JP2008112147A - Photosensitive resin composition and dielectric composition using the same and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition which can facilitate pattern formation of an interlayer insulation film having small leake current for a capaditor by photolithography. <P>SOLUTION: The photosensitive resin composition is prepared by mixing a dispersion liquid and a resin solution, wherein the dispersion liquid is obtained by mixing (a) high dielectric constant inorganic particles having an average particle diameter of 0.06-0.4 μm and a perovskite-type crystal structure or a complex perovskite-type crystal structure, (b) a phosphoric acid compound and (c) an organic solvent, and dispersing the inorganic particles with beads of a metal, ceramics or glass having an average particle diameter of 0.02-0.1 mm as dispersion media, and wherein the resin solution contains (d) a polyimide and (e) a polymerizable compound containing an unsaturated bond. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  Photosensitive resin composition for forming a high dielectric constant material used as an interlayer insulating film for a capacitor for a capacitor incorporated in a substrate for a system using a semiconductor such as a mounting substrate or a wafer level package, and a dielectric produced by using them The present invention relates to a body composition and a semiconductor device.

  In order to reduce the size, weight, and cost of electronic devices, the mounting density of modules and packages is being increased. As one means for high-density mounting, there is a method in which a passive component such as a capacitor is formed in a module substrate, a mounting substrate, or a semiconductor wafer after a transistor is manufactured. Since the capacitance of the capacitor is proportional to the dielectric constant of the interlayer insulating material, it is advantageous to use an interlayer insulating material having a large dielectric constant for increasing the capacitance. Conventionally, there has been known a method in which a high dielectric constant interlayer insulating film is obtained by applying, drying and curing a paste in which high dielectric constant particles are dispersed in a resin (see Patent Document 1).

  On the other hand, when a material having photosensitivity is used as a material for forming the interlayer insulating film, patterning of the interlayer insulating film can be easily performed by photolithography, and high dielectric constant particles or conductive particles are applied to the photosensitive acrylic resin. There is a technique for forming a pattern of a high dielectric constant interlayer insulating film by a photolithography method using a mixed material (see Patent Documents 2 to 7). A technique using photosensitive epoxy resin or photosensitive phenol resin and high dielectric constant particles is also known (see Patent Documents 8 and 9). However, a wafer level package formed on a semiconductor wafer may undergo a high temperature process of 200 to 300 ° C. after forming a high dielectric constant interlayer insulating film, and a material using acrylic resin or epoxy resin has insufficient heat resistance. In many cases.

Therefore, pattern formation of an interlayer insulating film is performed by a photolithography method using a composition in which high-heat-resistant positive polyimide is provided with photosensitivity and dispersed with high-permittivity ultrafine particles having an average particle diameter of less than 0.05 μm. There is a technique for manufacturing a capacitor (see Patent Document 10). However, it is very difficult to completely disaggregate ultrafine particles having an average particle diameter of less than 0.05 μm and achieve good dispersion, and minute voids tend to remain between the agglomerated particles. Further, the presence of voids not only greatly hinders the increase in dielectric constant, but also causes an increase in leakage current and a decrease in withstand voltage. A capacitor using such a material as an interlayer insulating film causes instability of each characteristic and it is difficult to obtain high reliability of the capacitor. Further, as the filling amount of the high dielectric constant ultrafine particles is increased, a residue is likely to be generated when the pattern of the interlayer insulating film is formed by the photolithography method, and it is difficult to form the pattern without the residue.
International Publication No. 04/090912 (Patents) JP 2000-30534 A (Claims) JP 2003-288813 A (Claims) JP-A-6-202323 (Claims) JP 2002-365794 A (Claims) Japanese Patent Laid-Open No. 2002-365796 (Claims) JP 2003-57811 A (Claims) JP 2004-339260 A (Claims) JP 2004-14297 A (Claims) JP 2003-287883 A (Claims)

  In view of such a situation, the present invention has a small leakage current of a capacitor interlayer insulation film built in a substrate or package for a system using a semiconductor such as a mounting substrate or a wafer level package, a small decrease in withstand voltage, and a residue by photolithography. Provided is a photosensitive resin composition that can easily form a pattern that does not generate a film, and a method for producing the photosensitive resin composition, and further includes a transistor and a semiconductor on which a dielectric composition obtained from the photosensitive resin composition is formed Provided is a semiconductor device having a capacitor including an element and an electrode.

  That is, the present invention relates to a photosensitive resin composition in which a dispersion and a resin solution are mixed, and the dispersion has (a) a perovskite crystal structure or composite having an average particle size of 0.06 μm to 0.4 μm. A high dielectric constant inorganic particle having a perovskite type crystal structure, (b) a phosphoric acid compound, and (c) an organic solvent are mixed, and the average particle size selected from any of metal, ceramics, and glass as a dispersion medium is 0.00. Photosensitivity obtained by dispersing the inorganic particles using beads of 02 mm or more and 0.1 mm or less, wherein the resin solution has (d) polyimide and (e) unsaturated bond-containing polymerizable compound. A resin composition, a deorganic solvent, a dielectric composition obtained by solidifying the resin composition, and a semiconductor device using the same.

According to the photosensitive resin composition of the present invention, a pattern in which no residue is generated can be formed on the interlayer insulating film for capacitors by photolithography, and the obtained insulating film leaks with high heat resistance and high voltage resistance. It has excellent characteristics with low current.
Furthermore, since the semiconductor device using the photosensitive resin composition of the present invention can form a capacitor on the semiconductor device, which has conventionally been formed on the substrate on which the semiconductor device is mounted, the semiconductor device that causes parasitic inductance can be used. Wiring to the capacitor mounted on the substrate becomes unnecessary. This contributes to higher speed and higher density of the system.

  The present invention relates to a photosensitive resin composition in which a dispersion and a resin solution are mixed, wherein the dispersion has (a) a perovskite crystal structure or a composite perovskite having an average particle size of 0.06 μm to 0.4 μm. High-permittivity inorganic particles having a type crystal structure, (b) a phosphoric acid compound, (c) an organic solvent are mixed, and the average particle size selected from any of metal, ceramics, and glass as a dispersion medium is 0.02 mm A photosensitive resin obtained by dispersing the inorganic particles using beads having a size of 0.1 mm or less, wherein the resin solution has (d) a polyimide and (e) an unsaturated bond-containing polymerizable compound. It is a composition.

  In the photosensitive resin composition, when a positive type is formed by alkali development, a negative type is formed by alkali development, or a negative type is formed by organic development. Since the photosensitive resin composition containing inorganic particles as in the present invention has almost no adhesion to other materials, the adhesion to other materials tends to be weaker than that of the resin alone. For this reason, when pattern processing is performed, suppression of pattern detachment during development tends to be a problem. Compared with the positive type, the negative type does not dissolve the part exposed to light at the time of exposure, so the remaining pattern is formed. The adhesive force with the substrate or the like can be controlled. In addition, since the photosensitive resin composition containing inorganic particles causes the inorganic particles to hinder the photosensitivity of the resin component, at the interface between the photosensitive resin composition and the adherend than when the inorganic particles are not included. Exposure tends to be insufficient, and when a positive photosensitive resin composition is used, a residue tends to occur on the adherend surface. Although a negative type can be formed by organic development, organic development is not preferred from the viewpoint of environmental problems. From the above points, those that form a negative type by alkali development are preferred.

  (D) The polyimide used in the present invention is not particularly limited as long as it is a polyimide that forms a negative type by alkali development, but one or more polyimides represented by the following general formulas (1) to (4) are used. Is preferred.

In the general formulas (1) to (4), R ⁸ is a 4 to 14 valent organic group, R ⁹ is a 2 to 12 valent organic group, R ¹⁰ and R ¹² are a hydrogen atom, a phenolic hydroxyl group, or a sulfonic acid group. Represents an organic group having at least one group selected from the group consisting of a thiol group and an organic group having 1 to 20 carbon atoms, which may be the same or different. R ¹¹ represents a divalent organic group that is not cyclic. X represents a monovalent aromatic group or a cyclic aliphatic group having at least one group selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group. Y represents a monovalent organic group having at least one group selected from a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group. n represents the range of 3-200. m, α and β each independently represents an integer of 0 to 10.

  X is a monovalent aromatic group or cyclic aliphatic group having at least one group selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group. X preferably has a phenolic hydroxyl group or a thiol group.

  Y is a monovalent organic group having at least one group selected from a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group and a thiol group. Preferably, it is a monovalent organic group having at least one phenolic hydroxyl group or thiol group.

  n represents the number of repeating structural units of the polymer. n is in the range of 3 to 200, preferably 5 to 100. When n is in the range of 3 to 200, the photosensitive resin composition of the present invention can be used in a thick film, and sufficient solubility in an alkali developer can be imparted to perform pattern processing.

In the above general formulas (1) to (4), R ⁸ represents a structural component derived from acid dianhydride and is a tetravalent to 14-valent organic group. Especially, it is preferable that it is a C5-C40 organic group containing an aromatic group or a cycloaliphatic group.

  Specific examples of acid dianhydrides 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-dicarboxyl Nyl) 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, butanetetracarboxylic dianhydride, 1,2,3,4-cyclopentane Tetracarboxylic acid dianhydride of aliphatic, such Rakarubon dianhydride, etc. and acid dianhydride having the structure shown below can be exemplified.

R ¹⁵ represents an oxygen atom, a group selected from C (CF ₃ ) ₂ , C (CH ₃ ) ₂ and SO ₂ , and R ¹⁶ and R ¹⁷ represent a group selected from a hydrogen atom, a hydroxyl group and a thiol group, respectively. These are used alone or in combination of two or more.

In the above general formulas (1) to (4), R ⁹ represents a structural component derived from diamine and is a divalent to divalent organic group. Among these, an organic group having 5 to 40 carbon atoms containing an aromatic group or a cyclic aliphatic group is preferable.

  Specific examples of diamines 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} -Ter, 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, 3,3 ′ , 4,4′-tetramethyl-4,4′-diaminobiphenyl, 2,2′-di (trifluoromethyl) -4,4′-diaminobiphenyl, 9,9-bis (4-aminophenyl) fluorene or These aromatic rings are substituted with alkyl groups or halogen atoms, aliphatic cyclohexyldiamine, methylenebiscyclohexylamine, and diamines with the structure shown below. It is below.

Here, R ¹⁵ is an oxygen atom, a group selected from C (CF ₃ ) ₂ , C (CH ₃ ) ₂ and SO ₂ , and R ^{16 to} R ¹⁹ are groups selected from a hydrogen atom, a hydroxyl group and a thiol group, respectively. To express. These are used alone or in combination of two or more.

In the general formulas (1) to (4), R ¹⁰ and R ¹² are each at least one selected from the group consisting of a hydrogen atom, a phenolic hydroxyl group, a sulfonic acid group, a thiol group, and an organic group having 1 to 20 carbon atoms. An organic group having a group is represented. From the stability of the resulting photosensitive resin composition solution, R ¹⁰ and R ¹² are preferably a hydrogen atom or an organic group having 1 to 20 carbon atoms. From the viewpoint of the solubility of the aqueous alkali solution, R ¹⁰ and R ¹² are preferably groups selected from the group consisting of phenolic hydroxyl groups, sulfonic acid groups, and thiol groups, which are alkali-soluble groups.

  In the present invention, a phenolic hydroxyl group, a sulfonic acid group or a thiol group can be mixed with a hydrogen atom or an alkyl group.

Since the dissolution rate of polyimide in an alkaline aqueous solution is changed by adjusting the amount of the alkali-soluble groups of R ¹⁰ and R ¹² and the hydrogen atoms and organic groups, the negative photosensitive resin composition having an appropriate dissolution rate. Can be obtained. It is preferable 5 to 100 mol% of R ¹⁰ and ^{R 12} is an alkali-soluble group. If the number of carbon atoms of R ¹⁰ and R ¹² exceeds 20, it will not dissolve in the aqueous alkali solution. From the above, it is more preferable that R ¹⁰ and R ¹² contain at least one hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and the others are alkali-soluble groups.

In the general formulas (1) and (2), —N— (R ¹¹ ) _m —X is preferably a structure represented by the following general formula (6).

In addition, —CO— (R ¹¹ ) _m —Y, which is a structural component of the general formulas (3) and (4), preferably has a structure represented by the following general formula (7) or (8). The end capping groups represented by the general formulas (7) and (8) may include only one or both.

In the general formula ^{(6) ~ (8),} R 11 represents a divalent organic group is not cyclic, among others ^-CR 25 ^R 26 -, - chosen from the group consisting of - _CH 2 O-and _-CH 2 SO ₂ A divalent group is preferred. R ²⁵ and R ²⁶ each represent a monovalent group selected from the group consisting of a hydrogen atom, a hydroxyl group, and a hydrocarbon group having 1 to 10 carbon atoms. R ²⁰ and R ²¹ are each a group selected from the group consisting of a hydrogen atom, a hydroxyl group, a carboxyl group, a sulfonic acid group, a thiol group, and a hydrocarbon group having 1 to 10 carbon atoms, at least one of which is a hydroxyl group , Carboxyl group, sulfonic acid group or thiol group. R ²² represents a monovalent group selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 10 carbon atoms. Among these, a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms is preferable, and a hydrogen atom, a methyl group, or a t-butyl group is particularly preferable. R ²³ and R ²⁴ each represent a monovalent group selected from the group consisting of a hydrogen atom and a hydrocarbon group having 1 to 4 carbon atoms, or a ring structure in which R ²³ and R ²⁴ are directly bonded (for example, nadiimide). Ring). A, E, and G are each a carbon atom or a nitrogen atom, and may be the same or different. m is an integer of 0 to 10, preferably an integer of 0 to 4. l is 0 or 1, preferably 0. u is 0 or 1, preferably 0. v is an integer of 1 to 3, preferably 1 or 2. w is 0 or 1. x and y are 0 or 1, respectively.

In the general formulas (1) and (2), —N— (R ¹¹ ) _m —X is derived from a primary monoamine that is a terminal blocking agent.

  Specific examples of the primary monoamine used as a terminal blocking agent include 5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline, 1-hydroxy-8-aminonaphthalene, and 1-hydroxy-7. -Aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 1-hydroxy-3-aminonaphthalene, 1-hydroxy-2-aminonaphthalene, 1 -Amino-7-hydroxynaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 2-hydroxy-4-aminonaphthalene, 2-hydroxy-3- Aminonaphthalene, 1-amino-2-hydroxynaphthalene, 1- Ruboxy-8-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 1-carboxy-4-aminonaphthalene, 1-carboxy-3-amino Naphthalene, 1-carboxy-2-aminonaphthalene, 1-amino-7-carboxynaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-carboxy -4-aminonaphthalene, 2-carboxy-3-aminonaphthalene, 1-amino-2-carboxynaphthalene, 2-aminonicotinic acid, 4-aminonicotinic acid, 5-aminonicotinic acid, 6-aminonicotinic acid, 4- Aminosalicylic acid, 5-aminosalicylic acid, 6-a Nosalicylic acid, 3-amino-o-toluic acid, amelide, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzene Sulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 5-amino-8-mercaptoquinoline, 4-amino-8-mercaptoquinoline, 1-mercapto -8-aminonaphthalene, 1-mercapto-7-aminonaphthalene, 1-mercapto-6-aminonaphthalene, 1-mercapto-5-aminonaphthalene, 1-mercapto-4-aminonaphthalene, 1-mercapto-3-aminonaphthalene 1-mercapto-2-aminonaphthalene, 1-amino- 7-mercaptonaphthalene, 2-mercapto-7-aminonaphthalene, 2-mercapto-6-aminonaphthalene, 2-mercapto-5-aminonaphthalene, 2-mercapto-4-aminonaphthalene, 2-mercapto-3-aminonaphthalene, Examples include 1-amino-2-mercaptonaphthalene, 3-amino-4,6-dimercaptopyrimidine, 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol.

