JP2014080541A - Resin composition and method of manufacturing organic layer using the same, organic layer, and semiconductor element having organic layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition capable of forming a pattern resin film having no residual in concavity in a process of forming the pattern resin film, a method of manufacturing an organic layer using the resin composition, the organic layer obtained by the method of manufacturing, and a semiconductor element having the organic layer.SOLUTION: A resin composition contains (a) an alkali soluble resin having a phenolic hydroxyl group and (b) an acrylic resin, and the (b) acrylic resin has absorbance at 660 nm measured by a spectrophotometer after agitating and mixing with tetramethylammonium hydroxide (TMAH) at the concentration of 0.3 mass% for 30 seconds and standing for 10 minutes of 0.06 or less. It is preferable to contain further (c) a photosensitizer and (d) a crosslinking agent. A method of manufacturing an organic layer includes a process of coating the resin composition on a base plate and drying it to form a resin film, a process of exposing and developing the resin film to form a pattern resin film, and a process of heating the pattern resin film to form an organic layer.

Description

  The present invention relates to a resin composition with little residue, a method for producing an organic layer using the resin composition, an organic layer obtained thereby, and a semiconductor element having the organic layer.

  Along with the high integration and miniaturization of semiconductor elements, the resin composition used to form the surface protection layer, interlayer insulating layer and rewiring layer of the semiconductor element has both superior sensitivity and resolution, and is finer. It is required that a precise organic layer can be formed. As a material having such properties, a resin composition containing an alkali-soluble resin having a phenolic hydroxyl group has been developed (see, for example, Patent Document 1).

  The resin composition comprises a step of applying and drying on a substrate to form a photosensitive resin film, a step of exposing and developing the photosensitive resin film to form a pattern resin film, and a step of forming the pattern resin film. An organic layer (hereinafter also referred to as a pattern cured film) can be formed by the heating step. The organic layer is used as a surface protective layer, an interlayer insulating layer, and a rewiring layer of a semiconductor element. The resin composition containing an alkali-soluble resin having a phenolic hydroxyl group described in Patent Document 1 also has an advantage that it can be cured by heating at a low temperature in the step of heating the pattern resin film.

JP 2003-215802 A

  In the step of forming a patterned resin film by exposing and developing the resin composition, if it is difficult to dissolve in the alkaline solution used for development, a component that is difficult to dissolve in the concave portion of the dissolved portion after development may occur as a residue. is there. If the residue is generated, there is a possibility that problems such as the inability to disconnect the conductor from the bottom of the recess can occur. Therefore, a resin composition in which no residue is generated is desired.

  In view of the above problems, the present invention provides a resin composition capable of forming a patterned resin film having no residue in a recess in the step of forming a patterned resin film, a method for producing an organic layer using the resin composition, and a method for producing the same It aims at providing the semiconductor layer which has the organic layer and organic layer which are obtained by this.

The present invention relates to the following.
<1> A resin composition comprising (a) an alkali-soluble resin having a phenolic hydroxyl group and (b) an acrylic resin,
The (b) acrylic resin was mixed with tetramethylammonium hydroxide (TMAH) at a concentration of 0.3% by mass for 30 seconds, then allowed to stand for 10 minutes, and then measured with a spectrophotometer. A resin composition having an absorbance of 0.06 or less.
<2> The resin composition further comprising (c) a photosensitizer.
<3> The resin composition further comprising (d) a crosslinking agent.
<4> A step of applying and drying the resin composition on a substrate to form a resin film, a step of exposing and developing the resin film to form a pattern resin film, and heating the pattern resin film. And a step of forming the organic layer.
<5> An organic layer obtained by the production method.
<6> A semiconductor element having the organic layer.

  With the resin composition using an acrylic resin having an absorbance of 0.06 or less by the TMAH of the present invention, in the step of forming the pattern resin film, a pattern resin film having no residue in the recessed portion after development can be formed. Problems such as inability to remove can be solved. And the resin composition which has this characteristic, the manufacturing method of an organic layer using the same, and the semiconductor element which has the organic layer and organic layer which are obtained by the manufacturing method can be provided.

It is the schematic perspective view and schematic sectional drawing explaining one Embodiment of the manufacturing process of a semiconductor device. It is the schematic perspective view and schematic sectional drawing explaining one Embodiment of the manufacturing process of a semiconductor device. It is the schematic perspective view and schematic sectional drawing explaining one Embodiment of the manufacturing process of a semiconductor device. It is the schematic perspective view and schematic sectional drawing explaining one Embodiment of the manufacturing process of a semiconductor device. It is the schematic perspective view and 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 the semiconductor element which has a rewiring structure. It is a schematic sectional drawing which shows one Embodiment of the semiconductor element which has a rewiring structure.

  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) acrylic acid” means “acrylic acid” and “methacrylic acid” corresponding thereto.

[Resin composition]
The resin composition of the present invention is a resin composition comprising (a) an alkali-soluble resin having a phenolic hydroxyl group and (b) an acrylic resin,
The (b) acrylic resin was stirred and mixed with tetramethylammonium hydroxide (TMAH) at a concentration of 0.3% by mass for 30 seconds, allowed to stand for 10 minutes, and then measured with a spectrophotometer. The resin composition has an absorbance of 0.06 or less. Hereinafter, each component will be described in detail.

