JP5515399B2 - Positive photosensitive resin composition, cured film, pattern cured film manufacturing method, and electronic component - Google Patents

Description

  The present invention relates to a positive photosensitive resin composition, a cured film, a method for producing a patterned cured film, and an electronic component. More specifically, it is possible to form a cured film having heat resistance, chemical resistance and excellent adhesion, and a positive photosensitive resin composition having excellent sensitivity and resolution, and curing obtained using the resin composition. The present invention relates to a film, a pattern cured film, and an electronic component including the pattern cured film.

A polyimide resin film having excellent heat resistance, electrical characteristics, mechanical characteristics, and the like is used for a surface protective film and an interlayer insulating film of a semiconductor device.
This polyimide resin film is generally formed by thinning a polyimide precursor (polyamic acid) solution (so-called varnish) obtained by reacting tetracarboxylic dianhydride and diamine in a polar solvent at room temperature and normal pressure by spin coating or the like. It is formed by thermally dehydrating and ring-closing (curing) (for example, Non-Patent Document 1).

  In recent years, photosensitive polyimides having a photosensitive property imparted to a polyimide resin or a precursor resin itself have been used. By using this photosensitive polyimide, the pattern forming process can be simplified and the complicated pattern manufacturing process can be shortened (for example, Patent Documents 1 to 3).

  Conventionally, an organic solvent such as N-methylpyrrolidone has been used for developing the photosensitive polyimide. Recently, a positive photosensitive resin that can be developed with an aqueous alkaline solution has been proposed from the viewpoint of environment and cost. Yes.

As a method of obtaining such a positive photosensitive resin that can be developed with an aqueous alkaline solution, a method of introducing an o-nitrobenzyl group into a polyimide precursor via an ester bond (for example, Non-Patent Document 2), a solvent-soluble hydroxylimide or Examples thereof include a method of mixing a naphthoquinone diazide compound with a polybenzoxazole precursor (see, for example, Patent Documents 4 and 5).
Since the positive type photosensitive resin obtained by such a method can be expected to have a low dielectric constant, the photosensitive poly- mer is a positive type photosensitive resin in which a polybenzoxazole resin or its precursor resin itself is provided with photosensitive characteristics together with the photosensitive polyimide. Benzoxazole has attracted attention.

  Photosensitive polyimide or photosensitive polybenzoxazole is used not only as a surface protective film but also as an interlayer insulating film such as a redistribution layer in accordance with recent changes in the package form of semiconductor devices.

The polyimide and polybenzoxazole-based materials, which are photosensitive resin compositions for dealing with such cases, require resistance to chemicals more than conventional materials. In particular, in the electroless plating process for producing the under bump metal (UBM), the surface protective film and the interlayer insulating film are formed and then exposed to several kinds of chemicals including various plating solutions. However, in the polyimide and polybenzoxazole-based materials, which are conventional photosensitive resin compositions, it has not been obtained yet that has both chemical resistance and photosensitive characteristics.
Moreover, although the solvent-soluble hydroxylimide is excellent in the photosensitive characteristics and heat resistance, the adhesiveness to the substrate when used as a cured film was not at a satisfactory level.

JP-A-49-115541 JP 59-108031 A JP 59-219330 A JP-A 64-60630 US Pat. No. 4,395,482

Japan Polyimide Study Group "Latest Polyimides-Fundamentals and Applications" (2002) J. Macromol. Sci., Chem., Vol. A24, 12, 1407 (1987)

  An object of the present invention is a positive photosensitive resin composition capable of forming a cured film having high chemical resistance and excellent adhesion to a substrate, and is particularly high for chemicals used in an electroless plating process. It is to provide a positive photosensitive resin composition that has chemical resistance and can be suitably used for manufacturing a pattern cured film such as an interlayer insulating film of a semiconductor device.

  As a result of intensive studies, experiments, and studies, the inventors have obtained a crosslinker that does not contain a phenol skeleton and a silane coupling agent having a urea bond, together with an alkali developable polymer. The present inventors have found that a positive-type photosensitive resin composition having good photosensitivity can be obtained while improving the heat resistance, chemical resistance and adhesion of the cured film.

（式中、Ｒ^７は、それぞれ水素原子又は一価の有機基である。
Ｒ^８は、それぞれ水素原子又は一価の有機基であり、Ｒ^８同士が互いに結合して環構造を形成してもよい。）
６．前記（ｃ）フェノール骨格を含有していない架橋剤が、下記式（２）で表される化合物である１〜４のいずれかに記載のポジ型感光性樹脂組成物。

（式中、Ｒ^１〜Ｒ^６は、それぞれ水素原子又は−ＣＨ_２ＯＲ（Ｒは、水素原子又は一価の有機基である）で表される置換基であり、Ｒ^１〜Ｒ^６の少なくとも１つは−ＣＨ_２ＯＲで表される置換基である。）
７．前記（ｃ）フェノール骨格を含有していない架橋剤が、下記式（３）で表される化合物である１〜４のいずれかに記載のポジ型感光性樹脂組成物。

（式中、Ｒ^１〜Ｒ^３は、それぞれ水素原子、下記式で表される置換基又は−ＣＨ_２ＯＲ（Ｒは、水素原子又は一価の有機基である）で表される置換基であり、Ｒ^１〜Ｒ^３の少なくとも１つは、下記式で表される置換基又は−ＣＨ_２ＯＲで表される置換基である）

８．前記（ｄ）ウレア結合を有するシランカップリング剤が、下記式（４）で表される化合物である１〜７のいずれかに記載のポジ型感光性樹脂組成物。

（式中、Ｒ^９及びＲ^１０は、それぞれ炭素数１〜５のアルキル基である。
ｑは、１〜１０の整数である。
ｒは、１〜３の整数である。）
９．前記（ｃ）フェノール骨格を含有していない架橋剤の含有量が、前記（ａ）アルカリ性水溶液に可溶なポリマー１００重量部に対して２０重量部以上である１〜８のいずれかに記載のポジ型感光性樹脂組成物。
１０．アンダーバンプメタル作製のための無電解めっきを必要とするデバイスの層間絶縁膜又は表面保護膜に使用される１〜９のいずれかに記載のポジ型感光性樹脂組成物。
１１．１〜１０のいずれかに記載のポジ型感光性樹脂組成物を塗布してなる硬化膜。
１２．１〜１０のいずれかに記載のポジ型感光性樹脂組成物を支持基板上に塗布し乾燥して感光性樹脂膜を形成する感光性樹脂膜形成工程と、
前記感光性樹脂膜を所定のパターンに露光する露光工程と、
前記露光後の感光性樹脂膜をアルカリ水溶液を用いて現像してパターン樹脂膜を得る現像工程と、
前記パターン樹脂膜を加熱処理してパターン硬化膜を得る加熱処理工程を含むパターン硬化膜の製造方法。
１３．１２に記載の製造方法により得られるパターン硬化膜に、無電解めっきをしてアンダーバンプメタルを作製する工程を含む電子部品の製造方法。
１４．１２に記載のパターン硬化膜の製造方法により得られるパターン硬化膜を、層間絶縁膜層及び／又は表面保護膜層として有する電子部品。
１５．１３に記載の製造方法により得られる電子部品。 According to the present invention, the following positive photosensitive resin composition and the like are provided.
1. A positive photosensitive resin composition containing the following components (a) to (d).
(A) Polymer soluble in alkaline aqueous solution (b) Compound that generates acid upon irradiation with light (c) Crosslinking agent not containing phenol skeleton (d) Silane coupling agent having urea bond 2. The positive photosensitive resin composition according to 1, wherein the polymer (a) soluble in an alkaline aqueous solution is at least one selected from the group consisting of polyimide, polybenzoxazole, and precursors thereof.
3. The positive photosensitive resin composition according to 1 or 2, wherein the compound that generates acid upon irradiation with light (b) is diazonaphthoquinone.
4). (C) The crosslinking agent not containing a phenol skeleton is a compound containing any of a urea bond, a melamine skeleton, and an isocyanurate skeleton, wherein one or more —CH ₂ OR (R is a hydrogen atom or a monovalent atom) The positive photosensitive resin composition according to any one of 1 to 3, which is a compound containing a substituent represented by:
5. The positive photosensitive resin composition according to any one of 1 to 4, wherein the (c) crosslinking agent not containing a phenol skeleton is a compound represented by the following formula (1).

