JP4595412B2 - Photosensitive resin precursor composition - Google Patents

Description

The present invention relates to a positive photosensitive resin precursor composition suitable for a surface protective film of a semiconductor element, an interlayer insulating film, an insulating layer of an organic electroluminescent element, etc., in which a portion exposed to ultraviolet rays is dissolved in an alkaline developer. .

  The positive heat-resistant resin precursor composition in which the exposed part is dissolved by development includes quinone diazide added to polyamic acid, quinone diazide added to a soluble polyimide having a hydroxyl group, and quinone diazide to a polyamide having a hydroxyl group. And the like were known.

  However, the addition of quinonediazide to ordinary polyamic acid has a problem that in most cases, the desired pattern cannot be obtained because the solubility of the carboxyl group of the polyamic acid is higher than the dissolution inhibiting effect of quinonediazide on alkali. there were. In addition, the addition of a soluble polyimide resin having a hydroxyl group in the main chain has less problems as described above, but the structure is limited to make it soluble, and the solvent resistance of the resulting polyimide resin The problem was a bad point. When a quinonediazide is added to a polyamide resin having a hydroxyl group, the structure is limited in order to obtain solubility, and therefore the solvent resistance of the resin obtained after heat treatment is inferior.

  Therefore, in order to control the alkali solubility of the polyamic acid, a polyamic acid derivative in which the carboxyl group of the polyamic acid is protected with an ester group has been developed. However, when naphthoquinone diazide is added to this polyamic acid derivative, the dissolution inhibition effect of naphthoquinone diazide on alkali becomes very large. In most cases, the desired pattern can be obtained, but the sensitivity is greatly reduced. There was a problem.

  Recently, as a technique for increasing sensitivity, a polyamic acid ester and / or a polyamic acid polymer to which a phenolic hydroxyl group-containing thermally crosslinkable compound is added (see Patent Document 1), an iodonium salt is added to the polyamic acid ester as a dissolution inhibitor. (See Patent Documents 2 and 3), a polyamide added with an iodonium salt as a dissolution inhibitor (see Patent Document 4), a polyamic acid ester added with a photoacid generator and a vinyloxy group-containing compound (Patent Document 5) Reference), a polyamic acid ester having an acid-dissociable group added with a photoacid generator (see Patent Document 6) has been developed, and when developed immediately after exposure, the desired sensitivity can be obtained. There has been a problem that sensitivity is remarkably lowered when developed after being left for several hours to several days after exposure.

In addition, when the heat-resistant resin composition is used for semiconductor applications, the heat-cured resin remains as a permanent film in the device, and thus the adhesiveness between the heat-cured film and the substrate is very important. The resin composition cannot be said to have sufficient adhesion to the substrate, and is unsuitable for practical use.
JP 2002-328472 A (Claim 1) JP 2001-42527 A (Claims 10 to 12) JP 2003-140340 A (Claims 2 and 14) JP 2002-169283 A (Claims 6 and 7) JP 2002-122993 A (Claim 1) JP 2002-284875 A (Claims 15 and 19)

The conventional technology for increasing the sensitivity has a problem that the sensitivity is remarkably lowered when it is developed after being left for several hours to several days after exposure, or when it is used for a semiconductor device, sufficient adhesion to the substrate cannot be secured. there were. It is an object of the present invention to provide a photosensitive resin precursor composition that maintains high sensitivity, has good post-exposure standing stability, and can secure adhesion to a substrate.

That is, the present invention contains (a) a polymer mainly composed of the structural unit represented by the general formula (1), (b) two or more photoacid generators, and (c) an alkoxymethyl group-containing compound, (B) A photosensitive resin precursor composition characterized in that at least one of two or more photoacid generators is a quinonediazide compound and at least one is a triarylsulfonium salt .

(R ¹ is a divalent to octavalent organic group having 2 or more carbon atoms, R ² is a divalent to hexavalent organic group having 2 or more carbon atoms, R ³ is hydrogen, or 1 carbon atom. Any one of organic groups from 1 to 20, wherein hydrogen or a hydrogen atom and an organic group having 1 to 20 carbon atoms are mixed, n is in the range from 10 to 100,000, m is 1 or 2 , P, q are integers from 0 to 4, where p + q> 0.)

  According to the present invention, a positive photosensitive resin precursor composition that can be developed with an alkaline aqueous solution and not only has excellent resolution and sensitivity, but also has excellent post-exposure standing stability and good adhesion to a substrate, is obtained. be able to.

  The polymer having as a main component the structural unit represented by the general formula (1) of the present invention can be a polymer having an imide ring, an oxazole ring, or other cyclic structure by heating or an appropriate catalyst. Yes, preferably a polyamic acid, a polyamic acid ester of a polyimide precursor, and a polyhydroxyamide of a polybenzoxazole precursor. With the ring structure, the heat resistance and solvent resistance are dramatically improved.

R ¹ is a divalent to octavalent organic group having 2 or more carbon atoms, R ² is a divalent to hexavalent organic group having 2 or more carbon atoms, R ³ is hydrogen, or from 1 carbon atom Any one of up to 20 organic groups, in which hydrogen or a hydrogen atom and an organic group having 1 to 20 carbon atoms are mixed is shown. n is a range from 10 to 100,000, m is 1 or 2 , p, q is an integer from 0 to 4. However, p + q> 0.