<(A) Alkali-soluble resin having phenolic hydroxyl group>
The resin composition of the present invention contains an alkali-soluble resin having a phenolic hydroxyl group.
Specific examples of the alkali-soluble resin containing a phenolic hydroxyl group include polyhydroxystyrene and a hydroxystyrene resin such as a copolymer containing hydroxystyrene as a monomer unit, a polybenzo such as a phenol resin and poly (hydroxyamide). Examples include oxazole precursors, poly (hydroxyphenylene) ether, polynaphthol and the like. Among these, a phenol resin is preferable and a novolac type phenol resin is more preferable because of its low cost and small volume shrinkage at the time of curing.

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

  Examples of the phenol derivative used for obtaining the phenol resin include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, and m-butylphenol. P-butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, Alkylphenols such as 3,4,5-trimethylphenol, alkoxyphenols such as methoxyphenol and 2-methoxy-4-methylphenol, alkenylphenols such as vinylphenol and allylphenol, aralkylphenols such as benzylphenol, Alkoxycarbonylphenol such as toxylcarbonylphenol, arylcarbonylphenol such as benzoyloxyphenol, halogenated phenol such as chlorophenol, polyhydroxybenzene such as catechol, resorcinol, pyrogallol, bisphenol such as bisphenol A and bisphenol F, α- or β A naphthol derivative such as naphthol; a hydroxyalkylphenol such as p-hydroxyphenyl-2-ethanol, p-hydroxyphenyl-3-propanol and p-hydroxyphenyl-4-butanol; a hydroxyalkylcresol such as hydroxyethylcresol; Ethylene oxide adducts; alcoholic hydroxyl group-containing 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-mentioned phenol or phenol derivative with an aldehyde together with a compound other than phenol such as m-xylene. In this case, the molar ratio of the compound other than phenol to the phenol derivative used for 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 alkali-soluble resin having a phenolic hydroxyl group used in the present invention is preferably 500 to 150,000, considering the balance with solubility in an aqueous alkali solution, photosensitive characteristics, and mechanical properties. More preferably, it is 100,000, and more preferably 1,000 to 50,000. Here, the weight average molecular weight is a value obtained by measuring by a gel permeation chromatography method and converting from a standard polystyrene calibration curve.

  The alkali-soluble resin containing a phenolic hydroxyl group used in the present invention preferably contains a phenol resin not having an unsaturated hydrocarbon group and a modified phenol resin having an unsaturated hydrocarbon group. More preferably, the modified phenolic resin is a modified phenolic resin that is further modified by the reaction of a phenolic hydroxyl group and a polybasic acid anhydride. When a modified phenol resin is used, an organic layer having excellent crack resistance can be formed, and a resin composition that can be developed with an alkaline aqueous solution can be provided.

  The modified phenol resin 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 modified phenol resin, 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 organic layer, and from the viewpoint of storage stability of the resin composition, the unsaturated bond is It is preferable that it is 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 organic layer. 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 modified phenol resin, 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 1 to 100 masses of the unsaturated hydrocarbon group-containing compound with respect to 100 parts by mass of the phenol derivative because the flexibility of the organic layer can be improved. Part is preferable, and 5 to 50 parts by mass is more preferable. 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 aldehydes to prepare a modified phenol resin having an unsaturated hydrocarbon group, which is a modified phenol resin. 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. In addition, the modified phenolic resin is polycondensed 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. The unsaturated hydrocarbon group of the modified phenol resin is preferably present at the ortho position or para position, and more preferably present at the para position with respect to the phenolic hydroxyl group of the phenol resin.

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

  The polybasic acid anhydride is not particularly limited as long as it has an acid anhydride group formed by dehydration condensation of 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 an organic layer having a 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 modified phenolic resin is preferably 1,000 to 500,000 in terms of weight average molecular weight, more preferably 2,000 to 200,000, considering the solubility in aqueous alkali solution and the balance between the photosensitive properties and the cured film properties. 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 resin composition of the present invention has a phenolic hydroxyl group used in the present invention in terms of sensitivity and resolution when forming a patterned resin film, and adhesion, mechanical properties and thermal shock resistance of the organic layer after curing. In the case of using a modified phenolic resin having an unsaturated hydrocarbon group as a mixed alkali-soluble resin, a phenolic resin not having an unsaturated hydrocarbon group and an unsaturated hydrocarbon in an alkali-soluble resin having a phenolic hydroxyl group The mass ratio of the modified phenolic resin having a group is preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, with the total amount of both being 100 and 15:15 : 85-85: 15 is most preferable.

<(B) Acrylic resin>
The resin composition of the present invention contains (b) an acrylic resin. The (b) acrylic resin used in the present invention is stirred and mixed for 30 seconds at a concentration of 0.3% by mass with tetramethylammonium hydroxide (TMAH) which is a colorless and transparent liquid at room temperature (25 ° C.). After standing for a minute, the absorbance at 660 nm measured by a spectrophotometer is 0.06 or less. When the absorbance is within this range, residues in the opening (concave portion) of the obtained pattern resin film can be suppressed. The reason for this is not clear, but it is thought that there is a large amount of unreacted carboxylic acid.
The absorbance at 660 nm is 0.06 or less, preferably 0.05 or less. The lower limit of the absorbance at 660 nm is not particularly limited, but is preferably 0.001 or more.
In addition, U-3300 type spectrophotometer (made by Hitachi High-Technologies Corporation) was used for the absorbance measurement.

  The acrylic resin preferably has a structural unit represented by the following general formula (1) or (2). When the resin composition contains the acrylic resin having the structural unit represented by the general formula (1) or (2), the thermal shock resistance can be improved while maintaining good photosensitive characteristics. The acrylic resin used in the present invention may consist of only one of the above acrylic resins, or may contain two or more.