  Of these, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 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-aminosalicylic 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 are preferable. These are used alone or in combination of two or more.

In the general formulas (3) and (4), —CO— (R ¹¹ ) _m —Y is derived from an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound that is a terminal blocking agent. To do.

  Specific examples of compounds selected from acid anhydrides, monocarboxylic acids, monoacid chloride compounds and monoactive ester compounds used as end-capping agents are phthalic anhydride, maleic anhydride, nadic acid, cyclohexanedicarboxylic anhydride, Acid anhydrides such as 3-hydroxyphthalic anhydride, 2-carboxyphenol, 3-carboxyphenol, 4-carboxyphenol, 2-carboxythiophenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy- 8-carboxynaphthalene, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-hydroxy-4-carboxynaphthalene, 1-hydroxy-3-carboxynaphthalene 1-hydroxy-2-carboxynaphthalene, 1-mercapto-8-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 1-mercapto- Monocarboxylic acids such as 4-carboxynaphthalene, 1-mercapto-3-carboxynaphthalene, 1-mercapto-2-carboxynaphthalene, 2-carboxybenzenesulfonic acid, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid and the like A monoacid chloride compound in which the carboxyl group of the compound is acid chloride, and terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 3-hydroxyphthalic acid, 5-norbornene-2,3-dicarboxylic acid, 1 2-dicarboxynaphthalene, 1,3-dicarboxynaphthalene, 1,4-dicarboxynaphthalene, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 1,8- Monoacid chloride compounds and monoacid chloride compounds in which only the monocarboxyl group of dicarboxylic acids such as dicarboxynaphthalene, 2,3-dicarboxynaphthalene, 2,6-dicarboxynaphthalene and 2,7-dicarboxynaphthalene is acid chlorided And active ester compounds obtained by the reaction of N-hydroxybenzotriazole and N-hydroxy-5-norbornene-2,3-dicarboximide.

  Among these, phthalic anhydride, maleic anhydride, nadic acid, cyclohexanedicarboxylic anhydride, acid anhydrides such as 3-hydroxyphthalic anhydride, 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 Monocarboxylic acids such as 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid and 4-carboxybenzenesulfonic acid, and monoacid chloride compounds and terephthalates in which these carboxyl groups are converted to acid chloride Monocarboxyl of dicarboxylic acids such as acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 2,6-dicarboxynaphthalene Preferred are monoacid chloride compounds in which only the group is acid chloride, active ester compounds obtained by reaction of monoacid chloride compounds with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboximide, etc. . These are used alone or in combination of two or more.

The introduction ratio of the component represented by the general formula (6) (—N— (R ¹¹ ) _m —X component of the general formulas (1) and (2)) is the first grade of the end-capping agent that is the original component. In terms of the monoamine component, the range is preferably from 0.1 to 60 mol%, particularly preferably from 5 to 50 mol%, based on the total acid dianhydride component.

The ratio of introduction of the components represented by the general formulas (7) and (8) (the —CO— (R ¹¹ ) _m —Y component of the general formulas (3) and (4)) is the original component, which is the end capping. In terms of the compound component selected from the acid anhydride, monocarboxylic acid, monoacid chloride compound and monoactive ester compound of the agent, the range of 0.1 to 60 mol% is preferable, particularly preferably 5 based on the diamine component. -55 mol%.

Furthermore, in order to improve the adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized in R ⁸ and R ⁹ within a range that does not decrease the heat resistance. Specifically, examples of the diamine component include those obtained by copolymerizing 1 to 10 mol% of bis (3-aminopropyl) tetramethyldisiloxane, bis (p-amino-phenyl) octamethylpentasiloxane, and the like.

  In addition, it is preferable to have fluorine atoms in the structures of the general formulas (1) to (4) because water repellency is imparted to the interface of the film and the penetration of the interface can be suppressed when developing with an alkaline aqueous solution. The fluorine atom content for each of the polyimides represented by the general formulas (1) to (4) is preferably 10% by weight in order to sufficiently obtain the effect of preventing the penetration of the interface, and is 20% from the viewpoint of solubility in an alkaline aqueous solution. % Or less is preferable.

  The polyimide as the component (d) used in the photosensitive resin composition of the present invention may be composed only of the structural units represented by the general formulas (1) to (4), and may be other structural units. A copolymer or a mixture thereof may be used. In that case, it is preferable to contain the structural unit represented by General Formula (1) to (4) in an amount of 10% by weight or more based on the whole polyimide. If it is 10 weight% or more, shrinkage | contraction at the time of thermosetting can be suppressed, and it is suitable for thick film preparation. The type and amount of structural units used for copolymerization or mixing are preferably selected within a range that does not impair the heat resistance of the polyimide obtained by the final heat treatment.

  In the component (d) polyimide, a part of the diamine is replaced with a monoamine that is a terminal blocking agent, or an acid dianhydride is replaced with a monocarboxylic acid, an acid anhydride, or a monoacid chloride compound that is a terminal blocking agent. Alternatively, the compound can be synthesized using a known method by replacing with a compound selected from mono-active ester compounds. For example, a method of reacting a tetracarboxylic dianhydride, a diamine compound and a monoamine at a low temperature, a reaction of a tetracarboxylic dianhydride and an acid anhydride, a monoacid chloride compound or a monoactive ester compound and a diamine compound at a low temperature. Method, a method of obtaining a diester by tetracarboxylic dianhydride and an alcohol, and then reacting the diamine, monoamine and alcohol in the presence of a condensing agent. Is converted to an acid chloride, and a polyimide precursor is obtained using a method such as a method of reacting a diamine and a monoamine with substitution. A method of completely imidizing the obtained polyimide precursor using a known imidization reaction method, a method of stopping the imidization reaction in the middle and partially introducing an imide structure, or a completely imidized polymer, By mixing the polyimide precursor, it is possible to synthesize polyimide using a method of partially introducing an imide structure.

  The photosensitive resin composition of the present invention contains (e) an unsaturated bond-containing polymerizable compound. The unsaturated bond-containing polymerizable compound is not particularly limited, but a polymerizable compound represented by the following general formula (9) is preferable.

R ¹ represents a 1-3 valent organic group having at least one aromatic ring, R ^{2 to} R ⁴ represent a polymerizable group having an unsaturated bond, and R ^{5 to} R ⁷ represent a divalent organic group. . R ^{2 to} R ⁴ and R ^{5 to} R ⁷ may be the same or different. Moreover, o, p, and q represent the integer of 0-1, r, s, and t represent the integer of 1-10 each independently. However, o + p + q ≧ 1.

Since the polymerizable compound represented by the general formula (9) has an aromatic ring, the strength of the cured film is improved. Specific examples of R ¹ include the structures shown below.

R ²⁷ each independently represents a methyl group, an ethyl group, a propyl group, a t-butyl group or a hydroxyl group, and z independently represents an integer of 0 to 2. Among these, those having a bisphenol skeleton are particularly preferable.

^R 2 to R ⁴ in the general formula (9) represents a polymerizable group having an unsaturated bond, o, p, q is an integer of 0-1. However, o + p + q ≧ 1. Examples of R ^{2 to} R ⁴ include unsaturated double bond-containing groups such as vinyl group, allyl group, acryloyl group, and methacryloyl group, and unsaturated triple bond-containing groups such as propargyl. Among these, a conjugated vinyl group, an acryloyl group, and a methacryloyl group are preferable in terms of polymerizability.

R ^{5 to} R ⁷ represent a divalent organic group. Since the polymerizable compound has a repeating structure of OR ⁱ (i = 5 to 7) in the molecule, the film after photocuring and curing does not lose flexibility, and the elongation of the cured film is improved. The number of repetitions (r, s and t) is 1-10. If the number of repetitions exceeds 10, the pattern cannot be formed well and the strength of the film is lowered.

R ^{5 to} R ⁷ are preferably hydrocarbon groups. Examples of preferable hydrocarbon groups include methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, neopentylene group, or those in which a hydroxyl group is substituted. R ^{5 to} R ⁷ may be the same or different, and may be the same or different for each repeating unit.

  The content of the (e) unsaturated bond-containing polymerizable compound in the photosensitive resin composition of the present invention is preferably 5 to 200 parts by weight with respect to 100 parts by weight of polyimide, and is 5 to 5 from the viewpoint of compatibility. More preferably, it is 150 parts by weight. By setting the content to 5 parts by weight or more, elution of the exposed portion of the film during development can be prevented, and a sufficient residual film can be obtained after development. Further, by setting the content to 200 parts by weight or less, a sufficient remaining film can be obtained while suppressing whitening of the film during film formation.

  In the present invention, an unsaturated bond-containing polymerizable compound further containing an alicyclic hydrocarbon group may be used. When such a polymerizable compound containing an alicyclic hydrocarbon group is used, developability is improved due to the hydrophobicity of the alicyclic hydrocarbon group, and a fine pattern can be obtained with high resolution. Examples of the functional group having an unsaturated bond include those having an unsaturated double bond such as vinyl group, allyl group, acryloyl group and methacryloyl group, and those having an unsaturated triple bond such as propargyl. Among these, a conjugated vinyl group, an acryloyl group, and a methacryloyl group are preferable in terms of polymerizability.

  Examples of the alicyclic hydrocarbon group include groups containing a cyclohexane structure, a dicyclopentadiene structure, a tricyclodecane structure, and the like. Preferred examples of the unsaturated bond-containing polymerizable compound containing an alicyclic hydrocarbon group include cyclohexyl vinyl ether, cyclohexane dimethanol divinyl ether, cyclohexyl acrylate, cyclohexyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, and dicyclopentenyloxyethyl. Acrylate, dicyclopentenyloxyethyl methacrylate, tricyclodecanyl acrylate, tricyclodecanyl methacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, isobornyl acrylate, isobornyl methacrylate, etc. . Of these, tricyclodecanyl acrylate, tricyclodecanyl dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, isobornyl acrylate and isobornyl methacrylate are preferred.

  In addition to (e) the unsaturated bond-containing polymerizable compound, other polymerizable compounds may be added. Specific examples of such compounds include, for example, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, Trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, styrene, α-methylstyrene, 1,2-dihydronaphthalene, 1,3-diisopropenylbenzene, 3-methylstyrene, 4-methylstyrene , 2-vinylnaphthalene, butyl acrylate, butyl methacrylate, isobutyl acrylate, hexyl urea Relate, isooctyl acrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, neopentyl glycol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1, 6-hexanediol diacrylate, 1,6-hexanediol methacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol Tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, 2-hydroxyethyl acrylate 2-hydroxyethyl methacrylate, 1,3-acryloyloxy-2-hydroxypropane, 1,3-methacryloyloxy-2-hydroxypropane, methylenebisacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide, 2 , 2,6,6-tetramethylpiperidinyl methacrylate, 2,2,6,6-tetramethylpiperidinyl acrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl methacrylate, N- Examples include methyl-2,2,6,6-tetramethylpiperidinyl acrylate, N-vinylpyrrolidone, N-vinylcaprolactam and the like. These can be used alone or in combination of two or more.

  When the polymerizable compound represented by the general formula (9) and the unsaturated bond-containing polymerizable compound containing an alicyclic hydrocarbon group are used in combination, the total content is 100 parts by weight of polyimide. 5 to 200 parts by weight, and more preferably 5 to 150 parts by weight from the viewpoint of compatibility. By setting the content to 5 parts by weight or more, elution of the exposed portion of the film during development can be prevented, and a sufficient residual film can be obtained after development. Further, by setting the content to 200 parts by weight or less, a sufficient remaining film can be obtained while suppressing whitening of the film during film formation.

  In the present invention, a photopolymerization initiator may be further used. Specific examples include benzophenones such as benzophenone, Michler's ketone, 4,4, -bis (diethylamino) benzophenone, 3,3,4,4, -tetra (t-butylperoxycarbonyl) benzophenone, and 3,5-bis (diethylamino). Benzylidene) -N-methyl-4-piperidone, benzylidenes such as 3,5-bis (diethylaminobenzylidene) -N-ethyl-4-piperidone, 7-diethylamino-3-nonylcoumarin, 4,6-dimethyl-3- Coumarins such as ethylaminocoumarin, 3,3-carbonylbis (7-diethylaminocoumarin), 7-diethylamino-3- (1-methylmethylbenzimidazolyl) coumarin, 3- (2-benzothiazolyl) -7-diethylaminocoumarin, 2 -T-Butylanthraquino , Anthraquinones such as 2-ethylanthraquinone and 1,2-benzanthraquinone, benzoins such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4 -Thioxanthones such as diisopropylthioxanthone and 2-isopropylthioxanthone; mercaptos such as ethylene glycol di (3-mercaptopropionate), 2-mercaptobenzthiazole, 2-mercaptobenzoxazole and 2-mercaptobenzimidazole; N- Glycines such as phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N- (p-chlorophenyl) glycine, N- (4-cyanophenyl) glycine, -Phenyl-1,2-butanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione -2- (o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-benzoyl) oxime, bis (α-isonitrosopropiophenone oxime) isophthal, 1,2-octanedione Oximes such as -1- [4- (phenylthio) phenyl] -2- (o-benzoyloxime) and OXE02 (trade name, Ciba Specialty Chemicals), 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) -butan-1-one, 2-methyl-1 [4- (methylthio) phenyl] -2-morif α- aminoalkylphenone such as Rinopuropan-1-one, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl biimidazole, and the like. Among these, the above benzophenones, glycines, mercaptos, oximes, α-aminoalkylphenones and 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl A combination of compounds selected from biimidazoles is preferred from the viewpoint of photoreaction. These photoinitiators are used individually or in combination of 2 or more types.

  When using a photoinitiator, the content is normally 0.1 to 40 parts by weight per one type with respect to 100 parts by weight of polyimide, and when combining two or more, the total amount is 0.2 to The amount is preferably 60 parts by weight.

  In the present invention, a thermally crosslinkable compound may be further contained. By containing a thermally crosslinkable compound, a thermal crosslinking reaction occurs during heat treatment, so that the shrinkage rate can be reduced. Examples of the thermally crosslinkable compound include a compound having a thermally crosslinkable group represented by the general formula (5) and a benzoxazine compound.

R ¹³ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, or an R ¹⁴ CO group. R ¹⁴ represents an alkyl group having 1 to 20 carbon atoms.

  As the compound having a thermally crosslinkable group, a compound containing at least two thermally crosslinkable groups is preferable. Particularly preferably, as those having two thermally crosslinkable groups, 46DMOC, 46DMOEP (trade name, manufactured by Asahi Organic Materials Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PC, DML- PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, DMOM-PTBP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) ), Nicalak MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), Ba type benzoxazine, Bm type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), 2,6-dimethoxy Methyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p TM-BIP-A (trade name, Asahi Organic Materials Co., Ltd.) has four such as cresol, such as TriML-P and TriML-35XL (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) Manufactured), TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), Nikarak MX-280, Nikarak MX-270 (trade name, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and the like are listed as having 6 such as Sanwa Chemical Co., Ltd.

  The content of such a heat-crosslinkable compound is preferably 0.5 to 150 parts by weight and more preferably 1 to 130 parts by weight with respect to 100 parts by weight of polyimide. By making content of the heat-crosslinkable compound with respect to 100 weight part of polyimide into 150 weight part or less, the heat resistance of the dielectric composition obtained is not reduced. On the other hand, when the content is 0.5 parts by weight or more, the heat resistance of the dielectric composition is improved due to the effect of increasing the molecular weight by sufficient crosslinking.

  In addition, for the purpose of controlling alkali developability, a compound having a phenolic hydroxyl group may be contained. For example, Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, BisOCHP-Z, BisOCR-CP, BisP-MZ, BisP-EZ, Bis26X-CP, BisP-PZ, BisP-IPZ, BisCR-IPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, BisOTBP-CP, TekP- 4HBPA (Tetrakis P-DO-BPA), TrisP-HAP, TrisP-PA, BisOFP-Z, BisRS-2P, BisPG-26X, BisRS-3P, BisOC-OCHP, BisPC-OCHP, Bis25X-OCHP, is26X-OCHP, BisOCHP-OC, Bis236T-OCHP, Methylenetris-FR-CR, BisRS-26X, BisRS-OCHP (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 (above, trade name, manufactured by Asahi Organic Materials Co., Ltd.).

  The content of such a compound having a phenolic hydroxyl group is preferably 1 to 60 parts by weight and more preferably 3 to 50 parts by weight with respect to 100 parts by weight of polyimide.

  The (a) high dielectric constant inorganic particles used in the present invention have an average particle diameter of 0.06 μm or more and 0.4 μm or less, more preferably 0.2 μm or less in primary particles. When the average particle diameter is 0.06 μm or more, a sufficient adhesive force is obtained between the photosensitive resin composition film and the adherend, and the pattern hardly peels during development. When the average particle size is 0.4 μm or less, when a dielectric composition obtained by curing a photosensitive resin composition having these particles is used as an interlayer insulating layer of a capacitor, a thin layer can be easily obtained. Since the capacitance is inversely proportional to the thickness of this layer, it is easy to obtain a capacitor having a large capacitance. When the average particle size is 0.2 μm or less, the surface roughness of the dielectric composition obtained by curing the photosensitive resin composition having these particles is small, and the in-plane film thickness variation is small. It becomes easy to form a thin film capacitor having a uniform capacitance distribution.

  In the measurement of the average particle diameter of the (a) high dielectric constant inorganic particles contained in the photosensitive resin composition and the dielectric composition of the present invention, a film made of the dielectric composition is formed, and the film thickness of the thin film It can be measured by performing X-ray microanalyzer (XMA) measurement and transmission electron microscope (TEM) observation on an ultrathin section obtained by cutting a film cross section in the direction. Since the high-permittivity inorganic particles and the resin have different transmittances with respect to the electron beam, the high-permittivity inorganic particles and the resin can be identified by the difference in contrast in the TEM observation image. When a plurality of kinds of high dielectric constant inorganic particles are used, each high dielectric constant inorganic particle can be identified by elemental analysis based on XMA measurement and crystal structure analysis by electron beam diffraction image observation. The distribution of the area of the high dielectric constant inorganic particles and the resin thus obtained is obtained by image analysis, and the particle diameter can be calculated from the area by approximating the cross section of the high dielectric constant inorganic particles to a circle. The particle diameter may be evaluated for TEM images with a magnification of 5000 times and 40000 times. The calculated particle size distribution is represented by a histogram in increments of 0.1 μm in a TEM image with a magnification of 5000 times and a histogram in 0.01 μm increments in a TEM image with a magnification of 40000 times. Is the average particle size. As an evaluation method of the particle size distribution, a scanning electron microscope (SEM) may be used instead of TEM in the above method.

  Generally, (a) the temperature at which the primary particle shape change such as grain growth or sintering of high dielectric constant inorganic particles occurs is much higher than the curing temperature of the resin. a) The particle diameter of the (a) high dielectric constant inorganic particles having a perovskite crystal structure may be evaluated in the raw material stage before the high dielectric constant inorganic particles are dispersed in the resin. In this case, (a) high dielectric constant inorganic particles can be directly observed using a TEM or SEM similar to that described above, and can be obtained by image analysis of an observation image obtained thereby.

  In addition to the above, (a) a dynamic light scattering method for measuring fluctuations of scattered light due to Brownian motion in a liquid of high dielectric constant inorganic particles, and (a) when high dielectric constant inorganic particles are electrophoresed The average particle diameter can be measured by an electrophoretic light scattering method for measuring the Doppler effect of the scattered light, an ultrasonic attenuation spectroscopy method for determining the attenuation state of the irradiated ultrasonic waves, or the like. Laser diffraction type and laser scattering type particle size distribution measuring devices include LA-920 manufactured by Horiba Ltd., SALD-1100 manufactured by Shimadzu Corp., MICROTRAC-UPA150 manufactured by Nikkiso Co., Ltd., and Zeta manufactured by Sysmex Corp. There are sizer nano ZS and the like.

  (A) As dielectric properties of the high dielectric constant inorganic particles, those having a relative dielectric constant of 50 to 30,000 are preferably used. When high dielectric constant inorganic particles having a relative dielectric constant of 50 or more are used, a dielectric composition having a sufficiently large relative dielectric constant can be easily obtained. A dielectric constant of 30000 or less is preferable because the temperature dependence of the dielectric constant tends to be small. The relative dielectric constant of the high dielectric constant inorganic particles referred to here refers to the relative dielectric constant of a sintered body obtained by heating and firing using high dielectric constant inorganic particles as a raw material powder. The relative dielectric constant of the sintered body is measured, for example, by the following procedure. A high-dielectric constant inorganic particle is mixed with a binder resin such as polyvinyl alcohol, an organic solvent or water to prepare a paste-like composition, which is then filled in a pellet molding machine and dried to give a pellet-like solid. obtain. By firing the pellet-like solid at, for example, about 900 to 1200 ° C., the binder resin can be decomposed and removed, the high dielectric constant inorganic particles can be sintered, and a sintered body consisting only of inorganic components can be obtained. . At this time, the voids of the sintered body are sufficiently small, and the porosity calculated from the theoretical density and the measured density is required to be 1% or less. Upper and lower electrodes are formed on this sintered pellet, and the relative dielectric constant is calculated from the measurement results of capacitance and dimensions.

  (A) The high dielectric constant inorganic particles have a perovskite crystal structure or a composite perovskite crystal structure. These include, for example, barium titanate, barium zirconate titanate, strontium titanate, calcium titanate, bismuth titanate, magnesium titanate, barium neodymium titanate, barium tin titanate , Barium magnesium niobate, barium magnesium tantalate, lead titanate, lead zirconate, lead zirconate titanate, lead niobate, lead magnesium niobate, lead nickel niobate, lead tungstate , Calcium tungstate, lead magnesium tungstate, titanium dioxide, and the like. The barium titanate system includes solid solutions based on barium titanate, in which some elements in the barium titanate crystal are replaced with other elements or other elements are infiltrated into the crystal structure. It is a generic name. Other barium zirconate titanate, strontium titanate, calcium titanate, bismuth titanate, magnesium titanate, barium neodymium titanate, barium tin titanate, barium magnesium niobate, magnesium tantalate Barium, lead titanate, lead zirconate, lead zirconate titanate, lead niobate, lead magnesium niobate, lead nickel niobate, lead tungstate, calcium tungstate, magnesium tungstic acid The same is true for lead-based materials, and is a generic term that includes solid solutions that use each as a base material.

  The high dielectric constant inorganic particles having a perovskite crystal structure or a composite perovskite crystal structure can be used alone or in combination of two or more, but at least 2 From the viewpoint of dielectric properties, it is preferable that the high dielectric constant inorganic particles having different average particle diameters have the same chemical composition. In particular, when obtaining a dielectric composition having a high dielectric constant, it is preferable to use a compound mainly composed of barium titanate from the viewpoint of compatibility with commercial convenience. However, for the purpose of improving dielectric properties and temperature stability, a small amount of a shifter, a depressor, etc. may be added.

  Examples of the method for producing the high dielectric constant inorganic particles include a solid phase reaction method, a hydrothermal synthesis method, a supercritical hydrothermal synthesis method, a sol-gel method, and an oxalate method. As a method for producing the high dielectric constant inorganic particles having the maximum average particle diameter, it is preferable to use a solid phase reaction method or an oxalate method from the viewpoint of high relative dielectric constant and quality stability. In addition, the method for producing the high dielectric constant inorganic particles having the minimum average particle size is easy to reduce the particle size, so any of hydrothermal synthesis method, supercritical hydrothermal synthesis method, sol-gel method, and alkoxide method can be used. It is preferable to use these.

  Examples of the shape of the high dielectric constant inorganic particles include a spherical shape, a substantially spherical shape, an elliptical spherical shape, a needle shape, a plate shape, a scale shape, and a rod shape, and a spherical shape or a substantially spherical shape is particularly preferable. This is because spherical or substantially spherical high dielectric constant inorganic particles have the smallest specific surface area, and therefore do not easily cause aggregation of high dielectric constant inorganic particles or a decrease in resin fluidity during filling. One of these can be used alone, or two or more can be mixed and used.

  In order to obtain a low linear expansion coefficient and a high relative dielectric constant, it is desirable to contain these high dielectric constant inorganic particles in a resin at a high filling rate.

  As the organic solvent (c) used in the present invention, a solvent capable of dissolving the resin can be appropriately selected. (C) Organic solvents include, for example, ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ale, 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 , Acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone , Ketones such as methyl ethyl ketone, cyclopentanone, 2-heptanone, butyl alcohol, isobutyl alcohol, isopropyl alcohol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl- Alcohols such as 3-methoxybutanol, diacetone alcohol, benzyl alcohol, methoxymethylbutanol, aromatic hydrocarbons such as toluene, xylene, etc., N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N , N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, methyl cellosolve, dioxane, acetone, cyclohexanone, cyclopentanone, tetrahydrofuran, chlorobenzene, trichloro Preferably, an organic solvent mixture containing ethylene or one or more of these is used. Of these, ethyl lactate is preferable in terms of good coatability.

  When an organic solvent having a boiling point of 120 ° C. or higher is used, when the photosensitive resin composition is applied with a spin coater, a uniform film can be easily obtained because the volatilization rate of the organic solvent is sufficiently slow. When the boiling point of the organic solvent is 160 ° C. or higher, the generation of voids is suppressed, and the dielectric constant of the dielectric composition can be increased. When the content of the high dielectric constant inorganic particles is large, if the boiling point is lower than 160 ° C., the volatilization rate of the organic solvent is fast. The relative dielectric constant of the composition may decrease. In terms of reducing the generation of voids when the high dielectric constant inorganic particles are highly filled, the boiling point of the organic solvent is more preferably 180 ° C. or higher, and further preferably 200 ° C. or higher. Moreover, it is preferable that the organic solvent used by this invention is 300 degrees C or less in boiling point, More preferably, it is 280 degrees C or less. When the boiling point is higher than 280 ° C., the treatment for the deorganic solvent becomes high temperature, the resin is decomposed by the high temperature, and the dielectric property is deteriorated. On the other hand, when the temperature exceeds 300 ° C., the decomposition of the resin becomes more severe and the mechanical strength is lowered. When the boiling point of the organic solvent is lower than 180 ° C., even when a resin that can be cured at a relatively low temperature of 180 to 200 ° C. is used, the organic solvent is completely removed by heat treatment for curing at 180 to 200 ° C. This is preferable when performing low temperature curing. When the organic solvent is not completely removed during the curing heat treatment, the organic solvent may swell due to desorption in a higher temperature heat treatment step such as solder reflow performed after the electrode metal layer is laminated, which is preferable. Absent.

The boiling point as used in the field of this invention is a boiling point under the pressure of 1 atmosphere, ie, 1.013 * 10 < ⁵ > N / m < ² >. The boiling point can be measured using a known technique and is not particularly limited. For example, the boiling point can be measured using a Swietoslawski boiling point meter.

  The total amount of organic solvent in the photosensitive resin composition of the present invention is preferably 35% by weight or less of the total amount of the composition. Preferably it is 30 weight% or less, More preferably, it is 25 weight% or less. Moreover, 1 weight% or more is preferable. When the amount of the organic solvent is 35% by weight or less, generation of voids due to volatilization of the organic solvent during drying is suppressed, and the relative dielectric constant of the dielectric composition can be increased. In addition, since the amount of voids that can cause moisture absorption is small, changes in physical properties due to the influence of humidity and moisture can be reduced. Furthermore, the storage durability is excellent. When the amount of the organic solvent is more than 35% by weight, voids increase in the drying step and the thermosetting step for removing the organic solvent, and the relative dielectric constant of the dielectric composition often decreases. When the amount of the organic solvent is 30% by weight or less, the generation of voids can be further suppressed, and when the amount of the organic solvent is 25% by weight or less, the generation of voids can be further suppressed, and the filling rate of the high dielectric constant inorganic particles The effect increases with increasing. When the amount of the organic solvent is less than 1% by weight, the organic solvent is small, so that the viscosity and uniformity of the photosensitive resin composition are impaired.

  As the filling rate of the high dielectric constant inorganic particles in the photosensitive resin composition increases, the influence of the amount of the organic solvent increases, and the solid content of the high dielectric constant inorganic particles contained in the photosensitive resin composition is 80. The effect of the present invention is particularly great when the amount is not less than wt%.

  The content of the high dielectric constant inorganic particles in the solid content contained in the photosensitive resin composition of the present invention is preferably 70% by weight or more, more preferably 75% by weight or more, and still more preferably 80% by weight or more. . Moreover, 90 weight% or less is preferable, More preferably, it is 85 weight% or less. When the content of the high dielectric constant electro-inorganic particles is 70% by weight or more, it becomes easy to increase the relative dielectric constant of the dielectric composition, and when it is 75% by weight or more, the relative dielectric constant can be further increased. In addition, the elastic modulus of the dielectric composition is improved, and the reliability in terms of strength of the dielectric composition is improved. If it is 80% by weight or more, not only the dielectric constant of the dielectric composition is increased, but also the thermal expansion coefficient becomes sufficiently small. In the case of a capacitor using the dielectric composition as an interlayer insulating film, a metal electrode or a capacitor is incorporated. The difference in thermal expansion coefficient from the mounting substrate or silicon substrate is reduced, and a capacitor with high reliability and stability can be obtained. When the content is 90% by weight or less, fine patterning by photosensitivity is facilitated despite containing high dielectric constant inorganic particles. When the content is 85% by weight or less, a thin film in which leakage portions such as pinholes in a dielectric composition obtained by curing a photosensitive resin composition having high dielectric constant inorganic particles are suppressed, leakage current is reduced, and withstand voltage is increased. It becomes easy to form a capacitor.

  In addition, solid content is the dielectric composition of the present invention such as (a) high dielectric constant inorganic particles, (b) phosphoric acid compound, (d) polyimide, (e) unsaturated bond-containing polymerizable compound, and other additives. It is a combination of components that do not volatilize or decompose by heat treatment to obtain a product. Therefore, the content of the high dielectric constant inorganic particles in the solid content contained in the photosensitive resin composition of the present invention is a dielectric composition obtained by solidifying the photosensitive resin composition with an organic solvent. In this case, it corresponds to the content of the high dielectric constant inorganic particles in the entire dielectric composition.

