JP2014010156A - Photosensitive resin composition, method for producing pattern cured film using the same and electronic component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition capable of forming a pattern cured film having satisfactory adhesion to various substrates and developable with an alkali aqueous solution, a method for producing a pattern cured film using the same, and an electronic component.SOLUTION: The photosensitive resin composition comprises: (A) an alkali soluble resin; (B) a compound producing acid with light; (C) a thermal crosslinking agent; and (D) an imidazole silane compound. The method for producing a pattern cured film comprises: a step of applying the photosensitive resin composition to the surface of a substrate and drying to form a photosensitive resin film; a step of exposing the photosensitive resin film; a step of developing the photosensitive resin film with an alkali aqueous solution after the exposure to form a pattern resin film; and a step of heating the pattern resin film.

Description

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

  With the high integration, miniaturization and miniaturization of semiconductor elements, the photosensitive resin composition used for forming the surface protective layer, interlayer insulating layer and rewiring layer of the semiconductor element has better sensitivity and resolution. In addition, it is required that a finer and more precise pattern cured 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 (for example, see Patent Document 1). Such a photosensitive resin composition has an advantage that it can be cured by heating at a low temperature in a process of heating and curing a patterned resin film formed through exposure and development.

JP 2003-215802 A JP 2010-256508 A

  Further, in recent years, with the high integration and miniaturization of semiconductor elements, the surface area of wiring made of gold, copper, Ni, or the like has increased with respect to the surface area of the semiconductor elements. Therefore, the photosensitive resin composition used for forming the surface protective layer, the interlayer insulating layer, and the rewiring layer of the semiconductor element needs to have excellent adhesion to these wirings. However, conventional photosensitive resin compositions have not always had sufficient adhesion to wiring. Therefore, a method of using two types of resins having phenolic hydroxyl groups has been proposed (see, for example, Patent Document 2).

  However, photosensitive resin compositions that have been developed so far have excellent mechanical properties, but adherends such as gold (Au), copper (Cu), titanium (Ti), and silicon (Si) ( Regardless of the type of substrate), it was difficult to achieve good adhesion.

  Therefore, the present invention provides a pattern having good photosensitive properties (sensitivity and resolution), sufficient mechanical properties (breaking elongation and elastic modulus), and good adhesion to various substrates (adherents). It is an object of the present invention to provide a photosensitive resin composition that can form a cured film and can be developed with an alkaline aqueous solution. Moreover, this invention aims at providing the manufacturing method of the pattern cured film using the photosensitive resin composition, and the electronic component obtained by it.

  The present invention relates to a photosensitive resin composition containing (A) an alkali-soluble resin, (B) a compound that generates an acid by light, (C) a thermal crosslinking agent, and (D) an imidazolesilane compound.

  The photosensitive resin composition according to the present invention can form a cured pattern film having good adhesion to various substrates. The photosensitive resin composition can be developed with an aqueous alkaline solution. Moreover, it is preferable that (D) imidazolesilane compound is a compound containing a hydroxyl group.

  The component (A) may be a phenol resin. (A) The component may contain the phenol resin (A1) which does not have an unsaturated hydrocarbon group, and the modified phenol resin (A2) which has an unsaturated hydrocarbon group. The component (A2) may be a modified phenol resin that is further modified by a reaction between a phenolic hydroxyl group and a polybasic acid anhydride.

  The component (B) may be an o-quinonediazide compound.

  The photosensitive resin composition according to the present invention may further contain (E) a silane compound represented by the following general formula (1).

In general formula (1), R ¹ represents a divalent organic group, R ² represents a monovalent organic group, and a plurality of R ² in the same molecule may be the same or different.

  The photosensitive resin composition according to the present invention may further contain (F) an acrylic resin.

  The present invention also includes a step of coating and drying the photosensitive resin composition on a substrate to form a photosensitive resin film, a step of exposing the photosensitive resin film, and a step of exposing the photosensitive resin film to an alkali. The present invention relates to a method for producing a cured pattern film, comprising: developing with an aqueous solution to form a patterned resin film; and heating the patterned resin film.

  Furthermore, this invention relates to the electronic component which has a pattern cured film obtained by the said manufacturing method as a surface protective layer, an interlayer insulation layer, a cover coat layer, a core, a color | collar, or an underfill.

  ADVANTAGE OF THE INVENTION According to this invention, it is possible to form the pattern cured film which has favorable adhesiveness irrespective of the kind of board | substrate, and can provide the photosensitive resin composition which can be developed with alkaline aqueous solution. In addition, the patterned cured film made of the photosensitive resin composition of the present invention exhibits excellent adhesion, has good photosensitive properties (sensitivity and resolution), and has sufficient mechanical properties (breaking elongation and elastic modulus). Have Since the photosensitive resin composition of the present invention can be cured at a low temperature, the electronic component can be prevented from being damaged by heat, and a highly reliable electronic component can be provided with a high yield.

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, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the present specification, “(meth) acrylate” 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 embodiment contains (A) an alkali-soluble resin, (B) a compound that generates an acid by light, (C) a thermal crosslinking agent, and (D) an imidazolesilane compound. To do.