In the general formulas (1) and (2), 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 (1), 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 (1) include (meth) acrylic acid alkyl esters. Examples of the (meth) acrylic acid alkyl ester include compounds represented by the following general formula (3).

上記一般式（３）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１〜２０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（３）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一種を単独で又は２種類以上を組み合わせて用いられる。

In the general formula (3), 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 1 to 20 carbon atoms represented by R ²⁰ include a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, and a tetradecyl group. , Pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group and structural isomers thereof. Examples of the polymerizable monomer represented by the general formula (3) include (meth) acrylic acid butyl ester, (meth) acrylic acid pentyl ester, (meth) acrylic acid hexyl ester, and (meth) acrylic acid heptyl. Ester, (Meth) acrylic acid octyl ester, (meth) acrylic acid nonyl ester, (meth) acrylic acid decyl ester, (meth) acrylic acid undecyl ester, (meth) acrylic acid dodecyl ester, (meth) acrylic acid tridecyl ester Ester, (meth) acrylic acid tetradecyl ester, (meth) acrylic acid pentadecyl ester, (meth) acrylic acid hexadecyl ester, (meth) acrylic acid heptadecyl ester, (meth) acrylic acid octadecyl ester, (meth) acrylic Acid nonadecyl ester, (meth) acrylic Acid eicosyl ester and the like. These polymerizable monomers are used singly or in combination of two or more.

  Examples of the polymerizable monomer that gives the structural unit represented by the general formula (2) include acrylic acid and methacrylic acid.

  In the acrylic resin used in the present invention, the composition ratio of the structural unit represented by the general formula (1) is preferably 50 to 95 mol% with respect to the total amount of the acrylic resin used in the present invention. More preferably, it is 90 mol%, and it is especially preferable that it is 70-85 mol%. When the composition ratio of the structural unit represented by the general formula (1) is 50 to 95 mol%, the thermal shock resistance of the cured film of the resin composition can be further improved.

  In the acrylic resin used in the present invention, the composition ratio of the structural unit represented by the general formula (2) is preferably 5 to 35 mol% with respect to the total amount of the acrylic resin used in the present invention. 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 (2) is 5 to 35 mol%, the compatibility with the alkali-soluble resin having a phenolic hydroxyl group used in the present invention and the developability of the resin composition Can be further improved.

  In the acrylic resin of the present invention, with respect to tetramethylammonium hydroxide (TMAH), after stirring and mixing at a concentration of 0.3 wt% for 30 seconds, after standing for 10 minutes, the absorbance at 660 nm is 0.06 or less by a spectrophotometer. It is preferable that it is 0.05 or less. If the absorbance is greater than 0.06, it will be difficult to dissolve in the alkaline solution, resulting in a defective residue as a residue remaining in the recess.

  From the viewpoint of further improving the compatibility with the alkali-soluble resin having a phenolic hydroxyl group used in the present invention, the adhesion of the organic layer to the substrate, the mechanical properties and the thermal shock resistance, the acrylic resin used in the present invention has the above general formula. It is more preferable to contain the acrylic resin which has a structural unit represented by (1), a structural unit represented by said (2), and a structural unit represented by following General formula (3). When the acrylic resin of the present invention is the acrylic resin, the interaction between the acrylic resin of the present invention and the alkali-soluble resin having a phenolic hydroxyl group of the present invention is improved, and the compatibility is further improved.

In the formula (3), 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 (3) 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-ethyl Minoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, aminopropyl (meth) acrylamide, N-methylaminopropyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N-ethylamino Propyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, piperidin-4-yl (meth) acrylate, 1-methylpiperidin-4-yl (meth) acrylate, 2,2,6,6-tetramethyl Piperidin-4-yl (meth) acrylate, 1,2,2,6,6-pentamethylpiperidin-4-yl (meth) acrylate, (piperidin-4-yl) methyl (meth) acrylate, 2- (piperidine- 4-yl) ethyl (meth) aqua Rate, and the like. These polymerizable monomers are used alone or in combination of two or more. Among these, from the viewpoint of further improving the adhesion of the resist pattern to the substrate, mechanical properties, and thermal shock resistance, in the general formula (3), R ¹⁹ is a monovalent group represented by the following general formula (4). Particularly preferred is an organic group.

In the general formula (4), 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 (3) in which R ¹⁹ is a monovalent organic group represented by the general formula (4) 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. (Both manufactured by Hitachi Chemical Co., Ltd.) and are commercially available.

  In the acrylic resin used in the present invention, the composition ratio of the structural unit represented by the general formula (3) is preferably 0.3 to 10 mol% with respect to the total amount of the acrylic resin used in the present invention. 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 acrylic resin used in the present invention is represented by the structural unit represented by the general formula (1), the structural unit represented by the general formula (2), and the following general formula (5) from the viewpoint of further improving 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 (3).

In the general formula (5), R represents a hydrogen atom or a methyl group, Y represents an alkylene group having 1 to 5 carbon ^atoms, R 25 ^{to R 29} each independently represents an alkyl group having 1 to 6 carbon atoms, p is an integer of 1-100.

  Examples of the polymerizable monomer that gives the structural unit represented by the general formula (5) 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 used in the present invention, the composition ratio of the structural unit represented by the general formula (5) is preferably 1 to 10 mol% with respect to the total amount of the acrylic resin of the present invention, and 2 to 5 It is more preferable that it is mol%, and it is further more preferable that it is 3-5 mol%.

