JP2018028690A - Photosensitive resin composition, method for producing patterned cured film, semiconductor device and electronic component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition that prevents the occurrence of residues during its development, that is, has excellent developability, and also has excellent contrast, and provide a method for producing a patterned cured film using the photosensitive resin composition, and an electronic component having the patterned cured film.SOLUTION: A photosensitive resin composition contains (A) an alkali-soluble resin having a phenolic hydroxyl group, (B) a compound that produces acid by light, (C) a heat crosslinker, and (D) a phenolic low-molecular-weight compound.SELECTED DRAWING: None

Description

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

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

JP 2003-215802 A JP 2007-079553 A

  On the other hand, with further higher integration, miniaturization, and miniaturization of semiconductor elements, the photosensitive resin composition can form a patterned cured film having a finer and more precise resist pattern (hereinafter also referred to as a pattern). It is demanded. In general, a method for producing a cured pattern film includes a step of drying a resin film formed by applying a photosensitive resin composition on a substrate, a step of exposing the resin film, and an exposed portion or an unexposed portion. It includes a developing step of removing with a developing solution and a step of curing the patterned resin film obtained by the development by heating. In the case of forming a fine and precise pattern as described above, there is a problem of pattern melting, in which the resin film melts and the shape of the pattern changes in the process of curing the pattern resin film by heating.

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 (for example, see Patent Document 2).
However, when the resin as in Patent Document 2 is used, there is a problem that a residue is generated in the opening of the pattern during development. If a residue is generated in the opening of the pattern, there is a possibility that the connectivity of the wiring formed after the pattern cured film is formed is lowered.
In order to suppress residues at the time of development, it is necessary to reduce the amount of the photosensitive agent. In this case, the dissolution rate of the unexposed portion with respect to the alkaline developer is increased, the film thickness is increased, and the contrast is lowered. In other words, it has been difficult to simultaneously achieve both development residue and film thickness reduction.

  Accordingly, the present invention has an object to provide a photosensitive resin composition that can suppress the occurrence of residues during development, that is, has excellent developability and good contrast, in order to solve such problems. . Moreover, this invention aims at providing the manufacturing method of the pattern cured film using 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層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 containing (A) an alkali-soluble resin having a phenolic hydroxyl group, (B) a compound that generates an acid by light, (C) a thermal crosslinking agent, and (D) a phenolic low-molecular compound. Resin composition.
[2] The photosensitive resin composition, wherein the component (D) is a compound represented by any one of the following general formulas (1) to (4).

(In formulas (1) to (4), R ^{1 to} R ⁴ each independently represents a hydrogen group or a methyl group. A to c, h and i represent integers of 0 to 3, and d to f represent 1 to 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) with respect 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, wherein the component (A) includes a phenol resin (A1) having no unsaturated hydrocarbon group and a modified phenol resin (A2) having an unsaturated hydrocarbon group.
[7] The photosensitive resin composition, wherein the component (A2) is further modified by a reaction between a phenolic hydroxyl group and a polybasic acid anhydride.
[8] The photosensitive resin composition, wherein the component (B) is an o-quinonediazide compound.
[9] The photosensitive resin composition further comprising (E) an acrylic resin.
[10] The photosensitive resin composition further comprising (F) a thermal acid generator.
[11] Applying the photosensitive resin composition on a substrate, drying the applied photosensitive resin composition to form a resin film, exposing the resin film, and the resin after exposure The manufacturing method of a pattern cured film containing the process of developing a film | membrane with aqueous alkali solution, forming the pattern resin film, and the process of heating the said pattern resin film.
[12] The method for producing a patterned cured film, wherein a 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 layer.
[14] An electronic component having a patterned cured film produced by the method for producing a patterned cured film as a cover coat layer, a core, a collar, or an underfill.

  According to the present invention, it is possible to suppress the generation of a residue during development, that is, to develop a photosensitive resin composition that is excellent in developability, has a good contrast, and has reduced film loss in an unexposed portion during development. Can be provided. Furthermore, the photosensitive resin composition of the present invention has good photosensitive properties (sensitivity and resolution) and mechanical properties (breaking elongation and elastic modulus). Moreover, this invention aims at providing the manufacturing method of the pattern cured film using the said photosensitive resin composition, and the electronic component which has the said pattern cured film.

It is a schematic sectional drawing explaining one Embodiment of the manufacturing process of a semiconductor device. It is a schematic sectional drawing explaining one Embodiment of the manufacturing process of a semiconductor device. It is a schematic sectional drawing explaining one Embodiment of the manufacturing process of a semiconductor device. It is a schematic sectional drawing explaining one Embodiment of the manufacturing process of a semiconductor device. It is a schematic sectional drawing explaining one Embodiment of the 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 “methacrylate” corresponding thereto. Similarly, “(meth) acryl” means “acryl” and “methacryl” corresponding thereto.

[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 that generates an acid by light, (C) a thermal crosslinking agent, and (D) a phenolic low And a molecular compound.

<(A) component: alkali-soluble resin having a phenolic hydroxyl group>
The component (A) is a resin having a phenolic hydroxyl group in the molecule and soluble in an alkali developer.
Here, one criterion that the component (A) is soluble in an alkaline aqueous solution will be described below. A resin solution obtained from the component (A) alone and an optional solvent, or the component (A), the component (B), the component (C), the component (D) and the optional solvent, which will be described below in order. Then, 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 tetramethylammonium hydroxide aqueous solution, metal hydroxide aqueous solution, and organic amine aqueous solution at 20-25 ° C. As a result, when it can be dissolved as a uniform solution, it is determined that the used component (A) is soluble in an 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 or a copolymer containing hydroxystyrene as a monomer unit, a phenol resin, poly (hydroxyamide), or the like. Examples thereof include polybenzoxazole precursors, poly (hydroxyphenylene) ether, polynaphthol and the like.

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

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

  Examples of the phenol derivative used for obtaining the phenol resin include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, and 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, aralkylphenols such as benzylphenol, Alkoxycarbonylphenol such as toxylcarbonylphenol, arylcarbonylphenol such as benzoyloxyphenol, halogenated phenol such as chlorophenol, polyhydroxybenzene such as catechol, resorcinol, pyrogallol, bisphenol such as bisphenol A and bisphenol F, α- or β A naphthol derivative such as naphthol; a hydroxyalkylphenol such as p-hydroxyphenyl-2-ethanol, p-hydroxyphenyl-3-propanol and p-hydroxyphenyl-4-butanol; a hydroxyalkylcresol such as hydroxyethylcresol; Ethylene oxide adducts; alcoholic hydroxyl group-containing phenols such as bisphenol monopropylene oxide adducts Carboxyl derivatives such as p-hydroxyphenylacetic acid, p-hydroxyphenylpropionic acid, p-hydroxyphenylbutanoic acid, p-hydroxycinnamic acid, hydroxybenzoic acid, hydroxyphenylbenzoic acid, hydroxyphenoxybenzoic acid, diphenol, etc. Examples thereof include phenol derivatives. Further, methylolated products of the above phenol derivatives such as bishydroxymethyl-p-cresol may be used as the phenol derivative.

