JP2019138995A - Photosensitive resin composition, photosensitive resin sheet, and semiconductor electronic component using them - Google Patents

Abstract

To provide a photosensitive resin composition, a photosensitive resin sheet, and a semiconductor electronic component using them which are excellent in flux resistance and room temperature storage stability and have fine pattern processability.SOLUTION: A photosensitive resin composition contains (A) an alkali-soluble resin, (B) a crosslinking agent being a compound represented by general formula (1), and (C) a photoacid generator compound. (In the formula, Rrepresents a glycidyl group, an allyl group, a thiol group or an isocyanate group.)SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive resin composition, a photosensitive resin sheet, and a semiconductor electronic component using the same. More specifically, the present invention relates to a photosensitive resin composition suitably used for a surface protective film of a semiconductor element or an inductor device, an interlayer insulating film, an insulating layer of an organic electroluminescence element, or the like.

  In recent years, as various electronic devices such as personal computers, digital cameras, and mobile phones are miniaturized and have high performance, demands for further miniaturization, thinning, and high density of semiconductor elements are rapidly increasing. The surface protective film, interlayer insulating film, and materials for rewiring layers of semiconductor packages used there are fine patterning to simplify the complicated pattern formation process and form a package with a unique structure. That is possible, that is, photosensitivity is required. For example, photosensitive polyimide has been studied as a material capable of fine pattern processing (for example, Patent Documents 1 and 2).

Further, as a further required characteristic, resistance to a flux used when solder balls are mounted is required (Patent Document 3).
Furthermore, in the manufacturing process, room temperature storage until the photosensitive material is used up is required.

International Publication No. 2012/002134 Pamphlet International Publication No. 2016/143580 Pamphlet JP, 2015-121775, A

  However, it has been difficult for conventional materials to have characteristics of flux resistance, room temperature storage stability, and fine pattern processability.

  In order to improve the flux resistance, a crosslinking agent having a high crosslinking density is used. However, the thermal cross-linking agent that exhibits flux resistance tends to leave a residue, making it difficult to process fine patterns. In addition, many photosensitive materials having fine pattern processability are likely to react at room temperature or easily decompose, and there is a problem in storage stability at room temperature. For example, although Patent Document 3 has photosensitivity and flux resistance, there are problems in fine pattern processability and room temperature storage stability.

  In view of such circumstances, an object of the present invention is to provide a photosensitive resin composition, a photosensitive resin sheet having excellent flux resistance and room temperature storage stability and having fine pattern processability, and an electronic component using these. To do.

  The present invention includes (A) an alkali-soluble resin, (B) a cross-linking agent, (C) a compound that generates an acid by light, and (B) a glycoluril compound represented by the general formula (1). It is a photosensitive resin composition characterized by being.

(Wherein R ¹ and R ² are the same or different and each represents a hydrogen atom, a lower alkyl group or a phenyl group; R ³ represents a glycidyl group, an allyl group, a thiol group or an isocyanate group; R ⁴ , R ⁵ And R ⁶ are the same or different and each represents a hydrogen atom, a glycidyl group, an allyl group, a thiol group or an isocyanate group (n is 0, 1 or 2).

  The present invention provides a photosensitive resin composition that is excellent in flux resistance and room temperature storage stability and has fine pattern processability.

  The photosensitive resin composition of the present invention contains (A) an alkali-soluble resin, (B) a crosslinking agent, (C) a compound that generates an acid by light, and (B) the crosslinking agent is represented by the following general formula (1). It is characterized by being a glycoluril compound shown.

(Wherein R ¹ and R ² are the same or different and each represents a hydrogen atom, a lower alkyl group or a phenyl group; R ³ represents a glycidyl group, an allyl group, a thiol group or an isocyanate group; R ⁴ , R ⁵ And R ⁶ are the same or different and each represents a hydrogen atom, a glycidyl group, an allyl group, a thiol group or an isocyanate group (n is 0, 1 or 2).
The (A) alkali-soluble resin in the present invention preferably has an alkali-soluble functional group for development with an aqueous alkali solution. The alkali-soluble functional group is a functional group having acidity, and specifically includes a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, and the like. The term “alkali-soluble” as used herein refers to a substance that dissolves 0.1 g or more at 25 ° C. with respect to 100 g of a 2.38% aqueous solution of tetramethylammonium hydroxide. Among the alkali-soluble functional groups described above, the alkali-soluble functional group is preferably a phenolic hydroxyl group from the viewpoint of storage stability of the photosensitive adhesive composition and corrosion of the copper wiring as a conductor.

  The alkali-soluble resin is not particularly limited as long as it is soluble in an alkaline aqueous solution. From the viewpoint of processability and heat resistance, one or more resins selected from polyamide, polyimide, polybenzoxazole, and copolymers thereof are used. It is preferable to contain.

The polyamide structure is a benzoxazole precursor in which two pairs of amino group and hydroxyl group are in an ortho position to each other, other polyhydroxyamide, polyamide, or a copolymer structure thereof.
Furthermore, the (A) alkali-soluble resin preferably comprises at least a copolymer of polyamide and polyimide.
Moreover, by having a polyimide structure, the interaction with the metal is enhanced as compared with the case of the polyamide structure alone, and the adhesion with the metal when it is used as a cured film can be improved.

  Furthermore, it is preferable that the content of the structural unit of the polyimide is in the range of 2 to 50 mol% with respect to 100 mol% of the structural unit of the polyamide and the polyimide of the alkali-soluble resin (A). By having a polyimide structure of 2 mol% or more, the interaction with the metal can be enhanced compared to the case of the polyamide structure alone, and the adhesion with the metal when made into a cured film can be improved. % Or less is preferable because high elongation by polyamide can be obtained.

  In the present invention, the (A) alkali-soluble resin has a structure in which the polyamide is represented by the general formula (2), and the polyimide precursor and the polyimide are represented by the general formula (3) and the general formula (4). It is preferable that the polybenzoxazole is a resin having a structure represented by the general formula (5).

