanthraquinone, 1,2-benzanthraquinone and the like; benzoin derivatives such as benzoin methyl, benzoin ethyl ether, α-methylbenzoin and α-phenylbenzoin; 2,2-dimethoxy-1,2-diphenylethane- 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-propane-1-one, 2-hydroxy-1-[4-{4-(2-hydroxy-2-methyl-propionyl)benzyl}-phenyl]-2-methyl-propane-1- on, 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)-butan-1-one alkylphenone compounds; bis(2 ,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and other acylphosphine oxide compounds; 2-(O-benzoyloxime)-1-[4-(phenylthio ) Oxime esters such as phenyl]-1,2-octanedione, 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone compound.
The photopolymerization initiator is available as a commercial product, for example, IRGACURE [registered trademark] 651, 184, 2959, 127, 907, 369, 379EG, 819, 819DW, 1800, 1870, 784, OXE01, OXE02, 250, 1173, MBF, TPO, 4265, TPO (manufactured by BASF), KAYACURE [registered trademark] DETX, MBP, DMBI, EPA, OA (manufactured by Nippon Kayaku Co., Ltd.), VICURE-10, 55 (manufactured by STAUFFER Co. LTD), ESACURE KIP150, TZT, 1001, KTO46, KB1, KL200, KS300, EB3, Triazine-PMS, Triazine A, Triazine B (manufactured by Nihon SiberHegner Co., Ltd.), ADEKA OPTOMER N-1717, N-1414, N-1606 (manufactured by ADEKA Co., Ltd.) ). These photopolymerization initiators may be used alone or in combination of two or more.
The 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 polyimide precursor (A), and from the viewpoint of photosensitivity characteristics, preferably 0.5 parts by mass to 15 parts by mass. Department. When 0.1 parts by mass or more of the photopolymerization initiator is blended with respect to 100 parts by mass of the polyimide precursor (A), the photosensitivity of the polyamic acid ester resin composition tends to be improved, while 20 parts by mass or less is blended. In this case, the thick-film curability of the polyamic acid ester resin composition is likely to be improved.

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

The solvent is in the range of, for example, 30 parts by mass to 1500 parts by mass, preferably 100 parts by mass, with respect to 100 parts by mass of the polyimide precursor (A), depending on the desired coating thickness and viscosity of the polyamic acid ester resin composition. parts to 1000 parts by mass.

In the embodiment, the polyamic acid ester resin composition may optionally contain a sensitizer 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-dimethylamino thinner mylideneindanone, p-dimethylaminobenzylideneindanone, 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-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7- Diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2- Mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylamino) styryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene and the like. These can be used alone or in multiple combinations.

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

In embodiments, an adhesion aid can optionally be added to the polyamic acid ester resin composition in order to improve the adhesion between the film formed using the polyamic acid ester resin composition and the substrate. Examples of adhesion promoters 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- Silanes such as 1,4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, and N-phenylaminopropyltrimethoxysilane Coupling agents, and aluminum-based adhesion aids such as aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), ethylacetoacetate aluminum diisopropylate, and the like.

Among these adhesion aids, the silane coupling agent is more preferable from the point of adhesion. The amount of the adhesion promoter compounded is preferably in the range of 0.5 parts by mass to 25 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor.

In the embodiment, a thermal polymerization inhibitor can be arbitrarily added in order to improve the stability of the viscosity and photosensitivity of the polyamic acid ester resin composition during storage, particularly in the state of a solution containing a solvent. Thermal polymerization inhibitors include, for example, 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 content 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 polyimide precursor (A).

For example, when using a substrate made of copper or a copper alloy, an azole compound can optionally be added to the polyamic acid ester resin composition to suppress discoloration of the substrate. Azole compounds include, for example, 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-butyl -5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, Hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3, 5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, 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. In addition, these azole compounds may be used singly or as a mixture of two or more.

The amount of the azole compound compounded is preferably 0.1 parts by mass to 20 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor, and from the viewpoint of photosensitivity characteristics, it is 0.5 parts by mass to 5 parts by mass. It is more preferable to have When the amount of the azole compound (A) mixed with 100 parts by mass of the polyimide precursor is 0.1 parts by mass or more, when the polyamic acid ester resin composition is formed on copper or a copper alloy, copper or copper Discoloration of the alloy surface is suppressed, and on the other hand, when the amount is 20 parts by mass or less, the photosensitivity is excellent, which is preferable.