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

  Examples of aldehydes used for obtaining a phenol 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, formyl acetic acid, methyl formyl acetate, 2-formylpropionic acid, methyl 2-formylpropionate and the like. Formaldehyde precursors such as paraformaldehyde and trioxane, and ketones such as acetone, pyruvic acid, repric acid, 4-acetylbutyric acid, acetonedicarboxylic acid, and 3,3′-4,4′-benzophenonetetracarboxylic acid May be used in the reaction. These are used singly or in combination of two or more.

  Examples of poly (hydroxystyrene) resins include polymerization (vinyl polymerization) in the presence of a catalyst (radical initiator) of an ethylenically unsaturated double bond of hydroxystyrene introduced with a protecting group, followed by deprotection. What is obtained by doing can be used. Commercially available branch type poly (hydroxystyrene) such as PHS-B (trade name, manufactured by DuPont) can also be used.

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

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

The component (A2) is generally a compound having phenol or a derivative thereof and an unsaturated hydrocarbon group (preferably having 4 to 100 carbon atoms) (hereinafter sometimes simply referred to as “unsaturated hydrocarbon group-containing compound”). Is a reaction product of a polycondensation product of aldehydes with a reaction product (hereinafter referred to as “unsaturated hydrocarbon group-modified phenol derivative”) or a reaction product of a phenol resin and an unsaturated hydrocarbon group-containing compound. .
As the phenol derivative used for obtaining the component (A2), the same phenol derivatives and aldehydes used for obtaining the 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 the adhesion of the pattern cured film and the 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 the flexibility of the cured film, the unsaturated hydrocarbon group-containing compound preferably has 8 to 80 carbon atoms, more preferably 10 to 60 carbon atoms. preferable.

  Examples of the unsaturated hydrocarbon group-containing compound include unsaturated hydrocarbons 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. . Suitable unsaturated fatty acids include crotonic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, erucic acid, nervonic acid, linoleic acid, α-linolenic acid, eleostearic acid, stearidone Examples include acids, arachidonic acid, eicosapentaenoic acid, sardine acid and docosahexaenoic acid. Among these, vegetable oils that are unsaturated fatty acid esters are particularly preferred.

  The vegetable oil is generally an ester of glycerin and an unsaturated fatty acid, and is an 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, Asa seed oil, cashew oil, potato oil, camellia oil, castor oil, and peanut oil. Examples of semi-drying oils include corn oil, cottonseed oil, and sesame oil. Examples of the drying oil include paulownia oil, linseed oil, soybean oil, walnut oil, safflower oil, sunflower oil, camellia 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 dry oil from the viewpoint of improving the adhesion, mechanical properties and thermal shock resistance of the pattern cured film. Among drying oils, tung oil, linseed oil, soybean oil, walnut oil, and safflower oil are more preferable, and tung oil and linseed oil are more preferable because the effects of the present invention can be more effectively and reliably exhibited. These vegetable oils are used alone or in combination of two or more.

  In preparing the component (A2), first, the phenol derivative and the unsaturated hydrocarbon group-containing compound are reacted to prepare an unsaturated hydrocarbon group-modified phenol derivative. The above reaction is usually preferably carried out at 50 to 130 ° C. The blending ratio of the phenol derivative and the unsaturated hydrocarbon group-containing compound is such that the flexibility of the pattern cured film can be improved, and therefore, the unsaturated hydrocarbon group-containing compound 1 to 100 with respect to 100 parts by mass of the phenol derivative. 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, p-toluenesulfonic acid, trifluoromethanesulfonic acid or the like may be used as a catalyst, if necessary.

  Next, the unsaturated hydrocarbon group-modified phenol derivative is reacted with an aldehyde to prepare a modified phenol resin having an unsaturated hydrocarbon group as component (A2). The reaction between the aldehydes and the unsaturated hydrocarbon group-modified phenol derivative is a polycondensation reaction, and conventionally known synthesis conditions for phenol resins can be used. The component (A2) is a polycondensation with aldehydes by combining a compound obtained by reacting the above-described phenol derivative with an unsaturated hydrocarbon group-containing compound and a compound other than phenol such as m-xylene. Can also be obtained. In addition, it is preferable that the unsaturated hydrocarbon group of (A2) component exists in ortho position or para position with respect to the phenolic hydroxyl group which a phenol resin has, and it is more preferable to exist in para position.

  Moreover, (A2) component can also be obtained by making the above-mentioned phenol resin and an unsaturated hydrocarbon group containing compound react. The reaction between the phenol resin and the unsaturated hydrocarbon group-containing compound is usually preferably performed at 50 to 130 ° C. Moreover, the blending ratio of the phenol derivative and the unsaturated hydrocarbon group-containing compound is such that the flexibility of the cured film can be improved, and the unsaturated hydrocarbon group-containing compound 1 to 100 parts by mass of the phenol resin. 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 or the like may be used as a catalyst. In addition, solvents, such as toluene, xylene, methanol, tetrahydrofuran, can be used for reaction.

  A phenol resin that is acid-modified by further reacting a polybasic acid anhydride with the phenolic hydroxyl group present in the component (A2) produced by the above method can also be used as the component (A2). Carboxy group is introduce | transduced by acid-modifying with a polybasic acid anhydride, and the solubility with respect to the aqueous alkali solution (developer) of (A2) component improves further.

  The polybasic acid anhydride is not particularly limited as long as it has an acid anhydride group formed by dehydration condensation of a carboxy group of a polybasic acid having a plurality of carboxy groups. Polybasic acid anhydrides include, for example, 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 methylhexahydrophthalic anhydride, nadic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, tetrabromophthalic anhydride and trimellitic anhydride, biphenyltetra Carboxylic dianhydride, naphthalene tetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyromellitic anhydride and benzophenone tetra Carboxylic acid aromatic tetracarboxylic acid dianhydride such as dianhydride. You may use these individually by 1 type or in combination of 2 or more types. Among these, the polybasic acid anhydride is preferably a dibasic acid anhydride, and more preferably at least one 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 between the phenolic hydroxyl group and 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, with respect to 1 mol of the phenolic hydroxyl group. More preferably, 2 to 0.4 mol is reacted. 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.