(In the formula, each R ⁷ is a hydrogen atom or a monovalent organic group.
R ⁸ is a hydrogen atom or a monovalent organic group, and R ⁸ may be bonded to each other to form a ring structure. )
6). The positive photosensitive resin composition in any one of 1-4 whose said (c) crosslinking agent which does not contain a phenol skeleton is a compound represented by following formula (2).

Wherein R ^{1 to} R ⁶ are each a substituent represented by a hydrogen atom or —CH ₂ OR (where R is a hydrogen atom or a monovalent organic group), and at least ^one of R ^{1 to} R ⁶ One is a substituent represented by —CH ₂ OR.)
7). The positive photosensitive resin composition in any one of 1-4 whose said (c) crosslinking agent which does not contain a phenol skeleton is a compound represented by following formula (3).

(Wherein R ^{1 to} R ³ are each a hydrogen atom, a substituent represented by the following formula, or a substituent represented by —CH ₂ OR (R is a hydrogen atom or a monovalent organic group). And at least one of R ^{1 to} R ³ is a substituent represented by the following formula or a substituent represented by —CH ₂ OR)

8). The positive photosensitive resin composition according to any one of 1 to 7, wherein the (d) silane coupling agent having a urea bond is a compound represented by the following formula (4).

(Wherein R ⁹ and R ¹⁰ are each an alkyl group having 1 to 5 carbon atoms.
q is an integer of 1-10.
r is an integer of 1 to 3. )
9. The content of the (c) crosslinking agent not containing a phenol skeleton is 20 parts by weight or more with respect to 100 parts by weight of the polymer soluble in the (a) alkaline aqueous solution. Positive photosensitive resin composition.
10. The positive photosensitive resin composition in any one of 1-9 used for the interlayer insulation film or surface protection film of a device which requires electroless plating for underbump metal preparation.
11. A cured film formed by applying the positive photosensitive resin composition according to any one of 11.1 to 10.
A photosensitive resin film forming step of applying the positive photosensitive resin composition according to any one of 12.1 to 10 onto a support substrate and drying to form a photosensitive resin film;
An exposure step of exposing the photosensitive resin film to a predetermined pattern;
A development step of developing the exposed photosensitive resin film using an alkaline aqueous solution to obtain a patterned resin film;
The manufacturing method of the pattern cured film including the heat processing process which heat-processes the said pattern resin film and obtains a pattern cured film.
The manufacturing method of an electronic component including the process of electroless-plating to the pattern cured film obtained by the manufacturing method of 13.12, and producing an under bump metal.
14. An electronic component having a patterned cured film obtained by the method for producing a patterned cured film according to 14.12 as an interlayer insulating film layer and / or a surface protective film layer.
An electronic component obtained by the manufacturing method according to 15.13.

  According to the present invention, it is a positive photosensitive resin composition capable of forming a cured film having high chemical resistance and excellent adhesion to a substrate, and is particularly high for chemicals used in an electroless plating process. A positive photosensitive resin composition that has chemical resistance and can be suitably used for the manufacture of a patterned cured film such as an interlayer insulating film of a semiconductor device can be provided.

It is a schematic sectional drawing explaining the manufacturing process of the semiconductor device which has a multilayer wiring structure concerning one Embodiment of this invention, Comprising: It is a figure which shows a 1st process. It is a schematic sectional drawing explaining the manufacturing process of the semiconductor device which has a multilayer wiring structure concerning one Embodiment of this invention, Comprising: It is a figure which shows a 2nd process. It is a schematic sectional drawing explaining the manufacturing process of the semiconductor device which has a multilayer wiring structure concerning one Embodiment of this invention, Comprising: It is a figure which shows a 3rd process. It is a schematic sectional drawing explaining the manufacturing process of the semiconductor device which has a multilayer wiring structure concerning one Embodiment of this invention, Comprising: It is a figure which shows a 4th process. It is a schematic sectional drawing explaining the manufacturing process of the semiconductor device which has a multilayer wiring structure concerning one Embodiment of this invention, Comprising: It is a figure which shows a 5th process. It is a schematic sectional drawing of the semiconductor substrate used for the UBM preparation process using the electroless plating which concerns on one Embodiment of this invention.

The positive photosensitive resin composition of the present invention contains the following components (a) to (d).
(A) Polymer soluble in alkaline aqueous solution (b) Compound that generates acid upon irradiation with light (c) Crosslinking agent not containing phenol skeleton (d) Silane coupling agent having urea bond

  The positive photosensitive resin composition of the present invention can be developed with an alkaline aqueous solution, and exhibits good sensitivity and good resolution. Moreover, the cured film obtained from the positive photosensitive resin composition of the present invention exhibits high heat resistance and is excellent in chemical resistance and adhesion to a substrate.

(A) The alkaline aqueous solution of a polymer soluble in an alkaline aqueous solution is an alkaline solution such as a tetramethylammonium hydroxide (TMAH) aqueous solution, a metal hydroxide aqueous solution, or an organic amine aqueous solution.
As a developer used for semiconductor production, a tetramethylammonium hydroxide aqueous solution having a concentration of 2.38% by weight is generally used. Therefore, the component (a) of the present invention is preferably a tetramethylammonium hydroxide aqueous solution, particularly preferably. The polymer is soluble in an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38% by weight.

  The term “soluble in an alkaline aqueous solution” means that a varnish obtained by dissolving the component (a) alone in an arbitrary solvent is spin-coated on a substrate such as a silicon wafer to form a film having a thickness of about 5 μm. The coating film was immersed in one of a tetramethylammonium hydroxide aqueous solution, a metal hydroxide aqueous solution and an organic amine aqueous solution at 20 to 25 ° C. As a result, the coating film was dissolved as a uniform solution. When obtained, component (a) can be considered soluble in an alkaline aqueous solution.

The polymer soluble in the alkaline aqueous solution (a) contained in the composition of the present invention is not particularly limited, but is preferably a polymer having a main chain skeleton of polyimide or polyoxazole from the viewpoint of processability and heat resistance. That is, it is at least one polymer selected from polyimide, polyamideimide, polyoxazole, polyamide, and precursors thereof (for example, polyamic acid, polyamic acid ester, polyhydroxyamide, etc.). From the viewpoint of solubility in alkaline aqueous solution, the polymer (a) soluble in alkaline aqueous solution is preferably a polymer having a plurality of phenolic hydroxyl groups, a plurality of carboxyl groups, or both groups.
(A) As the polymer soluble in the alkaline aqueous solution, a copolymer of the above skeleton or a mixture of two or more of the above polymers may be used.

  Since the solvent resistance of the cured film obtained using the composition of the present invention can be increased, examples of the component (a) include polyimide, polyamideimide, polyoxazole, precursors thereof, polyamide, and the like. Is at least one selected from the group consisting of polyimide, polyoxazole and their precursors, more preferably at least one selected from the group consisting of polyimide, polybenzoxazole and their precursors .

(A) As a specific example of a polymer soluble in an alkaline aqueous solution, a polyimide obtained by reacting tetracarboxylic dianhydride and diamine and dehydrating and ring-closing; reacting dicarboxylic dichloride and dihydroxydiamine and dehydrating and ring-closing Polyoxazole obtained by reacting tricarboxylic acid and diamine, polyamideimide obtained by dehydration and ring closure; Polyamide obtained by reacting dicarboxylic acid dichloride and diamine; Reacting tetracarboxylic dianhydride and diamine A polyamic acid (polyimide precursor) obtained by the reaction; a polyamic acid ester (polyimide precursor) obtained by reacting a tetracarboxylic acid diester dichloride and a diamine; and a dicarboxylic acid dichloride and dihydroxydiamine. Polyhydroxyamide (polyoxazole precursor) obtained by reacting is mentioned.
Any of the above polymers can be produced by a known method.

  Polyhydroxyamide (polybenzoxazole precursor), which has excellent heat resistance, mechanical properties, and electrical properties, and is currently being frequently used as a resin for electronic components, becomes a polybenzoxazole by ring closure by heating ( An example of the component a) will be described below.