(In General Formulas (2) to (5), X ¹ represents a divalent to hexavalent organic group, X ² and X ³ each independently represent a 4 to 10 valent organic group, and X ⁴ represents 2 to 6 Y ^{1 to} Y ³ each independently represents a 2 to 4 valent organic group, Y ⁴ represents a ⁴ to 6 valent organic group, and R represents a hydrogen atom or a carbon number of 1 to 20 Represents an organic group, and p, q, r, s, t, u, v, and w are each independently an integer of 0 to 4.)
In the general formulas (2) and (5), X ¹ and X ⁴ represent a divalent to hexavalent organic group having 2 or more carbon atoms and represent an acid structural component. X ¹ and X ⁴ are terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, naphthalenedicarboxylic acid, aromatic dicarboxylic acid such as bis (carboxyphenyl) propane, cyclobutanedicarboxylic acid, cyclohexanedicarboxylic acid, malonic acid, dimethylmalonic acid, ethyl Malonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid Glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, Octafluoroadipic acid, 3-methylazi Acid, octafluoroadipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonane Diacid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, heneicosanedioic acid, docosanedioic acid, tricosanedioic acid , Tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosandioic acid, triacontanedioic acid, hentriacontandioic acid, dotriacontanedioic acid, diglycolic acid and other aliphatic dicarboxylic acids Acids and dicarboxylic acids having the structure represented by the following general formula Tricarboxylic acids such as trimellitic acid and trimesic acid, those aromatic rings and hydrocarbon hydrogen atoms partially substituted with alkyl groups having 1 to 10 carbon atoms, fluoroalkyl groups, halogen atoms, etc. , —S—, —SO—, —SO ₂ —, —NH—, —NCH ₃ —, —N (CH ₂ CH ₃ ) —, —N (CH ₂ CH ₂ CH ₃ ) —, —N (CH ( It is a structure derived from one containing a bond such as CH ₃ ) ₂ ) —, —COO—, —CONH—, —OCONH—, or —NHCONH—.

Among these, a structure in which X ¹ and X ⁴ are derived from an aromatic dicarboxylic acid is preferable because ring closure hardly occurs at the time of thermosetting, thereby suppressing an increase in stress due to film shrinkage and improving adhesion.
In producing the resin, when polycondensation is performed, for example, a compound in which the carboxylic acid groups of X ¹ and X ⁴ are substituted with active carboxylic acid groups as shown in the following general formula is used.

(Wherein B and C are each independently a hydrogen atom, methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, trifluoromethyl group, halogen group, phenoxy group, nitro group, etc.) But is not limited to these.)
Among these, it is preferable to use an active carboxylic acid group other than the chloride compound. By using an active carboxylic acid group other than the chloride compound, chlorine ions in the resulting resin can be reduced, and peeling from the metal substrate due to the presence of chlorine ions can be prevented. Further, as the active carboxylic acid group, it is more preferable to use a diimidazolide compound. Since the leaving group of the diimidazolide compound becomes water-soluble imidazole, reprecipitation and washing of the obtained resin can be performed with water. Furthermore, since the detached imidazole is basic, it acts as a ring closure accelerator for the polyimide precursor structure during polymerization, and at the stage of producing the polyamide resin, it is possible to increase the ring closure rate of imidization. . As a result, the ring closure rate when a cured film is produced by heat treatment can be lowered.
Y ¹ to Y ³ in the general formulas (2) to (4) represent divalent to tetravalent organic groups, Y ⁴ represents a tetravalent to hexavalent organic group, and represents a diamine-derived organic group. .

In the (A) alkali-soluble resin, Y ¹ to Y ⁴ in the general formulas (2) to (5) preferably contain a diamine residue having a phenolic hydroxyl group. By including a diamine residue having a phenolic hydroxyl group, moderate solubility of the resin in an alkaline developer can be obtained, so that a high contrast between the exposed area and the unexposed area can be obtained, and a desired pattern can be formed.

  Specific examples of the diamine having a phenolic hydroxyl group include, for example, bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, and bis (3-amino- 4-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) methylene, bis (3-amino-4-hydroxyphenyl) ether, bis (3-amino-4-hydroxy) biphenyl, 2,2′- Ditrifluoromethyl-5,5′-dihydroxyl-4,4′-diaminobiphenyl, bis (3-amino-4-hydroxyphenyl) fluorene, 2,2′-bis (trifluoromethyl) -5,5′- Aromatic diamines such as dihydroxybenzidine, and some of these aromatic rings and hydrocarbon hydrogen atoms 1-10 alkyl group or a fluoroalkyl group, compounds substituted with a halogen atom, and the like can be given. Diamine having a structure shown below, but are not limited to. Other diamine to be copolymerized can be used as it is or as a corresponding diisocyanate compound or trimethylsilylated diamine. Moreover, you may use combining these 2 or more types of diamine components.

Y ^{1 to} Y ⁴ may include a diamine residue having an aromatic other than those described above. By copolymerizing these, heat resistance can be improved. Specific examples of the diamine residue having an aromatic group include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4 '-Diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 1,4-bis (4-aminophenoxy) benzene, benzine, m- Phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl Bis {4- (4-aminophenoxy Phenyl} ether, 1,4-bis (4-aminophenoxy) benzene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-diethyl-4,4′-diaminobiphenyl, 3,3 '-Dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2', 3,3'-tetramethyl-4,4'-diaminobiphenyl, 3, Aromatic diamines such as 3 ′, 4,4′-tetramethyl-4,4′-diaminobiphenyl, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, and aromatic rings thereof And a compound obtained by substituting a part of hydrogen atoms of hydrocarbon with an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group, a halogen atom, or the like, but is not limited thereto. Other diamine to be copolymerized can be used as it is or as a corresponding diisocyanate compound or trimethylsilylated diamine. Moreover, you may use combining these 2 or more types of diamine components.

Similarly, the general formula is a polyimide precursor structure (3) or the general formula a polyimide structure (4), X ² and X ³ represents a residue of a dianhydride, a tetravalent to 10-valent Organic group.

  Specific examples of the acid dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and 2,3,3 ′, 4′-biphenyltetracarboxylic acid. Dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3′- Benzophenone tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1- Bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxy Phenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid Anhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorenic dianhydride, 9,9-bis {4- (3,4-dicarboxyphenoxy) phenyl} fluorenic dianhydride, 2, 3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2- Aromatic tetracarboxylic dianhydrides such as bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, , 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3, 4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid Acid dianhydride, 2,3,5-tricarboxy-2-cyclopentaneacetic acid dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 3,5,6-tricarboxy-2-norbornane acetic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5 (Tet Hydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione and acid dianhydrides having the structure shown in the following formula, aromatic rings and hydrocarbons thereof. Although the compound etc. which substituted a part of hydrogen atom by the C1-C10 alkyl group, a fluoroalkyl group, a halogen atom, etc. can be mentioned, It is not limited to these.