  In the present invention, in order to improve the dispersibility of the high dielectric constant inorganic particles, it reacts with the hydroxyl groups on the surface of the high dielectric constant inorganic particles to cover the particle surface, and therefore (b) a phosphoric acid compound is used. As the phosphate compound, manufactured by BYK Japan Japan Co., Ltd .: trade name “Dysperbyk-111”, “BYK-W9010”, etc., alkyl phosphates such as trimethyl phosphate, triethyl phosphate, tributyl phosphate and phosphate acrylate Is mentioned. Further, (b) the phosphoric acid compound may be added to the composition, or may be used as a surface treatment agent for the high dielectric constant inorganic particles.

The content of (b) the phosphoric acid compound is preferably 0.6% by weight or more and 9% by weight or less with respect to (a) the high dielectric constant inorganic particles. More preferably, it is {0.35 / (D ^2/3 )}% by weight or more and {1.37 / (D ^2/3 )}% by weight or less. Here, D is equal to a numerical value when the average particle diameter of the high dielectric constant inorganic particles is expressed in units (μm), and 0.06 ≦ D ≦ 0.4. For example, when the average particle diameter is 0.4 μm, D = 0.4, which is a dimensionless numerical value.

Phosphoric acid for covering the surface of the high dielectric constant inorganic particles while increasing the specific surface area of the high dielectric constant inorganic particles and increasing the specific surface area of the high dielectric constant inorganic particles. Although a large amount of compound is required, if the content of (b) the phosphoric acid compound is {0.35 / (D ^2/3 )}% by weight or more with respect to (a) the high dielectric constant inorganic particles, aggregation occurs. The surface of the cracked particle can be covered with an appropriate amount, the reaggregation of the particle can be inhibited, and the good dispersion of the high dielectric constant particle can be maintained. Further, when the content of (b) the phosphoric acid compound is {1.37 / (D ^2/3 )}% by weight or less with respect to the high dielectric constant inorganic particles, the dielectric constant decreases due to an increase in the amount of the phosphoric acid compound. Therefore, it is easy to increase the dielectric constant of the obtained dielectric composition.

In addition, when it has two types of high dielectric constant inorganic particles having an average particle diameter, the content of (b) the phosphoric acid compound contained in the photosensitive composition of the present invention is relative to (a) the high dielectric constant inorganic particles. {A / (a + b)} × {0.35 / (D ₁ ^2/3 )} + {b / (a + b)} × {0.35 / (D ₂ ^2/3 )} wt% or more, {a / It is preferable that (a + b)} × {1.37 / (D ₁ ^2/3 )} + {b / (a + b)} × {1.37 / (D ₂ ^2/3 )}% by weight or less. D ₁ and D ₂ are equal to the numerical values when the average particle diameter of the high dielectric constant inorganic particles is expressed in units (μm), and 0.06 ≦ D ₁ and D ₂ ≦ 0.4. a and b are weight ratios of the high dielectric constant inorganic particles having average particle diameters D ₁ and D ₂ contained in the photosensitive composition of the present invention.

  In addition to the phosphoric acid compound, surface treatment of high dielectric constant inorganic particles, addition of a dispersant, addition of a surfactant, addition of an organic solvent, and the like may be performed in order to further improve dispersibility. Examples of the surface treatment of the high dielectric constant inorganic particles include rosin treatment, acid treatment, basic treatment, etc., in addition to treatment with various coupling agents such as silane, titanium, and aluminum, and fatty acids. Examples of the dispersant include a dispersant having an acid group such as carboxylic acid, fatty acid, and esters thereof.

  In addition, the photosensitive resin composition of the present invention includes nonionic, cationic and anionic surfactants, wetting agents such as polyvalent carboxylic acids, amphophilic substances, resins having substituents with high steric hindrance, etc. If necessary, a stabilizer, a dispersant, an anti-settling agent, a plasticizer, an antioxidant and the like may be contained. Moreover, the polarity of the system at the time of dispersion or after dispersion can be controlled by adding an organic solvent.

  The photosensitive resin composition of the present invention has (a) a high dielectric constant inorganic particle having a perovskite type crystal structure or a composite perovskite type crystal structure and having an average particle diameter of 0.06 μm or more and 0.4 μm or less, (b) Dispersion prepared by mixing phosphoric acid compound and (c) organic solvent and using beads having an average particle diameter of 0.02 mm or more and 0.1 mm or less selected from any of metal, ceramics and glass as dispersion media A liquid is mixed with a resin solution having (d) a polyimide and (e) an unsaturated bond-containing polymerizable compound.

  Since the high dielectric constant inorganic particles (a) used in the present invention have a small average particle size, fine beads are used as a dispersion medium in order to achieve a uniform dispersion by solving the aggregation between the particles. (A) Since the average particle diameter of the high dielectric constant inorganic particles is 0.06 μm or more and 0.4 μm or less, a dispersion medium having an average particle diameter of beads of 0.02 mm or more and 0.1 mm or less is used. It is more effective when the average particle diameter of the beads of the dispersion medium is 0.03 mm or more and 0.06 mm or less. When the average particle size of the beads is 0.1 mm or less, when the dispersion passes between the beads, the high dielectric constant inorganic particles are frequently in contact with the beads, and a sufficient dispersion effect is obtained. In order to obtain a higher dispersion effect, the average particle size of the beads is preferably 0.06 mm or less, and the particle size of the aggregate of high dielectric constant inorganic particles after the dispersion treatment tends to be small. This effect is particularly great when (a) the average particle diameter of the high dielectric constant inorganic particles is 0.1 μm or less. When the average particle diameter of the beads is 0.02 mm or more, the momentum possessed by each bead is sufficiently large, and a shearing stress sufficient for solving the aggregation of the high dielectric constant inorganic particles can be obtained. In order to give a stronger shearing stress to the aggregate of high dielectric constant inorganic particles, the average particle diameter of the beads is preferably 0.03 mm or more. The dielectric composition formed by curing the photosensitive resin composition produced by using this method can more densely fill high dielectric constant inorganic particles in the resin. The capacitor used for has a small leakage current and a high withstand voltage.

  First, the example about the manufacturing method of the dispersion liquid of a high dielectric constant inorganic particle is described below. High dielectric constant inorganic particles, phosphoric acid compound, and organic solvent are mixed in a predetermined amount and stirred. Immediately after mixing, since the air layer covers the surface of the high dielectric constant inorganic particles, the high dielectric constant inorganic particles and the organic solvent are not sufficiently wetted, and the viscosity may increase. In this case, it is preferable that the high dielectric constant inorganic particles and the organic solvent are stirred with a rotating blade or the like over time until they are completely wetted.

  After mixing and stirring the high dielectric constant inorganic particles, the phosphoric acid compound, and the organic solvent, the high dielectric constant inorganic particles are dispersed by a bead mill. First, a predetermined amount of beads having a predetermined particle diameter ranging from 0.02 mm to 0.1 mm is put into a bead mill vessel, and the same organic solvent as that used for the dispersion is rotated while the rotor is rotated. The solution is circulated into the inside / circulated to wash the beads. If organic solvent stains are noticeable during cleaning, replace with a new organic solvent and continue washing until the organic solvent stains are not noticeable. After washing the beads, the circulated organic solvent is recovered, and then the mixed liquid of the high dielectric constant inorganic particles, the phosphoric acid compound, and the organic solvent is fed / circulated into the vessel to perform dispersion treatment. The concentration of the dispersion sent from the inside of the vessel is constant depending on the size of the vessel because the concentration of the dispersion sent out from the inside of the vessel is thinned by the organic solvent remaining in the vessel. Remove the first stream until. The dispersion treatment may be performed with small beads at one time, or may be performed by gradually changing the size of the beads to small ones, and is not limited to any. For example, the pre-dispersion treatment may be performed prior to the dispersion treatment (main dispersion) using beads having an average particle diameter of 0.02 mm to 0.1 mm in the present invention. Examples of the pre-dispersion treatment include dispersion until the average particle size of the aggregate of high dielectric constant inorganic particles is about several times the primary particle size with beads having an average particle size of 0.5 mm. . The pre-dispersion process and the main dispersion process may be performed by different apparatuses, for example, the pre-dispersion process is performed by a homogenizer or a ball mill, and the main dispersion is performed by a bead mill. Many bead mills use a method in which a sample is fed to a mill body through a tube, and if the pre-dispersion treatment is performed with a bead mill, particles having a large particle size may be clogged in the liquid feed tube. This can be avoided if the pre-dispersion process is performed by another apparatus such as a homogenizer.

  When performing the pre-dispersion process with a homogenizer, for example, the peripheral speed of the tip of the rotary blade is set to 1 to 10 m / s and the process is performed for about 1 hour. Since heat is generated during the homogenizer treatment, treatment in an ice bath is preferred. Examples of the homogenizer that can be used include “Excel Auto” (trade name, manufactured by Nippon Seiki Seisakusho).

  When the pre-dispersion treatment is performed by a ball mill, for example, high dielectric constant inorganic particles, phosphoric acid compound, and organic solvent are put into a 1 liter ceramic or polyethylene sample bottle so that the total amount becomes 800 g, and further predetermined 800 to 2000 g of beads having a particle size are added, and the mixture is stirred for 1 hour or more at a rotation speed of 100 to 600 rpm on a ball mill frame.

  Since the viscosity of the dispersion during the dispersion treatment affects the dispersibility of the high dielectric constant inorganic particles and the efficiency of the dispersion treatment, it is preferable to grasp the viscosity change of the dispersion over the course of the dispersion treatment. For example, it is possible to grasp the change in viscosity over time by sampling the dispersion at regular intervals and measuring the viscosity. When the viscosity of the dispersion increases during the dispersion treatment, an appropriate amount of an organic solvent, a phosphoric acid compound, a dispersant, a pH adjuster, or the like can be added to the circulating dispersion to reduce the viscosity.

  The temperature of the dispersion during the dispersion treatment can be controlled by the temperature and flow rate of cooling water for cooling the outside of the vessel and the circulation speed of the dispersion. The temperature rise of the dispersion tends to occur when the viscosity of the dispersion during the dispersion treatment is high. If the temperature rise of the dispersion is too large, the dispersion may be altered.

  The solid content concentration of the dispersion is preferably 10% by weight or more, more preferably 30% by weight or more. Further, the solid concentration of the dispersion is preferably 85% by weight or less, more preferably 80% by weight or less. The solid content concentration of the dispersion of the present invention is the ratio of components other than the organic solvent contained in the dispersion to the total amount of the dispersion. When the solid content concentration of the dispersion liquid is 10% by weight or more, it becomes possible to produce a dispersion liquid having a low viscosity, and since the amount of heat generated by friction with the beads is small even during the dispersion treatment, the dispersion liquid is constituted. The material is less likely to be altered. When the solid content concentration of the dispersion is 30% by weight or more, it is easy to form a thick film of 1 μm or more when a dielectric composition film is formed using a photosensitive resin composition in which the dispersion and the resin liquid are mixed. Become. Further, when the solid content concentration of the dispersion is 85% by weight or less, beads are easily separated when a filtering type bead mill using centrifugal separation is used. Further, when the solid content concentration of the dispersion is 80% by weight or less, the viscosity of the dispersion is low, and the high dielectric constant inorganic particles in the dispersion frequently come into contact with the beads. Is easier to solve.

  The rotating peripheral speed of the bead mill rotor may be constant or may be changed stepwise during the dispersion process. Since the rotational peripheral speed of the rotor may affect the temperature of the dispersion during dispersion processing, when changing the rotational peripheral speed during dispersion processing, the temperature rise of the dispersion should not be too great. preferable. In addition, in the case of a bead mill that filters beads by centrifugal separation, the beads are mixed in the dispersion liquid sent out from the vessel when the liquid feed pump is operated before the rotor is rotated and the circulation of the dispersion liquid is started. In some cases, the pump is operated after rotating the rotor.

  The dispersion treatment time is appropriately set according to the type and composition ratio of materials constituting the dispersion liquid such as high dielectric constant inorganic particles, organic solvent, and phosphoric acid compound. For example, sampling the dispersion at regular intervals and measuring the average particle size of the high dielectric constant inorganic particles in the dispersion can determine the time-dependent change in the dispersion state and determine the end point of the dispersion process. Is preferable. In the case of a composition with good dispersibility, a dispersion treatment time of about 30 minutes is sufficient, but depending on the composition, the dispersion treatment may be performed for 24 hours or more. If the dispersion treatment time is long, the composition ratio of the dispersion may change due to volatilization of the material constituting the dispersion, such as an organic solvent, and the dispersibility may change. Add necessary ingredients to adjust the composition. By this method for producing a dispersion, the high dielectric constant inorganic particles in the dispersion can be efficiently dispersed, and the particle size distribution is easily dispersed to the vicinity of the primary particle diameter.

  The average particle diameter of the beads can be evaluated by the following method, for example. The beads can be observed using an optical microscope. A bead (sample) is placed on a transparent plate such as glass, light is applied from below the transparent plate, a transmitted light image is observed through an objective lens, and the particle size of the bead is evaluated. Arbitrary 100 beads are observed, and the average value of the particle diameters obtained for each bead can be used as the average particle diameter of the beads. The particle diameter of the beads can be obtained by performing spherical approximation on the observed image of the beads using various image processing software. Specifically, a digital image obtained by a CCD camera attached instead of the eyepiece portion of the microscope is processed on a computer. As such a CCD camera, there is ADP-240 manufactured by Flowbell Co., Ltd., and software capable of such image processing includes FlvFs manufactured by Flowbell Co., Ltd.

  As the beads as the dispersion medium, those made of metal, ceramic or glass are used. Specific examples of these materials include stainless steel, iron, copper, chromium, nickel, titania, silicon nitride, silicon carbide, alumina, zirconia, zirconium silicate, barium titanate, silicate glass, and quartz. In particular, zirconia beads having high hardness can be suitably used. As zirconia, it is preferable to use yttria-stabilized zirconia because of its high strength.

  The dispersion method using the beads in the present invention is not particularly limited, and examples of the apparatus used include a ball mill, a homogenizer, and a pin rotor bead mill. -“Star mill” (trade name) manufactured by Finetech Co., Ltd. is particularly suitable for dispersing fine particles. In these two types of bead mills, a portion called a vessel where high dielectric constant inorganic particles are dispersed is formed by a cylindrical stator that forms an outer wall and a rotor that rotates at the center of the stator. And the dispersion liquid which mixed the high dielectric constant inorganic particle and the organic solvent is sent between a stator and a rotor. A plurality of blades project radially from the rotor. Filling the vessel with beads, which are dispersion media, and rotating the rotor, the beads are agitated by the blade, and accordingly, the beads give shearing stress to the high dielectric constant inorganic particles in the dispersion, and the high dielectric constant inorganic The particles are dispersed in the fine particles. The dispersion once passed through the vessel is circulated and repeatedly fed into the vessel to gradually solve the aggregation of the high dielectric constant inorganic particles in the dispersion and advance the dispersion.

  Although the high dielectric constant inorganic particles contained in the dispersion are present as primary particles or aggregates, in the present invention, the size of the high dielectric constant inorganic particles when present in the dispersion is determined in the dispersion. This is the median diameter (50% particle diameter) when the primary particles of several high dielectric constant inorganic particles are aggregated and distributed on a volume basis. The dispersion is preferably subjected to a dispersion treatment so that the high dielectric constant inorganic particles are dispersed in the organic solvent in a state where the median diameter is not less than twice the primary particle diameter.

  As a method of measuring the average particle size of high dielectric constant inorganic particles in a dispersion liquid, there are a static light scattering method and a dynamic light scattering method by a laser. It is preferable to use the method. An example of a particle size measuring apparatus using this method is “Nanotrack” UPA-EX150 (trade name) manufactured by Nikkiso Co., Ltd.