（式中、Ｕは４価の有機基である。Ｖは２価の有機基である。） Polyhydroxyamide is a polymer containing a repeating unit represented by the following formula (I), for example. The amide unit containing a hydroxy group represented by the formula (I) is finally converted into an oxazole having excellent heat resistance, mechanical properties and electrical properties by dehydration and ring closure at the time of curing.

(In the formula, U is a tetravalent organic group. V is a divalent organic group.)

（式中、Ｕは４価の有機基である。
Ｖ及びＷは２価の有機基である。
ｊ及びｋは、それぞれモル分率を示し、ｊ及びｋの和は１００モル％であって、ｊが６０〜１００モル％、ｋが４０〜０モル％である。） The solubility of polyhydroxyamide in an alkaline aqueous solution is derived from a phenolic hydroxyl group.
The polyhydroxyamide used for component (a) is preferably a polyhydroxyamide represented by the formula (II) containing a certain proportion or more of amide units containing a hydroxy group represented by the formula (I).

(In the formula, U is a tetravalent organic group.
V and W are divalent organic groups.
j and k show a mole fraction, respectively, and the sum of j and k is 100 mol%, j is 60-100 mol%, and k is 40-0 mol%. )

  In the polyhydroxyamide represented by the formula (II), the molar fraction of j and k is preferably j = 80 to 100 mol% and k = 20 to 0 mol%.

The tetravalent organic group of U is preferably a tetravalent aromatic group. The number of carbon atoms of the tetravalent organic group is preferably 6-40. The tetravalent organic group of U is more preferably a tetravalent aromatic group having 6 to 40 carbon atoms.
The tetravalent aromatic group is preferably an aromatic group in which all four bonding sites are present on the aromatic ring.

  Since the tetravalent organic group represented by U is a polybenzoxazole precursor, for example, two hydroxy groups and two amino groups that react with dicarboxylic acid to form a polyamide structure are each an aromatic ring. It is a residue of a diamine having two sets of structures having a hydroxy group and an amino group located in the ortho position.

  Examples of the diamine include 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, bis (3-amino-4-hydroxyphenyl) propane, bis ( 4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 2,2-bis (3-amino-4-hydroxy) Phenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-amino-3-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane However, it is not limited to these. These compounds can be used alone or in combination of two or more.

The divalent organic group of W is, for example, a residue of a diamine that reacts with a dicarboxylic acid to form a polyamide structure, and is a residue other than the above U diamine.
The divalent organic group for W is preferably a divalent aromatic group or a divalent aliphatic group. The number of carbon atoms of the divalent organic group is preferably 4 to 40. The divalent organic group of W is more preferably a divalent aromatic group having 4 to 40 carbon atoms.

Examples of the diamine include 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfide, benzidine, m-phenylenediamine, and p-phenylenediamine. 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis [4- (4 -Aminophenoxy) phenyl] ether, aromatic diamine compounds such as 1,4-bis (4-aminophenoxy) benzene, and in addition to these, LP-7100, which is a diamine containing a silicone group, X- 22-161AS, X-22-161A, X-22 -161B, X-22-161C, X-22-161E (all manufactured by Shin-Etsu Chemical Co., Ltd.) and the like can be mentioned, but are not limited thereto.
These compounds can be used alone or in combination of two or more.

The divalent organic group of V is, for example, a residue of a dicarboxylic acid that reacts with diamine to form a polyamide structure.
The divalent organic group for V is preferably a divalent aromatic group. The number of carbon atoms in the divalent organic group is preferably 6-40. From the viewpoint of heat resistance of the cured film, the divalent organic group of V is more preferably a divalent aromatic group having 6 to 40 carbon atoms. Further, in the case where V is a divalent organic group having an aliphatic straight chain structure having 6 to 30 carbon atoms, it is preferable in that sufficient physical properties can be obtained even if the temperature at the time of thermosetting is lowered to 280 ° C. or lower. .
The divalent aromatic group is preferably an aromatic group in which two bonding sites are both present on the aromatic ring.

  Examples of the dicarboxylic acid include isophthalic acid, terephthalic acid, 2,2-bis (4-carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 4,4′-dicarboxybiphenyl, 4 , 4′-dicarboxydiphenyl ether, 4,4′-dicarboxytetraphenylsilane, bis (4-carboxyphenyl) sulfone, 2,2-bis (p-carboxyphenyl) propane, 5-tert-butylisophthalic acid, 5 -Aromatic dicarboxylic acids such as bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1, 3-cyclopentanedicarboxylic acid, a dicarboxylic acid having an aliphatic linear structure, malo Acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid Acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3- Methyl glutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, octafluoroadipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid , Sebacic acid, hexadecafluorosebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, tri Candioic acid, Tetradecanedioic acid, Pentadecanedioic acid, Hexadecanedioic acid, Heptadecanedioic acid, Octadecanedioic acid, Nonadecanedioic acid, Eicosandioic acid, Henicosandioic acid, Docosandioic acid, Tricosanedioic acid, Tetracosandioic acid, Pentacosandioic acid Acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosandioic acid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid and dicarboxylic acid represented by the following formula (III) Is mentioned. These compounds can be used alone or in combination of two or more.

（式中、Ｚは、それぞれ炭素数１〜６の炭化水素基である。ｎは１〜６の整数である。）

(In the formula, each Z is a hydrocarbon group having 1 to 6 carbon atoms. N is an integer of 1 to 6.)

(A) The molecular weight of the polymer soluble in the alkaline aqueous solution is preferably a weight average molecular weight of 3,000 to 200,000, and more preferably 5,000 to 100,000.
The molecular weight is a value obtained by measuring by a gel permeation chromatography method and converting from a standard polystyrene calibration curve.

  The polyhydroxyamide represented by the formula (II) can generally be synthesized from a dicarboxylic acid derivative and a hydroxy group-containing diamine. Specifically, it can be synthesized by converting a dicarboxylic acid derivative into a dihalide derivative and then reacting with a hydroxy group-containing diamine.

The dihalide derivative is preferably a dichloride derivative. The dichloride derivative can be synthesized by reacting a dicarboxylic acid derivative with a halogenating agent.
As the halogenating agent, thionyl chloride, phosphoryl chloride, phosphorus oxychloride, phosphorus pentachloride, and the like which can be used for a normal acid chloride reaction of a carboxylic acid can be used.

As a method of synthesizing the dichloride derivative, the dicarboxylic acid derivative and the halogenating agent are reacted in a solvent, or the dicarboxylic acid derivative and the halogenating agent are reacted in an excess of the halogenating agent, and then the excess is distilled off. The method of leaving is mentioned.
As the reaction solvent, N-methyl-2-pyrrolidone, N-methyl-2-pyridone, N, N-dimethylacetamide, N, N-dimethylformamide, toluene, benzene and the like can be used.

The amount of these halogenating agents to be used in a solvent is preferably 1.5 to 3.0 mol, more preferably 1.7 to 2.5 mol, relative to 1 mol of the dicarboxylic acid derivative. is there. When making it react in a halogenating agent, Preferably it is 4.0-50 mol with respect to 1 mol of dicarboxylic acid derivatives, More preferably, it is 5.0-20 mol.
The reaction temperature is preferably -10 to 70 ° C, more preferably 0 to 20 ° C.

The reaction between the dichloride derivative and the diamine is preferably performed in an organic solvent in the presence of a dehydrohalogenating agent.
As the dehydrohalogenating agent, organic bases such as pyridine and triethylamine are usually used. As the organic solvent, N-methyl-2-pyrrolidone, N-methyl-2-pyridone, N, N-dimethylacetamide, N, N-dimethylformamide and the like can be used.
The reaction temperature is preferably −10 to 30 ° C., more preferably 0 to 20 ° C.

  The compound (b) contained in the composition of the present invention that generates an acid upon irradiation with light (hereinafter sometimes simply referred to as a photoacid generator) is a light of a cured film formed from the composition of the present invention. It has a function of increasing the solubility of the irradiated part in an alkaline aqueous solution.

  Examples of the photoacid generator include diazonaphthoquinone, aryldiazonium salts, diaryliodonium salts, and triarylsulfonium salts. Among them, diazonaphthoquinone is preferable because of its high sensitivity.

  The content of the (b) photoacid generator is preferably 0.01 to 50 parts by weight, more preferably 100 parts by weight of the component (a) in order to improve the sensitivity and resolution during exposure. Is 0.01 to 20 parts by weight, more preferably 0.5 to 20 parts by weight.