(R ⁷ represents an oxygen atom, C (CF ₃ ) ₂ , C (CH ₃ ) ₂ or SO ₂ , and R ⁸ and R ⁹ represent a hydrogen atom, a hydroxyl group or a thiol group.)
Of these, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′- Biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenonetetracarboxylic dianhydride, 2,2-bis ( 3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, Bis (3,4-dicarboxyfe Nyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 3,3 ′, 4 4'-diphenylsulfonetetracarboxylic dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorenic dianhydride, 9,9-bis {4- (3,4-dicarboxyphenoxy) phenyl } Fluorenoic dianhydride, butanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1, 3,3a, 4,5,9b-Hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione is preferred. These are used alone or in combination of two or more.

  R in the general formula (3) represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. From the viewpoint of solubility in an alkali developer and the solution stability of the resulting resin composition, it is preferable that 10 mol% to 90 mol% of R are hydrogen atoms. Furthermore, it is more preferable that R contains at least one monovalent hydrocarbon group having 1 to 16 carbon atoms, and the others are hydrogen atoms.

  The molar ratio of the structures represented by the general formulas (2) to (5) in the present invention can be obtained by a method of calculating from the molar ratio of monomers used for polymerization or a nuclear magnetic resonance apparatus (NMR). It can be confirmed by a method for detecting a peak of a polyamide structure, an imide precursor structure or an imide structure in a cured resin, a resin composition, or a cured film. In the present invention, the (A) alkali-soluble resin preferably has a weight average molecular weight of 3,000 to 200,000. In this range, moderate solubility in an alkali developer can be obtained, so that a high contrast between the exposed area and the unexposed area can be obtained, and a desired pattern can be formed. In terms of solubility in an alkali developer, 100,000 or less is more preferable, and 50,000 or less is more preferable. Moreover, 10,000 or more are preferable from the surface of an elongation improvement. Here, the molecular weight can be measured by gel permeation chromatography (GPC) and converted from a standard polystyrene calibration curve.

  In order to improve the storage stability of the resin composition of the present invention, the polyamide resin is sealed at the end of the main chain with another end-capping agent such as monoamine, monocarboxylic acid, acid anhydride, or monoactive ester compound. Also good.

  Further, the end of the polyamide resin is sealed with an end-capping agent having a hydroxyl group, carboxyl group, sulfonic acid group, thiol group, vinyl group, ethynyl group, or allyl group, thereby dissolving the polyamide resin in an alkaline solution. The speed and mechanical properties of the resulting cured film can be easily adjusted to a preferred range.

  The introduction ratio of the end-capping agent is preferably 0.1 mol% or more, more preferably based on the total amine component, in order to prevent the polyamide resin from having a high weight average molecular weight and lowering the solubility in an alkaline solution. Is 5 mol% or more. Moreover, in order to suppress that the mechanical characteristic of the cured film obtained when the weight average molecular weight of a polyamide resin becomes low is suppressed, Preferably it is 60 mol% or less, More preferably, it is 50 mol% or less. Further, a plurality of terminal blocking agents may be reacted to introduce a plurality of different terminal groups.

  Specific examples of monoamines used as end-capping agents include M-600, M-1000, M-2005, and M-2070 (above trade names, manufactured by HUNTSMAN Co., Ltd.), aniline, 2-ethynylaniline, and 3-ethynyl. Aniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-amino Naphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy -5-aminonaphthalene, 2-carboxy-7-aminonaphthalene 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-amino Salicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2 -Aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like can be used. Two or more of these may be used.

  Monocarboxylic acid and monoactive ester compound as end-capping agents are 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy -6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4 -Monocarboxylic acids such as carboxybenzenesulfonic acid and active ester compounds in which these carboxyl groups are esterified, phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, 3-hydride Acid anhydrides such as xylphthalic anhydride, dicarboxylic acid phthalic acid, maleic acid, nadic acid, cyclohexanedicarboxylic acid, 3-hydroxyphthalic acid, 5-norbornene-2,3-dicarboxylic acid, and tricarboxylic acid, Trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 2, Active ester compounds obtained by reacting one carboxyl group of dicarboxylic acids such as 6-dicarboxynaphthalene with N-hydroxybenzotriazole, imidazole, N-hydroxy-5-norbornene-2,3-dicarboximide, these Aromatic And a part of hydrogen atoms of a hydrocarbon, an alkyl group or a fluoroalkyl group having 1 to 10 carbon atoms, or the like can be used compounds substituted with a halogen atom. Two or more of these may be used.

  Moreover, the structure by which the resin terminal and resin side chain of (A) alkali-soluble resin in this invention were sealed with imide is preferable. Since the (A) alkali-soluble resin terminal has more parts in contact with other components and the substrate than the main chain of the (A) alkali-soluble resin, the adhesion can be improved and the storage stability of the resin composition can be improved. For this reason, it is preferable to have an imide structure, and it is more preferable that general formula (4) which is a polyimide structure exists in the vicinity of the terminal of (A) alkali-soluble resin. Thereby, adhesiveness can be improved and the storage stability of (A) alkali-soluble resin can further be improved. In order to obtain a structure in which the polyamide resin terminal and the polyamide resin side chain are imide-sealed, it is preferable to copolymerize the polyamide structure with a polyimide structure after polymerization.

  (A) The structure in which the alkali-soluble resin is polyamide and the polyamide resin terminal and the polyamide resin side chain are sealed with imide can be obtained by reacting an acid anhydride in the case of an amine residue. Moreover, in the case of an active ester residue, it is obtained by copolymerizing a diamine and an acid anhydride.

  The end capping agent that can be used in the present invention can be easily detected by the following method. For example, (A) an alkali-soluble resin having an end-capping agent introduced therein is dissolved in an acidic solution and decomposed into an amine component and an acid anhydride component, which are constituent units, and this is decomposed into gas chromatography (GC), NMR Thus, the end-capping agent used in the present invention can be easily detected. Apart from this, the resin component into which the end-capping agent has been introduced can also be easily detected by directly measuring it with a pyrolysis gas chromatograph (PGC), infrared spectrum and 13C-NMR spectrum.

