JP6513596B2 - PHOTOSENSITIVE RESIN COMPOSITION, METHOD FOR MANUFACTURING PATTERN CURED FILM, SEMICONDUCTOR DEVICE AND ELECTRONIC COMPONENT - Google Patents

Description

  The present invention relates to a photosensitive resin composition, a method for producing a cured pattern film, a semiconductor device and an electronic component.

  In recent years, with the high integration and miniaturization of semiconductor devices, the photosensitive resin composition to be the surface protection layer, interlayer insulating film and rewiring layer of the semiconductor device has more excellent sensitivity and resolution, and is finer and more precise. It is required that a pattern cured film is possible. A photosensitive resin composition containing an alkali-soluble resin having a phenolic hydroxyl group has been developed as a material having such properties as well (see, for example, Patent Document 1).

Unexamined-Japanese-Patent No. 2003-215802 Unexamined-Japanese-Patent No. 2007-079553

  On the other hand, the photosensitive resin composition is capable of forming a cured pattern having a finer and more precise resist pattern (hereinafter also referred to as a pattern) as the semiconductor element is further highly integrated, miniaturized and miniaturized. Is required. Generally, the method for producing a patterned cured film comprises the steps of: drying a resin film formed by applying a photosensitive resin composition on a substrate; exposing the resin film; And a step of developing by removing with a developer and a step of curing the pattern resin film obtained by development by heating. In the case of forming such a fine and precise pattern as described above, in the step of curing the pattern resin film by heating, there is a problem of pattern melt, in which the resin film is melted and the shape of the pattern is changed.

In order to solve such a problem, a method using a photosensitive resin composition containing an alkali-soluble resin and an epoxy resin has been proposed (see, for example, Patent Document 2).
However, when a resin as described in Patent Document 2 is used, there is a problem that a residue is generated at the opening of the pattern during development. If residue is generated at the opening of the pattern, the connectivity of the wiring formed after the formation of the cured pattern may be reduced.
In order to suppress residues during development, it is necessary to reduce the amount of photosensitizer, but in that case, the dissolution rate of the unexposed area in the alkaline developer increases, film loss increases, and contrast decreases. That is, it was difficult to simultaneously achieve both the residue during development and the suppression of film loss.

  Then, this invention aims at providing such a photosensitive resin composition which can suppress generation | occurrence | production of the residue at the time of image development, that is, is excellent in developability and has favorable contrast, in order to solve such a subject. . Moreover, this invention aims at providing the manufacturing method of the pattern cured film which used the said photosensitive resin composition, and the electronic component which has the said pattern cured film.

（式（１）〜（４）中、Ｒ^１〜Ｒ^４は各々独立に水素基又はメチル基を示す。ａ〜ｃ、ｈ及びｉは０〜３の整数を示し、ｄ〜ｆは１〜３の整数を示し、ａとｄの合計は５以下であり、ｂとｅの合計は５以下であり、ｃとｆの合計は５以下であり、ｈとｉの合計は４以下である。ｎは１又は２である。）
［３］前記（Ｄ）成分が、下記一般式（１）又は（３）で表される化合物である、前記感光性樹脂組成物。
［４］前記（Ａ）成分１００質量部に対し、前記（Ｄ）成分を５〜３５質量部含有する、前記感光性樹脂組成物。
［５］前記（Ａ）成分がフェノール樹脂である、前記感光性樹脂組成物。
［６］前記（Ａ）成分が、不飽和炭化水素基を有しないフェノール樹脂（Ａ１）と不飽和炭化水素基を有する変性フェノール樹脂（Ａ２）を含むものである、前記感光性樹脂組成物。
［７］前記（Ａ２）成分が、フェノール性水酸基と多塩基酸無水物との反応によって更に変性されているものである、前記感光性樹脂組成物。
［８］前記（Ｂ）成分がｏ−キノンジアジド化合物である、前記感光性樹脂組成物。
［９］（Ｅ）アクリル樹脂を更に含有する、前記感光性樹脂組成物。
［１０］（Ｆ）熱酸発生剤を更に含有する、前記感光性樹脂組成物。
［１１］前記感光性樹脂組成物を基板上に塗布し、塗布された感光性樹脂組成物を乾燥して樹脂膜を形成する工程と、前記樹脂膜を露光する工程と、露光後の前記樹脂膜をアルカリ水溶液によって現像して、パターン樹脂膜を形成する工程と、前記パターン樹脂膜を加熱する工程と、を含有する、パターン硬化膜の製造方法。
［１２］前記パターン樹脂膜を加熱する工程における加熱温度が２００℃以下である、前記パターン硬化膜の製造方法。
［１３］前記パターン硬化膜の製造方法により製造されるパターン硬化膜を層間絶縁層又は表面保護膜として有する電子部品。
［１４］前記パターン硬化膜の製造方法により製造されるパターン硬化膜をカバーコート層、コア、カラー、又はアンダーフィルとして有する電子部品。 The present invention relates to the following.
[1] Photosensitivity comprising (A) an alkali-soluble resin having a phenolic hydroxyl group, (B) a compound capable of generating an acid by light, (C) a thermal crosslinking agent, and (D) a phenolic low molecular weight compound Resin composition.
[2] The photosensitive resin composition, wherein the component (D) is a compound represented by any of the following general formulas (1) to (4).

(In the formulas (1) to (4), R ^{1 to} R ⁴ each independently represent a hydrogen group or a methyl group. A to c, h and i each represents an integer of 0 to 3, and d to f are 1 to An integer of 3 is shown, the sum of a and d is 5 or less, the sum of b and e is 5 or less, the sum of c and f is 5 or less, and the sum of h and i is 4 or less. n is 1 or 2.)
[3] The photosensitive resin composition, wherein the component (D) is a compound represented by the following general formula (1) or (3).
[4] The photosensitive resin composition containing 5 to 35 parts by mass of the component (D) relative to 100 parts by mass of the component (A).
[5] The photosensitive resin composition, wherein the component (A) is a phenol resin.
[6] The photosensitive resin composition as described above, wherein the component (A) contains a phenolic resin (A1) having no unsaturated hydrocarbon group and a modified phenolic resin (A2) having an unsaturated hydrocarbon group.
[7] The photosensitive resin composition as described above, wherein the component (A2) is further modified by the reaction of a phenolic hydroxyl group and a polybasic acid anhydride.
[8] The photosensitive resin composition as described above, wherein the component (B) is an o-quinone diazide compound.
[9] The photosensitive resin composition, which further comprises (E) an acrylic resin.
[10] The photosensitive resin composition, which further comprises (F) a thermal acid generator.
[11] A step of applying the photosensitive resin composition onto a substrate and drying the applied photosensitive resin composition to form a resin film, a step of exposing the resin film, and the resin after exposure A method for producing a patterned cured film, comprising the steps of: developing a film with an aqueous alkaline solution to form a patterned resin film; and heating the patterned resin film.
[12] The method for producing a cured pattern, wherein the heating temperature in the step of heating the patterned resin film is 200 ° C. or less.
[13] An electronic component having a patterned cured film produced by the method for producing a patterned cured film as an interlayer insulating layer or a surface protective film.
[14] An electronic component having a pattern cured film produced by the method for producing a pattern cured film as a cover coat layer, a core, a color or an underfill.

  According to the present invention, it is possible to suppress the generation of residue during development, that is, to improve the developability, and to suppress the film loss of the unexposed area during development, and to obtain a photosensitive resin composition having a good contrast. Can be provided. Furthermore, the photosensitive resin composition of the present invention has good photosensitive properties (sensitivity and resolution) and mechanical properties (elongation at break and elastic modulus). Moreover, this invention aims at providing the manufacturing method of the pattern cured film which used the said photosensitive resin composition, and the electronic component which has the said pattern cured film.

FIG. 7 is a schematic cross-sectional view for explaining one embodiment of a manufacturing process of a semiconductor device. FIG. 7 is a schematic cross-sectional view for explaining one embodiment of a manufacturing process of a semiconductor device. FIG. 7 is a schematic cross-sectional view for explaining one embodiment of a manufacturing process of a semiconductor device. FIG. 7 is a schematic cross-sectional view for explaining one embodiment of a manufacturing process of a semiconductor device. FIG. 7 is a schematic cross-sectional view for explaining one embodiment of a manufacturing process of a semiconductor device. It is a schematic sectional drawing which shows one Embodiment of an electronic component (semiconductor device). It is a schematic sectional drawing which shows one Embodiment of an electronic component (semiconductor device).

Hereinafter, "(meth) acrylate" in the present specification means "acrylate" and the corresponding "methacrylate". Similarly, "(meth) acrylic" means "acrylic" and the corresponding "methacrylic".

[Photosensitive resin composition]
The photosensitive resin composition according to the present invention comprises (A) an alkali-soluble resin having a phenolic hydroxyl group, (B) a compound capable of generating an acid by light, (C) a thermal crosslinking agent, and (D) a phenolic low And a molecular compound.

<(A) Component: Alkali-Soluble Resin Having Phenolic Hydroxyl Group>
The component (A) is a resin having a phenolic hydroxyl group in the molecule and being soluble in an alkali developer.
Here, one criterion of the solubility of the component (A) in an aqueous alkali solution will be described below. A resin solution obtained from the component (A) alone and an optional solvent, or the component (A) and the component (B), the component (C), the component (D) and the optional solvent described in order below A resin film having a thickness of about 5 μm is formed by spin coating on a substrate such as a silicon wafer. This is immersed in any one of tetramethyl ammonium hydroxide aqueous solution, metal hydroxide aqueous solution, and organic amine aqueous solution at 20 to 25 ° C. As a result, when it can melt | dissolve as a uniform solution, it is judged that the used (A) component is soluble in alkaline aqueous solution.

  The alkali-soluble resin having a phenolic hydroxyl group as the component (A) is, for example, a hydroxystyrene resin such as polyhydroxystyrene and a copolymer containing hydroxystyrene as a monomer unit, a phenol resin, a poly (hydroxyamide), etc. Examples include polybenzoxazole precursors, poly (hydroxyphenylene) ethers, polynaphthols and the like.

  Among these, a phenol resin is preferable and a novolac type phenol resin is more preferable because of low cost and small volume shrinkage at the time of curing.

  The phenolic resin is a polycondensation product of phenol or a derivative thereof with an aldehyde. The polycondensation is carried out in the presence of a catalyst such as an acid or a base. The phenolic resin obtained when using an acid catalyst is referred to as novolac type phenolic resin. Specific examples of the novolac type phenolic resin include phenol / formaldehyde novolak resin, cresol / formaldehyde novolac resin, xylylenol / formaldehyde novolac resin, resorcinol / formaldehyde novolac resin and phenol-naphthol / formaldehyde novolac resin.