<(A) component: alkali-soluble resin>
The alkali-soluble resin as the component (A) is soluble in an alkaline aqueous solution. One criterion that the component (A) is soluble in an alkaline aqueous solution will be described below. A solution obtained from the component (A) alone and an arbitrary solvent, or a solution obtained from the component (A), the component (B), the component (C) and the component (D) and an arbitrary solvent, A resin film having a thickness of about 5 μm is formed by spin coating on a substrate such as a 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 the resin dissolves to form a uniform solution, it is determined that the component (A) is soluble in the alkaline aqueous solution. The density | concentration of aqueous alkali solution is the density | concentration at the time of image development used for the general photosensitive resin, is the range of 0.1-10 mass%, and is a reference | standard within about 10 minutes.

  As the component (A), specifically, polyhydroxystyrene and a hydroxystyrene-based resin such as a copolymer containing hydroxystyrene as a monomer unit, a phenol resin, a polybenzoxazole precursor such as poly (hydroxyamide), Examples include poly (hydroxyphenylene) ether and polynaphthol. 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 bisphenol monopropylene oxide adducts, etc. Knol derivatives; containing carboxyl groups such as p-hydroxyphenylacetic acid, p-hydroxyphenylpropionic acid, p-hydroxyphenylbutanoic acid, p-hydroxycinnamic acid, hydroxybenzoic acid, hydroxyphenylbenzoic acid, hydroxyphenoxybenzoic acid, diphenol A phenol derivative etc. are mentioned. 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-described 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 polycondensation 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, acetone dicarboxylic acid, and 3,3′-4,4′-benzophenone tetracarboxylic acid May be used in the reaction. These are used singly or in combination of two or more.

  Poly (hydroxystyrene) -based resin, for example, polymerizes (vinyl polymerization) an ethylenically unsaturated double bond of hydroxystyrene having a protective group introduced in the presence of a catalyst (radical initiator), and further deprotects it. Can be obtained. Commercially available branch type poly (hydroxystyrene) such as PHS-B (trade name of DuPont) can also be used.

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

  (A) It is preferable that a component contains the phenol resin (A1) which does not have an unsaturated hydrocarbon group, and modified phenol resin (A2) which has an unsaturated hydrocarbon group. The component (A2) is more preferably a modified phenolic resin that is further modified by the reaction between a phenolic 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 a compound having 4 to 100 carbon atoms) (hereinafter sometimes simply referred to as “unsaturated hydrocarbon group-containing compound”). Reaction product (hereinafter referred to as “unsaturated hydrocarbon group-modified phenol derivative”) and a polycondensation product of aldehydes, 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-containing compound preferably contains two or more unsaturated bonds from the viewpoint of adhesion and thermal shock resistance of the pattern cured film, and from the viewpoint of storage stability of the resin composition, the unsaturated bond Is preferably 30 or less. In addition, from the viewpoint of compatibility when the resin composition is used and the flexibility of the cured film, the unsaturated hydrocarbon group-containing compound preferably has 8 to 80 carbon atoms, and more preferably 10 to 60 carbon atoms.

  The unsaturated hydrocarbon group-containing compound is, for example, an unsaturated hydrocarbon having 4 to 100 carbon atoms, polybutadiene having a carboxyl group, epoxidized polybutadiene, linoleyl alcohol, oleyl alcohol, unsaturated fatty acid, and unsaturated fatty acid ester. 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.

  The component (A2) can also be obtained by reacting the above-described phenol resin with an unsaturated hydrocarbon group-containing compound. The reaction between the phenol resin and the unsaturated hydrocarbon group-containing compound is usually preferably performed at 50 to 130 ° C. From the point which can improve the flexibility of a cured film, the compounding ratio of a phenol derivative and an unsaturated hydrocarbon group containing compound is 1-100 mass of unsaturated hydrocarbon group containing compounds with respect to 100 mass parts of phenol resins. Part is preferable, and 5 to 50 parts by mass is more preferable. At this time, if necessary, p-toluenesulfonic acid, trifluoromethanesulfonic acid or the like may be used as a catalyst. For the reaction, a solvent such as toluene, xylene, methanol, tetrahydrofuran or the like can be used.

  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. Examples of the polybasic acid anhydride include phthalic anhydride, succinic anhydride, octenyl succinic anhydride, pentadodecenyl succinic anhydride, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride Dibasic acid anhydrides such as 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.

  The above reaction may be performed in the presence of a catalyst, if necessary, from the viewpoint of rapidly performing the reaction. 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 in the former (A1): the latter (A2) with the total amount of both being 100, more preferably 10:90 to 90:10. Preferably, 15:85 to 85:15 is most preferably 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 is 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 hydroxyl 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 hydroxyl 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-dimethylind [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-hydroxyphenyl) Examples include xafluoropropane and bis (4-amino-3-hydroxyphenyl) hexafluoropropane.

  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. As the reaction solvent, dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, diethyl ether, N-methylpyrrolidone, or the like is used.

  o-quinonediazide sulfonyl chloride and hydroxyl compound and / or amino compound are blended so that the total number of moles of hydroxyl group and amino group is 0.5 to 1 per mole of o-quinonediazide sulfonyl 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. 5-50 mass parts is more preferable, and 5-30 mass parts is further more preferable.