  The photoacid generator diazonaphthoquinone can be obtained, for example, by subjecting o-quinonediazide sulfonyl chlorides, hydroxy compounds, amino compounds and the like to a condensation reaction in the presence of a dehydrochlorinating agent.

  Examples of the o-quinonediazide sulfonyl chlorides include benzoquinone-1,2-diazide-4-sulfonyl chloride, naphthoquinone-1,2-diazide-5-sulfonyl chloride, and naphthoquinone-1,2-diazide-4-sulfonyl chloride. Etc. can be used.

  Examples of the hydroxy compound include hydroquinone, resorcinol, pyrogallol, bisphenol A, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,2 ′, 3′-pentahydroxybenzophenone, 2,3,4,3 ', 4', 5'-hexahydroxybenzophenone, bis (2,3,4-trihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) propane, 4b, 5,9b, 10-tetrahydro- 1,3,6,8-tetrahydroxy-5,10-dimethylindeno [2,1 a] indene, tris (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) ethane and the like can be used.

  Examples of the amino compound include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 4,4′-diaminodiphenyl sulfide. , O-aminophenol, m-aminophenol, p-aminophenol, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, bis (3- Amino-4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, bis ( 3-Amino-4-hydroxyphenyl) hexaflu Ropuropan, bis (4-amino-3-hydroxyphenyl) hexafluoropropane and the like can be used.

The above-mentioned o-quinonediazide sulfonyl chloride and hydroxy compound and / or amino compound are hydroxy compound and amino compound so that the total of hydroxy group and amino group is 0.5 to 1 equivalent with respect to 1 mol of o-quinonediazide sulfonyl chloride. Is preferably blended.
A preferred ratio of the dehydrochlorinating agent and o-quinonediazide sulfonyl chloride is in the range of 0.95 / 1 to 1 / 0.95.
Moreover, preferable reaction temperature is 0-40 degreeC, and preferable reaction time is 1 to 10 hours.

As a reaction solvent for the above reaction, a solvent such as dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, diethyl ether, N-methylpyrrolidone and the like can be used.
Examples of the dehydrochlorination agent include sodium carbonate, sodium hydroxide, sodium hydrogen carbonate, potassium carbonate, potassium hydroxide, trimethylamine, triethylamine, pyridine and the like.

The (c) cross-linking agent not containing a phenol skeleton contained in the composition of the present invention is a compound that has a function of reacting with the polymer of the component (a) to form a bridge and does not contain a phenol skeleton. .
Component (c) is a step in which the compound as component (c) reacts with the polymer to form a bridge in the step of heat treatment after application, exposure and development of the photosensitive resin composition, or in the step of heat treatment described above. The compound itself as the component (c) is polymerized. By these reactions, the mechanical properties and chemical resistance of the resulting cured film can be improved.

  The phenol skeleton means a skeleton having a structure in which a hydroxyl group (—OH) is directly bonded to an aromatic ring. With a crosslinking agent that is a compound containing a phenol skeleton, it is difficult to obtain sufficient characteristics.

(C) The crosslinking agent not containing a phenol skeleton is preferably a compound containing any one of a urea bond, a melamine skeleton and an isocyanurate skeleton, wherein one or more —CH ₂ OR (R is a hydrogen atom or one It is a compound containing a substituent represented by a valent organic group.
(C) The crosslinking agent not containing a phenol skeleton is more preferably any one or more of the compounds represented by the following formulas (1) to (3).

（式中、Ｒ^７は、それぞれ水素原子又は一価の有機基である。
Ｒ^８は、それぞれ水素原子又は一価の有機基であり、Ｒ^８同士が互いに結合して環構造を形成してもよい。） The compound which is a compound represented by Formula (1) is the following.

(In the formula, each R ⁷ is a hydrogen atom or a monovalent organic group.
R ⁸ is a hydrogen atom or a monovalent organic group, and R ⁸ may be bonded to each other to form a ring structure. )

（式中、Ｚは、それぞれ炭素数１〜１０のアルキル基である。
Ｒは、それぞれ炭素数１〜２０のアルキル基である。） The compound represented by the formula (1) is more preferably a compound represented by the following formula (1 ′).

(In formula, Z is a C1-C10 alkyl group, respectively.
R is an alkyl group having 1 to 20 carbon atoms. )

（式中、Ｒ^１〜Ｒ^６は、それぞれ水素原子又は−ＣＨ_２ＯＲ（Ｒは、水素原子又は一価の有機基である）で表される置換基であり、Ｒ^１〜Ｒ^６の少なくとも１つは−ＣＨ_２ＯＲで表される置換基である。） The compound represented by Formula (2) is a compound having a melamine skeleton.

Wherein R ^{1 to} R ⁶ are each a substituent represented by a hydrogen atom or —CH ₂ OR (where R is a hydrogen atom or a monovalent organic group), and at least ^one of R ^{1 to} R ⁶ One is a substituent represented by —CH ₂ OR.)

  Examples of the monovalent organic group for R include a hydrocarbon group, preferably an alkyl group having 1 to 6 carbon atoms.

The compound represented by the formula (2) may have many substituents represented by —CH ₂ OR, and the compound represented by the formula (2) is more preferably all of R ^{1 to} R ⁶ . It is a substituent represented by —CH ₂ OR.

（式中、Ｒ^１〜Ｒ^３は、それぞれ水素原子、下記式で表される基又は−ＣＨ_２ＯＲ（Ｒは、水素原子又は一価の有機基である）で表される置換基であり、Ｒ^１〜Ｒ^３の少なくとも１つは−ＣＨ_２ＯＲで表される置換基である。）

The compound represented by the formula (3) is a compound having an isocyanurate skeleton.

(Wherein R ^{1 to} R ³ are each a hydrogen atom, a group represented by the following formula or a substituent represented by —CH ₂ OR (R is a hydrogen atom or a monovalent organic group). And at least one of R ^{1 to} R ³ is a substituent represented by —CH ₂ OR.)

  Examples of the monovalent organic group for R include a hydrocarbon group, preferably an alkyl group having 1 to 6 carbon atoms.

The compound represented by the formula (3) may have many substituents represented by —CH ₂ OR, and the compound represented by the formula (3) is more preferably that all of R ^{1 to} R ³ are It is a substituent represented by —CH ₂ OR.

  From the viewpoint of development time, allowable width of unexposed part remaining film ratio and cured film properties, (c) the content of the crosslinking agent not containing a phenol skeleton is preferably based on 100 parts by weight of component (a). 1 to 100 parts by weight. On the other hand, from the viewpoint of chemical resistance and plating solution resistance of the cured film, the content of (c) the crosslinking agent not containing a phenol skeleton is particularly preferably 20 parts by weight or more with respect to 100 parts by weight of component (a). It is. Further, from the viewpoint of balance with the photosensitive characteristics, the content of the component (c) is preferably 20 to 50 parts by weight with respect to 100 parts by weight of the component (a).

  (D) The silane coupling agent having a urea bond contained in the composition of the present invention reacts with the polymer to form a bridge or heat in the step of heat treatment after application, exposure and development of the photosensitive resin composition. It is presumed that it will polymerize itself during the processing step. Thereby, the adhesiveness of the cured film obtained and a board | substrate can be improved.

（式中、Ｒ^９及びＲ^１０は、それぞれ炭素数１〜５のアルキル基である。
ｑは、１〜１０の整数である。
ｒは、１〜３の整数である。） (D) Although the silane coupling agent which has a urea bond will not be specifically limited if it is a compound which has a urea bond (-NH-CO-NH-), Preferably it is a compound represented by following formula (4).

(Wherein R ⁹ and R ¹⁰ are each an alkyl group having 1 to 5 carbon atoms.
q is an integer of 1-10.
r is an integer of 1 to 3. )

  Specific examples of the compound represented by the formula (4) include ureidomethyltrimethoxysilane, ureidomethyltriethoxysilane, 2-ureidoethyltrimethoxysilane, 2-ureidoethyltriethoxysilane, and 3-ureidopropyltrimethoxysilane. , 3-ureidopropyltriethoxysilane, 4-ureidobutyltrimethoxysilane, 4-ureidobutyltriethoxysilane, and the like, preferably 3-ureidopropyltriethoxysilane.