  In addition, you may contain a catalyst in the said reaction as needed from a viewpoint of performing reaction rapidly. Examples of the catalyst include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium 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 mgKOH / g, more preferably 40 to 170 mgKOH / g, and further preferably 50 to 150 mgKOH / g. . When the acid value is less than 30 mgKOH / g, it tends to require a longer time for alkali development than when the acid value is in the above range, and when it exceeds 200 mgKOH / g, the acid value is in the above range. In comparison with the above, the developer resistance of the unexposed portion tends to be lowered.

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

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

<(B) component: Compound that generates acid by light>
The compound which produces | generates an acid with the light which is (B) component is used as a photosensitive agent. The component (B) has a function of generating an acid by light irradiation and increasing the solubility of the light-irradiated portion in the alkaline aqueous 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, and triarylsulfonium salts. Of these, o-quinonediazide compounds are preferred because of their high sensitivity.

  The o-quinonediazide compound can be obtained, for example, by a method in which o-quinonediazidesulfonyl chloride is subjected to a condensation reaction in the presence of a dehydrochlorinating agent with a hydroxy compound or an amino compound.

  Examples of the o-quinonediazidesulfonyl 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- A sulfonyl chloride is mentioned.

  Examples of the hydroxy compound used in 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 ′, 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-dimethyli Deno [2,1-a] indene, tris (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1- [4- {1- ( 4-hydroxyphenyl) -1-methylethyl} phenyl] ethane.

  Examples of the amino compound used in the reaction include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 4,4 ′. -Diaminodiphenyl sulfide, o-aminophenol, m-aminophenol, p-aminophenol, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, Bis (3-amino-4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) Sulfone, bis (3-amino-4-hydroxypheny ) Hexafluoropropane, bis (4-amino-3-hydroxyphenyl) hexafluoropropane and the like.

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

  Examples of the dehydrochlorinating agent used in the reaction include sodium carbonate, sodium hydroxide, sodium hydrogen carbonate, potassium carbonate, potassium hydroxide, trimethylamine, triethylamine, pyridine and the like. Moreover, as a reaction solvent, dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, diethyl ether, N-methylpyrrolidone, or the like is used.

o-quinonediazidosulfonyl chloride and hydroxy compound and / or amino compound are blended so that the total number of moles of hydroxy group and amino group is 0.5 to 1 per mole of o-quinonediazidesulfonyl chloride. It is preferred that A preferred blending ratio of the dehydrochlorinating agent and o-quinonediazide sulfonyl chloride is in the range of 0.95 / 1 molar equivalent to 1 / 0.95 molar equivalent.

  The preferable reaction temperature of the above reaction is 0 to 40 ° C., and the preferable 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 increases and the sensitivity becomes better. From the viewpoint of suppressing residues after development, 5 to 50 parts by mass is more preferable, 5 to 30 parts by mass is further preferable, and 5 to 15 parts by mass is particularly preferable.

<(C) component: thermal crosslinking agent>
The thermal crosslinking agent as component (C) is a compound having a structure that can react with component (A) to form a bridge structure when the photosensitive resin film after pattern formation is cured by heating. Thereby, brittleness of the film and melting of the film can be prevented. 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 component (A) and the component (D) and has a crosslinking group with the component (A). Specific examples include those described later. Such a compound having a phenolic hydroxyl group is preferable not only as a thermal cross-linking 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. 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 preferably has about two benzene rings in the molecule. In consideration of the solubility in an aqueous alkali solution and the balance between the photosensitive properties and the cured film properties, the number average molecular weight is preferably 94 to 2,000, more preferably 108 to 2,000, and even 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, a conventionally known compound can be used, but the compound represented by the following general formula (5) is effective in promoting the dissolution of the exposed portion and melting during curing of the photosensitive resin film. This is particularly preferable because of the excellent balance of the effects to be prevented.

(In formula (5), X represents a single bond or a divalent organic group, R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represents a hydrogen atom or a monovalent organic group, and s and t are 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), the compound in which X is a single bond is a biphenol (dihydroxybiphenyl) derivative. Examples of the divalent organic group represented by X include alkylene groups having 1 to 10 carbon atoms such as methylene group, ethylene group and propylene group, alkylidene groups having 2 to 10 carbon atoms such as ethylidene group, and phenylene groups. An arylene group having 6 to 30 carbon atoms, such as a group in which some or all of the hydrogen atoms of these hydrocarbon groups are substituted 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.

  Examples of the compound having a hydroxymethylamino group include (poly) (N-hydroxymethyl) melamine, (poly) (N-hydroxymethyl) glycoluril, (poly) (N-hydroxymethyl) benzoguanamine, (poly) (N- And nitrogen-containing compounds obtained by alkyl etherifying all or part of active methylol groups such as hydroxymethyl) urea. Here, the alkyl group of the alkyl ether includes a methyl group, an ethyl group, a butyl group, or a mixture thereof, and may contain an oligomer component that is partially self-condensed. Specific examples include hexakis (methoxymethyl) melamine, hexakis (butoxymethyl) melamine, tetrakis (methoxymethyl) glycoluril, tetrakis (butoxymethyl) glycoluril, and tetrakis (methoxymethyl) urea.

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

  As component (C), in addition to the above, hydroxymethyl groups such as bis [3,4-bis (hydroxymethyl) phenyl] ether and 1,3,5-tris (1-hydroxy-1-methylethyl) benzene 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 A compound having an oxetanyl group, a compound having a vinyl group, or a blocked isocyanate compound 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, a compound having a phenolic hydroxyl group and a compound having a hydroxymethylamino group are preferable because the sensitivity and heat resistance can be further improved, and the resolution and elongation of the coating film can be further improved. More preferred are compounds having a hydroxymethylamino group, particularly preferred are compounds having an alkoxymethylamino group in which all or part of the hydroxymethylamino group has been alkyletherified, and alkoxymethyl in which all of the hydroxymethylamino group has been alkyletherified. Most preferred are compounds having an amino group.
Of the compounds having an alkoxymethylamino group obtained by alkyl etherifying all of the hydroxymethylamino groups, compounds represented by the following general formula (6) are preferred.