<(C) component: thermal crosslinking agent>
The thermal crosslinking agent is a compound having a structure that can react with the 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 specific structures 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 weight average molecular weight of such a compound having a phenolic hydroxyl group is preferably 2,000 or less. 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. . 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.

  As the compound having a phenolic hydroxyl group, conventionally known compounds can be used, but the compound represented by the following general formula (2) is effective in promoting the dissolution of the exposed portion and melting at the time of curing the photosensitive resin film. This is particularly preferable because of the excellent balance of the effects to be prevented.

In general formula (2), X represents a single bond or a divalent organic group, R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent 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 (2), the compound in which X is a single bond is a biphenol (dihydroxybiphenyl) derivative. Examples of the divalent organic group represented by X include an alkylene group having 1 to 10 carbon atoms such as a methylene group, an ethylene group and a propylene group, an alkylidene group having 2 to 10 carbon atoms such as an ethylidene group, and a phenylene group. Arylene groups having 6 to 30 carbon atoms, groups in which some or all of the hydrogen atoms of these hydrocarbon groups are substituted with halogen atoms such as fluorine atoms, sulfonyl groups, carbonyl groups, ether bonds, thioether bonds, amide bonds, etc. Can be mentioned.

  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, tetrakis (methoxymethyl) urea and the like.

  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. Etc.

  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 maleimide groups 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.

  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 (3) are preferred.

In general formula (3), R < ⁷ > -R < ¹² > shows a C1-C10 alkyl group each 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, with respect to 100 parts by weight of the component (A). 1 to 50 parts by mass is preferred, 2 to 30 parts by mass is more preferred, and 3 to 25 parts by mass is even more preferred. Moreover, the thermal crosslinking agent mentioned above is used individually by 1 type or in combination of 2 or more types.

<(D) component: imidazole silane compound>
The (D) imidazole silane compound used in the present invention is a compound having an imidazole group and an alkoxysilyl group. (D) Since an imidazole silane compound contains an imidazole group and an alkoxysilyl group, it exhibits excellent adhesion to various substrates. In addition, the (D) imidazolesilane compound is preferably a compound further containing a hydroxyl group. Conventional adhesive aids form an adhesive aid layer on the substrate surface, and the adhesive aid layer and the photosensitive resin cured film express the adhesiveness between the photosensitive resin cured film and various substrates by electrostatic interaction. doing. On the other hand, (D) the imidazole silane compound contains a hydroxyl group, thereby forming a network of (C) thermal crosslinker- (A) alkali-soluble resin by reaction with (C) thermal crosslinker. To do. Therefore, it adheres more effectively than the conventional adhesion assistant.
Such (D) imidazole silane compound includes an imidazole compound represented by the following general formula (4) and a glycidyl group-containing silane compound (for example, 3-glycidoxypropylsilane represented by the general formula (5)). It can be made to react at 80-200 degreeC and an imidazole silane compound can be obtained.

(一般式（４）、（５）において、Ｒ^１３は水素又は炭素数が１〜２０のアルキル基、Ｒ^１４は水素、ビニル基又は炭素数が１〜５のアルキル基、Ｒ^１５及びＲ^１６は炭素数が１〜３のアルキル基、ｎは１〜３の整数である。)

(In General Formulas (4) and (5), R ¹³ is hydrogen or an alkyl group having 1 to 20 carbon atoms, R ¹⁴ is hydrogen, a vinyl group or an alkyl group having 1 to 5 carbon atoms, R ¹⁵ and R ¹⁶ Is an alkyl group having 1 to 3 carbon atoms, and n is an integer of 1 to 3.)

  More specifically, for example, the reaction between the imidazole compound and the glycidyl group-containing silane compound is performed by dropping 0.1 to 10 mol times the amount of the glycidyl group-containing silane compound into the imidazole compound heated to a temperature of 80 to 200 ° C. Can be done by the method. The reaction time is preferably 5 minutes to 2 hours. This reaction does not particularly require a solvent, but an organic solvent such as chloroform, dioxane, methanol, or ethanol may be used as a reaction solvent. In addition, since this reaction tends to be inhibited by moisture, it is preferable to perform the reaction in an atmosphere of a gas that does not contain moisture such as dried nitrogen and argon so that moisture does not enter. Details are described in Japanese Patent Publication No. 10-186657.

  For example, when the compound represented by the general formula (4) is used as the imidazole compound and the 3-glycidoxypropylsilane compound represented by the general formula (5) is used as the glycidyl group-containing silane compound, The imidazole silane compounds represented by the following general formulas (6), (7) and (8) are obtained in a mixture state.