  The polymerizable monomer used for the synthesis of the acrylic resin used in the present invention is a polymerizable that gives each structural unit represented by the general formula (1), (2), (3), (4), (5). A polymerizable monomer other than the monomer may further be included. Examples of such a polymerizable monomer include styrene, α-methylstyrene, (meth) acrylic acid benzyl ester, (meth) acrylic acid 4-methylbenzyl ester, (meth) acrylic acid 2-hydroxyethyl ester, Esters of vinyl alcohol such as (meth) acrylic acid 2-hydroxypropyl ester, (meth) acrylic acid 3-hydroxypropyl ester, (meth) acrylic acid 4-hydroxybutyl ester, acrylonitrile, vinyl-n-butyl ether, ) Acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid glycidyl ester, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, (meth) acrylic Acid, α-bromo (meth) a Crylic acid, α-chloro (meth) acrylic acid, β-furyl (meth) acrylic acid, β-styryl (meth) acrylic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate And maleic acid monoesters such as fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, and propiolic acid. These polymerizable monomers are used alone or in combination of two or more.

  The weight average molecular weight of the acrylic resin used in the present invention is preferably from 2,000 to 100,000, more preferably from 3,000 to 60,000, and preferably from 4,000 to 50,000. Further preferred. When the weight average molecular weight is 2,000 or more, the thermal shock resistance of the organic layer tends to be better, and when it is 100,000 or less, compatibility with the resin and developability tend to be better. The weight average amount is a value obtained by measuring by a gel permeation chromatography method and converting from a standard polystyrene calibration curve.

  When the resin composition of the present invention contains an acrylic resin, the content is 100 parts by mass in total of the resin in the resin composition from the viewpoint of further improving the adhesion, mechanical properties, thermal shock resistance, and photosensitive properties. On the other hand, 1-50 mass parts is preferable, 3-40 mass parts is more preferable, and 5-30 mass parts is still more preferable.

<(C) Photosensitive agent>
The resin composition of the present invention preferably contains (c) a compound that generates light upon receiving light as a photosensitizer.

  A compound that generates an acid by light has a function of generating an acid by irradiation with light and increasing the solubility of the irradiated portion in an alkaline aqueous solution. As the compound that generates an acid by light used in the present invention, a compound generally referred to as a photoacid generator can be used. Specific examples of the compound that generates an acid by light used in the present invention include an o-quinonediazide compound, an aryldiazonium salt, a diaryliodonium salt, and a triarylsulfonium salt. Of these, o-quinonediazide compounds are preferred because of their high sensitivity.

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

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

  Examples of the hydroxy compound used in the reaction include hydroquinone, resorcinol, pyrogallol, bisphenol A, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,3,4- Trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,2 ′, 3′-pentahydroxybenzophenone, 2,3 , 4,3 ′, 4 ′, 5′-hexahydroxybenzophenone, bis (2,3,4-trihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) propane, 4b, 5,9b, 10-tetrahydro-1,3,6,8-tetrahydroxy-5,10-dimethylindeno [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. Moreover, as a reaction solvent, dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, diethyl ether, N-methylpyrrolidone, or the like is used.

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

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

  In the resin composition of the present invention, the content in the case of containing a compound that generates an acid by light is such that the difference in dissolution rate between the exposed part and the unexposed part becomes large, and the sensitivity becomes better. 3-100 mass parts is preferable with respect to a part, 5-50 mass parts is more preferable, and 5-30 mass parts is further more preferable.

<(D) Crosslinking agent>
The resin composition of the present invention preferably contains a crosslinking agent as necessary. The crosslinking agent used in the present invention is a compound having a structure capable of reacting with a resin 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. Examples of the crosslinking agent include a compound having a phenolic hydroxyl group, a compound having a hydroxymethylamino group, and an epoxy group.

  The compound having a phenolic hydroxyl group as a crosslinking agent used in the present invention is different from an alkali-soluble resin containing a phenolic hydroxyl group, and specific structures thereof include those described later. Such a compound having a phenolic hydroxyl group is preferred not only as a crosslinking agent but also because it can increase the dissolution rate of the exposed area when developing with an aqueous alkaline 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 physical properties of the cured film, the weight 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 amount 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 (6) is effective in promoting the dissolution of the exposed portion and melting at the time of curing the photosensitive resin film. It is preferable because of the excellent balance of the effects to be prevented.

In General Formula (6), 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 (6), 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, and tetrakis (methoxymethyl) urea.

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

  As the crosslinking agent used in the present invention, in addition to those described above, hydroxymethyl such as bis [3,4-bis (hydroxymethyl) phenyl] ether and 1,3,5-tris (1-hydroxy-1-methylethyl) benzene Aromatic compounds having a group, compounds having a maleimide group such as bis (4-maleimidophenyl) methane and 2,2-bis [4- (4′-maleimidophenoxy) phenyl] propane, compounds having a norbornene skeleton, multifunctional An acrylate compound, a compound having an oxetanyl group, a compound having a vinyl group, or a blocked isocyanate compound can be used.

  Among the above-mentioned crosslinking agents, 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 the elongation of the coating film can be further improved. A compound having a methylamino group is more preferable, a compound having an alkoxymethylamino group in which all or part of the hydroxymethylamino group is alkyletherified is particularly preferable, and an alkoxymethylamino group in which all of the hydroxymethylamino group is alkyletherified Most preferred are compounds having Among the compounds having an alkoxymethylamino group obtained by alkyl etherifying all of the hydroxymethylamino groups, compounds represented by the following general formula (7) are preferable.

In general formula (7), R < ⁷ > -R < ¹² > shows a C1-C10 alkyl group each independently.