  In the present invention, (A) the alkali-soluble resin is synthesized, for example, by the following method, but is not limited thereto. The polyamide structure is obtained by first dissolving a compound in which a dicarboxylic acid is substituted with an active carboxylic acid group, a diamine having an aliphatic group, and other copolymerization components in an organic solvent at room temperature, possibly at an elevated temperature. Polymerize by heating. From the viewpoint of the stability of the solution at the time of reaction, it is preferable that the order of dissolution is performed first with a highly soluble diamine compound. In the case of copolymerizing with a polyimide precursor or polyimide, an acid dianhydride, and optionally other copolymerization components are then added, and an acid or acid anhydride serving as a terminal blocker is added and polymerized.

  In the polyimide used in the present invention, a part of the diamine is replaced with a primary monoamine which is a terminal blocking agent, or a tetracarboxylic dianhydride is replaced with a dicarboxylic acid anhydride which is a terminal blocking agent, It is synthesized by a known method. For example, a method of reacting tetracarboxylic dianhydride, diamine compound and monoamine at low temperature, a method of reacting tetracarboxylic dianhydride, dicarboxylic anhydride and diamine compound at low temperature, tetracarboxylic dianhydride and Diester is obtained with alcohol, and then a polyimide precursor is obtained using a method such as a method of reacting diamine, monoamine and a condensing agent. Thereafter, a polyimide can be synthesized using a known imidization reaction method.

  In the present invention, it is preferable that (A) the alkali-soluble resin is polymerized by the above-described method, then poured into a large amount of water or a mixed solution of methanol and water, precipitated, filtered, dried and isolated. . The drying temperature is preferably 40 to 100 ° C, more preferably 50 to 80 ° C. By this operation, unreacted monomers and oligomer components such as dimers and trimers are removed, and the film characteristics after thermosetting can be improved.

In the present invention, the imidization rate can be easily determined by, for example, the following method. First, measuring the infrared absorption spectrum of the polymer, absorption peaks of an imide structure caused by a polyimide (1780 cm around ^-1, 1377 cm around ^-1) to confirm the presence of. Next, the polymer was heat-treated at 350 ° C. for 1 hour, an infrared absorption spectrum was measured using a sample with an imidization ratio of 100%, and the peak intensity around 1377 cm ⁻¹ of the resin before and after the heat treatment was compared, thereby performing heat treatment. The content of imide groups in the pre-resin is calculated to determine the imidization rate. The imidation rate is preferably 50% or more, and more preferably 80% or more, because the change in the ring closure rate during thermosetting is suppressed and the effect of reducing the stress is obtained.

  The crosslinking agent (B) in the present invention is a glycoluril compound represented by the general formula (1).

(Wherein R ¹ and R ² are the same or different and each represents a hydrogen atom, a lower alkyl group or a phenyl group; R ³ represents a glycidyl group, an allyl group, a thiol group or an isocyanate group; R ⁴ , R ⁵ And R ⁶ are the same or different and each represents a hydrogen atom, a glycidyl group, an allyl group, a thiol group or an isocyanate group (n is 0, 1 or 2).
The glycoluril compound represented by the chemical formula (1) is preferably a compound having at least two reactive groups. By having at least two reactive groups, it can react with the resin and / or the same kind of molecule to form a crosslinked structure. In particular, a glycol compound having a glycidyl group is preferable because it thermally crosslinks with (A) the alkali-soluble resin and does not cause a dehydration reaction due to crosslinking, so that film shrinkage hardly occurs.

Examples of the glycol compound having a glycidyl group include 1-glycidyl glycoluril, 1,3-diglycidyl glycoluril, 1,4-diglycidylglycoluril, 1,6-diglycidylglycoluril, 1,3,4- Triglycidyl glycoluril, 1,3,4,6-tetraglycidylglycoluril, 1-glycidyl-3a-methylglycoluril, 1,3-diglycidyl-3a-methylglycoluril, 1,4-diglycidyl-3a-methylglycol Uril, 1,6-diglycidyl-3a-methylglycoluril, 1,3,4-triglycidyl-3a-methylglycoluril, 1,3,4,6-tetraglycidyl-3a-methylglycoluril, 1-glycidyl- 3a, 6a-dimethylglycol Le, 1,3-diglycidyl -3a, 6a- dimethyl glycoluril, 1,4-diglycidyl -3a, 6a- dimethyl glycoluril,
1,6-diglycidyl-3a, 6a-dimethylglycoluril, 1,3,4-triglycidyl-3a, 6a-dimethylglycoluril, 1,3,4,6-tetraglycidyl-3a, 6a-dimethylglycoluril, 1-glycidyl-3a, 6a-diphenylglycoluril, 1,3-diglycidyl-3a, 6a-diphenylglycoluril, 1,4-diglycidyl-3a, 6a-diphenylglycoluril, 1,6-diglycidyl-3a, 6a- Examples include diphenyl glycoluril, 1,3,4-triglycidyl-3a, 6a-diphenylglycoluril, 1,3,4,6-tetraglycidyl-3a, 6a-diphenylglycoluril and the like. Specific examples include TG-G (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.).

  These glycoluril compounds may be used alone or in combination of two or more. (A) It is preferable that it is 10-50 mass parts with respect to 100 mass parts of alkali-soluble resin. If it is 10 parts by mass or more, chemical resistance is improved, and if it is 50 parts by mass or less, developability is not significantly deteriorated.

  The photosensitive resin composition of the present invention has positive photosensitivity by containing (C) a compound that generates an acid by light. That is, the photoacid generator has a characteristic that an acid is generated by light irradiation, and the solubility of the light irradiation portion in an alkaline aqueous solution is increased. Photoacid generators include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, iodonium salts, and the like.

  The quinonediazide compound is a compound in which a sulfonic acid of quinonediazide is bonded to a polyhydroxy compound with an ester, a sulfonic acid of quinonediazide is bonded to a polyamino compound in a sulfonamide, and a sulfonic acid of quinonediazide is bonded to a polyhydroxypolyamino compound in an ester bond and / or sulfonamide. Examples include those that are combined. Although all the functional groups of these polyhydroxy compounds and polyamino compounds may not be substituted with quinonediazide, it is preferable that 50 mol% or more of the entire functional groups are substituted with quinonediazide. When the substitution with quinonediazide is 50 mol% or more, the solubility in an alkali developer is not excessively high, a contrast with an unexposed portion is obtained, and a desired pattern can be obtained. By using such a quinonediazide compound, it is possible to obtain a positive photosensitive resin composition that is sensitive to i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp that is a general ultraviolet ray. it can. Such compounds may be used alone or in combination of two or more. Further, by using two types of photoacid generators, the ratio of the dissolution rate between the exposed part and the unexposed part can be increased, and as a result, a highly sensitive photosensitive resin composition can be obtained.