（上記中、Ｒ^１３は水素又は炭素数が1〜２０のアルキル基、Ｒ^１４は水素、ビニル基又は炭素数が１〜５のアルキル基、Ｒ^１５及びＲ^１６は炭素数１〜３のアルキル基、ｎは１〜３の整数である。）
これらの化合物は、溶解度の差を利用する方法、カラムクロマトグラフィー等の既知の手段により精製され、単離されうるので、単離されたものを使用することも可能である。一般的には必ずしも単離する必要はなく、混合物のまま用いることが簡便であるため好ましい。なお、生成物中の各成分組成は一般的に、（６）：（７）：（８）＝（４０〜８０）：（１０〜３０）：（５〜４０）(液体クロマトグラフィーで分析したときの面積比)である。

(In the above, R ¹³ is hydrogen or an alkyl group having 1 to 20 carbon atoms, R ¹⁴ is hydrogen, a vinyl group or an alkyl group having 1 to 5 carbon atoms, and R ¹⁵ and R ¹⁶ are alkyl groups having 1 to 3 carbon atoms. Group n is an integer from 1 to 3)
Since these compounds can be purified and isolated by a known method such as a method utilizing a difference in solubility, column chromatography, etc., it is also possible to use an isolated one. In general, it is not always necessary to isolate, and it is preferable to use the mixture as it is because it is simple. In addition, each component composition in a product is generally analyzed by (6) :( 7) :( 8) = (40-80) :( 10-30) :( 5-40) (liquid chromatography). Area ratio).

  Since the imidazolesilane compound (6) obtained by the above reaction contains a hydroxyl group, it reacts with (C) the thermal crosslinking agent and is included in the network of the cured film. Moreover, since the imidazole silane compound (6) contains an imidazole group and an alkoxysilyl group, it exhibits excellent adhesion to various substrates. For this reason, the cured film of the photosensitive resin composition obtained by this invention and various substrates show the outstanding adhesiveness.

(D) The imidazole compound represented by the general formula (4) used when synthesizing the imidazolesilane compound is preferably imidazole, 2-alkylimidazole, 2,4-dialkylimidazole, 4-vinylimidazole, 2-methylimidazole, 2-ethylimidazole, 2-undecylimidazole, 2-heptaimidazole, and 2-ethyl-4-methylimidazole are more preferable.
Further, as the glycidyl group-containing silane compound used when synthesizing (D) the imidazolesilane compound, it is preferable to use a 3-glycidoxypropylsilane compound represented by the general formula (5). It is more preferable to use glycidoxypropyltrialkoxysilane, 3-glycidoxypropyl dialkoxyalkylsilane, 3-glycidoxypropylalkoxydialkylsilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxy More preferably, propyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, and 3-glycidoxypropylethoxydimethylsilane are used.

  The blending amount of the imidazolylsilane compound containing an imidazolyl group and an alkoxysilyl group, which is the component (D), is 0.1% relative to 100 parts by mass of the component (A) from the viewpoint of providing good adhesion to a substrate and sensitivity. 01-20 mass parts is preferable, 0.015-10 mass parts is more preferable, and 0.02-7 mass parts is still more preferable. Moreover, the compound containing the imidazolyl group and alkoxysilyl group mentioned above is used individually by 1 type or in combination of 2 or more types.

<(E) component: Silane compound>
The photosensitive resin composition which concerns on this embodiment contains the silane compound which has an epoxy group represented by General formula (1) as (E) component from a viewpoint of improving adhesiveness with a board | substrate further. May be.

In the general formula (1), R ¹ represents a divalent organic group, and the R ² group represents a monovalent organic group. A plurality of R ² in the same molecule may be the same or different.

In general formula (1), from the viewpoint of improving sensitivity and resolution, R ¹ is preferably a linear alkylene group represented by — (CH ₂ ) _n — (n is an integer of 1 to 6). R ² is preferably an alkoxy group, an alkoxyalkyl group, or an alkyl group from the viewpoint of improving sensitivity and resolution. Among them, R ² is particularly preferably an alkoxy group such as a methoxy group and 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.

The photosensitive resin composition according to the present embodiment may further contain a silane compound different from the silane compound as the component (E) represented by the general formula (1). Examples of such silane compounds include ureidopropyltriethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, urea propyltriethoxysilane, methylphenylsilanediol, ethylphenylsilanediol, and n-propylphenyl. Silanediol, isopropylphenylsilanediol, n-butylphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n- Butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol Ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n -Butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, phenylsilanetriol, 1,4-bis (trihydroxysilyl) benzene, 1,4-bis (methyldihydroxysilyl) benzene, 1,4-bis (ethyl) Dihydroxysilyl) benzene, 1,4-bis (propyldihydroxysilyl) benzene, 1,4-bis (butyldihydride) Loxysilyl) benzene, 1,4-bis (dimethylhydroxysilyl) benzene, 1,4-bis (diethylhydroxysilyl) benzene, 1,4-bis (dipropylhydroxysilyl) benzene, 1,4-bis (dibutylhydroxysilyl) ) Benzene and the like. These silane compounds are used alone or in combination of two or more.
The photosensitive resin composition according to this embodiment is a wide substrate by using (D) an imidazole silane compound and (E) a silane compound having an epoxy group represented by the general formula (1) or the silane compound shown above. Adhesion to is improved.

  From the viewpoint of adhesiveness to wiring and storage stability of the photosensitive resin composition, the total amount of the silane compound other than the component (E) and the component (E) is 0.001 to 100 parts by mass of the component (A). It is preferably 20 parts by mass, more preferably 0.005 to 15 parts by mass, and still more preferably 0.01 to 10 parts by mass.