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

  The blending amount of the component (C) is such that the difference in dissolution rate between the exposed part and the unexposed part is increased, the sensitivity becomes better, and the characteristics of the cured film, relative to 100 parts by weight of the component (A) 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 this invention, a phenolic low molecular weight compound is contained as (D) component. Component (D) was added for the purpose of accelerating the dissolution rate of the resin film in the alkaline developer. (D) As a component, what has about 3-4 benzene rings in a molecule | numerator is preferable, and it is preferable that a weight average molecular weight is 200-990. 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。） From the viewpoint of the dissolution rate in an alkali developer, the component (D) is preferably a compound represented by any one of the following general formulas (1) to (4).

(In formulas (1) to (4), R ^{1 to} R ⁴ each independently represents a hydrogen group or a methyl group. A to c, h and i represent integers of 0 to 3, and d to f represent 1 to 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 are mentioned as a compound represented by 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 , 6-Trimethyl-2-hydroxyphenyl) -1- (2-hydroxyphenyl) methane, 1,1-bis (2,3,5-trimethyl-4-hydroxyphenyl) -1- (3-hydroxyphenyl) methane 1,1-bis (2,3,5-trimethyl-4-hydroxyphenyl) -1- (4-hydroxyphenyl) methane, 1,1-bis (3-methyl-4-hydroxyphenyl) -1- ( 2-hydroxyphenyl) 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- -Hydroxyphenyl) -1- (3,4-dihydroxyphenyl) methane, 1,1-bis (2,3,5-trimethyl-4-hydroxyphenyl) -1- (3,4-hydroxyphenyl) methane, , 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-bis (3,4,6-trimethyl-2-hydroxyphenyl) -1- (3-hydroxyphenyl) methane, 1,1-bis (3,4,6-trimethyl-2- Hydroxyphenyl) -1- (4-hydroxyphenyl) methane, 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-hydroxy Phenyl) methane, 1,1-bis (4-hydroxyphenyl) -1-benzylethane, 1,1-bis (4-hydroxyphenyl) -1-benzylmethane, 1- (4-hydroxyphenyl) -1- ( 3,4-dihydroxyphenyl) -1-benzylethane, 1,1-bis (3-methyl-4-hydroxyphenyl) -1-benzylethane, 1,1-bis (2, , 5-trimethyl-4-hydroxyphenyl) -1-benzylmethane, 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 individually by 1 type or in combination of 2 or more types.

  For example, the following compounds are mentioned as a compound represented by General formula (2). 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) L) methyl] -3,4-dimethyl-1-hydroxybenzene, 1,1-bis [3-{(5-methyl-2-hydroxyphenyl) methyl} -5-methyl-2-hydroxyphenyl] methane, , 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-methyl-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-trihydroxy) Enyl) -1-methylethyl] benzene, 1,4-bis [(3,5-dimethyl-4-hydroxyphenyl) methyl] benzene, 1,4-bis [(2,4,5-trimethyl-3-hydroxy) Phenyl) 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-hydroxy) Phenyl) -1-methylethyl] -1,3-dihydroxybenzene, 4,6-bis [1- (4-hydroxyphenyl) -1-methylethyl] -1,3-dihydroxy-2-methylben N, 1,3-bis [1- (2,4-dihydroxyphenyl) -1-methylethyl] benzene, 1,4-bis [1- (2,4-dihydroxyphenyl) -1-methylethyl] benzene. These compounds can be used individually by 1 type or in combination of 2 or more types.

  For example, the following compounds are mentioned as a compound represented by General formula (3). 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 individually by 1 type or in combination of 2 or more types.

  For example, the following compounds are mentioned as a compound represented by 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 individually by 1 type or in combination of 2 or more types.

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

  For example, when the content of the component (B) is reduced in order to suppress the residue after development, the effect of inhibiting dissolution of the unexposed portion of the resin film is reduced, and the film reduction after development is increased. By containing the compound represented by the formula (1) or (3), film loss could be effectively suppressed. This is because the dissolution rate of the compound represented by the general formula (1) or (3) in the alkaline developer is not too high, and as a result, the solubility of the unexposed portion of the resin film is the general formula (2) or (4). ) Is considered to be lower than when added.

  Furthermore, as the component (D), a compound represented by the general formula (3) is more preferable from the viewpoint that pattern melt can be further suppressed. This is considered to be 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 the pattern melt at the time of heat-hardening can be suppressed. It 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 the acrylic resin having the structural unit represented by the general formula (7) or (8), the thermal shock resistance can be improved while maintaining good photosensitive characteristics. (E) A component may consist only of 1 type of the said acrylic resin, and may contain 2 or more types.

(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.)

In the general formula (7), R ⁹ is preferably an alkyl group having 4 to 16 carbon atoms, more preferably an alkyl group having 4 carbon atoms, particularly an n-butyl group, from the viewpoint of improving sensitivity, resolution and thermal shock. preferable.

Examples of the polymerizable monomer that gives the structural unit represented by the general formula (7) include (meth) acrylic acid alkyl esters. Examples of the (meth) acrylic acid alkyl ester include compounds represented by the following general formula (9).
^{_{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. Examples of the alkyl group having 1 to 20 carbon atoms represented by R ¹² include 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. Examples of the polymerizable monomer represented by the general formula (9) include (meth) acrylic acid butyl ester, (meth) acrylic acid pentyl ester, (meth) acrylic acid hexyl ester, and (meth) acrylic acid heptyl. 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 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 are used singly 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 general formula (7) is preferably 50 to 95 mol%, and 60 to 90 mol% with respect to the total amount of the component (E). More preferably, it is particularly 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 general formula (8) is preferably 5 to 35 mol% with respect to the total amount of the component (E). More preferably, 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 can be 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。） From the viewpoint of further improving the compatibility with the component (A), the adhesion of the patterned cured film to the substrate, the mechanical properties and the thermal shock resistance, the component (E) is represented by the general formula (7). It is more preferable to contain the acrylic resin which has a structural unit, the structural unit represented by said (8), and the structural unit represented by following General formula (10). When the component (E) is the acrylic resin, the interaction between the component (E) and the alkali-soluble resin (A) having a phenolic hydroxyl group 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 that gives the structural unit represented by the general formula (10) include aminoethyl (meth) acrylate, N-methylaminoethyl (meth) acrylate, and 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-eth 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 Methylpiperidin-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 are used alone or in combination of two or more. Among these, from the viewpoint of further improving 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 group represented by the following general formula (11). Particularly preferred is an organic group.

