JP2010276631A - Positive photosensitive resin composition, method for producing patterned cured film using the same, and electronic part and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive photosensitive resin composition which ensures high adhesion of a substrate after heat curing, has high adhesion to a metal layer and is suitable for producing a patterned cured film, such as, an interlayer insulating film in a semiconductor device. <P>SOLUTION: The positive photosensitive resin composition comprises: (a) a polymer soluble in an alkaline aqueous solution; (b) a compound which generates an acid upon irradiation with light; (c) a silane coupling compound having a hydroxy group or a glycidyl group; and (d) a silane coupling compound having a urea bond. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a positive photosensitive resin composition excellent in heat resistance, a method for producing a patterned cured film using the resin composition, an electronic component, and a method for producing the same, and in particular, sensitivity, resolution, heat resistance, chemical resistance. The present invention relates to a positive photosensitive resin composition having excellent properties and adhesion, a method for producing a patterned cured film using the resin composition, an electronic component, and a method for producing the same. In addition, a positive photosensitive resin composition suitable for use in an electronic component including a process of electroless plating for forming UBM (Under Bump Metal) after forming a cured pattern film and a method for manufacturing the same. The present invention relates to a method for producing a cured pattern film using the resin composition, an electronic component, and a method for producing the same.

  Conventionally, a polyimide resin film having excellent heat resistance, electrical characteristics, mechanical characteristics, and the like has been used for a surface protective film and an interlayer insulating film of a semiconductor device. This polyimide resin film is generally made by reacting tetracarboxylic dianhydride and diamine in a polar solvent at room temperature and normal pressure, and thinning a polyimide precursor (polyamic acid) solution (so-called varnish) by spin coating or the like. It is formed by dehydration ring closure (curing) (see, 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. When this photosensitive polyimide is used, the pattern forming process can be simplified, and the complicated pattern manufacturing process can be shortened (for example, see Patent Documents 1 to 3).

Conventionally, an organic solvent such as N-methylpyrrolidone has been used for developing the photosensitive polyimide. Recently, however, there has been a proposal of a positive photosensitive resin that can be developed with an aqueous alkaline solution from the viewpoint of environment and cost. Has been made.
As a method for obtaining such an alkali-developable positive photosensitive resin, a method of introducing an o-nitrobenzyl group into a polyimide precursor via an ester bond (for example, see Non-Patent Document 2), a soluble hydroxylimide or There is a method of mixing a naphthoquinone diazide compound with a polybenzoxazole precursor (for example, see Patent Documents 4 and 5). A resin obtained by such a method can be expected to have a low dielectric constant, and photosensitive polybenzoxazole is attracting attention together with photosensitive polyimide from such a viewpoint.

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

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

  In recent years, photosensitive polyimide or photosensitive polybenzoxazole has been increasingly used as an interlayer insulating film such as a semiconductor surface protective film or a rewiring layer in accordance with a change in package form in a semiconductor device. Usually, these precursor compositions are coated on various substrates, exposed with actinic radiation, patterned by subsequent development with an organic solvent or an alkaline aqueous solution, and finally formed into a polyimide film or a polybenzoxazole film by high-temperature heat treatment. . However, the adhesion between the film after heat curing and the substrate is poor, and there are often cases where the fine pattern is peeled off from the substrate by the chemical treatment performed after heat curing. With regard to these adhesive properties, attempts have been made to pre-treat the substrate to be used, a method of giving the base polymer itself adhesive properties, a method of adding an adhesion assistant, etc., but the process is complicated. In addition, there are problems such as a decrease in photosensitive properties and film physical properties in exchange for adhesiveness, a problem of precipitation in the composition due to the addition of another compound and a decrease in the stability of the composition. The current situation is that it has not been obtained. In particular, there is an urgent need to improve the adhesion to the aluminum wiring layer.

The present invention has been made in view of the above-described conventional problems, and the problem is that the adhesion of a substrate is high after heat curing, and the adhesion to a metal layer such as an aluminum wiring layer is high. Another object of the present invention is to provide a positive photosensitive resin composition suitable for producing a cured pattern film such as an interlayer insulating film.
In addition, a positive photosensitive resin composition excellent in chemical resistance to chemicals including chemicals used in the electroless plating process performed particularly for the production of UBM (under bump metal), and the resin composition are used. Another object of the present invention is to provide a method for producing a cured pattern film and an electronic component.

  In order to solve the above-mentioned problems, the present inventors have intensively studied, experimented, and studied, and found that an alkali-developable polymer is combined with an organosilane coupling agent and a silane coupling agent having a urea bond. By using it, in addition to high heat resistance and mechanical properties, it has been found that high adhesion to the substrate can be obtained after heat curing.

  The present invention has been made based on the above knowledge, and in order to solve the above problems, a positive photosensitive resin composition adopting the following configuration, a method for producing a patterned cured film using the resin composition, and an electron Provide parts.

（式（１）中、ｎは１〜１０の整数、Ｒ^１はヒドロキシ基又はグリシジル基を有する１価の有機基、Ｒ^２及びＲ^３は各々独立の炭素数１〜５のアルキル基、ｐは０〜２の整数を示す。
式（２）中、ｑは１〜１０の整数、Ｒ^４及びＲ^５は各々独立に炭素数１〜５のアルキル基、ｒは０〜２である。）
５．ＵＢＭ（Ｕｎｄｅｒ Ｂｕｍｐ Ｍｅｔａｌ）作製のための無電解メッキを有する電子部品の層間絶縁膜又は表面保護膜に使用されることを特徴とする１〜４のいずれか１項に記載のポジ型感光性樹脂組成物。
６．上記１〜５のいずれか１項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と、を含むことを特徴とするパターン硬化膜の製造方法。
７．上記６記載の製造方法により得られるパターン硬化膜に、ＵＢＭ（Ｕｎｄｅｒ Ｂｕｍｐ Ｍｅｔａｌ）作製のために無電解メッキする工程を有することを特徴とする電子部品の製造方法。
８．上記６に記載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ことを特徴とする電子部品。
９．上記７に記載の製造方法により得られる電子部品。 1. (A) a polymer soluble in an alkaline aqueous solution;
(B) a compound that generates acid upon irradiation with light;
(C) a silane coupling compound having a hydroxy group or a glycidyl group;
(D) a silane coupling compound having a urea bond;
A positive-type photosensitive resin composition comprising:
2. 2. The positive photosensitive resin composition according to 1, wherein the component (a) 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 component (b) is diazonaphthoquinone.
4). The component (c) is a compound represented by the following general formula (1):
The positive photosensitive resin composition according to any one of 1 to 3, wherein the component (d) is a compound represented by the following general formula (2).

