JP2006309202A - Photosensitive resin composition and semiconductor device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition which enables easy pattern formation of an interlayer insulation film for a capacitor having a high dielectric constant and high heat resistance by photolithography. <P>SOLUTION: The photosensitive resin composition comprises (a) a polyimide and/or a polyimide precursor, (b) a photosensitizing agent, (c) high-dielectric-constant inorganic particles and (d) a solvent, wherein the high-dielectric-constant inorganic particles (c) have one average particle diameter or two or more average particle diameters, the minimum average particle diameter of which is ≥0.06 μm, and have a perovskite crystal structure or a compound perovskite crystal structure. <P>COPYRIGHT: (C)2007,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 semiconductor manufactured using them Relates to the 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, a method is known 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, if a material having photosensitivity is used as the 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, using a composition that imparts photosensitivity to highly heat-resistant polyimide and disperses high-permittivity ultrafine particles with an average particle diameter of less than 0.05 μm, pattern formation of an interlayer insulating film is performed by a photolithography method, and a capacitor is formed. There is a technique for manufacturing (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 moisture adsorption in the atmosphere. 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.
International Publication WO04 / 090912 Pamphlet (Claims) 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 2003-287833 A (Claims)

  In view of such a situation, the present invention has a high dielectric constant, high reliability, and high heat resistance in an interlayer insulating film for a capacitor incorporated in a substrate or package for a system using a semiconductor such as a mounting substrate or a wafer level package. Provided is a photosensitive resin composition that can be easily patterned by lithography, and further provides a semiconductor device including a transistor, a semiconductor element on which a cured film obtained from the photosensitive resin composition is formed, and a capacitor including electrodes.

  That is, the present invention has (a) polyimide and / or polyimide precursor, (b) photosensitive agent, (c) high dielectric constant inorganic particles, (d) solvent, and (c) one kind of high dielectric constant inorganic particles. Having a perovskite-type crystal structure or a composite perovskite-type crystal structure having an average particle diameter of 2 or more, and having two or more kinds of average particle diameters, and a minimum average particle diameter of 0.06 μm or more A photosensitive resin composition having a perovskite crystal structure or a composite perovskite crystal structure, and a semiconductor device using the same.

  According to the photosensitive resin composition of the present invention, the interlayer insulating film for capacitors can be patterned by photolithography, and the obtained insulating film has excellent characteristics such as high dielectric constant, high reliability, and high heat resistance. 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 polymer contained in the photosensitive resin composition of the present invention is (a) polyimide and / or a polyimide precursor. The structures of the polyimide and polyimide precursor used are not particularly limited, but the following polymers are preferably roughly classified according to the mechanism for forming the pattern. When a positive type is formed by alkali development, a negative type may be formed by alkali development, or a negative type may be formed by organic development. In the photosensitive resin composition containing inorganic particles, since the inorganic particles have almost no adhesive force to other materials, as a composition, the adhesive force with other materials tends to be weaker than that of the resin alone. For this reason, when fine pattern processing is performed, suppression of pattern detachment during development tends to be a problem. In the case of the negative type, the part exposed to light at the time of exposure is not dissolved by development, and a remaining pattern is formed, so the progress of the reaction of the part remaining as a pattern is controlled according to the exposure condition, and the part and the substrate etc. It is possible to control the adhesion force. In this respect, the negative type is preferable.

  In the case of forming a positive type by alkali development, a polyimide precursor mainly having a structure represented by the general formula (1) is preferable. This polyimide precursor can be a polymer having an imide ring, an oxazole ring, or other cyclic structure by heating or an appropriate catalyst. With the ring structure, the heat resistance and solvent resistance are dramatically improved.

R ⁶ is a divalent to octavalent organic group having 2 or more carbon atoms, R ⁷ is a divalent to hexavalent organic group having 2 or more carbon atoms, R ⁸ is hydrogen, or from 1 carbon number Up to 20 organic groups are shown. h is a range from 10 to 100,000, f is an integer from 0 to 2, d and e are integers from 0 to 4, and d + e> 0.

  The general formula (1) represents a polyamic acid and / or a polyamic acid ester having a hydroxyl group, and due to the presence of this hydroxyl group, the solubility in an alkaline aqueous solution is better than that of a polyamic acid having no hydroxyl group. Become. In particular, among the hydroxyl groups, a phenolic hydroxyl group is preferable because of its good solubility in an aqueous alkali solution. In addition, when the fluorine atom is contained in the general formula (1) by 10% by weight or more, water repellency appears moderately at the interface of the film when developing with an alkaline aqueous solution, so that the penetration of the interface can be suppressed. However, if the fluorine atom content exceeds 20% by weight, the solubility in an alkaline aqueous solution is lowered, and the organic solvent resistance of a polymer having a cyclic structure by heat treatment is not preferred. Thus, the fluorine atom is preferably contained in an amount of 10% by weight to 20% by weight.

R ^{6 in the} above general formula (1) represents a structural component of an acid dianhydride, and the acid dianhydride contains an aromatic ring and has 2 to 4 hydroxyl groups. It is preferably a divalent to octavalent organic group having the following carbon atoms, more preferably a trivalent or tetravalent organic group having 6 to 30 carbon atoms. Specifically, preferred structures include trimellitic acid, trimesic acid, naphthalene tricarboxylic acid residues and the like. Furthermore, the hydroxyl group is preferably located adjacent to the amide bond. As such an example, bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-hydroxy-4-aminophenyl) hexafluoropropane containing a fluorine atom, bis ( 3-amino-4-hydroxyphenyl) propane, bis (3-hydroxy-4-aminophenyl) propane, 3,3′-diamino-4,4′-dihydroxybiphenyl, 3,3′-diamino-4,4 ′ Examples include dihydroxybiphenyl, 2,4-diamino-phenol, 2,5-diaminophenol, and 1,4-diamino-2,5-dihydroxybenzene having an amino group bonded thereto.

  Moreover, it can also modify | denature with the tetracarboxylic acid and dicarboxylic acid which do not have a hydroxyl group in the range which does not impair the solubility with respect to an alkali, photosensitive performance, and heat resistance. Examples of this include aromatic tetracarboxylic acids such as pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, diphenyl ether tetracarboxylic acid, and diphenylsulfone tetracarboxylic acid, and two carboxyl groups thereof as methyl or ethyl groups. Diester compounds, aliphatic tetracarboxylic acids such as butanetetracarboxylic acid and cyclopentanetetracarboxylic acid, diester compounds in which two carboxyl groups are methyl or ethyl groups, terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, naphthalene dicarboxylic acid Examples thereof include aromatic dicarboxylic acids such as acids, and aliphatic dicarboxylic acids such as adipic acid. These are preferably modified by 50 mol% or less of the acid component, more preferably 30 mol% or less. If the modification is more than 50 mol%, the alkali solubility and photosensitivity may be impaired.

R ^{7 in the} general formula (1) represents a structural component of diamine. Among these, preferred examples of R ⁷ include those having an aromatic and hydroxyl group from the heat resistance of the resulting polymer, and specific examples include bis (aminohydroxyphenyl) having a fluorine atom. ) Hexafluoropropane, compounds having no fluorine atom, such as diaminodihydroxypyrimidine, diaminodihydroxypyridine, hydroxydiaminopyrimidine, diaminophenol, dihydroxybenzidine and the like can be mentioned.

R ^{8 in the} general formula (1) represents hydrogen or an organic group having 1 to 20 carbon atoms. From the viewpoint of the stability of the resulting photosensitive resin composition solution, R ⁸ is preferably an organic group, but hydrogen is preferable from the viewpoint of the solubility in an aqueous alkali solution. In the present invention, a hydrogen atom and an alkyl group can be mixed. By controlling the amount of hydrogen and organic groups of R ^8, the dissolution rate in the aqueous alkali solution changes, and this adjustment makes it possible to obtain a photosensitive resin composition having an appropriate dissolution rate. A preferred range is that 10% to 90% of R ⁸ are hydrogen atoms. If the carbon number of R ⁸ exceeds 20, it will not dissolve in the alkaline aqueous solution. From the above, R ⁸ preferably contains one or more hydrocarbon groups having 1 to 16 carbon atoms, and the others are hydrogen atoms.

  Moreover, f of General formula (1) has shown the number of the carboxyl group, and has shown the integer from 0-2. In the general formula (1), h represents the number of repeating structural units of the polymer, and is preferably in the range of 10 to 100,000.

  Polyhydroxyamide can be used in place of polyamic acid as a heat-resistant polymer precursor similar to polyamic acid. Such a polyhydroxyamide can be obtained by a condensation reaction of a bisaminophenol compound and a dicarboxylic acid. Specifically, a dehydrating condensing agent such as dicyclohexylcarbodiimide (DCC) is reacted with an acid, and a bisaminophenol compound is added thereto, or a solution of a bisaminophenol compound added with a tertiary amine such as pyridine is added to a dicarboxylic acid. For example, a solution of dichloride is dropped.

  When polyhydroxyamide is used, a positive photosensitive resin composition capable of removing a portion exposed to ultraviolet rays with an alkaline aqueous solution is obtained by adding a photosensitizer such as naphthoquinonediazide sulfonate to the polyhydroxyamide solution. be able to.

Furthermore, in order to improve the adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized with R ⁶ and R ⁷ in the general formula (1) 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. The polymer represented by the general formula (1) may be composed only of the structural unit, or may be a copolymer or blend with other structural units. In that case, it is preferable to contain 90 mol% or more of the structural unit represented by General formula (1). The type and amount of structural units used for copolymerization or blending are preferably selected within a range that does not impair the heat resistance of the polyimide polymer obtained by the final heat treatment.

  The polymer represented by the general formula (1) is, for example, a method in which a tetracarboxylic dianhydride and a diamine compound are reacted at a low temperature, a diester is obtained by tetracarboxylic dianhydride and an alcohol, and then an amine and a condensing agent. It can be synthesized by a method in which a diester is obtained by reacting in the presence of, a tetracarboxylic dianhydride and an alcohol, and then the remaining dicarboxylic acid is acid chlorideed and reacted with an amine.

  Next, when a negative type is formed by alkali development, a polyimide having a structure represented by general formulas (2) to (5) as a main component is preferable.

R ¹ is a 4- to 14-valent organic group, R ² is a 2- to 12-valent organic group, R ³ and R ⁵ are hydrogen atoms, phenolic hydroxyl groups, sulfonic acid groups, thiol groups, or those having 1 to 20 carbon atoms. An organic group having at least one group selected from organic groups may be the same or different. R ⁴ represents a divalent organic group. X and Y each represent a divalent to octavalent 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 a range from 3 to 200. m, α, and β are integers from 0 to 10.

R ^{1 in the} above general formulas (2) to (5) represents a structural component of an acid dianhydride, and this acid dianhydride is a tetravalent to 14-valent organic group containing an aromatic ring or an aliphatic ring. Among them, an organic group having 5 to 40 carbon atoms is preferable.

  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, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride and the like. These are used alone or in combination of two or more.

R ² in the above general formulas (2) to (5) represents a structural component of a diamine, and the diamine represents a divalent to divalent organic group containing an aromatic ring or an aliphatic ring. An organic group having 5 to 40 carbon atoms is preferred.

  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 A compound in which these aromatic rings are substituted with an alkyl group or a halogen atom, aliphatic cyclohexyldiamine, methylenebiscyclohexylamine and the like can be mentioned. These are used alone or in combination of two or more.

R ³ and R ^{5 in the} general formulas (2) to (5) each represent a hydrogen atom, a phenolic hydroxyl group, a sulfonic acid group, a thiol group, or an organic group having 1 to 20 carbon atoms. From the stability of the resulting photosensitive resin composition solution, R ³ and R ⁵ are preferably a hydrogen atom or an organic group. A thiol group is preferred.

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

By controlling the amount of the alkali-soluble groups of R ³ and R ⁵ and the amount of hydrogen or organic group, the dissolution rate with respect to the aqueous alkali solution is changed. Therefore, the negative photosensitive resin composition having an appropriate dissolution rate by this adjustment. Can be obtained. As a preferable range, 5% to 100% of R ³ and R ⁵ are alkali-soluble groups. If the number of carbon atoms in R ³ and R ⁵ exceeds 20, it will not dissolve in the alkaline aqueous solution. From the above, it is more preferable that R ³ and R ⁵ contain at least one hydrogen atom or a hydrocarbon group having 1 to 16 carbon atoms, and the others are alkali-soluble groups.

It is preferable that —NH— (R ⁴ ) m—X, which is a structural component of the general formulas (2) and (3), is represented by the following general formula (7), and these are end-capping agents. It is a component derived from a certain primary monoamine. X is preferably a divalent to octavalent organic group having at least one group selected from a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group, and more preferably selected from a carboxyl group, a phenolic hydroxyl group, and a thiol group. A divalent to octavalent organic group having at least one group is preferred.

In addition, —CO— (R ⁴ ) mY, which is a structural component of the general formulas (4) and (5), is preferably those represented by the general formula (8) and the general formula (9). Is a component derived from one selected from an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, and a monoactive ester compound which is a terminal blocking agent. Y is preferably a divalent to octavalent organic group having at least one group selected from a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group and a thiol group, more preferably a group selected from a carboxyl group, a phenolic hydroxyl group and a thiol group. A divalent to octavalent organic group having at least one is preferable. Further, Y constituting the general formulas (4) and (5) represents only the terminal blocking group represented by the general formula (8), only the terminal blocking group represented by the general formula (9), and the general formula (8). ) And general formula (9).