In embodiments, a hindered phenolic compound can optionally be incorporated into the polyamic acid ester resin composition to inhibit discoloration on copper. Hindered phenol compounds include, for example, 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl -4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4′-methylenebis(2,6-di-t-butylphenol), 4,4′-thio-bis(3-methyl-6-t-butylphenol), 4,4′-butylidene-bis(3-methyl-6-t-butylphenol), triethylene glycol-bis[3-(3 -t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2 -thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydro cinnamamide), 2,2′-methylene-bis(4-methyl-6-t-butylphenol), 2,2′-methylene-bis(4-ethyl-6-t-butylphenol), pentaerythrityl-tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5 -trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl )-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl )-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl )-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6 -dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6- dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl )-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5,6- trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy- 2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl- 3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6- ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t- Butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris( 4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4- t-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4- t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione and the like, but are limited thereto. not to be 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 amount of the hindered phenol compound is preferably 0.1 parts by mass to 20 parts by mass with respect to 100 parts by mass of the (A) polyimide precursor, and from the viewpoint of photosensitivity characteristics, 0.5 parts by mass to 10 parts by mass. Part is more preferred. When the amount of the hindered phenol compound (A) per 100 parts by mass of the polyimide precursor is 0.1 parts by mass or more, for example, when the polyamic acid ester resin composition is formed on copper or a copper alloy, copper or Discoloration and corrosion of the copper alloy are prevented, and on the other hand, when the amount is 20 parts by mass or less, the photosensitivity is excellent, which is preferable.

[Method for manufacturing substrate with cured relief pattern]
In an embodiment, the steps are:
(1) a step of applying the polyamic acid ester resin composition according to the present invention onto a substrate to form a polyamic acid ester resin layer on the substrate;
(2) exposing the polyamic acid ester resin layer;
(3) developing the exposed polyamic acid ester resin layer to form a relief pattern;
(4) It is possible to provide a method for producing a substrate with a hardened relief pattern, comprising the step of heat-treating the relief pattern to form a hardened relief pattern.

Each step will be described below.

(1) A step of applying the polyamic acid ester resin composition according to the present invention onto a substrate to form a polyamic acid ester resin layer on the substrate. It is applied onto the material and, if necessary, dried afterwards to form a polyamic acid ester resin layer. As the coating method, a method conventionally used for coating a polyamic acid ester resin composition, for example, a method of coating with a spin coater, a bar coater, a blade coater, a curtain coater, a screen printer, etc., or a method of spray coating with a spray coater. and the like can be used.

If necessary, the coating film composed of the polyamic acid ester resin composition can be dried, and drying methods include, for example, air drying, heat drying using an oven or hot plate, and vacuum drying. Moreover, it is desirable to dry the coating film under conditions that do not cause imidization of the (A) polyimide precursor in the polyamic acid ester resin composition. Specifically, when air drying or heat drying is performed, drying can be performed at 20° C. to 200° C. for 1 minute to 1 hour. As described above, a polyamic acid ester resin layer can be formed on the substrate.

(2) Step of exposing the polyamic acid ester resin layer In this step, the polyamic acid ester resin layer formed in the above step (1) is patterned using an exposure device such as a contact aligner, mirror projection, or stepper. It is exposed to an ultraviolet light source or the like through a photomask or reticle or directly.
Light sources used for exposure include, for example, g-line, h-line, i-line, ghi-line broadband, and KrF excimer laser. The exposure amount is desirably 25 mJ/cm ² to 1000 mJ/cm ² .

After that, for the purpose of improving photosensitivity, if necessary, post-exposure baking (PEB) and/or pre-development baking may be performed at any combination of temperature and time. The range of the baking conditions is preferably 50° C. to 200° C. and a time of 10 seconds to 600 seconds. Not limited to a range.

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

(4) A step of heat-treating the relief pattern to form a substrate with a cured relief pattern. is converted into a cured relief pattern of polyimide by imidizing it. As the heat-curing method, various methods can be selected, for example, using a hot plate, using an oven, or using a heating oven capable of setting a temperature program. 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 during heat curing, or an inert gas such as nitrogen or argon may be used.