  As a phenol derivative used to obtain a phenol resin, for example, phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol P-butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, Alkylphenols such as 3,4,5-trimethylphenol, alkoxyphenols such as methoxyphenol and 2-methoxy-4-methylphenol, alkenylphenols such as vinylphenol and allylphenol, and aralkylphenols such as benzylphenol Alkoxy carbonyl phenols such as toxoxycarbonyl phenol, aryl carbonyl phenols such as benzoyloxy phenol, halogenated phenols such as chlorophenol, polyhydroxybenzenes such as catechol, resorcinol and pyrogallol, bisphenols such as bisphenol A and bisphenol F, α- or β Naphthol derivatives such as naphthol; hydroxyalkyl phenols such as p-hydroxyphenyl-2-ethanol, p-hydroxyphenyl-3-propanol, p-hydroxyphenyl-4-butanol; hydroxyalkyl cresols such as hydroxyethyl cresol; bisphenol mono Ethylene oxide adducts; Alcoholic hydroxyl group-containing salts such as monopropylene oxide adducts of bisphenols Derivatives; p-hydroxyphenylacetic acid, p-hydroxyphenylpropionic acid, p-hydroxyphenylbutanoic acid, p-hydroxycinnamic acid, hydroxybenzoic acid, hydroxyphenylbenzoic acid, hydroxyphenoxybenzoic acid, carboxyl group such as diphenol Containing phenol derivatives are mentioned. In addition, methylolated compounds of the above-mentioned phenol derivatives such as bishydroxymethyl-p-cresol may be used as phenol derivatives.

  Furthermore, the phenol resin may be a product obtained by condensation polymerization of the above-mentioned phenol or phenol derivative with aldehydes together with a compound other than phenol such as m-xylene. In this case, the molar ratio of a compound other than phenol to the phenol derivative used for condensation polymerization is preferably less than 0.5. The compounds other than the above-mentioned phenol derivatives and phenol compounds may be used alone or in combination of two or more.

  Examples of aldehydes used to obtain a phenolic resin include formaldehyde, acetaldehyde, furfural, benzaldehyde, hydroxybenzaldehyde, methoxybenzaldehyde, hydroxyphenylacetaldehyde, methoxyphenylacetaldehyde, crotonaldehyde, chloroacetaldehyde, chlorophenylacetaldehyde, glyceraldehyde, It is selected from glyoxylic acid, methyl glyoxylate, phenyl glyoxylate, hydroxyphenyl glyoxylate, formylacetic acid, methyl formylacetate, 2-formylpropionic acid, methyl 2-formylpropionate and the like. In addition, precursors of formaldehyde such as paraformaldehyde and trioxane, ketones such as acetone, pyruvic acid, replic acid, 4-acetylbutyric acid, acetonedicarboxylic acid, and 3,3'-4,4'-benzophenonetetracarboxylic acid May be used for the reaction. These may be used alone or in combinations of two or more.

  As the poly (hydroxystyrene) resin, for example, the ethylenically unsaturated double bond of hydroxystyrene having a protective group introduced is polymerized (vinyl polymerization) in the presence of a catalyst (radical initiator), and then deprotected. What is obtained by performing can be used. Alternatively, commercially available branched poly (hydroxystyrene) such as PHS-B (manufactured by DuPont) may be used.

  The weight average molecular weight of the component (A) is preferably 500 to 150,000, and preferably 500 to 100,000, in consideration of the solubility in an aqueous alkali solution, and the balance between the photosensitive properties and the mechanical properties of the patterned cured film. It is more preferable that it is 1000-50,000. Here, the weight average molecular weight is a value obtained by measuring by gel permeation chromatography and converting it from a standard polystyrene calibration curve.

  The component (A) in the present invention preferably contains a phenolic resin (A1) having no unsaturated hydrocarbon group and a modified phenolic resin (A2) having an unsaturated hydrocarbon group, and the component (A2) is a phenol. It is more preferable that it is further modified by the reaction of the hydroxyl group with the polybasic acid anhydride.

The component (A2) is generally a compound having a phenol or a derivative thereof and an unsaturated hydrocarbon group (preferably having a carbon number of 4 to 100) (hereinafter sometimes simply referred to as an "unsaturated hydrocarbon group-containing compound") A reaction product of (hereinafter referred to as "unsaturated hydrocarbon group-modified phenol derivative") and a condensation product of an aldehyde, or a reaction product of a phenol resin and an unsaturated hydrocarbon group-containing compound .
As the phenol derivative used to obtain the component (A2), those similar to phenol derivatives and aldehydes used to obtain a phenol resin can be used.

  The unsaturated hydrocarbon group of the unsaturated hydrocarbon group-containing compound preferably contains two or more unsaturated bonds from the viewpoint of adhesion of the patterned cured film and thermal shock resistance, and the storage stability of the resin composition From the viewpoint, the unsaturated bond is preferably 30 or less. In addition, from the viewpoint of compatibility with the resin composition and flexibility of the cured film, the unsaturated hydrocarbon group-containing compound preferably has 8 to 80 carbon atoms, and more preferably 10 to 60 carbon atoms. preferable.

  As the unsaturated hydrocarbon group-containing compound, for example, unsaturated hydrocarbon having 4 to 100 carbon atoms, polybutadiene having a carboxyl group, epoxidized polybutadiene, linoleyl alcohol, oleyl alcohol, unsaturated fatty acid and unsaturated fatty acid ester . Preferred unsaturated fatty acids include crotonic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, bacenic acid, gadeuric acid, erucic acid, nervonic acid, linoleic acid, α-linolenic acid, eleostearic acid, stearidone The acids include arachidonic acid, eicosapentaenoic acid, sardine acid and docosahexaenoic acid. Among these, vegetable oils which are unsaturated fatty acid esters are particularly preferred.

  The vegetable oil is generally an ester of glycerin and unsaturated fatty acid, and is a non-drying oil having an iodine value of 100 or less, a semi-drying oil of more than 100 and less than 130, or a drying oil of 130 or more. Non-drying oils include, for example, olive oil, morning glory seed oil, cashew seed oil, sazan oil, camellia oil, castor oil and peanut oil. Semi-drying oils include, for example, corn oil, cottonseed oil and sesame oil. Drying oils include, for example, soy sauce, linseed oil, soybean oil, walnut oil, safflower oil, sunflower oil, persimmon oil and coconut oil. Moreover, you may use the processed vegetable oil obtained by processing these vegetable oils.

  Among these vegetable oils, it is preferable to use a drying oil from the viewpoint of improving the adhesion, mechanical properties and thermal shock resistance of the cured pattern film. Further, among the drying oils, soy sauce oil, linseed oil, soybean oil, walnut oil and safflower oil are more preferable because the effects of the present invention can be exhibited more effectively and surely, and soy sauce oil and linseed oil are more preferable. These vegetable oils may be used alone or in combination of two or more.

  In preparing the component (A2), first, the above-mentioned phenol derivative and the above-mentioned unsaturated hydrocarbon group-containing compound are reacted to prepare an unsaturated hydrocarbon group-modified phenol derivative. It is preferable to perform the said reaction normally at 50-130 degreeC. The compounding ratio of the phenol derivative to the unsaturated hydrocarbon group-containing compound is 1 to 100 of the unsaturated hydrocarbon group-containing compound with respect to 100 parts by mass of the phenol derivative from the viewpoint that the flexibility of the pattern cured film can be improved. It is preferable that it is a mass part, and it is more preferable that it is 5-50 mass parts. In the above reaction, if necessary, p-toluenesulfonic acid, trifluoromethanesulfonic acid or the like may be used as a catalyst.

  Next, the above-mentioned unsaturated hydrocarbon group-modified phenol derivative is reacted with an aldehyde to prepare a modified phenol resin having an unsaturated hydrocarbon group which is the component (A2). The reaction of the aldehyde with the unsaturated hydrocarbon group-modified phenol derivative is a polycondensation reaction, and conditions for synthesis of conventionally known phenol resins can be used. The component (A2) is a combination of a compound obtained by reacting the above-mentioned phenol derivative with an unsaturated hydrocarbon group-containing compound and a compound other than a phenol such as m-xylene to produce an aldehyde and a polycondensation. It can also be obtained by The unsaturated hydrocarbon group of the component (A2) is preferably present in the ortho or para position with respect to the phenolic hydroxyl group possessed by the phenolic resin, and more preferably in the para position.

  The component (A2) can also be obtained by reacting the above-mentioned phenolic resin with an unsaturated hydrocarbon group-containing compound. It is preferable to usually carry out the reaction of the phenolic resin and the unsaturated hydrocarbon group-containing compound at 50 to 130 ° C. In addition, the compounding ratio of the phenol derivative to the unsaturated hydrocarbon group-containing compound is an unsaturated hydrocarbon group-containing compound 1 to 100 parts by mass of the phenol resin from the viewpoint that the flexibility of the cured film can be improved. The amount is preferably 100 parts by mass, and more preferably 5 to 50 parts by mass. At this time, if necessary, p-toluenesulfonic acid, trifluoromethanesulfonic acid, etc. may be used as a catalyst. In addition, solvents, such as toluene, xylene, methanol, tetrahydrofuran, can be used for reaction.

  An acid-modified phenolic resin can also be used as the component (A2) by further reacting polybasic acid anhydride with the phenolic hydroxyl group present in the component (A2) produced by the above method. By acid-modifying with a polybasic acid anhydride, a carboxy group is introduced, and the solubility of the component (A2) in an aqueous alkali solution (developer) is further improved.

  The polybasic acid anhydride is not particularly limited as long as it has an acid anhydride group formed by dehydration condensation of the carboxy group of a polybasic acid having a plurality of carboxy groups. Examples of polybasic acid anhydrides include phthalic anhydride, succinic anhydride, octenyl succinic anhydride, pentadodecenyl succinic anhydride, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride , Dibasic acid anhydrides such as methyl hexahydrophthalic anhydride, nadic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methyl endomethylenetetrahydrophthalic anhydride, tetrabromophthalic anhydride and trimellitic anhydride, biphenyltetra Carboxylic acid dianhydride, naphthalene tetracarboxylic acid dianhydride, diphenyl ether tetracarboxylic acid dianhydride, butane tetracarboxylic acid dianhydride, cyclopentane tetracarboxylic acid dianhydride, pyromellitic anhydride and benzophenone tetra Carboxylic acid aromatic tetracarboxylic acid dianhydride such as dianhydride. These may be used alone or in combination of two or more. Among these, the polybasic acid anhydride is preferably a dibasic acid anhydride, and more preferably one or more selected from the group consisting of tetrahydrophthalic anhydride, succinic anhydride and hexahydrophthalic anhydride. In this case, there is an advantage that a patterned cured film having an even better shape can be formed.

The reaction of the phenolic hydroxyl group with the polybasic acid anhydride can be carried out at 50 to 130 ° C. In this reaction, the polybasic acid anhydride is preferably reacted in an amount of 0.1 to 0.8 mol, more preferably 0.15 to 0.6 mol, per 1 mol of phenolic hydroxyl group, 0 It is further preferable to react .2-0.4 mol. If the polybasic acid anhydride is less than 0.1 mol, the developability tends to decrease, and if it exceeds 0.8 mol, the alkali resistance of the unexposed area tends to decrease.

  A catalyst may be contained in the above reaction, as needed, from the viewpoint of rapidly performing the reaction. Examples of the catalyst include tertiary amines such as triethylamine; quaternary ammonium salts such as triethylbenzyl ammonium chloride; imidazole compounds such as 2-ethyl-4-methylimidazole; and phosphorus compounds such as triphenylphosphine.

  The acid value of the phenol resin further modified with polybasic acid anhydride is preferably 30 to 200 mg KOH / g, more preferably 40 to 170 mg KOH / g, and still more preferably 50 to 150 mg KOH / g. . When the acid value is less than 30 mg KOH / g, the alkali development tends to take a long time compared to when the acid value is in the above range, and when it exceeds 200 mg KOH / g, the acid value is in the above range As compared with the above, the developing solution resistance of the unexposed area tends to decrease.