In general formula (7), general formula (8), and general formula (9), R ⁴ represents a divalent group selected from —CR ¹⁷ R ¹⁸ —, —CH ₂ O—, and —CH ₂ SO ₂ —. , R ¹⁷ and R ¹⁸ represent a monovalent group selected from a hydrogen atom, a hydroxyl group, and a hydrocarbon group having 1 to 10 carbon atoms. R ¹⁴ represents a hydrogen atom or a monovalent group selected from hydrocarbon groups having 1 to 10 carbon atoms. Of these, a hydrogen atom and a hydrocarbon group having 1 to 4 carbon atoms are preferable, and a hydrogen atom, a methyl group, and a t-butyl group are particularly preferable. R ¹⁵ and R ^{16 each} represent a hydrogen atom, a monovalent group selected from a hydrocarbon group having 1 to 4 carbon atoms, or a ring structure in which R ¹⁵ and R ¹⁶ are directly bonded (for example, a nadiimide ring). R ¹² and R ¹³ are selected from 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, a carboxyl group, a sulfonic acid group, Indicates a thiol group. A, E, and G are carbon atoms or nitrogen atoms, and each may be the same or different. m is an integer from 0 to 10, preferably an integer from 0 to 4. l is 0 or 1, preferably 0. p is 0 or 1, preferably 0. q is an integer from 1 to 3, preferably 1 and 2. r, s, and t are 0 or 1.

  Specific examples of the primary monoamine related to the general formula (7) include 5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline, 1-hydroxy-8-aminonaphthalene, 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-amino Naphthalene, 1-amino-2-hydroxynaphthalene, 1-carbo Ci-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-aminosalic Tyric 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-me Lucaptonaphthalene, 2-mercapto-7-aminonaphthalene, 2-mercapto-6-aminonaphthalene, 2-mercapto-5-aminonaphthalene, 2-mercapto-4-aminonaphthalene, 2-mercapto-3-aminonaphthalene, 1 -Amino-2-mercaptonaphthalene, 3-amino-4,6-dimercaptopyrimidine, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like. These are used alone or in combination of two or more.

  Specific examples of the acid anhydride, monocarboxylic acid, monoacid chloride compound, and monoactive ester compound related to the general formula (8) and the general formula (9) are phthalic anhydride, maleic anhydride, nadic acid, and 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-hydro Ci-2-carboxynaphthalene, 1-mercapto-8-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 1-mercapto-4-carboxy Monocarboxylic acids such as naphthalene, 1-mercapto-3-carboxynaphthalene, 1-mercapto-2-carboxynaphthalene, 2-carboxybenzenesulfonic acid, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, and their carboxyl groups Monoacid chloride compound obtained by acid chloride, and terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 3-hydroxyphthalic acid, 5-norbornene-2,3-dicarboxylic acid, 1,2-dicarboxyna Talene, 1,3-dicarboxynaphthalene, 1,4-dicarboxynaphthalene, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 1,8-dicarboxynaphthalene, Monoacid chloride compounds, monoacid chloride compounds and N-hydroxy compounds in which only the monocarboxyl group of dicarboxylic acids such as 2,3-dicarboxynaphthalene, 2,6-dicarboxynaphthalene and 2,7-dicarboxynaphthalene is converted to acid chloride Examples include active ester compounds obtained by reaction with benzotriazole or N-hydroxy-5-norbornene-2,3-dicarboximide. These are used alone or in combination of two or more.

  The introduction ratio of the component represented by the general formula (7) (the X component of the general formulas (2) and (3)) is 0 with respect to the total amine component when converted with the primary monoamine component of the end-capping agent. The range of 1 to 60 mol% is preferable, and 5 to 50 mol% is particularly preferable.

  The introduction ratio of the components represented by the general formula (8) and the general formula (9) (the Y component of the general formulas (4) and (5)) is as follows: acid anhydride, monocarboxylic acid, monoacid of the end-capping agent When converted in terms of a chloride compound and a monoactive ester compound component, the range of 0.1 to 60 mol% is preferable with respect to the diamine component, and particularly preferably 5 to 55 mol%.

  In the general formulas (2) to (5), n represents the number of repeating structural units of the polymer of the present invention, and is preferably in the range of 3 to 200, particularly preferably 5 to 100. When n is smaller than 3, the composition viscosity may not be increased, and it may not be possible to use the thick film. On the other hand, if n exceeds 200, it may not be dissolved in an alkaline developer.

  In the present invention, it may be composed only of the structural units represented by the general formulas (2) to (5), or may be a copolymer or blend with other structural units. In that case, it is preferable to contain 50 mol% or more of the structural units represented by the general formulas (2) to (5). The type and amount of structural units used for copolymerization or blending are preferably selected within a range that does not impair the heat resistance of the polyimide polymer obtained by the final heat treatment.

  The polyimide has a terminal blocker in which a part of the diamine is replaced with a terminal blocker that is a monoamine, or the acid dianhydride is a monocarboxylic acid, an acid anhydride, a monoacid chloride compound, or a monoactive ester compound. It replaces with and is synthesize | combined using a well-known method. For example, a method of reacting a tetracarboxylic dianhydride and a diamine compound (partially replaced with a monoamine end-capping agent) at a low temperature, a tetracarboxylic dianhydride (a part of an acid anhydride or A method of reacting a monoacid chloride compound or a mono-active ester compound with an end-capping agent) and a diamine compound, a diester is obtained by tetracarboxylic dianhydride and an alcohol, and then a diamine (a part of which is a monoamine) A method of reacting in the presence of a condensing agent and a tetracarboxylic dianhydride and an alcohol to obtain a diester, and then converting the remaining dicarboxylic acid to an acid chloride to form a diamine (a part of which is a monoamine) Using a method such as a method of reacting with a sealing agent, a polyimide precursor is obtained, and this is converted into a known imidization reaction. A method of completely imidizing using a polymer, a method of stopping imidization reaction in the middle and introducing a partially imide structure, and further blending a completely imidized polymer with the polyimide precursor. It can synthesize | combine using the method of introduce | transducing a partial imide structure.

Furthermore, the end-capping agent introduced into the polymer can be easily detected by the following method. For example, a polymer having an end-capping agent introduced therein is dissolved in an acidic solution and decomposed into an amine component and an acid anhydride component that are constituent units of the polymer, and this is measured by gas chromatography (GC) or NMR measurement. The used end capping agent can be easily detected. Apart from this, the polymer component into which the end-capping agent is introduced can be easily detected directly by pyrolysis gas chromatography (PGC), infrared spectrum and C13 NMR spectrum measurement.
Moreover, it is preferable that the polyimide precursor in the case where a negative type is formed with a developer whose main component is an organic solvent has a structure represented by the general formula (6).

R ²⁰ is a trivalent or tetravalent organic group having 2 or more carbon atoms, R ²¹ is a divalent organic group having 2 or more carbon atoms, R ²² is a hydrogen atom or an alkali metal ion, an ammonium ion or An organic group having 1 to 30 carbon atoms is shown. k represents a range from 5 to 100,000. g is 1 or 2.

In the general formula (6), R ²⁰ is a trivalent or tetravalent organic group having two or more carbon atoms. From the viewpoint of heat resistance, R ²⁰ preferably contains an aromatic ring or an aromatic heterocyclic ring and is a trivalent or tetravalent group having 6 to 30 carbon atoms. Specific examples include a phenyl group, a biphenyl group, a terphenyl group, a naphthalene group, a perylene group, a diphenyl ether group, a diphenyl sulfone group, a diphenylpropane group, a benzophenone group, and a biphenyltrifluoropropane group, but are not limited thereto. .

In the general formula (6), R ²¹ is a divalent organic group having two or more carbon atoms, but from the viewpoint of heat resistance, R ²¹ contains an aromatic ring or an aromatic heterocyclic ring, and A divalent group having 6 to 30 carbon atoms is preferred. Specific examples include a phenyl group, a biphenyl group, a terphenyl group, a naphthalene group, a perylene group, a diphenyl ether group, a diphenyl sulfone group, a diphenylpropane group, a benzophenone group, and a biphenyltrifluoropropane group, but are not limited thereto. .

R ²² represents hydrogen, an alkali metal ion, an ammonium ion, or an organic group having 1 to 30 carbon atoms. Preferable specific examples of R ²² include, but are not limited to, hydrogen, methyl group, ethyl group, isopropyl group, butyl group, ethyl methacrylate group, ethyl acrylate group, o-nitrobenzyl group and the like. In particular, R ²² is preferably hydrogen.

In the polymer represented by the general formula (6), R ²⁰ , R ²¹ , and R ²² may be composed of one of each of these, or a copolymer composed of two or more of each. Alternatively, it may be composed of only the structural unit represented by the general formula (6), or may be a copolymer or blend with other structural units. In that case, it is preferable to contain 90 mol% or more of the structural unit represented by General formula (6). The type and amount of structural units used for copolymerization or blending are preferably selected within a range that does not impair the heat resistance obtained by the final heat treatment.

  Specific examples of the polymer represented by the general formula (6) include pyromellitic dianhydride, 4,4′-diaminodiphenyl ether, 3,3 ′, 4,4′-benzophenone tetracarboxylic Acid dianhydride and 4,4′-diaminodiphenyl ether, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 4,4′-diaminodiphenyl ether, 3,3 ′, 4,4′-biphenyltrifluoropropanetetracarboxylic dianhydride and 4,4′-diaminodiphenyl ether, 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic dianhydride and 4,4 ′ Diaminodiphenyl ether, pyromellitic dianhydride and 3,3 ′-(or 4,4 ′) diaminodiphenyl sulfone, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride 3,3 ′-(or 4,4 ′) diaminodiphenyl sulfone, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 3,3 ′-(or 4,4 ′) diaminodiphenyl sulfone, Pyromellitic dianhydride and 4,4'-diaminodiphenyl sulfide, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride and 4,4'-diaminodiphenyl sulfide, 3,3', 4 4'-biphenyltetracarboxylic dianhydride and 4,4'-diaminodiphenyl sulfide, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride and paraphenylenediamine, 3,3', 4,4 '-Biphenyltetracarboxylic dianhydride and paraphenylenediamine, 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride and parafe Range amine, 3,3 ′, 4,4′-biphenyltrifluoropropanetetracarboxylic dianhydride and paraphenylenediamine, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and terphenyldiamine 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride and paraphenylenediamine, pyromellitic dianhydride and 3, 3 ′, 4,4′-benzophenonetetracarboxylic dianhydride and 3,3 ′-(or 4,4 ′) diaminodiphenyl ether, pyromellitic dianhydride and 3,3 ′, 4,4 ′ -Biphenyltetracarboxylic dianhydride and paraphenylenediamine, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride and 4,4'-diamino Diphenyl ether and bis (3-aminopropyl) tetramethyldisiloxane, pyromellitic dianhydride and 4,4′-diaminodiphenyl ether and bis (3-aminopropyl) tetramethyldisiloxane, 3,3 Polyamic acid synthesized from ', 4,4'-biphenyltetracarboxylic dianhydride, 4,4'-diaminodiphenyl ether and bis (3-aminopropyl) tetramethyldisiloxane, and its ester compound For example, but not limited to.

  These polyamic acids and their esterified products are selectively combined with tetracarboxylic dianhydride and diamine, and these are mainly composed of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and the like. It is synthesize | combined by making it react in the polar solvent and (gamma) -butyrolactone.

  Moreover, although there is no restriction | limiting in particular in the weight average molecular weight (Mw) of (a) polyimide used by this invention, and a polyimide precursor, Preferably it is less than 50000 in polystyrene conversion measured by GPC, More preferably, it is 40000 or less, Furthermore Preferably it is 30000 or less. Moreover, when Mw is smaller than 2000, it becomes difficult to ensure the viscosity of the composition, or the coating properties deteriorate. When the composition is 50000 or more, the composition may not be dissolved in a solvent or the solubility in a developing solution during pattern formation may be deteriorated.

  The photosensitive agent (b1) contained in the photosensitive resin composition of the present invention has a quinonediazide compound that forms an alkali-developable positive type, and is a compound in which a sulfonic acid of naphthoquinonediazide is bonded to a compound having a phenolic hydroxyl group with an ester. Is preferred. Examples of the compound having a phenolic hydroxyl group used here include 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, Bis26X-OCHP, BisOC P-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 (trade name, manufactured by Asahi Organic Materials Co., Ltd.), 4,4'-sulfonyldiphenol (Manufactured by Wako Pure Chemical Industries, Ltd.) and BPFL (trade name, manufactured by JFE Chemical Co., Ltd.). A compound in which 4-naphthoquinone diazide sulfonic acid or 5-naphthoquinone diazide sulfonic acid is introduced into the compound having a phenolic hydroxyl group by an ester bond can be exemplified, and other compounds can also be used. These photosensitizers are preferably used in combination with the polymer represented by the general formula (1).

  The 4-naphthoquinone diazide sulfonyl ester compound has absorption in the i-line region of the mercury lamp and is suitable for i-line exposure, and the 5-naphthoquinone diazide sulfonyl ester compound has absorption extended to the g-line region of the mercury lamp. Suitable for exposure. In the present invention, both a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound can be preferably used. Depending on the wavelength to be exposed, 4-naphthoquinone diazide sulfonyl ester compound, 5-naphthoquinone diazide sulfonyl ester compound Is preferably selected. In addition, a naphthoquinone diazide sulfonyl ester compound in which 4-naphthoquinone diazide sulfonyl group and 5-naphthoquinone diazide sulfonyl group are used in the same molecule can be obtained, or 4-naphthoquinone diazide sulfonyl ester compound and 5-naphthoquinone diazide sulfonyl ester compound. Can also be used in combination.