In the general formula (1), R ¹ represents a divalent to octavalent organic group having two or more carbon atoms, and represents an acid structural component. Examples of the divalent compounds include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, naphthalenedicarboxylic acid, and bis (carboxyphenyl) propane, and aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid and adipic acid. it can. Trivalent ones include tricarboxylic acids such as trimellitic acid and trimesic acid, and tetravalent ones include tetracarboxylic acids such as pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, and diphenyl ether tetracarboxylic acid. . Moreover, acids having a hydroxyl group such as hydroxyphthalic acid and hydroxytrimellitic acid can also be used. These acid components may be used alone or in combination of two or more, but it is preferable to use 1 to 40 mol% of tetracarboxylic acid as a copolymer.

The tetracarboxylic acid preferably contains an aromatic ring and has a trivalent to octavalent organic group having 2 or more carbon atoms having 1 to 4 hydroxyl groups, and has 3 to 6 carbon atoms. A valent or tetravalent organic group is more preferable. Specifically, it is preferable that R ¹ (COOR ³ ) m (OH) p in the general formula (1) has a structure as shown in the general formula (5).

R ²³ and R ²⁵ may be the same or different and each represents a divalent to tetravalent organic group selected from 2 to 20 carbon atoms, and R ²⁴ is a trivalent having a hydroxyl group selected from 3 to 20 carbon atoms. A hexavalent organic group, R ²⁶ and R ²⁷ may be the same or different and each represents hydrogen or an organic group having 1 to 20 carbon atoms. o and t are integers from 0 to 2, and r is an integer from 1 to 4.

From the viewpoint of the heat resistance of the resulting polymer, those containing an aromatic ring are more preferred, and among them, particularly preferred structures include trimellitic acid, trimesic acid, naphthalene tricarboxylic acid residue and the like. R ²⁴ represents a trivalent to hexavalent organic group having a hydroxyl group selected from 3 to 20 carbon atoms. Furthermore, the hydroxyl group is preferably located adjacent to the amide bond. Examples of this include bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-hydroxy-4-aminophenyl) hexafluoropropane containing fluorine atoms, bis ( 3-amino-4-hydroxyphenyl) propane, bis (3-hydroxy-4-aminophenyl) propane, 3,3′-diamino-4,4′-dihydroxybiphenyl, 3,3′-dihydroxy-4,4 ′ Examples include diaminobiphenyl, 2,4-diamino-phenol, 2,5-diaminophenol, and 1,4-diamino-2,5-dihydroxybenzene having an amino group bonded thereto.

Moreover, R <^26> , R < ²⁷ > of General formula (5) may be the same or different, and has shown either hydrogen or an organic group having 1 to 20 carbon atoms. When the number of carbon atoms exceeds 20, the solubility in an alkaline developer is lowered. o and t are integers from 0 to 2, but are preferably selected from integers from 1 to 2. R represents an integer of 1 to 4. When r is 5 or more, the properties of the resulting heat-resistant resin film deteriorate.

  Examples of preferred compounds among the compounds represented by the general formula (5) include the structures shown below, but are not limited 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, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenylethertetracarboxylic acid, diphenylsulfonetetracarboxylic acid, and diesters in which two carboxyl groups are methyl or ethyl groups. 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, naphthalenedicarboxylic acid And aromatic 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 carried out in an amount larger than 50 mol%, the solubility in alkali and the photosensitivity may be impaired.

In the general formula (1), R ² represents a divalent to hexavalent organic group having 2 or more carbon atoms, and represents a structural component of diamine. Among these, as a preferable example of R ² , those having aromaticity and having a hydroxyl group or a carboxyl group are preferable from the viewpoint of heat resistance of the obtained polymer, and specific examples include a fluorine atom. Bis (amino-hydroxy-phenyl) hexafluoropropane, no fluorine atom, diaminodihydroxypyrimidine, diaminodihydroxypyridine, hydroxy-diamino-pyrimidine, diaminophenol, dihydroxybenzidine, diaminobenzoic acid, diaminoterephthalic acid, etc. Examples of the compound and R ² (OH) q in the general formula (1) include structures represented by the general formulas (6), (7), and (8).

R ²⁸ and R ^{30 in} the general formula (6) may be the same or different and represent a trivalent to tetravalent organic group having a hydroxyl group selected from 2 to 20 carbon atoms, and R ²⁹ represents 2 to 2 carbon atoms. 30 represents a divalent organic group selected from 30. u and v are integers of 1 or 2. R ³¹ and R ^{33 in} the general formula (7) may be the same or different and each represents a divalent organic group having 2 to 20 carbon atoms, and R ³² has a hydroxyl group selected from 3 to 20 carbon atoms. The trivalent to hexavalent organic group. w represents an integer of 1 to 4. R ^{34 in the} general formula (8) represents a divalent organic group selected from 2 to 20 carbon atoms, and R ³⁵ represents a trivalent to hexavalent organic group having a hydroxyl group selected from 3 to 20 carbon atoms. Show. x represents an integer of 1 to 4.