  Polyhydroxy compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP -IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ , TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR -PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (above, trade name, manufactured by Asahi Organic Materials Co., Ltd.) ), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, gallic acid methyl ester, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name, Honshu Chemical Industry Co., Ltd.) and the like, but are not limited thereto.

  Polyamino compounds are 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenyl. Examples thereof include, but are not limited to, sulfhydrides.

  Examples of the polyhydroxypolyamino compound include 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 3,3'-dihydroxybenzidine, but are not limited thereto.

  In the present invention, quinonediazide is preferably a 5-naphthoquinonediazidosulfonyl group or a 4-naphthoquinonediazidesulfonyl group. The 4-naphthoquinonediazide sulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. The 5-naphthoquinone diazide sulfonyl ester compound has an absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure. In the present invention, it is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound or a 5-naphthoquinone diazide sulfonyl ester compound depending on the wavelength to be exposed. Further, a naphthoquinone diazide sulfonyl ester compound in which a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group are used in the same molecule can be obtained, or a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound can be obtained. Can also be used as a mixture.

  In addition, when the molecular weight of the quinonediazide compound is greater than 5000, the quinonediazide compound is not sufficiently thermally decomposed in the subsequent heat treatment, so that the heat resistance of the resulting film is lowered, the mechanical properties are lowered, the adhesiveness is lowered, and the like. Problems can arise. From such a viewpoint, the molecular weight of a preferable quinonediazide compound is 300 to 3000. More preferably, it is 350-1500.

  The quinonediazide compound used in the present invention is synthesized from a specific phenol compound by the following method. For example, a method of reacting 5-naphthoquinonediazide sulfonyl chloride and a phenol compound in the presence of triethylamine can be mentioned. Examples of the method for synthesizing a phenol compound include a method in which an α- (hydroxyphenyl) styrene derivative is reacted with a polyhydric phenol compound under an acid catalyst.

  Among the photoacid generators used in the present invention, the photoacid generator that moderately stabilizes the acid component generated by exposure is preferably a sulfonium salt, a phosphonium salt, or a diazonium salt. Since the resin composition obtained from the photosensitive resin composition of the present invention is used as a permanent film, it is environmentally undesirable for phosphorus or the like to remain, and it is necessary to consider the color tone of the film. In this case, a sulfonium salt is preferably used. Particularly preferred is a triarylsulfonium salt.

  The content of the photoacid generator used in the present invention is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (A). Among these, the quinonediazide compound has a preferable range of 3-40 mass parts. Further, the compound selected from sulfonium salt, phosphonium salt and diazonium salt is preferably in the range of 0.05 to 40 parts by mass, more preferably in the range of 0.1 to 30 parts by mass. By setting the content of the photoacid generator within this range, higher sensitivity can be achieved. Furthermore, you may contain a sensitizer etc. as needed.

The photosensitive resin composition of the present invention may contain a crosslinking agent other than the crosslinking agent (B), and is preferably a compound having an epoxy group, a glycidyl group, an alkoxymethyl group, or a methylol group.
Epoxy groups and glycidyl groups are thermally cross-linked with polymers at 200 ° C. or lower, and do not cause dehydration reaction due to cross-linking, so that film shrinkage hardly occurs. Therefore, in addition to mechanical properties, it is effective for low-temperature curing and low warpage. . Examples having an epoxy group or glycidyl group include bisphenol A type epoxy resin, bisphenol F type epoxy resin, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polymethyl (glycidyloxypropyl) siloxane and the like, silicone However, the present invention is not limited to these. Specifically, Epicron 850-S, Epicron HP-4032, Epicron HP-7200, Epicron HP-820, Epicron HP-4700, Epicron EXA-4710, Epicron HP-4770, Epicron EXA-859CRP, Epicron EXA-1514, Epicron EXA-4880, Epicron EXA-4850-150, Epicron EXA-4850-1000, Epicron EXA-4816, Epicron EXA-4822 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.), Recare Resin BEO-60E Product name, Shin Nippon Rika Co., Ltd.), EP-4003S, EP-4000S (Adeka Co., Ltd.), and the like.

  Examples having an alkoxymethyl group or a methylol group include, for example, DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMO -BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC (registered trademark) MX-290, NIKACALAC MX-280 , NIKACALAC MW-100LM, NIKACALAC MX-750LM (trade name, manufactured by Sanwa Chemical Co., Ltd.).

  The photosensitive resin composition of the present invention can further contain a silane compound. By containing the silane compound, the adhesion of the heat-resistant resin film is improved. Specific examples of the silane compound include N-phenylaminoethyltrimethoxysilane, N-phenylaminoethyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, N-phenylaminopropyltriethoxysilane, N-phenylaminobutyltri Methoxysilane, N-phenylaminobutyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltri Examples include methoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 3-methacryloxypropylmethyldiethoxysilane. The content of the silane compound is preferably 0.01 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the resin whose main component is the structure represented by the general formula (1) and / or (2). .

  In addition, the photosensitive resin composition having positive photosensitivity of the present invention is optionally provided with a surfactant, an ester such as ethyl lactate or propylene glycol monomethyl ether acetate for the purpose of improving the wettability with the substrate. And alcohols such as ethanol, ketones such as cyclohexanone and methyl isobutyl ketone, and ethers such as tetrahydrofuran and dioxane. In addition, inorganic particles such as silicon dioxide and titanium dioxide, or polyimide powder may be contained for the purpose of suppressing the thermal expansion coefficient, increasing the dielectric constant, and reducing the dielectric constant.

  As for the photosensitive resin composition of this invention, the shape before hardening is not limited, For example, a varnish shape, a film form, etc. are mentioned. In the case of a film, it may be a sheet formed on a support. When used in the form of a varnish, those obtained by dissolving the components (A) to (C) and components added as necessary in the above organic solvent can be used. The photosensitive resin composition film can be obtained, for example, by applying the photosensitive resin composition of the present invention on a support, and then drying it if necessary.

  Next, a method for producing a photosensitive adhesive film using the photosensitive adhesive composition of the present invention will be described. The photosensitive adhesive film of this invention is obtained by apply | coating the solution (varnish) of a photosensitive adhesive composition on a support body, and drying this as needed. The photosensitive adhesive composition varnish can be obtained by adding an organic solvent to the photosensitive adhesive composition. Any organic solvent may be used as long as it dissolves the photosensitive adhesive composition.