  When the resin composition of the present invention contains a cross-linking agent, the content increases the difference in dissolution rate between the exposed and unexposed areas, and the sensitivity becomes better, and the characteristics of the cured film, 1-50 mass parts is preferable with respect to 100 mass parts of alkali-soluble resin which has a phenolic hydroxyl group used by this invention, 2-30 mass parts is more preferable, and 3-25 mass parts is more preferable. Moreover, the crosslinking agent mentioned above is used individually by 1 type or in combination of 2 or more types.

<(E) Adhesion aid>
From the viewpoint of further improving the adhesion to the substrate, the resin composition of the present invention may contain an adhesion assistant as necessary.

  Examples of the adhesion assistant in the present invention include silane compounds having an epoxy group, imidazole silane compounds, and silane compounds having an epoxy group represented by the general formula (8).

In the general formula (8), 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 (8), from the viewpoint of improving sensitivity and resolution, R ¹ is preferably a linear alkyl group represented by — (CH ₂ ) _n — (n is an integer of 1 to 6). R ² is preferably an alkoxy group or an alkoxyalkyl 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.

  As an adhesion assistant in the present invention, ureidopropyltriethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, urea propyltriethoxysilane, methylphenylsilanediol, ethylphenylsilanediol, n-propylphenyl Silanediol, isopropylphenylsilanediol, n-butylphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n- Butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, 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 (butyldihydroxy) Sisilyl) benzene, 1,4-bis (dimethylhydroxysilyl) benzene, 1,4-bis (diethylhydroxysilyl) benzene, 1,4-bis (dipropylhydroxysilyl) benzene, 1,4-bis (dibutylhydroxysilyl) ) Silane compounds such as benzene.

  Examples of the adhesion assistant in the present invention include an imidazolesilane compound. The imidazole silane compound is a compound having an imidazolyl group and an alkoxysilyl group. Such an imidazole silane compound includes an imidazole compound represented by the following general formula (9) and a glycidyl group-containing silane compound (for example, 3-glycidoxypropylsilane represented by the general formula (10)) in 80 to 80. It can be obtained by reacting at 200 ° C.

（一般式（９）、（１０）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 (9) and (10), 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, the reaction between the imidazole compound and the glycidyl group-containing silane compound is, for example, dropping 0.1 to 10 mole 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, ethanol or the like 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. 7-68256.

  For example, when the compound represented by the general formula (9) is used as the imidazole compound and the 3-glycidoxypropylsilane compound represented by the general formula (10) is used as the glycidyl group-containing silane compound, the above reaction is performed. Thus, an imidazolesilane compound represented by the following general formulas (11), (12), and (13) is obtained in a mixture state.

（上記中、Ｒ^{１３、１４}は水素又は炭素数が1〜２０のアルキル基、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。）

(In the above, R ^{13 and 14} are hydrogen or an alkyl group having 1 to 20 carbon atoms, 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. , 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 the product is generally represented by the general formula (11): same (12): same (13) = (40-80): (10-30): (5-40) (liquid chromatography) Area ratio when analyzed by graphy).

  Since the imidazole silane compound (11) obtained by the above reaction contains a hydroxyl group, it is included in the network of the cured film by a reaction with a crosslinking agent used as necessary in the resin composition of the present invention. Moreover, since the imidazole silane compound (11) contains an imidazole group and an alkoxysilyl group, it exhibits excellent adhesion to various substrates.

The imidazole compound represented by the general formula (9) used when synthesizing the imidazolesilane compound of the present invention 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.
Moreover, as the glycidyl group-containing silane compound used when synthesizing the imidazolesilane compound of the present invention, it is preferable to use a 3-glycidoxypropylsilane compound represented by the general formula (10). 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.

  Examples of the adhesion assistant in the present invention include a nitrogen-containing aromatic ring compound having a structure represented by the following general formula (14).

（一般式（１４）中、Ｒ^１は水素又は炭化水素基、Ｒ^２は水素、アミノ基、又はフェニル基を示す。Ａ及びＢはそれぞれ独立に窒素原子又は、水素を１つ有する炭素原子（Ｃ−Ｈ）を示す。）

(In General Formula (14), R ¹ represents hydrogen or a hydrocarbon group, R ² represents hydrogen, an amino group, or a phenyl group. A and B are each independently a nitrogen atom or a carbon atom having one hydrogen ( C-H).)

  Of the nitrogen-containing aromatic ring compounds having the structure represented by the general formula (14), from the viewpoint of further improving the adhesion to the substrate, the nitrogen-containing aromatic having the structure represented by the following general formula (15) A compound is preferred.

（一般式（１５）中、Ｒ^２は水素、炭化水素基、アミノ基、又はフェニル基を示す。）
上記一般式（１５）で表される構造を有する含窒素芳香族化合物として、具体的には、１Ｈ−テトラゾール、５−アミノテトラゾール、５−フェニルテトラゾール、５−メチルテトラゾール等が挙げられ、これらの中でも、より良好な基板への密着性を与える観点から、１Ｈ−テトラゾール又は５−アミノテトラゾールを用いることが好ましい。

(In general formula (15), R ² represents hydrogen, a hydrocarbon group, an amino group, or a phenyl group.)
Specific examples of the nitrogen-containing aromatic compound having the structure represented by the general formula (15) include 1H-tetrazole, 5-aminotetrazole, 5-phenyltetrazole, 5-methyltetrazole, and the like. Among these, 1H-tetrazole or 5-aminotetrazole is preferably used from the viewpoint of providing better adhesion to a substrate.