<(F) component>
The photosensitive resin composition according to the present embodiment may contain an acrylic resin as the component (F). The acrylic resin preferably has a structural unit represented by the following general formula (9) or (10). When the photosensitive resin composition contains the acrylic resin having the structural unit represented by the general formula (9) or (10), the thermal shock resistance can be improved while maintaining good photosensitive characteristics. (F) A component may consist only of 1 type of the said acrylic resin, and may contain 2 or more types.

In the general formulas (9) and (10), R ¹⁷ represents an alkyl group having 4 to 20 carbon atoms, and R ¹⁸ represents a hydrogen atom or a methyl group.

In the general formula (9), R ¹⁷ is preferably an alkyl group having 4 to 16 carbon atoms, and preferably an alkyl group having 4 carbon atoms, particularly an n-butyl group, from the viewpoint of improving sensitivity, resolution, and thermal shock. It is more preferable.

  Examples of the polymerizable monomer that gives the structural unit represented by the general formula (9) include (meth) acrylic acid alkyl esters. Examples of the (meth) acrylic acid alkyl ester include compounds represented by the following general formula (11).

上記一般式（１１）中、Ｒ^１９は水素原子又はメチル基を示し、Ｒ^２０は炭素数４〜２０のアルキル基を示す。Ｒ^２０で示される炭素数４〜２０のアルキル基としては、例えば、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、エイコシル基及びこれらの構造異性体が挙げられる。上記一般式（１１）で表される重合性単量体としては、例えば、（メタ）アクリル酸ブチルエステル、（メタ）アクリル酸ペンチルエステル、（メタ）アクリル酸ヘキシルエステル、（メタ）アクリル酸ヘプチルエステル、（メタ）アクリル酸オクチルエステル、（メタ）アクリル酸ノニルエステル、（メタ）アクリル酸デシルエステル、（メタ）アクリル酸ウンデシルエステル、（メタ）アクリル酸ドデシルエステル、（メタ）アクリル酸トリデシルエステル、（メタ）アクリル酸テトラデシルエステル、（メタ）アクリル酸ペンタデシルエステル、（メタ）アクリル酸ヘキサデシルエステル、（メタ）アクリル酸ヘプタデシルエステル、（メタ）アクリル酸オクタデシルエステル、（メタ）アクリル酸ノナデシルエステル、（メタ）アクリル酸エイコシルエステル等が挙げられる。これらの重合性単量体は１種を単独で又は２種類以上を組み合わせて用いられる。

In the general formula (11), R ¹⁹ represents a hydrogen atom or a methyl group, and R ²⁰ represents an alkyl group having 4 to ²⁰ carbon atoms. Examples of the alkyl group having 4 to 20 carbon atoms represented by R ²⁰ include butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, and tetradecyl. , 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 (11) 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) acyl Le acid eicosyl ester and the like. These polymerizable monomers are used alone or in combination of two or more.

  Examples of the polymerizable monomer that gives the structural unit represented by the general formula (10) include acrylic acid and methacrylic acid.

  In the component (F), the composition ratio of the structural unit represented by the general formula (9) is preferably 50 to 95 mol%, and 60 to 90 mol% with respect to the total amount of the component (F). More preferably, it is particularly preferably 70 to 85 mol%. When the composition ratio of the structural unit represented by the general formula (9) is 50 to 95 mol%, the thermal shock resistance of the cured film of the photosensitive resin composition can be further improved.

  In the acrylic resin as the component (F), the composition ratio of the structural unit represented by the general formula (10) is preferably 5 to 35 mol% with respect to the total amount of the component (F). More preferably, it is 30 mol%, and it is still more preferable that it is 15-25 mol%. When the composition ratio of the structural unit represented by the general formula (10) 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.

  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 (F) is a structural unit represented by the general formula (9). It is more preferable to contain an acrylic resin having the structural unit represented by the above (10) and the structural unit represented by the following general formula (12). When (F) component is the said acrylic resin, interaction with (F) component and (A) alkali-soluble resin, especially alkali-soluble resin which has a phenolic hydroxyl group becomes favorable, and compatibility improves more.

In General Formula (12), R ¹⁸ represents a hydrogen atom or a methyl group, and R ¹⁹ represents a monovalent organic group having a primary, secondary, or tertiary amino group.

Examples of the polymerizable monomer that gives the structural unit represented by the general formula (12) 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 improving the adhesion of the resist pattern to the substrate, mechanical properties, and thermal shock resistance, in the general formula (12), R ¹⁹ is a monovalent group represented by the following general formula (13). Particularly preferred is an organic group.

In the general formula (13), X represents an alkylene group having 1 to 5 carbon ^atoms, R 20 ^{to R 24} each independently represent a hydrogen atom or an alkyl group having a carbon number of 1 to 20, m is 0 to an integer of It is.

Examples of the polymerizable monomer that gives the structural unit of the general formula (12) in which R ¹⁹ is a monovalent organic group represented by the general formula (13) include piperidin-4-yl (meth) acrylate, 1-methylpiperidin-4-yl (meth) acrylate, 2,2,6,6-tetramethylpiperidin-4-yl (meth) acrylate, 1,2,2,6,6-pentamethylpiperidin-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 (all manufactured by Hitachi Chemical Co., Ltd.) are commercially available.