In the general formula (6), R ²⁸ and R ³⁰ represent a trivalent to tetravalent organic group having a hydroxyl group selected from 2 to 20 carbon atoms, and an aromatic ring from the viewpoint of the heat resistance of the resulting polymer. Those having the above are preferred. Specifically, hydroxyphenyl group, dihydroxyphenyl group, hydroxynaphthyl group, dihydroxynaphthyl group, hydroxybiphenyl group, dihydroxybiphenyl group, bis (hydroxyphenyl) hexafluoropropane group, bis (hydroxyphenyl) propane group, bis (hydroxyphenyl) ) Represents a sulfone group, a hydroxydiphenyl ether group, a dihydroxydiphenyl ether group, and the like. In addition, aliphatic groups such as a hydroxycyclohexyl group and a dihydroxycyclohexyl group can also be used. R ²⁹ represents a divalent organic group selected from 2 to 30 carbon atoms. From the viewpoint of the heat resistance of the resulting polymer, an aromatic divalent group is preferable, and examples thereof include a phenyl group, a biphenyl group, a diphenyl ether group, a diphenylhexafluoropropane group, a diphenylpropane group, and a diphenylsulfone group. In addition, an aliphatic cyclohexyl group can also be used.

In the general formula (7), R ³¹ and R ³³ represent a divalent organic group selected from 2 to 20 carbon atoms. From the heat resistance of the resulting polymer, a divalent group having an aromatic group is preferable, and examples thereof include a phenyl group, a biphenyl group, a diphenyl ether group, a diphenylhexafluoropropane group, a diphenylpropane group, and a diphenylsulfone group. In addition, aliphatic cyclohexyl groups and the like can also be used. R ³² represents a trivalent to hexavalent organic group having a hydroxyl group selected from 3 to 20 carbon atoms, and preferably has an aromatic ring from the heat resistance of the resulting polymer. Specifically, hydroxyphenyl group, dihydroxyphenyl group, hydroxynaphthyl group, dihydroxynaphthyl group, hydroxybiphenyl group, dihydroxybiphenyl group, bis (hydroxyphenyl) hexafluoropropane group, bis (hydroxyphenyl) propane group, bis (hydroxyphenyl) ) Represents a sulfone group, a hydroxydiphenyl ether group, a dihydroxydiphenyl ether group, and the like. In addition, aliphatic groups such as a hydroxycyclohexyl group and a dihydroxycyclohexyl group can also be used.

In the general formula (8), R ³⁴ represents a divalent organic group selected from 2 to 20 carbon atoms. From the heat resistance of the resulting polymer, an aromatic divalent group is preferable, and examples thereof include a phenyl group, a biphenyl group, a diphenyl ether group, a diphenylhexafluoropropane group, a diphenylpropane group, and a diphenylsulfone group. In addition, an aliphatic cyclohexyl group or the like can also be used. R ³⁵ represents a trivalent to hexavalent organic group having a hydroxyl group selected from 3 to 20 carbon atoms, and preferably has an aromatic ring from the heat resistance of the resulting polymer. Specifically, hydroxyphenyl group, dihydroxyphenyl group, hydroxynaphthyl group, dihydroxynaphthyl group, hydroxybiphenyl group, dihydroxybiphenyl group, bis (hydroxyphenyl) hexafluoropropane group, bis (hydroxyphenyl) propane group, bis (hydroxyphenyl) ) Sulfone group, hydroxydiphenyl ether group, dihydroxydiphenyl ether group and the like. In addition, aliphatic groups such as a hydroxycyclohexyl group and a dihydroxycyclohexyl group can also be used.

  In the general formula (6), u and v are integers of 1 or 2, w in the general formula (7) and x in the general formula (8) are integers from 1 to 4.

  Examples of preferred compounds among the compounds represented by the general formula (6) include the structures shown below, but are not limited thereto.

  Moreover, when a preferable compound is illustrated in the compound represented by General formula (7), the structure as shown below is mentioned, However, It is not limited to these.

  Examples of preferred compounds among the compounds represented by the general formula (8) include the structures shown below, but are not limited thereto.

  The diamines represented by the general formulas (6), (7), and (8) can be modified with other diamine components in the range of 1 to 40 mol%. Examples include phenylenediamine, diaminodiphenyl ether, aminophenoxybenzene, diaminodiphenylmethane, diaminodiphenylsulfone, bis (trifluoromethyl) benzidine, bis (aminophenoxyphenyl) propane, bis (aminophenoxyphenyl) sulfone or their fragrances. Examples thereof include compounds in which the aromatic ring is substituted with an alkyl group or a halogen atom, aliphatic cyclohexyldiamine, methylenebiscyclohexylamine, hexamethylenediamine, and the like. If such an aliphatic diamine component is copolymerized in excess of 40 mol%, the heat resistance of the resulting polymer is lowered, so care must be taken.

R ^{3 in the} general formula (1) represents either hydrogen or an organic group having 1 to 20 carbon atoms. From the solution stability of the resulting photosensitive resin precursor solution, R ³ is preferably an organic group, but hydrogen is more preferable than the solubility of an aqueous alkali solution. In the present invention, hydrogen atoms and organic groups can be mixed. By controlling the amounts of hydrogen and organic groups of R ^3, the dissolution rate with respect to the aqueous alkali solution is changed, so that a photosensitive resin precursor composition having an appropriate dissolution rate can be obtained by this adjustment. A preferred range is that 10% to 90% of each R ³ is a hydrogen atom. If the carbon number of R ³ exceeds 20, it will not dissolve in the alkaline aqueous solution. As described above, R ³ preferably contains at least one hydrocarbon group having 1 to 16 carbon atoms, and the others are hydrogen atoms.