  Further, when the molecular weight of the naphthoquinone diazide compound that can be used in the present invention is larger than 1000, the naphthoquinone diazide compound is not sufficiently thermally decomposed in the subsequent heat treatment, so that the heat resistance of the obtained film is lowered, and the mechanical properties are lowered. There is a possibility that problems such as deterioration of adhesiveness may occur. From this point of view, the molecular weight of the preferred naphthoquinonediazide compound is 300 to 1000. More preferably, it is 350 to 800. The amount of the naphthoquinonediazide compound added is preferably 1 to 50 weights when the total of (a) the polymer represented by the general formula (1) and (c) high dielectric constant inorganic particles is 100 parts by weight. Part. In addition, it is also possible to add the compound which has the phenolic hydroxyl group shown above for the purpose of making the melt | dissolution rate of the unexposed part at the time of image development small.

  Next, when a negative type is formed by alkali development, (b2) the photosensitive agent includes a compound containing a polymerizable unsaturated functional group. Examples of the functional group include a vinyl group, an allyl group, an acryloyl group, and a methacryloyl group. Unsaturated double bond functional groups such as propargyl and / or unsaturated triple bond functional groups such as propargyl, among which conjugated vinyl groups, acryloyl groups, and methacryloyl groups are preferred in view of polymerizability. Moreover, it is preferable that it is 1-4 from the point of stability as the number which the functional group contains, and it does not need to be the same group, respectively. Moreover, the compound said here shows the thing of molecular weight 30-800.

  Examples of the compound having a polymerizable group include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, Methylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, styrene, α-methylstyrene, 1,2-dihydronaphthalene, 1,3-diisopropenylbenzene, 3-methylstyrene, 4-methylstyrene, 2-vinyl naphthalene, butyl acrylate, butyl methacrylate, isobutyl acrylate, hexyl acetate Rate, isooctyl acrylate, isobornyl acrylate, isobornyl methacrylate, cyclohexyl methacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, neopentyl glycol diacrylate, 1,4-butanediol di Acrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol methacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclo Decane diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetrameth Tacrylate, 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-tetramethylpiperidi Nyl methacrylate, N-methyl-2,2,6,6-tetramethylpiperidinyl acrylate, N-vinylpyrrolidone, N-vinylcaprolactam and the like. These may be used alone or in combination of two or more.

    These (b2) photosensitizers are preferably used in combination with the polymers represented by the general formulas (2) to (5). The amount of (b2) photosensitizer used in the present invention is 5 when the total of (a) the polymer represented by the general formulas (2) to (5) and (c) high dielectric constant inorganic particles is 100 parts by weight. It is preferable to set it as -200 weight part, and it is more preferable to set it as 5-150 weight part from a compatible point. When the amount used is less than 5 parts by weight, the exposed portion is eluted during development, and thus there is a tendency that no film remains after development. Similarly, when the amount exceeds 200 parts by weight, there is a tendency that a film after development does not remain, and the film may be whitened during film formation.

  In the present invention, (b2) a compound having a thermally crosslinkable group represented by the following general formula (10) when used in combination with a photosensitizer and a polymer represented by the general formulas (2) to (5), and A thermally crosslinkable compound of a benzoxazine compound is preferably used.

    As the thermally crosslinkable compound, for example, ML-26X, ML-24X, ML-236TMP, 4-methylol 3M6C, ML-MC, ML-TBC (which has a trade name, as a compound having one of these thermally crosslinkable groups) DM-BI25X-F, 46DMOC, 46DMOIPP, 46DMOEP (above, trade names) such as Honshu Chemical Industry Co., Ltd.), Pa-type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.) 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, DML-OC , Dimethylol-Bis-C, dimethylol-BisOC-P, DML-BisOC-Z, DML-BisOCHP-Z DML-PFP, DML-PSBP, DML-MB25, DML-MTrisPC, DML-Bis25X-34XL, DML-Bis25X-PCHP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), Nicarak MX-290 (trade name, Sanwa Chemical Co., Ltd.), Ba type benzoxazine, Bm type benzoxazine (trade name, manufactured by Shikoku Chemicals Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, TriML-P, TriML-35XL, TriML-TrisCR-HAP (above, trade name, Honshu Chemical Co., Ltd.) have three such as 2,6-dimethoxymethyl-p-cresol and 2,6-diacetoxymethyl-p-cresol TM-BIP-A (trade name, manufactured by Asahi Organic Materials Co., Ltd.) TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), Nikarac MX-280, Nikalac MX-270 (above, trade name) HML-TPPHBA, HML-TPHAP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), Nikarac MW-390, Nikalac MW-100LM (above, etc.) Trade name, manufactured by Sanwa Chemical Co., Ltd.).

    The amount of such a heat-crosslinkable compound added is preferably 0.5 to 150 parts by weight, more preferably 1 to 130 parts by weight with respect to 100 parts by weight of the polymer of component (a). . When the amount of the thermally crosslinkable compound added relative to 100 parts by weight of component (a) is greater than 150 parts by weight, there is a problem that the heat resistance of the photosensitive resin film is lowered because the resin ratio is too small. On the other hand, when the amount is less than 0.5 parts by weight, the effect of increasing the molecular weight due to crosslinking is small, and the heat resistance of the photosensitive resin film is lowered.

  In the case of forming a negative type with a developer containing an organic solvent as a main component, the photosensitive agent (b3) is preferably an organic compound having an ethylenically unsaturated double bond and an amino group and having 3 to 30 carbon atoms. Furthermore, a C3-C30 aliphatic organic compound is preferable. Examples of the organic group contained include, but are not limited to, a hydrocarbon group, a hydroxyl group, a carbonyl group, a carboxyl group, a urethane group, a urea group, and an amide group in addition to an amino group.

  Preferred specific examples of the compound having an ethylenically unsaturated double bond and an amino group include dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminopropyl methacrylate, N, N-dimethylaminoethyl methacrylamide, N, N-dimethylaminopropyl methacrylamide, N, N-diethylaminoethyl methacrylamide, N, N-diethylaminopropyl methacrylamide, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl acrylate, N, N-dimethylaminoethyl Acrylamide, N, N-dimethylaminopropyl acrylamide, N, N-diethylaminoethyl acrylamide, N, N-diethylaminopropyl acrylamide, etc. Compounds of al is used alone or as a mixture of two or more thereof.

  (B3) The compound having an ethylenically unsaturated double bond and an amino group of the photosensitizer is preferably used in combination with the polymer represented by the general formula (6). At this time, the photosensitive agent is equivalent to 5%, preferably 30% or more of the total of (a) all the structural units of the polymer and (c) high dielectric constant inorganic particles, and the equivalent of all the carboxyl groups in the polymer. It is desirable that they are mixed at a ratio of 50 times or less. If the value is out of this range, the sensitivity may be deteriorated, and restrictions on development may increase. Alternatively, the photosensitive agent is preferably 1 to 50 parts by weight when the total of (a) the polymer represented by the general formula (6) and (c) high dielectric constant inorganic particles is 100 parts by weight.

  Further, when (b3) a photosensitizer is used, a photoinitiator that generates radicals by an exposure light source (visible light or ultraviolet light) may be used. Preferred are benzophenone, benzoin isopropyl ether, benzyl, Michler's ketone, 3,3′-carbonyl-bis (7-diethylamino) coumarin, 7-diethylamino-3-benzoinkine, N-phenyldiethanolamine, N-phenylglycine, 4 , 4′-bis (diethylamino) benzophenone, 2,6-di- (4′-azidobenzal) -4-carboxycyclohexanone, 2,6-di- (4′-azidobenzal) -4-hydroxycyclohexanone, 4-azidoben Salacetophenone and the like can be mentioned, and only one type may be used, or two or more types may be used in combination.

  It is desirable that the photoinitiator is added in a total amount of 0.1% by weight or more, more preferably 0.5 to more than the total weight of the polymer represented by the general formula (6) and (c) the high dielectric constant inorganic particles. A range of 30% by weight is preferred. Outside this range, the developability and the stability of the composition may be reduced.

  Additives such as nitrophthalic acid, sodium salt of benzothiazole, triethanolamine salt may be added to suppress residues during development. The additive is preferably in the range of 0.1 to 10% by weight based on the total weight of the polymer represented by the general formula (6) and (c) the high dielectric constant inorganic particles. If it is out of this range, the developability and the stability of the composition are liable to be lowered.

  The high dielectric constant inorganic particles (c) used in the present invention are those composed of one kind of average particle diameter, or those having an average particle diameter of 2 or more and 5 or less, and the smallest average particle thereof The diameter needs to be 0.06 μm or more and 5 μm or less. More preferably, it is 0.08 μm or more.

  When using high dielectric constant particles having two or more types of average particle diameters, small particles can enter the gaps between the large particle diameters, thereby increasing the particle filling rate. Even if high dielectric constant particles having an average particle diameter of more than five types are used, the effect of increasing the packing ratio obtained compared to the complexity of the process is reduced. However, when the minimum average particle diameter is 0.06 μm or more, the particles are less likely to aggregate and tend to be substantially small particles, so that the increase in the filling rate proceeds and the effect of using small particles is easily obtained. When the minimum average particle diameter is 0.08 μm or more, the dielectric constant of the particles becomes larger, so that the effect of combining with larger particles and increasing the packing becomes remarkable. When the minimum average particle diameter is 5 μm or less, when a cured film obtained by curing the photosensitive resin composition is used as an interlayer insulating layer of a capacitor, a thin layer is easily obtained, and the capacitance of the capacitor is Since it is inversely proportional to the thickness of the layer, it is easy to obtain a capacitor having a large capacity.

  The term “having two or more types of average particle diameters” as used in the present invention means a graph representing the particle size distribution when the particle size distribution of all particles contained in the entire composition or the region representing the entire composition is measured. In this case, there are two or more local maximum values.

  When high dielectric constant inorganic particles having one type of average particle diameter are used, the particle diameter is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.04 μm or more. More preferably, it is 0.06 μm or more. Moreover, 10 micrometers or less are preferable, 5 micrometers or less are more preferable, More preferably, it is 0.4 micrometers or less. When the average particle size is 0.04 μm or more, re-aggregation after dispersion hardly occurs and the dispersion stability of the high dielectric constant inorganic particles is good. Further, when the thickness is 0.01 μm or more, these high dielectric constant inorganic particles are less likely to agglomerate secondary, so that the aggregates can be easily dissolved and dispersed. If it is 0.06 μm or less, sufficient adhesive force cannot be obtained between the photosensitive resin composition film and the adherend, and pattern peeling tends to occur during development. When the average particle diameter is larger than 10 μm, the high dielectric constant inorganic particles easily settle in the photosensitive resin composition having these particles, and it becomes difficult to ensure sufficient storage stability. When the average particle size is 5 μm or less, when a cured film obtained by curing the photosensitive resin composition having these particles is used as an interlayer insulating layer of a capacitor, a thin layer is easily obtained, and the capacitance of the capacitor Is inversely proportional to the thickness of this layer, making it easy to obtain a capacitor with a large capacitance. When the average particle size is 0.4 μm or less, the surface roughness of the photosensitive resin composition film is reduced and the in-plane film thickness variation is reduced, so that a thin film capacitor with a uniform electrostatic capacitance distribution is formed. It becomes easy.

  In the present invention, one kind of average particle size is a maximum value of 1 in a graph showing the particle size distribution when the particle size distribution of all particles contained in the entire composition or the region representing the entire composition is measured. It means a group of particles that become one.

  The measurement of the average particle size contained in the photosensitive resin composition and the cured film of the present invention is XMA measurement on an ultrathin slice obtained by forming a cured film and cutting the film cross section in the film thickness direction of the thin film. It can be measured by observation with a transmission electron microscope (TEM). 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 types 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 size 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.

  Other methods include dynamic light scattering, which measures the fluctuation of scattered light due to Brownian motion of high-permittivity inorganic particles, and electrophoresis, which measures the Doppler effect of scattered light when electrophoresis is performed on high-permittivity inorganic particles. The average particle diameter can be measured by a light scattering method or the like. Examples of laser diffraction and scattering type particle size distribution measuring apparatuses include LA-920 manufactured by Horiba, SALD-1100 manufactured by Shimadzu, and MICROTRAC-UPA150 manufactured by Nikkiso.

  As dielectric properties of the high dielectric constant inorganic particles, those having a relative dielectric constant of 50 to 30,000 are preferably used. Use of high dielectric constant inorganic particles having a relative dielectric constant of 50 or more facilitates obtaining a cured film having a sufficiently large relative dielectric constant. 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 the 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 into 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 in 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.

  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 cured film having a high relative 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 a high relative dielectric constant and quality stability. In addition, the method for producing the high dielectric constant inorganic particles having the smallest average particle size is easy to reduce the particle size, and therefore 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 a ratio of the high dielectric constant inorganic particles and the resin contained in the photosensitive resin composition and the cured film of the present invention, the high dielectric constant inorganic particles with respect to the total volume of the total volume of the high dielectric constant inorganic particles and the total volume of the resin solid content It is preferable that the ratio Vf satisfies the range of 40% to 95%. More preferably, it is 60% or more and 90% or less. When the high dielectric constant inorganic particle content Vf is 40% or more, a sufficiently large relative dielectric constant can be obtained, and a small thermal expansion coefficient can be obtained. Moreover, when the high dielectric constant inorganic particle content Vf is 60% or more, the effect of using the high dielectric constant inorganic particles having at least two kinds of average particle diameters becomes remarkable, and a large relative dielectric constant is obtained. On the other hand, when the high dielectric constant inorganic particle content Vf is 95% or less, the generation of voids in the composition can be suppressed, a sufficiently large relative dielectric constant can be obtained, the moisture absorption due to the voids is small, and the physical properties are low. Less susceptible to moisture and humidity. Moreover, when the high dielectric constant inorganic particle content Vf is 90% or less, the adhesiveness after PCT (pressure cooker test), which is a durability promotion test, is unlikely to decrease.