  In the acrylic resin as the component (F), the composition ratio of the structural unit represented by the general formula (12) is preferably 0.3 to 10 mol% with respect to the total amount of the component (F). It is more preferable that it is 0.4-8 mol%, and it is further more preferable that it is 0.5-7 mol%.

  The component (F) is represented by the structural unit represented by the general formula (9), the structural unit represented by the general formula (10), and the following general formula (14) from the viewpoint of further improving the sensitivity. 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 (12).

In General Formula (14), R represents a hydrogen atom or a methyl group, Y represents an alkylene group having 1 to 5 carbon atoms, and R ^{25 to} R ²⁹ each independently represents an alkyl group having 1 to 6 carbon atoms.

  Examples of the polymerizable monomer that gives the structural unit represented by the general formula (14) 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 (F), the composition ratio of the structural unit represented by the general formula (14) is preferably 1 to 10 mol% with respect to the total amount of the component (F). It is more preferably 5 mol%, and further preferably 3 to 5 mol%.

  The polymerizable monomer used for the synthesis of the acrylic resin constituting the component (F) includes structural units represented by the general formulas (9, 11), (10), (12, 13), and (14). It may further contain a polymerizable monomer other than the polymerizable monomer to be provided. 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, α-bromo ( (Meth) acrylic acid, α-chloro Maleic acid monoesters such as (meth) acrylic acid, β-furyl (meth) acrylic acid, β-styryl (meth) acrylic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, Examples include 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.

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

  In the case of containing the component (F), the content 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. 3-40 mass parts is more preferable, and 5-30 mass parts is especially preferable.

<Other ingredients>
The photosensitive resin composition according to the present embodiment can 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 as necessary.

<Other components (G): Thermal acid generator>
The photosensitive resin composition may contain (G) a thermal acid generator. (G) The thermal acid generator is a compound that generates an acid by heat, and can further suppress the melt of the pattern. This makes it possible to generate an acid when the photosensitive resin film after development is heated, and the reaction between the component (A) (alkali-soluble resin) and the component (C) (thermal crosslinking agent), that is, thermal crosslinking. Since the reaction starts at a lower temperature, the melt of the pattern is further suppressed. Moreover, since many thermal acid generators can generate an acid even when irradiated with light, the use of such a thermal acid generator can increase the solubility of an 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, and the resolution is improved. However, the thermal acid generator said here is a compound different from the said (B) component (compound which produces | generates an acid by light).

  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 (15) is preferable, a trialkylsulfonium salt of methanesulfonic acid is more preferable, and a trimethylsulfonium salt is particularly preferable.

In the general formula (15), R ³⁰ , R ³¹ and R ³² each independently represents an alkyl group or an aryl group, and R ³³ represents hydrogen or fluorine. The aryl group is preferably a phenyl group or a phenyl group having a substituent.

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

  (G) 0.1-30 mass parts is preferable with respect to 100 mass parts of total amounts of (A) component and (B) component, when containing a thermal acid generator, 0.2-20 A mass part is more preferable and 0.3-10 mass parts is still more preferable.

<Other components (H): Elastomer>
The photosensitive resin composition may further contain (H) an elastomer. Thereby, the obtained pattern cured film becomes further excellent in terms of flexibility, and the mechanical properties and thermal shock resistance of the pattern cured film 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.

<Other components (I): Solvent>
The photosensitive resin composition may contain (I) a solvent from the viewpoint of application on a substrate and formation of a resin film having a uniform thickness. Specific examples of the solvent include γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, 3-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 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 may contain (K) 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 component (A), in terms of sensitivity and the allowable range of development time, and 0.01 to 15 Mass parts are more preferable, and 0.05 to 10 parts by mass are even more preferable.

<Other components (L): surfactant or leveling agent>
The photosensitive resin composition 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 (manufactured by DIC Corporation, trade name), Florard FC430, FC431 (Sumitomo 3M Corporation, trade name), organosiloxane polymers KP341, KBM303, KBM803 (Shin-Etsu Chemical Co., Ltd.) Product name).
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 can be developed using an aqueous alkali 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).

[Method for producing patterned cured film]
The method for producing a pattern cured film using the photosensitive resin composition according to the above-described embodiment is, for example, a process of forming a photosensitive resin film by applying and drying the photosensitive resin composition on a substrate (film formation process). 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 A 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. After exposure, post-exposure heating (PEB) can be performed as necessary. The post-exposure heating temperature is preferably 70 to 140 ° C., and the post-exposure heating time is preferably 1 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 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 an Si substrate having circuit elements, a protective film 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 a polyimide resin or the like formed on the protective film 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 according to the present embodiment.