  (D) Content of the silane coupling agent which has a urea bond becomes like this. Preferably it is 1-20 weight part with respect to 100 weight part of (a) component, More preferably, it is 2-10 weight part.

The composition of the present invention may further contain (e) a thermal acid generator. (E) The thermal acid generator can efficiently function as a catalyst when the polyhydric hydroxyl group-containing polyamide structure of the polybenzoxazole precursor undergoes a dehydration reaction and cyclizes.
For example, when the component (a) is a polymer having a high dehydration ring closure rate of about 280 ° C. or less, the composition of the present invention includes (e) an acid heat generator, thereby further reducing the dehydration cyclization reaction at a lower temperature. Therefore, even if the curing is performed at a low temperature, the performance of the cured film is comparable to that of the cured film cured at a high temperature.

The acid generated from the thermal acid generator (thermal latent acid generator) is preferably a strong acid, for example, an aryl sulfonic acid such as p-toluenesulfonic acid or benzenesulfonic acid; camphorsulfonic acid, trifluoromethanesulfonic acid, Examples include perfluoroalkylsulfonic acids such as nonafluorobutanesulfonic acid; alkylsulfonic acids such as methanesulfonic acid, ethanesulfonic acid, and butanesulfonic acid. These acids efficiently act as a catalyst when the polybenzoxazole precursor phenolic hydroxyl group-containing polyamide structure undergoes a dehydration reaction and cyclizes.
In contrast, acid generators that generate hydrochloric acid, bromic acid, iodic acid, and nitric acid have weak acidity and are likely to volatilize by heating. It is considered that it is hardly involved in the dehydration reaction, and it is difficult to obtain a sufficient effect of the present invention.

  The thermal acid generator can be added to the composition of the present invention in the form of a covalent bond such as an onium salt or an imide sulfonate, for example.

Examples of the onium salt include diaryliodonium salts such as diphenyliodonium salt, di (alkylaryl) iodonium salts such as di (t-butylphenyl) iodonium salt, trialkylsulfonium salts such as trimethylsulfonium salt, dimethylphenyl Dialkyl monoaryl sulfonium salts such as sulfonium salts, diaryl monoalkyl iodonium salts such as diphenylmethylsulfonium salts, and the like are preferable.
These onium salts have decomposition initiation temperatures in the range of 150 to 250 ° C., and can be efficiently decomposed during the cyclization dehydration reaction of the polybenzoxazole precursor at 280 ° C. or less.

  From the above points, examples of suitable onium salts for the thermal acid generator used in the present invention include aryl sulfonic acid, camphor sulfonic acid, perfluoroalkyl sulfonic acid or diaryl iodonium salt of alkyl sulfonic acid, di (alkylaryl) Examples include iodonium salts, trialkylsulfonium salts, dialkylmonoarylsulfonium salts, and diarylmonoalkyliodonium salts. These are preferable from the viewpoint of storage stability and developability.

  Preferred examples of the onium salt that is a thermal acid generator include di (t-butylphenyl) iodonium salt of paratoluenesulfonic acid (1% weight reduction temperature 180 ° C., 5% weight reduction temperature 185 ° C.), trifluoromethanesulfone. Di (t-butylphenyl) iodonium salt of acid (1% weight loss temperature 151 ° C., 5% weight loss temperature 173 ° C.), trimethylsulfonium salt of trifluoromethanesulfonic acid (1% weight loss temperature 255 ° C., 5% weight loss) Temperature 278 ° C), dimethylphenylsulfonium salt of trifluoromethanesulfonic acid (1% weight loss temperature 186 ° C, 5% weight loss temperature 214 ° C), diphenylmethylsulfonium salt of trifluoromethanesulfonic acid (1% weight loss temperature 154 ° C, 5% weight loss temperature 179 ° C.) of nonafluorobutanesulfonic acid (T-butylphenyl) iodonium salt, diphenyliodonium salt of camphorsulfonic acid, diphenyliodonium salt of ethanesulfonic acid, dimethylphenyl sulfonium salt of benzenesulfonic acid, diphenylmethyl sulfonium salt of toluenesulfonic acid, and the like.

  Triphenylsulfonium salt is also an onium salt, but is not desirable as a thermal acid generator contained in the composition of the present invention. Since triphenylsulfonium salt has high thermal stability and generally has a decomposition temperature exceeding 300 ° C., no decomposition occurs during the cyclization dehydration reaction of the polybenzoxazole precursor at 280 ° C. or less, and a catalyst for cyclization dehydration. It seems that it does not work enough.

As the imide sulfonate, naphthoyl imide sulfonate is desirable.
Preferable specific examples of naphthoylimide sulfonate which is a thermal acid generator include 1,8-naphthoylimide trifluoromethylsulfonate (1% weight loss temperature 189 ° C., 5% weight loss temperature 227 ° C.), 2, 3-naphthoylimide trifluoromethyl sulfonate (1% weight loss temperature 185 ° C., 5% weight loss temperature 216 ° C.) and the like.

  Although phthalimide sulfonate is also imide sulfonate, it has poor thermal stability, so that acid may be generated before the curing reaction, which may deteriorate storage stability and the like. Undesirable as a thermal acid generator.

(E) As a thermal acid generator, R ¹ R ² C═N—O—SO ₂ —R (wherein R is an aryl group such as a p-methylphenyl group or a phenyl group, a methyl group, an ethyl group, An alkyl group such as an isopropyl group, a perfluoroalkyl group such as a trifluoromethyl group and a nonafluorobutyl group, etc. R ¹ is a cyano group, and R ² is, for example, a methoxyphenyl group or a phenyl group. ) Can be used.

Examples of the thermal acid generator having the above structure include compounds represented by the following formula (IV) (1% weight reduction temperature 204 ° C., 5% weight reduction temperature 235 ° C.).

(E) As a thermal acid generator, an amide structure —HN—SO ₂ —R (wherein R is an alkyl group such as a methyl group, an ethyl group or a propyl group, an aryl group such as a methylphenyl group or a phenyl group, A compound having a trifluoromethyl group, a perfluoroalkyl group such as nonafluorobutyl, etc.) can be used.
Examples of the group bonded to the amide structure —HN—SO ₂ —R include 2,2, -bis (4-hydroxyphenyl) hexafluoropropane, 2,2, -bis (4-hydroxyphenyl) propane, and di (4-hydroxyphenyl) ether and the like.

Examples of the thermal acid generator having the above structure include compounds represented by the following formula (V) (1% weight reduction temperature 104 ° C., 5% weight reduction temperature 270 ° C.).

(E) As the thermal acid generator, a salt formed from a strong acid other than an onium salt and a base can be used.
Examples of the strong acid include p-toluenesulfonic acid, arylsulfonic acid such as benzenesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, perfluoroalkylsulfonic acid such as nonafluorobutanesulfonic acid, methanesulfonic acid, and ethane. Alkyl sulfonic acids such as sulfonic acid and butane sulfonic acid are preferred.
Further, as the base, for example, pyridine, alkylpyridine such as 2,4,6-trimethylpyridine, N-alkylpyridine such as 2-chloro-N-methylpyridine, halogenated-N-alkylpyridine and the like are preferable. .

  From the viewpoint of storage stability and developability, a preferred specific example of the thermal acid generator which is a salt formed from a strong acid other than an onium salt and a base is a pyridine salt of p-toluenesulfonic acid (1% weight loss temperature 147). , 5% weight reduction temperature 190 ° C.), L-aspartic acid dibenzyl ester salt of p-toluenesulfonic acid (1% weight reduction temperature 202 ° C., 5% weight reduction temperature 218 ° C.), p-toluenesulfonic acid 2 , 4,6-trimethylpyridine salt, 1,4-dimethylpyridine salt of p-toluenesulfonic acid, and the like. These thermal acid generators are also decomposed during the cyclization dehydration reaction of the polybenzoxazole precursor at 280 ° C. or lower and can act as a catalyst.

  (E) The content of the thermal acid generator is preferably 0.1 to 30 parts by weight, more preferably 0.2 to 20 parts by weight, and still more preferably with respect to 100 parts by weight of the component (a). Is 0.5 to 10 parts by weight.

The composition of the present invention may contain (i) a dissolution accelerator that promotes dissolution of the component (a) in an alkaline aqueous solution.
Examples of the dissolution accelerator include compounds having a phenolic hydroxyl group. By adding a compound having a phenolic hydroxyl group to the composition of the present invention, when developing with an alkaline aqueous solution, the dissolution rate of the exposed area can be increased and the sensitivity can be increased. Melting of the film can be prevented when the film is cured.

  Examples of the compound having a phenolic hydroxyl group include o-cresol, m-cresol, p-cresol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, bisphenol A, B, C, E, F and G, 4,4 ′, 4 ″ -methylidyne trisphenol, 2,6-[(2-hydroxy-5-methylphenyl) methyl] -4-methylphenol, 4,4 ′-[1- [ 4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol, 4,4 ′-[1- [4- [2- (4-hydroxyphenyl) -2-propyl] phenyl] Ethylidene] bisphenol, 4,4 ′, 4 ″ -ethylidinetrisphenol, 4- [bis (4-hydroxyphenyl) methyl] -2-ethoxyphenol 4,4 ′-[(2-hydroxyphenyl) methylene] bis [2,3-dimethylphenol], 4,4 ′-[(3-hydroxyphenyl) methylene] bis [2,6-dimethylphenol], 4, 4 ′-[(4-hydroxyphenyl) methylene] bis [2,6-dimethylphenol], 2,2 ′-[(2-hydroxyphenyl) methylene] bis [3,5-dimethylphenol], 2,2 ′ -[(4-hydroxyphenyl) methylene] bis [3,5-dimethylphenol], 4,4 '-[(3,4-dihydroxyphenyl) methylene] bis [2,3,6-trimethylphenol], 4- [Bis (3-cyclohexyl-4-hydroxy-6-methylphenyl) methyl] -1,2-benzenediol, 4,6-bis [(3,5-dimethyl-4-hydro Cyphenyl) methyl] -1,2,3-benzenetriol, 4,4 ′-[(2-hydroxyphenyl) methylene] bis [3-methylphenol], 4,4 ′, 4 ″-(3-methyl- 1-propanyl-3-ylidine) trisphenol, 4,4 ′, 4 ″, 4 ′ ″-(1,4-phenylenedimethylidyne) tetrakisphenol, 2,4,6-tris [(3,5- Dimethyl-4-hydroxyphenyl) methyl] -1,3-benzenediol, 2,4,6-tris [(3,5-dimethyl-2-hydroxyphenyl) methyl] -1,3-benzenediol, 4,4 '-[1- [4- [1- (4-hydroxyphenyl) -3,5-bis [(hydroxy-3-methylphenyl) methyl] phenyl] -phenyl] ethylidene] bis [2,6-bis (hydrido Roxy-3-methylphenyl) methyl] phenol and the like.

  From the viewpoint of the allowable range of the development time and the unexposed part remaining film ratio, the content of the (i) dissolution accelerator is preferably 1 to 30 parts by weight, more preferably 100 parts by weight of the component (a). Is 3 to 25 parts by weight.

The composition of the present invention may contain (ii) a dissolution inhibitor that inhibits the solubility of the component (a) in an alkaline aqueous solution.
Specific examples of the dissolution inhibitor include diphenyliodonium nitrate, bis (p-tert-butylphenyl) iodonium nitrate, diphenyliodonium bromide, diphenyliodonium chloride, diphenyliodonium iodide and the like.

These compounds can easily volatilize the acid generated and do not participate in the cyclization dehydration reaction of the polybenzoxazole precursor or the like, but can control the remaining film thickness and development time.
From the viewpoint of sensitivity and allowable width during development, the content of (ii) the dissolution inhibitor is preferably 0.01 to 50 parts by weight, more preferably 0.8 to 100 parts by weight of component (a). It is 01-30 weight part, More preferably, it is 0.1-20 weight part.

  The composition of the present invention may contain (iii) an adhesion-imparting agent such as an organosilane compound and an aluminum chelate compound other than the component (d) in order to enhance the adhesion of the cured film to the substrate.

  Examples of organic silane compounds other than the above component (d) include vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, methylphenylsilanediol, ethylphenylsilanediol, n- Propylphenylsilanediol, isopropylphenylsilanediol, n-butylphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyl n-propyl Propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyl Diphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, phenylsilanetriol, 1,4-bis (trihydroxysilyl) benzene, 1,4-bis (methyldihydroxysilyl) benzene, 1,4-bis (ethyldihydroxysilyl) ) Benzene, 1,4-bis (propyldihydroxysilyl) benzene, 1,4-bis (butyldihydroxysilyl) Benzene, 1,4-bis (dimethylhydroxysilyl) benzene, 1,4-bis (diethylhydroxysilyl) benzene, 1,4-bis (dipropylhydroxysilyl) benzene, 1,4-bis (dibutylhydroxysilyl) benzene Etc.

  Examples of the aluminum chelate compound include tris (acetylacetonate) aluminum and acetylacetate aluminum diisopropylate.

  (Iii) The content of the adhesion-imparting agent is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 20 parts by weight with respect to 100 parts by weight of component (a).

  The composition of the present invention may contain (iv) a surfactant or a leveling agent in order to prevent, for example, striation (film thickness unevenness) to improve applicability or developability.

Examples of the surfactant or leveling agent include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and the like.
Commercially available products include “Megafax F171”, “F173”, “R-08” (manufactured by Dainippon Ink and Chemicals, Inc.), and “Florard FC430”, “FC431” (summer, Sumitomo 3M). Co., Ltd.), trade names "organosiloxane polymer KP341", "KBM303", "KBM403", "KBM803" (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

The positive photosensitive resin composition of the present invention usually contains a solvent, and the above components are dissolved or dispersed. The solvent is not particularly limited, and γ-butyrolactone (BLO), propylene glycol monomethyl ether acetate (PGMEA), N-methylpyrrolidone (NMP), toluene, xylene, tetrahydrofuran, alcohol and the like can be used.
Although the usage-amount of the said solvent is not restrict | limited in particular, Preferably it uses so that solid content (components other than a solvent) may be 5 to 50 weight%.

A cured film can be obtained by applying the positive photosensitive resin composition of the present invention.
In particular, the composition of the present invention can be developed with an alkaline aqueous solution, exhibits good sensitivity, good resolution and high heat resistance, and is excellent in chemical resistance and adhesion to a substrate. A cured film can be produced.

  The method for producing a patterned cured film of the present invention includes a photosensitive resin film forming step of forming a photosensitive resin film by applying the positive photosensitive resin composition of the present invention onto a support substrate and drying, and a photosensitive resin film An exposure process for exposing the pattern resin film to a predetermined pattern, a development process for developing the exposed photosensitive resin film with an alkaline aqueous solution to obtain a pattern resin film, and a heating process for heating the pattern resin film to obtain a pattern cured film Including processing steps.

Examples of the support substrate to which the composition of the present invention is applied include a glass substrate, a semiconductor, a metal oxide insulator (for example, TiO ₂ , SiO _2, etc.), silicon nitride, and the like.
Examples of the coating method include a coating method such as a spinner, and a photosensitive resin film can be formed by drying a coating film made of the composition of the present invention coated on a support substrate using a hot plate, an oven or the like.

  The exposure of the photosensitive resin film formed as a film on the support substrate can be performed by irradiating active light rays such as ultraviolet rays, visible rays, and radiations through a mask having a predetermined pattern.

  Development of the photosensitive resin film after exposure is performed using an alkaline aqueous solution (alkaline developer). A pattern resin film is obtained by removing an exposed portion of the photosensitive resin film by actinic rays using an alkaline aqueous solution.

The alkaline developer is preferably an aqueous alkali solution such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide.
The base concentration of these alkaline aqueous solutions is preferably 0.1 to 10% by weight.

Alcohols and / or surfactants may be added to the alkaline developer.
Each of these can be added in an amount of preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the alkaline developer.

By heat-treating the obtained pattern resin film, the pattern resin film is thermally cured to obtain a pattern cured film made of a resin having high heat resistance.
The temperature of the heat treatment may be 160 to 400 ° C. Since the temperature range is lower than the conventional heating temperature, damage to the support substrate and the device can be suppressed to a low level, and the device yield can be improved and the process energy can be saved.

  The heat treatment time is a time until the dehydration ring-closing reaction sufficiently proceeds, but is approximately 5 hours or less in view of work efficiency.