  As the organic solvent, specifically, ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, Acetates such as ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propyl acetate, butyl acetate, isobutyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate, butyl lactate , Acetone, methyl ethyl ketone, acetyl acetone, methyl propyl ketone, Ketones such as rubutyl ketone, methyl isobutyl ketone, cyclopentanone, 2-heptanone, butyl alcohol, isobutyl alcohol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3 Alcohols such as methoxybutanol and diacetone alcohol, aromatic hydrocarbons such as toluene and xylene, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone and the like can be mentioned.

  Further, the photosensitive adhesive composition varnish may be filtered using a filter paper or a filter. The filtration method is not particularly limited, but a method of filtration by pressure filtration using a filter having a reserved particle diameter of 0.4 μm to 10 μm is preferable.

  The photosensitive adhesive film of the present invention is preferably used after being formed on a support. The support is not particularly limited, and various commercially available films such as a polyethylene terephthalate (PET) film, a polyphenylene sulfide film, and a polyimide film can be used. The joint surface between the support and the photosensitive adhesive film may be subjected to a surface treatment such as silicone, a silane coupling agent, an aluminum chelating agent, or polyurea in order to improve adhesion and peelability. The thickness of the support is not particularly limited, but is preferably in the range of 10 to 100 μm from the viewpoint of workability.

Moreover, in order to protect the surface, the photosensitive adhesive film of this invention may have a protective film on a film | membrane. Thereby, the photosensitive adhesive film surface can be protected from contaminants such as dust and dust in the atmosphere.
Examples of the protective film include polyolefin films and polyester films. The protective film preferably has a small adhesive force with the photosensitive adhesive film.

  As a method of applying the photosensitive adhesive composition varnish to the support, spin coating using a spinner, spray coating, roll coating, screen printing, blade coater, die coater, calendar coater, meniscus coater, bar coater, roll coater, Examples include a comma roll coater, a gravure coater, a screen coater, and a slit die coater. Moreover, although a coating film thickness changes with application methods, solid content concentration of composition, viscosity, etc., it is preferable that the film thickness after drying is usually 0.5 μm or more and 100 μm or less.

  An oven, a hot plate, infrared rays, or the like can be used for drying. The drying temperature and the drying time may be in a range where the organic solvent can be volatilized, and it is preferable to appropriately set a range in which the photosensitive adhesive film is in an uncured or semi-cured state. Specifically, it is preferable to carry out from 1 minute to several tens of minutes in the range of 40 ° C to 120 ° C. Moreover, you may heat up in steps, combining these temperatures, for example, you may heat-process at 70 degreeC, 80 degreeC, and 90 degreeC for 1 minute each.

Next, the method for patterning the photosensitive adhesive composition of the present invention or the photosensitive adhesive film using the same and the method for thermocompression bonding to other members will be described with examples.
First, a method for forming a photosensitive adhesive composition film on a substrate using the photosensitive adhesive composition varnish of the present invention or a photosensitive adhesive film using the same will be described. When using the photosensitive adhesive composition varnish, first, the varnish is applied on the substrate. Examples of the coating method include spin coating using a spinner, spray coating, roll coating, and screen printing. Further, the coating film thickness varies depending on the coating method, the solid content concentration and the viscosity of the resin composition, and it is usually preferable that the coating film thickness is 0.5 μm or more and 100 μm or less after drying. Next, the substrate coated with the photosensitive adhesive composition varnish is dried to obtain a photosensitive adhesive composition film. For drying, an oven, a hot plate, infrared rays, or the like can be used. The drying temperature and the drying time may be within a range where the organic solvent can be volatilized, and it is preferable to appropriately set a range in which the photosensitive adhesive composition film is in an uncured or semi-cured state. Specifically, it is preferably carried out in the range of 50 to 150 ° C. for 1 minute to several hours.

  On the other hand, when using a photosensitive adhesive film, if it has a protective film, it is peeled off, and the photosensitive adhesive film and the substrate are opposed to each other and bonded together by thermocompression bonding to form a photosensitive adhesive composition coating. obtain. The thermocompression bonding can be performed by a heat press process, a heat laminating process, a heat vacuum laminating process, or the like. The bonding temperature is preferably 40 ° C. or higher from the viewpoint of adhesion to the substrate and embedding. Further, the bonding temperature is preferably 150 ° C. or lower in order to prevent the photosensitive adhesive film from being cured at the time of bonding and deteriorating the pattern formation resolution in the exposure / development process.

  In any case, examples of the substrate used include silicon wafers, ceramics, gallium arsenide, organic circuit substrates, inorganic circuit substrates, and those in which circuit constituent materials are arranged on these substrates. It is not limited to these. Examples of organic circuit boards include glass-based copper-clad laminates such as glass cloth / epoxy copper-clad laminates, composite copper-clad laminates such as glass nonwoven fabrics / epoxy copper-clad laminates, polyetherimide resin substrates, Examples include heat-resistant / thermoplastic substrates such as ether ketone resin substrates and polysulfone resin substrates, polyester copper-clad film substrates, and polyimide copper-clad film substrates. Examples of the inorganic circuit board include ceramic substrates such as an alumina substrate, an aluminum nitride substrate, and a silicon carbide substrate, and metal substrates such as an aluminum base substrate and an iron base substrate. Examples of circuit components include conductors containing metals such as silver, gold and copper, resistors containing inorganic oxides, low dielectrics containing glass materials and / or resins, resins and high Examples thereof include high dielectric materials containing dielectric constant inorganic particles, insulators containing glass-based materials, and the like.

  Next, the photosensitive adhesive composition film formed by the above method is exposed to actinic radiation through a mask having a desired pattern. As the actinic radiation used for exposure, there are ultraviolet rays, visible rays, electron beams, X-rays and the like. In the present invention, it is preferable to use i-ray (365 nm), h-ray (405 nm), and g-ray (436 nm) of a mercury lamp. . In the photosensitive adhesive film, when the support is made of a material transparent to these rays, the exposure may be performed without peeling the support from the photosensitive adhesive film.

  In order to form a pattern, the exposed portion is removed with a developer after exposure. As developer, aqueous solution of tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol An aqueous solution of a compound exhibiting alkalinity such as dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine and the like is preferable. In some cases, these alkaline aqueous solutions may contain polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, dimethylacrylamide, methanol, ethanol, Contains alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone alone or in combination of several kinds Good.