  The bead filling amount in the vessel of the bead mill is preferably 20% by volume or more and 85% by volume or less of the vessel volume. When the bead filling amount is 20% by volume or more, since the gap between adjacent beads is narrow, the high dielectric constant inorganic particles in the dispersion are frequently in contact with the beads, and the dispersion proceeds efficiently in a short time. In order to further enhance this effect, the filling amount of beads is more preferably 50% by volume or more. On the other hand, when the filled amount of beads is 85% by volume or less, there is a sufficient gap between adjacent beads, so that the dispersion can be smoothly fed without clogging the vessel. In addition, when the filling amount of the beads is 85% by volume or less, the amount of heat generated by friction between the beads or between the beads and the stator or rotor of the vessel is small, so that the material constituting the dispersion is not easily altered. In addition, in a bead mill that filters beads by centrifugal force, if the amount of beads filled increases, the filtering function does not work sufficiently, and the possibility of beads being mixed into the dispersion recovered from the vessel increases. If the filling amount is 85% by volume or less, the beads are not mixed or very small. Further, in order to exert this effect greatly, the bead filling amount is more preferably 75% by volume or less.

  The rotational peripheral speed of the rotor of the bead mill is preferably 5 m / s or more and 15 m / s or less, more preferably 5 m / s or more and 10 m / s or less. The rotational peripheral speed in the present invention is a speed at which the tip of the blade protruding from the rotor rotates. When the rotational peripheral speed is 5 m / s or more, a shear stress sufficient to disperse to an average particle diameter of 0.4 μm or less can be obtained. Further, when the rotational peripheral speed is 5 m / s or more, in the bead mill in which the beads are filtered by centrifugal force, the beads are hardly mixed into the recovered dispersion. On the other hand, when the rotational peripheral speed is 15 m / s or less, the amount of heat generated by friction between the beads or between the beads and the stator or rotor of the vessel is small. This effect is significant when the viscosity of the dispersion is 100 mPa · s or less. In addition, when the rotational peripheral speed is 10 m / s or less, particle crushing when the beads and the high dielectric constant inorganic particles come into contact can be suppressed. A dielectric composition formed by curing a photosensitive resin composition prepared using a dispersion in which the rotational peripheral speed of a rotor of a bead mill is 10 m / s or less is a high dielectric constant inorganic particle with reduced crushing. Can be densely packed in a resin, and a capacitor using this dielectric composition as a film can easily obtain a high relative dielectric constant. This effect is significant when the viscosity of the dispersion is 30 mPa · s or less and the average particle diameter of the high dielectric constant inorganic particles is 0.1 μm or more.

  The temperature of the dispersion during the dispersion treatment is preferably 10 ° C or higher and 40 ° C or lower. Here, the temperature of the dispersion during the dispersion treatment is the temperature of the dispersion immediately after being delivered from the vessel. When the dispersion liquid temperature is 40 ° C. or lower, the volatilization amount of the organic solvent in the dispersion liquid is small, and the concentration change of the high dielectric constant inorganic particles and organic components in the dispersion liquid is small. When the liquid temperature is higher than 40 ° C., the concentration of the dispersion composition changes, and the dispersibility of the dispersion liquid may deteriorate. For example, the dispersibility of the dispersion may be affected by the pH, but the pH value of the dispersion varies with changes in the concentration of the dispersion composition. Therefore, temperature control of the dispersion liquid is one of important conditions for controlling the pH value of the dispersion liquid and the dispersibility of the high dielectric constant inorganic particles in the dispersion liquid. In addition, when the dispersion contains a material that chemically reacts with temperature or a material that changes quality with temperature, it is preferable to control the temperature during dispersion because the characteristics of the dispersion change due to temperature change. In order to further enhance this effect, the temperature of the dispersion is preferably 35 ° C. or lower. On the other hand, when the temperature of the dispersion during the dispersion treatment is lower than 10 ° C., condensation occurs in the container for collecting the dispersion sent from the vessel, moisture is mixed in the dispersion, and the characteristics of the dispersion are deteriorated. Since there is a possibility, the temperature of the dispersion during the dispersion treatment is preferably 10 ° C. or higher. Further, when the temperature of the dispersion liquid is 10 ° C. or higher, the viscosity of the dispersion liquid becomes low, so that loss of kinetic energy of the beads can be avoided and the dispersion efficiency becomes high. In order to further enhance this effect, the temperature of the dispersion is more preferably 20 ° C. or higher.

  The viscosity of the dispersion during the dispersion treatment is preferably 1 mPa · s or more and 100 mPa · s or less. Here, the viscosity of the dispersion during the dispersion treatment is the viscosity when the dispersion sent from the vessel is sampled and measured 5 minutes after the sampling. The measurement temperature is 25 ° C. Viscosity measurement can be performed using, for example, a viscometer RE-115L manufactured by Toki Sangyo Co., Ltd. The beads in the bead mill vessel acquire kinetic energy from the rotating rotor blades and contact with the high dielectric constant inorganic particles in the dispersion to generate shear stress. However, when the viscosity of the dispersion is high, the kinetic energy is greatly reduced in the organic solvent before the beads come into contact with the high dielectric constant inorganic particles, and sufficient shear stress cannot be applied to the high dielectric constant inorganic particles. There is a case. The above problem can be avoided when the viscosity of the dispersion during the dispersion treatment is 100 mPa · s or less. In order to further enhance this effect, the viscosity of the dispersion during the dispersion treatment is more preferably 20 mPa · s or less. On the other hand, if the viscosity of the dispersion is 1 mPa · s or more, the viscosity of the photosensitive resin composition prepared by mixing the produced dispersion and the resin is not lowered, and the photosensitive resin composition is applied onto the substrate. When manufacturing a film-shaped resin composition, it becomes easy to form a continuous film.

  Next, the manufacturing method of the photosensitive resin composition containing the dispersion liquid obtained by the manufacturing method of said high dielectric constant inorganic particle dispersion liquid and the resin or the resin solution which has a resin and an organic solvent is demonstrated.

  Mixing of the dispersion liquid and the resin or the resin solution having the resin and the organic solvent may be performed by injecting the dispersion liquid into the resin or the resin solution having the resin and the organic solvent until a predetermined amount is reached. A resin or a resin solution containing a resin and an organic solvent may be injected until a predetermined amount is reached. The resin solution at this time may be a liquid resin or a resin solution obtained by dissolving a solid resin in an organic solvent. In this case, the resin solution having the resin and the organic solvent may be a resin solution obtained by dissolving a liquid resin or a solid resin in an organic solvent.

  Alternatively, any or all of the dispersion, the resin solution, the liquid resin, and the photosensitive resin composition obtained by mixing the dispersion and the resin solution 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.

  In order to make the photosensitive resin composition obtained by mixing a dispersion having a predetermined amount of high dielectric constant inorganic particles and a resin solution more uniform, a ball mill or a roll mill can be used. In addition, when bubbles are mixed in the photosensitive resin composition by the mixing process, the resin produced using the photosensitive resin composition is left by standing or using a stirring defoaming machine to remove the bubbles. Bubbles can be prevented from being mixed into the composition.

  As a method for obtaining the dielectric composition of the present invention, for example, a photosensitive resin composition is applied to an adherend (for example, a substrate), an organic solvent is removed, and heat treatment for exposure, development, and resin curing is performed. The method of obtaining the dielectric composition which has a desired pattern shape by is mentioned. However, since the dielectric composition of the present invention is not a sintered body, it is not necessary to completely decompose and remove the resin, and it is preferable to heat at a temperature within the heat resistant temperature range of the electronic component, for example, 500 ° C. or less. .

  Further, in order to improve the adhesion to the base substrate such as a silicon wafer, 0.5 to 10% by weight of a silane coupling agent or the like is added to the photosensitive resin composition, or the base substrate is pretreated with such a chemical solution. You can also.

  When treating the adherend surface, 0.5% of silane coupling agent is added to an organic solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate, etc. The solution in which 20% by weight is dissolved is subjected to spin coating, dipping, spray coating, steam treatment, and the like. In some cases, the reaction between the substrate and the coupling agent is allowed to proceed by applying a temperature from 50 ° C. to 300 ° C.

  It is also effective as a surface treatment method to heat the adherend at a high temperature to remove adsorbed water on the adherend surface. In this case, as the heat treatment temperature, for example, a temperature of 80 ° C. to 400 ° C. can be used.

  Next, a method for forming a dielectric composition pattern using the photosensitive resin composition of the present invention will be described.

  The adherend to which the photosensitive resin composition is applied is selected from, for example, silicon wafers, ceramics, gallium arsenide, organic circuit boards, inorganic circuit boards, and those in which circuit constituent materials are arranged on these boards Yes, but not limited to. Examples of organic circuit boards include glass-based copper-clad laminates such as glass cloth and epoxy-copper-clad laminates, composite copper-clad laminates such as glass nonwoven fabric and epoxy-copper-clad laminates, polyetherimide resin substrates, and poly Examples thereof include heat-resistant / thermoplastic substrates such as ether ketone resin substrates and polysulfone-based 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.

  Examples of methods for applying the photosensitive resin composition to the adherend include spin coating using a spinner, spray coating, roll coating, screen printing, blade coater, die coater, calendar coater, meniscus coater, bar coater, and the like. . The coating film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, and the like, but is usually applied so that the film thickness after drying is 0.1 to 150 μm.

  Next, the substrate coated with the photosensitive resin composition is dried to obtain a photosensitive resin composition film. Drying is preferably performed using an oven, a hot plate, infrared rays, or the like at a temperature of 50 ° C. to 180 ° C. for 1 minute to several hours.

  Next, the photosensitive resin composition film 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. .

  Formation of the pattern of the dielectric composition is achieved by removing the unexposed portions using a developer after exposure. As the developer, when an alkaline developer is used, an aqueous solution of tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylamino acetate An aqueous solution of an alkaline compound such as ethyl, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine is preferred. 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, 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 may be added singly or in combination. Good.

When developing with an organic solvent, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, hexa A polar solvent such as methyl phosphortriamide can be used alone or in combination with methanol, ethanol, isopropyl alcohol, xylene, water, methyl carbitol, ethyl carbitol and the like.
Development can be performed by spraying the developer on the coating film surface, immersing in the developer, applying ultrasonic waves while immersing, or spraying the developer while rotating the substrate.

  If the resolution of the pattern at the time of development is improved or the allowable range of development conditions is increased, a baking process may be incorporated before development. As this temperature, the range of 50-180 degreeC is preferable, and the range of 60-150 degreeC is especially more preferable. The time is preferably 10 seconds to several hours.

  After development, rinsing with water may be performed. 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.

  The film thickness reduction after development is preferably 0.7 μm or less. More preferably, it is 0.5 μm or less. When the film thickness reduction after development is 0.7 μm or less, an error due to fluctuations in the film thickness after development tends to be small, which is preferable. Further, when the thickness is 0.5 μm or less, it is easy to reduce the influence of variations in film thickness within the surface when formed on a large-diameter substrate.

After development, there may be a step of irradiating the unexposed portion with ultraviolet rays at 100 mJ / cm ² to 4000 mJ / cm ² . Furthermore, a temperature of 120 ° C. to 400 ° C. is applied to obtain a dielectric composition. This heat treatment is carried out for 5 minutes to 5 hours by selecting the temperature and raising the temperature stepwise, or selecting a certain temperature range and continuously raising the temperature. As an example, heat treatment is performed at 130 ° C., 200 ° C., and 350 ° C. for 30 minutes each. Alternatively, a method such as linearly raising the temperature from room temperature to 400 ° C. over 2 hours may be mentioned.

  The smaller the porosity of the dielectric composition, the better. When the porosity is small, the proportion of high dielectric constant inorganic particles in the film volume increases, and a dielectric composition having a relative dielectric constant of 30 or more is easily obtained. In addition, when the porosity is small, there is no decrease in insulation resistance, increase in leakage current, or decrease in bending strength.

  The form of the dielectric composition of the present invention is not particularly limited and can be selected according to the application, such as a film shape, a rod shape, and a spherical shape, but a film shape is particularly preferable. The film here includes a film, a sheet, a plate, a pellet and the like. Of course, it is also possible to perform pattern formation according to applications such as via hole formation for conduction, adjustment of impedance, capacitance or internal stress, or provision of a heat dissipation function.

  The film thickness in the case of forming a film from the dielectric composition can be arbitrarily set within a range where the capacitance satisfies a desired value, but is preferably 0.5 μm or more, more preferably 1.5 μm or more. . Moreover, 10 micrometers or less are preferable and 5 micrometers or less are more preferable. In order to secure a large capacitance as a capacitor, it is preferable that the film thickness is small. However, if the thickness is smaller than 0.5 μm, pinholes are easily generated, and it is difficult to obtain electrical insulation. When the thickness is 1.5 μm or more, defects such as pinholes in the dielectric composition are suppressed, and the leakage current can be reduced. In addition, the dielectric loss tangent hardly increases after PCT (pressure cooker test) which is a durability promotion test. On the other hand, if the film thickness exceeds 10 μm, a large relative dielectric constant is required to obtain sufficient capacitor performance, and it may be difficult to improve the mounting density. When the thickness is 5 μm or less, it is easy to obtain a capacitor having a large capacitance, and when used as a decoupling capacitor, a sufficient function as a decoupling capacitor can be achieved.

  The in-plane variation of the film thickness of the dielectric composition is preferably 5% or less with respect to the average value. When the in-plane variation of the film thickness is 5% or less with respect to the average value, the in-plane variation of the capacitance of the capacitor becomes small, and it becomes easy to obtain a capacitor having a uniform capacitance distribution.

  The method for identifying the in-plane variation of the film thickness can be appropriately selected according to the application, such as a stylus step meter, a laser microscope, a scanning electron microscope, an atomic force microscope, and the like. If measurement is not possible by the above method, such as when a metal layer is formed on the dielectric composition, a cross-sectional sample is prepared, and the film is observed by scanning electron microscope (SEM) or transmission electron microscope (TEM) observation. The thickness can be determined. When a cross-sectional sample is prepared, layers having different contrasts can be detected at the interface between the dielectric composition of the present invention and the metal layer, and the interface can be specified. When the interface is not specified because the contrast difference is small, the interface position can be specified by analyzing the composition of the cross section using an energy dispersive X-ray analyzer (EDX). The film thickness of each part can be determined from the obtained interface, and the in-plane variation of the film thickness can be determined.

  The surface roughness Ra of the dielectric composition is preferably 0.02 μm or more and 0.1 μm or less. When the surface roughness Ra is larger than 0.02 μm, it becomes easy to obtain a sufficient adhesive force with the layer laminated on the dielectric composition. When the surface roughness Ra is less than 0.1 μm, the influence of the unevenness of the dielectric composition on the uniformity of the capacitance distribution becomes small, and it becomes easy to obtain a capacitor having a uniform capacitance distribution.

  The surface roughness Ra is an arithmetic average roughness, which is extracted from the extracted curve by the reference length L, and the extracted curve is represented by y = f (x) with the average line of the extracted portion as the X axis and the direction of the vertical magnification as the Y axis. Can be obtained by the following equation (1). A model diagram of the extraction curve of the surface irregularities is shown in FIG.

  The method for measuring the surface roughness Ra and the method for specifying the extraction curve can be appropriately selected according to the application, such as a stylus step meter, a laser microscope, a scanning electron microscope, an atomic force microscope, and the like.