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

In the general formula (10), R ¹³ is a polymerizable monomer that gives a structural unit represented by a monovalent organic group represented by the general formula (11). For example, piperidin-4-yl (meta ) Acrylate, 1-methylpiperidin-4-yl (meth) acrylate, 2,2,6,6-tetramethylpiperidin-4-yl (meth) acrylate, 1,2,2,6,6-pentamethylpiperidine- Examples include 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 FA-711MM, and 2,2,6,6-tetramethylpiperidin-4-yl methacrylate is FA-712HM. (Both manufactured by Hitachi Chemical Co., Ltd.) are commercially available.

  In the acrylic resin as the component (E), the composition ratio of the structural unit represented by the 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） Moreover, (E) component is represented by the structural unit represented by the said General formula (7), the structural unit represented by the said General formula (8), and the following general formula (12) from a viewpoint which can improve a sensitivity more. It is preferable to contain an acrylic resin having a structural unit. Such an acrylic resin may further have a structural unit represented by the general formula (10).

In (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} represents an alkyl group having 1 to 6 carbon atoms each independently , P is an integer from 1 to 100)

  Examples of the polymerizable monomer that gives the structural unit represented by the general formula (12) include methacryl-modified silicone oil, and X-22-174DX, X-22-2426, X-22-2475 (any Are also commercially available as Shin-Etsu Chemical Co., Ltd.).

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

  Moreover, the polymerizable monomer used for the synthesis | combination of the acrylic resin which comprises (E) component is 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. Examples of such a polymerizable monomer include styrene, α-methylstyrene, (meth) acrylic acid benzyl ester, (meth) acrylic acid 4-methylbenzyl ester, (meth) acrylic acid 2-hydroxyethyl ester, Esters of vinyl alcohol such as (meth) acrylic acid 2-hydroxypropyl ester, (meth) acrylic acid 3-hydroxypropyl ester, (meth) acrylic acid 4-hydroxybutyl ester, acrylonitrile, 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) a Crylic 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 monoesters such as fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, and propiolic acid. These polymerizable monomers are used alone or in combination of two or more.

  (E) It is preferable that the weight average molecular weights of a component are 2,000-100,000, It is more preferable that it is 3,000-60,000, It is further more preferable that it is 4,000-50,000. . 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 viewpoints 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 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 aid as necessary. it can.

<Other components (F): Thermal acid generator>
The photosensitive resin composition of the present invention may contain (F) a thermal acid generator. Component (F) is a compound that generates an acid by heat and can further suppress ants and pattern melt. This is because an acid can be generated when the photosensitive resin film after development is heated, and the reaction between the component (A) and the component (C), that is, the thermal crosslinking reaction starts from a lower temperature. This is because the melt of the pattern due to is suppressed more. In addition, since many of the components (F) can generate an acid even when irradiated with light, the use of such a component can increase the solubility of the exposed portion in an alkaline aqueous solution. Therefore, the difference in solubility in the alkaline aqueous solution between the unexposed area and the exposed area is further increased, thereby improving the resolution. 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 with such a heat | fever produces | generates an acid by heating to the temperature of 50-200 degreeC, for example. Specific examples of the compound that generates an acid by heat include a strong acid and a base such as an onium salt that is different from the compound that generates an acid by the light of the component (B) and has a function of generating an acid by heat. And salts formed from imide sulfonate.

  Examples of such an onium salt include diaryliodonium salts such as aryldiazonium salts and diphenyliodonium salts; diaryliodonium salts and di (alkylaryl) iodonium salts such as di (t-butylphenyl) iodonium salts; trimethylsulfonium A trialkylsulfonium salt such as a salt; a dialkylmonoarylsulfonium salt such as a dimethylphenylsulfonium salt; a diarylmonoalkyliodonium salt such as a diphenylmethylsulfonium salt; and a triarylsulfonium salt. Among these, di (t-butylphenyl) iodonium salt of paratoluenesulfonic 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 Preferred examples include dimethylphenylsulfonium salt and diphenylmethylsulfonium salt of toluenesulfonic acid.

  Among these, a sulfonium salt represented by the following general formula (13) is preferable, a trialkylsulfonium salt of methanesulfonic acid is more preferable, and a trimethylsulfonium salt is 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, a sulfonium salt represented by the following general formula (13) is preferable, a trialkylsulfonium salt of methanesulfonic acid is more preferable, and a trimethylsulfonium salt is particularly preferable.

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

  As the imide sulfonate, for example, naphthoyl imide sulfonate or phthalimide sulfonate can be used.

  (F) 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, 0.2-20 mass parts is more preferable. 3-10 mass parts is more preferable.

<Other components (G): Elastomer>
In the present invention, an elastomer can be used in combination. Thereby, the obtained resist pattern becomes further excellent in terms of flexibility, and the mechanical characteristics and thermal shock resistance of the resist pattern can be further improved. A conventionally known elastomer can be used as the elastomer, but the glass transition temperature (Tg) of the polymer constituting the elastomer is preferably 20 ° C. or lower.

  Examples of such elastomers include styrene elastomers, olefin elastomers, urethane elastomers, polyester elastomers, polyamide elastomers, and silicone elastomers. The elastomer may be a fine particle elastomer. These elastomers can be used alone 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 this invention may contain the silane compound which has an epoxy group represented by General formula (14) as (H) component from a viewpoint of improving adhesiveness with a board | substrate.

(In formula (14), R ³ represents a divalent organic group, and 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 easily available and improving the adhesion to the substrate. Examples of such compounds include 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane.

  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). Examples of such silane compounds include ureidopropyltriethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, urea propyltriethoxysilane, and methylphenylsilanediol. , Ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butylsiphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, ethylmethylphenylsilanol, n-propyl Methylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol Tert-butylmethylphenylsilanol, ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n- Propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, phenylsilanetriol, 1,4-bis (trihydroxysilyl) benzene, 1,4-bis (methyldihydroxysilyl) Benzene, 1,4-bis (ethyldihydroxysilyl) benzene, 1,4-bis (propyldihydroxy) Silyl) benzene, 1,4-bis (butyldihydroxysilyl) benzene, 1,4-bis (dimethylhydroxysilyl) benzene, 1,4-bis (diethylhydroxysilyl) benzene, 1,4-bis (dipropyldroxy) Silyl) benzene, 1,4-bis (dibutylhydroxysilyl) benzene and the like. These silane compounds are used alone or in combination of two or more.

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

<Other components (I): Solvent>
The photosensitive resin composition of this invention may contain the (I) solvent from a viewpoint that the applicability | paintability on a board | substrate and the resin film of uniform thickness can be formed. Specific examples of the solvent include γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, 3-methylmethoxypropionate, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphorylamide, tetramethylene sulfone, diethyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene Examples include glycol monobutyl ether and dipropylene glycol monomethyl ether. These solvents can be used alone or in combination of two or more.
Although content in the case of containing (I) component is not specifically limited, It is preferable to adjust so that the ratio of the solvent in the photosensitive resin composition may be 20-90 mass%.

<Other components (J): Dissolution 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 the pattern resin film is developed with an alkaline aqueous solution, thereby improving the sensitivity and resolution. A conventionally well-known thing can be used as a dissolution promoter. Specific examples thereof include compounds having a carboxyl group, a sulfonic acid, and a sulfonamide group.
The content in the case of containing such a dissolution accelerator can be determined by the dissolution rate of the pattern resin film in the alkaline aqueous solution. For example, the content is 0.01 to 30 with respect to 100 parts by mass of the component (A). It is preferable to set it as a mass part.

<Other components (K): Dissolution inhibitor>
The photosensitive resin composition of the present invention may contain (K) a dissolution inhibitor. The (K) dissolution inhibitor is a compound that inhibits the solubility of the component (A) in an alkaline aqueous solution, and is used to control the remaining film thickness, development time, and contrast. Specific examples thereof include diphenyliodonium nitrate, bis (p-tert-butylphenyl) iodonium nitrate, diphenyliodonium bromide, diphenyliodonium chloride, diphenyliodonium iodide and the like. In the case of containing a dissolution inhibitor, the content is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the total amount of the component (A), from the viewpoint of sensitivity and an allowable range of development time, and 0.01 to 15 mass parts is more preferable, and 0.05-10 mass parts is further 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 such as striation (film thickness unevenness) can be prevented, and developability can be improved. Examples of such a surfactant or leveling agent include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene octylphenol ether. Commercially available products include Megafax F171, F173, R-08 (Dainippon Ink Chemical Co., Ltd., trade name), Fluorard FC430, FC431 (Sumitomo 3M Co., Ltd., trade name), organosiloxane polymers KP341, KBM303, KBM803. (Trade 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 tetramethylammonium hydroxide (TMAH). Furthermore, by using the above-described photosensitive resin composition, it is possible to form a patterned cured film having good adhesion and crack resistance in a thermal shock cycle. Moreover, the pattern cured film which consists of the photosensitive resin composition of this invention has a favorable photosensitive characteristic (sensitivity and resolution), and has sufficient mechanical characteristics (breaking elongation and elastic modulus).

  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 usually comprises a step of forming a photosensitive resin film by applying and drying the photosensitive resin composition on a support substrate (film formation step), and A step of exposing the photosensitive resin film (exposure step), a step of developing the exposed photosensitive resin film with an alkaline aqueous solution to form a pattern resin film (developing step), and heating the pattern resin film Process (heating process).

<Film formation process>
In the film formation process, the photosensitive resin composition described above is spin-coated using a spinner or the like on a support substrate such as a glass substrate, a semiconductor, a metal oxide insulator (eg, TiO ₂ , SiO _2, etc.), silicon nitride, or the like. To do. The applied photosensitive resin composition is dried by heating using a hot plate, oven or the like. Thereby, the 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 actinic rays such as ultraviolet rays, visible rays, and radiations through a mask. Since the component (A) has high transparency to i-line, i-line irradiation can be suitably used. In addition, after exposure, post-exposure heating (PEB) can be performed as necessary. The post-exposure heating temperature is preferably 70 ° C. to 140 ° C., and the post-exposure heating time is preferably 1 minute to 5 minutes.

<Development process>
In the development process, the photosensitive resin film is patterned by removing the exposed portion of the photosensitive resin film after the exposure process with a developer. As the developer, for example, an alkaline aqueous solution such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide (TMAH) is preferably 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 developer and used. Each of these can be blended in the 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 referred to as a pattern 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 referred to as a pattern cured film. The heating temperature is preferably 250 ° C. or lower, more preferably 225 ° C. or lower, and further preferably 140 to 200 ° C. from the viewpoint of sufficiently preventing damage to the electronic device due to heat. The heat treatment can be performed using 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. In addition, either air or an inert atmosphere such as nitrogen can be selected. However, it is preferable to perform the process under nitrogen because the oxidation of the pattern can be prevented. Since the above-mentioned desirable heating temperature range is lower than the conventional heating temperature, damage to the support substrate and the electronic device can be suppressed to a small level. Therefore, electronic devices can be manufactured with a high yield by using the resist pattern manufacturing method of the present embodiment. It also leads to energy savings in 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 or the like is small, it is possible to prevent a reduction in dimensional accuracy.

  The heating time in the heating step may be a time sufficient for the photosensitive resin composition to cure, but is preferably approximately 5 hours or less in view of work efficiency. In addition to the oven described above, the heating can also be performed using a microwave curing device or a frequency variable microwave curing device. By using these apparatuses, it is possible to effectively heat only the photosensitive resin film while keeping the temperature of the substrate and the electronic device at, for example, 200 ° C. or lower.

  In the variable frequency microwave curing apparatus, the microwave is irradiated in pulses while changing its frequency, so that standing waves can be prevented and the substrate surface can be heated uniformly. In addition, when a metal wiring is included as an electronic device to be described later as a substrate, if microwaves are applied in a pulsed manner while changing the frequency, discharge from the metal can be prevented and the electronic device is protected from destruction. This is preferable. Furthermore, it is preferable to heat using a frequency-variable microwave because the cured film properties do not deteriorate even when 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 frequency variable microwave is generally in the range of 0.5 to 20 GHz, but is practically preferably in the range of 1 to 10 GHz, and more preferably in the range of 2 to 9 GHz. In addition, it is desirable to continuously change the frequency of the microwave to be irradiated, but actually the irradiation is performed by changing the frequency stepwise. At that time, the shorter the time for irradiating a single-frequency microwave, the less likely it is to generate a standing wave or a metal discharge. Therefore, the irradiation time is preferably 1 millisecond or less, particularly preferably 100 microseconds or less.

  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, practically preferably 100 to 1000 W, more preferably 100 to 700 W, further preferably 100 to 700 W. 500 W is most preferred. If the output is less than 10 W, it is difficult to heat the object to be heated in a short time, and if it exceeds 2000 W, a rapid temperature rise tends to occur.