[Semiconductor device]
In an embodiment, there is also provided a semiconductor device comprising a hardened relief pattern obtained by the method of manufacturing a hardened relief pattern described above. Therefore, it is possible to provide a semiconductor device having a base material which 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 semiconductor device manufacturing method that uses a semiconductor element as a base material and includes the above-described cured relief pattern manufacturing method as part of the process. The semiconductor device of the present invention is a semiconductor device 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, in which the cured relief pattern formed by the method for producing a cured relief pattern described above is used. It can be manufactured by forming it as a protective film or the like and combining it with a known method for manufacturing a semiconductor device.

[Display device]
In an embodiment, there is provided a display device comprising a display element and a cured film provided on top of the display element, wherein the cured film is the cured relief pattern described above. Here, the cured relief pattern may be laminated in direct contact with the display element, or may be laminated with another layer interposed therebetween. Examples of the cured film include surface protective films, insulating films, and flattening films for TFT liquid crystal display elements and color filter elements, projections for MVA type liquid crystal display devices, and barrier ribs for cathodes of organic EL devices. .

The polyamic acid ester resin composition of the present invention, in addition to application to the above semiconductor devices, is also used for interlayer insulation of multilayer circuits, cover coats for flexible copper-clad plates, solder resist films, liquid crystal alignment films, and the like. Useful.

The weight average molecular weights shown in the synthesis examples below in this specification are the results of measurement by gel permeation chromatography (hereinafter abbreviated as GPC in this specification). A GPC apparatus (HLC-8320GPC) manufactured by Tosoh Corporation was used for measurement under the following measurement conditions.
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 (manufactured by GL Sciences)

¹ H-NMR spectra were measured by JNM-ECX500 (500 MHz, manufactured by JEOL Ltd.) in the measurement of NMR spectra shown in the following examples of this specification.

<Production Example 1> Synthesis of dicarboxylic acid diester (1) 280.00 g (0.903 mol) of 4,4′-oxydiphthalic dianhydride (Tokyo Chemical Industry Co., Ltd.) was placed in a 2-liter four-necked flask, and 2 - 232.50 g (0.181 mol) of hydroxyethyl methacrylate (Aldrich), 0.98 g (0.009 mol) of hydroquinone (Tokyo Chemical Industry Co., Ltd.) and 840 g of γ-butyrolactone (Kanto Kagaku, deer special grade) were added and heated at 23°C. After stirring, pyridine (Kanto Kagaku, dehydrated) 142.78 g (1.805 mol) was added, the temperature was raised to 50 ° C., and the mixture was stirred at 50 ° C. for 2 hours to obtain a compound represented by the following formula (1). A solution containing

<Production Example 2> Synthesis of Polymer (2) as Polyimide Precursor 43.68 g (0.026 mol) of the solution prepared in Production Example 1 and 34.57 g of γ-butyrolactone were placed in a 200 mL four-necked flask. ° C. or lower, a solution of 6.43 g (0.053 mol) of N,N′-diisopropylcarbodiimide (DIC, Tokyo Chemical Industry Co., Ltd.) dissolved in 15 g of γ-butyrolactone was added dropwise to the reaction solution over 20 minutes while stirring. Subsequently, 8.74 g (0.03 mol) of 4,4′-bis(4-aminophenoxy)biphenyl (Seika Co., Ltd.) was dissolved in 15 g of N-methyl-2-pyrrolidinone (Kanto Kagaku, deer special grade). The mixture was added dropwise over 20 minutes while stirring. After that, the temperature was raised to 23° C. and the mixture was stirred for 26.5 hours, then 2.25 g of ethanol (Kanto Kagaku, special grade) was added and the mixture was stirred for 1 hour.

The obtained reaction mixture was added to 375 g of methanol (Kanto Kagaku, special grade) to form a precipitate consisting of a crude polymer. The supernatant liquid was decanted to separate the crude polymer, which was dissolved in 60.0 g of tetrahydrofuran and 15.0 g of N-methyl-2-pyrrolidinone to obtain a crude polymer solution. The resulting crude polymer solution was added dropwise to 750 g of water to precipitate the polymer. The obtained precipitate was separated by filtration, washed twice with 75 g of methanol, and dried under vacuum to obtain a fibrous polymer (2). Obtained. When the molecular weight of polymer (2) was measured by GPC (converted to standard polystyrene), the weight average molecular weight (Mw) was 12,059. Yield was 74.7%. This reaction product has a repeating unit structure represented by the following formula (2).