In the general formula (1), m represents the number of carboxyl groups and represents 1 or 2 . P one general formula (1), q represents an integer of 0 to 4, a p + q> 0. In the general formula (1), n represents the number of repeating structural units of the polymer of the present invention, 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 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 using polyhydroxyamide, a positive photosensitive heat-resistant resin precursor that can be removed with an alkaline aqueous solution by adding a photosensitizer such as naphthoquinonediazide sulfonate to the polyhydroxyamide solution. A composition can be obtained.

Furthermore, in order to improve the adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized with R ¹ and R ² 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 photosensitive resin precursor composition of the present invention may be composed only of the structural unit represented by the general formula (1), 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 unit represented by General formula (1), 70 mol% or more, Furthermore, it is more preferable to contain 90 mol% or more. 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.

  Moreover, this invention can make terminal blocker react with the terminal of the polymer of General formula (1). As the terminal capping agent, monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, monoactive ester compound and the like can be used. By making terminal blocker react, it is preferable at the point which can control the repeating number of the structural unit of (a) component, ie, molecular weight, in a preferable range. Moreover, various organic groups can be introduce | transduced as a terminal group by making terminal blocker react with the terminal of (a) component. The example in which the end capping agent is reacted with the polymer of the general formula (1) is preferably a resin having a structure represented by the general formulas (9) to (12).

^{R 36} in the general formula (9) to ^{(12), -CR 37 R 38 -, -} CH 2 O- and _-CH 2 SO ₂ - a divalent group from selected. R ³⁷ and R ³⁸ each represent a monovalent group selected from a hydrogen atom and a hydrocarbon group having 1 to 10 carbon atoms. Of these, a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms is preferable, and a hydrogen atom, a methyl group, or a t-butyl group is particularly preferable. j is an integer from 0 to 10, preferably an integer from 0 to 4.

—NH— (R ³⁶ ) _j —X in the general formulas (9) and (10) is a component derived from a primary monoamine that is a terminal blocking agent, and —CO in the general formulas (11) and (12) — (R ³⁶ ) _j —Y is a component derived from an acid anhydride, a monocarboxylic acid, a monoacid chloride compound or a monoactive ester compound which is a terminal blocking agent.

  Monoamines used for the end capping agents are 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-aminonaphthalene, 1-amino-2 -Hydroxynaphthalene, 1-carboxy-8-amino Phthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 1-carboxy-4-aminonaphthalene, 1-carboxy-3-aminonaphthalene, 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-aminosalicylic acid, 3-a No-O-toluic acid, amelide, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-aminobenzene Amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 5-amino-8-mercaptoquinoline, 4-amino-8-mercaptoquinoline, 1-mercapto-8-aminonaphthalene 1-mercapto-7-aminonaphthalene, 1-mercapto-6-aminonaphthalene, 1-mercapto-5-aminonaphthalene, 1-mercapto-4-aminonaphthalene, 1-mercapto-3-aminonaphthalene, 1-mercapto- 2-aminonaphthalene, 1-amino-7-mercaptonaphthalene 2-mercapto-7-aminonaphthalene, 2-mercapto-6-aminonaphthalene, 2-mercapto-5-aminonaphthalene, 2-mercapto-4-aminonaphthalene, 2-mercapto-3-aminonaphthalene, 1-amino 2-mercaptonaphthalene, 3-amino-4,6-dimercaptopyrimidine, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline 2,4-diethynylaniline, 2,5-diethynylaniline, 2,6-diethynylaniline, 3,4-diethynylaniline, 3,5-diethynylaniline, 1-ethynyl-2-aminonaphthalene, 1-ethynyl-3-aminonaphthalene, 1-ethynyl-4-aminonaphthalene 1-ethynyl-5-aminonaphthalene, 1-ethynyl-6-aminonaphthalene, 1-ethynyl-7-aminonaphthalene, 1-ethynyl-8-aminonaphthalene, 2-ethynyl-1-aminonaphthalene, 2-ethynyl-3 -Aminonaphthalene, 2-ethynyl-4-aminonaphthalene, 2-ethynyl-5-aminonaphthalene, 2-ethynyl-6-aminonaphthalene, 2-ethynyl-7-aminonaphthalene, 2-ethynyl-8-aminonaphthalene, 3 , 5-diethynyl-1-aminonaphthalene, 3,5-diethynyl-2-aminonaphthalene, 3,6-diethynyl-1-aminonaphthalene, 3,6-diethynyl-2-aminonaphthalene, 3,7-diethynyl-1 -Aminonaphthalene, 3,7-diethynyl-2-aminonaphthalene, 4,8-diethini 1-aminonaphthalene, 4,8-diethynyl-2-Amino-naphthalene, but it is not limited thereto.

  Of these, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2 -Hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5 Aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4- Aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2- Aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, 3-ethynylaniline, 4-ethynylaniline, 3,4-diethynylaniline, 3,5-diethynylaniline and the like are preferable.