  It is preferable to irradiate the microwave by turning it on / off in a pulsed manner. By irradiating the microwaves in a pulsed manner, it is preferable in that the set heating temperature can be maintained and damage to the cured film and the substrate can be avoided. Although the time for irradiating the pulsed microwave at one time varies depending on the conditions, it is preferably about 10 seconds or less.

  According to the above method for producing a cured pattern film, a photosensitive resin composition having good photosensitive characteristics can be obtained, and a patterned cured film having a good pattern shape can be obtained. By using the photosensitive resin composition according to this embodiment, curing can be performed even at a low temperature of 200 ° C. or lower in the above heating step that conventionally required 300 ° C. or higher. Furthermore, the pattern cured film formed from the photosensitive resin composition of the present invention has a high glass transition temperature. Therefore, it becomes a pattern cured film excellent in heat resistance. As a result, an electronic device such as a semiconductor device having excellent reliability can be obtained with high yield and high yield.

[Semiconductor device manufacturing process]
Next, as an example of the method for producing a cured pattern film according to the present invention, a process for producing a semiconductor device will be described with reference to the drawings. 1 to 5 are schematic sectional views showing an embodiment of a manufacturing process of a semiconductor device having a multilayer wiring structure.

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

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

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

  Furthermore, the 2nd conductor layer 7 is formed in the part corresponding to the window part 6B, and the structure 400 shown in FIG. 4 is obtained. A known photolithography technique can be used to form the second conductor layer 7. As a result, the second conductor layer 7 and the first conductor layer 3 are electrically connected.

  Finally, the surface protective 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 on the interlayer insulating layer 4 and the second conductor layer 7 by spin coating, and dried to form a photosensitive resin film. Next, after light irradiation through a mask on which a pattern corresponding to the window 6C is drawn at a predetermined portion, the photosensitive resin film is patterned by developing with an alkaline aqueous solution. 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 is excellent in reliability.

  In the above-described embodiment, the method for manufacturing a semiconductor device having a two-layer wiring structure is shown. However, when a multilayer wiring structure having three or more layers is formed, the above steps are repeated to form each layer. Can do. That is, it is possible to form a multilayer pattern by repeating each step of forming the interlayer insulating layer 4 and each step of forming the surface protective layer 8. 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 various structures developed in recent years. 6 and 7 show a 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. A semiconductor device 600 shown in FIG. 6 includes a silicon chip 23, an interlayer insulating layer 11 provided on one side of the silicon chip 23, and an Al having a pattern including a pad portion 15 formed on the interlayer insulating layer 11. A wiring layer 12, an insulating layer 13 (for example, a P-SiN layer) and a surface protective layer 14, which are sequentially stacked on the interlayer insulating layer 11 and the Al wiring layer 12 while forming an opening on the pad portion 15, and a surface protective layer 14 in contact with the pad portion 15 in the openings of the insulating layer 13 and the surface protective layer 14 and the surface of the core 18 opposite to the surface protective layer 14. And a rewiring layer 16 extending on the surface protective layer 14. Further, the semiconductor device 600 is formed so as to cover the surface protective layer 14, the core 18, and the rewiring layer 16, and a cover coat layer 19 in which an opening is formed in a portion of the rewiring layer 16 on the core 18. The conductive ball 17 connected to the rewiring layer 16 with the barrier metal 20 interposed therebetween in the opening of the layer 19, the collar 21 that holds the conductive ball, and the cover coat layer 19 around the conductive ball 17 are provided. The underfill 22 is provided. The conductive ball 17 is used as an external connection terminal and is 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 one embodiment of a semiconductor device. In the semiconductor device 700 of FIG. 7, an Al wiring layer (not shown) and a pad portion 15 of the Al wiring layer are formed on the silicon chip 23, and an insulating layer 13 is formed on the Al wiring layer. A surface protective layer 14 is formed. A rewiring layer 16 is formed on the pad portion 15, and the rewiring layer 16 extends to an upper portion of the connection portion 24 with the conductive ball 17. Further, a cover coat layer 19 is formed on the surface protective layer 14. The rewiring layer 16 is connected to the conductive ball 17 through the barrier metal 20.

  6 and 7, the above-described photosensitive resin composition 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. Can be used as a material for. The cured body using the photosensitive resin composition described above is excellent in adhesiveness with metal layers (for example, Cu, Au, Ni, Ti, etc.) such as the Al wiring layer 12 and the rewiring layer 16, sealants, Since the stress relaxation effect is also high, a semiconductor device in which this cured body is used for the surface protective layer 14, the cover coat layer 19, the core 18, the collar 21 such as solder, the underfill 22 used in a flip chip or the like is extremely reliable. It will be 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 film 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 of 200 ° C. or lower is possible in the heat treatment step that conventionally required 300 ° C. or higher. In the heat treatment step, the heating temperature is preferably 100 ° C to 200 ° C, more preferably 150 ° C to 200 ° C. Furthermore, since the photosensitive resin composition of the present invention has a small volume shrinkage (curing shrinkage) in the heat treatment step found in photosensitive polyimide and the like, it can prevent a reduction in dimensional accuracy. The pattern cured film which consists of the photosensitive resin composition of this invention has a high glass transition temperature. Accordingly, the surface protective layer and the interlayer insulating layer are excellent in heat resistance. As a result, an electronic component such as a semiconductor device having excellent reliability can be obtained with high yield and high yield.

  As mentioned above, although preferred embodiment of this invention was described, this invention is not restrict | limited to this.

  Hereinafter, the present invention will be described more specifically with reference to 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 = 13,000, 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 an unsaturated hydrocarbon group having 4 to 100 carbon atoms 100 parts by mass of phenol, 43 parts by mass of linseed oil and 0.1 part by mass of trifluoromethanesulfonic acid Were mixed and stirred at 120 ° C. for 2 hours to obtain a vegetable oil-modified phenol derivative (a). Next, 130 g of the 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. Subsequently, after heating up to 120 degreeC and stirring under reduced pressure for 3 hours, 29 g of succinic anhydride and 0.3 g of triethylamine were added to the reaction liquid, and it stirred at 100 degreeC under atmospheric pressure for 1 hour. The reaction solution was cooled to room temperature to obtain a phenol resin (hereinafter referred to as A2) modified with a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms (acid value: 120 mgKOH / g). . The weight average molecular weight calculated | required by standard polystyrene conversion of this GPC method of A2 was about 25,000.