<Production Example 3> Synthesis of Polymer (3) as Polyimide Precursor 52.41 g (0.032 mol) of the solution prepared in Production Example 1 and 11.86 g of γ-butyrolactone were placed in a 200 mL four-necked flask. ° C. or below, a solution prepared by dissolving 7.72 g (0.063 mol) of N,N′-diisopropylcarbodiimide (DIC, Tokyo Chemical Industry Co., Ltd.) in 18 g of γ-butyrolactone was added to the reaction solution over 0.5 hours while stirring. Then, 10.49 g (0.03 mol) of 4,4′-bis(4-aminophenoxy)biphenyl (Seika Co., Ltd.) was added dropwise to 18.1 g of N-methyl-2-pyrrolidinone (Kanto Kagaku, deer special grade). The dissolved material was added dropwise over 45 minutes while stirring. After that, the temperature was raised to 25° C. and the mixture was stirred for 2 hours, then 2.7 g of ethanol (Kanto Kagaku, special grade) was added and the mixture was stirred for 1 hour.

The obtained reaction mixture was added to 450 g of methanol (Kanto Kagaku, special grade) to form a precipitate consisting of a crude polymer. The supernatant liquid was decanted to separate the crude polymer, which was dissolved in 72.0 g of tetrahydrofuran and 18.0 g of N-methyl-2-pyrrolidinone to obtain a crude polymer solution. The resulting crude polymer solution was added dropwise to 900 g of water to precipitate the polymer. The resulting precipitate was separated by filtration, washed twice with 90 g of methanol, and dried under vacuum to obtain fibrous polymer (3). Obtained. When the molecular weight of polymer (3) was measured by GPC (converted to standard polystyrene), the weight average molecular weight (Mw) was 11,283. Yield was 82.6%. This reaction product has a repeating unit structure represented by the following formula (3).

<Example 1>
A composition was prepared by adding 0.03 g of phthalic acid to 0.32 g of the polymer obtained in Production Example 2 and further adding 0.65 g of N-methyl-2-pyrrolidinone.

<Example 2>
A composition was prepared by adding 0.02 g of phthalic acid to 0.33 g of the polymer obtained in Production Example 2 and further adding 0.65 g of N-methyl-2-pyrrolidinone.

<Example 3>
To 0.35 g of the polymer obtained in Production Example 3, 0.17 g of a solution obtained by diluting phthalic acid with N-methyl-2-pyrrolidinone to 1% by weight was added, and further 0.48 g of N-methyl-2-pyrrolidinone was added. Additionally, compositions were prepared.

<Example 4>
To 0.35 g of the polymer obtained in Production Example 3, 0.17 g of a solution obtained by diluting maleic acid with N-methyl-2-pyrrolidinone to 1% by weight was added, and further 0.48 g of N-methyl-2-pyrrolidinone was added. Additionally, compositions were prepared.

<Example 5>
A composition was prepared by adding 0.0035 g of phthalic acid and 0.65 g of cyclohexanone to 0.35 g of the polymer obtained in Production Example 3.

<Example 6>
To 0.35 g of the polymer obtained in Production Example 3, 0.35 g of a solution obtained by diluting phthalic acid with N-methyl-2-pyrrolidinone to 1% by weight was added, and further 0.18 g of N-methyl-2-pyrrolidinone was added. The composition was prepared by adding 0.13 of ethyl lactate.

<Comparative Example 1>
A composition was prepared by adding 0.65 g of N-methyl-2-pyrrolidinone to 0.35 g of the polymer obtained in Production Example 2.

<Comparative Example 2>
A composition was prepared by adding 0.65 g of cyclohexanone to 0.35 g of the polymer obtained in Production Example 3.

<Comparative Example 3>
A composition was prepared by adding 0.03 g of succinic acid and 0.65 g of N-methyl-2-pyrrolidinone to 0.32 g of the polymer obtained in Production Example 2.

<Comparative Example 4>
A composition was prepared by adding 0.03 g of terephthalic acid and 0.65 g of N-methyl-2-pyrrolidinone to 0.32 g of the polymer obtained in Production Example 2.