(In the formula (1), n is an integer of 1 to 10, R ¹ is a monovalent organic group having a hydroxy group or a glycidyl group, R ² and R ³ are each independently an alkyl group having 1 to 5 carbon atoms, p. Represents an integer of 0-2.
In Formula (2), q is an integer of 1 to 10, R ⁴ and R ⁵ are each independently an alkyl group having 1 to 5 carbon atoms, and r is 0 to 2. )
5). 5. The positive photosensitive resin according to any one of 1 to 4, which is used for an interlayer insulating film or a surface protective film of an electronic component having electroless plating for producing an UBM (Under Bump Metal) Composition.
6). A photosensitive resin film forming step of forming the photosensitive resin film by applying the positive photosensitive resin composition according to any one of the above 1 to 5 on a support substrate and drying the composition;
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 aqueous alkaline solution to obtain a patterned resin film;
And a heat treatment step of obtaining a pattern cured film by heat-treating the pattern resin film.
7). 7. A method for producing an electronic component, comprising a step of electroless plating a patterned cured film obtained by the production method described in 6 above for producing an UBM (Under Bump Metal).
8). 7. An electronic component comprising a patterned cured film obtained by the production method according to 6 above as an interlayer insulating film layer and / or a surface protective film layer.
9. 8. An electronic component obtained by the manufacturing method according to 7 above.

The positive photosensitive resin composition of the present invention can improve substrate adhesion after curing, particularly adhesion to an aluminum substrate or aluminum wiring.
Further, the method for producing a cured pattern film of the present invention can be developed with an aqueous alkaline solution and has excellent sensitivity and resolution. According to this production method, the substrate has chemical resistance and particularly an aluminum substrate or an aluminum wiring. Therefore, it is a manufacturing method suitable for an interlayer insulating film of a semiconductor device.
The electronic component of the present invention has high heat resistance, mechanical properties, and chemical resistance, and has high adhesion to an aluminum substrate or a substrate having an aluminum wiring, and thus has high reliability.
Furthermore, since the electronic component of the present invention is formed by using the photosensitive resin composition of the present invention as a cured film that is a component of the electronic component, a pattern cured film excellent in shape, chemical resistance, and heat resistance is formed. Have.

It is a schematic sectional drawing explaining the manufacturing process of the semiconductor device which has a multilayer wiring structure by embodiment of this invention. It is a schematic sectional drawing explaining the manufacturing process of the semiconductor device which has a multilayer wiring structure by embodiment of this invention. It is a schematic sectional drawing explaining the manufacturing process of the semiconductor device which has a multilayer wiring structure by embodiment of this invention. It is a schematic sectional drawing explaining the manufacturing process of the semiconductor device which has a multilayer wiring structure by embodiment of this invention. It is a schematic sectional drawing explaining the manufacturing process of the semiconductor device which has a multilayer wiring structure by embodiment of this invention. It is sectional drawing of the structure which shows an example of the semiconductor substrate used for the UBM preparation process using the electroless plating by embodiment of this invention.

  Hereinafter, an embodiment of a positive photosensitive resin composition according to the present invention, a method for producing a patterned cured film using the resin composition, an electronic component, and a method for producing the same will be described in detail. Note that the present invention is not limited to the following embodiments.

[Positive photosensitive resin composition]
The positive photosensitive resin composition of the present invention is characterized by containing the following components (a) to (d).
(A) Polymer soluble in alkaline aqueous solution (b) Compound that generates acid upon irradiation with light (c) Silane coupling compound having hydroxy group or glycidyl group (d) Silane coupling compound having urea bond

In the composition of the present invention, in particular, by using together the silane coupling agent of the component (c) and the component (d), a substrate having high heat resistance and mechanical properties, and an aluminum substrate or aluminum wiring after heat curing. High substrate adhesion can be obtained.
Hereinafter, each component will be described.

(A) Component: Polymer Aqueous in Alkaline Aqueous Solution The component (a) used in the present invention is not particularly limited as long as it is a polymer soluble in an aqueous alkali solution.
In addition, alkaline aqueous solution is alkaline solutions, such as tetramethylammonium hydroxide (TMAH) aqueous solution, metal hydroxide aqueous solution, and organic amine aqueous solution. In general, since an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38% by weight is used, the component (a) is preferably soluble in this aqueous solution.

One criterion that the component (a) of the present invention is soluble in an alkaline developer is described below.
(A) A component alone or a varnish obtained by dissolving in any solvent together with the components (b) and (c) described below in order is spin-coated on a substrate such as a silicon wafer. Thus, a coating film having a thickness of about 5 μm is obtained. This is immersed in any one of tetramethylammonium hydroxide aqueous solution, metal hydroxide aqueous solution, and organic amine aqueous solution at 20 to 25 ° C. As a result, when it can be dissolved as a uniform solution, the component (a) is considered soluble in an alkaline developer.

The polymer as the component (a) has a main chain skeleton of a polyimide polymer or a polyoxazole polymer, that is, polyimide, polyamideimide, polyoxazole, polyamide, and precursors thereof (for example, polyamic acid, polyamic acid ester). It is preferable to introduce from at least one polymer compound selected from, for example, polyhydroxyamide, etc. from the viewpoint of processability and heat resistance.
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.