  If measurement is not possible by the above method, such as when a metal layer is formed on the dielectric composition film, a cross-sectional sample is prepared and observed by a scanning electron microscope (SEM) or transmission electron microscope (TEM). An extraction curve can be specified. When a cross-sectional sample is prepared, layers having different contrasts can be detected at the interface between the dielectric composition of the present invention and the metal layer, and an extraction curve can be specified. In addition, when the contrast difference is small and the interface cannot be specified, the interface position can be specified by analyzing the composition of the cross section using an energy dispersive X-ray analyzer (EDX), and the extraction curve can be specified. . The surface roughness Ra can be obtained from the obtained extraction curve using Equation (1).

  The use of the photosensitive resin composition and the dielectric composition film of the present invention is not particularly limited. For example, it is used as an interlayer insulating material for a built-in capacitor of a printed wiring board as a high dielectric constant layer, or an interlayer insulating film of a multilayer board. It can be applied to various electronic parts and devices such as frequency filters, radio antennas, and electromagnetic shields.

  The dielectric composition of the present invention is preferably used as an interlayer insulating material for capacitors. A method for forming an interlayer insulating material for a capacitor using the dielectric composition is not particularly limited. For example, as described above, after forming a film of the dielectric composition on the substrate, it can be obtained by appropriately forming an electrode. Further, since the photosensitive resin composition of the present invention has photosensitivity, it is possible to form a capacitor having a fine pattern, and the capacitor can be provided on a semiconductor element on which a transistor is formed. This eliminates the need for wiring from the semiconductor device causing parasitic inductance to the capacitor mounted on the substrate, contributing to higher speed and higher density of the system.

The capacitance per area of the interlayer insulating material for capacitors produced using the dielectric composition of the present invention is preferably in the range of 5 nF / cm ² or more. More preferably, it is in the range of 10 nF / cm ² or more. When the capacitance is less than 5 nF / cm ² , when used as a decoupling capacitor, the entire system cannot be sufficiently separated from the power supply system and cannot function sufficiently as a decoupling capacitor.

  Examples of the present invention will be described below, but the present invention is not limited to these examples. In addition, evaluation of the photosensitive resin composition in an Example was performed with the following method.

(1) Viscosity measurement of dispersion The viscosity of the dispersion was measured at 25 ° C. using a viscometer RE-115L (manufactured by Toki Sangyo Co., Ltd.).

(2) Particle size distribution in dispersion of high dielectric constant inorganic particles The particle size distribution of the dispersion was measured using a particle size distribution measuring device Microtrac UPA150 (manufactured by Nikkiso Co., Ltd.). As the particle size distribution, values of 50% diameter and 90% diameter were used. The 50% diameter is the particle diameter and cumulative median point (median diameter) at which the cumulative curve is 50% when the total curve of the powder aggregate is 100%. The 90% diameter is the particle diameter at which the cumulative curve becomes 90%.

(3) Measuring method of film thickness Using a Surfcom 1400 manufactured by Tokyo Seimitsu Co., Ltd., measurement was performed with a stylus type. The film thickness was measured at three points at random, and the average value of the three points was taken as the film thickness. The length measurement was 1 mm, and the scanning speed was 0.3 mm / s.

(4) Method for measuring in-plane variation in film thickness A dielectric composition film is formed on a 6-inch silicon wafer, and is positioned at 0, 20, 40, and 60 mm from the wafer center, and 90 ° apart from the wafer center. 4 points were measured, and the average of 15 points in total was taken as the average value of the film thickness. The film thickness at one place is an average value obtained by measuring a total of three points shifted by 5 mm to the left and right around the measurement point. The in-plane variation was calculated according to the following formula.
In-plane variation (%) = (maximum value of film thickness−minimum value of film thickness) ÷ average value of film thickness × 100.

(5) Surface roughness Ra
Measurement was carried out with a stylus type according to JIS B0601-1982 using Surfcom 1400 manufactured by Tokyo Seimitsu Co., Ltd.

(6) Leakage current A titanium and copper were sputtered on a silicon wafer in this order to produce an adherend. The film thickness of titanium was 100 nm, and the film thickness of copper was 500 nm. The photosensitive resin composition was applied onto the adherend using a spin coater, and appropriately heated, exposed, baked, developed, and cured to form a dielectric composition film on the adherend. The film thickness of the dielectric composition was in the range of 0.4 μm to 12 μm. An aluminum electrode was formed on the dielectric composition film by vapor deposition. The aluminum electrode is a circular pattern electrode having a thickness of 300 nm and an area of 5 mm ² . A portion sandwiched between the copper electrode and the aluminum electrode is a measurement target. A voltage of 1 V to 100 V was applied between the copper electrode and the aluminum electrode, and the current was measured 20 seconds after voltage application. For this measurement, an electrometer / high resistance system type 6517A manufactured by Keithley Instruments Co., Ltd. was used.

Example 1
Under a dry nitrogen stream, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF) 30.03 g (0.082 mol), 1,3-bis (3-aminopropyl) tetramethyldi 1.24 g (0.005 mol) of siloxane and 2.7 g (0.025 mol) of 3-aminophenol as an end-capping agent were dissolved in 100 g of N-methyl-2-pyrrolidone (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. Then, it stirred at 180 degreeC for 5 hours, and obtained the 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 200 ° C. for 5 hours. When the resulting measuring the infrared absorption spectrum of the polymer powder, 1780 cm around ^-1, absorption peaks of an imide structure caused by a polyimide was detected near 1377 cm ^-1. Next, 10 g of this polymer powder, 1.4 g of photopolymerization initiator OXE02 (trade name, manufactured by Ciba Specialty Chemicals), 0.6 g of 0.5% phenothiazine solution of polymerization inhibitor, and HMOM- TPHAP (trade name, Honshu Chemical Industry Co., Ltd., concentration 20%) 8.6 g, PDBE-250 (trade name, manufactured by Nippon Oil & Fats Co., Ltd., compound having a polymerizable unsaturated double bond) 5.1 g, di A solution prepared by dissolving 0.6 g of methylol tricyclodecane diacrylate (compound having a polymerizable unsaturated double bond) in 5.1 g of diacetone alcohol and 3.7 g of ethyl lactate was stirred and degassed, and the retained particle diameter was 2 μm. Pressure filtration was performed using a filter to obtain a resin solution A-1. The viscosity of the dispersion was measured at 25 ° C. using a viscometer RE-115L (manufactured by Toki Sangyo Co., Ltd.). The results are shown in Table 1.

500 parts by weight of ethyl lactate, 72 parts by weight of a phosphoric acid compound (a copolymer having a phosphate ester skeleton, BYK-W9010), barium titanate (BaTiO ₃ , Sakai Chemical Industry Co., Ltd.), BT −01: Average primary particle size 0.1 μm) was mixed in the order of 1428 parts by weight to obtain a dispersion B-1A. In a vessel of Ultra Apex Mill UAM-015 (manufactured by Kotobuki Kogyo Co., Ltd.), 0.4 kg of zirconia balls (Nikkato Co., Ltd., YTZ balls, size φ0.5 mm) are filled, and the dispersion is performed while rotating the rotor. B-1A was fed into the vessel and circulated. The manufacturer value in the inspection report regarding the particle diameter of zirconia balls (manufactured by Nikkato Corporation, YTZ balls, size φ0.5 mm) is an average particle diameter of 0.537 mm. After dispersion for 1 hour at a rotor peripheral speed of 8 m / s, dispersion B-1B was obtained. The beads in the vessel were collected and newly filled with 0.4 kg of zirconia balls (manufactured by Nikkato Corporation, YTZ balls, size φ0.05 mm). The manufacturer value in the inspection report regarding the particle diameter of zirconia balls (manufactured by Nikkato Corporation, YTZ balls, size φ0.05 mm) is an average particle diameter of 0.058 mm. After the bead exchange, the dispersion B-1B was fed and circulated in the vessel while rotating the rotor. Dispersion was carried out at a rotor peripheral speed of 12 m / s for 2 hours to obtain Dispersion B-1C. Further, the dispersion B-1C was subjected to pressure filtration using a filter having a reserved particle diameter of 10 μm and 6 μm to obtain a dispersion B-1D.

  Place 100 parts by weight of Dispersion B-1D and 19.1 parts by weight of Resin Solution A-1 in a sample bottle made of polyethylene with a volume of 250 ml. The photosensitive resin composition C-1 was produced by rotating and mixing at 200 rpm for 1 hour. The filler filling rate of photosensitive resin composition C-1 (the amount of inorganic particles in the total solid content of C-1) was 83.8% by weight.

Using a spin coater, the photosensitive resin composition C-1 was applied on a 4-inch silicon wafer in which a Cr film having a thickness of 10 nm and a Cu film having a thickness of 100 nm were formed in this order by sputtering. And pre-baked at 100 ° C. for 3 minutes. Next, 500/500, 250/250, 100/100, 50/50, 40/40, 30/30, 25/25, 20/20, 15 / are applied to an exposure apparatus (PEM-6M manufactured by Union Optics Co., Ltd.). A 15 μm line and space (L / S) mask was set, and exposure was performed at an exposure amount of 500 mJ / cm ² (intensity of 365 nm) under close contact between the sample and the mask. After exposure, baking was performed at 120 ° C. for 1 minute using a hot plate. Development is performed using a spray type developing device of AD-2000 manufactured by Takizawa Sangyo Co., Ltd., spraying with a developer for 10 seconds at a spray pressure of 0.15 MPa while rotating at 100 rpm, immersion development for 10 seconds, removal of the developer, 10 Spraying for 10 seconds, immersion development for 10 seconds, removal of the developer, and spraying for 10 seconds were repeated, followed by rinsing with water. As the developer, a 2.38% aqueous solution of tetramethylammonium hydroxide was used. The developed film was heat-treated at 200 ° C. for 60 minutes in an N ₂ atmosphere using an inert oven INL-60 manufactured by Koyo Thermo System Co., Ltd. to obtain a patterned dielectric composition film. When the film thickness was measured, the film thickness of the dielectric composition film was 2 μm. The reduction in film thickness due to development obtained from the measurement results before and after development was 0.3 μm. When the line and space (L / S) pattern of the dielectric composition film was confirmed using an optical microscope, it was confirmed that the L / S pattern was formed without any residue up to 15/15 μm.

Next, the photosensitive resin composition C-1 is separately applied to the entire surface of an aluminum substrate having an area of 6 cm × 6 cm and a thickness of 0.3 mm using a spinner, prebaked at 100 ° C. for 3 minutes using a hot plate, and exposed. Exposure is performed at an amount of 500 mJ / cm ² (intensity of 365 nm), and heat treatment is performed at 200 ° C. for 60 minutes in an N ₂ atmosphere using an inert oven INL-60 manufactured by Koyo Thermo System Co., Ltd., and a dielectric composition is formed on the aluminum substrate. A film made of material was obtained. Subsequently, an aluminum electrode was formed on this film by vapor deposition. The aluminum electrode is a circular pattern measuring electrode having a diameter of 10 mm and a ring-shaped guard electrode having an inner diameter of 11.5 mm. The film thickness of the dielectric composition film was in the range of 5 μm to 10 μm. A portion sandwiched between the measurement electrode and the aluminum substrate is a measurement target region. The capacitance at a frequency of 1 MHz in the measurement target region was measured using an impedance analyzer 4294A and a sample holder 16451B (both manufactured by Agilent Technologies). The relative dielectric constant was calculated from the capacitance and the dimensions of the measurement target region. This film had a relative dielectric constant of 32 and a dielectric loss tangent of 0.03 at a measurement frequency of 1 MHz.

Further, the photosensitive resin composition C-1 was applied onto a 6-inch silicon wafer substrate using a spinner, pre-baked at 100 ° C. for 3 minutes using a hot plate, and an exposure amount of 500 mJ / cm ² (intensity of 365 nm). exposure is performed, it cured 60 minutes at 200 ° C. under a N ₂ atmosphere using Koyo thermo system Co. inert oven INL-60, to obtain a dielectric composition film on a 6-inch silicon wafer substrate. The in-plane variation of the film thickness was within ± 0.1 μm. The surface roughness Ra was 0.02 μm.

In addition, the photosensitive resin composition C-1 was applied on a 6-inch silicon wafer in which a Ti film having a thickness of 100 nm and a Cu film having a thickness of 500 nm were laminated in this order by a sputtering method using a spin coater. The plate was pre-baked at 100 ° C. for 3 minutes. Next, a mask was set in an exposure apparatus (PEM-6M manufactured by Union Optics Co., Ltd.), and exposure was performed between the sample and the mask under close contact conditions with an exposure amount of 500 mJ / cm ² (intensity of 365 nm). After exposure, it was baked at 120 ° C. for 1 minute. Development is performed using a spray type developing device of AD-2000 manufactured by Takizawa Sangyo Co., Ltd., spraying with a developer for 10 seconds at a spray pressure of 0.15 MPa while rotating at 100 rpm, immersion development for 10 seconds, removal of the developer, 10 Spraying for 10 seconds, immersion development for 10 seconds, removal of the developer, and spraying for 10 seconds were repeated, followed by rinsing with water. As the developer, a 2.38% aqueous solution of tetramethylammonium hydroxide was used. The developed film was heat-treated at 200 ° C. for 60 minutes in an N ₂ atmosphere using an inert oven INL-60 manufactured by Koyo Thermo System Co., Ltd. to obtain a dielectric composition film having a land pattern of 30 mm □. A circular pattern electrode having an area of 5 mm ² was formed on the dielectric composition film by vapor deposition. Table 2 shows the results of applying a voltage of 1 to 100 V between the copper electrode and the aluminum electrode and measuring the current value 20 seconds after the voltage application.

  Further, a leakage current measurement sample composed of the above-mentioned aluminum / dielectric composition / Cu / Ti / silicon wafer was cut out in the film thickness direction using an ultrathin section method, and a film cross-section sample D-1 was produced. The thickness of the membrane cross-section sample cut out by the ultrathin section method is 0.06 μm. This membrane cross-sectional sample was observed with a transmission electron microscope (TEM), and the content ratio of high dielectric constant inorganic particles was calculated from image analysis. The obtained TEM image is shown in FIG. The magnification is 100,000 times. The content rate of the high dielectric constant inorganic particles contained in the area of 1800 nm □ of the cross section of the film was calculated from image analysis. In the image analysis method, the obtained TEM image was binarized using image analysis software (Matrox Inspector), and the amount of high dielectric constant inorganic particles occupying the area was calculated. In binarization, the contrast of the obtained TEM image was divided into 256 gradations, and a value of 180 was used as a threshold value. A binarized TEM image is shown in FIG. The content ratio of the high dielectric constant inorganic particles calculated from the binarized black portion as the high dielectric constant inorganic particles was 82.6%.

Example 2
In a vessel of Ultra Apex Mill UAM-015 (manufactured by Kotobuki Kogyo Co., Ltd.), 0.4 kg of zirconia balls (Nikkato Co., Ltd., YTZ balls, size φ0.03 mm) are filled, and while rotating the rotor, the dispersion B-1B was fed into the vessel and circulated. Dispersion was performed at a peripheral speed of the rotor of 12 m / s for 4 hours to obtain Dispersion B-1E. Further, the dispersion B-1E was subjected to pressure filtration using a filter having a reserved particle diameter of 10 μm and 6 μm to obtain a dispersion B-1F. The average particle size of the above-mentioned zirconia balls (manufactured by Nikkato Co., Ltd., YTZ balls, TZ-B30, size φ 0.03 mm) is 0.028 mm as determined from the manufacturer particle size distribution measurement value.