<Comparative Example 5>
To 0.23 g of the polymer obtained in Production Example 3, 0.03 g of dimethyl phthalate was added, and 0.75 g of N-methyl-2-pyrrolidinone was added to prepare a composition.

[Storage stability evaluation test]
Regarding the compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 5, the results measured immediately after preparation were taken as storage day 0, and each composition was stored at room temperature for the number of days shown in Table 1 below. , the appearance was visually confirmed after storage. All the compositions on the 0th day of storage were transparent. Also, 0.1 g of the compositions prepared in Examples 1 to 6 and Comparative Examples 2 to 4 were diluted with 0.58 ml of hexadeuterodimethylsulfoxide, and ¹ H-NMR was measured. The results measured immediately after dilution were taken as the 0th day of storage, and each composition was stored at room temperature for the number of days shown in Table 1 below, and then measured again, and the results were compared. The comparison is for the peaks at 4.2-4.7 ppm and 10.3-10.7 ppm, with the peak intensity on day 0 as 100%, when measured after storage for the number of days shown in Table 1 below. The intensity ratio was calculated from the peak intensity of Table 1 shows the evaluation results.

The peak at 10.3-10.7 ppm compared with ¹ H-NMR is a peak derived from an amide bond contained in the polymer. A decrease in this peak intensity means that the amide bond decreased due to bond breakage or imidization in the polymer. Also, the peak at 4.2-4.7 ppm is a peak derived from a side chain bonded via an ester bond, and a decrease in this peak intensity means that the side chain is detached.

From Table 1, in Comparative Examples 1 to 5, the composition became cloudy after less than 10 days of storage, and the ¹ H-NMR measurement of Comparative Examples 2 to 4 showed that the peak intensity ratio derived from amide was less than 7 days of storage. 80% or less, and the peak intensity ratio derived from side chains bonded via ester bonds was also 80% or less. In other words, it can be seen that the storage stability is poor and the polymer is denatured.

On the other hand, in Examples 1 to 6, the appearance of the compositions remained transparent even after storage for 28 days. In addition, in ^{the 1} H-NMR measurements of Examples 1 to 6, after storage at room temperature for 28 days, the peak intensity ratio derived from amide was 90% or more, and side chains bonded via ester bonds The peak intensity ratio derived from was also 90% or more. In other words, it can be seen that the effect of the present invention significantly suppresses side chain detachment and imidization.

INDUSTRIAL APPLICABILITY The polyamic acid ester resin composition of the present invention can be suitably used in the field of polyimide materials that are useful in the production of electrical and electronic materials such as semiconductor devices and multilayer wiring boards.

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, and R ¹ and R ² are each independently a monovalent organic group. ] A polyimide precursor having a unit structure represented by;
and (B) a carboxylic acid compound selected from the group of compounds below:

including,
A polyamic acid ester resin composition. The resin composition according to claim 1, comprising 0.1 to 10 parts by weight of the carboxylic acid compound (B) with respect to 100 parts by weight of the polyimide precursor (A). 3. The resin composition according to claim 1, further comprising 1 part by mass to 50 parts by mass of a crosslinkable compound (C) relative to 100 parts by mass of the polyimide precursor (A). A resin film characterized by being a baked product of a coating film of the polyamic acid ester resin composition according to any one of claims 1 to 3. The following steps:
(1) a step of applying the polyamic acid ester resin composition according to any one of claims 1 to 3 onto a substrate to form a polyamic acid ester resin layer on the substrate;
(2) exposing the polyamic acid ester resin layer;
(3) developing the exposed polyamic acid ester resin layer to form a relief pattern;
(4) heat-treating the relief pattern to form a cured relief pattern;
A method of manufacturing a cured relief patterned substrate comprising: The following steps:
(1) a step of applying the polyamic acid ester resin composition according to any one of claims 1 to 3 onto a substrate to form a polyamic acid ester resin layer on the substrate;
(2) exposing the polyamic acid ester resin layer;
(3) developing the exposed polyamic acid ester resin layer to form a relief pattern;
(4) heat-treating the relief pattern to form a cured relief pattern;
(5) providing the cured relief pattern as a cured film on the top or bottom of the semiconductor element;
A method of manufacturing a semiconductor device comprising: