JP5651917B2 - Positive photosensitive resin composition, method for producing patterned cured film using the resin composition, and electronic component - Google Patents

Description

  The present invention relates to a positive-type photosensitive resin composition excellent in heat resistance containing a polybenzoxazole precursor, a method for producing a patterned cured film using the resin composition, and an electronic component, and in particular, sensitivity, resolution, development. The present invention relates to a positive photosensitive resin composition that is excellent in adhesion, heat resistance and chemical resistance at the time, and can obtain a pattern with a good shape, a method for producing a cured pattern film using the resin composition, and an electronic component .

  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, a photosensitive polyimide obtained by imparting photosensitive characteristics to a polyimide resin itself has 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), 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 rewiring layer in accordance with a change in package form in a semiconductor device. The polyimide and polybenzoxazole-based material (photosensitive resin composition) to cope with such a case needs to have resistance to chemicals more than conventional materials. However, in conventional polyimide and polybenzoxazole-based materials (photosensitive resin compositions), it has not been obtained yet that has both chemical resistance and photosensitive characteristics or film characteristics.

  The present invention has been made in view of the above-described conventional problems, and the problem is that it is a positive type that has high chemical resistance and can be suitably used for manufacturing a pattern cured film such as an interlayer insulating film of a semiconductor device. It is providing the photosensitive resin composition.

  In order to solve the above-mentioned problems, the present inventors have made extensive studies, experiments, and studies. By using a compound having a urea bond in combination with a polymer that can be developed with an alkali, high heat resistance and mechanical properties can be obtained. In addition, the chemical resistance can be improved, and by adding a compound that inhibits the solubility of the polymer, a moderate difference in dissolution rate can be achieved between the exposed and unexposed areas. The inventors have come to know that good photosensitivity with excellent resistance can be obtained.

  Furthermore, by using the resin composition having the above configuration, a pattern cured film can be produced by a low temperature process. Therefore, if a patterned cured film such as an interlayer insulating film in a semiconductor device is manufactured using the resin composition having such a configuration, damage to the semiconductor device associated with the manufacturing process can be reduced. As a result, since the reliability of the obtained semiconductor device is improved, an electronic component including such a semiconductor device can also be provided with high reliability and high yield.

  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.

[1] (a) a polymer soluble in an alkaline aqueous solution;
(B) a compound that generates acid upon irradiation with light;
(C) a compound having a urea bond;
(D) a compound that inhibits dissolution of the component (a) in the alkaline aqueous solution;
A positive-type photosensitive resin composition comprising:

[2] The positive photosensitive resin composition as described in [1] above, wherein the component (a) is at least one selected from the group consisting of polyimide, polybenzoxazole, and precursors thereof. object.

[3] The positive photosensitive resin composition as described in [1] or [2] above, wherein the component (b) is diazonaphthoquinone.

[4] The component (c) is represented by the following general formula (1):

（式（１）中、複数のＲ^７は各々独立に水素原子または１価の有機基を示し、複数のＲ^８は各々独立に水素原子または１価の有機基を示し、互いが結合することで環構造となっていても良い）
で表される化合物であることを特徴とする、上記［１］〜［３］のいずれか一つに記載のポジ型感光性樹脂組成物。

(In the formula (1), each of the plurality of R ⁷ independently represents a hydrogen atom or a monovalent organic group, and each of the plurality of R ⁸ independently represents a hydrogen atom or a monovalent organic group, and is bonded to each other) It may be a ring structure)
The positive photosensitive resin composition according to any one of the above [1] to [3], which is a compound represented by

[5] The component (d) is represented by the following general formula (2):

（式（２）中、Ｘ⁻は対陰イオンを示し、Ｒ^７及びＲ^８は各々独立に１価の有機基を示し、ａ及びｂは各々独立に０〜５の整数である）
で表されるジアリールヨードニウム塩を含むことを特徴とする、上記［１］〜［４］のいずれか一つに記載のポジ型感光性樹脂組成物。

(In formula (2), X ⁻ represents a counter anion, R ⁷ and R ⁸ each independently represents a monovalent organic group, and a and b are each independently an integer of 0 to 5)
The positive photosensitive resin composition according to any one of the above [1] to [4], comprising a diaryl iodonium salt represented by the formula:

[6] As described in any one of [1] to [5], the component (c) is used in an amount of 20 parts by weight or more based on 100 parts by weight of the component (a). Positive photosensitive resin composition.

[7] The positive photosensitive resin composition as described in [6] above, wherein the component (d) is used in an amount of 3 parts by weight or more based on 100 parts by weight of the component (a). .

[8] A photosensitive resin film forming step in which the positive photosensitive resin composition according to any one of [1] to [7] is applied on a support substrate and dried to form a photosensitive resin film; An exposure process for exposing the photosensitive resin film to a predetermined pattern; a development process for developing the exposed photosensitive resin film using an alkaline aqueous solution to obtain a pattern resin film; and a heat treatment for the pattern resin film. And a heat treatment process for obtaining a patterned cured film.

[9] An electronic component comprising a patterned cured film obtained by the method for producing a patterned cured film as described in [8] above as an interlayer insulating film layer and / or a surface protective film layer.

The positive photosensitive resin composition of the present invention uses a compound having a urea bond and a compound that inhibits the solubility of the polymer, and is excellent in sensitivity and resolution due to such structural features.
A pattern cured film obtained by pattern formation and heat curing using the positive photosensitive resin composition of the present invention is excellent in heat resistance and mechanical properties, and has high resistance to various chemicals, particularly interlayer insulation of semiconductor devices. It is suitable for the membrane.
Moreover, according to the method for producing a cured pattern film of the present invention, a pattern having a good shape excellent in sensitivity, resolution, and chemical resistance can be obtained by using the photosensitive resin composition.
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.

  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, and an electronic component will be described in detail with reference to the drawings. In addition, this invention is not limited by the following embodiment.

((A) component: polymer soluble in alkaline aqueous solution)
The component (a) used in the present invention is not particularly limited as long as it is a polymer that is soluble in an aqueous alkali solution.

  The 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. 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.

In addition, one criterion that the component (a) of the present invention is soluble in an alkaline developer will be described below.
(A) A component alone or a varnish obtained by dissolving in any solvent together with the components (b) and (c) described in order below is formed by spin coating 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.

  Here, as the main chain skeleton of the component (a), (i) polyimide polymer or polyoxazole polymer, that is, polyimide, polyamideimide, polyoxazole, polyamide, and precursors thereof (for example, polyamic acid, polyamide) It is preferably introduced from at least one (polymeric compound) selected from acid esters, polyhydroxyamides, etc. from the viewpoint of processability and heat resistance, and (ii) a plurality of phenolic hydroxyl groups and carboxyl groups. It is preferable that it has a structure having an aqueous alkali solution solubility. Therefore, the component (a) can also be used as the two or more types of copolymers and mixtures. Among these, if polyimide, polyoxazole or precursors corresponding to each are used as the component (a), the cured film obtained using the resin composition of the present invention has higher solvent resistance. As a component, it is preferable to use at least one selected from the group consisting of polyimide, polyoxazole, and their precursors, and in particular, at least one selected from the group consisting of polyimide, polybenzoxazole, and their precursors. Is preferably used.

Each of the specific polymer and precursor that can be used as the component (a) will be described below.
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 can be obtained, for example, by reacting tetracarboxylic dianhydride with diamine.
The polyamic acid ester can be obtained, for example, by reacting tetracarboxylic acid diester dichloride with diamine.

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 for current electronic components. It is being used widely as a thing.
This polyhydroxyamide has the following general formula (3):

（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。

(In formula (3), U represents a tetravalent organic group, and V represents a divalent organic group)
It has the repeating unit represented by these.
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 ratio or more.
As such, preferably the following formula (4):

（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。

(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%.)
It is polyhydroxyamide represented by these.
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%.

In the present invention, the polyhydroxyamide having a repeating unit represented by the general formula (4) can be generally 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 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 to be used in a solvent is preferably 1.5 to 3.0 mol, more preferably 1.7 to 2.5 mol relative to the dicarboxylic acid derivative. When making it react in an 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.

(Tetravalent organic group represented by U in the general formula (4))
In the general formula (4), the tetravalent organic group represented by U generally forms a polyamide structure by reacting with a dicarboxylic acid, “a structure in which two hydroxy groups are located at the ortho positions of the amine, respectively. A tetravalent aromatic group, preferably having 6 to 40 carbon atoms, and more preferably a tetravalent aromatic group having 6 to 40 carbon atoms. As the tetravalent aromatic group, those in which all four bonding sites are present on the aromatic ring are preferable.

  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.

(Divalent organic group represented by W in the general formula (4))
In the general formula (4), the divalent organic group represented by W is generally a “diamine residue” that reacts with a dicarboxylic acid to form a polyamide structure, and other than the diamine that forms the U. And a divalent aromatic group or aliphatic group is preferred, and those having 4 to 40 carbon atoms are preferred, and divalent aromatic groups having 4 to 40 carbon atoms are more preferred.

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 Aromatic diamine compounds such as-(4-aminophenoxy) phenyl] ether and 1,4-bis (4-aminophenoxy) benzene can be mentioned. Besides these, as diamines containing silicone groups, LP -7100, X-22-161AS, X-22- 161A, X-22-161B, X-22-161C, and X-22-161E (all are trade names manufactured by Shin-Etsu Chemical Co., Ltd.) and the like, but are not limited thereto.
These compounds can be used alone or in combination of two or more.

(Divalent organic group represented by V in the general formula (4))
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. .

  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):

（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。

(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: a compound that generates acid upon irradiation with light)
In the composition of the present invention, a compound capable of generating an acid upon irradiation with actinic rays (hereinafter also referred to as an acid generator) is used as the component (b) together with the polymer soluble in an aqueous alkali solution used as the component (a). .

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

  The component (b) “compound that generates an acid upon irradiation with light (photoacid generator)” has a function of increasing the solubility of the irradiated portion in an alkaline aqueous solution. Examples of such a photoacid generator include an o-quinonediazide compound, an aryldiazonium salt, a diaryliodonium salt, a triarylsulfonium salt, and the like. Among them, an o-quinonediazide compound is preferable because of its high sensitivity.

  The o-quinonediazide compound can be obtained, for example, by subjecting o-quinonediazidesulfonyl 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, and tris (4-hydroxyphenyl) ethane 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, such as bis (4-amino-3-hydroxyphenyl) hexafluoropropane 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-quinonediazide sulfonyl chloride is in the range of 0.95 / 1 to 1 / 0.95.
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 dehydrochlorination agent include sodium carbonate, sodium hydroxide, sodium hydrogen carbonate, potassium carbonate, potassium hydroxide, trimethylamine, triethylamine, and pyridine.

((C) component: a compound having a urea bond)
The compound having a urea bond, which is the component (c) used in the present invention, reacts with the polymer, that is, crosslinks, in the step of heat treatment after coating, exposing and developing the photosensitive resin composition. Alternatively, in the heat treatment step, the compound itself is polymerized. Thereby, the mechanical characteristics, chemical resistance, and flux resistance of the obtained cured film can be improved. In addition, since the component (c) has a urea bond, the interaction with the “compound that generates acid upon irradiation with light” as the component (b) increases, and the component (d) described later is “ Combined with the “compound inhibiting the dissolution of the component (a) in the aqueous alkali solution”, the difference in dissolution rate between the exposed and unexposed areas can be improved.

  The component (c) is preferably the following general formula (1):

（式（１）中、複数のＲ^７は各々独立に水素原子または１価の有機基を示し、複数のＲ^８は各々独立に水素原子または１価の有機基を示し、互いが結合することで環構造となっていても良い。）
で示される構造を有する化合物を挙げることができる。

(In the formula (1), each of the plurality of R ⁷ independently represents a hydrogen atom or a monovalent organic group, and each of the plurality of R ⁸ independently represents a hydrogen atom or a monovalent organic group, and is bonded to each other) It may be a ring structure.)
The compound which has a structure shown by can be mentioned.

  By using the compound represented by the general formula (1) as the component (c), the resin film obtained from the positive photosensitive resin composition of the present invention can be cured even at a low temperature of 220 ° C. or lower. The obtained cured film has excellent chemical resistance (solvent resistance) and flux resistance.

  More specifically, examples of the compound represented by the general formula (1) include the following general formula (6):

（式（６）中、Ｚは炭素数１〜１０の１価のアルキル基を表し、複数のＲは各々独立に炭素数１〜２０の１価のアルキル基を表す。）
で示される構造を有する化合物を挙げることができるが、これらに限定されるものではない。また、これらの化合物を、単独でまたは２種以上を組み合わせて使用することができる。

(In Formula (6), Z represents a C1-C10 monovalent alkyl group, and several R represents a C1-C20 monovalent alkyl group each independently.)
A compound having a structure represented by: can be exemplified, but is not limited thereto. Moreover, these compounds can be used individually or in combination of 2 or more types.

  In the photosensitive resin composition of the present invention, the amount of component (c) is (a) component (base polymer) 100 from the viewpoints of development time, allowable width of unexposed area remaining film ratio, and cured film properties. The amount is preferably 1 to 50 parts by weight with respect to parts by weight. On the other hand, it is particularly preferably 20 parts by weight or more from the viewpoint of chemical resistance and flux resistance of the cured film. Moreover, from a viewpoint of balance with a tourist characteristic, it is preferable that the compounding quantity of (c) component shall be 20-100 weight part with respect to 100 weight part of (a) component, and shall be 25-80 weight part. It is more preferable, and it is more preferable to set it as 30-50.

(Component (d): a compound that inhibits dissolution of component (a) in an alkaline aqueous solution)
In the present invention, the component (d) further contains a dissolution inhibitor, which is a compound that inhibits the dissolution of the base polymer as the component (a) in an alkaline aqueous solution.
The component (d) that can be used includes: “(a) component alone or a varnish obtained by dissolving in any solvent together with the components (b) and (c) on a substrate such as a silicon wafer. There is no particular limitation as long as the effect of reducing the dissolution rate of the “coating formed by coating” is exhibited. Preferred examples of such effects that can be expected more significantly include onium salts, diaryl compounds, and tetraalkylammonium salts.

  Examples of the onium salts include diaryl iodonium salts such as diphenyliodonium salts, di (alkylaryl) iodonium salts such as di (t-butylphenyl) iodonium salts, trialkylsulfonium salts such as trimethylsulfonium salts, dimethyl Examples thereof include dialkyl monoaryl sulfonium salts such as phenylsulfonium salts and diaryl monoalkyl iodonium salts such as diphenylmethylsulfonium salts. Of these, particularly preferred are diphenyliodonium nitrate, bis (p-tert-butylphenyl) iodonium nitrate, diphenyliodonium bromide, diphenyliodonium chloride, diphenyliodonium iodide, and the like.

Examples of the diaryl compound include those in which two aryl groups such as diaryl urea, diaryl sulfone, diaryl ketone, diaryl ether, diaryl propane, diaryl hexafluoropropane and the like are bonded via a bonding group. A phenylene group is preferred.
Examples of the tetraalkylammonium salt include tetraalkylammonium halides having an alkyl group such as a methyl group or an ethyl group.

  Among the above specific dissolution inhibiting compounds, those showing a better dissolution inhibiting effect include diaryliodonium salts, diarylurea compounds, diarylsulfone compounds, tetramethylammonium halide compounds, and the like as diarylurea compounds. Examples of the tetramethylammonium halide compound include tetramethylammonium chloride, tetramethylammonium bromide, and tetramethylammonium iodide.

  Among the above-described dissolution inhibiting compounds, the following general formula (2):

（式（２）中、Ｘ⁻は対陰イオンを示し、Ｒ^７及びＲ^８は各々独立に１価の有機基を示し、ａ及びｂは各々独立に０〜５の整数である）
で表されるジアリールヨードニウム塩が、好ましい。
上記陰イオンとしては、硝酸イオン、４フッ化ホウ素イオン、過塩素酸イオン、トリフルオロメタンスルホン酸イオン、ｐ−トルエンスルホン酸イオン、チオシアン酸イオン、塩素イオン、臭素イオン、ヨウ素イオン等が挙げられる。

(In formula (2), X ⁻ represents a counter anion, R ⁷ and R ⁸ each independently represents a monovalent organic group, and a and b are each independently an integer of 0 to 5)
The diaryl iodonium salt represented by these is preferable.
Examples of the anion include nitrate ion, boron tetrafluoride ion, perchlorate ion, trifluoromethanesulfonate ion, p-toluenesulfonate ion, thiocyanate ion, chlorine ion, bromine ion, iodine ion and the like.

  Specific examples of the diaryliodonium salt include diphenyliodonium nitrate, bis (p-tert-butylphenyl) iodonium nitrate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium bromide, diphenyliodonium chloride, and diphenyliodonium iodide. Can be used.

  Among these, diphenyliodonium nitrate, diphenyliodonium trifluoromethanesulfonate, and diphenyliodonium-8-anilinonanaphthalene-1-sulfonate are preferable because of their high effects.

  The onium salts include those that generate an acid upon irradiation with ultraviolet rays, such as component (b), but when used for such purposes, those that do not absorb in the wavelength region used for exposure. It is important to choose. Those having absorption may inhibit the photoreaction of the component (b) and cause a decrease in sensitivity.

  By adding these components (d), it is possible to control the remaining film thickness and development time when obtaining a cured film from the photosensitive resin composition to an appropriate one, so there is a wide range of allowable amounts of other components. The effect of individual components can be made more prominent.

  The blending amount of component (d) is preferably 0.01 to 50 parts by weight, and 0.01 to 30 parts by weight with respect to 100 parts by weight of component (a) (base polymer) from the viewpoints of sensitivity and allowable width of development time. Part is more preferable, and 0.1 to 20 parts by weight is further preferable. In view of balance with the amount of component (c), when component (c) is 20 parts by weight or more, it is particularly preferable that component (d) is further 3 to 20 parts by weight.

(Other ingredients)
In order to improve the adhesiveness with the board | substrate of a cured film, the photosensitive resin composition of this invention can contain adhesiveness imparting agents, such as an organosilane compound and an aluminum chelate compound.

  Examples of the organic silane compound include vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, ureapropyltriethoxysilane, methylphenylsilanediol, ethylphenylsilanediol, n -Propylphenylsilanediol, isopropylphenylsilanediol, n-butylphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol , N-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol , Ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenyl Silanol, 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, 1,4-bis (butyl Hydroxysilyl) benzene, 1,4-bis (dimethylhydroxysilyl) benzene, 1,4-bis (diethylhydroxysilyl) benzene, 1,4-bis (dipropylhydroxysilyl) benzene, 1,4-bis (dibutylhydroxy) And silyl) benzene.

  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 polymer), and 0.5-20 weight part is more preferable.

  In addition, an appropriate surfactant or leveling agent is added to the photosensitive resin composition of the present invention in order to prevent coating properties such as striation (film thickness unevenness) or improve developability. be able to.

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

[Method for producing patterned cured film]
Next, the manufacturing method of the pattern cured film by this invention is demonstrated.
The method for producing a cured pattern film according to the present invention includes a photosensitive resin film forming step in which the above-described photosensitive resin composition is applied onto a support substrate and dried to form a photosensitive resin film. An exposure process for exposing the 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)
First, in this step, a support substrate such as a glass substrate, a semiconductor, a metal oxide insulator (for example, TiO ₂ , SiO _2, etc.), silicon nitride or the like is prepared. On the prepared support substrate, the photosensitive resin composition of the present invention is applied using an application method such as a spinner. 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)
Next, in the exposure step, exposure is performed by irradiating the photosensitive resin film formed as a film on the support substrate with actinic rays such as ultraviolet rays, visible rays, and radiations through a mask having a predetermined pattern.

(Development process)
In the development step, the exposed portion of the photosensitive resin film by actinic rays is removed with a developer. A patterned resin film is obtained by removing the exposed portion.
The developer used is an alkaline developer, for example, an aqueous alkali solution such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide is preferable. As mentioned. The base concentration of these aqueous alkali 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)
Next, in the heat treatment step, a patterned cured film made of a highly heat-resistant resin can be formed by heat-treating the patterned resin film obtained after development.

  The temperature of the heat treatment may be 160 to 400 ° C., and it is one of the characteristics 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 kept small. 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 time for thermally curing the patterned resin film is the time until the dehydration ring-closing reaction 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 for performing 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.

  For example, in Japanese Patent Nos. 2587148 and 3031434, dehydration and ring closure of a polyimide precursor using microwaves are studied. In US Pat. No. 5,739,915, when a polyimide precursor thin film is dehydrated and closed using microwaves, there is a method for avoiding damage to the polyimide thin film or the base material by irradiating with the frequency changed in a short period. Proposed.

  When microwaves are irradiated in a pulsed manner while changing the frequency, standing waves can be prevented and the substrate surface can be heated uniformly. In addition, when the substrate includes metal wiring like an electronic component, it is possible to prevent the occurrence of discharge from the metal and to protect the electronic component from destruction by irradiating the microwave in pulses while changing the frequency. It is preferable in that it can be performed.

  The frequency of the microwave irradiated when the pattern resin film is thermally cured is in the range of 0.5 to 20 GHz, but is practically preferably in the range of 1 to 10 GHz, and more preferably in the range of 2 to 9 GHz.

  Although it is desirable to continuously change the frequency of the microwave to be irradiated, the irradiation is actually performed by changing the frequency stepwise. At that time, the shorter the time for irradiating a single-frequency microwave, the less likely it is that standing waves or metal discharges occur, and the time is preferably 1 millisecond or less, particularly preferably 100 microseconds or less.

  Although the output of the microwave to be irradiated varies depending on the size of the apparatus and the amount of the object to be heated, it is generally in the range of 10 to 2000 W, practically preferably 100 to 1000 W, more preferably 100 to 700 W, further preferably 100 to 500 W. Is most preferred. If the output is 10 W or less, it is difficult to heat the object to be heated in a short time, and if it is 2000 W or more, a rapid temperature rise tends to occur.

  It is preferable to turn on / off the microwaves applied when the pattern resin film is thermally cured. By irradiating the microwaves in a pulsed manner, the set heating temperature can be maintained, and damage to the polybenzoxazole thin film and the substrate can be avoided. Although the time for irradiating the pulsed microwave at one time varies depending on the conditions, it is approximately 10 seconds or less.

[Semiconductor device manufacturing process]
Next, an example of the manufacturing process of the manufacturing method of the semiconductor device which has the pattern cured film of this invention is demonstrated based on drawing. 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 is formed by a known photolithography technique. A window 6A is provided so that 4 is 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 for forming a window 6C is formed at a predetermined portion, and then developed with an alkaline aqueous solution. A pattern 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.

[Electronic parts]
Next, the electronic component according to the present invention will be described. The electronic component according to the present invention has a pattern cured film formed by the above-described method for producing a pattern cured film using the photosensitive resin composition described above. Here, the electronic component includes a semiconductor device, a multilayer wiring board, various electronic devices, and the like.

  In addition, the pattern cured film can be used specifically for forming a surface protective film for an electronic component such as a semiconductor device, an interlayer insulating film, an interlayer insulating film for 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 have various structures.

  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 Example 1) Synthesis 1 of polybenzoxazole precursor (component (a))
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 tetracarboxylic acid 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 added. Dissolved with stirring. 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 chloride 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 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 weight average molecular weight obtained was 17,600, and the degree of dispersion was 1.6.
In addition, the same measurement is performed also about the polymer obtained in the following synthesis examples, and the weight average molecular weight is calculated | required.

Synthesis Example 2 Synthesis 2 of polybenzoxazole precursor (component (a))
In Synthesis Example 1, diphenyl ether dicarboxylic acid was not used and replaced with sebacic acid. Except that, the synthesis was performed under the same conditions as in Synthesis Example 1. The obtained polyhydroxyamide (hereinafter referred to as polymer II) had a weight average molecular weight of 28,700 and a dispersity of 2.2 determined by standard polystyrene conversion.

(Synthesis Example 3) Synthesis 3 of polybenzoxazole precursor (component (a))
In Synthesis Example 1, diphenyl ether dicarboxylic acid was not used and replaced with dodecanoic acid. Except that, the synthesis was performed under the same conditions as in Synthesis Example 1. The obtained polyhydroxyamide (hereinafter referred to as polymer III) had a weight average molecular weight of 27,200 and a dispersity of 1.9 determined by standard polystyrene conversion.

(Synthesis Example 4) Synthesis 1 of polyimide precursor (component (a))
In a 0.2 liter flask equipped with a stirrer and a thermometer, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride (ODPA) 10 g (32 mmol) and isopropyl alcohol 3.87 g (65 mmol) Is dissolved in 45 g of N-methylpyrrolidone, a catalytic amount of 1,8-diazabicycloundecene is added, and then heated at 60 ° C. for 2 hours, followed by 15 hours at room temperature (25 ° C.). Stirring and esterification were 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. This solution is called 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 previously prepared acid chloride solution I was added dropwise over 30 minutes, and then stirring was continued for 30 minutes. It was.

  The reaction solution after stirring was dropped into distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain a polyamic acid ester having a carboxyl group terminal (hereinafter referred to as polymer IV). Polymer IV had a weight average molecular weight of 19,400 and a dispersity of 2.2.

(Synthesis Example 5) Synthesis 2 of polyimide precursor (component (a))
A 0.5 liter flask equipped with a stirrer and a thermometer was charged with 60 g of N-methylpyrrolidone, and 11.71 g (32 mmol) of bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 0 phthalic anhydride were added. .59 g (4 mmol) was added and dissolved by stirring. To this, 8.68 g (28 mmol) of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride was added over 30 minutes at room temperature (25 ° C.), and stirring was continued for 12 hours.

  20g of m-xylene was added with respect to the reaction liquid after the said stirring, and it heated and refluxed at 150 degreeC for 2 hours. At this time, the water generated by cyclization of the imide ring was refluxed while being removed from the system by azeotropy. Then, after cooling to room temperature, this reaction solution was dropped into distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain a polyimide having a benzene ring at the end (hereinafter referred to as polymer V). The polymer V had a weight average molecular weight of 21,500 and a dispersity of 1.9.

(Measurement conditions of weight average molecular weight by GPC method)
Measuring device; Detector L4000 UV manufactured by Hitachi, Ltd.
Pump: Hitachi Ltd. L6000
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
The 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.

(Examples 1-10 and Comparative Examples 1-3)
The components (b), (c), and (d) are blended together with the solvent in the predetermined amounts shown in (Table 1) with respect to 100 parts by weight of each polymer as the component (a). A solution of the resin composition was obtained.

  In Table 1, “BLO” in the solvent column represents γ-butyrolactone, “PGMEA” represents propylene glycol monomethyl ether acetate, “NMP” represents N-methylpyrrolidone, and “BLO / PGMEA” represents both. This indicates that the mixture was used at a weight ratio of 9: 1. The numbers in parentheses in each column of the components (b), (c), and (d) indicate the amount (parts by weight) added to 100 parts by weight of the polymer. The amount of the solvent used is 250 parts by weight with respect to 100 parts by weight of the polymer.

  In (Table 1), “B1”, “B2” in the (b) component column, “C1”, “C2”, “C3”, “C4” in the (c) component column, and “d” in the “d” component column. “D1”, “D2”, and “D3” are compounds represented by the following chemical formulas, respectively.

Each solution of the composition shown above (Table 1) is spin-coated on a silicon wafer to form a coating film having a dry film thickness of 7 to 12 μm, and an ultrahigh pressure mercury lamp is used for the obtained coating film, Exposure was performed by irradiating a predetermined pattern with i-rays of 100 to 1000 mJ / cm ² through an interference filter.

  After the 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 A membrane was obtained.

  In each pattern resin film formation, the minimum exposure amount (sensitivity) and resolution required for pattern formation with which a remaining film ratio (ratio of film thickness before and after development) of 80% or more was obtained were determined. The results are summarized in the following (Table 2).

Next, a cured film was prepared using each resin composition, and the mechanical strength of the film was evaluated.
First, the solution was spin-coated on a silicon wafer and heated at 120 ° C. for 3 minutes to form a coating film having a thickness of 15 μm.

  Thereafter, the coating film was heated in an inert gas oven at 100 ° C. for 60 minutes in a nitrogen atmosphere, and further heated at 320 ° C. for 1 hour to obtain a cured film. The cured film was immersed in a hydrofluoric acid aqueous solution together with the silicon substrate, the cured film was peeled off from the substrate, washed with water and dried, and then measured for elongation at break (measured with a tensile tester). These results are shown below (Table 3).

上記（表３）に見るように、実施例で示したものはいずれも実用上問題ない機械特性を有すると分かった。一方、（ｃ）成分を用いなかった比較例２では、破断伸びが低かった。また、（ｃ）成分としてウレア結合を持たない化合物（Ｃ４）を用いた比較例３の破断伸びはさらに低かった。

As can be seen from the above (Table 3), it was found that all of the examples shown in the examples have mechanical properties that are practically acceptable. On the other hand, in Comparative Example 2 in which the component (c) was not used, the elongation at break was low. Moreover, the elongation at break of Comparative Example 3 using the compound (C4) having no urea bond as the component (c) was even lower.

  Further, in the same manner as the measurement of elongation at break, a film cured at a predetermined temperature (heated at 100 ° C. for 60 minutes and further heated at 320 ° C. for 1 hour) was added to the presence or absence of cracks when immersed in each solvent. The presence or absence of membrane swelling was also examined.

  The results are shown below (Table 4). The evaluation criteria are indicated in the table as x with crack and ◯ with no crack. Regarding the swelling evaluation, depending on the degree, if the film thickness is less than 1 μm before and after immersion in the solvent, the increase in film thickness is 1 μm or more and less than 1.5 μm, and the increase in film thickness is 1.5 μm or more. X. The smaller the change in film thickness, the better.

（表４）に見るように、比較例２、３は（ｃ）成分としてウレア結合を持つ化合物を添加していないため、耐溶剤性が実施例に比べ著しく悪くなっていることが確認できる。

As shown in Table 4, since Comparative Examples 2 and 3 did not add a compound having a urea bond as the component (c), it can be confirmed that the solvent resistance is remarkably deteriorated as compared with Examples.

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.

Explanation of symbols

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

Claims (7)

(A) a polymer soluble in an alkaline aqueous solution;
(B) a compound that generates acid upon irradiation with light;
(C) a compound having a urea bond;
(D) a compound that inhibits dissolution of the component (a) in the alkaline aqueous solution;
Containing
The component (c) is used in an amount of 25 to 80 parts by weight based on 100 parts by weight of the component (a).
Further, the positive photosensitive resin composition, wherein the component (d) is used in an amount of 3 parts by weight or more based on 100 parts by weight of the component (a).   2. 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 represented by the following general formula (1):

(In the formula (1), each of the plurality of R ⁷ independently represents a hydrogen atom or a monovalent organic group, and each of the plurality of R ⁸ independently represents a hydrogen atom or a monovalent organic group, and is bonded to each other) It may be a ring structure)
The positive photosensitive resin composition according to claim 1, wherein the positive photosensitive resin composition is a compound represented by the formula: The component (d) is represented by the following general formula (2):

(In formula (2), X ⁻ represents a counter anion, R ⁷ and R ⁸ each independently represents a monovalent organic group, and a and b are each independently an integer of 0 to 5)
5. The positive photosensitive resin composition according to claim 1, comprising a diaryliodonium salt represented by the formula:   A photosensitive resin film forming step of forming a photosensitive resin film by applying the positive photosensitive resin composition according to any one of claims 1 to 5 on a support substrate and drying the composition, and the photosensitive resin film An exposure step of exposing the pattern resin film to a predetermined pattern; a development step of developing the exposed photosensitive resin film using an aqueous alkaline solution to obtain a pattern resin film; and a heat treatment of the pattern resin film to form a pattern cured film. And a heat treatment step for obtaining a pattern cured film.   An electronic component comprising a patterned cured film obtained by the method for producing a patterned cured film according to claim 6 as an interlayer insulating film layer and / or a surface protective film layer.

Images