  The adhesion assistant used as necessary in the present invention is used alone or in combination of two or more. Further, when the resin composition contains an adhesion assistant, the adhesion assistant is contained with respect to 100 parts by mass of the resin in the resin composition from the viewpoint of adhesion to the substrate and storage stability of the resin composition. The amount is preferably 0.001 to 20 parts by mass, more preferably 0.005 to 15 parts by mass, and still more preferably 0.01 to 10 parts by mass.

  The resin composition of the present invention can contain other components such as a thermal acid generator, an elastomer, a solvent, a dissolution accelerator, a dissolution inhibitor, a surfactant, a dye, or a leveling agent as necessary.

[Method for producing organic layer]
The present invention provides a method for producing a residue-free organic layer. The organic layer production method of the present invention includes, for example, a step of forming a resin film by applying and drying a resin composition (film formation step), and exposing (exposure step) and developing (developing step) the resin film. An organic layer manufacturing method comprising: a step of forming a pattern resin film; and a step of heating the pattern resin film to form an organic layer (heating step). Hereinafter, each step will be described.

<Film formation process>
In the film forming step, the resin composition is spin-coated on a substrate using a spinner or the like. The applied resin composition is dried by heating using a hot plate, oven or the like. Thereby, the film (photosensitive resin film) of the resin composition is formed on the substrate. As the base material, it is preferable to use a glass substrate, a semiconductor, a metal oxide insulator (for example, titanium oxide (TiO ₂ ), silicon oxide (SiO ₂ ), silicon nitride (SiN)), a molding resin, or the like. Moreover, it is preferable that it is the conditions which a solvent volatilizes without a resin composition thermally decomposing, and a drying process is preferably performed at 50-200 degreeC, and it is preferable to carry out for 1 to 10 minutes.

  In the substrate according to the present embodiment, examples of the molding resin include epoxy resin, phenol resin, polyimide resin, polybenzoxazole, bismaleimide triazine resin, benzocyclobutene resin, and silicone resin.

  In the present embodiment, a part or the whole of the substrate surface may be coated with an insulating resin, and a part or all of the metal may be present. Examples of the insulating resin include epoxy resin, phenol resin, polyimide resin, polybenzoxazole, bismaleimide triazine resin, benzocyclobutene resin, silicone resin, siloxane resin, and polyarylene ether resin.

<Exposure process>
In the exposure step, the resin film obtained in the film formation step is irradiated with actinic rays such as ultraviolet rays, visible rays, and radiations through a mask. Although there is no restriction | limiting in the wavelength of actinic light, Irradiation of i line | wire or a ghi mixed line can be used suitably. After exposure, post-exposure heating (PEB) can be performed as necessary. The post-exposure heating temperature is preferably 70 ° C. to 140 ° C., and the post-exposure heating time is preferably 1 minute to 5 minutes.

<Development process>
In the development step, the resin film is patterned by removing the exposed portion of the resin film after the exposure step with a developer. Examples of the developer include flame retardant solvents such as 1,1,1-trichloroethane, N, N-dimethylformamide, dimethyl sulfoxide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone, etc. Organic solvents (X), mixed solvents of solvents (Y) such as lower alcohols, water and aromatic hydrocarbons and the above-mentioned organic solvents (X), and sodium hydroxide, potassium hydroxide, sodium silicate, ammonia An alkaline aqueous solution such as ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide (TMAH) is preferably used. The base concentration of these alkaline aqueous solutions is preferably 0.1 to 10% by mass. Furthermore, alcohols and surfactants can be added to the alkaline aqueous solution. 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 resin film is referred to as a pattern resin film.

<Heating process>
In the heating step, the resin composition is cured by heating the patterned resin film obtained in the developing step. A film obtained by curing the pattern resin film is referred to as an organic layer (pattern cured film). There is no restriction | limiting in heating temperature, The curing temperature from which a desired organic layer is obtained is selected suitably. However, it is preferably 250 ° C. or lower, more preferably 230 ° 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 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 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 pattern resin film (photosensitive resin film) while keeping the temperature of the substrate and the electronic device at, for example, 200 ° C. or lower.

  According to the method for producing an organic layer described above, a resin composition having good photosensitive characteristics can be obtained, and an organic layer having a good pattern shape can be obtained. By using the resin composition according to the present 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 organic layer formed from the resin composition of the present invention has a high glass transition temperature. Accordingly, the organic layer has excellent 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 element having organic layer>
The present invention provides an organic layer obtained by the method for producing an organic layer. The organic layer of the present invention is used in a semiconductor element, for example, as an interlayer insulating film, a surface protective film, or a rewiring layer. Moreover, this invention provides the semiconductor element which has this organic layer. Here, the semiconductor element having the organic layer of the present invention will be described with reference to the drawings. In addition, this invention is not limited by the following description and drawing.
Although there is no restriction | limiting in particular in the semiconductor element of this embodiment, The memory, a package, etc. which have a multilayer wiring structure, a rewiring structure, etc. are pointed out.
Here, an example of the manufacturing process of the semiconductor element will be described with reference to the drawings. 1 to 5 are a schematic perspective view and a schematic cross-sectional view showing an embodiment of a manufacturing process of a semiconductor element having a multilayer wiring structure. 1 to 5, (a) is a schematic perspective view, and (b) is a schematic cross-sectional view showing Ib-Ib to Vb-Vb cross sections in (a), respectively.