  Place 100 parts by weight of Dispersion B-1F and 19.1 parts by weight of Resin Solution A-1 into a polyethylene sample bottle with a volume of 250 ml. The photosensitive resin composition C-2 was prepared by rotating and mixing at 200 rpm for 1 hour. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 2.

Example 3
In a vessel of Ultra Apex Mill UAM-015 (manufactured by Kotobuki Kogyo Co., Ltd.), 0.4 kg of zirconia balls (Nikkato Co., Ltd., YTZ balls, size φ0.1 mm) are filled, and while rotating the rotor, the dispersion B-1B was fed into the vessel and circulated. Dispersion was carried out at a rotor peripheral speed of 12 m / s for 2 hours to obtain Dispersion B-1G. Further, the dispersion B-1G was subjected to pressure filtration using a filter having a reserved particle diameter of 10 μm and 6 μm to obtain a dispersion B-1H. The manufacturer value in the inspection report regarding the particle diameter of zirconia balls (manufactured by Nikkato Corporation, YTZ balls, size φ0.1 mm) is an average particle diameter of 0.113 mm.

  Place 100 parts by weight of Dispersion B-1H and 19.1 parts by weight of Resin Solution A-1 in a polyethylene 250 ml sample bottle, and put only the dispersion and resin solution on the ball mill stand without putting balls. The photosensitive resin composition C-3 was produced by rotating and mixing at 200 rpm for 1 hour. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 2.

Example 4
250 parts by weight of ethyl lactate, 36 parts by weight of a phosphoric acid compound (a copolymer having a phosphate ester skeleton, BYK-W9010), barium titanate (BaTiO ₃ , Sakai Chemical Industry Co., Ltd.), BT -01: Average primary particle size 0.1 μm) 714 parts by weight were mixed in this order, and mixed for 1 hour under ice-cooling using a homogenizer to obtain dispersion B-2A. In a homogenizer cup, 714 parts by weight of zirconia balls (manufactured by Nikkato Co., Ltd., YTZ balls, size φ0.5 mm) was filled and mixed and dispersed. Next, 0.4 kg of zirconia balls (manufactured by Nikkato Co., Ltd., YTZ balls, size φ0.05 mm) are filled in the vessel of Ultra Apex Mill UAM-015 (manufactured by Kotobuki Industries Co., Ltd.), and while rotating the rotor, Dispersion B-2A was fed into the vessel and circulated. Dispersion was carried out at a rotor peripheral speed of 12 m / s for 2 hours to obtain dispersion B-2B. Further, the dispersion B-2B was subjected to pressure filtration using a filter having a reserved particle diameter of 10 μm and 6 μm to obtain a dispersion B-2C.

  Place 100 parts by weight of Dispersion B-2C and 19.1 parts by weight of Resin Solution A-1 into a polyethylene sample bottle with a volume of 250 ml, and put only the dispersion and resin solution without placing the balls on the ball mill stand. The mixture was rotated for 1 hour at 200 rpm to prepare a photosensitive resin composition C-4. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 2.

Example 5
In a vessel of Ultra Apex Mill UAM-015 (manufactured by Kotobuki Industries Co., Ltd.), 0.4 kg of zirconia balls (manufactured by Nikkato Co., Ltd., YTZ balls, size φ0.05 mm) are filled, and while rotating the rotor, the dispersion B-1A was fed into the vessel and circulated. Dispersion was carried out at a rotor peripheral speed of 12 m / s for 2 hours to obtain dispersion B-3B. Further, dispersion B-3B was subjected to pressure filtration using a filter having a reserved particle diameter of 10 μm and 6 μm to obtain dispersion B-3C.

  Place 100 parts by weight of Dispersion B-3C and 19.1 parts by weight of Resin Solution A-1 in a polyethylene sample bottle with a volume of 250 ml, and put only the dispersion and resin solution without placing the balls on the ball mill stand. Rotational mixing was performed by rotating at 200 rpm for 1 hour to prepare a photosensitive resin composition C-5. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 2.

Example 6
500 parts by weight of ethyl lactate, 44 parts by weight of phosphoric acid compound (a copolymer having a phosphate ester skeleton, BYK-W9010), barium titanate (BaTiO ₃ , Sakai Chemical Industry Co., Ltd.), BT -01: Average primary particle size 0.1 μm) was mixed in the order of 1456 parts by weight to obtain dispersion B-4A. In a vessel of Ultra Apex Mill UAM-015 (manufactured by Kotobuki Kogyo Co., Ltd.), 0.4 kg of zirconia balls (Nikkato Co., Ltd., YTZ balls, size φ0.5 mm) are filled, and the dispersion is performed while rotating the rotor. B-4A was fed into the vessel and circulated. After dispersing for 1 hour at a rotor peripheral speed of 8 m / s, dispersion B-4B was obtained. The beads in the vessel were collected and newly filled with 0.4 kg of zirconia balls (manufactured by Nikkato Corporation, YTZ balls, size φ0.05 mm). After the bead exchange, the dispersion B-4B was fed into the vessel and circulated while rotating the rotor. Dispersion was carried out at a rotor peripheral speed of 12 m / s for 2 hours to obtain Dispersion B-4C. Furthermore, dispersion B-4C was subjected to pressure filtration using a filter having a reserved particle diameter of 10 μm and 6 μm to obtain dispersion B-4D.

  Place 100 parts by weight of Dispersion B-4D and 22.1 parts by weight of Resin Solution A-1 in a polyethylene sample bottle with a volume of 250 ml, and put only the dispersion and resin solution without placing balls on the ball mill stand. Rotational mixing was performed by rotating at 200 rpm for 1 hour to prepare a photosensitive resin composition C-6. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 2.

Example 7
500 parts by weight of ethyl lactate, 44 parts by weight of phosphoric acid compound (a copolymer having a phosphate ester skeleton, BYK-W9010), barium titanate (BaTiO ₃ , Sakai Chemical Industry Co., Ltd.), BT -02: Average primary particle size 0.2 μm) was mixed in the order of 1456 parts by weight to obtain dispersion B-5A. In a vessel of Ultra Apex Mill UAM-015 (manufactured by Kotobuki Kogyo Co., Ltd.), 0.4 kg of zirconia balls (Nikkato Co., Ltd., YTZ balls, size φ0.5 mm) are filled, and the dispersion is performed while rotating the rotor. B-5A was fed into the vessel and circulated. After dispersing for 1 hour at a peripheral speed of the rotor of 8 m / s, dispersion B-5B was obtained. The beads in the vessel were collected and newly filled with 0.4 kg of zirconia balls (manufactured by Nikkato Corporation, YTZ balls, size φ0.05 mm). After the beads were exchanged, the dispersion B-5B was fed into the vessel and circulated while rotating the rotor. Dispersion was carried out at a rotor peripheral speed of 12 m / s for 2 hours to obtain Dispersion B-5C. Further, the dispersion B-5C was subjected to pressure filtration using a filter having a reserved particle diameter of 10 μm and 6 μm to obtain a dispersion B-5D.

  Place 100 parts by weight of Dispersion B-5D and 22.1 parts by weight of Resin Solution A-1 in a 250 ml polyethylene sample bottle, and put only the dispersion and resin solution without placing the balls on the ball mill stand. The mixture was rotated for 1 hour at 200 rpm to produce a photosensitive resin composition C-7.

  Development is performed using a spray type developing device of AD-2000 manufactured by Takizawa Sangyo Co., Ltd., while rotating at 100 rpm, spraying the developer at a spray pressure of 0.15 MPa for 10 seconds, immersion development for 15 seconds, removal of the developer, 10 Spraying for 1 second and immersion development for 15 seconds were repeated, followed by rinsing with water. As the developer, a 2.38% aqueous solution of tetramethylammonium hydroxide was used. Evaluation was performed in the same manner as in Example 1 except for the development step. The results are shown in Table 2.

Example 8
800 parts by weight of ethyl lactate, 6 parts by weight of a phosphoric acid compound (a copolymer having a phosphate ester skeleton, BYK-W9010), barium titanate (BaTiO ₃ , Sakai Chemical Industry Co., Ltd.), BT −02: Average primary particle size 0.2 μm) was mixed in the order of 1194 parts by weight to obtain Dispersion B-6A. In a vessel of Ultra Apex Mill UAM-015 (manufactured by Kotobuki Kogyo Co., Ltd.), 0.4 kg of zirconia balls (Nikkato Co., Ltd., YTZ balls, size φ0.5 mm) are filled, and the dispersion is performed while rotating the rotor. B-6A was fed into the vessel and circulated. After dispersion at a rotor peripheral speed of 8 m / s for 1 hour, dispersion B-6B was obtained. The beads in the vessel were collected and newly filled with 0.4 kg of zirconia balls (manufactured by Nikkato Corporation, YTZ balls, size φ0.05 mm). After the beads were exchanged, the dispersion B-6B was fed into the vessel and circulated while rotating the rotor. Dispersion was carried out at a rotor peripheral speed of 12 m / s for 2 hours to obtain Dispersion B-6C. Further, dispersion B-6C was filtered under pressure using a filter having a reserved particle diameter of 6 μm, but could not be filtered due to clogging immediately, so it was filtered under pressure using a 10 μm filter, and dispersion B-6D was obtained. Obtained.

  Put 100 parts by weight of Dispersion B-6D and 21.6 parts by weight of Resin Solution A-1 in a polyethylene sample bottle with a volume of 250 ml. Then, rotational mixing was performed by rotating at 200 rpm for 1 hour to prepare a photosensitive resin composition C-8.

  Development is performed using a spray type developing device of AD-2000 manufactured by Takizawa Sangyo Co., Ltd., while rotating at 100 rpm, spraying the developer at a spray pressure of 0.15 MPa for 10 seconds, immersion development for 15 seconds, removal of the developer, 10 Spraying for 1 second and immersion development for 15 seconds were repeated, followed by rinsing with water. As the developer, a 2.38% aqueous solution of tetramethylammonium hydroxide was used. Evaluation was performed in the same manner as in Example 1 except for the development step. The results are shown in Table 2.

Example 9
500 parts by weight of ethyl lactate, 112 parts by weight of a phosphoric acid compound (a copolymer having a phosphate ester skeleton, BYK-W9010), barium titanate (BaTiO ₃ , manufactured by Cabot Corp., K-Plus16, The average primary particle size 0.06 μm) was mixed in the order of 1388 parts by weight to obtain dispersion B-7A. In a vessel of Ultra Apex Mill UAM-015 (manufactured by Kotobuki Kogyo Co., Ltd.), 0.4 kg of zirconia balls (Nikkato Co., Ltd., YTZ balls, size φ0.5 mm) are filled, and the dispersion is performed while rotating the rotor. B-7A was fed into the vessel and circulated. After dispersing for 1 hour at a rotor peripheral speed of 8 m / s, dispersion B-7B was obtained. The beads in the vessel were collected and newly filled with 0.4 kg of zirconia balls (manufactured by Nikkato Corporation, YTZ balls, size φ0.05 mm). After the beads were exchanged, the dispersion B-7B was fed into the vessel and circulated while rotating the rotor. Dispersion was carried out at a rotor peripheral speed of 12 m / s for 3 hours to obtain Dispersion B-7C. Further, dispersion B-7C was subjected to pressure filtration using a filter having a reserved particle diameter of 10 μm and 6 μm to obtain dispersion B-7D.

  Place 100 parts by weight of Dispersion B-7D and 22.1 parts by weight of Resin Solution A-1 in a polyethylene sample bottle with a volume of 250 ml, and put only the dispersion and resin solution without placing balls on the ball mill stand. The mixture was rotated at 200 rpm for 1 hour to prepare a photosensitive resin composition C-9. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 2.

Example 10
450 parts by weight of ethyl lactate, 50 parts by weight of a phosphoric acid compound (a copolymer having a phosphate ester skeleton, BYK-W9010), barium titanate (BaTiO ₃ , Sakai Chemical Industry Co., Ltd.), BT -01: Average primary particle diameter 0.1 μm) was mixed in the order of 1500 parts by weight to obtain Dispersion B-8A. In a vessel of Ultra Apex Mill UAM-015 (manufactured by Kotobuki Kogyo Co., Ltd.), 0.4 kg of zirconia balls (Nikkato Co., Ltd., YTZ balls, size φ0.5 mm) are filled, and the dispersion is performed while rotating the rotor. B-8A was fed into the vessel and circulated. After dispersion for 1 hour at a peripheral speed of the rotor of 8 m / s, dispersion B-8B was obtained. The beads in the vessel were collected and newly filled with 0.4 kg of zirconia balls (manufactured by Nikkato Corporation, YTZ balls, size φ0.05 mm). After the beads were exchanged, the dispersion B-8B was fed into the vessel and circulated while rotating the rotor. Dispersion was carried out at a rotor peripheral speed of 12 m / s for 2 hours to obtain Dispersion B-8C. Further, dispersion B-8C was subjected to pressure filtration using a filter having a reserved particle diameter of 10 μm and 6 μm to obtain dispersion B-8D.

  Place 100 parts by weight of Dispersion B-8D and 10.3 parts by weight of Resin Solution A-1 in a polyethylene sample bottle with a volume of 250 ml, and put only the dispersion and the resin solution on the ball mill stand without putting balls. Rotational mixing was performed by rotating at 200 rpm for 1 hour to prepare a photosensitive resin composition C-10. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 2.

Example 11
Place 100 parts by weight of Dispersion B-1D and 50.4 parts by weight of Resin Solution A-1 in a polyethylene sample bottle with a volume of 250 ml, and put only the dispersion and resin solution without placing balls on the ball mill stand. Rotational mixing was performed by rotating at 200 rpm for 1 hour to prepare photosensitive resin composition C-11. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 2.

Example 12
Place 100 parts by weight of Dispersion B-1D and 35.4 parts by weight of Resin Solution A-1 in a sample bottle made of polyethylene with a volume of 250 ml. Rotational mixing was performed by rotating at 200 rpm for 1 hour to prepare a photosensitive resin composition C-12. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 2.

Example 13
100 parts by weight of the dispersion B-1D and 15 parts by weight of the resin solution A-1 are put in a polyethylene 250 ml sample bottle, and only the dispersion and the resin solution are put on the ball mill frame without putting the balls. Rotational mixing was performed by rotating at 200 rpm for a period of time to prepare photosensitive resin composition C-13. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 2.

Example 14
Put 100 parts by weight of Dispersion B-1D and 4.9 parts by weight of Resin Solution A-1 in a polyethylene sample bottle with a volume of 250 ml, and put only the dispersion and resin solution without putting balls on the ball mill stand. The mixture was rotated for 1 hour at 200 rpm to produce a photosensitive resin composition C-14. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 2.

Examples 15-17
Evaluation was performed in the same manner as in Example 1 except that a film made of a dielectric composition having a film thickness of 0.4 μm, 5 μm, and 12 μm was prepared using the photosensitive resin composition C-1. The results are shown in Table 2.

Comparative Example 1
Place 100 parts by weight of Dispersion B-2A and 19.1 parts by weight of Resin Solution A-1 into a polyethylene sample bottle with a volume of 250 ml, and put only the dispersion and resin solution without placing the balls on the ball mill stand. The mixture was rotated for 1 hour at 200 rpm to produce a photosensitive resin composition C-15. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 4. Moreover, the transmission cross-sectional electron microscope (TEM) observation was performed about the film | membrane cross-section sample D-2 like Example 1, and the content rate of the high dielectric constant inorganic particle was calculated | required from the image analysis. The obtained TEM image is shown in FIG. 4 and the binarized TEM image is shown in FIG. The content of the high dielectric constant inorganic particles calculated from the binarized black portion as high dielectric constant inorganic particles was 72.9%.