[Electronic parts]
The electronic component according to the present embodiment has a pattern 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, sealing materials, etc. 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 according to this embodiment is particularly suitable for use in 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 from 100 to 200 ° C, more preferably from 150 to 200 ° C. Furthermore, since the photosensitive resin composition according to the present embodiment has a small volume shrinkage (curing shrinkage) in the heat treatment step found in photosensitive polyimide and the like, it is possible to prevent a reduction in dimensional accuracy. The pattern cured film formed from the photosensitive resin composition according to the present embodiment 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.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

<Preparation of photosensitive resin composition>
The following A1 and A2 were prepared as the component (A) (alkali-soluble resin).
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”)
A2: Modified phenol resin prepared by the method described in Synthesis Example 1 below

Synthesis Example 1: Synthesis of phenol resin (A2) modified with a compound having 4 to 100 carbon atoms having an unsaturated hydrocarbon group 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. After raising the temperature to 120 ° C. and stirring under reduced pressure for 3 hours, 29 g of succinic anhydride and 0.3 g of triethylamine were added to the reaction solution, followed by stirring at 100 ° C. for 1 hour under atmospheric pressure. The reaction liquid was cooled to room temperature (25 ° C.), and a phenol resin (hereinafter referred to as A2) modified with a compound having 4 to 100 carbon atoms having an unsaturated hydrocarbon group was obtained as a reaction product (acid value). 120 mg KOH / g). The weight average molecular weight of this modified phenolic resin A2 determined by standard polystyrene conversion by the GPC method was about 25,000.

As component (B) (compound that generates acid by light), 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 component (C) (thermal crosslinking agent), hexakis (methoxymethyl) melamine (manufactured by Sanwa Chemical Co., Ltd., trade name “Nicalak MW-30HM”) was prepared.

As component (D) (imidazolesilane compound), D1, D2, and D3 containing an imidazolyl group and an alkoxysilyl group were prepared.
D1: IS-1000 (trade name, manufactured by JX Nippon Mining & Metals) (N- (2-hydroxypropyl-trimethoxysilylether) -imidazole)
D2: SP-10 (Brand name, manufactured by JX Nippon Mining & Metals Co., Ltd.) (containing IS-1000 in phenol novolac resin)
D3: Reactive organism of 2-methylimidazole and 3-glycidoxypropyltrimethoxysilane

As the component (E) (the silane compound represented by the general formula (1)), the following silane compounds E1 and E2 were prepared.
E1: 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM-403”)
E2: Ureidopropyltriethoxysilane (manufactured by Toray Dow Chemical Co., Ltd., trade name “AY-43-031”)

As the component (F) (acrylic resin), an acrylic resin F1 was prepared by the method of Synthesis Example 2 below.
Synthesis Example 2: Synthesis of acrylic resin F1 To a 500 ml three-necked flask equipped with a stirrer, a nitrogen inlet tube and a thermometer, 75 g of toluene and 75 g of isopropanol (IPA) were weighed and separately weighed butyl acrylate. (BA) 85 g, lauryl acrylate (DDA) 24 g, acrylic acid (AA) 14 g, and 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate (trade name: FA-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 (1 / min), nitrogen gas was passed 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 F1. The polymerization rate was 98%. It was the weight average molecular weight (MW) of acrylic resin F1 calculated | required by standard polystyrene conversion of GPC method = 36,000.

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

(Examples 1-9, Comparative Examples 1-3)
(A)-(I) component was mix | blended in the predetermined ratio shown in Table 1. The obtained solution was pressure-filtered using a 0.5 micrometer pore Teflon (trademark) filter, and the solution of the photosensitive resin composition of Examples 1-9 and Comparative Examples 1-3 was prepared.

<Evaluation of adhesion>
Resin having a film thickness of about 11 to 12 μm was prepared by spin-coating the photosensitive resin composition solutions of Examples 1 to 9 and Comparative Examples 1 to 3 on various substrates described below and heating at 120 ° C. for 3 minutes. A film was formed. This resin film was coated in a vertical diffusion furnace (manufactured by Koyo Thermo System Co., Ltd., trade name “μ-TF”) in nitrogen at a temperature of 180 ° C. (temperature increase time: 1.5 hours) for 2 hours. Was heat-treated (cured) to obtain a cured film having a thickness of about 10 μm. The cured film was cut into 10 × 10 grids with a razor using a cross cut guide (Cortech Co., Ltd.), and the cured film was divided into 100 small pieces. After sticking an adhesive tape (made by Nichiban Co., Ltd.) there, it was peeled off. When peeling the adhesive tape, the adhesion was evaluated as follows according to the number of small pieces peeled from the substrate. The results are shown in Table 1.
A: No peeling B: 1-25 pieces peeling C: 26-50 pieces peeling D: 51-75 pieces peeling E: 76-100 pieces peeling The board | substrate used for evaluation of adhesiveness is as follows.
Ti substrate: A substrate obtained by sputtering a Ti film on a silicon substrate.
Au substrate: A substrate obtained by sputtering a TiN film on a silicon substrate and then forming an Au film on the TiN film by sputtering.
Cu substrate: A substrate obtained by forming a TiN film on a silicon substrate by sputtering, then forming a copper film on the TiN film by sputtering, and copper plating using the copper film as a seed layer.
Si substrate: A silicon substrate.