The heat treatment can be performed using a quartz tube furnace, a hot plate, rapid thermal annealing, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, a microwave curing furnace, or the like. As the heating environment, either air or an inert atmosphere such as nitrogen can be selected. However, it is preferable to perform the heating under nitrogen because the oxidation of the pattern resin film can be prevented.
As a heating environment for performing the heat treatment, a microwave curing device or a variable frequency microwave curing device can be used in addition to using an ordinary nitrogen-substituted oven as described above. By using these, it is possible to effectively heat only the pattern resin film.

The method for producing a patterned cured film of the present invention will be described with reference to the drawings, taking as an example a process for producing a semiconductor device having a patterned cured film.
1 to 5 are schematic cross-sectional views for explaining a manufacturing process of a semiconductor device having a multilayer wiring structure, and represent a series of processes from a first process to a fifth process.

  1 to 5, a semiconductor substrate 1 such as a Si substrate having a circuit element (not shown) is covered with a protective film 2 such as a silicon oxide film except for a predetermined portion of the circuit element, and on the exposed circuit element. A first conductor layer 3 is formed. A film made of polyimide resin or the like as the interlayer insulating film layer 4 is formed on the semiconductor substrate 1 by a spin coating method or the like (first step, FIG. 1).

  Next, a photosensitive resin layer 5 such as chlorinated rubber or phenol novolac is formed on the interlayer insulating film layer 4 as a mask by a spin coating method, and a predetermined portion of the interlayer insulating film layer 4 is formed by a known photolithography technique. A window 6A is provided so as to be exposed (second step, FIG. 2). The interlayer insulating film layer 4 exposed to the window 6A is selectively etched by a dry etching means using a gas such as oxygen or carbon tetrafluoride to open the window 6B. Next, the photosensitive resin layer 5 is completely removed using an etching solution that corrodes only the photosensitive resin layer 5 without corroding the first conductor layer 3 exposed from the window 6B (third step, FIG. 3).

  Further, the second conductor layer 7 is formed by using a known photolithography technique, and the electrical connection with the first conductor layer 3 is completely performed (fourth step, FIG. 4). When a multilayer wiring structure having three or more layers is formed, each layer can be formed by repeating the above steps.

Next, the surface protective film 8 is formed. In FIG. 5, the positive photosensitive resin composition of the present invention is applied and dried by a spin coating method, and after irradiating light from a mask on which a pattern for forming a window 6C is formed in a predetermined portion, an alkaline aqueous solution is used. Development is performed to form a patterned resin film. Thereafter, the patterned resin film is heated to form a patterned cured film of a photosensitive resin as the surface protective film layer 8 (fifth step, FIG. 5).
This surface protective film layer (patterned cured film of photosensitive resin) 8 protects the conductor layer from external stress, α rays, etc., and the resulting semiconductor device is excellent in reliability.

  The pattern cured film obtained from the positive photosensitive resin composition of the present invention is suitable as an interlayer insulating film layer and a surface protective film layer of electronic components such as semiconductor devices, multilayer wiring boards, and various electronic devices. Among them, since the pattern cured film of the present invention has high chemical resistance, for example, it is possible to reduce the influence of a plating solution used for electroless plating for UBM production, and interlayer insulation of devices requiring electroless plating. It is particularly suitable as a film or a surface protective film.

  With the downsizing of semiconductor devices, the flip chip method, which is a mounting method for semiconductor devices that has recently been adopted, is electrically connected by bump electrodes between the external terminals (bonding pads) of the semiconductor chip and the external terminals of the wiring board. The UBM is formed between the wiring board and the bump electrode. This flip chip method is not limited to the mounting between the semiconductor chip and the wiring board, but is also used for mounting between semiconductor chips and between wiring boards.

  A substrate to which the process of manufacturing the UBM is applied is shown in FIG. In FIG. 6, a plurality of layers of wiring and the like are collectively shown as the base layer 103 on the silicon substrate 102. In the base layer, a plurality of wiring layers, an interlayer insulating film layer formed between them, and the like are formed. External electrode terminals 104 are formed on the base layer 103. Furthermore, a surface protective film layer 105 is formed of a pattern cured film formed from the positive photosensitive resin composition of the present invention.

  A UBM can be produced on the external electrode terminal 104 in this state by using electroless plating. For example, when the external electrode terminal 104 is an aluminum pad, a step of degreasing using a degreasing agent, a step of etching using sulfuric acid or the like to dissolve an oxide film, a step of replacing zinc on aluminum using a zinc replacing agent The UBM is manufactured through a step of performing nickel plating by a substitution reaction of zinc and nickel using an electroless nickel plating solution, and a step of performing gold plating by a substitution reaction of nickel and gold using an electroless gold plating solution. be able to.

  Next, bump electrodes are formed, and generally solder is used. Solder can be mounted using a screen printing method or a solder ball, and a bump electrode having good shape and adhesion is formed through a reflow process.

  The electronic component of the present invention can have various structures, and preferably has a surface protective film layer and / or an interlayer insulating film layer formed using the positive photosensitive resin composition of the present invention. The electronic component of the present invention has a highly reliable pattern cured film having excellent chemical resistance and adhesion in addition to good shape and heat resistance.

Hereinafter, based on an Example and a comparative example, it demonstrates further more concretely about this invention. In addition, this invention is not limited to the following Example.

[Synthesis of Polybenzoxazole Precursor (Component (a))]
Synthesis example 1
In a 0.5 liter flask equipped with a stirrer and a thermometer, 15.48 g (60 mmol) of 4,4′-diphenyl ether dicarboxylic acid and 90 g of N-methylpyrrolidone were charged, and the flask was cooled to 5 ° C. Then, it was added dropwise thionyl chloride 23.9 g (120 mmol), allowed to react for 30 minutes to obtain a solution of 4,4'-diphenyl ether dicarboxylic acid di chloride.

Next, 87.5 g of N-methylpyrrolidone was charged into a 0.5 liter flask equipped with a stirrer and a thermometer, and 18.30 g (50 mmol) of bis (3-amino-4-hydroxyphenyl) hexafluoropropane was stirred. Dissolved. Then, pyridine was added 9.48 g (120 mmol), keeping the temperature at 0 to 5 ° C., a solution of the resulting 4,4'-diphenyl ether dicarboxylic acid di chloride was added dropwise for 30 minutes, and stirring continued for 30 minutes It was. The stirred solution was poured into 3 liters of water, and the precipitate was collected, washed with pure water three times, and then dried under reduced pressure to obtain carboxyl group-terminated polyhydroxyamide (hereinafter referred to as polymer I).

  The polymer I was subjected to GPC measurement under the measurement conditions described below, and the weight average molecular weight was determined from the obtained measurement value in terms of GPC standard polystyrene. The obtained polymer I had a weight average molecular weight of 17,600 and a dispersity of 1.6.

The measurement conditions of the weight average molecular weight by GPC method are as follows.
Measuring device: Detector L4000 UV manufactured by Hitachi, Ltd.
Pump: Hitachi Ltd. L6000
C-R4A Chromatopac made by Shimadzu Corporation
Measurement conditions: Column Gelpack GL-S300MDT-5 x 2 eluent: THF / DMF = 1/1 (volume ratio)
LiBr (0.03 mol / L), H ₃ PO ₄ (0.06 mol / L)
Flow rate: 1.0 mL / min, detector: UV 270 nm

  In Synthesis Example 1, measurement was performed using a solution of 1 mL of a solvent [THF / DMF = 1/1 (volume ratio)] with respect to 0.5 mg of the polymer. Also in the following synthesis examples, the same measurement was performed on the obtained polymer to determine the weight average molecular weight.

[Synthesis of Polybenzoxazole Precursor (Component (a))]
Synthesis example 2
Polyhydroxy amide (hereinafter referred to as polymer II) except for using dodecanedioic acid in place of diphenyl ether dicarboxylic acid in the same manner as in Synthesis Example 1 were synthesized.
The obtained polymer II had a weight average molecular weight of 27,200 determined by standard polystyrene conversion, and the dispersity was 1.9.

[Synthesis of polyimide precursor (component (a))
Synthesis example 3
In a 0.2 liter flask equipped with a stirrer and a thermometer, 10 g (32 mmol) of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride (ODPA) and 3.87 g (65 mmol) of isopropyl alcohol were added. Was dissolved in 45 g of N-methylpyrrolidone, a catalytic amount of 1,8-diazabicycloundecene was added, and then heated at 60 ° C. for 2 hours. Then, it stirred at room temperature (25 degreeC) for 15 hours, and esterification was performed. Thereafter, 7.61 g (64 mmol) of thionyl chloride was added under ice cooling, and the mixture was returned to room temperature and reacted for 2 hours to obtain an acid chloride solution (hereinafter referred to as acid chloride solution I).

Next, 40 g of N-methylpyrrolidone was charged into a 0.5 liter flask equipped with a stirrer and a thermometer, and 10.25 g (28 mmol) of bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added. After stirring and dissolving, 7.62 g (64 mmol) of pyridine was added, and while maintaining the temperature at 0 to 5 ° C., the prepared acid chloride solution I was added dropwise over 30 minutes, and then stirring was continued for 30 minutes. The stirred reaction solution was dropped into distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain a carboxylate terminal polyamic acid ester (hereinafter referred to as polymer III).
Polymer III had a weight average molecular weight of 19,400 and a dispersity of 2.2.

[Preparation of positive photosensitive resin composition]
Examples 1-7 and Comparative Examples 1-4
The weight ratio of γ-butyrolactone / propylene glycol monomethyl ether acetate to 100 parts by weight of the polymer (a) component prepared in the synthesis example and the components (b), (c) and (d) in the blending amounts shown in Table 1 It melt | dissolved in the solvent mixed by 9: 1 and prepared the photosensitive resin composition, respectively.
In Table 1, the numbers in parentheses in the respective columns of the components (b), (c), and (d) indicate the amount added (parts by weight) relative to 100 parts by weight of the polymer. The amount of the solvent used is 200 parts by weight with respect to 100 parts by weight of the polymer.

In Table 1, (b) components B1 and B2, (c) components C1, C2, C3, C4 and C5, and (d) components D1, D2, D3 and D4 are as follows. .

[Manufacture of patterned cured film]
The photosensitive resin compositions prepared in Examples 1 to 7 and Comparative Examples 1 to 4 were each spin-coated on a silicon wafer to form a coating film having a dry film thickness of 7 to 12 μm. The obtained coating film was exposed by irradiating a predetermined pattern with i-rays of 100 to 1000 mJ / cm ² through an interference filter using an ultrahigh pressure mercury lamp. After exposure, the substrate is heated at 120 ° C. for 3 minutes, developed with a 2.38 wt% aqueous solution of tetramethylammonium hydroxide (TMAH) until the exposed silicon wafer is exposed, rinsed with water, and patterned resin film Respectively.

In the formation of the pattern resin film, the minimum exposure amount (sensitivity) required to open the pattern of the exposed portion was determined at a remaining film ratio of the unexposed portion (ratio of film thickness before and after development) of 80%. The results are shown in Table 2.
The exposure was performed by pattern irradiation while increasing the exposure amount in steps of 100 mJ / cm ³ to 10 mJ / cm ³ , and the minimum exposure amount was judged while observing the opening pattern with a microscope.

  Next, the manufactured wafer with a patterned resin film was heated at 150 ° C. for 1 hour in a nitrogen atmosphere using a vertical diffusion furnace μ-TF (manufactured by Koyo Thermo System Co., Ltd.), and further heated at 320 ° C. for 1 hour. Pattern cured films (film thickness after curing, 5 to 10 μm) were obtained.

  The manufactured wafer with a patterned film is immersed in a 30% by weight aqueous sodium hydroxide solution at 50 ° C. for 10 minutes, washed with ion-exchanged water, and the opening pattern part before and after the treatment is observed with a metal microscope and changed after the treatment. The chemical resistance was evaluated by ◯ when there was no ink and by x when the permeation was observed in the opening pattern portion. The results are shown in Table 2.

The adhesion of the manufactured wafer with a patterned cured film was evaluated using a stud pull method.
Specifically, an aluminum pin with an epoxy resin is placed on a cured film on a wafer with a patterned cured film treated for 300 hours under PCT conditions (121 ° C./100 RH% / 2 atm), and 150 ° C. / The stud pin with the epoxy resin was adhered to the cured film by heating for 1 hour. This pin was pulled using ROMULUS (Quad Group Inc.), and the peeled state when peeled off was visually observed. The case where it peeled from the interface of a cured film and an epoxy resin, or the interface of an epoxy resin and an aluminum pin was set as (circle), and the case where it peeled at the interface of a silicon substrate and a cured film was evaluated as x, respectively. The results are shown in Table 2.

  As can be seen from Table 2, each of the cured films of the examples was found to have characteristics that are practically acceptable. On the other hand, in Comparative Example 2 in which component (c) was not used, and in Comparative Examples 1 and 3 in which a phenol group-containing cross-linking agent (C5) was used, it can be confirmed that the chemical resistance was remarkably deteriorated as compared with Examples. Further, in Comparative Example 4 where the component (d) was not used, it was confirmed that the adhesion strength was reduced.

  The positive photosensitive resin composition of the present invention has high chemical resistance and excellent adhesion to a substrate, and particularly has high chemical resistance to chemicals used in electroless plating processes. It is suitable for manufacturing highly reliable electronic parts as a protective film or interlayer insulating film.

DESCRIPTION OF SYMBOLS 1 Semiconductor substrate 2 Protective film 3 1st conductor layer 4 Interlayer insulating film layer 5 Photosensitive resin layer 6A, 6B, 6C Window 7 2nd conductor layer 8 Surface protective film layer 101 Semiconductor substrate 102 Silicon substrate 103 Underlayer 104 External electrode terminal 105 Surface protective film layer

Claims (11)

A positive photosensitive resin composition containing the following components (a) to (d).
(A) Polymer soluble in alkaline aqueous solution (b) Compound that generates acid upon irradiation with light (c) Crosslinking agent that is a compound represented by the following formula (3) (d) Silane coupling having urea bond Agent

(Wherein R ^{1 to} R ³ are each a hydrogen atom, a substituent represented by the following formula, or a substituent represented by —CH ₂ OR (R is a hydrogen atom or a monovalent organic group). And at least one of R ^{1 to} R ³ is a substituent represented by the following formula or a substituent represented by —CH ₂ OR)

  2. The positive photosensitive resin composition according to claim 1, wherein the polymer (a) soluble in an alkaline aqueous solution is at least one selected from the group consisting of polyimide, polybenzoxazole, and precursors thereof.   The positive photosensitive resin composition according to claim 1 or 2, wherein the compound (b) that generates acid upon irradiation with light is diazonaphthoquinone. Wherein (d) a silane coupling agent having a urea bond, positive photosensitive resin composition according to any one of claims 1 to 3, which is a compound represented by the following formula (4).

(Wherein R ⁹ and R ¹⁰ are each an alkyl group having 1 to 5 carbon atoms.
q is an integer of 1-10.
r is an integer of 1 to 3. ) The positive photosensitive resin composition according to any one of claims 1 to 4 , wherein the content of the (c) crosslinking agent is 20 parts by weight or more with respect to 100 parts by weight of the polymer (a) soluble in the alkaline aqueous solution. object. The positive photosensitive resin composition according to any one of claims 1 to 5 , which is used for an interlayer insulating film or a surface protective film of a device requiring electroless plating for producing an under bump metal. The cured film formed by apply | coating the positive photosensitive resin composition in any one of Claims 1-6 . A photosensitive resin film forming step of applying the positive photosensitive resin composition according to any one of claims 1 to 6 onto a support substrate and drying to form a photosensitive resin film;
An exposure step of exposing the photosensitive resin film to a predetermined pattern;
A development step of developing the exposed photosensitive resin film using an alkaline aqueous solution to obtain a patterned resin film;
The manufacturing method of the pattern cured film including the heat processing process which heat-processes the said pattern resin film and obtains a pattern cured film. The manufacturing method of an electronic component including the process of electroless-plating the pattern cured film obtained by the manufacturing method of Claim 8 , and producing an under bump metal. The electronic component which has a pattern cured film obtained by the manufacturing method of the pattern cured film of Claim 8 as an interlayer insulation film layer and / or a surface protective film layer. An electronic component obtained by the manufacturing method according to claim 9 .

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