As the component (B), the following B1 was prepared.
B1: 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane 1-naphthoquinone-2-diazide-5-sulfonic acid Esters (Esterification rate of about 90%, manufactured by AZ Electronic Materials, trade name “TPPA528”)

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

As the component (D), the following compounds D1 to D4 and D′ 1 were prepared.
D1: 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 phenolic resin

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

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

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

As the component (H), a silane compound of H1 was prepared.
H1: 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicone, trade name “KBM-403”)

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

(Examples 1-7, Comparative Examples 1-3)
(A)-(I) component was mix | blended in the predetermined ratio displayed on Table 2. This solution was pressure filtered using a 3 μm pore Teflon (registered trademark) filter to prepare solutions of the photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3. In Table 2, unless otherwise specified, the unit is parts by mass.

<Evaluation of photosensitive characteristics (sensitivity, resolution, developability and residue after development)>
The photosensitive resin compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 3 were spin coated on a silicon substrate and heated at 120 ° C. for 3 minutes to form a coating film having a thickness of about 12 to 14 μm. . Next, reduction projection exposure was performed with i-line (365 nm) through a mask using an i-line stepper (trade name “FPA-3000i” manufactured by Canon). After the exposure, development was performed with a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH), and development was performed so that the remaining film thickness was about 80 to 95% of the initial film thickness. Then, it rinsed with water and obtained the pattern 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 the opening part was observed using SEM. The case where the residue was within 0.5 μm from the end face of the opening was designated as A, the case where it was 0.5-1 μm was designated as B, and the case where the residue was 1 μm or more was designated as C.
Regarding the evaluation of film loss after development, the remaining film ratio of the unexposed part after development was 95% or more as A, less than 95% 90% or more 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 (trade name “μ-TF”, manufactured by Koyo Thermo System), the pattern resin film was coated in the above method for 2 hours at a temperature of 175 ° C. (temperature increase time: 1.5 hours). Was heat-treated (cured) to obtain a cured film having a thickness of about 10 μm. The results are shown in Table 2.
Regarding the evaluation of the pattern melt, A having a minimum opening diameter after heat curing of less than 15 μm is A, B having a minimum opening of 15 μm to less than 30 μm, and C having a minimum opening of 30 μm or more.

<Evaluation of cured film properties (elongation at break and elastic modulus)>
The photosensitive resin compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 3 were spin coated on a silicon substrate and heated at 120 ° C. for 3 minutes to form a coating film having a thickness of about 12 to 14 μm. . 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 10 mm wide rectangular pattern. Then, the rectangular pattern was heated in a vertical diffusion furnace (product name “μ-TF”, manufactured by Koyo Thermo System) 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 having a thickness of about 10 μm obtained by the above method was peeled off from the silicon substrate, and the elongation at break (EL) and elastic modulus (YM) of the peeled film were measured by “Autograph AGS-H100N” manufactured by Shimadzu Corporation. . The sample width was 10 mm, the film thickness was 9 to 11 μm, and the distance between chucks was 20 mm. The pulling speed 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 defined as “breaking elongation (EL)” and “elastic modulus (YM)”. The obtained results are shown in Table 2.

  In Examples 1 to 7, residues after development and film loss could be suppressed simultaneously. Furthermore, in Examples 1 to 4 using the component (D1), it was possible to provide a photosensitive resin composition capable of simultaneously suppressing pattern melt in addition to residues after development and film reduction. In Comparative Example 1 in which the component of Example (D) was not used, the sensitivity of the resin film was greatly reduced because the solubility of the resin film in the alkaline developer was low. In Comparative Examples 2 and 3 in which D'1 was used instead of the component (D), it was impossible to achieve both the residue after development and the suppression of film loss.

  The photosensitive resin composition of this invention can be used for formation of the surface protection layer and interlayer insulation film of the semiconductor element mounted in an electronic device, and the rewiring layer of a semiconductor package.

  DESCRIPTION OF SYMBOLS 1 ... Semiconductor substrate, 2 ... Protective layer, 3 ... 1st conductor layer, 4 ... Interlayer insulation layer, 5 ... Photosensitive resin layer, 6A, 6B, 6C ... Window part, 7 ... 2nd conductor layer, 8 ... Surface protection 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 ... collar, 22 ... underfill, 23 ... silicon chip, 24 ... connection part, 100, 200, 300, 400 ... structure, 500, 600, 700 ... semiconductor device.

Claims (14)

(A) an alkali-soluble resin having a phenolic hydroxyl group;
(B) a compound that generates an acid by light;
(C) a thermal crosslinking agent;
(D) The photosensitive resin composition containing a phenolic low molecular weight compound. (D) The photosensitive resin composition of Claim 1 whose component is a compound represented by either of General formula (1)-(4).

(In formulas (1) to (4), R ^{1 to} R ⁴ each independently represents a hydrogen group or a methyl group. A to c, h and i represent integers of 0 to 3, and d to f represent 1 to 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.)   (D) The photosensitive resin composition of Claim 1 or 2 whose component is a compound represented by General formula (1) or (3).   The photosensitive resin composition as described in any one of Claims 1 thru | or 3 which contains 5-35 mass parts of (D) component with respect to 100 mass parts of (A) component.   The photosensitive resin composition as described in any one of Claims 1 thru | or 4 whose (A) component is a phenol resin.   The component (A) includes a phenol resin (A1) having no unsaturated hydrocarbon group and a modified phenol resin (A2) having an unsaturated hydrocarbon group, according to any one of claims 1 to 5. Photosensitive resin composition.   The photosensitive resin composition according to claim 6, wherein the component (A2) is further modified by a reaction between a phenolic hydroxyl group and a polybasic acid anhydride.   The photosensitive resin composition according to any one of claims 1 to 7, wherein the component (B) is an o-quinonediazide compound.   (E) The photosensitive resin composition as described in any one of Claims 1 thru | or 8 which further contains an acrylic resin.   (F) The photosensitive resin composition as described in any one of Claim 1 thru | or 9 which further contains a thermal acid generator.   The process of apply | coating the photosensitive resin composition as described in any one of Claim 1 thru | or 10 on a board | substrate, drying the apply | coated photosensitive resin composition and forming a resin film, and exposing the said resin film And a step of developing the resin film after exposure with an alkaline aqueous solution to form a pattern resin film, and a step of heating the pattern resin film.   The manufacturing method of the pattern cured film of Claim 11 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 manufactured by the manufacturing method of the pattern cured film of Claim 11 as an interlayer insulation layer or a surface protective layer.   The electronic component which has a pattern cured film manufactured by the manufacturing method of the pattern cured film of Claim 11 as a cover coat layer, a core, a color | collar, or an underfill.

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