  As the solvent (d) used in the present invention, it is preferable to use a solvent in which at least one of them has a lactone structure and the content thereof is 10% by weight or more and 100% by weight or less based on the total amount of the solvent. The most preferable solvent among the solvents having a lactone structure is γ-butyrolactone. When the content of the solvent having a lactone structure is 10% by weight or more and 100% by weight or less, the void ratio in the cured film is reduced, so that the amount of moisture adsorption sites that inhibit the stability of the dielectric characteristics is reduced. To preferred. Since the void ratio in the cured film becomes smaller and the effect of increasing the relative dielectric constant becomes remarkable when the high dielectric constant inorganic particles are highly filled, the content of the solvent having a lactone structure is 50% by weight or more and 100%. More preferably, it is less than or equal to weight percent.

  As other solvents used in the present invention, those capable of dissolving the resin can be appropriately selected. Solvents include, for example, methyl cellosolve, N, N-dimethylformamide, methyl ethyl ketone, dioxane, acetone, diacetone alcohol, cyclohexanone, cyclopentanone, isobutyl alcohol, isopropyl alcohol, tetrahydrofuran, toluene, chlorobenzene, trichloroethylene, benzyl alcohol, methoxymethyl Butanol, ethyl lactate, propylene glycol monomethyl ether and acetate thereof, and organic solvent mixtures containing one or more of these are preferably used. Among these, ethyl lactate is preferably used with the above-mentioned solvent having a lactone structure, and the content of ethyl lactate is within a range of 1/10 to 10 times by weight with respect to the solvent having a lactone structure. It is preferable at the point which becomes favorable.

  A solvent having a boiling point of 120 ° C. or higher may be used. When a solvent having a boiling point of 120 ° C. or higher is used, when the photosensitive resin composition is applied by a spin coater, a uniform film can be easily obtained because the volatilization rate of the solvent is sufficiently slow. When the boiling point of the solvent is 160 ° C. or higher, the generation of voids is suppressed and the relative dielectric constant of the cured film 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 solvent volatilization rate is fast, so that densification due to mass transfer during heat treatment cannot catch up, voids increase, The relative dielectric constant 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 solvent is preferably 180 ° C. or higher, more preferably 200 ° C. or higher. In addition, the solvent used in the present invention preferably has a boiling point of 300 ° C. or lower, more preferably 280 ° C. or lower. When the boiling point is higher than 280 ° C., the treatment for removing the 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 decreases. When the solvent has a boiling point of 180 ° C. or lower, even when a resin that can be cured at a relatively low temperature of 180 to 200 ° C. is used, the solvent is completely removed by heat treatment for curing at 180 to 200 ° C. Since it becomes easy to remove, it is preferable when performing low temperature curing. When the solvent is not completely removed during the curing heat treatment, the 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 not preferable.

The solvent used in the photosensitive resin composition of the present invention may be only one having a boiling point of 120 ° C. or higher, but may contain other solvents as long as it contains a solvent having a boiling point of 120 ° C. or higher. .
Solvents having a boiling point of 160 ° C. or higher are mesitylene, acetonylacetone, methylcyclohexanone, diisobutylketone, methylphenylketone, dimethylsulfoxide, γ-butyrolactone, isophorone, diethylformamide, dimethylacetamide, N-methylpyrrolidone, γ-butyrolactam, ethylene glycol Examples thereof include acetate, 3-methoxy-3-methylbutanol and its acetate, 3-methoxybutyl acetate, 2-ethylhexyl acetate, oxalate ester, diethyl malonate, maleate ester, propylene carbonate, butyl cellosolve, ethyl carbitol and the like.

  Solvents having a boiling point of 120 ° C. or higher and 180 ° C. or lower include methyl cellosolve, N, N-dimethylformamide, diacetone alcohol, cyclohexanone, cyclohexanol, cyclopentanone, cyclopentanol, tetrahydrofurfuryl alcohol, chlorobenzene, dichlorobenzene, and trichloro. Ethanol, methoxymethylbutanol, ethyl lactate, methyl lactate, propylene glycol monomethyl ether and its acetate, ethyl toluene, ethyl styryl ketone, ethylene glycol monobutyl ether, ethoxyethanol, diethyl oxaloacetate, ethyl methyl pyridine, isopentyl alcohol, 2-octanol 2-octanone, chloroethanol, chloropyridine, chlorotoluene, 1-chloro-2-propanol 2-chloro-1-propanol, 3-chloro-1-propanol, butyl acetate, pentyl acetate, diisopentyl ether, diethylene glycol dimethyl ether, cyclohexanol, cyclobutanol, cineol, coumaranone, m-divinylbenzene, 1,2 -Diphenylethanol, dimethylpyridine, dimethylpyrrole, 3,3-dimethyl-2-butanol, tetrachloroethane, tetrachlorobenzene, trichlorolactic acid, 1-pentanol, 1-methylhexanol, 3-methyl-3-knitted tanol and the like.

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 photosensitive resin composition of this invention can also contain additives, such as a crosslinking agent, a crosslinking accelerator, a sensitizer, a dissolution regulator, surfactant, a stabilizer, and an antifoamer, as needed.

  The total amount of 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 solvent is 35% by weight or less, generation of voids due to solvent volatilization during drying is suppressed, and the relative dielectric constant of the cured film 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 solvent is more than 35% by weight, voids increase in the drying process and the thermosetting process for removing the solvent, and the relative dielectric constant of the cured film often decreases. If the amount of the solvent is less than 1% by weight, the amount of 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 increases, the influence of the amount of the solvent increases, and when the high dielectric constant inorganic particles are 80% by weight or more of the solid content contained in the photosensitive resin composition, The effect of the invention is particularly great.

  The photosensitive resin composition of the present invention can be obtained by dispersing high dielectric constant inorganic particles in a solution containing a resin, a photosensitive agent and a solvent (hereinafter referred to as a photosensitive resin solution). For example, a method in which high dielectric constant inorganic particles are added to a photosensitive resin solution and mixed and dispersed, or a dispersion in which high dielectric constant inorganic particles are dispersed in an appropriate solvent in advance are prepared, and the dispersion and the photosensitive resin solution are mixed. It is produced by a let-down method of mixing. Further, the method for dispersing the high dielectric constant inorganic particles in the photosensitive resin solution or the solvent is not particularly limited, and for example, a method such as ultrasonic dispersion, ball mill, roll mill, clear mix, homogenizer, or media disperser may be used. However, it is particularly preferable to use a ball mill or a homogenizer in terms of dispersibility.

  When dispersing the high dielectric constant inorganic particles, for example, surface treatment of the high dielectric constant inorganic particles, addition of a dispersant, addition of a surfactant, addition of a solvent, and the like may be performed. 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 addition of the dispersant include dispersants having an acid group such as phosphoric acid, carboxylic acid, fatty acid, and esters thereof. In particular, they react with hydroxyl groups on the surface of the high dielectric constant inorganic particles. Since the particle surface can be covered, a compound having a phosphate ester skeleton is preferably used. In addition, addition of nonionic, cationic, anionic surfactants, wetting agents such as polyvalent carboxylic acids, amphoteric substances, and resins having highly sterically hindered substituents can be mentioned. Moreover, the polarity of the system at the time of dispersion or after dispersion can be controlled by addition of a solvent. Moreover, the photosensitive resin composition may contain a stabilizer, a dispersant, an anti-settling agent, a plasticizer, an antioxidant, and the like, if necessary.

  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 50% by weight or more and 95% by weight or less, more preferably 60% by weight or more, and still more preferably. Is 80% by weight or more. When the content of the high dielectric constant electric inorganic particles is 50% by weight or more, it becomes easy to increase the relative dielectric constant of the cured film, and when it is 60% by weight or more, the relative dielectric constant can be further increased. In addition, the elastic modulus of the cured film is improved, and the reliability in terms of strength of the cured film is improved. If it is 80% by weight or more, not only the relative dielectric constant of the cured film is increased, but also the thermal expansion coefficient is sufficiently small. In the case of a capacitor using the cured film as an interlayer insulating film, a mounting substrate or silicon in which a metal electrode or capacitor is incorporated The difference in thermal expansion coefficient from the substrate is reduced, and a capacitor with high reliability and stability can be obtained. When the content is 95% by weight or less, fine patterning by photosensitivity is facilitated even though high dielectric constant inorganic particles are contained. In addition, solid content means what combined high dielectric constant inorganic particle, resin, and other additives.

  As a method for obtaining the cured film of the present invention, for example, first, a photosensitive resin composition in which high dielectric constant inorganic particles are mixed with a photosensitive resin solution is prepared, and the photosensitive resin composition is applied to an adherend (for example, There is a method of obtaining a cured film having a desired pattern shape by applying to a substrate), removing the solvent, and performing heat treatment for exposure, development, and resin curing. However, since the cured film 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.

  If necessary, for the purpose of improving the wettability between the photosensitive resin composition and the substrate, surfactants, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, alcohols such as ethanol, cyclohexanone, methyl Ketones such as isobutyl ketone and ethers such as tetrahydrofuran and dioxane may be mixed. In addition, other high dielectric constant inorganic particles or polyimide powder may be added.

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

  When the chemical solution is added to the photosensitive resin composition, a silane coupling agent such as methylmethacryloxydimethoxysilane, 3-aminopropyltrimethoxysilane, or the like, and an aluminum chelating agent are used in an amount of 0.5 to 10 with respect to the polymer in the varnish. Add weight percent.

  When processing a substrate, the coupling agent described above is added to a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate, and the like in an amount of 0.5 to 20. Surface treatment is performed by spin coating, dipping, spray coating, steam treatment, etc. on the solution in which the weight% is dissolved. 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-treat the substrate at a high temperature to remove adsorbed water on the substrate 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 resin composition pattern using the photosensitive resin composition of the present invention will be described.

  The adherend to which the photosensitive resin composition is applied includes, for example, a silicon wafer, ceramics, gallium arsenide, an organic circuit board, an inorganic circuit board as a substrate, and circuit constituent materials disposed on these substrates. Can be selected from, but not limited to. Examples of organic circuit boards include glass-based copper-clad laminates such as glass cloth / epoxy copper-clad laminates, composite copper-clad laminates such as glass nonwoven fabrics / epoxy copper-clad laminates, polyetherimide resin substrates, Examples include heat-resistant / thermoplastic substrates such as ether ketone resin substrates and polysulfone resin substrates, polyester copper-clad film substrates, and polyimide copper-clad film substrates.

  Examples of the inorganic circuit board include ceramic substrates such as an alumina substrate, an aluminum nitride substrate, and a silicon carbide substrate, and metal substrates such as an aluminum base substrate and an iron base substrate. Examples of circuit components include conductors containing metals such as silver, gold and copper, resistors containing inorganic oxides, low dielectrics containing glass materials and / or resins, resins and high Examples thereof include high dielectric materials containing dielectric constant inorganic particles, insulators containing glass-based materials, and the like.

  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 150 ° 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 resin pattern is achieved by removing the exposed portion using a developer after exposure, or removing the unexposed portion depending on the combination of the polyimide precursor and the photosensitive agent. 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, dimethylsulfoxide, γ-butyrolaclone, 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.

  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.

After development, the unexposed areas are irradiated with ultraviolet rays at 100 mJ / cm ² to 4000 mJ / cm ² , and a temperature of 200 ° C. to 400 ° C. is applied to convert into a cured film. In addition, the ultraviolet irradiation before the above-mentioned heat treatment also acts as photodecomposing the (b1) photosensitive agent (quinonediazide compound) remaining in the photosensitive resin composition of the present invention.

  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. Beyond this range, care must be taken because the reaction may not proceed or the entire region may not dissolve.

  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, it is preferable that an error due to fluctuations in the film thickness after development tends to be small. Moreover, when it 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, a temperature of 120 to 400 ° C. is applied to form a cured film. 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 porosity of the cured film needs to be 30% by volume or less, preferably 20% by volume or less, and more preferably 10% by volume or less. When the porosity is larger than 30% by volume, the proportion of high dielectric constant inorganic particles in the film volume is low, and it is difficult to obtain a cured film having a relative dielectric constant of 50 or more. Further, it is not preferable because a decrease in insulation resistance, an increase in leakage current, and a decrease in bending strength occur.

  Here, the method for reducing the porosity to 30% by volume or less can be achieved, for example, by appropriately selecting polyimide, polyimide precursor, photosensitive agent, high dielectric constant inorganic particles, and solvent from the above. Specifically, this can be achieved, for example, when the photosensitive resin composition contains at least one solvent having a boiling point of 160 ° C. or higher and the total solvent amount is 35% or less of the total photosensitive resin composition. .

The method for measuring the porosity of the cured film can be appropriately selected according to the application, such as a gas adsorption method, a mercury intrusion method, a positron annihilation method, and a small-angle X-ray scattering method. The porosity is obtained by the following procedures (1) to (3).
(1) The weight of the cured film obtained by applying the photosensitive resin composition onto a weighed fixed substrate, removing the solvent, and solidifying is measured.
(2) When the weight of the substrate is W1, the weight of the substrate and the cured film is W2, the density of the cured film is D, and the volume is V, the density of the cured film D = (W2−W1) / V.
(3) Using a thermogravimetric apparatus (TGA), the cured film is heated to 900 ° C. at a temperature rising rate of 10 ° C./min in the air atmosphere and held at 900 ° C. for 30 minutes for debinding. The ratio of the high dielectric constant inorganic particles and the resin contained in the cured film was measured. When the volume of the high dielectric constant inorganic particles is Wc, the specific gravity is ρc, the volume of the resin is Wp, the specific gravity is ρp, and the porosity is P, the porosity P can be obtained by the following equation.

  Porosity P (volume%) = {(V−Wc / ρc−Wp / ρp) / V} × 100.

  The form of the cured film 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 membrane 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 thickness of the cured film can be arbitrarily set within a range where the capacitance satisfies a desired value, but is preferably 0.5 μm or more and 20 μm or less. More preferably, it is not less than 2 μm and not more than 20 μm. In order to secure a large capacitance as a capacitor, it is preferable that the film thickness is thin. However, if the thickness is less than 0.5 μm, pinholes are easily generated, and electrical insulation is difficult to obtain. When the thickness is 2 μm or more, 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 20 μm, a large relative dielectric constant is required to obtain sufficient capacitor performance, and it may be difficult to improve the mounting density.

  The in-plane variation in the thickness of the cured film 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 is reduced, and it is 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. Moreover, when a metal layer is formed on the cured film of the photosensitive resin composition and measurement cannot be performed by the above method, a cross-sectional sample is prepared, and a scanning electron microscope (SEM) or a transmission electron microscope (TEM) is prepared. ) The film thickness can be obtained by observation. 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. 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). 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 cured film of the photosensitive resin 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 sufficient adhesion with a layer laminated on the cured film. When the surface roughness Ra is smaller than 0.1 μm, the influence of the unevenness of the cured film 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, and is extracted from the extracted curve by a reference length L. The average curve of the extracted portion is the X axis, and the direction of the vertical magnification is the Y axis, and the extracted curve is y = f (x) 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.

  Moreover, when a metal layer is formed on the cured film of the photosensitive resin composition and measurement cannot be performed by the above method, a cross-sectional sample is prepared, and a scanning electron microscope (SEM) or a transmission electron microscope (TEM) is prepared. ) The extraction curve can be specified by observation. 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 cured film of the present invention is not particularly limited. For example, the photosensitive resin composition and the cured film are used as an interlayer insulating material for a built-in capacitor of a printed wiring board as a high dielectric constant layer. It can be applied to various electronic parts and devices such as radio antennas and electromagnetic shields.

  The cured film of the present invention is preferably used as an interlayer insulating material for capacitors. The method for forming the interlayer insulating material for capacitors using the cured film is not particularly limited. For example, as described above, after forming a cured film on a substrate, it can be obtained by appropriately forming an electrode.

The capacitance per area of the capacitor interlayer insulating material produced using the cured film 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.

  The smaller the capacitance change in temperature and the in-plane variation, the better in terms of circuit design. The temperature change is preferably as small as possible. For example, it is preferable to satisfy the X7R characteristic (capacitance temperature change rate within −15% at −55 to 125 ° C.). The in-plane variation in capacitance is preferably 5% or less (average capacitance value−5% ≦ capacitance ≦ average capacitance value + 5%) with respect to the average value.

  In order to reduce the power loss of the power source, the dielectric loss tangent of the capacitor is preferably in the range of 0.01 to 5%. Here, electrical characteristics such as capacitance and dielectric loss tangent are measured values at a frequency of 20 KHz to 1 GHz.

  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) 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.

(2) Method for measuring in-plane variation in film thickness A cured film is formed on a 6-inch silicon wafer, positioned at 0, 20, 40, and 60 mm from the wafer center, and at four locations every 90 ° about the wafer center. Measurement was made and the average of a total of 15 places 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
(3) 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.

(4) Dielectric properties The capacitance, relative dielectric constant, and dielectric loss tangent of the cured film of the photosensitive resin composition were measured as follows. A cured film of the photosensitive resin composition was formed on the entire surface of an aluminum substrate having an area of 6 cm × 6 cm and a thickness of 0.3 mm. This cured film was formed by appropriately heating a spin-coated photosensitive resin composition, evaporating the solvent, and curing the resin. Subsequently, an aluminum electrode was formed on the cured 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 cured film of the photosensitive resin composition 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 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.

Synthesis Example 1 Synthesis of hydroxyl group-containing acid anhydride (a) In a dry nitrogen stream, 18.3 g (0.05 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF) 34.2 g (0.3 mol) of allyl glycidyl ether was dissolved in 100 g of γ-butyrolactone and cooled to −15 ° C. Here, 22.1 g (0.11 mol) of trimellitic anhydride chloride dissolved in 50 g of γ-butyrolactone was added dropwise so that the temperature of the reaction solution did not exceed 0 ° C. After completion of dropping, the reaction was carried out at 0 ° C. for 4 hours. This solution was concentrated by a rotary evaporator and charged into 1 L of toluene to obtain an acid anhydride (a).

Synthesis Example 2 Synthesis of hydroxyl group-containing diamine compound (b) 18.3 g (0.05 mol) of BAHF was dissolved in 100 mL of acetone and 17.4 g (0.3 mol) of propylene oxide, and cooled to -15 ° C. A solution prepared by dissolving 20.4 g (0.11 mol) of 4-nitrobenzoyl chloride in 100 mL of acetone was added dropwise thereto. After completion of dropping, the mixture was reacted at −15 ° C. for 4 hours and then returned to room temperature. The precipitated white solid was filtered off and vacuum dried at 50 ° C.

  30 g of the solid was placed in a 300 mL stainless steel autoclave, dispersed in 250 mL of methyl cellosolve, and 2 g of 5% palladium-carbon was added. Hydrogen was introduced here with a balloon and the reduction reaction was carried out at room temperature. After about 2 hours, the reaction was terminated by confirming that the balloons did not squeeze any more. After completion of the reaction, the palladium compound as a catalyst was removed by filtration, and concentrated by a rotary evaporator to obtain a diamine compound (b). The obtained solid was used for the reaction as it was.

Synthesis Example 3 Synthesis of hydroxyl group-containing diamine (c) 2-Amino-4-nitrophenol (15.4 g, 0.1 mol) was dissolved in acetone (50 mL) and propylene oxide (30 g, 0.34 mol). Cooled down. A solution prepared by dissolving 11.2 g (0.055 mol) of isophthalic acid chloride in 60 mL of acetone was gradually added dropwise thereto. After completion of dropping, the reaction was carried out at −15 ° C. for 4 hours. Thereafter, the precipitate formed by returning to room temperature was collected by filtration.

  This precipitate was dissolved in 200 mL of GBL, 3 g of 5% palladium-carbon was added, and the mixture was vigorously stirred. A balloon filled with hydrogen gas was attached thereto, and stirring was continued until the balloon of hydrogen gas did not contract any further at room temperature, and further stirred for 2 hours with the balloon of hydrogen gas attached. After completion of the stirring, the palladium compound was removed by filtration, and the solution was concentrated to half by a rotary evaporator. Ethanol was added thereto and recrystallization was performed to obtain crystals of the target compound.

Synthesis Example 4 Synthesis of quinonediazide compound (1) In a dry nitrogen stream, 7.21 g (0.05 mol) of 2-naphthol and 13.43 g (0.05 mol) of 5-naphthoquinonediazidesulfonyl acid chloride were added to 1,4-dioxane. Dissolved in 450 g and brought to room temperature. Here, 5.06 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise. After completion of the dropwise addition, the mixture was reacted at room temperature for 2 hours, and then the triethylamine salt was filtered, and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration. This precipitate was dried with a vacuum dryer to obtain a quinonediazide compound (1).

Synthesis Example 5 Synthesis of quinonediazide compound (2) TrisP-HAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), 15.31 g (0.05 mol) and 5-naphthoquinonediazidesulfonyl acid chloride 40. 28 g (0.15 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. A quinonediazide compound (2) was obtained in the same manner as in Synthesis Example 4 using 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane.

Synthesis Example 6 Synthesis of Active Ester Compound (I) In a dry nitrogen stream, 18.5 g (0.1 mol) of 4-carboxybenzoic acid chloride and 13.5 g (0.1 mol) of hydroxybenzotriazole were added to 100 g of tetrahydrofuran (THF). And cooled to -15 ° C. 10 g (0.1 mol) of triethylamine dissolved in 50 g of THF was added dropwise so that the temperature of the reaction solution did not exceed 0 ° C. After completion of the dropwise addition, the mixture was reacted at 25 ° C. for 4 hours. This solution was concentrated by a rotary evaporator to obtain an active ester compound (I).

  The compounds used in each example and comparative example are shown below.

Example 1
Under a nitrogen stream, 4.1 g (0.0205 mol) of 4,4′-diaminodiphenyl ether and 1.24 g (0.005 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane were added to N-methyl- It was dissolved in 50 g of 2-pyrrolidone (NMP). To this, 21.4 g (0.03 mol) of a hydroxy group-containing acid anhydride (a) was added together with 14 g of NMP, reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 4 hours. Thereafter, a solution prepared by diluting 7.14 g (0.06 mol) of N, N-dimethylformamide dimethylacetal with 5 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 50 ° C. for 3 hours to obtain a resin solution. After completion of the reaction, the resin solution was poured into 2 L of water, and the polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 80 ° C. for 20 hours. It was 25000 when the weight average molecular weight of the polymer was calculated | required in polystyrene conversion using GPC.

  11.8 g of the polymer solid thus obtained was weighed, 4 g of the naphthoquinonediazide compound (1) shown above was added, and dissolved in 30 g of γ-butyrolactone as a varnish solvent to obtain varnish A-1.

  Barium titanate (manufactured by Sakai Chemical Co., Ltd., BT-05, average particle size: 0.5 μm) 323 parts by weight, 57 parts by weight of γ-butyrolactone, dispersing agent (BYK-W9010, manufactured by BYK Chemie) 3.2 A part by weight was mixed and dispersed for 1 hour under ice-cooling using a homogenizer to obtain dispersion B-1.

26 parts by weight of varnish A-1 was mixed with 60 parts by weight of dispersion B-1 using a ball mill to prepare photosensitive resin composition C-1. A 6-inch silicon wafer subjected to HMDS (hexamethylene disilazane) vapor treatment was applied using a spin coater and prebaked at 120 ° C. for 3 minutes using a hot plate. Next, line / space (L / S) masks of 50/50, 40/40, 30/30, 25/25, 20/20, 15/15 μm are applied to the exposure apparatus (PEM-6M manufactured by Union Optics Co., Ltd.). The sample was exposed to light at an exposure dose of 150 mJ / cm ² (intensity of 365 nm) under close contact between the sample and the mask. The exposed film was sprayed with a 2.38% aqueous solution of tetramethylammonium hydroxide for 6 minutes using an AD-2000 spray type developing device manufactured by Takizawa Sangyo Co., Ltd. at a spray pressure of 1.5 kg / cm ² . The exposed part was removed and rinsed with water. The developed film was cured at 140 ° C. for 60 minutes and 350 ° C. for 1 hour in an N ₂ atmosphere using an inert oven INL-60 manufactured by Koyo Thermo System Co., Ltd. to obtain a cured film. The thickness of the cured film was 5 μm when measured with a stylus type using Surfcom 1400 manufactured by Tokyo Seimitsu Co., Ltd., and the thickness reduction due to development was 0.8 μm. When the line and space pattern of the cured film was confirmed using an optical microscope, it was confirmed that the accuracy was within ± 0.5 μm for a pattern with L / S of 15/15 μm or more.

Next, the photosensitive resin composition C-1 was separately applied onto an Al substrate using a spinner, pre-baked at 120 ° C. for 3 minutes using a hot plate, and an inert oven INL-60 manufactured by Koyo Thermo System Co., Ltd. was used. It was used and cured by heating at 140 ° C. for 60 minutes and at 350 ° C. for 1 hour in an N ₂ atmosphere to obtain a cured film on the Al substrate. An aluminum electrode having a diameter of 11 mm was formed on the cured film by a vapor deposition method, and dielectric characteristics at 1 MHz were measured according to JIS K 6911 using an impedance analyzer HP4294A and a sample holder HP16451B (both manufactured by Agilent Technologies). The relative dielectric constant at 1 MHz was 43, and the dielectric loss tangent was 0.02. Although the environmental test was performed for 500 hours at 85 ° C. and 85%, the relative dielectric constant was not changed.

Further, photosensitive resin composition C-1 was applied onto a 6-inch silicon wafer substrate using a spinner, prebaked at 120 ° C. for 3 minutes using a hot plate, and inert oven INL-60 manufactured by Koyo Thermo Systems Co., Ltd. Was used for heat treatment at 140 ° C. for 60 minutes and 350 ° C. for 60 minutes in a N ₂ atmosphere to obtain a cured film on a 6-inch silicon wafer substrate. The in-plane variation of the film thickness was 7%. The surface roughness Ra was 0.11 μm.

Example 2
A photosensitive resin composition C-2 was prepared in the same manner as in Example 1 except that 30 g of varnish solvent γ-butyrolactone was replaced with a mixed solvent of 18.8 g of γ-butyrolactone and 11.2 g of ethyl lactate. Used to obtain a cured film. The film thickness of the cured film was 10 μm, and the film thickness decrease due to development was 0.9 μm. When the line and space pattern of the cured film was confirmed using an optical microscope, it was confirmed that the accuracy was within ± 0.5 μm for a pattern with L / S of 20/20 μm or more.

  When the dielectric properties of the cured film were measured in the same manner as in Example 1, the relative dielectric constant at 1 MHz was 43 and the dielectric loss tangent was 0.02. Although the environmental test was performed for 500 hours at 85 ° C. and 85%, the relative dielectric constant was not changed.

  Furthermore, a cured film was obtained on a 6-inch silicon wafer substrate based on the method of Example 1. The in-plane variation of the film thickness was 7%. The surface roughness Ra was 0.11 μm.

Example 3
Under a dry nitrogen stream, 13.6 g (0.0225 mol) of diamine (b) and 4-ethynylaniline (trade name: P-APAC, manufactured by Fuji Photo Film Co., Ltd.) 0.29 g (0) as a terminal blocking agent .0025 mol) was dissolved in 50 g of NMP. 17.5 g (0.025 mol) of a hydroxy group-containing acid anhydride (a) was added thereto together with 30 g of pyridine, and reacted at 60 ° C. for 6 hours to obtain a resin solution. After completion of the reaction, the resin solution was poured into 2 L of water, and the polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 80 ° C. for 20 hours. It was 26000 when the weight average molecular weight of the polymer was calculated | required in polystyrene conversion using GPC.
10 g of the polymer solid thus obtained was weighed, and 3.9 g of the naphthoquinonediazide compound (2) shown above and 1 g of vinyltrimethoxysilane were dissolved in 30 g of γ-butyrolactone to obtain varnish A-3.

60 parts by weight of dispersion B-1 and 38 parts by weight of varnish A-3 were mixed using a ball mill to prepare photosensitive resin composition C-3. An exposure amount of 105 mJ / cm ² (intensity of 365 nm), P-7G (manufactured by Tokyo Ohka Kogyo Co., Ltd.) is sprayed for 2 minutes in the developer, and an inert oven INL-60 manufactured by Koyo Thermo System Co., Ltd. is used. A cured film was obtained based on the method of Example 1 except that it was cured by heat treatment at 140 ° C. for 60 minutes and at 250 ° C. for 1 hour in an N ₂ atmosphere. The film thickness of the cured film was 4 μm, and the decrease in film thickness due to development was 0.9 μm. When the line and space pattern of the cured film was confirmed using an optical microscope, the accuracy was within ± 0.5 μm for a pattern with L / S of 15/15 μm or more.

  When the dielectric properties of the cured film were measured in the same manner as in Example 1, the relative dielectric constant at 1 MHz was 30 and the dielectric loss tangent was 0.01. Although the environmental test was performed for 500 hours at 85 ° C. and 85%, the relative dielectric constant was not changed.

Furthermore, photosensitive resin composition C-3 was applied onto a 6-inch silicon wafer substrate using a spinner, prebaked at 120 ° C. for 3 minutes using a hot plate, and inert oven INL-60 manufactured by Koyo Thermo System Co., Ltd. Was used for heat treatment at 140 ° C. for 60 minutes and 250 ° C. for 60 minutes in an N ₂ atmosphere to obtain a cured film on a 6-inch silicon wafer substrate. The in-plane variation of the film thickness was 6%. The surface roughness Ra was 0.1 μm.

Example 4
239 parts by weight of barium titanate (manufactured by Sakai Chemical Co., Ltd., BT-05, average particle size: 0.5 μm), barium titanate (manufactured by Cabot Corp., K-Plus 16, average particle size: 0.06 μm) 83 parts by weight Then, 57 parts by weight of γ-butyrolactone and 3.2 parts by weight of a dispersant (BYK-W9010, manufactured by BYK Chemie Corp.) were mixed and dispersed for 1 hour under ice cooling using a homogenizer to obtain dispersion B-2. 16 parts by weight of varnish A-1 was mixed with 60 parts by weight of dispersion B-2 using a ball mill to prepare photosensitive resin composition C-4.

A cured film was obtained based on the method of Example 1 except that the photosensitive resin composition C-4 was used, and the exposure amount was 450 mJ / cm ² and the developer was sprayed for 28 minutes using a 2.38% aqueous solution of TMAH. . The film thickness of the cured film was 8 μm, and the film thickness decrease due to development was 0.7 μm. When the line and space pattern of the cured film was confirmed using an optical microscope, the accuracy was within ± 0.5 μm for a pattern with L / S of 20/20 μm or more. When the dielectric properties of the cured film were measured in the same manner as in Example 1, the relative dielectric constant at 1 MHz was 55, and the dielectric loss tangent was 0.015. Although the environmental test was performed for 500 hours at 85 ° C. and 85%, the relative dielectric constant was not changed.

  Furthermore, based on the method of Example 1, a cured film was obtained on a 6-inch silicon wafer substrate. The in-plane variation of the film thickness was 6%. The surface roughness Ra was 0.08 μm.

Example 5
Under a dry nitrogen stream, 11.41 g (0.057 mol) of 4,4′-diaminodiphenyl ether, 1.24 g (0.005 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane, end-capping As an agent, 8.18 g (0.075 mol) of 3-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 80 g of NMP. Bis (3,4-dicarboxyphenyl) ether dianhydride 31.02 g (0.1 mol) was added thereto together with 20 g of NMP, and the mixture was reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 4 hours. Thereafter, 15 g of xylene was added and stirred at 150 ° C. for 5 hours while azeotropically distilling water with xylene to obtain a resin solution. After the completion of stirring, the resin solution was poured into 3 L of water to collect a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80 ° C. for 20 hours. When the resulting measuring the infrared absorption spectrum of the polymer solids, 1780 cm around ^-1, absorption peaks of an imide structure caused by a polyimide was detected near 1377 cm ^-1. The imidation ratio of the obtained polymer solid was 100%. It was 30000 when the weight average molecular weight of the polymer was calculated | required in polystyrene conversion using GPC.

In addition, it calculated as follows about the imidation ratio of the used polymer. First, measuring the infrared absorption spectrum of the polymer, the absorption peak (1780 cm around ^-1, 1377 cm around ^-1) of an imide structure caused by the polyimide of the presence of confirmed, then 1 hour nitrogen atmosphere the polymer 350 ° C. The imidation rate in the polymer before heat treatment was calculated by measuring the infrared absorption spectrum after heat treatment, and comparing the peak intensity near 1377 cm ⁻¹ with the intensity before heat treatment.

  Next, 10 g of this polymer solid was added with 0.5 g of photopolymerization initiator bis (α-isonitrosopropiophenone oxime) isophthalate, a heat-crosslinkable compound NIKALAC MX-270 (trade name, Sanwa Co., Ltd.) Chemical) 1 g, 2 g TrisP-PA, trimethylolpropane diacrylate (a compound having a polymerizable group composed of an unsaturated double bond functional group) 7.5 g was dissolved in 12 g of ethyl lactate, and varnish A-5 was obtained. Obtained.

60 parts by weight of dispersion B-1 and 15 parts by weight of varnish A-5 were mixed using a ball mill to prepare photosensitive resin composition C-5. The exposure and development are the same as in Example 1 except that the exposure amount is 400 mJ / cm ² (intensity of 365 nm), pre-baking is performed at 100 ° C. for 2 minutes, post-exposure baking is performed at 60 ° C. for 1 minute, and unexposed portions are removed. I went there. Next, the cured film was obtained by curing at 170 ° C. for 60 minutes in an N ₂ atmosphere using an inert oven INL-60 manufactured by Koyo Thermo System Co., Ltd. The film thickness of the cured film was 5 μm, and the decrease in film thickness due to development was 0.5 μm. The accuracy of the pattern having L / S of 15/15 μm or more was within ± 0.5 μm.

  When the dielectric properties of the cured film were measured in the same manner as in Example 1, the relative dielectric constant at 1 MHz was 32, and the dielectric loss tangent was 0.01. Although the environmental test was performed for 500 hours at 85 ° C. and 85%, the relative dielectric constant was not changed.

  Furthermore, based on the method of Example 1, a cured film was obtained on a 6-inch silicon wafer substrate. The in-plane variation of the film thickness was 7%. The surface roughness Ra was 0.09 μm.

Example 6
Under a dry nitrogen stream, 49.57 g (0.082 mol) of a hydroxyl group-containing diamine compound (b) and 9.91 g (0.035 mol) of an active ester compound (I) as an end-capping agent were dissolved in 150 g of NMP. . Bis (3,4-dicarboxyphenyl) ether dianhydride 31.02 g (0.1 mol) was added thereto together with 30 g of NMP, and the mixture was reacted at 20 ° C. for 1 hour and then at 50 ° C. for 4 hours. Then, it stirred at 180 degreeC for 5 hours, and obtained the resin solution. After the completion of stirring, the resin solution was poured into 3 L of water to collect a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80 ° C. for 20 hours. It was 28000 when the weight average molecular weight of the polymer was calculated | required in polystyrene conversion using GPC.

The resulting polymer solids, in the same manner as in Example 5, was measured for infrared absorption spectrum, 1780 cm around ^-1, absorption peaks of an imide structure caused by a polyimide around 1377 cm ^-1 is detected, resulting The imidization ratio of the polymer solid was 100%. Next, 10 g of this polymer solid was weighed, 2 g of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 as a photopolymerization initiator, pentaerythritol triacrylate (unsaturated double). 5 g of a compound having a polymerizable group consisting of a binding functional group) and 1 g of vinyltrimethoxysilane were dissolved in 10 g of γ-butyrolactone to obtain varnish A-6.

60 parts by weight of dispersion B-1 and 14 parts by weight of varnish A-6 were mixed using a ball mill to prepare photosensitive resin composition C-6. The exposure and development are the same as in Example 1 except that the exposure amount is 400 mJ / cm ² (intensity of 365 nm), pre-baking is performed at 100 ° C. for 2 minutes, post-exposure baking is performed at 60 ° C. for 1 minute, and unexposed portions are removed. I went there. Next, heat treatment was 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. to obtain a cured film. The film thickness of the cured film was 10 μm, and the film thickness decrease due to development was 0.5 μm. For patterns with L / S of 15/15 μm or more, the accuracy was within ± 0.5 μm.

  When the dielectric properties of the cured film were measured in the same manner as in Example 1, the relative dielectric constant at 1 MHz was 31 and the dielectric loss tangent was 0.01. Although the environmental test was performed for 500 hours at 85 ° C. and 85%, the relative dielectric constant was not changed.

  Furthermore, based on the method of Example 1, a cured film was obtained on a 6-inch silicon wafer substrate. The in-plane variation of the film thickness was 5%. The surface roughness Ra was 0.05 μm.

Example 7
Under a dry nitrogen stream, 46.55 g (0.077 mol) of hydroxyl group-containing diamine (b) was dissolved in 250 g of NMP. Here, 71.45 g (0.1 mol) of a hydroxy group-containing acid anhydride (a), and 7.38 g (0.045 g) of 3-hydroxyphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) as an end-capping agent. Mol) was added and reacted at 60 ° C. for 6 hours. Thereafter, 15 g of xylene was added and stirred at 150 ° C. for 5 hours while azeotropically reacting with xylene to obtain a resin solution. After stirring, the solution was poured into 2 L of water to collect a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80 ° C. for 20 hours. It was 27000 when the weight average molecular weight of the polymer was calculated | required in polystyrene conversion using GPC.

The resulting polymer solids, was measured infrared absorption spectrum in the same manner as in Example 5, 1780 cm around ^-1, absorption peaks of an imide structure caused by a polyimide near 1377 cm ^-1 was detected. Next, 10 g of this polymer solid was measured, 2.5 g of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 as a photopolymerization initiator, pentaerythritol triacrylate (unsaturated dioxygen). 8 g of a compound having a polymerizable group composed of a heavy bond functional group), 5 g of DML-PC (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) as a thermally crosslinkable compound, and 1 g of vinyltrimethoxysilane are mixed with 3-methyl-3-methoxy. Varnish A-7 was obtained by dissolving in 10 g of butanol.

60 parts by weight of dispersion B-1 and 14 parts by weight of varnish A-7 were mixed using a ball mill to prepare photosensitive resin composition C-7. Except that the exposure amount was 400 mJ / cm ² (intensity of 365 nm), pre-baking was performed at 100 ° C. for 2 minutes, post-exposure baking was performed at 60 ° C. for 1 minute, and unexposed portions were removed. The same was done. Next, heat treatment was performed at 180 ° 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 cured film. The film thickness of the cured film was 10 μm, and the film thickness decrease due to development was 0.5 μm. For patterns with L / S of 20/20 μm or more, the accuracy was within ± 0.5 μm.

  When the dielectric properties of the cured film were measured in the same manner as in Example 1, the relative dielectric constant at 1 MHz was 31 and the dielectric loss tangent was 0.01. Although the environmental test was performed for 500 hours at 85 ° C. and 85%, the relative dielectric constant was not changed.

  Furthermore, based on the method of Example 1, a cured film was obtained on a 6-inch silicon wafer substrate. The in-plane variation of the film thickness was 5%. The surface roughness Ra was 0.06 μm.

Example 8
A photosensitive resin composition C-8 was prepared by mixing 60 parts by weight of dispersion B-1 with 50 parts by weight of a polyimide resin (trade name Photo Nice UR3100, manufactured by Toray Industries, Inc.) using a ball mill. It apply | coated using the spin coater on the 6-inch silicon wafer, and prebaked for 3 minutes each at 90 degreeC and 95 degreeC using the hotplate. Next, 50/50, 40/40, 30/30, 25/25, 20/20, and 15/15 μm line and space masks are set on the exposure apparatus (PEM-6M manufactured by Union Optics Co., Ltd.) And the mask were exposed under close contact conditions with an exposure amount of 100 mJ / cm ² (intensity of 365 nm). After the exposure, immersion development was performed for 1 minute using a mixed solvent of NMP (70 parts) and xylene (30 parts). Next, the unexposed portion was removed, rinsed with isopropanol for 20 seconds, and spin-dried with a spinner. Thereafter, heat treatment was performed at 200 ° C. and 350 ° C. for 30 minutes under an N ₂ atmosphere using an inert oven INL-60 manufactured by Koyo Thermo System Co., Ltd. to obtain a cured film. The film thickness of the cured film was 5 μm, and the decrease in film thickness due to development was 0.5 μm. The accuracy of the pattern having L / S of 15/15 μm or more was within ± 0.5 μm.

  When the dielectric properties of the cured film were measured in the same manner as in Example 1, the relative dielectric constant at 1 MHz was 33, and the dielectric loss tangent was 0.01. Although the environmental test was performed for 500 hours at 85 ° C. and 85%, the relative dielectric constant was not changed.

  Furthermore, based on the method of Example 1, a cured film was obtained on a 6-inch silicon wafer substrate. The in-plane variation of the film thickness was 5%. The surface roughness Ra was 0.05 μm.