<Evaluation of photosensitive characteristics (sensitivity and resolution)>
A solution of the photosensitive resin composition obtained in Examples 1 to 9 and Comparative Examples 1 to 3 was spin coated on a silicon substrate and heated at 120 ° C. for 3 minutes to form a resin film having a thickness of about 8 to 9 μm. Formed. Subsequently, reduction projection exposure with i-line (365 nm) was performed through a mask using an i-line stepper (trade name “FPA-3000i” manufactured by Canon Inc.). After the exposure, development was performed using a 2.38 mass% 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 calculated | required the magnitude | size of the minimum exposure amount required for pattern formation, and the size of the minimum square hole pattern opened. The minimum exposure amount was used as sensitivity, and the size of the smallest square hole pattern opened was evaluated as resolution. Sensitivity and resolution indicate that the smaller the value, the better.

<Evaluation of cured film properties (elongation at break and elastic modulus)>
A solution of the photosensitive resin composition obtained in Examples 1 to 9 and Comparative Examples 1 to 3 was spin coated on a silicon substrate and heated at 120 ° C. for 3 minutes to form a resin film having a thickness of about 12 to 14 μm. Formed. This resin film was exposed at all wavelengths through a mask using a proximity exposure machine (trade name “PLA-600FA” manufactured by Canon Inc.). After the exposure, development was performed using a 2.38% by mass aqueous solution of TMAH to obtain a pattern resin film having a 10 mm wide rectangular cross section. Thereafter, the patterned cured film was heat-treated in a vertical diffusion furnace (manufactured by Koyo Thermo System Co., Ltd., trade name “μ-TF”) in nitrogen at a temperature of 175 ° C. (heating time 1.5 hours) for 2 hours. (Curing) to obtain a cured pattern film having a thickness of about 10 μm. The cured film was peeled from the silicon substrate, and the peeled cured film was used as a sample, and the elongation at break and elastic modulus were measured by “Autograph AGS-H100N” manufactured by Shimadzu Corporation. The width of the sample was 10 mm, the film thickness was about 10 μm, and the gap between chucks was 20 mm. The pulling speed was 5 mm / min, and the measurement temperature was room temperature (20 ° C. to 25 ° C.). The average of the measured values of five test pieces obtained from the cured film obtained under the same conditions was defined as elongation at break and elastic modulus. The results are shown in Table 1.

  The photosensitive resin composition of Examples 1-9 could provide the pattern cured film which has favorable adhesiveness with respect to any board | substrate. Moreover, when the photosensitive resin composition of Examples 1-9 was used, the photosensitive characteristic and the mechanical characteristic were also favorable. On the other hand, in Comparative Examples 1 to 3 in which the imidazolesilane compound as the component (D) was not used, the adhesion was different depending on the adherend, and the adhesion was lowered depending on the substrate.

  ADVANTAGE OF THE INVENTION According to this invention, it is possible to form the pattern cured film which has favorable adhesiveness irrespective of the kind of board | substrate, and can provide the photosensitive resin composition which can be developed with alkaline aqueous solution. Furthermore, since the photosensitive resin composition of the present invention can be cured at a low temperature, it can prevent damage to the electronic component due to heat, and can provide a highly reliable electronic component with a high yield, An electronic component having the patterned cured film made of the photosensitive resin composition of the present invention as a surface protective layer, an interlayer insulating layer, a cover coat layer, a core, a collar, or an underfill can be provided.

  DESCRIPTION OF SYMBOLS 1 ... Semiconductor substrate, 2 ... Protective film, 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 (11)

(A) an alkali-soluble resin;
(B) a compound that generates an acid by light;
(C) a thermal crosslinking agent;
(D) an imidazolesilane compound;
Containing a photosensitive resin composition.   (D) The photosensitive resin composition of Claim 1 whose imidazole silane compound is a compound containing a hydroxyl group.   (A) The photosensitive resin composition of Claim 1 or 2 whose component is a phenol resin.   The photosensitive resin composition of Claim 3 in which (A) component contains the phenol resin (A1) which does not have an unsaturated hydrocarbon group, and the modified phenol resin (A2) which has an unsaturated hydrocarbon group.   The photosensitive resin composition according to claim 4, wherein the component (A2) is a modified phenol resin further modified by a reaction between a phenolic hydroxyl group and a polybasic acid anhydride.   (B) The photosensitive resin composition as described in any one of Claims 1-5 whose component is an o-quinonediazide compound. (E) The photosensitive resin composition as described in any one of Claims 1-6 which further contains the silane compound represented by following General formula (1).

[In General Formula (1), R ¹ represents a divalent organic group, R ² represents a monovalent organic group, and a plurality of R ² in the same molecule may be the same or different. ]   (F) The photosensitive resin composition as described in any one of Claims 1-7 which further contains an acrylic resin.   A step of applying and drying the photosensitive resin composition according to any one of claims 1 to 8 on a substrate to form a photosensitive resin film, a step of exposing the photosensitive resin film, and after exposure A method for producing a cured pattern film, comprising: developing the photosensitive resin film with an aqueous alkaline solution to form a pattern resin film; and heating the pattern resin film.   The electronic component which has a pattern cured film obtained by the manufacturing method of Claim 9 as a surface protective layer or an interlayer insulation layer.   The electronic component which has a pattern cured film obtained by the manufacturing method of Claim 9 as a cover coat layer, a core, a color | collar, or an underfill.

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