Comparative Example 2
250 parts by weight of ethyl lactate, 36 parts by weight of a phosphoric acid compound (a copolymer having a phosphate ester skeleton, BYK-W9010), barium titanate (BaTiO ₃ , Sakai Chemical Industry Co., Ltd.), BT -01: average primary particle diameter 0.1 μm) 714 parts by weight was put into a 500 ml polyethylene sample bottle, and the mixture was rotated and mixed at a rotation speed of 200 rpm for 4 hours without placing a ball on a ball mill mount. -9 was obtained.

  Put 100 parts by weight of Dispersion B-9 and 19.1 parts by weight of Resin Solution A-1 in a polyethylene sample bottle with a volume of 250 ml, and put only the dispersion and resin solution without putting balls on the ball mill stand. The mixture was rotated at 200 rpm for 1 hour to prepare a photosensitive resin composition C-16. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 4.

Comparative Example 3
500 parts by weight of ethyl lactate, 14 parts by weight of a phosphoric acid compound (a copolymer having a phosphate ester skeleton, BYK-W9010), barium titanate (BaTiO ₃ , Sakai Chemical Industry Co., Ltd.), BT -05: Average primary particle size 0.5 μm) was mixed in the order of 1486 parts by weight to obtain dispersion B-10A. In a vessel of Ultra Apex Mill UAM-015 (manufactured by Kotobuki Kogyo Co., Ltd.), 0.4 kg of zirconia balls (Nikkato Co., Ltd., YTZ balls, size φ0.5 mm) are filled, and the dispersion is performed while rotating the rotor. B-10A was fed into the vessel and circulated. After dispersion at a rotor peripheral speed of 8 m / s for 1 hour, dispersion B-10B was obtained. The beads in the vessel were collected and newly filled with 0.4 kg of zirconia balls (manufactured by Nikkato Corporation, YTZ balls, size φ0.05 mm). After the beads were exchanged, the dispersion B-10B was fed into the vessel and circulated while rotating the rotor. Dispersion was carried out at a rotor peripheral speed of 12 m / s for 2 hours to obtain Dispersion B-10C. Further, the dispersion B-10C was subjected to pressure filtration using a filter having a reserved particle diameter of 10 μm and 6 μm to obtain a dispersion B-10D.

  Place 100 parts by weight of Dispersion B-10D and 10.3 parts by weight of Resin Solution A-1 in a polyethylene sample bottle with a volume of 250 ml. The mixture was rotated at 200 rpm for 1 hour to prepare a photosensitive resin composition C-17. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 4.

Comparative Example 4
1400 parts by weight of ethyl lactate, 78 parts by weight of phosphoric acid compound (copolymer having phosphate ester skeleton, BYK-W9010, BYK-W9010), barium titanate (BaTiO ₃ , manufactured by Toda Kogyo Co., Ltd.), T- BTO-030R: average primary particle size 0.03 μm) 522 parts by weight were mixed in this order to obtain dispersion B-11. In a vessel of Ultra Apex Mill UAM-015 (manufactured by Kotobuki Kogyo Co., Ltd.), 0.4 kg of zirconia balls (Nikkato Co., Ltd., YTZ balls, size φ0.5 mm) are filled, and the dispersion is performed while rotating the rotor. B-11A was fed into the vessel and circulated. After dispersion for 1 hour at a rotor peripheral speed of 8 m / s, dispersion B-11B was obtained. The beads in the vessel were collected and newly filled with 0.4 kg of zirconia balls (manufactured by Nikkato Corporation, YTZ balls, size φ0.05 mm). After the beads were exchanged, the dispersion B-11B was fed into the vessel and circulated while rotating the rotor. Dispersion was carried out at a rotor peripheral speed of 12 m / s for 2 hours to obtain Dispersion B-11C. Further, dispersion B-11C was subjected to pressure filtration using a filter having a reserved particle diameter of 10 μm and 6 μm to obtain dispersion B-11D.

  Place 100 parts by weight of Dispersion B-11D and 10.3 parts by weight of Resin Solution A-1 into a polyethylene sample bottle with a volume of 250 ml, and place only the dispersion and resin solution without placing balls on the ball mill stand. The mixture was rotated for 1 hour at 200 rpm to produce a photosensitive resin composition C-18. Evaluation was carried out in the same manner as in Example 1, but the pattern peeled off during development, and evaluation requiring a development step could not be performed. The other results are shown in Table 4.

Comparative Example 5
500 parts by weight of ethyl lactate, 72 parts by weight of a phosphoric acid compound (a copolymer having a phosphate ester skeleton, BYK-W9010), barium titanate (BaTiO ₃ , Sakai Chemical Industry Co., Ltd.), BT -01: Average primary particle size 0.1 μm) was mixed in the order of 1428 parts by weight to obtain dispersion B-12A. In a vessel of Ultra Apex Mill UAM-015 (manufactured by Kotobuki Industries Co., Ltd.), 0.4 kg of zirconia balls (manufactured by Nikkato Co., Ltd., YTZ balls, size φ0.015 mm) are filled, and while rotating the rotor, the dispersion B-12A was fed into the vessel and circulated. Dispersion was performed at a peripheral speed of the rotor of 12 m / s for 12 hours to obtain dispersion B-12B. Further, dispersion B-12B was subjected to pressure filtration using filters having a reserved particle diameter of 10 μm and 6 μm to obtain dispersion B-12C.

  Place 100 parts by weight of Dispersion B-12C and 19.1 parts by weight of Resin Solution A-1 in a sample bottle made of polyethylene with a volume of 250 ml, and put only the dispersion and resin solution without placing the balls on the ball mill stand. The mixture was rotated at 200 rpm for 1 hour to prepare a photosensitive resin composition C-19. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 4.

Example 18
Using a photosensitive polyimide (trade name Photo Nice PW1200, manufactured by Toray Industries, Inc.) on a 6-inch silicon wafer on which a transistor is formed, a hole of 50 μm diameter is formed on the silicon wafer by hole processing by photolithography. An insulating layer having a thickness of 2 μm having via holes was formed. Next, a capacitor lower electrode having a thickness of 5 μm and a 500 μm square was prepared by a semi-additive method. The seed layer for forming the capacitor lower electrode was used by forming a Ni—Cr layer by sputtering. As the electrode layer, a copper layer formed on the seed layer by electrolytic plating was used.

  Photosensitive resin composition C-1 was applied on the capacitor lower electrode to form a dielectric composition film made of the dielectric composition. The conditions for producing the film were the same as in Example 1. Subsequently, aluminum was deposited to form an upper electrode of the capacitor. Then, using a dicing apparatus, the semiconductor device was cut into chips to obtain a semiconductor device with a built-in capacitor.

Example 19
800 parts by weight of ethyl lactate, 57.1 parts by weight of phosphoric acid compound (copolymer having phosphate ester skeleton, manufactured by BYK-W9010), barium titanate (BaTiO ₃ , manufactured by Sakai Chemical Industry Co., Ltd.) BT-01: average primary particle size 0.1 μm) was mixed in the order of 1142.9 parts by weight to obtain a dispersion B-13A. Dispersion B-13A was subjected to rotational mixing by rotating the dispersion B-13A at 200 prm without placing a ball on a ball mill gantry, and further subjected to ultrasonic waves for 3 minutes with an ultrasonic cleaner to obtain dispersion B-13B. In a vessel of Ultra Apex Mill UAM-015 (manufactured by Kotobuki Industries Co., Ltd.), 0.4 kg of zirconia balls (manufactured by Nikkato Co., Ltd., YTZ balls, size φ0.05 mm) are filled, and while rotating the rotor, the dispersion B-13B was fed into the vessel and circulated. After dispersion for 1 hour at a peripheral speed of the rotor of 2 m / s, dispersion B-13C was obtained. Further, Dispersion B-13C was subjected to pressure filtration using a filter having a reserved particle diameter of 10 μm and 6 μm to obtain Dispersion B-13D.
Place 100 parts by weight of Dispersion B-13D and 15.3 parts by weight of Resin Solution A-1 in a polyethylene sample bottle with a volume of 250 ml, and put only the dispersion and resin solution without placing the balls on the ball mill stand. The mixture was rotated at 200 rpm for 1 hour to prepare a photosensitive resin composition C-20. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 6.

Example 20
In a vessel of Ultra Apex Mill UAM-015 (manufactured by Kotobuki Industries Co., Ltd.), 0.4 kg of zirconia balls (manufactured by Nikkato Co., Ltd., YTZ balls, size φ0.05 mm) are filled, and while rotating the rotor, the dispersion B-13B was fed into the vessel and circulated. Dispersion was performed at a peripheral speed of the rotor of 2 m / s for 2 hours to obtain Dispersion B-13E. Further, dispersion B-13E was subjected to pressure filtration using a filter having a reserved particle diameter of 10 μm and 6 μm to obtain dispersion B-13F.

  Place 100 parts by weight of Dispersion B-13F and 15.3 parts by weight of Resin Solution A-1 in a sample bottle made of polyethylene with a volume of 250 ml, and put only the dispersion and resin solution without placing the balls on the ball mill stand. Rotational mixing was performed by rotating at 200 rpm for 1 hour to prepare a photosensitive resin composition C-21. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 6.

Example 21
A dispersion B-13G and a photosensitive resin composition C-22 were produced in the same manner as in Example 19 except that the peripheral speed of the rotor was 5.7 m / s. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 4.

Example 22
Dispersion B-13H and photosensitive resin composition C-23 were produced in the same manner as in Example 20 except that the peripheral speed of the rotor was 5.7 m / s. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 6.

Example 23
A dispersion B-13I and a photosensitive resin composition C-24 were produced in the same manner as in Example 19 except that the circumferential speed of the rotor was 9.5 m / s. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 6.

Example 24
Dispersion B-13J and photosensitive resin composition C-25 were produced in the same manner as in Example 20 except that the circumferential speed of the rotor was 9.5 m / s. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 6.

Example 25
Under a dry nitrogen stream, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF) 30.03 g (0.082 mol), 1,3-bis (3-aminopropyl) tetramethyldi 1.24 g (0.005 mol) of siloxane and 2.7 g (0.025 mol) of 3-aminophenol as an end-capping agent were dissolved in 100 g of N-methyl-2-pyrrolidone (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. Then, it stirred at 180 degreeC for 5 hours, and obtained the 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 200 ° C. for 5 hours. When the resulting measuring the infrared absorption spectrum of the resin powder, 1780 cm around ^-1, absorption peaks of an imide structure caused by a polyimide was detected near 1377 cm ^-1. The imidation ratio was 100%. Next, 1.4 g of 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (o-benzoyloxime) as a photopolymerization initiator and 0. 0.6 g of 5% phenothiazine solution, 1.7 g of thermally crosslinkable compound “NIKACALAC” (registered trademark) MW-100LM (trade name, manufactured by Sanwa Chemical Co., Ltd.), compound PDBE having a polymerizable unsaturated double bond -250 (trade name, manufactured by Nippon Oil & Fats Co., Ltd.) 5.1 g, a solution prepared by dissolving 0.6 g of dimethylol tricyclodecane diacrylate in 5.4 g of diacetone alcohol and 10.3 g of ethyl lactate was stirred and degassed. Furthermore, pressure filtration was performed using a filter having a reserved particle diameter of 2 μm to obtain a negative photosensitive polyimide composition varnish A-2.

  Place 100 parts by weight of Dispersion B-1D and 19.1 parts by weight of Resin Solution A-2 in a polyethylene sample bottle with a volume of 250 ml. The mixture was rotated at 200 rpm for 1 hour to prepare a photosensitive resin composition C-26. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 6.

Comparative Example 6
250 parts by weight of ethyl lactate, 22 parts by weight of phosphoric acid compound (a copolymer having a phosphate ester skeleton, BYK-W9010), barium titanate (BaTiO ₃ , Sakai Chemical Industry Co., Ltd.), BT -02: average primary particle size 0.2 μm) was mixed in the order of 728 parts by weight, and mixed for 1 hour under ice-cooling using a homogenizer to obtain dispersion B-14A. In a homogenizer cup, 728 parts by weight of zirconia balls (manufactured by Nikkato Co., Ltd., YTZ balls, size φ0.5 mm) was filled and mixed and dispersed. Place 100 parts by weight of dispersion B-14A and 22.1 parts by weight of resin solution A-1 in a sample bottle made of polyethylene with a volume of 250 ml, and put only the dispersion and resin solution without putting balls on the ball mill stand. The mixture was rotated at 200 rpm for 1 hour to prepare a photosensitive resin composition C-27. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 4.

Model diagram of extraction curve TEM image of membrane cross section sample D-1 Binarized TEM image of membrane cross section sample D-1 TEM image of membrane cross section sample D-2 Binarized TEM image of membrane cross section sample D-2

Explanation of symbols

1 Extraction curve f (x)

Claims (7)

A photosensitive resin composition in which a dispersion and a resin solution are mixed, wherein the dispersion has (a) a perovskite crystal structure or a composite perovskite crystal structure having an average particle size of 0.06 μm to 0.4 μm. (B) a phosphoric acid compound and (c) an organic solvent are mixed, and an average particle diameter selected from any of metal, ceramics, and glass as a dispersion medium is 0.02 mm to 0.1 mm A photosensitive resin composition obtained by dispersing the inorganic particles using the following beads, wherein the resin solution has (d) a polyimide and (e) an unsaturated bond-containing polymerizable compound. 2. The photosensitive resin composition according to claim 1, wherein the content of (b) the phosphoric acid compound is 0.6 wt% or more and 9 wt% or less with respect to (a) the high dielectric constant inorganic particles. (D) The photosensitive resin composition according to claim 1 or 2, wherein the polyimide is a polymer having a structure represented by general formulas (1) to (4) as a main component.
(R ⁸ is a 4- to 14-valent organic group, R ⁹ is a 2- to 12-valent organic group, R ¹⁰ and R ¹² are hydrogen atoms, phenolic hydroxyl groups, sulfonic acid groups, thiol groups, or from 1 to 20 carbon atoms. R ¹¹ represents a divalent organic group, X represents a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol. Y represents a monovalent aromatic group or cycloaliphatic group having at least one group selected from the group consisting of groups, and Y represents at least one group selected from a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group. And n represents a range from 3 to 200. m, α, and β represent integers from 0 to 10.) A dielectric composition obtained by solidifying the photosensitive resin composition according to any one of claims 1 to 3, wherein (a) the amount of the high dielectric constant inorganic particles is 70% of the dielectric composition. A dielectric composition that is not less than 90% by weight. A semiconductor device in which a capacitor having a layer made of the dielectric composition according to claim 4 and an electrode having a film thickness of 0.5 μm or more and 10 μm or less is formed on a semiconductor element on which a transistor is formed. A bead mill vessel having a bead having an average particle size of 0.02 mm to 0.1 mm and (a) a perovskite crystal structure or a composite perovskite crystal structure having an average particle size of 0.06 μm to 0.4 μm. Filling with dielectric constant inorganic particles, (b) phosphoric acid compound, (c) organic solvent, rotating the rotor of the bead mill to prepare a dispersion liquid in which the inorganic particles are dispersed in the organic solvent, and then (d) polyimide and (E) The manufacturing method of the photosensitive resin composition in any one of Claims 1-3 which mixes the resin solution which has an unsaturated bond containing polymeric compound. The method for producing a photosensitive resin composition according to claim 6, wherein the rotational peripheral speed of the rotor of the bead mill is 5 m / s or more and 15 m / s or less.