  Compounds selected from acid anhydrides, monocarboxylic acids, monoacid chloride compounds and monoactive ester compounds used as end-capping agents are phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, 3 -Acid anhydrides such as hydroxyphthalic anhydride, 2-carboxyphenol, 3-carboxyphenol, 4-carboxyphenol, 2-carboxythiophenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-8 -Carboxynaphthalene, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-hydroxy-4-carboxynaphthalene, 1-hydroxy-3-carboxynaphthalene, 1 Hydroxy-2-carboxynaphthalene, 1-mercapto-8-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 1-mercapto-4-carboxy Naphthalene, 1-mercapto-3-carboxynaphthalene, 1-mercapto-2-carboxynaphthalene, 2-carboxybenzenesulfonic acid, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, 2-ethynylbenzoic acid, 3-ethynyl Benzoic acid, 4-ethynylbenzoic acid, 2,4-diethynylbenzoic acid, 2,5-diethynylbenzoic acid, 2,6-diethynylbenzoic acid, 3,4-diethynylbenzoic acid, 3,5-diethynylbenzoic acid, 2 -Ethynyl-1-naphtho Acid, 3-ethynyl-1-naphthoic acid, 4-ethynyl-1-naphthoic acid, 5-ethynyl-1-naphthoic acid, 6-ethynyl-1-naphthoic acid, 7-ethynyl-1-naphthoic acid, 8-ethynyl -1-naphthoic acid, 2-ethynyl-2-naphthoic acid, 3-ethynyl-2-naphthoic acid, 4-ethynyl-2-naphthoic acid, 5-ethynyl-2-naphthoic acid, 6-ethynyl-2-naphthoic acid Monocarboxylic acids such as 7-ethynyl-2-naphthoic acid and 8-ethynyl-2-naphthoic acid, monoacid chloride compounds in which these carboxyl groups are acid chloride, and terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid Acid, 3-hydroxyphthalic acid, 5-norbornene-2,3-dicarboxylic acid, 1,2-dicarboxynaphthalene, 1,3-dicarboxyl Naphthalene, 1,4-dicarboxynaphthalene, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 1,8-dicarboxynaphthalene, 2,3-dicarboxynaphthalene, Monoacid chloride compounds in which only the monocarboxyl group of dicarboxylic acids such as 2,6-dicarboxynaphthalene and 2,7-dicarboxynaphthalene is acid chloride, monoacid chloride compounds and N-hydroxybenzotriazole and N-hydroxy-5 -Active ester compounds obtained by reaction with norbornene-2,3-dicarboximide.

  Of these, phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, acid anhydrides such as 3-hydroxyphthalic anhydride, 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxy Naphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, 3-ethynylbenzoic acid, 4-ethynylbenzoic acid, 3,4-diethynylbenzoic acid, 3,5-diethynyl benzoic acid Monocarboxylic acids, and monoacid chloride compounds in which these carboxyl groups are converted to an acid chloride, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1 , 7-dicarboxynaphthalene, 2,6-dicarboxynaphthalene and the like monocarboxylic acid compounds in which only the monocarboxyl group of the dicarboxylic acid is converted to acid chloride, monoacid chloride compound and N-hydroxybenzotriazole or N-hydroxy-5- Active ester compounds obtained by reaction with norbornene-2,3-dicarboximide are preferred.

  The introduction ratio of the monoamine used for the end-capping agent is preferably in the range of 0.1 to 60 mol%, particularly preferably 5 to 50 mol%, based on the total amine component. The introduction ratio of the compound selected from the acid anhydride, monocarboxylic acid, monoacid chloride compound and monoactive ester compound used as the end-capping agent ranges from 0.1 to 100 mol% with respect to the diamine component. Preferably, it is 5-90 mol% especially preferably. A plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.

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 is dissolved in an acidic solution and decomposed into an amine component and an acid anhydride component, which are constituent units of the polymer, and this is analyzed by gas chromatography (GC) or NMR measurement. The sealant can be easily detected. In addition, the polymer component into which the end-capping agent is introduced can be easily detected directly by pyrolysis gas chromatograph (PGC), infrared spectrum, and C ¹² NMR spectrum measurement.

  The polymer having the structural unit represented by the general formula (1) of the present invention as a main component is synthesized by the following method. In the case of polyamic acid or polyamic acid ester, for example, a method of reacting tetracarboxylic dianhydride and a diamine compound at low temperature, a diester is obtained by tetracarboxylic dianhydride and alcohol, and then in the presence of an amine and a condensing agent And a method in which a diester is obtained with tetracarboxylic dianhydride and an alcohol, and then the remaining dicarboxylic acid is acid chlorideed and reacted with an amine.

  Polyhydroxyamide can be obtained by a production method in which a bisaminophenol compound and a dicarboxylic acid are subjected to a condensation reaction. 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. There is a method of dropping a solution of dichloride.

In the present invention, two or more photoacid generators are used as the component (b). At least one type is used for the purpose of developing positive photosensitivity, and at least one type is used for the purpose of appropriately stabilizing the acid component generated by exposure by the photoacid generator that develops the positive type. As a result, a photosensitive resin composition having excellent post-exposure storage stability can be obtained. Photoacid generator which express positive photosensitivity is Ru der quinonediazide compound. The quinonediazide compound is a compound in which a sulfonic acid of quinonediazide is bonded to a polyhydroxy compound with an ester, a compound in which a sulfonic acid of quinonediazide is bonded to a polyamino compound, and a sulfonamide of quinonediazide is bonded to a polyhydroxypolyamino compound and / or sulfonamide. Examples include those that are combined. Although all the functional groups of these polyhydroxy compounds and polyamino compounds may not be substituted with quinonediazide, it is preferable that 50 mol% or more of the entire functional groups are substituted with quinonediazide. If it is less than 50 mol%, the solubility in an alkali developer becomes too high, and a contrast with an unexposed portion cannot be obtained, and a desired pattern may not be obtained. By using such a quinonediazide compound, a positive photosensitive resin precursor composition sensitive to i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp, which is a general ultraviolet ray, is obtained. be able to.