Example 9
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 having a diameter of 50 μm 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 formed by a semi-additive method. Note that the seed layer of the semi-additive method was used by forming a Ni—Cr layer by a sputtering method. 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 cured film. The conditions for producing the cured film were the same as in Example 1. Subsequently, Al was vapor-deposited to form the upper electrode of the capacitor. A dicing apparatus was used to cut the chip unit to obtain a semiconductor device with a built-in capacitor.

Example 10
Instead of the HMDS treatment, a cured film was obtained in the same manner as in Example 1 except that a 6-inch silicon wafer was heat-treated at 200 ° C. for 3 minutes in the air atmosphere. The film thickness of the cured film was 5 μm, and the film thickness decrease due to development was 0.8 μm. When the line and space pattern of the cured film was confirmed using an optical microscope, it was confirmed that the accuracy was within ± 0.5 μm for a pattern with L / S of 15/15 μm or more.

  When the dielectric properties of the cured film were measured in the same manner as in Example 1, the relative dielectric constant at 1 MHz was 43 and the dielectric loss tangent was 0.02. Although the environmental test was performed for 500 hours at 85 ° C. and 85%, the relative dielectric constant was not changed.

  Furthermore, based on the method of Example 1, a cured film was obtained on a 6-inch silicon wafer substrate. The in-plane variation of the film thickness was 7%. The surface roughness Ra was 0.11 μm.

Example 11
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 4.1 g (0.025 mol) of 3-hydroxyphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) as an end-capping agent are added to N-methyl-2-pyrrolidone. (NMP) was dissolved in 100 g. 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. After stirring, 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 was added to 0.4 g of 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (o-benzoyloxime) as a photopolymerization initiator, and Nicalac as a thermally crosslinkable compound. (NIKALAC) MW-100LM (trade name, manufactured by Sanwa Chemical Co., Ltd.) 1.5 g, PDBE-250 (trade name, manufactured by NOF Corporation. Compound having a polymerizable unsaturated double bond) 8 g, di 2 g of methylol tricyclodecane diacrylate (compound having a polymerizable unsaturated double bond) was dissolved in 7 g of diacetone alcohol and 13.5 g of ethyl lactate to obtain varnish A-8 of a negative photosensitive polyimide composition.

  Barium titanate (manufactured by Sakai Chemical Co., Ltd., BT-02, average particle size: 0.2 μm) 82.5 parts by weight, ethyl lactate 28.3 parts by weight, dispersant (by BYK-Chemie, BYK-W9010) 2.5 parts by weight were mixed and dispersed for 1 hour under ice-cooling using a homogenizer to obtain dispersion B-3.

  60 parts by weight of dispersion B-3 and 13.6 parts by weight of varnish A-8 were mixed using a ball mill to prepare photosensitive resin composition C-11.

A 6-inch silicon wafer on which a Cr film having a thickness of 10 nm and a Cu film having a thickness of 100 nm were stacked was applied by a sputtering method using a spin coater, and prebaked at 120 ° C. for 1 minute using a hot plate. 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, it was baked at 60 ° C. for 1 minute. 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 1.5 kg / cm ² for 10 seconds, static development for 50 seconds, Removal, this step was repeated twice, and then rinsed 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 cured film. When the film thickness was measured, the film thickness of the cured film was 5 μm. The reduction in film thickness due to development, determined from the measurement results before and after development, was 0.5 μm. When the line and space pattern of the cured film was confirmed using an optical microscope, it was confirmed that the pattern with L / S of 15/15 μm or more was formed with accuracy within ± 0.5 μm.

Next, the photosensitive resin composition C-11 is separately applied onto an Al substrate using a spinner, prebaked at 120 ° C. for 1 minute using a hot plate, and an inert oven INL-60 manufactured by Koyo Thermo System Co., Ltd. is used. It was used and heat-treated at 200 ° C. for 60 minutes under an N ₂ atmosphere to obtain a cured film on the Al substrate. This cured film had a relative dielectric constant of 42 at 1 MHz and a dielectric loss tangent of 0.04. Although the environmental test was conducted for 500 hours at 85 ° C. and 85%, the relative dielectric constant was not changed.

Furthermore, photosensitive resin composition C-11 was applied onto a 6-inch silicon wafer substrate using a spinner, prebaked at 120 ° C. for 1 minute using a hot plate, and inert oven INL-60 manufactured by Koyo Thermo System Co., Ltd. Was cured in an N ₂ atmosphere at 200 ° C. for 60 minutes to obtain a cured film on a 6-inch silicon wafer substrate. The in-plane variation of the film thickness was 4%. The surface roughness Ra was 0.05 μm.

Example 12
Barium titanate (manufactured by Sakai Chemical Co., Ltd., BT-05, average particle size: 0.5 μm) 84.1 parts by weight, ethyl lactate 28.3 parts by weight, dispersant (by BYK Chemie, BYK-W9010) 0.8 part by weight was mixed and dispersed for 1 hour under ice cooling using a homogenizer to obtain dispersion B-4.

  A photosensitive resin composition C-12 was produced by mixing 14 parts by weight of varnish A-8 with 60 parts by weight of dispersion B-4 using a ball mill.

  A patterned cured film was obtained in the same manner as in Example 11 except that the photosensitive resin composition C-12 was used. The film thickness of the cured film was 5 μm, and the decrease in film thickness due to development was 0.5 μm. In the case where the L / S of the cured film was 15 μm / 15 μm or more, the accuracy was within ± 0.5 μm.

  Next, a cured film was separately formed on an Al substrate in the same manner as in Example 11 except that the photosensitive resin composition C-12 was used, and the dielectric characteristics were measured. The relative dielectric constant at 1 MHz was 41 and the dielectric loss tangent was 0.03. Although the environmental test was conducted for 500 hours at 85 ° C. and 85%, the relative dielectric constant was not changed.

  Furthermore, a cured film was obtained on a 6-inch silicon wafer substrate in the same manner as in Example 11 except that the photosensitive resin composition C-12 was used. The in-plane variation of the film thickness was 6%. The surface roughness Ra was 0.11 μm.

Example 13
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 was added with 0.4 g of 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (o-benzoyloxime) as a photopolymerization initiator, and HMOM as a thermally crosslinkable compound. -TPHAP (trade name, Honshu Chemical Industry Co., Ltd.) 1.5 g, PDBE-250 (trade name, manufactured by NOF Corporation. Compound having a polymerizable unsaturated double bond) 8 g, dimethylol tricyclodecandi 2 g of acrylate (a compound having a polymerizable unsaturated double bond) was dissolved in 7 g of diacetone alcohol and 13.5 g of ethyl lactate to obtain a negative photosensitive polyimide composition varnish A-9.

  60 parts by weight of dispersion B-3 and 13.6 parts by weight of varnish A-9 were mixed using a ball mill to prepare photosensitive resin composition C-13.

  A patterned cured film was obtained in the same manner as in Example 11 except that the photosensitive resin composition C-13 was used. The film thickness of the cured film was 5 μm, and the decrease in film thickness due to development was 0.5 μm. In the case where the L / S of the cured film was 15 μm / 15 μm or more, the accuracy was within ± 0.5 μm.

  Next, a cured film was separately formed on an Al substrate in the same manner as in Example 11 except that the photosensitive resin composition C-13 was used, and the dielectric characteristics were measured. The relative dielectric constant at 1 MHz was 42, and the dielectric loss tangent was 0.04. Although the environmental test was conducted for 500 hours at 85 ° C. and 85%, the relative dielectric constant was not changed.

  Further, a cured film was obtained on a 6-inch silicon wafer substrate in the same manner as in Example 11 except that the photosensitive resin composition C-13 was used. The in-plane variation of the film thickness was 4%. The surface roughness Ra was 0.04 μm.

Example 14
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 having a diameter of 50 μm 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 formed by a semi-additive method. Note that the seed layer of the semi-additive method was used by forming a Ni—Cr layer by a sputtering method. As the electrode layer, a copper layer formed on the seed layer by electrolytic plating was used.

  Photosensitive resin composition C-13 was applied on the capacitor lower electrode to form a cured film. The conditions for producing the cured film were the same as in Example 11. Subsequently, Al was vapor-deposited to form the upper electrode of the capacitor. A dicing apparatus was used to cut the chip unit to obtain a semiconductor device with a built-in capacitor. When this semiconductor device was subjected to a high temperature standing test at 150 ° C. for 1000 hours, no occurrence of blistering was observed, and good results were obtained. Further, when a solder reflow resistance test at 260 ° C. for 1 minute was performed on a semiconductor device manufactured in the same manner, occurrence of blistering was not observed and good results were obtained.

Example 15
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. After stirring, 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 was added with 0.4 g of 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (o-benzoyloxime) as a photopolymerization initiator, and HMOM as a thermally crosslinkable compound. -TPHAP (trade name, Honshu Chemical Industry Co., Ltd.) 1.5 g, PDBE-250 (trade name, manufactured by NOF Corporation. Compound having a polymerizable unsaturated double bond) 8 g, dimethylol tricyclodecandi 2 g of acrylate (compound having a polymerizable unsaturated double bond) was dissolved in 20.5 g of γ-butyrolactone to obtain a negative photosensitive polyimide composition varnish A-10.

  Barium titanate (manufactured by Sakai Chemical Co., Ltd., BT-02, average particle size: 0.2 μm) 82.5 parts by weight, 28.3 parts by weight of γ-butyrolactone, dispersant (by BYK Chemie, BYK-W9010) ) 2.5 parts by weight were mixed and dispersed for 1 hour under ice-cooling using a homogenizer to obtain dispersion B-5.

  60 parts by weight of dispersion B-5 and 13.6 parts by weight of varnish A-10 were mixed using a ball mill to prepare photosensitive resin composition C-15. A patterned cured film was obtained in the same manner as in Example 11 except that the photosensitive resin composition C-15 was used. The film thickness of the cured film was 5 μm, and the decrease in film thickness due to development was 0.5 μm. In the case where the L / S of the cured film was 15 μm / 15 μm or more, the accuracy was within ± 0.5 μm.

  Next, a cured film was separately formed on an Al substrate in the same manner as in Example 11 except that the photosensitive resin composition C-15 was used, and the dielectric characteristics were measured. The relative dielectric constant at 1 MHz was 48, and the dielectric loss tangent was 0.04. Although the environmental test was conducted for 500 hours at 85 ° C. and 85%, the relative dielectric constant was not changed.

  Furthermore, a cured film was obtained on a 6-inch silicon wafer substrate in the same manner as in Example 11 except that the photosensitive resin composition C-15 was used. The in-plane variation of the film thickness was 4%. The surface roughness Ra was 0.05 μm.

Example 16
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 having a diameter of 50 μm 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 formed by a semi-additive method. Note that the seed layer of the semi-additive method was used by forming a Ni—Cr layer by a sputtering method. As the electrode layer, a copper layer formed on the seed layer by electrolytic plating was used.

  Photosensitive resin composition C-15 was applied on the capacitor lower electrode to form a cured film. The conditions for producing the cured film were the same as in Example 11. Subsequently, Al was vapor-deposited to form the upper electrode of the capacitor. A dicing apparatus was used to cut the chip unit to obtain a semiconductor device with a built-in capacitor. When this semiconductor device was subjected to a high temperature standing test at 150 ° C. for 1000 hours, no occurrence of blistering was observed, and good results were obtained. Further, when a similarly manufactured semiconductor device was subjected to a solder reflow resistance test at 260 ° C. for 1 minute, swelling was observed.

Example 17
Barium titanate (manufactured by Sakai Chemical Co., Ltd., BT-01, average particle size: 0.1 μm) 82.5 parts by weight, ethyl lactate 28.3 parts by weight, dispersant (by BYC Chemie, BYK-W9010) 2.5 parts by weight were mixed and dispersed for 1 hour under ice-cooling using a homogenizer to obtain Dispersion B-6.

  60 parts by weight of dispersion B-6 and 13.6 parts by weight of varnish A-9 were mixed using a ball mill to prepare photosensitive resin composition C-17. A patterned cured film was obtained in the same manner as in Example 11 except that the photosensitive resin composition C-17 was used. The film thickness of the cured film was 5 μm, and the decrease in film thickness due to development was 0.5 μm. The accuracy of the cured film with L / S of 20 μm / 20 μm or more was within ± 0.5 μm.

  Next, a cured film was separately formed on an Al substrate in the same manner as in Example 11 except that the photosensitive resin composition C-17 was used, and the dielectric characteristics were measured. The relative dielectric constant at 1 MHz was 41 and the dielectric loss tangent was 0.04. Although the environmental test was conducted for 500 hours at 85 ° C. and 85%, the relative dielectric constant was not changed.

  Further, a cured film was obtained on a 6-inch silicon wafer substrate in the same manner as in Example 11 except that the photosensitive resin composition C-17 was used. The in-plane variation of the film thickness was 4%. The surface roughness Ra was 0.05 μm.

Example 18
Barium titanate (manufactured by Cabot Corp., K-Plus16, average particle size 0.06 μm) 80.9 parts by weight, ethyl lactate 28.3 parts by weight, dispersing agent (BYK-W9010, BYK-W9010) 4.1 A part by weight was mixed and dispersed for 1 hour under ice-cooling using a homogenizer to obtain a dispersion B-7.

  60 parts by weight of dispersion B-7 and 13.6 parts by weight of varnish A-9 were mixed using a ball mill to prepare photosensitive resin composition C-18. A patterned cured film was obtained in the same manner as in Example 11 except that the photosensitive resin composition C-18 was used. The film thickness of the cured film was 3 μm, and the film thickness decrease due to development was 0.5 μm. In the case where the L / S of the cured film was 30 μm / 30 μm or more, the accuracy was within ± 0.5 μm.

  Next, a cured film was separately formed on an Al substrate in the same manner as in Example 11 except that the photosensitive resin composition C-18 was used, and the dielectric characteristics were measured. The relative dielectric constant at 1 MHz was 25, and the dielectric loss tangent was 0.06. Although the environmental test was conducted for 500 hours at 85 ° C. and 85%, the relative dielectric constant was not changed.