The component (a) may be a copolymer having two or more main chain skeletons described above, or a mixture of two or more of the above polymers.
Among these, if polyimide, polyoxazole or a precursor corresponding to each is used as the component (a), the cured film obtained by using the resin composition of the present invention has higher solvent resistance, which is preferable. Therefore, as the component (a), it is preferable to use at least one selected from the group consisting of polyimide, polyoxazole, and their precursors, and selected from the group consisting of polyimide, polybenzoxazole, and their precursors. It is more preferable to use at least one selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor.

The polymer and precursor that can be used as the component (a) can be synthesized, for example, by the following method.
The polyimide can be obtained, for example, by reacting tetracarboxylic dianhydride and diamine and dehydrating and ring-closing.
The polyoxazole can be obtained, for example, by reacting dicarboxylic acid dichloride with dihydroxydiamine and dehydrating and ring-closing.
The polyamideimide can be obtained, for example, by reacting tricarboxylic acid and diamine and dehydrating and ring-closing.
The polyamide can be obtained, for example, by reacting dicarboxylic acid dichloride with diamine.
The polyamic acid (polyimide precursor) can be obtained, for example, by reacting tetracarboxylic dianhydride with diamine.
The polyamic acid ester (polyimide precursor) can be obtained, for example, by reacting tetracarboxylic acid diester dichloride with a diamine.
The polyhydroxyamide (polyoxazole precursor) can be obtained, for example, by reacting dicarboxylic acid dichloride and dihydroxydiamine (usually those in which an amino group and a phenolic hydroxyl group are bonded to the ortho position of the aromatic ring).
Any of the above-described methods for producing a polymer can be a known method.

  Among the above-mentioned specific polymers, polyhydroxyamides (polybenzoxazole precursors) that are closed by heating to become polybenzoxazoles are excellent in heat resistance, mechanical properties, and electrical properties. It is being used widely as a thing. Hereinafter, examples of polyhydroxyamide will be described in detail.

（式（３）中、Ｕは４価の有機基を示し、Ｖは２価の有機基を示す）で表される繰り返し単位を有する。
この一般式（３）で表される「ヒドロキシ基を含有するアミドユニット」は、最終的には硬化時の脱水閉環により、耐熱性、機械特性、電気特性に優れるオキサゾール体に変換される。 The polyhydroxyamide has the following general formula (3):

(In formula (3), U represents a tetravalent organic group, and V represents a divalent organic group).
The “amide unit containing a hydroxy group” represented by the general formula (3) 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.

  The polyhydroxyamide that can be used in the present invention only needs to have the repeating unit represented by the general formula (3). However, the solubility of the polyhydroxyamide in an alkaline aqueous solution is derived from a phenolic hydroxyl group. The “amide unit containing a hydroxy group” represented by the general formula (3) is preferably contained in a certain proportion or more.

（式（４）中、Ｕは４価の有機基を示し、ＶとＷは２価の有機基を示す。ｊとｋは、モル分率を示し、ｊとｋの和は１００モル％であり、ｊが６０〜１００モル％、ｋが４０〜０モル％である。）で表されるポリヒドロキシアミドである。
ここで、式（４）中のｊとｋのモル分率は、ｊ＝８０〜１００モル％、ｋ＝２０〜０モル％であることがより好ましい。 As such, preferably the following formula (4):

(In Formula (4), U represents a tetravalent organic group, V and W represent a divalent organic group, j and k represent a mole fraction, and the sum of j and k is 100 mol%. And j is 60 to 100 mol%, and k is 40 to 0 mol%).
Here, the molar fraction of j and k in formula (4) is more preferably j = 80 to 100 mol% and k = 20 to 0 mol%.

The polyhydroxyamide having one type of structural unit or two types of structural units represented by the general formula (4) is generally a dicarboxylic acid derivative, a hydroxy group-containing diamine, and, if necessary, a diamine other than those described above. Can be synthesized. Specifically, it can be synthesized by converting a dicarboxylic acid derivative into a dihalide derivative and then reacting with the diamines.
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, etc., which are used in the usual acid chlorideation reaction of carboxylic acid can be used.

As a method of synthesizing the dichloride derivative, it can be synthesized by reacting the dicarboxylic acid derivative and the halogenating agent in a solvent, or reacting in an excess halogenating agent and then distilling off the excess.
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 used 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 when reacted in a solvent. When making it react in a halogenating agent, 4.0-50 mol is preferable and 5.0-20 mol is more preferable.
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.

  In the general formula (4), the tetravalent organic group represented by U is preferably a tetravalent aromatic group, preferably having 6 to 40 carbon atoms, and tetravalent having 6 to 40 carbon atoms. The aromatic group is more preferable. As the tetravalent aromatic group, those in which all four bonding sites are present on the aromatic ring are preferable. In addition, since the tetravalent organic group represented by U is a polybenzoxazole precursor, it generally reacts with a dicarboxylic acid to form a polyamide structure with “two hydroxy groups and two amino groups. "Residues of diamines each having two sets of structures each having an hydroxy group and an amino group located in the ortho position" on an aromatic ring.

  Such diamines 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-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-amino-3-hydroxyphenyl) -1,1,1,3,3,3- Although hexafluoropropane etc. are mentioned, it is not limited to these. These compounds can be used alone or in combination of two or more.

  In the general formula (4), the divalent organic group represented by W is generally a “diamine residue” that forms a polyamide structure by reacting with a dicarboxylic acid, and other than the diamine that forms the U. It is a residue and is preferably a divalent aromatic group or an aliphatic group. The number of carbon atoms is preferably 4 to 40, and more preferably a divalent aromatic group having 4 to 40 carbon atoms.

Examples of such diamines include 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenyl sulfide, benzidine, m-phenylenediamine, p. -Phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis [4 And aromatic diamine compounds such as-(4-aminophenoxy) phenyl] ether and 1,4-bis (4-aminophenoxy) benzene. In addition to these, diamines containing silicone groups include LP-7100, X-22-161AS, X-22-161A, X-22-161B, X-22-161C, and X-22-161E ( Any of these include, but are not limited to, Shin-Etsu Chemical Co., Ltd., trade name).
These compounds can be used alone or in combination of two or more.

  In the general formula (4), the divalent organic group represented by V is a dicarboxylic acid residue that reacts with diamine to form a polyamide structure, and is preferably a divalent aromatic group, preferably a carbon atom. The number is preferably 6 to 40, and a divalent aromatic group having 6 to 40 carbon atoms is more preferable from the viewpoint of heat resistance of the cured film. As the divalent aromatic group, those in which two bonding sites are both present on the aromatic ring are preferred. 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. .

（式（５）中、Ｚは炭素数１〜６の炭化水素基、式中ｎは１〜６の整数である。）で示されるジカルボン酸等が挙げられるが、これらに限定されるものではない。
これらの化合物を、単独で又は２種以上を組み合わせて使用することができる。 Examples of such dicarboxylic acids include isophthalic acid, terephthalic acid, 2,2-bis (4-carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane, and 4,4′-dicarboxybiphenyl. 4,4′-dicarboxydiphenyl ether, 4,4′-dicarboxytetraphenylsilane, bis (4-carboxyphenyl) sulfone, 2,2-bis (p-carboxyphenyl) propane, 5-tert-butylisophthalic acid Aromatic dicarboxylic acids such as 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-Cyclopentanedicarboxylic acid, having an aliphatic linear structure, malonic 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, Dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutar Acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, octafluoroadipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacin Acid, hexadecafluorosebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, trideca Diacid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosandioic acid, heneicosandioic acid, docosandioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosandioic acid , Hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosandioic acid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, and the following general formula (5):

(In formula (5), Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6 in the formula.) Absent.
These compounds can be used alone or in combination of two or more.

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

(B) Component: Compound that generates acid upon irradiation with light In the composition of the present invention, together with the aqueous polymer soluble in alkali solution used as component (a), the acid is irradiated with active light as component (b). A generated compound (hereinafter also referred to as an acid generator) is used.

  The component (b) has a function of increasing the solubility of the light irradiation part in the alkaline aqueous solution. Examples of such photoacid generators include diazonaphthoquinone, aryldiazonium salts, diaryliodonium salts, and triarylsulfonium salts. Among them, diazonaphthoquinone is preferable because it has high sensitivity.

  The diazonaphthoquinone can be obtained, for example, by subjecting o-quinonediazidosulfonyl chlorides to a hydroxy compound, an amino compound or the like 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, and 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] i Den, 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) hexafluoropro Emissions, bis (4-amino-3-hydroxyphenyl) hexafluoropropane and the like can be used.

The o-quinonediazide sulfonyl chloride and the hydroxy compound and / or amino compound are blended 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 preferred. A preferred ratio of the dehydrochlorinating agent and o-quinonediazidesulfonyl chloride is in the range of 0.95 / 1 to 1 / 0.95 (equivalent ratio).
A preferable reaction temperature is 0 to 40 ° C., and a 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 or the like is used. Examples of the dehydrochlorinating agent include sodium carbonate, sodium hydroxide, sodium hydrogen carbonate, potassium carbonate, potassium hydroxide, trimethylamine, triethylamine, pyridine and the like.

  The blending amount of component (b) is preferably 0.01 to 50 parts by weight with respect to 100 parts by weight of component (a) in order to improve the sensitivity and resolution during exposure. It is more preferably 20 parts by weight, and further preferably 0.5 to 20 parts by weight.

（式（１）中、ｎは１〜１０の整数、Ｒ^１はヒドロキシ基又はグリシジル基を有する１価の有機基、Ｒ^２及びＲ^３は各々独立の炭素数１〜５のアルキル基、ｐは０〜２の整数を示す。） (C) Component: Silane Coupling Compound Having Hydroxy Group or Glycidyl Group The component (c) in the present invention is not particularly limited as long as it is a silane coupling compound having a hydroxy group or glycidyl group.
Examples of the silane coupling compound having a hydroxy group or a glycidyl group include methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butylphenylsilanediol, isobutylphenylsilanediol, tert- Butylphenylsilanediol, diphenylsilanediol, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyl n-propylphenyl Silanol, ethyl isopropyl phenyl silanol, n-butyl ethyl phenyl silanol , Isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, phenylsilanetriol 1,4-bis (trihydroxysilyl) benzene, 1,4-bis (methyldihydroxysilyl) benzene, 1,4-bis (ethyldihydroxysilyl) benzene, 1,4-bis (propyldihydroxysilyl) benzene, , 4-bis (butyldihydroxysilyl) benzene, 1,4-bis (dimethylhydroxysilyl) benzene, 1,4-bis (diethylhydroxysilane) Le) benzene, 1,4-bis (dipropyl hydroxy silyl) benzene, and 1,4-bis (dibutyl hydroxy silyl) benzene, and a compound represented by the following general formula (1).

(In the formula (1), n is an integer of 1 to 10, R ¹ is a monovalent organic group having a hydroxy group or a glycidyl group, R ² and R ³ are each independently an alkyl group having 1 to 5 carbon atoms, p. Represents an integer of 0 to 2.)

Among the above compounds, the compound represented by the general formula (1) is particularly preferable because of its high effect of improving adhesion.
Such silane coupling agents include hydroxymethyltrimethoxysilane, hydroxymethyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyl. Triethoxysilane, 4-hydroxybutyltrimethoxysilane, 4-hydroxybutyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2-glycid Xylethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 4-glycidoxybutyltrimethoxysilane, 4-glycidoxybuty Triethoxysilane, and the like.
In addition, a silane coupling agent containing a nitrogen atom, specifically an amino group or an amide bond, together with a hydroxy group or a glycidyl group in its structure is also preferable. As such a bis (2-hydroxymethyl) ) -3-Aminopropyltriethoxysilane, bis (2-hydroxymethyl) -3-aminopropyltrimethoxysilane, bis (2-glycidoxymethyl) -3-aminopropyltriethoxysilane, bis (2-hydroxymethyl) ) -3-silane coupling agent having an amino group such as aminopropyltrimethoxysilane,
Formula _{X- (CH 2) m-CO} -NH- (CH 2) n-Si (OR) 3 ( where, X is a hydroxyl group or a glycidyl group, m and n each independently represent an integer of 1 to 3 , R is a methyl group, an ethyl group or a propyl group), and a silane coupling agent having an amide bond.

  The amount of component (c) is preferably 0.1 to 20 parts by weight, more preferably 0.3 to 10 parts by weight, based on 100 parts by weight of component (a).

（式（２）中、ｑは１〜１０の整数、Ｒ^４及びＲ^５は各々独立に炭素数１〜５のアルキル基、ｒは０〜２である） (D) Component: Silane Coupling Compound Having Urea Bond The component (d) in the present invention may be a silane coupling compound having a urea bond (—NH—CO—NH—). Preferable examples include compounds represented by the following general formula (2).

(In Formula (2), q is an integer of 1 to 10, R ⁴ and R ⁵ are each independently an alkyl group having 1 to 5 carbon atoms, and r is 0 to 2).

  Specifically, ureidomethyltrimethoxysilane, ureidomethyltriethoxysilane, 2-ureidoethyltrimethoxysilane, 2-ureidoethyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 4 -Ureidobutyltrimethoxysilane, 4-ureidobutyltriethoxysilane, etc. are mentioned. Of these, 3-ureidopropyltriethoxysilane is preferable.

  The amount of component (d) is preferably 0.1 to 30 parts by weight, more preferably 4 to 20 parts by weight, based on 100 parts by weight of component (a).

  In the positive photosensitive resin composition of the present invention, in addition to the components (a) to (d), (e) a thermal acid generator, (f) a dissolution accelerator, (g) a dissolution inhibitor, (h) You may mix | blend components, such as adhesiveness imparting agent, (i) surfactant or leveling agent, and (j) solvent.

(E) Component: Thermal acid generator In the present invention, when a thermal acid generator is used, it effectively functions as a catalyst when the phenolic hydroxyl group-containing polyamide structure of the polybenzoxazole precursor undergoes a dehydration reaction and cyclizes. Therefore, it is preferable. In addition, by using this acid heat generating agent in combination with a specific resin having a high dehydration ring closure rate of about 280 ° C. or less according to the present invention, the dehydration cyclization reaction can be further reduced in temperature. The performance of the physical properties of the later film is comparable to that obtained by curing at a high temperature.

  The acid generated from the thermal acid generator (thermal latent acid generator) is preferably a strong acid. Specifically, for example, p-toluenesulfonic acid, arylsulfonic acid such as benzenesulfonic acid, camphorsulfonic acid, Preference is given to perfluoroalkylsulfonic acids such as trifluoromethanesulfonic acid and 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 when heated. 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 above-mentioned acid is added to the photosensitive resin composition of the present invention as a thermal acid generator in the form of a salt as an onium salt or in the form of a covalent bond such as imide sulfonate.

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, dimethyl A dialkyl monoarylsulfonium salt such as a phenylsulfonium salt, a diarylmonoalkyliodonium salt such as a diphenylmethylsulfonium salt, and the like are preferable. These are preferable because the decomposition start temperature is in the range of 150 to 250 ° C., and the polybenzoxazole precursor is efficiently decomposed during the cyclization dehydration reaction at 280 ° C. or less.
On the other hand, triphenylsulfonium salt is not desirable as the thermal acid generator 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 is because it is thought that it does not work enough.

  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.

  More specifically, di (t-butylphenyl) iodonium salt of paratoluenesulfonic acid (1% weight reduction temperature 180 ° C., 5% weight reduction temperature 185 ° C.), di (t-butylphenyl) trifluoromethanesulfonic acid Iodonium salt (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), trifluoromethanesulfonic acid Dimethylphenylsulfonium salt (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.), Nonafluorobutanesulfonic acid di (t-butylphenyl) iodoni Can be mentioned salts, diphenyliodonium salts of camphorsulfonic acid, diphenyliodonium salt of ethanesulfonic acid, dimethylphenyl sulfonium salt of benzenesulfonic acid, as preferred diphenyl methyl sulfonium salts of toluenesulfonic acid and the like.

The imide sulfonate is preferably naphthoyl imide sulfonate.
On the other hand, phthalimide sulfonate is not desirable because it has poor thermal stability, so that an acid is generated before the curing reaction and deteriorates storage stability.

  Specific examples of the naphthoylimide sulfonate include 1,8-naphthoylimide trifluoromethyl sulfonate (1% weight loss temperature 189 ° C., 5% weight loss temperature 227 ° C.), 2,3-naphthoyl. Preferred examples include imidotrifluoromethylsulfonate (1% weight loss temperature 185 ° C., 5% weight loss temperature 216 ° C.).

Furthermore, as the component (e) (thermal acid generator), as shown in the following chemical formula (7), a compound having a structure of R ¹ R ² C═N—O—SO ₂ —R (1% weight loss) A temperature of 204 ° C., a 5% weight loss temperature of 235 ° C.) can also be used. Here, as R, for example, an aryl group such as a p-methylphenyl group and a phenyl group, an alkyl group such as a methyl group, an ethyl group and an isopropyl group, a perfluoroalkyl group such as a trifluoromethyl group and a nonafluorobutyl group Etc. Examples of R ¹ include a cyano group, and examples of R ² include a methoxyphenyl group and a phenyl group.

Further, as the component (e) (thermal acid generator), as shown in the following chemical formula (8), a compound having an amide structure —HN—SO ₂ —R (1% weight reduction temperature 104 ° C., 5% weight) A decreasing temperature of 270 ° C. can also be used. Examples of R include alkyl groups such as a methyl group, ethyl group, and propyl group, aryl groups such as a methylphenyl group and a phenyl group, perfluoroalkyl groups such as a trifluoromethyl group and nonafluorobutyl, and the like. . Examples of the group to which —HN—SO ₂ —R is bonded include 2,2, -bis (4-hydroxyphenyl) hexafluoropropane, 2,2, -bis (4-hydroxyphenyl) propane, and di ( 4-hydroxyphenyl) ether and the like.

  Furthermore, as the component (e) (thermal acid generator) used in the present invention, a salt formed from a strong acid other than an onium salt and a base can also be used. Examples of such strong acids include arylsulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, perfluoroalkylsulfonic acids such as camphorsulfonic acid, trifluoromethanesulfonic acid and nonafluorobutanesulfonic acid, and methanesulfone. Alkyl sulfonic acids such as acids, ethane sulfonic acids, butane sulfonic acids are preferred. 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. More specifically, p-toluenesulfonic acid pyridine salt (1% weight loss temperature 147 ° C., 5% weight reduction temperature 190 ° C.), p-toluenesulfonic acid L-aspartic acid dibenzyl ester salt (1% weight) Decrease temperature 202 ° C, 5% weight loss temperature 218 ° C), 2,4,6-trimethylpyridine salt of p-toluenesulfonic acid, 1,4-dimethylpyridine salt of p-toluenesulfonic acid, etc., storage stability, development It is mentioned as a preferable thing from the point of property. These are also decomposed during the cyclization dehydration reaction of the polybenzoxazole precursor at 280 ° C. or less, and can act as a catalyst.

  The blending amount of the component (e) (thermal acid generator) is preferably 0.1 to 30 parts by weight, more preferably 0.2 to 20 parts by weight based on 100 parts by weight of the component (a) (base resin). 0.5-10 weight part is further more preferable.

(F) Component: Dissolution Accelerator In the present invention, a dissolution accelerator that promotes the solubility of the base resin (a) component in an alkaline aqueous solution, for example, a compound having a phenolic hydroxyl group can be contained. When the compound having a phenolic hydroxyl group is added to the photosensitive resin composition of the present invention, the development rate using the aqueous alkaline solution increases the dissolution rate of the exposed area and increases the sensitivity. During curing, the film can be prevented from melting.

  There is no restriction | limiting in particular in the compound which has the said phenolic hydroxyl group which can be used for this invention. Examples of the low molecular weight 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, and C. , E, F and G, 4,4 ′, 4 ″ -methylidynetrisphenol, 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-ethoxy Enol, 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- -Hydroxyphenyl) 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 (hydroxy-3-methylphenyl) methyl] phenol and the like can be mentioned.

  The compounding amount of the compound having a phenolic hydroxyl group is preferably 1 to 30 parts by weight relative to 100 parts by weight of the component (a) (base resin) from the viewpoint of development time and the allowable width of the unexposed part remaining film ratio. 3 to 25 parts by weight is more preferable.

(G) Component: Dissolution Inhibitor In the present invention, a dissolution inhibitor that is a compound that inhibits the solubility of the base resin as the component (a) in an alkaline aqueous solution can be further contained. Specific examples of the dissolution inhibitor include compounds such as diphenyliodonium nitrate, bis (p-tert-butylphenyl) iodonium nitrate, diphenyliodonium bromide, diphenyliodonium chloride, and diphenyliodonium iodide.

  These compounds are not involved in the cyclization dehydration reaction of the polybenzoxazole precursor because the generated acid is likely to volatilize. However, these compounds effectively cause dissolution inhibition and are useful for controlling the remaining film thickness and development time. The blending amount of the dissolution inhibitor is preferably 0.01 to 50 parts by weight, preferably 0.01 to 30 parts by weight based on 100 parts by weight of the component (a) (base resin), from the viewpoint of sensitivity and allowable width at the time of development. Part is more preferable, and 0.1 to 20 parts by weight is further preferable.

(H) Component: Adhesiveness imparting agent The photosensitive resin composition of the present invention comprises an organosilane compound other than the above (c) component and (d) component, and an aluminum chelate in order to enhance the adhesion of the cured film to the substrate. An adhesion-imparting agent such as a compound can be included.
Examples of such an organic silane compound include vinyltriethoxysilane and γ-methacryloxypropyltrimethoxysilane.
Examples of the aluminum chelate compound include tris (acetylacetonate) aluminum, acetylacetate aluminum diisopropylate, and the like.
When using the said adhesiveness imparting agent, 0.1-30 weight part is preferable with respect to 100 weight part of (a) component (base resin), and 0.5-20 weight part is more preferable.

(I) Component: Surfactant or leveling agent The photosensitive resin composition of the present invention is suitable for preventing applicability, for example, striation (thickness unevenness) or improving developability. Surfactants or leveling agents can be added.

  Examples of such surfactants or leveling agents include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and the like. “Megafax F171”, “F173”, “R-08” (above, manufactured by Dainippon Ink & Chemicals, Inc.), trade names “Florard FC430”, “FC431” (above, manufactured by Sumitomo 3M Limited), trade names “ And organosiloxane polymers KP341, KBM303, KBM403, KBM803 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.

(J) Component: Solvent 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%.

[Method for producing patterned cured film]
Next, the manufacturing method of the pattern cured film by this invention is demonstrated.
The pattern cured film manufacturing method of the present invention includes a photosensitive resin film forming step in which the above-described photosensitive resin composition of the present invention is applied onto a support substrate and dried to form a photosensitive resin film. An exposure process for exposing to a predetermined pattern; a development process for developing the exposed photosensitive resin film to obtain a pattern resin film; and a heat treatment process for obtaining a pattern cured film by heat-treating the pattern resin film.
Hereinafter, each step will be described.

(Photosensitive resin film forming process)
In this step, the photosensitive resin composition of the present invention is applied to a support substrate such as a glass substrate, a semiconductor, a metal oxide insulator (for example, TiO ₂ , SiO ₂ ), or silicon nitride using a spinner or the like coating method. Apply. Note that constituent members of electronic parts such as pattern electrodes and interlayer insulating film layers may be formed in advance on the support substrate, and the composition may be applied on these members.
The obtained coating film is dried using a hot plate, an oven or the like. Thereby, the photosensitive resin film which is a film of the photosensitive resin composition is obtained.

(Exposure process)
In the exposure step, exposure is performed by irradiating the photosensitive resin film formed on the support substrate with an actinic ray such as ultraviolet ray, visible ray, or radiation through a mask having a predetermined pattern.

(Development process)
In the development process, the exposed portion of the photosensitive resin film in the exposure process is removed with a developer. A patterned resin film is obtained by removing the exposed portion.
The developer to be used is an alkaline developer, and for example, an alkaline aqueous solution such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide is preferable. The base concentration of these alkaline aqueous solutions is preferably 0.1 to 10% by weight.
Alcohols and surfactants can be added to the alkaline developer and used. Each of these can be blended 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.

(Heat treatment process)
In the heat treatment step, the pattern resin film obtained by development is heat treated. Thereby, the pattern cured film which consists of resin with high heat resistance can be formed.
The temperature of the heat treatment is preferably 160 to 400 ° C. It is one of the features of the present invention that a patterned cured film of a resin having high heat resistance can be obtained at such a low temperature. Since this heating temperature range is lower than the conventional heating temperature, damage to the support substrate and the device can be reduced. Therefore, a device can be manufactured with a high yield by using the method for producing a cured pattern film of the present invention. It also leads to energy savings in the process.

  The heating time is a time until the dehydration ring-closing reaction of the pattern resin film sufficiently proceeds in the above temperature range, but is approximately 5 hours or less in consideration of work efficiency.

  The heat treatment is performed using a quartz tube furnace, hot plate, rapid thermal annealing, vertical diffusion furnace, infrared curing furnace, electron beam curing furnace, 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 the heating environment of the heat treatment in the method of the present invention, as described above, a microwave curing device or a variable frequency microwave curing device can be used in addition to using an ordinary nitrogen-substituted oven. By using these, it is possible to effectively heat only the pattern resin film.

[Electronic components and their manufacturing processes]
Next, as an embodiment of a method for manufacturing an electronic component having a patterned cured film according to the present invention, a method for manufacturing a semiconductor device will be described with reference to the drawings.
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 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 the example of FIGS. 1-5, this surface protective film is formed as follows. That is, the photosensitive resin composition of the present invention is applied and dried by a spin coating method, irradiated with light from a mask on which a pattern forming a window 6C is formed at a predetermined portion, and then developed with an alkaline aqueous solution to form a pattern. A resin film is formed. 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 obtained semiconductor device is excellent in reliability. Since this surface protective film layer has particularly high adhesion to an aluminum substrate or aluminum wiring, it is suitable to be formed on the top of such a substrate or wiring.

The electronic component of this invention has the pattern cured film formed by the manufacturing method of the said pattern cured film using the photosensitive resin composition of this invention like the example of the semiconductor device mentioned above. Here, the electronic component includes a semiconductor device, a multilayer wiring board, various electronic devices, and the like.
Specifically, the pattern cured film of the present invention can be used for forming a surface protective film, an interlayer insulating film of an electronic component such as a semiconductor device, an interlayer insulating film of a multilayer wiring board, and the like. The electronic component according to the present invention is not particularly limited except that it has a surface protective film and an interlayer insulating film formed using the photosensitive resin composition, and can take various structures.

[UBM fabrication process using electroless plating]
The photosensitive resin composition of the present invention includes a method for producing an electronic component, wherein a pattern cured film obtained by using the photosensitive resin composition is subjected to an electroless plating process for producing an UBM (Under Bump Metal), and the method It is also suitable for an interlayer insulating film or a surface protective film of an electronic component obtained by the manufacturing method. This will be described below.

  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. And is mechanically joined. The flip chip method is not limited to the mounting between the semiconductor chip and the wiring board, but is also used for mounting between the semiconductor chips and between the wiring boards.

  A substrate to which this process 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.

  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. Thereafter, 23.9 g (120 mmol) of thionyl chloride was added dropwise and reacted for 30 minutes to obtain a solution of 4,4′-diphenyl ether dicarboxylic acid dichloride.

  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. Thereafter, 9.48 g (120 mmol) of pyridine was added, and while maintaining the temperature at 0 to 5 ° C., a solution of 4,4′-diphenyl ether dicarboxylic acid dichloride was added dropwise over 30 minutes, and stirring was continued for 30 minutes.

The stirred solution was poured into 3 liters of water, and the precipitate was collected, washed three times with pure water, and then dried under reduced pressure to obtain carboxyl group-terminated polyhydroxyamide (hereinafter referred to as polymer 1). The polymer 1 was subjected to GPC measurement under the measurement conditions described later, and the obtained measurement value was determined for the weight average molecular weight by GPC standard polystyrene conversion. The weight average molecular weight obtained was 17,600, and the degree of dispersion was 1.6.
In addition, the same measurement is performed about the polymer obtained in the following synthesis examples, and the weight average molecular weight is calculated | required.

・ Measurement condition of weight average molecular weight by GPC method Measuring device: Detector L4000UV manufactured by Hitachi, Ltd.
Pump: Hitachi Ltd. L6000
Recorder: C-R4A Chromatopac manufactured 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
A polyhydroxyamide (hereinafter referred to as polymer II) was synthesized in the same manner as in Synthesis Example 1 except that dodecanedioic acid was used instead of diphenyl ether dicarboxylic acid.
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.

Examples 1-9 and Comparative Examples 1-3
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 were used in a weight ratio of 9 to γ-butyrolactone / propylene glycol monomethyl ether acetate. 1 was dissolved in a solvent mixed at 1: to prepare a photosensitive resin composition.
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, B1 and B2 which are (b) components, C1 and C2 which are (c) components, and D1, D2 and D3 which are (d) components are as follows.

  D3 is not the component (d) of the present invention. That is, it is not a silane coupling agent having a urea bond. For the sake of convenience, a silane coupling agent having no urea bond is used instead, and it is classified and described here as component D for convenience.

[Manufacture of patterned cured film]
The photosensitive resin compositions prepared in Examples 1 to 9 and Comparative Examples 1 to 3 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 irradiated with a predetermined pattern on the wafer by changing the i-ray irradiation dose from 100 to 1000 mJ / cm ^{2 in} increments of 10 mJ / cm ³ through an interference filter using an ultra-high pressure mercury lamp as a light source. , Exposure was performed. 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 pattern resin film formation, the development time is adjusted so that the remaining film ratio (ratio of film thickness before and after development) in the unexposed area is 80%, and the minimum exposure amount necessary for opening the pattern in the exposed area is set. It was defined as sensitivity. The opening pattern was judged while observing with a microscope. The results are shown in Table 2. All samples of the examples showed sufficient sensitivity characteristics.

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.
About the obtained cured film, chemical resistance and adhesiveness were evaluated by the following method.

Chemical resistance evaluation method The cured film is immersed in a dilution solution (FZ-7350: water = 1: 4) of Melplate FZ-7350 (trade name, manufactured by Meltex Co., Ltd.) for 30 minutes at room temperature, and a 100 μm square opening The penetration into the membrane was investigated. Melplate FZ-7350 used for the test is known as a strong alkaline plating chemical with a strong penetration.
Since the part in which the chemical solution is soaked changes to black, the presence or absence of the soak can be clearly determined. The quality was judged based on the permeation shape around the 100um square opening pattern. In other words, because the amount of dyeing is large, the case where the stain spreads in a circle around the square pattern is ×, the amount of dyeing is small and the shape of the stain is keeping the square of the opening, Δ, the amount of dyeing is slight, Or the thing which did not soak was judged as (circle).

-Evaluation method of adhesiveness Adhesiveness was evaluated using a stud pull tester. The cured film was placed in a pressure cooker and treated for 500 hours under conditions of 121 ° C., 2 atm, 100% HR (PCT treatment). The adhesive strength before and after the PCT treatment was evaluated using a stud pull tester (ROMULUS, manufactured by Quad Group Inc.).
Specifically, an aluminum pin with an epoxy resin is placed on a cured film on a wafer with a patterned cured film treated for 500 hours under the above PCT conditions (121 ° C./100 RH% / 2 atm), and 150 ° C. in an oven. / 1 hour was applied to adhere the stud pin with the epoxy resin to the cured film. The pin was pulled using the stud pull tester, and the peeled state when peeled off was visually observed.
In the stud pull test, any sample other than Comparative Example 2 showed a sufficient adhesive strength of 600 to 800 kg / cm ² , but a difference was observed in the peeling mode (form). The peeling mode is one of the important indicators for estimating the adhesive strength.
The evaluation criteria for the peeling mode were as follows. When peeled off at the aluminum / cured film interface, it indicates that the adhesive force between the aluminum substrate and the cured film is not sufficient, and x, and when the epoxy adhesive layer breaks instead of peeling at the interface, it is sufficient with the aluminum substrate. Since the adhesive strength was maintained, it was evaluated as “good”.
However, Comparative Example 2 was very weak in adhesive force, and measurement was impossible because the cured film was peeled off before the stud pull test. The results are shown in Table 2.

As can be seen from Table 2, the cured films of the examples all have a sensitivity that is not problematic in practice, and have sufficient resistance and adhesion to the plating solution on the aluminum substrate.
On the other hand, in Comparative Example 1 in which the component (d) was not used, the penetration resistance into the plating solution was significantly deteriorated. Further, in Comparative Example 2 in which both the components (c) and (d) were not used, the adhesion after PCT was significantly deteriorated in addition to the deterioration of the plating solution penetration resistance. In Comparative Example 3, when a silane coupling compound having no urea bond was used, the penetration resistance into the plating solution was remarkably deteriorated.

  The positive photosensitive resin composition of the present invention can be used as a material for a pattern cured film that becomes a surface protective film or an interlayer insulating film of an electronic component.

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 (9)

(A) a polymer soluble in an alkaline aqueous solution;
(B) a compound that generates acid upon irradiation with light;
(C) a silane coupling compound having a hydroxy group or a glycidyl group;
(D) a silane coupling compound having a urea bond;
A positive-type photosensitive resin composition comprising:   The positive photosensitive resin composition according to claim 1, wherein the component (a) is at least one selected from the group consisting of polyimide, polybenzoxazole, and precursors thereof.   The positive photosensitive resin composition according to claim 1, wherein the component (b) is diazonaphthoquinone. The component (c) is a compound represented by the following general formula (1):
The positive photosensitive resin composition according to claim 1, wherein the component (d) is a compound represented by the following general formula (2).

(In the formula (1), n is an integer of 1 to 10, R ¹ is a monovalent organic group having a hydroxy group or a glycidyl group, R ² and R ³ are each independently an alkyl group having 1 to 5 carbon atoms, p. Represents an integer of 0-2.
In Formula (2), q is an integer of 1 to 10, R ⁴ and R ⁵ are each independently an alkyl group having 1 to 5 carbon atoms, and r is 0 to 2. )   5. The positive photosensitive film according to claim 1, wherein the positive photosensitive film is used for an interlayer insulating film or a surface protective film of an electronic component having electroless plating for manufacturing an UBM (Under Bump Metal). Resin composition. A photosensitive resin film forming step of applying the positive photosensitive resin composition according to any one of claims 1 to 5 on 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 aqueous alkaline solution to obtain a patterned resin film;
And a heat treatment step of obtaining a pattern cured film by heat-treating the pattern resin film.   An electronic component manufacturing method comprising a step of electroless plating a patterned cured film obtained by the manufacturing method according to claim 6 in order to produce an UBM (Under Bump Metal).   An electronic component comprising the cured pattern film obtained by the production method according to claim 6 as an interlayer insulating film layer and / or a surface protective film layer.   An electronic component obtained by the manufacturing method according to claim 7.

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