The molecular weight of the component (A2) is preferably 1,000 to 500,000 as a weight average molecular weight, and 2,000 to 200,000, in consideration of the solubility in an alkaline aqueous solution, and the balance between the photosensitive characteristics and the physical properties of the cured film. More preferably, it is more preferably 2,000 to 100,000. Here, the weight average molecular weight is a value obtained by measuring by gel permeation chromatography and converting it from a standard polystyrene calibration curve.

  The photosensitive resin composition is unsaturated as the component (A) from the viewpoints of sensitivity and resolution at the time of forming a patterned resin film, and adhesion of a cured pattern film, mechanical properties and thermal shock resistance. When a modified phenolic resin (A2) having a hydrocarbon group is mixed and used, a phenolic resin (A1) having no unsaturated hydrocarbon group and a modified phenolic resin having an unsaturated hydrocarbon group in component (A) The mass ratio of (A2) is preferably 5: 95 to 95: 5 in the former: the latter, preferably 10: 90 to 90: 10, with the total amount of both being 100, more preferably 15: 85 Most preferably, 85:15 is included.

<(B) Component: Compound that produces an acid by light>
The compound (B) which generates an acid by light, which is a component, is used as a photosensitizer. The component (B) has a function of generating an acid by light irradiation and increasing the solubility of the light irradiated part in an aqueous alkali solution. As the component (B), a compound generally called a photoacid generator can be used. Specific examples of the component (B) include o-quinonediazide compounds, aryldiazonium salts, diaryliodonium salts, triarylsulfonium salts and the like. Among these, o-quinonediazide compounds are preferable because of high sensitivity.

The o-quinonediazide compound can be obtained, for example, by a condensation reaction of o-quinonediazide sulfonyl chloride and a hydroxy compound or an amino compound in the presence of a dehydrochlorination agent.

  Examples of o-quinonediazide sulfonyl chloride used in the reaction include benzoquinone-1,2-diazide-4-sulfonyl chloride, naphthoquinone-1,2-diazide-5-sulfonyl chloride, and naphthoquinone-1,2-diazide-4- Sulfonyl chloride is mentioned.

Examples of the hydroxy compound used for the reaction include hydroquinone, resorcinol, pyrogallol, bisphenol A, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,3,4- Trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4,2', 3'-pentahydroxybenzophenone, 2,3 4,3,4 ', 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-dimethyl ester Deno [2,1-a] indene, tris (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (1-) 4-hydroxyphenyl) -1-methylethyl} phenyl] ethane.

  As an amino compound used for the reaction, for example, p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 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-hydroxypheny ) Hexafluoropropane, bis (4-amino-3-hydroxyphenyl) hexafluoropropane and the like.

  Among these, 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane and 1 from the viewpoint of absorption wavelength range and reactivity. 1-Naphthoquinone-2-diazide-5 obtained by condensation reaction with 2-naphthoquinone-2-diazide-5-sulfonyl chloride, or tris (4-hydroxyphenyl) methane or tris (4-hydroxyphenyl) ethane It is preferable to use one obtained by condensation reaction with -sulfonyl chloride.

  As a dehydrochlorination agent used for the reaction, sodium carbonate, sodium hydroxide, sodium hydrogencarbonate, potassium carbonate, potassium hydroxide, trimethylamine, triethylamine, pyridine and the like can be mentioned. Further, as a reaction solvent, dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, diethyl ether, N-methyl pyrrolidone and the like are used.

The o-quinonediazide sulfonyl chloride and the hydroxy compound and / or the amino compound are blended so that the total number of moles of hydroxy group and amino group is 0.5 to 1 with respect to 1 mole of o-quinone diazide sulfonyl chloride Preferably. The preferable blending ratio of the dehydrochlorination agent and the o-quinonediazide sulfonyl chloride is in the range of 0.95 / 1 molar equivalent to 1 / 3.95 molar equivalent.

  The preferred reaction temperature of the above reaction is 0 to 40 ° C., and the preferred reaction time is 1 to 10 hours.

  The content of the component (B) is preferably 3 to 100 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint that the difference in dissolution rate between the exposed part and the unexposed part becomes large and the sensitivity becomes better. From the viewpoint of suppressing the residue after development, 5 to 50 parts by mass is more preferable, 5 to 30 parts by mass is more preferable, and 5 to 15 parts by mass is particularly preferable.

<(C) component: thermal crosslinking agent>
The thermal crosslinking agent which is the component (C) is a compound having a structure capable of reacting with the component (A) to form a crosslinked structure when the photosensitive resin film after pattern formation is heated and cured. This can prevent the fragility of the film and the melting of the film. The thermal crosslinking agent is preferably selected from, for example, a compound having a phenolic hydroxyl group, a compound having a hydroxymethylamino group, and a compound having an epoxy group.

  The compound having a phenolic hydroxyl group used as a thermal crosslinking agent is different from the (A) component and the (D) component, and has a crosslinking group with the (A) component. Specific structures include those described later. A compound having such a phenolic hydroxyl group is preferable not only as a thermal crosslinking agent, but also because it can increase the dissolution rate of the exposed area when developing with an alkaline aqueous solution and improve the sensitivity, and so this is preferable. The molecular weight of such a compound having a phenolic hydroxyl group is preferably 2,000 or less. Further, the compound having a phenolic hydroxyl group is preferably one having about two benzene rings in the molecule. In consideration of the solubility in an alkaline aqueous solution, and the balance between the photosensitive properties and the physical properties of a cured film, the number average molecular weight is preferably 94 to 2,000, more preferably 108 to 2,000, and still more preferably 108 to 1,500. .

（式（５）中、Ｘは単結合又は２価の有機基を示し、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８はそれぞれ独立に水素原子又は１価の有機基を示し、ｓ及びｔはそれぞれ独立に１〜３の整数を示し、ｕ及びｖはそれぞれ独立に０〜４の整数を示す。） As the compound having a phenolic hydroxyl group, conventionally known compounds can be used, but the compound represented by the following general formula (5) has the effect of promoting the dissolution of the exposed portion and melting at the time of curing of the photosensitive resin film. It is particularly preferable because the balance of the preventing effect is excellent.

(In the formula (5), X represents a single bond or a divalent organic group, R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or a monovalent organic group, and s and t represent Each independently represents an integer of 1 to 3, and u and v each independently represent an integer of 0 to 4.)

  In the general formula (5), a compound in which X is a single bond is a biphenol (dihydroxybiphenyl) derivative. Further, as the divalent organic group represented by X, an alkylene group having 1 to 10 carbon atoms such as a methylene group, an ethylene group and a propylene group, an alkylidene group having 2 to 10 carbon atoms such as an ethylidene group, and a phenylene group And the like, an arylene group having 6 to 30 carbon atoms, a group obtained by substituting part or all of hydrogen atoms of these hydrocarbon groups with a halogen atom such as a fluorine atom, a sulfonyl group, a carbonyl group, an ether bond, a thioether bond, an amide bond Etc.

  As compounds having a hydroxymethylamino group, (poly) (N-hydroxymethyl) melamine, (poly) (N-hydroxymethyl) glycoluril, (poly) (N-hydroxymethyl) benzoguanamine, (poly) (N- The nitrogen-containing compound which alkyl-etherified all or one part of active methylol group, such as hydroxymethyl) urea, is mentioned. Here, examples of the alkyl group of the alkyl ether include a methyl group, an ethyl group, a butyl group, or a mixture thereof, and may contain an oligomer component formed by partial self condensation. Specifically, hexakis (methoxymethyl) melamine, hexakis (butoxymethyl) melamine, tetrakis (methoxymethyl) glycoluril, tetrakis (butoxymethyl) glycoluril, tetrakis (methoxymethyl) urea are mentioned.

  As a compound which has an epoxy group, a conventionally well-known thing can be used. Specific examples thereof include bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolak epoxy resin, cresol novolac epoxy resin, alicyclic epoxy resin, glycidyl amine, heterocyclic epoxy resin, polyalkylene glycol diglycidyl ether Can be mentioned.

  As component (C), in addition to those mentioned above, a hydroxymethyl group such as bis [3,4-bis (hydroxymethyl) phenyl] ether or 1,3,5-tris (1-hydroxy-1-methylethyl) benzene is used. Aromatic compounds, compounds having a maleimide group such as bis (4-maleimidophenyl) methane and 2,2-bis [4- (4'-maleimidophenoxy) phenyl] propane, compounds having a norbornene skeleton, polyfunctional acrylate compounds Compounds having an oxetanyl group, compounds having a vinyl group, and blocked isocyanate compounds can be used.

（式（６）中、Ｒ^３１〜Ｒ^３６は、それぞれ独立に炭素数１〜１０のアルキル基を示す。） Among the components (C) described above, from the viewpoint that the sensitivity and heat resistance can be further improved, compounds having a phenolic hydroxyl group and compounds having a hydroxymethylamino group are preferable, and from the point that resolution and elongation of the coating can be further improved. And a compound having a hydroxymethylamino group is more preferable, a compound having an alkoxymethylamino group obtained by alkylating all or a part of a hydroxymethylamino group is particularly preferable, and an alkoxymethyl obtained by alkylating all the hydroxymethylamino groups Most preferred are compounds having an amino group.
Among the compounds having an alkoxymethylamino group obtained by alkylating all of the above hydroxymethylamino groups, a compound represented by the following general formula (6) is particularly preferable.

(In formula (6), R ^{31 to} R ³⁶ each independently represent an alkyl group having 1 to 10 carbon atoms.)

  With respect to the compounding amount of the component (C), relative to 100 parts by mass of the component (A) from the viewpoint that the dissolution rate difference between the exposed part and the unexposed part becomes large and the sensitivity becomes better and the characteristics of the cured film. 1 to 50 parts by mass is preferable, 2 to 30 parts by mass is more preferable, and 3 to 25 parts by mass is more preferable. Moreover, the thermal crosslinking agent mentioned above is used individually by 1 type or in combination of 2 or more types.

<(D) component: phenolic low molecular weight compound>
In the present invention, a phenolic low molecular weight compound is contained as the component (D). The component (D) was added in order to accelerate the dissolution rate of the resin film in an alkali developer. As the component (D), one having about 3 to 4 benzene rings in the molecule is preferable, and a weight average molecular weight of 200 to 990 is preferable. Here, the component (D) is different from the component (A) or the component (C).

（式（１）〜（４）中、Ｒ^１〜Ｒ^４は各々独立に水素基又はメチル基を示す。ａ〜ｃ、ｈ及びｉは０〜３の整数を示し、ｄ〜ｆは１〜３の整数を示し、ａとｄの合計は５以下であり、ｂとｅの合計は５以下であり、ｃとｆの合計は５以下であり、ｈとｉの合計は４以下である。ｎは１又は２である。） It is preferable that it is a compound represented by either of following General formula (1)-(4) as (D) component from a viewpoint of the melt | dissolution rate with respect to alkaline developing solution.

(In the formulas (1) to (4), R ^{1 to} R ⁴ each independently represent a hydrogen group or a methyl group. A to c, h and i each represents an integer of 0 to 3, and d to f are 1 to An integer of 3 is shown, the sum of a and d is 5 or less, the sum of b and e is 5 or less, the sum of c and f is 5 or less, and the sum of h and i is 4 or less. n is 1 or 2.)

For example, the following compounds may be mentioned as the compound represented by the general formula (1).
1,1,1-tris (4-hydroxyphenyl) methane, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) -1- (4-hydroxyphenyl) methane, 1,1-bis (2,3,5-trimethyl-4-hydroxyphenyl) -1- (2-hydroxyphenyl) methane, 1,1,1-tris (3-methyl-) 4-hydroxyphenyl) ethane, 1,1-bis (3-methyl-4-hydroxyphenyl) -1- (4-hydroxyphenyl) methane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) -1- (3-hydroxyphenyl) methane, 1,1-bis (4,6-dimethyl-2-hydroxyphenyl) -1- (4-hydroxyphenyl) methane, 1,1-bis (3,4,6 -Trime Ethyl 2-hydroxyphenyl) -1- (2-hydroxyphenyl) methane, 1,1-bis (2,3,5-trimethyl-4-hydroxyphenyl) -1- (3-hydroxyphenyl) methane, 1,1 1-bis (2,3,5-trimethyl-4-hydroxyphenyl) -1- (4-hydroxyphenyl) methane, 1,1-bis (3-methyl-4-hydroxyphenyl) -1- (2-hydroxy) Phenyl) methane, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, bis (3,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, 1,1-bis ( 3-Methyl-4-hydroxyphenyl) -1- (3,4-dihydroxyphenyl) methane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) -1 -(3,4-dihydroxyphenyl) methane, 1,1-bis (2,3,5-trimethyl-4-hydroxyphenyl) -1- (3,4-hydroxyphenyl) methane, 1,1-bis (4) -Hydroxyphenyl) -1- (3,4-dihydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) -1- (2-hydroxyphenyl) methane, 1,1-bis (2-methyl-4) -Hydroxyphenyl) -1- (2-hydroxyphenyl) methane, 1,1-bis (4,6-dimethyl-2-hydroxyphenyl) -1- (3-hydroxyphenyl) methane, 1,1-bis (3) 1,4,6-trimethyl-2-hydroxyphenyl) -1- (3-hydroxyphenyl) methane, 1,1-bis (3,4,6-trimethyl-2-hydroxyphenyl) -1- (4-hydroxyphenyl) And 1,1-bis (4,6-dimethyl-4-hydroxyphenyl) -1- (3,4-dihydroxyphenyl) methane, 1,1-bis (3,4,6-trimethyl-2-) Hydroxyphenyl) -1- (3,4-dihydroxyphenyl) methane, 1,1-bis (5-methyl-2,3-dihydroxyphenyl) -1- (2-hydroxyphenyl) methane, 1,1-bis ( 4-hydroxyphenyl) -1-benzylethane, 1,1-bis (4-hydroxyphenyl) -1-benzylmethane, 1- (4-hydroxyphenyl) -1- (3,4-dihydroxyphenyl) -1- Benzyl ethane, 1,1-bis (3-methyl-4-hydroxyphenyl) -1-benzyl ethane, 1,1-bis (2,3,5-trimethyl-4-hydroxyphenyl) -1-benzyl ester Methane, 1,1-bis (2,3,6-trimethyl-4-hydroxyphenyl) -1- (4-methylbenzyl) methane, 1,1-bis (2,3,5-trimethyl-4-hydroxyphenyl) ) -1- (4-Methylbenzyl) methane. These compounds can be used singly or in combination of two or more.

  For example, as a compound represented by General formula (2), the following compounds are mentioned. 2,6-bis [(5-methyl-2-hydroxyphenyl) methyl] -4-methyl-1-hydroxybenzene, 4,6-bis [(4-hydroxyphenyl) methyl] -1,3-dihydroxybenzene, 4,6-Bis [(3,5-dimethyl-4-hydroxyphenyl) methyl] -1,2,3-trihydroxybenzene, 2,6-bis [(3,5-dimethyl-4-hydroxyphenyl) methyl ] -4-Methyl-1-hydroxybenzene, 2,6-bis [(4-hydroxyphenyl) methyl] -4-methyl-1-hydroxybenzene, 2,4-bis [(3-methyl-4-hydroxyphenyl) ) Methyl] -6-methyl-1-hydroxybenzene, 2,6-bis [(3-methyl-4-hydroxyphenyl) methyl] -4-methyl-1-hydroxybenzene 2,6-Bis [(3,5-dimethyl-2-hydroxyphenyl) methyl] -4-methyl-1-hydroxybenzene, 2,6-bis [(4,6-dimethyl-2-hydroxyphenyl) methyl] -4-Methyl-1-hydroxybenzene, 2,6-bis [(2,5-dimethyl-4-hydroxyphenyl) methyl] -3,4-dimethyl-1-hydroxybenzene, 2,6-bis [(2 , 3,6-Trimethyl-4-hydroxyphenyl) methyl] -4-methyl-1-hydroxybenzene, 3,6-bis [(3,5-dimethyl-4-hydroxyphenyl) methyl] -1,2-dihydroxy Benzene, 4,6-bis [(3,5-dimethyl-4-hydroxyphenyl) methyl] -1,3-dihydroxybenzene, 2,6-bis [(2,4-dihydroxyphenyl)メ チ ル yl) -3,4-dimethyl-1-hydroxybenzene, 1,1-bis [3-{(5-methyl-2-hydroxyphenyl) methyl} -5-methyl-2-hydroxyphenyl] methane, 1 1,1-Bis [3-{(3,5-dimethyl-4-hydroxyphenyl) methyl} -5-methyl-2-hydroxyphenyl] methane, 1,1-bis [3-{(2,3,5-) Trimethyl-4-hydroxyphenyl) methyl} -5-methyl-2-hydroxyphenyl] methane, 1,1-bis [3-{(2,4-dihydroxyphenyl) methyl} -5-methyl-4-hydroxyphenyl] Methane, 1,1-bis [3-{(2,4-dihydroxyphenyl) methyl} -2,5-methyl-4-hydroxyphenyl] methane, 1,1-bis [3-{(3-methyl-2 , 4-Dihydroxyphenyl) methyl} -2,5- Ethyl 4-hydroxyphenyl! Methane, 4,6-bis [1- (4-hydroxyphenyl) ethyl] -1,3-dihydroxybenzene, 4,6-bis [1- (4-hydroxyphenyl) ethyl]- 1,2,3-trihydroxybenzene, 4,6-bis [(3,6-dimethyl-4-hydroxyphenyl) methyl] -2-methyl-1-dihydroxybenzene, 1,4-bis [1- (3) -Methyl-4-hydroxyphenyl) -1-methylethyl] benzene, 1,4-bis [1- (3,5-dimethyl-4-hydroxyphenyl) -1-methylethyl] benzene, 1,4-bis [ 1- (3,4-dihydroxyphenyl) -1-methylethyl] benzene, 1,4-bis [1- (3,4,5-trihydroxyphenyl) -1-methylethyl] benzene, 1, -Bis [(3,5-dimethyl-4-hydroxyphenyl) methyl] benzene, 1,4-bis [(2,4,5-trimethyl-3-hydroxyphenyl) methyl] benzene, 1,3-bis [1 -(3-Methyl-4-hydroxyphenyl) -1-methylethyl] benzene, 1,3-bis [1- (2,3,5-trimethyl-4-hydroxyphenyl) -1-methylethyl] benzene, 1 , 4-Bis [1- (5-methyl-2-hydroxyphenyl) -1-methylethyl] benzene, 4,6-bis [1- (4-hydroxyphenyl) -1-methylethyl] -1,3- Dihydroxybenzene, 4,6-bis [1- (4-hydroxyphenyl) -1-methylethyl] -1,3-dihydroxy-2-methylbenzene, 1,3-bis [1- (2,4-dihydroki) Phenyl) -1-methylethyl] benzene, 1,4-bis [1- (2,4-dihydroxyphenyl) -1-methylethyl] benzene. These compounds can be used singly or in combination of two or more.

  For example, as a compound represented by General formula (3), the following compounds are mentioned. 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane, 1,1-bis (3,5-dimethyl-4-) Hydroxyphenyl) -1- [4- {1- (3,5-dimethyl-4-hydroxyphenyl) -1-methylethyl} phenyl] ethane, 1,1-bis (3-methyl-4-hydroxyphenyl)- 1- [4- {1- (3-Methyl-4-hydroxyphenyl) -1-methylethyl} phenyl] ethane. These compounds can be used singly or in combination of two or more.

  For example, the following compounds may be mentioned as the compound represented by the general formula (4). 1- (3-Methyl-4-hydroxyphenyl) -4- (4-hydroxyphenyl) benzene, 1- (3,5-dimethyl-4-hydroxyphenyl) -4- (4-hydroxyphenyl) benzene, 1, 4-bis (3,5-dimethyl-4-hydroxyphenyl) benzene, 1,4-bis (2,3,5-trimethyl-4-hydroxyphenyl) benzene. These compounds can be used singly or in combination of two or more.

  The photosensitive resin composition of the present invention does not have too high solubility in an alkali developer as the component (D), and can suppress film loss in the unexposed area, and therefore, it is represented by the general formula (1) or (3) It is preferable to contain the compound represented.

  For example, when the content of the component (B) is reduced to suppress the residue after development, the effect of inhibiting the dissolution of the unexposed area of the resin film is reduced, and the film reduction after development is increased. By containing the compound represented by Formula (1) or (3), film loss was able to be suppressed effectively. This is because the dissolution rate of the compound represented by the general formula (1) or (3) in the alkali developer is not too high, and as a result, the solubility of the unexposed area of the resin film is the general formula (2) or (4) It is considered to be because it decreased compared with the case of adding).

  Furthermore, as a component (D), from the viewpoint that the pattern melt can be further suppressed, a compound represented by General Formula (3) is more preferable. It is considered that this is because the glass transition temperature of the general formula (3) is high.

  In the photosensitive resin composition of the present invention, the component (D) is preferably contained in an amount of 5 to 35 parts by mass with respect to 100 parts by mass of the component (A). By setting it as 5-35 mass parts, the residue after image development can be suppressed, and suppression of the pattern melt at the time of heat-hardening can be performed. The amount is more preferably 5 to 30 parts by mass, further preferably 10 to 28 parts by mass, and particularly preferably 15 to 25 parts by mass.

（式（７）及び（８）中、Ｒ^９は炭素数４〜２０のアルキル基を表し、Ｒ^１０は水素原子又はメチル基を表す。） <(E) component: acrylic resin>
The photosensitive resin composition of the present invention may contain an acrylic resin as the component (E). The acrylic resin is preferably an acrylic resin having a structural unit represented by the following general formula (7) or (8). When the photosensitive resin composition contains an acrylic resin having a structural unit represented by the general formula (7) or (8), it is possible to improve the thermal shock resistance while maintaining good photosensitive properties. The component (E) may consist of only one of the above acrylic resins, or may contain two or more.

(In formulas (7) and (8), R ⁹ represents an alkyl group having 4 to 20 carbon atoms, and R ¹⁰ represents a hydrogen atom or a methyl group.)

Further, in the above general formula (7), from the viewpoint of being able to improve the sensitivity, resolution and thermal shock resistance, an alkyl group having 4 to 16 carbon atoms is preferable as R ⁹ , an alkyl group having 4 carbon atoms, and more preferably an n-butyl group. preferable.

As a polymerizable monomer which gives a structural unit represented by General formula (7), (meth) acrylic-acid alkylester is mentioned. As a (meth) acrylic-acid alkylester, the compound etc. which are represented by following General formula (9) are mentioned, for example.
CH ₂ = C (R ¹¹ ) -COOR ¹² (9)
Here, in the above general formula ^{(9), R 11} represents a hydrogen atom or a methyl ^{group, R 12} represents an alkyl group having 4 to 20 carbon atoms. The alkyl group having 1 to 20 carbon atoms represented by R ^12, for example, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, Examples include tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group and structural isomers thereof. As a polymerizable monomer represented by the said General formula (9), (meth) acrylic acid butyl ester, (meth) acrylic acid pentyl ester, (meth) acrylic acid hexyl ester, (meth) acrylic acid heptyl is mentioned, for example Ester, (meth) acrylic acid octyl ester, (meth) acrylic acid nonyl ester, (meth) acrylic acid decyl ester, (meth) acrylic acid undecyl ester, (meth) acrylic acid dodecyl ester, (meth) acrylic acid tridecyl Ester, (meth) acrylic acid tetradecyl ester, (meth) acrylic acid pentadecyl ester, (meth) acrylic acid hexadecyl ester, (meth) acrylic acid heptadecyl ester, (meth) acrylic acid octadecyl ester, (meth) acrylic Acid nonadecyl ester, (meth) acrylic Acid eicosyl ester and the like. These polymerizable monomers may be used alone or in combination of two or more.
Moreover, acrylic acid and methacrylic acid are mentioned as a polymerizable monomer which gives the structural unit represented by General formula (8).

  In the component (E), the composition ratio of the structural unit represented by the above general formula (7) is preferably 50 to 95 mol%, more preferably 60 to 90 mol%, with respect to the total amount of the component (E). And more preferably 70 to 85 mol%. When the composition ratio of the structural unit represented by the general formula (7) is 50 to 95 mol%, the thermal shock resistance of the cured film of the photosensitive resin composition can be further improved.

  Moreover, in the acrylic resin which is the component (E), the composition ratio of the structural unit represented by the above general formula (8) is preferably 5 to 35 mol% with respect to the total amount of the component (E), It is more preferable that it is 10-30 mol%, and it is further more preferable that it is 15-25 mol%. When the composition ratio of the structural unit represented by the general formula (8) is 5 to 35 mol%, the compatibility with the component (A) and the developability of the photosensitive resin composition are further improved. it can.

(式（１０）中、Ｒは水素原子又はメチル基を表し、Ｒ^１３は１級、２級又は３級アミノ基を有する１価の有機基を表す。) Further, from the viewpoint of being able to further improve the compatibility with the component (A), the adhesion of the pattern cured film to the substrate, the mechanical properties and the thermal shock resistance, the component (E) is represented by the above general formula (7) It is more preferable to contain an acrylic resin having a structural unit, a structural unit represented by the above (8) and a structural unit represented by the following general formula (10). When the component (E) is the acrylic resin, the interaction between the component (E) and the alkali-soluble resin having a phenolic hydroxyl group (A) is improved, and the compatibility is further improved.

(In formula (10), R represents a hydrogen atom or a methyl group, and R ¹³ represents a monovalent organic group having a primary, secondary or tertiary amino group.)

(一般式（１１）中、Ｘは炭素数１〜５のアルキレン基を表し、Ｒ^１４〜Ｒ^１８はそれぞれ独立に水素原子又は炭素数１〜２０のアルキル基を表し、ｍは０〜１０の整数である) Examples of the polymerizable monomer giving the structural unit represented by the general formula (10) include aminoethyl (meth) acrylate, N-methylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) Acrylate, N-ethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, aminopropyl (meth) acrylate, N-methylaminopropyl (meth) acrylate, N, N-dimethylaminopropyl (meth) Acrylate, N-ethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, aminoethyl (meth) acrylamide, N-methylaminoethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) Acrylamide, N-Ethic Aminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, aminopropyl (meth) acrylamide, N-methylaminopropyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N-ethyl Aminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, piperidin-4-yl (meth) acrylate, 1-methylpiperidin-4-yl (meth) acrylate, 2,2,6,6-tetra Methyl piperidin-4-yl (meth) acrylate, 1,2,2,6,6-pentamethylpiperidin-4-yl (meth) acrylate, (piperidin-4-yl) methyl (meth) acrylate, 2- (piperidine -4-yl) ethyl (meth) a Relate and the like. These polymerizable monomers may be used alone or in combination of two or more. Among these, from the viewpoint of being able to further improve the adhesion of the resist pattern to the substrate, mechanical properties and thermal shock resistance, in the general formula (10), R ¹³ is a monovalent compound represented by the following general formula (11) Particularly preferred is an organic group.

(In the general formula (11), X represents an alkylene group of 1 to 5 carbon atoms, R ^{14 to} R ¹⁸ each independently represent a hydrogen atom or an alkyl group of 1 to 20 carbon atoms, and m is 0 to 10) Is an integer)

In the general formula (10), the polymerizable monomer giving the structural unit R ¹³ is represented by a monovalent organic group represented by the above general formula (11), for example, piperidin-4-yl (meth ) Acrylate, 1-methylpiperidin-4-yl (meth) acrylate, 2,2,6,6-tetramethylpiperidin-4-yl (meth) acrylate, 1,2,2,6,6-pentamethylpiperidine 4-yl (meth) acrylate, (piperidin-4-yl) methyl (meth) acrylate, 2- (piperidin-4-yl) ethyl (meth) acrylate and the like. Among these, 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate is as FA-711MM, and 2,2,6,6-tetramethylpiperidin-4-yl methacrylate is as FA-712HM. Both are commercially available, manufactured by Hitachi Chemical Co., Ltd., respectively.

  In the acrylic resin which is the component (E), the composition ratio of the structural unit represented by the above general formula (10) is preferably 0.3 to 10 mol% with respect to the total amount of the component (E), It is more preferable that it is 0.4-8 mol%, and it is further more preferable that it is 0.5-7 mol%.

（一般式（１２）中、Ｒは水素原子又はメチル基を表し、Ｙは炭素数１〜５のアルキレン基を表し、Ｒ^１９〜Ｒ^２３はそれぞれ独立に炭素数１〜６のアルキル基を表し、ｐは１〜１００の整数である） Further, the component (E) is a structural unit represented by the above general formula (7), a structural unit represented by the above general formula (8), and the following general formula (12) from the viewpoint of being able to further improve the sensitivity. It is preferable to contain an acrylic resin having a structural unit. The acrylic resin may further have a structural unit represented by the above general formula (10).

(In the general formula (12), R represents a hydrogen atom or a methyl group, Y represents an alkylene group having 1 to 5 carbon atoms, R ^{19 to} R ²³ each independently represents an alkyl group having 1 to 6 carbon atoms , P is an integer of 1 to 100)

  As a polymerizable monomer which gives a structural unit represented by General formula (12), methacryl modified silicone oil is mentioned, for example, X-22-174DX, X-22-2426, X-22-2475 (any one They are also commercially available as Shin-Etsu Chemical Co., Ltd.).

In the acrylic resin which is the component (E), the composition ratio of the structural unit represented by the above general formula (12) is preferably 1 to 10 mol% with respect to the total amount of the component (E). It is more preferable that it is 5 mol%, and it is further more preferable that it is 3 to 5 mol%.

  Moreover, the polymerizable monomer used for the synthesis | combination of the acrylic resin which comprises (E) component has each structure represented by General formula (7), (8), (10), (11), (12) It may further contain a polymerizable monomer other than the polymerizable monomer giving the unit. As such a polymerizable monomer, for example, styrene, α-methylstyrene, (meth) acrylic acid benzyl ester, (meth) acrylic acid 4-methylbenzyl ester, (meth) acrylic acid 2-hydroxyethyl ester, (Meth) acrylic acid 2-hydroxypropyl ester, (meth) acrylic acid 3-hydroxypropyl ester, (meth) acrylic acid 4-hydroxybutyl ester, acrylonitrile, esters of vinyl alcohol such as vinyl-n-butyl ether, ) Acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid glycidyl ester, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, (meth) acrylic Acid, α-bromo (meth) acid Acrylic acid, α-chloro (meth) acrylic acid, β-furyl (meth) acrylic acid, β-styryl (meth) acrylic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate And maleic acid monoester, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid and the like. These polymerizable monomers may be used alone or in combination of two or more.

  The weight average molecular weight of the component (E) is preferably 2,000 to 100,000, more preferably 3,000 to 60,000, and still more preferably 4,000 to 50,000. . If the weight average molecular weight is less than 2,000, the thermal shock resistance of the cured film tends to decrease, and if it exceeds 100,000, the compatibility with the component (A) and the developability tend to decrease.

  The content in the case of containing the component (E) is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the total amount of the component (A) from the viewpoint of adhesion, mechanical properties, thermal shock resistance, and photosensitive properties. 3-30 mass parts is more preferable, and 5-20 mass parts is especially preferable.

<Other ingredients>
The photosensitive resin composition of the present invention may, if necessary, contain other components such as a thermal acid generator, an elastomer, a solvent, a dissolution accelerator, a dissolution inhibitor, a surfactant or a leveling agent, and an adhesion assistant. it can.

<Other Components (F): Thermal Acid Generator>
The photosensitive resin composition of the present invention may contain (F) a thermal acid generator. The component (F) is a compound that generates an acid by heat and can suppress ants and pattern melt more. This makes it possible to generate an acid when heating the photosensitive resin film after development, and the reaction between the components (A) and (C), that is, the thermal crosslinking reaction starts from a lower temperature, It is because the melt of the pattern by is more suppressed. Moreover, since many components (F) can generate an acid even by light irradiation, the use of such a component can also increase the solubility of the exposed portion in an alkaline aqueous solution. Therefore, the difference in solubility between the unexposed area and the exposed area in the aqueous alkali solution is further increased, and the resolution is improved. However, in the present invention, a compound different from the component (B) is used as the component (F).

  It is preferable that the compound which produces | generates an acid by such heat is what produces | generates an acid, for example by heating to the temperature of 50-200 degreeC. Specific examples of the compound capable of generating an acid by heat are compounds different from the compounds capable of generating an acid by light of the component (B) and which have a function of generating an acid by heat and strong acids such as onium salts and bases And salts formed therefrom, and imidosulfonates.

  Such onium salts include, for example, aryldiazonium salts, diaryliodonium salts such as diphenyliodonium salts; diaryliodonium salts, di (alkylaryl) iodonium salts such as di (t-butylphenyl) iodonium salts; trimethylsulfonium Examples include trialkyl sulfonium salts such as salts; dialkyl monoaryl sulfonium salts such as dimethylphenyl sulfonium salts; diaryl monoalkyl iodonium salts such as diphenylmethyl sulfonium salts; triaryl sulfonium salts. Among these, di (t-butylphenyl) iodonium salt of para-toluenesulfonic acid, di (t-butylphenyl) iodonium salt of trifluoromethanesulfonic acid, trimethylsulfonium salt of trifluoromethanesulfonic acid, dimethyl of trifluoromethanesulfonic acid Phenylsulfonium salt, diphenylmethylsulfonium salt of trifluoromethanesulfonic acid, di (t-butylphenyl) iodonium salt of nonafluorobutanesulfonic acid, diphenyliodonium salt of camphorsulfonic acid, diphenyliodonium salt of ethanesulfonic acid, benzenesulfonic acid A dimethyl phenyl sulfonium salt, a diphenylmethyl sulfonium salt of toluene sulfonic acid, etc. can be mentioned as a preferable thing.

  Among these, sulfonium salts as represented by the following general formula (13) are preferable, trialkylsulfonium salts of methanesulfonic acid are more preferable, and trimethylsulfonium salts are particularly preferable.

（式（１３）中、Ｒ^２４、Ｒ^２５及びＲ^２６は各々独立にアルキル基又はアリール基を表し、Ｒ^２７は水素又はフッ素を表す。）前記アリール基としては、フェニル基又は置換基を有するフェニル基が好ましい。 Among these, sulfonium salts as represented by the following general formula (13) are preferable, trialkylsulfonium salts of methanesulfonic acid are more preferable, and trimethylsulfonium salts are particularly preferable.

(In formula (13), R ²⁴ , R ²⁵ and R ²⁶ each independently represent an alkyl group or an aryl group, and R ²⁷ represents hydrogen or fluorine.) The aryl group has a phenyl group or a substituent Phenyl is preferred.

  As the imidosulfonate, for example, naphthoyl imidosulfonate and phthalimidosulfonate can be used.

  0.1-30 mass parts is preferable with respect to 100 mass parts of (A) component, and, as for content in the case of containing a thermal acid generator (F), 0.2-20 mass parts is more preferable, 0. 3 to 10 parts by mass is more preferable.

<Other Components (G): Elastomers>
In the present invention, an elastomer can further be used in combination. As a result, the obtained resist pattern is further excellent in flexibility, and the mechanical properties and thermal shock resistance of the resist pattern can be further improved. As an elastomer, although a conventionally well-known thing can be used, it is preferable that the glass transition temperature (Tg) of the polymer which comprises an elastomer is 20 degrees C or less.

  Examples of such an elastomer include styrene-based elastomers, olefin-based elastomers, urethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, and silicone-based elastomers. The elastomer may be a fine particle elastomer. These elastomers can be used singly or in combination of two or more.

（式（１４）中、Ｒ^３は２価の有機基を表し、Ｒ^４基は１価の有機基を表す） <(H) Component: Silane Compound>
The photosensitive resin composition of the present invention may contain, as the component (H), a silane compound having an epoxy group represented by General Formula (14), from the viewpoint of improving the adhesion to the substrate.

(In formula (14), R ³ represents a divalent organic group, and the R ⁴ group represents a monovalent organic group)

In the general formula (14), R ³ is not particularly limited as long as it is a divalent organic group. From the viewpoint of improving sensitivity and resolution, R ³ is preferably a linear alkyl group represented by — (CH ₂ ) _n — (n is an integer of 1 to 6). In the general formula (14), R ⁴ is not particularly limited as long as it is an organic radical. From the viewpoint of improving sensitivity and resolution, R ⁴ preferably contains an alkoxy group or an alkoxyalkyl group. Among them, it is particularly preferable to contain an alkoxy group such as a methoxy group or an ethoxy group, from the viewpoint of being inexpensive and easy to obtain, and improving adhesion to a substrate. Examples of such a compound include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane and the like.

  Moreover, the photosensitive resin composition of this invention may further contain the silane compound other than the silane compound which has an epoxy group shown by General formula (14). As such a silane compound, for example, ureidopropyltriethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, ureapropyltriethoxysilane, methylphenylsilanediol Ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butylphenylphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, ethylmethylphenylsilanol, n-propyl Methylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilano , Tert-butylmethylphenylsilanol, ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyl diphenylsilanol, ethyl diphenylsilanol, n- Propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, phenylsilanetriol, 1,4-bis (trihydroxysilyl) benzene, 1,4-bis (methyldihydroxysilyl) Benzene, 1,4-bis (ethyl dihydroxysilyl) benzene, 1,4-bis (propyl dihydroxy ester) Silyl) benzene, 1,4-bis (butyldihydroxysilyl) benzene, 1,4-bis (dimethylhydroxysilyl) benzene, 1,4-bis (diethylhydroxysilyl) benzene, 1,4-bis (dipropyldroxy) And silyl) benzene, 1,4-bis (dibutylhydroxysilyl) benzene and the like. These silane compounds may be used alone or in combination of two or more.

  The content in the case of using the component (H) is the component (H) and the component (H) with respect to 100 parts by mass of the component (A) from the viewpoint of the adhesion to the wiring and the storage stability of the photosensitive resin composition. The total amount of the other silane compounds is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, and still more preferably 1 to 5 parts by mass.

<Other Component (I): Solvent>
The photosensitive resin composition of the present invention may contain (I) a solvent from the viewpoint of coating properties on a substrate and formation of a resin film having a uniform thickness. Specific examples of the solvent include γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, 3-methyl methoxy propionate, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphorylamide, tetramethylene sulfone, diethyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene And glycol monobutyl ether and dipropylene glycol monomethyl ether. These solvents can be used singly or in combination of two or more.
The content in the case of containing the component (I) is not particularly limited, but the content of the solvent in the photosensitive resin composition is preferably adjusted to be 20 to 90% by mass.

<Other ingredients (J): Solubility promoter>
The photosensitive resin composition of the present invention may contain (J) a dissolution accelerator. (J) By containing a dissolution accelerator, it is possible to increase the dissolution rate of the exposed area when developing the pattern resin film with an alkaline aqueous solution, and to improve the sensitivity and resolution. As the dissolution accelerator, conventionally known ones can be used. Specific examples thereof include compounds having a carboxyl group, a sulfonic acid, and a sulfonamide group.
Although the content in the case of including such a dissolution accelerator can be determined by the dissolution rate of the pattern resin film in an aqueous alkaline solution, for example, 0.01 to 30 with respect to 100 parts by mass of the component (A). Preferably, it is in parts by mass.

<Other components (K): Dissolution inhibitor>
The photosensitive resin composition of the present invention may contain (K) a dissolution inhibitor. The dissolution inhibitor (K) is a compound that inhibits the solubility of the component (A) in an aqueous alkaline solution, and is used to control the residual film thickness, the development time, and the contrast. Specific examples thereof are diphenyliodonium nitrate, bis (p-tert-butylphenyl) iodonium nitrate, diphenyliodonium bromide, diphenyliodonium chloride, diphenyliodonium iodide and the like. The content in the case of containing the dissolution inhibitor is preferably 0.01 to 20 parts by mass, based on 100 parts by mass of the total amount of the component (A), from the viewpoint of the sensitivity and the allowable range of development time. 15 parts by mass is more preferable, and 0.05 to 10 parts by mass is more preferable.

<Other components (L): surfactant or leveling agent>
The photosensitive resin composition of the present invention may contain (L) a surfactant or a leveling agent. When the photosensitive resin composition contains the component (L), coating properties, for example, striation (unevenness in film thickness) can be prevented, and developability can be improved. As such surfactant or leveling agent, for example, polyoxyethylene uralyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether can be mentioned. Commercially available products include Megafax F171, F173, R-08 (trade name of Dainippon Ink and Chemicals, Inc.), Florard FC 430, FC 431 (Sumitomo 3M Ltd., trade name), organosiloxane polymers KP 341, KBM 303, KBM 803. (Product name, manufactured by Shin-Etsu Chemical Co., Ltd.).
When it contains (L) component, 0.001-5 mass parts is preferable with respect to 100 mass parts of (A) component, and 0.01-3 mass parts is more preferable.

  The photosensitive resin composition of the present invention can be developed using an aqueous alkaline solution such as tetramethyl ammonium hydroxide (TMAH). Furthermore, by using the above-mentioned photosensitive resin composition, it becomes possible to form a pattern cured film having good adhesion and crack resistance in a thermal shock cycle. Moreover, the pattern cured film which consists of a photosensitive resin composition of this invention has a favorable photosensitive characteristic (sensitivity and resolution), and has sufficient mechanical characteristics (break elongation and a modulus of elasticity).

  The photosensitive resin composition of the present invention is generally a positive photosensitive resin composition, but is not limited thereto.

[Method for producing patterned cured film]
The method for producing a patterned cured film comprising the photosensitive resin composition of the present invention generally comprises the steps of forming a photosensitive resin film by applying and drying the photosensitive resin composition on a support substrate (film forming step); A step of exposing the photosensitive resin film (exposure step), a step of developing the photosensitive resin film after exposure using an alkaline aqueous solution to form a patterned resin film (developing step), and heating the patterned resin film And a process (heating process).

<Film formation process>
In the film forming step, the photosensitive resin composition described above is spin-coated on a supporting substrate such as a glass substrate, semiconductor, metal oxide insulator (for example, TiO ₂ , SiO _2, etc.), silicon nitride, etc. using a spinner or the like. Do. The applied photosensitive resin composition is dried by heating using a hot plate, an oven or the like. Thereby, a film (photosensitive resin film) of the photosensitive resin composition is formed on the substrate.

<Exposure process>
In the exposure step, the photosensitive resin film formed on the substrate is irradiated with active light such as ultraviolet light, visible light and radiation through a mask. Since the component (A) has high transparency to i-line, irradiation of i-line can be suitably used. After exposure, post-exposure heating (PEB) can also be performed if necessary. The temperature of post-exposure heating is preferably 70 ° C. to 140 ° C., and the time of post-exposure heating is preferably 1 minute to 5 minutes.

<Development process>
In the development step, the photosensitive resin film is patterned by removing the exposed portion of the photosensitive resin film after the exposure step with a developer. As a developing solution, for example, an aqueous alkaline solution such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide (TMAH) is suitably used. The base concentration of these aqueous solutions is preferably 0.1 to 10% by mass. Furthermore, alcohols and surfactants can be added to the above-mentioned developer and used. Each of these can be blended in a range of preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the developer. The patterned photosensitive resin film is called a patterned resin film.

<Heating process>
In the heat treatment step, the photosensitive resin composition is cured by heating the pattern resin film. A film obtained by curing the pattern resin film is called a pattern cured film. The heating temperature is preferably 250 ° C. or less, more preferably 225 ° C. or less, and still more preferably 140 to 200 ° C. from the viewpoint of sufficiently preventing heat damage to the electronic device. The heat treatment can be performed using, for example, an oven such as a quartz tube furnace, a hot plate, rapid thermal annealing, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, and a microwave curing furnace. Further, either of the methods can be selected in the air or in an inert atmosphere such as nitrogen, but it is preferable to carry out under nitrogen because this can prevent the oxidation of the pattern. Since the above-mentioned desirable heating temperature range is lower than the conventional heating temperature, damage to the supporting substrate and the electronic device can be reduced. Therefore, the electronic device can be manufactured with high yield by using the method for manufacturing a resist pattern according to the present embodiment. In addition, it leads to energy saving of the process. Furthermore, according to the photosensitive resin composition of the present embodiment, since the volume shrinkage (curing shrinkage) in the heat treatment step found in the photosensitive polyimide resin and the like is small, it is possible to prevent the deterioration of the dimensional accuracy.

  The heating time in the heating step may be a time sufficient for curing of the photosensitive resin composition, but it is preferably about 5 hours or less from the balance with the working efficiency. Moreover, heating can also be performed using a microwave curing apparatus or a variable frequency microwave curing apparatus other than the above-mentioned oven. By using these devices, it is possible to effectively heat only the photosensitive resin film while keeping the temperature of the substrate or the electronic device at, for example, 200 ° C. or less.

  In the variable-frequency microwave curing apparatus, since the microwaves are irradiated in a pulse shape while changing the frequency, it is preferable in that standing waves can be prevented and the substrate surface can be uniformly heated. Further, in the case where a metal wiring is included as an electronic device to be described later as the substrate, when the microwave is irradiated in a pulse shape while changing the frequency, generation of discharge from the metal can be prevented and the electronic device is protected from destruction. Because it can be Furthermore, heating using a variable frequency microwave is preferable because the physical properties of the cured film do not decrease even if the curing temperature is lowered as compared with the case of using an oven (J. Photopolym. Sci. Technol., 18, 327-332 (2005 )reference).

  The frequency of the variable frequency microwaves is generally in the range of 0.5 to 20 GHz, but practically, the range of 1 to 10 GHz is preferable, and further, the range of 2 to 9 GHz is more preferable. In addition, it is desirable to continuously change the frequency of the microwaves to be irradiated, but in practice the frequency is changed stepwise and irradiation is performed. At that time, the irradiation time is preferably 1 millisecond or less, and more preferably 100 microseconds or less, since the standing wave and the discharge from the metal are less likely to occur when the irradiation time of the single frequency microwave is as short as possible.

  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, but is generally in the range of 10 to 2000 W, 100 to 1000 W is more preferable in practical use, 100 to 700 W is more preferable, and 100 to 700 500 W is most preferred. If the output is less than 10 W, it is difficult to heat the body to be heated in a short time, and if it exceeds 2000 W, a rapid temperature rise is likely to occur.

  It is preferable that the microwaves be pulsed on / off and irradiated. By irradiating microwaves in a pulse shape, it is possible to maintain the set heating temperature, and it is preferable in that damage to the cured film and the base material can be avoided. The time for irradiating the pulsed microwaves at one time varies depending on the conditions, but it is preferably about 10 seconds or less.

  According to the above-described method for producing a cured pattern film, a photosensitive resin composition having good photosensitive characteristics can be obtained, and a cured pattern film having a good pattern shape can be obtained. By using the photosensitive resin composition according to the present embodiment, curing is possible even at a low temperature of 200 ° C. or less in the above-described heating process which conventionally required 300 ° C. or more. Furthermore, the pattern cured film formed from the photosensitive resin composition of this invention has a high glass transition temperature. Therefore, it becomes a pattern hardening film excellent in heat resistance. As a result, electronic devices such as semiconductor devices having excellent reliability can be obtained with high yield and high yield.

[Manufacturing process of semiconductor device]
Next, as an example of the method for producing a patterned cured film of the present invention, steps for producing a semiconductor device will be described based on the drawings. 1 to 5 are schematic cross-sectional views showing an embodiment of a manufacturing process of a semiconductor device having a multilayer interconnection structure.

  First, the structure 100 shown in FIG. 1 is prepared. Structure 100 includes a semiconductor substrate 1 such as a Si substrate having a circuit element, a protective layer 2 such as a silicon oxide film having a predetermined pattern to which the circuit element is exposed, and covering the semiconductor substrate 1, and the exposed circuit element. And an interlayer insulating layer 4 made of polyimide resin or the like formed on the protective layer 2 and the first conductor layer 3 by spin coating or the like.

  Next, the photosensitive resin layer 5 having the window portion 6A is formed on the interlayer insulating layer 4 to obtain the structure 200 shown in FIG. The photosensitive resin layer 5 is formed, for example, by applying a photosensitive resin such as a chlorinated rubber type, a phenol novolac type, a polyhydroxystyrene type, or a polyacrylic acid ester type by a spin coating method. The window portion 6A is formed by a known photolithographic technique so that the interlayer insulating layer 4 of a predetermined portion is exposed.

  After interlayer insulating layer 4 is etched to form window portion 6B, photosensitive resin layer 5 is removed to obtain a structure 300 shown in FIG. For etching the interlayer insulating layer 4, a dry etching method using a gas such as oxygen or carbon tetrafluoride can be used. By this etching, the interlayer insulating layer 4 in the portion corresponding to the window 6A is selectively removed, and the interlayer insulating layer 4 provided with the window 6B so as to expose the first conductor layer 3 is obtained. Then, the photosensitive resin layer 5 is removed using an etching solution which corrodes only the photosensitive resin layer 5 without corroding the first conductor layer 3 exposed from the window 6B.

  Furthermore, the second conductor layer 7 is formed in a portion corresponding to the window portion 6B to obtain a structure 400 shown in FIG. For the formation of the second conductor layer 7, known photolithography techniques can be used. Thereby, the electrical connection between the second conductor layer 7 and the first conductor layer 3 is performed.

  Finally, the surface protection layer 8 is formed on the interlayer insulating layer 4 and the second conductor layer 7 to obtain the semiconductor device 500 shown in FIG. In the present embodiment, the surface protective layer 8 is formed as follows. First, the photosensitive resin composition according to the above-described embodiment is applied onto the interlayer insulating layer 4 and the second conductor layer 7 by spin coating, and dried to form a photosensitive resin film. Next, light is irradiated through a mask in which a pattern corresponding to the window 6C is drawn on a predetermined portion, and then development is performed with an aqueous alkali solution to pattern the photosensitive resin film. Thereafter, the photosensitive resin film is cured by heating to form a film as the surface protective layer 8. The surface protective layer 8 protects the first conductor layer 3 and the second conductor layer 7 from external stress, α rays, and the like, and the obtained semiconductor device 500 has excellent reliability.

  In the above embodiment, a method of manufacturing a semiconductor device having a two-layer wiring structure is described. However, when forming a multilayer wiring structure having three or more layers, the above steps are repeated to form each layer. Can. That is, it is possible to form a multi-layered pattern by repeating each step of forming interlayer insulating layer 4 and each step of forming surface protective layer 8. Further, in the above example, not only the surface protective layer 8 but also the interlayer insulating layer 4 can be formed using the photosensitive resin composition of the present invention.

[Electronic parts]
Next, the electronic component of the present invention will be described. The electronic component of the present invention has a patterned cured film formed by the above-described manufacturing method as an interlayer insulating layer or a surface protective layer. Specifically, the patterned cured film can be used as a surface protective layer or an interlayer insulating layer of a semiconductor device, an interlayer insulating layer of a multilayer wiring board, or the like. The electronic component of the present invention is not particularly limited except that it has a surface protective layer and an interlayer insulating layer formed using the above-described photosensitive resin composition, and can have various structures.

  Moreover, since the above-mentioned photosensitive resin composition is excellent also in stress relaxation property, adhesiveness, etc., it can be used also as various structural materials in the package of the various structure developed in recent years. 6 and 7 show the cross-sectional structure of an example of such a semiconductor device.

  FIG. 6 is a schematic cross-sectional view showing a wiring structure as an embodiment of the semiconductor device. The semiconductor device 600 shown in FIG. 6 includes an Al having a pattern including a silicon chip 23, an interlayer insulating layer 11 provided on one surface side of the silicon chip 23, and a pad portion 15 formed on the interlayer insulating layer 11. Wiring layer 12, insulating layer 13 (for example, P-SiN layer) and surface protection layer 14 sequentially stacked on interlayer insulating layer 11 and Al wiring layer 12 while forming an opening on pad portion 15, and surface protection layer In contact with the pad portion 15 in the opening of the insulating layer 13 and the surface protection layer 14 and in contact with the surface of the core 18 opposite to the surface protection layer 14, the island-shaped core 18 disposed in the vicinity of the opening 14. And a redistribution layer 16 extending over the surface protection layer 14. Furthermore, the semiconductor device 600 is formed to cover the surface protection layer 14, the core 18 and the redistribution layer 16, and a cover coat layer 19 in which an opening is formed in the portion of the redistribution layer 16 on the core 18. The conductive ball 17 is connected to the rewiring layer 16 with the barrier metal 20 interposed in the opening of the layer 19, the collar 21 for holding the conductive ball, and the cover coat layer 19 around the conductive ball 17 And an underfill 22. The conductive balls 17 are used as external connection terminals, and are formed of solder, gold or the like. The underfill 22 is provided to relieve stress when the semiconductor device 600 is mounted.

  FIG. 7 is a schematic cross-sectional view showing a wiring structure as an embodiment of the semiconductor device. In the semiconductor device 700 of FIG. 7, the Al wiring layer (not shown) and the pad portion 15 of the Al wiring layer are formed on the silicon chip 23, and the insulating layer 13 is formed on the upper portion thereof. The surface protective layer 14 is formed. A rewiring layer 16 is formed on the pad portion 15, and the rewiring layer 16 extends to the upper portion of the connection portion 24 with the conductive ball 17. Furthermore, a cover coat layer 19 is formed on the surface protective layer 14. The redistribution layer 16 is connected to the conductive balls 17 via the barrier metal 20.

  In the semiconductor device of FIGS. 6 and 7, the photosensitive resin composition described above forms not only the interlayer insulating layer 11 and the surface protective layer 14 but also the cover coat layer 19, the core 18, the collar 21, the underfill 22 and the like. It can be used as a material for A cured product using the above-mentioned photosensitive resin composition is excellent in adhesion to metal layers (eg, Cu, Au, Ni, Ti, etc.) such as Al wiring layer 12 and rewiring layer 16 and sealants, etc. Since the stress relaxation effect is also high, the semiconductor device using this cured product for the surface protective layer 14, the cover coat layer 19, the core 18, the collar 21 such as solder, the underfill 22 used for flip chip etc. is extremely reliable. Excellent.

  The photosensitive resin composition of the present invention is particularly preferably used for the surface protective layer 14 and / or the cover coat layer 19 of the semiconductor device having the rewiring layer 16 in FIGS.

  The thickness of the surface protective layer or the cover coat layer is preferably 3 to 20 μm, and more preferably 5 to 15 μm.

  As described above, by using the above-described photosensitive resin composition, curing using low-temperature heating at 200 ° C. or less is possible in the above-described heat treatment process which conventionally required 300 ° C. or more. In the heat treatment step, the heating temperature is preferably 100 ° C to 200 ° C, and more preferably 150 ° C to 200 ° C. Furthermore, since the volumetric resin shrinkage (curing shrinkage) in the heat treatment process found in photosensitive polyimide and the like is small, the photosensitive resin composition of the present invention can prevent a decrease in dimensional accuracy. The patterned cured film comprising the photosensitive resin composition of the present invention has a high glass transition temperature. Therefore, it becomes a surface protection layer and an interlayer insulation layer excellent in heat resistance. As a result, electronic components such as semiconductor devices having excellent reliability can be obtained with high yield and high yield.

  Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto.

  Hereinafter, the present invention will be more specifically described by way of examples. However, the present invention is not limited to these.

<Preparation of Photosensitive Resin Composition>
First, the following A1 and A2 were prepared as the component (A).
A1: cresol novolak resin (cresol / formaldehyde novolak resin, m-cresol / p-cresol (molar ratio) = 60/40, polystyrene equivalent weight average molecular weight = 13000, manufactured by Asahi Organic Materials Co., Ltd., trade name "EP4020G") Got ready.
A2: Prepared by the method described in Synthesis Example 1 below.