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

  Polyamino compounds are 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenyl. Although sulfide etc. are mentioned, it is not limited to these.

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

  In the present invention, quinonediazide is preferably a 5-naphthoquinonediazidesulfonyl group or a 4-naphthoquinonediazidesulfonyl group. The 4-naphthoquinonediazide sulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. The 5-naphthoquinone diazide sulfonyl ester compound has an absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure. In the present invention, it is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound or a 5-naphthoquinone diazide sulfonyl ester compound depending on the wavelength to be exposed. 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, if the molecular weight of the quinonediazide compound is larger than 1500, the quinonediazide compound is not sufficiently thermally decomposed in the subsequent heat treatment, so that the heat resistance of the resulting film is lowered, the mechanical properties are lowered, the adhesiveness is lowered, etc. Problems can arise. From this point of view, the molecular weight of the preferred quinonediazide compound is 300-1500. More preferably, it is 350-1200.

  The addition amount of the quinonediazide compound is preferably 1 or more and 50 or less parts by weight, and more preferably 3 or more and 40 or less parts by weight with respect to 100 parts by weight of the polymer.

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

Among the photoacid generators used as the component (b) of the present invention, the photoacid generator that moderately stabilizes the acid component generated by exposure is a triarylsulfonium salt . Storage stability after exposure by using the Re this is remarkably improved. The resin composition obtained from the photosensitive resin precursor composition of the present invention for use as a permanent film, environmentally not preferable that the phosphorus or the like remains, also the color tone of the film is also necessary Ru considered.

  Particularly preferred is a triarylsulfonium salt represented by the general formula (13).

In the formula, each R ³⁹ may be the same or different, and represents either hydrogen or an organic group having 1 to 20 carbon atoms. R ⁴⁰ represents an organic group having 1 to 20 carbon atoms. α, β, and γ each represent an integer from 0 to 5.

  Specific examples of the triarylsulfonium salt represented by the general formula (13) are shown below, but are not limited thereto.

  The amount of the photoacid generator used as the component (b) in the present invention is preferably 0.01 to 50 parts by weight with respect to 100 parts by weight of the polymer. Of these, the quinonediazide compound is preferably in the range of 3 to 40 parts by weight, and the compound selected from sulfonium salts, phosphonium salts, and diazonium salts is preferably in the range of 0.05 to 10 parts by weight.

  In the present invention, an alkoxymethyl group-containing compound is used as the component (c). In the case where no alkyl group is attached, that is, in the case of a methylol group, stability after standing after exposure is impaired, which is not preferable. The alkoxymethyl group-containing compound is preferably a compound having a phenolic hydroxyl group and / or a compound containing a urea organic group represented by the general formula (2).

    Examples of compounds having a phenolic hydroxyl group include, but are not limited to, the following compounds.

R ^{4 in the} general formula (2) represents an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms from the viewpoint of solubility with the resin composition, and having 1 to 3 carbon atoms. The alkyl group is more preferable. Specific examples of the compound containing the urea-based organic group whose component (c) is represented by the general formula (2) are shown below, but are not limited thereto.

  By adding these thermal crosslinkable compounds, the resulting photosensitive resin precursor composition hardly dissolves in an alkali developer before exposure, and easily dissolves in an alkali developer upon exposure. The film loss due to development is small, and development can be performed in a short time. In addition, the shrinkage after curing is reduced.

  In particular, in the case of a compound containing a group represented by the general formula (2), the absorption with respect to light having an exposure wavelength is extremely small as compared with an aromatic heat-crosslinkable compound. Photosensitivity is increased, and it can be easily dissolved in an alkaline developer, and development can be performed in a short time. Moreover, since it is an alicyclic system compared with an aliphatic system, it is excellent in heat resistance.

  The addition amount of the alkoxymethyl group-containing compound is preferably 0.5 to 50 parts by weight, more preferably 3 to 40 parts by weight with respect to 100 parts by weight of the polymer.

  The present invention has at least one compound selected from the compounds represented by the following general formulas (3) and (4) and a vinylsilane compound as the component (d). This can be a component for improving adhesion to the substrate.

Ar ¹ and Ar ^{2 in the} general formulas (3) and (4) each represent an aromatic ring having 6 or more carbon atoms or an aromatic heterocyclic structure having 2 or more carbon atoms. Specific examples include, but are not limited to, a phenyl group, a naphthalene group, a biphenyl group, a triazine group, and a pyridine group.

R ⁵ , R ⁶ , R ¹² , R ¹⁴ , R ²¹ and R ²² in the general formulas (3) and (4) may be the same or different and each represents hydrogen or an organic group having 1 to 4 carbon atoms. . Specific examples of the organic group having 1 to 4 carbon atoms include hydrocarbon such as methyl group, ethyl group and propyl group, and carbonyl group such as acetyl group. If the number of carbon atoms is 5 or more, the film shrinkage during curing becomes large, so care must be taken. R ⁷ , R ¹⁵ and R ²⁰ may be the same or different and each represents an organic group having 1 to 6 carbon atoms; R ^{8 to} R ¹² and R ^{16 to} R ¹⁹ may be the same or different; It represents a hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenyl group. Furthermore, at least one of R ^{8 to} R ¹² and R ^{16 to} R ¹⁹ has an alkoxy group having 1 to 6 carbon atoms. Specific examples of the hydrocarbon group include, but are not limited to, a methyl group, an ethyl group, and a propyl group. Specific examples of the alkoxy group include, but are not limited to, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and an isobutoxy group. If the hydrocarbon group or alkoxy group has 7 or more carbon atoms, the film shrinkage at the time of curing will increase, so care must be taken. Preferable specific examples of this compound include the following structures, but are not limited thereto.

  Of these, the structure shown below is most preferred.

  Examples of the vinyl silane compound include vinyl trimethoxy silane, vinyl triethoxy silane, vinyl trichloro silane, vinyl tris (β-methoxy ethoxy) silane, etc. In addition to this, 3-methacryloxypropyl trimethoxy silane, 3- Carbon-carbon unsaturated bond-containing silane compounds such as acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 3-methacryloxypropylmethyldiethoxysilane can also be used. Vinyltrimethoxysilane and vinyltriethoxysilane are preferable.

  The compounds represented by the above general formulas (3) and (4) and the vinylsilane compound may be used alone or in combination, and in either case, good adhesion to various substrates is exhibited.

  The compounds represented by the general formulas (3) and (4) and the vinylsilane compound are added in an amount of 0.001 to 30 parts by weight with respect to 100 parts by weight of the polymer. Preferably it is 0.005 or more and 20 or less weight part, More preferably, it is 0.01 or more and 15 or less weight part. If the amount is less than this amount, the effect of improving the adhesion is not observed. If the amount is more than this amount, the heat resistance of the composition may be deteriorated.

  In the present invention, the component (d) is preferably added to the composition after the polymerization of the polymer. When a compound corresponding to the component (d) is added at the time of polymer polymerization, it may be incorporated into the polymer main chain by a covalent bond in the polymer and the adhesion effect may be reduced. When the polymer is reprecipitated, unreacted substances of the above compound are removed during the reprecipitation, resulting in a decrease in the adhesion effect, and problems such as gelation due to condensation of alkoxy groups. A preferred method of addition is to add the reprecipitated polymer at the time of re-dissolving in the solvent or after re-dissolution.

  Moreover, the compound which has a phenolic hydroxyl group can be added as needed for the purpose of improving the sensitivity of the said photosensitive resin precursor composition.

  Examples of the compound having a phenolic hydroxyl group 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, TrisP-SA, TrisOCR-PA, BisOFP-Z, BisRS-2P, BisPG-26X, BisRS-3P, BisOC-OCHP, BisPC-OCHP, Bis25X-OCHP, Bis26 -OCHP, BisOCHP-OC, Bis236T-OCHP, Methylenetris-FR-CR, BisRS-26X, BisRS-OCHP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR -PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A (above, trade name, manufactured by Asahi Organic Materials Co., Ltd.).

  Among these, preferred compounds having a phenolic hydroxyl group used in the present invention include, for example, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ. , BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X, BIP-PC, BIR-PC, BIR-PTBP, BIR- BIPC-F etc. are mentioned. Among these, particularly preferred compounds having a phenolic hydroxyl group include, for example, Bis-Z, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisRS-2P, BisRS-3P, BIR-PC, BIR-PTBP, BIR- BIPC-F. By adding this phenolic hydroxyl group-containing compound, the resulting resin composition hardly dissolves in an alkali developer before exposure, and easily dissolves in an alkali developer upon exposure. Development is easy in a short time.

  The addition amount of such a compound having a phenolic hydroxyl group is preferably 1 to 50 parts by weight, more preferably 3 to 40 parts by weight with respect to 100 parts by weight of the polymer.

  Further, if necessary, for the purpose of improving the coatability between the photosensitive precursor composition and the substrate, surfactants, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, alcohols such as ethanol, cyclohexanone, Ketones such as methyl isobutyl ketone and ethers such as tetrahydrofuran and dioxane may be mixed. In addition, inorganic particles such as silicon dioxide and titanium dioxide, or polyimide powder can be added.

  Further, in order to enhance the adhesion to a base substrate such as a silicon wafer, the base substrate can be pretreated with an adhesion improving component used in the present invention. In this case, 0.5 to 20% by weight of the adhesion improving component described above is dissolved in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, or diethyl adipate. The solution is subjected to surface treatment by spin coating, dipping, spray coating, steam treatment or the like. In some cases, the reaction between the substrate and the adhesion improving component is allowed to proceed by applying a temperature from 50 ° C. to 300 ° C. thereafter.

  For the purpose of coloring the heat-resistant resin film after the heat treatment, a colorant can be added as a component (e) as necessary to the composition of the present invention. Examples of the colorant include (e1) dye, (e2) organic pigment, (e3) inorganic pigment, and (e4) a thermochromic compound that develops color by heating.