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

  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 described above is applied onto the interlayer insulating layer 4 and the second conductor layer 7 by spin coating, and dried to form a photosensitive resin film. Next, after irradiating light through a mask on which a pattern corresponding to the window portion 6C is drawn at a predetermined portion, the exposed resin film is developed with an alkaline aqueous solution to form a patterned resin film. Thereafter, the pattern resin film used as the surface protective layer 8 is formed by curing the pattern resin film by heating. 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 semiconductor device 500 using the surface protective layer 8 of the present embodiment is reliable. Excellent in properties.

In the above-described embodiment, a method for manufacturing a semiconductor device having a two-layer wiring structure has been described. 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 resin composition (photosensitive resin composition) of the present embodiment.
The electronic device of the present embodiment is not limited to one having a surface protective layer, a cover coat layer, or an interlayer insulating layer formed using the positive photosensitive resin composition described above, and can have various structures.

  6 and 7 are schematic cross-sectional views showing an embodiment of a semiconductor device having a rewiring structure. Since the photosensitive resin composition of this embodiment is excellent in stress relaxation property, adhesiveness, and the like, it can be used in a semiconductor element having a rewiring structure as shown in FIGS.

  FIG. 6 is a schematic cross-sectional view showing a wiring structure as one embodiment of a semiconductor element. A semiconductor device 600 shown in FIG. 6 includes an Al substrate having a pattern including a silicon substrate 23, an interlayer insulating layer 11 provided on one side of the silicon substrate 23, and 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.

  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 substrate 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 resin composition (photosensitive resin composition) includes not only the interlayer insulating layer 11 and the surface protective layer 14, but also the cover coat layer 19, the core 18, the collar 21, the underfill 22, and the like. It can be used as a material for forming. Since the pattern cured film using the photosensitive resin composition of the present embodiment is excellent in adhesion with a metal layer such as the Al wiring layer 12 or the rewiring layer 16 or a sealing agent, and has a high stress relaxation effect, A semiconductor element in which a pattern cured film is used for an interlayer insulating layer 11, a surface protective layer 14, a cover coat layer 19, a core 18, a collar 21 such as solder, an underfill 22 used in a flip chip or the like is extremely excellent in reliability. It will be a thing.

  The photosensitive resin composition of this embodiment is preferably used for the interlayer insulating layer 11, the surface protective layer 14, and / or the cover coat layer 19 of the semiconductor element having the rewiring layer 16 in FIGS.

  The film thicknesses of the interlayer insulating layer 11, the surface protective layer 14, and the cover coat layer 19 are preferably 3 to 20 μm, and more preferably 5 to 15 μm.

  According to the present invention, in the step of forming the pattern resin film by exposing and developing the photosensitive resin film, the step of removing the components that are difficult to dissolve in the alkaline solution and forming the pattern resin film by exposure and development. It becomes possible to provide the resin composition which does not have the residue to a recessed part.

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 resin composition>
The following I-1 and I-2 were prepared as alkali-soluble resins having a phenolic hydroxyl group as component (a).
I-1: Cresol novolak resin (cresol / formaldehyde novolak resin, m-cresol / p-cresol (molar ratio) = 60/40, polystyrene-equivalent weight average molecular weight = 13000, manufactured by Asahi Organic Materials Co., Ltd., trade name “EP4020G ")
I-2: Modified phenol resin prepared by the method described in Synthesis Example 1 below

Synthesis Example 1: Synthesis of phenol resin (I-2) modified with a compound having 4 to 100 carbon atoms having an unsaturated hydrocarbon group 100 parts by weight of phenol, 43 parts by weight of linseed oil and 0.1% of trifluoromethanesulfonic acid Mass parts 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 solution is cooled to room temperature (25 ° C.), and a phenol resin modified with a compound having 4 to 100 carbon atoms having an unsaturated hydrocarbon group (hereinafter referred to as (I-2)) is obtained as a reaction product. (Acid value 120 mg KOH / g). The weight average molecular weight calculated | required by standard polystyrene conversion of GPC method of this modified phenol resin (I-2) was about 25000.
Specifically, the weight average molecular weight was measured with the following apparatus and conditions.
Measuring device: Detector L4000UV manufactured by Hitachi, Ltd.
Pump: Hitachi Ltd. L6000
C-R4A Chromatopac made by Shimadzu Corporation
Measurement conditions: Column Gelpack GL-S300MDT-5 x 2 eluent: THF
LiBr (0.03 mol / l), H ₃ PO ₄ (0.06 mol / l)
Flow rate: 1.0 ml / min, detector: UV 270 nm
Measurement was performed using a solution of 1 ml of a solvent [THF / DMF = 1/1 (volume ratio)] with respect to 0.5 mg of the sample.

The following (II-1) was prepared as a photosensitive agent for component (c).
II-1: 1-naphthoquinone-2-diazide-5 of 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane Sulfonic acid ester (Esterification rate: about 90%, manufactured by AZ Electronic Materials, trade name “TPPA528”)

The following (III-1) was prepared as a crosslinking agent for the component (d).
III-1: Hexakis (methoxymethyl) melamine (manufactured by Sanwa Chemical Co., Ltd., trade name “Nicalak MW-30HM”) was prepared.

A silane compound of the following formula (IV-1) was prepared as an adhesion assistant for the component (e).
IV-1: 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM-403”)
IV-2: Ureidopropyltriethoxysilane represented by the following formula (IV-2) (trade name “AY-43-031” manufactured by Toray Dow Corning Co., Ltd.)

As the acrylic resin (b), an acrylic resin (V-1) was prepared by the method of Synthesis Example 2 below.
Synthesis Example 2: Synthesis of acrylic resin (V-1) 75 g of toluene and 75 g of isopropanol (IPA) were weighed in a 500 ml three-necked flask equipped with a stirrer, a nitrogen introduction tube and a thermometer, and separately weighed there. 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, 7.9 g polymerizable monomer and 0.13 g azobisisobutyronitrile (AIBN) were added. While stirring at room temperature (25 ° C.) at a stirring speed of about 270 rpm, 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 (V-1). The polymerization rate was 98%. It was the weight average molecular weight (MW) of the acrylic resin (V-1) calculated | required by standard polystyrene conversion of GPC method = 36,000.

  (VI): Ethyl lactate was prepared as a solvent for the component (f).

  The above components (I) to (VI) were blended in the predetermined proportions shown in Table 1. The obtained solution was filtered under pressure using a polytetrafluoroethylene filter having a pore size of 0.5 μm to prepare a resin composition.

<Base material>
A mirror-finished dummy silicon substrate was prepared as a base material.

Example 1
After stirring and mixing with tetramethylammonium hydroxide (TMAH) at a concentration of 0.3% by mass for 30 seconds, the mixture was allowed to stand for 10 minutes, and then an acrylic resin a having an absorbance at 660 nm of 0.034 was measured with a spectrophotometer. Resin composition A1 was produced with the composition of A.
(Example 2)
After stirring and mixing with tetramethylammonium hydroxide (TMAH) at a concentration of 0.3% by mass for 30 seconds, the mixture was allowed to stand for 10 minutes, and then an acrylic resin b having an absorbance at 660 nm of 0.026 was measured with a spectrophotometer. Resin composition B1 was produced with the composition of B.
The prepared A1 and B1 solutions were spin-coated on a dummy silicon substrate and heated at 120 ° C. for 3 minutes to form a resin film having a thickness of about 10 to 11 μm. Subsequently, reduction projection exposure with i-line (365 nm) was performed through a mask on which a test pattern was drawn using an i-line stepper (trade name “FPA-3000i” manufactured by Canon Inc.). After exposure, development is performed using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) so that the residual film thickness is about 80 to 100% of the initial film thickness, and then rinsed with water to form a pattern. A resin film was obtained.

(Comparative Example 1)
After stirring and mixing with tetramethylammonium hydroxide (TMAH) at a concentration of 0.3% by mass for 30 seconds, the mixture was allowed to stand for 10 minutes, and then an acrylic resin c having an absorbance at 660 nm of 0.072 was measured with a spectrophotometer. Resin composition B2 was produced using the composition of B.

(Comparative Example 2)
After stirring and mixing with tetramethylammonium hydroxide (TMAH) at a concentration of 0.3% by mass for 30 seconds, the mixture was allowed to stand for 10 minutes, and then an acrylic resin d having an absorbance at 660 nm of 0.065 was measured with a spectrophotometer. Resin composition A2 was produced using the composition of A.
The prepared B2 and A2 liquids were spin-coated on a dummy silicon substrate and heated at 120 ° C. for 3 minutes to form a resin film having a thickness of about 10 to 11 μm. Subsequently, reduction projection exposure with i-line (365 nm) was performed through a mask on which a test pattern was drawn using an i-line stepper (trade name “FPA-3000i” manufactured by Canon Inc.). After exposure, development is performed using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) so that the residual film thickness is about 80 to 100% of the initial film thickness, and then rinsed with water to form a pattern. A resin film was obtained.
The developed and removed recesses obtained above were observed and evaluated as “Yes” when there was a residue and “No” when there was no residue. The results are summarized in Table 3.

As shown in Table 2, the acrylic resin of the resin composition was mixed with tetramethylammonium hydroxide (TMAH) at a concentration of 0.3% by mass for 30 seconds, and then allowed to stand for 10 minutes. When an acrylic resin having an absorbance at 660 nm measured by a spectrophotometer of 0.06 or less was used, there was no residue after exposure and development, and good results were obtained. On the other hand, the residue was seen in the comparative example using the acrylic resin whose absorbance exceeded 0.06 and was high.
In the step of forming the patterned resin film by exposing and developing the resin composition, components that are difficult to dissolve in the alkaline solution can be removed, and in the step of forming the patterned resin film by exposing and developing, there is no residue in the recess. It becomes possible to provide a resin composition.

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 layer 11 ... Interlayer insulation layer 12 Al wiring layer 13 Insulating layer 14 Surface protection layer 15 Pad part 16 Re-wiring layer 17 Conductive ball 18 Island core 19 Cover coat layer 20 Barrier metal 21 Color 22 Underfill 23 ··· Silicon substrate 24 · Connection portion 100, 200, 300, 400 · Structure 500, 600, 700 · Semiconductor device

Claims (6)

(A) a resin composition comprising an alkali-soluble resin having a phenolic hydroxyl group and (b) an acrylic resin;
The (b) acrylic resin was mixed with tetramethylammonium hydroxide (TMAH) at a concentration of 0.3% by mass for 30 seconds, then allowed to stand for 10 minutes, and then measured with a spectrophotometer. A resin composition having an absorbance of 0.06 or less.   The resin composition according to claim 1, further comprising (c) a photosensitizer.   The resin composition according to claim 1 or 2, further comprising (d) a crosslinking agent.   Applying and drying the resin composition according to any one of claims 1 to 3 on a substrate to form a resin film, exposing and developing the resin film to form a patterned resin film, And a step of forming the organic layer by heating the pattern resin film.   An organic layer obtained by the production method according to claim 4.   A semiconductor device having the organic layer according to claim 5.

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