Synthesis example 1: Synthesis of phenol resin (A2) modified with a compound having a C 4-100 unsaturated hydrocarbon group 100 parts by mass of phenol, 43 parts by mass of linseed oil, and 0.1 parts by mass of trifluoromethanesulfonic acid The mixture was mixed and stirred at 120.degree. C. for 2 hours to obtain a vegetable oil-modified phenol derivative (a). Next, 130 g of vegetable oil-modified phenol derivative (a), 16.3 g of paraformaldehyde and 1.0 g of oxalic acid were mixed and stirred at 90 ° C. for 3 hours. Then, the temperature was raised to 120 ° C. and stirred under reduced pressure for 3 hours, then 29 g of succinic anhydride and 0.3 g of triethylamine were added to the reaction liquid, and stirred at 100 ° C. for 1 hour under atmospheric pressure. The reaction solution was cooled to room temperature to obtain a phenolic resin (hereinafter referred to as A2) modified with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms, which is a reaction product (acid value: 120 mg KOH / g) . The weight average molecular weight calculated | required by standard polystyrene conversion of the GPC method of this A2 was about 25,000.

The following B1 was prepared as the component (B).
B: 1-naphthoquinone-2-diazide-5-sulfonic acid of 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane Ester (esterification rate approx. 90%, manufactured by AZ Electronic Materials, trade name "TPPA 528")

As the component (C), a thermal crosslinking agent of the following C1 was prepared.
C1: Hexakis (methoxymethyl) melamine (manufactured by Sanwa Chemical Co., Ltd., trade name "Nikalac MW-30HM")

The following compounds D1 to D4 and D'1 were prepared as the component (D).
D 1: 1, 1-Bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane D2: 1,1,1-tris (4-hydroxy) Phenyl) methane D3: 2,6-bis [(5-methyl-2-hydroxyphenyl) methyl] -4-methyl-1-hydroxybenzene D4: 1- (3-methyl-4-hydroxyphenyl) -4- ( 4-hydroxyphenyl) benzene D'1: novolac type phenol resin

An acrylic resin of E1 was prepared as the component (E).
Synthesis Example 2 Synthesis of Acrylic Resin E1 75 g of toluene and 75 g of isopropanol (IPA) were weighed into a 500 ml three-necked flask equipped with a stirrer, a nitrogen introducing pipe and a thermometer, and separately weighed butyl acrylate (BA) 85 g, lauryl acrylate (DDA) 24 g, acrylic acid (AA) 14 g, and 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate (trade name: FA-711 MM, Hitachi Chemical Co., Ltd.) 7.9 g of a polymerizable monomer, and 0.13 g of azobisisobutyronitrile (AIBN) were added. Nitrogen gas was flowed at a flow rate of 400 ml / min for 30 minutes while stirring at a stirring speed of about 270 rpm at room temperature to remove dissolved oxygen. Thereafter, the flow of nitrogen gas was stopped, the flask was sealed, and the temperature was raised to 65 ° C. in about 25 minutes in a thermostatic water bath. The polymerization reaction was carried out by maintaining the temperature for 14 hours to obtain an acrylic resin E1. The polymerization rate at this time was 98%. Also, the weight average molecular weight (MW) determined by standard polystyrene conversion of the GPC method of E1 is shown in Table 1.

FA-711 MM: 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate (manufactured by Hitachi Chemical Co., Ltd.)
BA: acrylic acid n-butyl DDA: lauryl acrylate AA: acrylic acid

As component (F), (F1): trimethylsulfonium methyl sulfate (manufactured by Fluorochem) was prepared.

As a component (H), a silane compound of H1 was prepared.
H1: 3-glycidoxypropyl trimethoxysilane (Shin-Etsu Silicone, trade name "KBM-403")

  As a component (I), I1: ethyl lactate was prepared.

(Examples 1 to 4 , Reference Examples 5 to 7, Comparative Examples 1 to 3)
The components (A) to (I) were blended at a predetermined ratio shown in Table 2. This solution was subjected to pressure filtration using a 3 [mu] m pore Teflon (registered trademark) filter to prepare solutions of photosensitive resin compositions of Examples 1 to 4 , Reference Examples 5 to 7, and Comparative Examples 1 to 3. In Table 2, a unit is a mass part unless otherwise specified.

<Evaluation of photosensitivity (sensitivity, resolution, developability and residue after development)>
The photosensitive resin compositions obtained in Examples 1 to 4 and Reference Examples 5 to 7 and Comparative Examples 1 to 3 are spin-coated on a silicon substrate, heated at 120 ° C. for 3 minutes, and the film thickness is about 12 to 14 μm. Was formed. Then, reduction projection exposure with i-line (365 nm) was performed through a mask using an i-line stepper (trade name "FPA-3000i" manufactured by Canon). After exposure, development was performed with a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH), and development was performed so that the residual film thickness was about 80 to 95% of the initial film thickness. Thereafter, it was rinsed with water to obtain a patterned resin film. The minimum exposure required for pattern formation was evaluated as sensitivity.
Moreover, about evaluation of developability (residue after image development), the presence or absence of the residue of an opening part was observed using SEM. The case where the residue is within 0.5 μm from the end face of the opening is A, the case 0.5 to 1 μm is B, and the case 1 μm or more is C.
In addition, for the evaluation of film loss after development, the residual film ratio of the unexposed area after development is 95% or more as A, less than 95% B as B, and less than 90% as C.
The results of the above photosensitive characteristics are shown in Table 2.

<Evaluation of pattern melt>
Using the vertical diffusion furnace (manufactured by Koyo Thermo Systems, trade name “μ-TF”), the patterned resin film is coated in nitrogen at a temperature of 175 ° C. (heating time 1.5 hours) for 2 hours using the method described above Was heated (cured) to obtain a cured film having a thickness of about 10 μm. The results are shown in Table 2.
Further, for the evaluation of the pattern melt, those having a minimum opening diameter after heat curing of less than 15 μm were designated as A, those having a minimum opening diameter of not less than 15 μm and less than 30 μm as B, and those having 30 μm or more as C.

<Evaluation of cured film physical properties (elongation at break and elastic modulus)>
The photosensitive resin compositions obtained in Examples 1 to 4 and Reference Examples 5 to 7 and Comparative Examples 1 to 3 are spin-coated on a silicon substrate, heated at 120 ° C. for 3 minutes, and the film thickness is about 12 to 14 μm. Was formed. The coating film was exposed at all wavelengths through a mask using a proximity exposure machine (trade name "PLA-600FA" manufactured by Canon). After exposure, development was performed using a 2.38% aqueous solution of TMAH to obtain a rectangular pattern of 10 mm width. Then, using a vertical diffusion furnace (manufactured by Koyo Thermo Systems, trade name "μ-TF"), the rectangular pattern is heat-treated in nitrogen at a temperature of 175 ° C (heating time 1.5 hours) for 2 hours (Curing) to obtain a cured film having a thickness of about 10 μm. The cured film with a thickness of about 10 μm obtained by the above method was peeled off from the silicon substrate, and the breaking elongation (EL) and elastic modulus (YM) of the peeled film were measured by “Autograph AGS-H100N” manufactured by Shimadzu Corporation. . The width of the sample was 10 mm, the film thickness was 9 to 11 μm, and the distance between the chucks was 20 mm. The pulling rate was 5 mm / min, and the measurement temperature was about room temperature (20 ° C. to 25 ° C.). The average of the measured values of five or more test pieces obtained from the cured film obtained under the same conditions was taken as "break elongation (EL)" and "elastic modulus (YM)". The obtained results are shown in Table 2.

In Examples 1 to 4 and Reference Examples 5 to 7 , the residue after development and the film reduction could be simultaneously suppressed. Further, in Examples 1 to 4 using the component (D1), it was possible to provide a photosensitive resin composition capable of simultaneously suppressing the pattern melt as well as the residue and film reduction after development. In Comparative Example 1 where the component (D) was not used in the example (D), the solubility of the resin film in an alkali developing solution was low, so the sensitivity was significantly reduced. Further, in Comparative Examples 2 and 3 in which D'1 was used instead of the component (D), it was not possible to achieve both the residue after development and the suppression of film loss.

  The photosensitive resin composition of the present invention can be used to form a surface protective layer and an interlayer insulating film of a semiconductor element mounted on an electronic device, and a rewiring layer of a semiconductor package.

  DESCRIPTION OF SYMBOLS 1 ... Semiconductor substrate, 2 ... Protective layer, 3 ... 1st conductor layer, 4 ... Interlayer insulating layer, 5 ... Photosensitive resin layer, 6A, 6B, 6C ... Window part, 7 ... 2nd conductor layer, 8 ... Surface protection Layers 11 interlayer insulating layer 12 wiring layer 13 insulating layer 14 surface protective layer 15 pad portion 16 rewiring layer 17 conductive ball 18 core 19 cover coat layer 20: barrier metal 21: color 22: underfill 23: silicon chip 24: connection portion 100, 200, 300, 400: structure, 500, 600, 700: semiconductor device

Claims (9)

(A) an alkali-soluble resin having a phenolic hydroxyl group,
(B) o-quinonediazide compounds,
(C) a thermal crosslinking agent,
(D) a phenolic low molecular weight compound,
(E) containing an acrylic resin,
(C) The thermal crosslinking agent is a compound represented by the following general formula (6),
(D) The phenolic low molecular weight compound is a compound represented by the following general formula (3),
(E) The acrylic resin has a structural unit represented by the following general formula (7) and a structural unit represented by the following general formula (8), and the composition ratio of the structural unit represented by the general formula (7) Is 60 to 90 mol% with respect to the total amount of the component (E), and the composition ratio of the structural units represented by the general formula (8) is 10 to 30 mol with respect to the total amount of the component (E) % der is,
The photosensitive resin composition which contains 5-35 mass parts of (D) components with respect to 100 mass parts of (A) components .

Wherein ^{(6), R} 31 ~R ³⁶ is an alkyl group having 1 to 10 carbon atoms independently. ]

[In Formula (3), R ¹ represents a hydrogen group or a methyl group. ac represents an integer of 0 to 3, df represents an integer of 1 to 3, the sum of a and d is 5 or less, and the sum of b and e is 5 or less; The total is 5 or less. ]

Wherein (7) and (8), ^{R 9} represents an alkyl group having 4 to 20 carbon ^{atoms, R 10} represents a hydrogen atom or a methyl group. ] The photosensitive resin composition according to claim 1, wherein the component (A) is a phenol resin. The photosensitive resin composition according to claim 1 or 2 , wherein the component (A) comprises a phenolic resin (A1) having no unsaturated hydrocarbon group and a modified phenolic resin (A2) having an unsaturated hydrocarbon group. . The photosensitive resin composition according to claim 3 , wherein the component (A2) is further modified by the reaction of a phenolic hydroxyl group and a polybasic acid anhydride. The photosensitive resin composition according to any one of claims 1 to 4 , further comprising (F) a thermal acid generator. A step of applying the photosensitive resin composition according to any one of claims 1 to 5 onto a substrate, drying the applied photosensitive resin composition to form a resin film, and exposing the resin film A method for producing a patterned cured film, comprising the steps of: developing the exposed resin film with an aqueous alkaline solution to form a patterned resin film; and heating the patterned resin film. The manufacturing method of the pattern cured film of Claim 6 whose heating temperature in the process of heating the said pattern resin film is 200 degrees C or less. The electronic component which has a pattern cured film of the photosensitive resin composition as described in any one of Claims 1-5 as an interlayer insulation layer or a surface protective film. The electronic component which has a pattern cured film of the photosensitive resin composition as described in any one of Claims 1 to 5 as a cover coat layer, a core, a color, or an underfill.

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