  The development can be carried out by spraying the developer onto the coating surface, depositing the developer on the coating surface, immersing in the developer, or immersing and applying ultrasonic waves. The development conditions such as the development time and the temperature of the development step developer may be any conditions as long as the exposed portion is removed and the pattern can be formed.

After development, it is preferable to perform a rinsing treatment with water. Here, alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water for rinsing treatment.
Moreover, you may perform a baking process before image development as needed. Thereby, the resolution of the pattern after development may be improved, and the allowable range of development conditions may be increased. The baking temperature is preferably in the range of 50 to 180 ° C, more preferably in the range of 60 to 120 ° C. The time is preferably 5 seconds to several hours.

  After pattern formation, the quinonediazide compound remains in the photosensitive resin composition film. For this reason, they may be pyrolyzed and generate nitrogen during thermocompression bonding or curing. In order to avoid this, it is preferable that the entire surface of the photosensitive resin composition film after pattern formation is irradiated with the exposure light described above to decompose the quinonediazide compound in advance. This process is called bleaching exposure.

  Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto.

<Evaluation of pattern processability>
The protective film of the photosensitive adhesive film produced in each Example and Comparative Example was peeled off, and the peeled surface was placed on a silicon wafer by using a laminating apparatus (manufactured by Takatori Co., Ltd., VTM-200M) at a stage temperature. Lamination was performed under the conditions of 120 ° C., roll temperature 120 ° C., degree of vacuum 150 Pa, sticking speed 5 mm / second, sticking pressure 0.5 MPa, and a photosensitive adhesive film was formed on the silicon wafer. Then, after peeling off the support film, a mask having a pattern with a via size of 50 μmφ, 40 μmφ, 30 μmφ, 20 μmφ, 15 μmφ, 10 μmφ, 5 μmφ is set in the exposure apparatus, and the condition of the exposure gap of the mask and the photosensitive adhesive film is 100 μm Below, it exposed with the exposure amount of 400 mJ / cm < ² > (i line conversion) using the ultrahigh pressure mercury lamp. After exposure, the unexposed portion was removed by dip development using a 2.38% aqueous solution of tetramethylammonium hydroxide, and rinsed with water. The development time was 1.5 times as long as the unexposed area was completely dissolved. The pattern thus obtained was observed with an optical microscope, and the minimum size in the case where the pattern had no abnormality such as tsumari was used as the resolution evaluation. In addition, a pattern in which a pattern with a via size of 50 μmφ was not developed was marked with “x”.

<Evaluation of flux resistance>
In the same manner as described above, a photosensitive adhesive film was formed on a copper clad laminate. Then, after peeling the support film, an inert oven (Koyo Thermo System Co., INL-60) with, _{N 2} atmosphere, and heat treated for 60 minutes at 220 ° C., to obtain a cured film.

After applying an amine-based flux (WF-6317) to the cured film formed on the copper clad laminate, it is put into a reflow furnace (manufactured by Panasonic Device Sunx Tatsuno Co., Ltd., RN-S) and heated at 260 ° C. for 30 seconds. Heat-treated. Then, it was immersed in a 40 ° C. water bath for 1 minute, and the flux was washed with water while rocking the substrate.
After washing with water, the state of the cured film was observed visually and with an optical microscope, and these operations were repeated until abnormalities such as cracks, swelling and peeling occurred in the film. The number of times that no abnormality occurred was used as the evaluation result of flux resistance. Further, the case where abnormality occurred at the first time was x, and the case where abnormality did not occur at the fifth time was set to 5 without repeating the test thereafter.

<Evaluation of storage stability>
The photosensitive adhesive films produced in each Example and Comparative Example were stored in an environment of 23 ° C. and 50%, and the resolution was evaluated every week in the same manner as the above-described resolution evaluation. The number of storage weeks in which the resolution did not change compared to 0 week (no storage) was used as the evaluation result of storage stability. In addition, the case where the resolution deteriorated after 1 week passed, and the case where the change did not change after 4 weeks passed, the test was not conducted thereafter, and the time was 4 weeks.
The polyimide used in each example and comparative example was synthesized by the following method.

Synthesis example 1
Under a nitrogen stream, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (hereinafter referred to as BAHF) 30.95 g (0.0845 mol), 1,3-bis (3-aminopropyl) ) 1.24 g (0.005 mol) of tetramethyldisiloxane was dissolved in 100 g of NMP. Here, 31.02 g (0.1 mol) of bis (3,4-dicarboxyphenyl) ether dianhydride (hereinafter referred to as ODPA) was added together with 30 g of NMP, stirred at 20 ° C. for 1 hour, and then at 50 ° C. Stir for 4 hours. To this, 2.5 g (0.02 mol) of 3-aminophenol was added, stirred at 50 ° C. for 2 hours, and then stirred at 180 ° C. for 5 hours to obtain a resin solution. Next, the resin solution was poured into 3 L of water to collect a white precipitate. This precipitate was collected by filtration, washed 3 times with water, and then dried in a vacuum dryer at 80 ° C. for 5 hours.

Synthesis example 2
Under a dry nitrogen stream, RT-1000 (10.00 g, 0.010 mol) containing BAHF (32.96 g, 0.090 mol), propylene oxide and a tetramethylene ether glycol structure was dissolved in 205 g of NMP. To this, PBOM (29.38 g, 0.082 mol) was added together with 20 g of NMP and reacted at 85 ° C. for 3 hours. Subsequently, 2,2′-bis [N- (3-aminobenzoyl) -3-amino-4-hydroxyphenyl] hexafluoropropane (hereinafter referred to as HFHA) (0.60 g, 0.0010 mol), 1, 3-Bis (3-aminopropyl) tetramethyldisiloxane (1.49 g, 0.0060 mol) was added together with 20 g of NMP and reacted at 85 ° C. for 30 minutes. Subsequently, 5-norbornene-2,3-dicarboxylic acid anhydride (5.91 g, 0.036 mol) was added together with 10 g of NMP as a terminal blocking agent, and the mixture was reacted at 85 ° C. for 30 minutes. Further, ODPA (2.17 g, 0.0070 mol) was added together with 30 g of NMP and reacted at 85 ° C. for 1 hour. After completion of the reaction, the mixture was cooled to room temperature, acetic acid (49.22 g, 0.82 mol) was added together with 70 g of NMP, and the mixture was stirred at room temperature for 1 hour. Next, the resin solution was poured into 3 L of water to collect a white precipitate. This precipitate was collected by filtration, washed 3 times with water, and then dried in a vacuum dryer at 80 ° C. for 5 hours.