  Further, a cured film was obtained on a 6-inch silicon wafer substrate in the same manner as in Example 11 except that the photosensitive resin composition C-18 was used. The in-plane variation of the film thickness was 4%. The surface roughness Ra was 0.02 μm.

Example 19
Barium titanate (manufactured by Hokuko Chemical Co., Ltd., BaTiO ₃ powder, average particle size 0.05 μm) 80.9 parts by weight, ethyl lactate 28.3 parts by weight, dispersant (by BYK Chemie, BYK-W9010) 4.1 parts by weight were mixed and dispersed for 1 hour under ice cooling using a homogenizer to obtain dispersion B-8.

  60 parts by weight of dispersion B-8 and 13.6 parts by weight of varnish A-9 were mixed using a ball mill to prepare photosensitive resin composition C-19. Pattern formation was attempted in the same manner as in Example 11 except that the photosensitive resin composition C-19 was used. However, when the pattern having an L / S of 50 μm / 50 μm or less was peeled off during development, the pattern could be obtained. could not. The accuracy of the cured film with L / S of 100 μm / 100 μm or more was within ± 5 μm. The film thickness of the cured film was 3 μm, and the film thickness decrease due to development was 0.5 μm.

  Next, a cured film was separately formed on an Al substrate in the same manner as in Example 11 except that the photosensitive resin composition C-19 was used, and the dielectric characteristics were measured. The relative dielectric constant at 1 MHz was 24 and the dielectric loss tangent was 0.06. Although the environmental test was conducted for 500 hours at 85 ° C. and 85%, the relative dielectric constant was not changed.

  Furthermore, a cured film was obtained on a 6-inch silicon wafer substrate in the same manner as in Example 11 except that the photosensitive resin composition C-19 was used. The in-plane variation of the film thickness was 4%. The surface roughness Ra was 0.02 μm.

Example 20
280 parts by weight of barium titanate (manufactured by Toda Kogyo Co., Ltd., T-BTO-030R, average particle size 0.03 μm), 770 parts by weight of ethyl lactate, 43 parts by weight of dispersing agent (BYK-W9010, manufactured by BYK Chemie) Was dispersed using an ultra apex mill (manufactured by Kotobuki Industries Co., Ltd.) to obtain a dispersion B-9.

  60 parts by weight of dispersion B-9 and 4.9 parts by weight of varnish A-9 were mixed using a ball mill to prepare photosensitive resin composition C-20. Pattern formation was attempted in the same manner as in Example 11 except that the photosensitive resin composition C-20 was used. However, a pattern with an L / S of 250 μm / 250 μm or less was peeled off during development to obtain a pattern. could not. The accuracy was within ± 10 μm for patterns with a cured film having L / S of 500 μm / 500 μm or more. The film thickness of the cured film was 1 μm, and the film thickness decrease due to development was 0.5 μm.

  Next, a cured film was separately formed on an Al substrate in the same manner as in Example 11 except that the photosensitive resin composition C-20 was used, and the dielectric characteristics were measured. The relative dielectric constant at 1 MHz was 21, and the dielectric loss tangent was 0.07. Although the environmental test was conducted for 500 hours at 85 ° C. and 85%, the relative dielectric constant was not changed.

  Further, a cured film was obtained on a 6-inch silicon wafer substrate in the same manner as in Example 11 except that the photosensitive resin composition C-20 was used. The in-plane variation of the film thickness was 4%. The surface roughness Ra was 0.004 μm.

Example 21
280 parts by weight of barium titanate (manufactured by Toda Kogyo Co., Ltd., T-BTO-020RF, average particle size 0.02 μm), 770 parts by weight of ethyl lactate, 43 parts by weight of dispersant (BYK-W9010, manufactured by BYK Chemie) Was dispersed using an ultra apex mill (manufactured by Kotobuki Industry Co., Ltd.) to obtain a dispersion B-10.

  60 parts by weight of dispersion B-10 and 4.9 parts by weight of varnish A-9 were mixed using a ball mill to prepare photosensitive resin composition C-21. Pattern formation was attempted in the same manner as in Example 11 except that the photosensitive resin composition C-21 was used. However, when the pattern having an L / S of 250 μm / 250 μm or less was peeled off during development, the pattern could be obtained. could not. In the pattern of 500 μm / 500 μm or more, a pattern was obtained, but peeling was partially observed.

  Next, a cured film was separately formed on an Al substrate in the same manner as in Example 11 except that the photosensitive resin composition C-21 was used, and the dielectric characteristics were measured. The relative dielectric constant at 1 MHz was 21, and the dielectric loss tangent was 0.07. Although the environmental test was conducted for 500 hours at 85 ° C. and 85%, the relative dielectric constant was not changed.

  Further, a cured film was obtained on a 6-inch silicon wafer substrate in the same manner as in Example 11 except that the photosensitive resin composition C-21 was used. The thickness of the cured film was 1 μm, and the in-plane variation of the film thickness was 4%. The surface roughness Ra was 0.004 μm.

Example 22
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. After stirring, 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 was added with 0.4 g of 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (o-benzoyloxime) as a photopolymerization initiator, and HMOM as a thermally crosslinkable compound. -TPHAP (trade name, Honshu Chemical Industry Co., Ltd.) 1.5 g, PDBE-250 (trade name, manufactured by NOF Corporation. Compound having a polymerizable unsaturated double bond) 8 g, dimethylol tricyclodecandi 2 g of acrylate (compound having a polymerizable unsaturated double bond) was dissolved in 20.5 g of methyl isobutyl ketone to obtain varnish A-11 of a negative photosensitive polyimide composition.

  82.5 parts by weight of barium titanate (manufactured by Sakai Chemical Co., Ltd., BT-02, average particle size: 0.2 μm), 28.3 parts by weight of methyl isobutyl ketone, dispersant (BYK-W9010, BYK-W9010) ) 2.5 parts by weight was mixed and dispersed for 1 hour under ice-cooling using a homogenizer to obtain dispersion B-11.

  60 parts by weight of dispersion B-11 and 13.6 parts by weight of varnish A-11 were mixed using a ball mill to prepare photosensitive resin composition C-22. A patterned cured film was obtained in the same manner as in Example 11 except that the photosensitive resin composition C-22 was used. The film thickness of the cured film was 5 μm, and the decrease in film thickness due to development was 0.5 μm. In the case where the L / S of the cured film was 15 μm / 15 μm or more, the accuracy was within ± 0.5 μm.

  Next, a cured film was separately formed on an Al substrate in the same manner as in Example 11 except that the photosensitive resin composition C-22 was used, and the dielectric characteristics were measured. The relative dielectric constant at 1 MHz was 34, and the dielectric loss tangent was 0.04. Although the environmental test was conducted for 500 hours at 85 ° C. and 85%, the relative dielectric constant was not changed.

  Further, a cured film was obtained on a 6-inch silicon wafer substrate in the same manner as in Example 11 except that the photosensitive resin composition C-22 was used. The in-plane variation of the film thickness was 5%. The surface roughness Ra was 0.08 μm.

Example 23
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. After the completion of stirring, 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 was added with 0.4 g of 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (o-benzoyloxime) as a photopolymerization initiator, and HMOM as a thermally crosslinkable compound. -TPHAP (trade name, Honshu Chemical Industry Co., Ltd.) 1.5 g, PDBE-250 (trade name, manufactured by NOF Corporation. Compound having a polymerizable unsaturated double bond) 8 g, dimethylol tricyclodecandi 2 g of acrylate (compound having a polymerizable unsaturated double bond) was dissolved in 20.5 g of methyl ethyl ketone to obtain varnish A-12 of a negative photosensitive polyimide composition.

  Barium titanate (manufactured by Sakai Chemical Co., Ltd., BT-02, average particle size: 0.2 μm) 82.5 parts by weight, 28.3 parts by weight of methyl ethyl ketone, dispersant (BYK-W9010 manufactured by BYK Chemie) 2 .5 parts by weight were mixed and dispersed for 1 hour under ice-cooling using a homogenizer to obtain dispersion B-12.

  60 parts by weight of dispersion B-12 and 13.6 parts by weight of varnish A-12 were mixed using a ball mill to prepare photosensitive resin composition C-23. A patterned cured film was obtained in the same manner as in Example 11 except that the photosensitive resin composition C-23 was used. The film thickness of the cured film was 5 μm, and the decrease in film thickness due to development was 0.5 μm. The accuracy of the cured film with L / S of 15 μm / 15 μm or more was within ± 1 μm.

  Next, a cured film was separately formed on an Al substrate in the same manner as in Example 11 except that the photosensitive resin composition C-23 was used, and the dielectric characteristics were measured. The relative dielectric constant at 1 MHz was 32, and the dielectric loss tangent was 0.04. Although the environmental test was conducted for 500 hours at 85 ° C. and 85%, the relative dielectric constant was not changed.

  Further, a cured film was obtained on a 6-inch silicon wafer substrate in the same manner as in Example 11 except that the photosensitive resin composition C-23 was used. The in-plane variation of the film thickness was 12%. The surface roughness Ra was 0.18 μm.

Comparative Example 1
A cured film was produced in the same manner as in Example 1 except that photosensitive polyimide (trade name Photo Nice PW1200, manufactured by Toray Industries, Inc.) was used instead of the photosensitive resin composition C-1. The film thickness of the cured film was 5 μm, and the decrease in film thickness due to development was 1.6 μm. When the line and space pattern of the cured film was confirmed using an optical microscope, it was confirmed that the accuracy was within ± 0.5 μm for a pattern with L / S of 20/20 μm or more. When the relative dielectric constant was measured in the same manner as in Example 1, the relative dielectric constant at 1 MHz was as low as 2.8. Further, an environmental test was performed for 500 hours at 85 ° C. and 85%, but there was no change in the relative dielectric constant.

  Furthermore, a cured film was obtained on a 6-inch silicon wafer substrate in the same manner as in Example 1 except that PW1200 was used instead of the photosensitive resin composition C-1. The in-plane variation of the film thickness was within 2%. The surface roughness Ra was 0.01 μm.

Comparative Example 2
10 parts by weight of epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EPPN502H), 10 parts by weight of phenol novolac resin (manufactured by Dainippon Ink Industries, Ltd., TD-2131), curing accelerator (manufactured by Hokuko Chemical Co., Ltd.) 0.6 parts by weight of phenylphosphine) and 20 parts by weight of γ-butyrolactone were mixed to obtain an epoxy resin solution.

  A cured film was produced in the same manner as in Example 1 except that the epoxy resin solution was used instead of varnish A-1 and the heat treatment conditions for curing were 175 ° C. and 1 hour. When the line and space pattern of the cured film was confirmed using an optical microscope, no pattern was formed.

Model diagram of extraction curve

Explanation of symbols

1 Extraction curve f (x)

Claims (9)

(A) polyimide and / or polyimide precursor, (b) photosensitive agent, (c) high dielectric constant inorganic particles, (d) solvent, (c) high dielectric constant inorganic particles from one type of average particle diameter A perovskite crystal structure or a composite perovskite crystal structure, or a perovskite crystal structure having two or more average particle diameters and a minimum average particle diameter of 0.06 μm or more. A photosensitive resin composition having a composite perovskite crystal structure. (C) The photosensitive resin composition according to claim 1, wherein the high dielectric constant inorganic particles comprise one kind of average particle diameter. (D) The photosensitive resin composition according to claim 1, wherein the solvent has a compound having a lactone structure, and the content thereof is 10 wt% or more and 100 wt% or less with respect to the total amount of the solvent. (D) The solvent contains a compound having a lactone structure and ethyl lactate, and the content of ethyl lactate is 1/10 to 10 times by weight with respect to the compound having a lactone structure. 3. The photosensitive resin composition according to 3. The photosensitive resin composition according to claim 1, wherein (d) the solvent contains at least one solvent having a boiling point of 120 ° C. or higher and 180 ° C. or lower. The photosensitive resin composition according to claim 1, comprising a compound having a phosphate ester skeleton. (A) The molecular weight of a polyimide or a polyimide precursor is 2000 or more and less than 50000, The photosensitive resin composition of Claim 1 characterized by the above-mentioned. (A) The photosensitive resin composition according to claim 1, wherein the polyimide or polyimide precursor is a polymer having a structure represented by general formulas (1) to (6) as a main component.

(R ⁶ is a divalent to octavalent organic group having 2 or more carbon atoms, R ⁷ is a divalent to hexavalent organic group having 2 or more carbon atoms, R ⁸ is hydrogen, or 1 carbon atom. An organic group from 1 to 20. s is in a range from 10 to 100000, f is an integer from 0 to 2, d and e are integers from 0 to 4, and d + e> 0.

(R ¹ is a 4- to 14-valent organic group, R ² is a 2- to 12-valent organic group, R ³ and R ⁵ are hydrogen atoms, phenolic hydroxyl groups, sulfonic acid groups, thiol groups, or from 1 to 20 carbon atoms. R ⁴ represents a divalent organic group, and X and Y are a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid. And a divalent to octavalent organic group having at least one group selected from a group and a thiol group, n represents a range from 3 to 200, and m, α, and β represent integers from 0 to 10.

(R ²⁰ is a trivalent or tetravalent organic group having 2 or more carbon atoms, R ²¹ is a divalent organic group having 2 or more carbon atoms, R ²² is a hydrogen atom or an alkali metal ion ammonium ion or C represents an organic group having 1 to 30 carbon atoms, k represents a range from 5 to 100,000, and g is 1 or 2. A semiconductor device, wherein a capacitor comprising a cured film obtained from the photosensitive resin composition according to claim 1 and an electrode is formed on a semiconductor element on which a transistor is formed.

Images