Synthesis example 3
Under a dry nitrogen stream, [bis (4-amino-3-carboxy) phenyl] methane 24. 19 g (0.0845 mol), 1.3-bis (3-aminopropyl) tetramethyldisiloxane 1.24 g (0. 005 mol) was dissolved in 100 g of NMP. Bis (3,4-dicarboxyphenyl) ether dianhydride 31.02 g (0.1 mol) was added thereto together with 30 g of NMP, and the mixture was stirred at 20 ° C. for 1 hour, and then stirred at 50 ° C. for 4 hours. To this, 2.5 g (0.02 mol) of 3-aminophenol was added, stirred at 50 ° C. for 2 hours, and then stirred at 180 ° C. for 5 hours to obtain a resin solution. Next, the resin solution was poured into 3 L of water to collect a white precipitate. This precipitate was collected by filtration, washed 3 times with water, and then dried in a vacuum dryer at 80 ° C. for 5 hours.

Synthesis example 4
Under a dry nitrogen stream, 16.90 g (0.0845 mol) of 4,4′-diaminodiphenyl ether, 1.24 g (0.005 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane and end-capping As an agent, 1.86 g (0.02 mol) of aniline was dissolved in 80 g of NMP. To this, 31.02 g (0.1 mol) of ODPA was added together with 20 g of NMP, stirred at 20 ° C. for 1 hour, and then stirred at 50 ° C. for 4 hours. Thereafter, 15 g of xylene was added, and the mixture was stirred at 180 ° C. for 5 hours while azeotropically distilling water with xylene. After stirring, the solution was poured into 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80 ° C. for 20 hours. The imidation ratio of the obtained polymer powder was 94%, and Tg was 203 ° C.

Example 1
100 g of the polyimide obtained in Synthesis Example 1 as the component (A), 20 g of TG-G (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.) as the component (B), 20 g of the naphthoquinone diazide compound having the following structure as the component (C) Was dissolved in γ-butyrolactone. The addition amount of the solvent was adjusted so that an additive other than the solvent was a solid content and the solid content concentration was 40%. Then, pressure filtration was carried out using a filter having a reserved particle diameter of 2 μm to obtain a photosensitive adhesive composition varnish.

  The obtained varnish was coated on a PET film having a thickness of 50 μm using a comma roll coater, dried at 80 ° C. for 8 minutes, and then laminated with a PP film having a thickness of 10 μm as a protective film. Adhesive film was obtained. The film thickness of the photosensitive adhesive film was adjusted to 10 μm. Using the obtained photosensitive adhesive film, pattern processability, flux resistance, and storage stability were evaluated as described above. The results are shown in Table 1.

Examples 2-6
The photosensitive adhesive was changed in the same manner as in Example 1 except that the components (A) to (C) and other components were changed to compounds having the following structures and the mixing ratio was changed as shown in Table 1. Films were prepared and evaluated for resolution, flux resistance, and storage stability as described above. The results are shown in Table 1.

Comparative Examples 1-5
The photosensitive adhesive was changed in the same manner as in Example 1 except that the components (A) to (C) and other components were changed to compounds having the following structures and the mixing ratio was changed as shown in Table 1. Films were prepared and evaluated for resolution, flux resistance, and storage stability as described above. The results are shown in Table 1.

In Comparative Examples 1 and 2, since the crosslinking agent of the component (B) was not used, flux resistance was not obtained. Since Comparative Example 3 did not use the crosslinking agent of component (B), resolution and storage stability could not be obtained. Since Comparative Example 4 was not a soluble resin, no resolution was obtained. In Comparative Example 5, since the component (C) was not used, the entire film was dissolved and pattern processing could not be performed.
In addition, (B) component used in Table 1, the crosslinking agent other than (B) component, and the structure of (C) component were shown below.

Claims (14)

(A) An alkali-soluble resin, (B) a crosslinking agent, (C) a compound that generates an acid by light, and the crosslinking agent of (B) is a compound represented by the general formula (1). Photosensitive resin composition.

(Wherein R ¹ and R ² are the same or different and each represents a hydrogen atom, a lower alkyl group or a phenyl group; R 3 represents a glycidyl group, an allyl group, a thiol group or an isocyanate group; R ⁴ , R ⁵ and R ⁶ is the same or different and represents a hydrogen atom, a glycidyl group, an allyl group, a thiol group or an isocyanate group, where n is 0, 1 or 2. The photosensitive resin composition according to claim 1, wherein the crosslinking agent (B) is a glycoluril compound represented by the general formula (2).

(In the formula, R ¹ and R ² are the same or different and each represents a hydrogen atom, a lower alkyl group or a phenyl group.) The photosensitive resin composition according to claim 1, wherein the alkali-soluble resin (A) is polyimide and / or polyamideimide. The photosensitive resin composition according to any one of claims 1 to 3, wherein (A) the alkali-soluble resin is a polyimide and / or a polyamideimide having a phenolic hydroxyl group. The photosensitive resin sheet formed from the photosensitive resin composition in any one of Claims 1-4. A cured film obtained by curing the photosensitive resin composition according to claim 1. A cured film obtained by curing the photosensitive resin sheet according to claim 5. An interlayer insulating film or a semiconductor protective film, on which the cured film according to claim 6 or 7 is disposed. A photosensitive resin composition according to any one of claims 1 to 4 is applied on a substrate, dried to form a photosensitive resin film, exposed through a mask, and the irradiated portion is an alkaline solution. A method for producing a cured relief pattern, which is obtained by a step of elution or removal with a developing step and a step of heat-treating the photosensitive resin film after the development. 6. A semiconductor comprising: laminating the photosensitive resin sheet according to claim 5 on a substrate, forming a pattern through an ultraviolet irradiation step and a development step, and further heating to form a relief pattern layer of a cured film. Manufacturing method of electronic component or semiconductor device. A semiconductor electronic component or semiconductor device comprising the relief pattern layer of the cured film according to claim 6. The semiconductor electronic component or semiconductor device according to claim 11, wherein the cured film according to claim 6 or 7 is disposed as an interlayer insulating film between rewirings. The semiconductor electronic component or semiconductor device according to claim 12, wherein the rewiring and the interlayer insulating film are repeatedly arranged in 2 to 10 layers. A semiconductor electronic component or a semiconductor device, wherein the cured film according to claim 6 or 7 is disposed as an interlayer insulating film of an adjacent substrate composed of two or more materials.