  The dye (e1) is preferably a dye that is soluble in an organic solvent that dissolves a polymer mainly composed of the structural unit represented by the general formula (1) and is compatible with a resin. Examples of preferable dyes include oil-soluble dyes, disperse dyes, reactive dyes, acid dyes, and direct dyes. As the skeleton structure of the dye, anthraquinone series, azo series, phthalocyanine series, methine series, oxazine series, and metal complex complexes of these dyes can be used. Among them, phthalocyanine series and metal complex complexes are available. Excellent in heat resistance and light resistance, and more preferable. Specifically, Sumilan, Lanyl dye (manufactured by Sumitomo Chemical Co., Ltd.), Orasol, Oracet, Filamid, Irgasperse dye (manufactured by Ciba Specialty Chemicals) Zapon, Neozapon, Neptune, Acidol dye (BASF Corporation) )) Kayaset, Kayakalan dye (Nippon Kayaku Co., Ltd.), Valifast colors dye (Orient Chemical Co., Ltd.) Savinyl, Sandoplast, Polysynthren, Lanasyn dye (Clariant Japan Co., Ltd.), Aizen Spilon dye ( Hodogaya Chemical Co., Ltd.). These dyes are used alone or in combination.

  The organic pigment (e2) is preferably a pigment having high color developability and high heat resistance, and particularly preferably a combination of carbon black and / or two or more organic pigments. Examples of the carbon black include furnace black such as HCF, MCF, LFF, RCF, SAF, ISAF, HAF, XCF, FEF, GPF, and SRF, thermal black such as FT and MT, channel black, and acetylene black. be able to. These carbon blacks can be used alone or in admixture of two or more.

  The organic pigment used in the present invention is preferably a material excellent in heat resistance. Specific examples of typical pigments are indicated by color index (CI) numbers. Examples of yellow pigments include Pigment Yellow 12, 13, 14, 17, 20, 24, 31, 55, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 155, 166, 168, 173, 180, 185 and the like. Examples of the orange pigment include Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71 and the like. Examples of red pigments include Pigment Red 9, 97, 122, 123, 144, 149, 166, 168, 176, 177, 180, 190, 192, 209, 215, 216, 224, 242, 254, and the like. Examples of purple pigments include pigment violet 19, 23, 29, 32, 33, 36, 37, 38, and the like. Examples of blue pigments include Pigment Blue 15 (15: 3, 15: 4, 15: 6, etc.), 21, 22, 60, 64, and the like. Examples of the green pigment include Pigment Green 7, 10, 36, 47, and the like.

The inorganic pigment (e3) is preferably an insulating metal compound. When an inorganic pigment having poor electrical insulation is used, the function as an insulating layer becomes insufficient. For example, when a light emitting element of an organic light emitting display device is manufactured, an electrical short circuit is caused and a serious problem occurs. Examples of the insulating metal compound include manganese oxide, titanium oxide, titanium oxynitride, chromium oxide, vanadium oxide, iron oxide, cobalt oxide, and niobium oxide. In particular, manganese oxide and titanium oxynitride are preferably used in the present invention. The manganese oxide generally has a composition of Mn _x O _y (1 <y <x ≦ 2). Specifically gamma-MnO _2, and the like _{β-MnO 2, α-MnO} 2, Mn 2 O 3, Mn 3 O 4, further, noncrystalline _{Mn x O y (1 <y} <x ≦ 2) is also used. The temporary particle diameter of the manganese oxide powder is preferably 100 nm or less, more preferably 60 nm or less. The primary particle diameter can be determined by arithmetic average using an electron microscope.

The titanium oxynitride preferably used in the present invention generally has a composition of TiN _α O _β (0 <α <2.0, 0.1 <β <2.0). The primary particle diameter of the titanium oxynitride is preferably 100 nm or less, more preferably 60 nm or less, like the manganese oxide.

  The thermochromic compound that develops color by heating in (e4) may be a general heat-sensitive dye or pressure-sensitive dye, or other compounds. These thermochromic compounds are those that develop color by changing their chemical structure or charge state due to the action of acidic groups that coexist in the system during heating, or cause thermal oxidation reaction due to the presence of oxygen in the air. Examples are those that develop color. Examples of the skeleton structure of the thermochromic compound include triarylmethane skeleton, diarylmethane skeleton, fluorane skeleton, bislactone skeleton, phthalide skeleton, xanthene skeleton, rhodamine lactam skeleton, fluorene skeleton, phenothiazine skeleton, phenoxazine skeleton, and spiropyran skeleton. . Specifically, 4,4 ′, 4 ″ -tris (dimethylamino) triphenylmethane, 4,4 ′, 4 ″ -tris (diethylamino) -2,2 ′, 2 ″ -trimethyltriphenylmethane, 2, 4 ′, 4 ″ -methylidenetrisphenol, 4,4 ′, 4 ″ -methylidenetrisphenol, 4,4 ′-[(4-hydroxyphenyl) methylene] bis (benzeneamine), 4,4 ′-[ (4-Aminophenyl) methylene] bisphenol, 4,4 ′-[(4-aminophenyl) methylene] bis [3,5-dimethylphenol], 4,4 ′-[(2-hydroxyphenyl) methylene] bis [ 2,3,6-trimethylphenol], 4- [bis (4-hydroxyphenyl) methyl] -2-methoxyphenol, 4,4 '-[(2-hydroxyphenyl) methylene Bis [2-methylphenol], 4,4 ′-[(4-hydroxyphenyl) methylene] bis [2-methylphenol], 4- [bis (4-hydroxyphenyl) methyl] -2-ethoxyphenol, 4, 4 ′-[(3-hydroxyphenyl) methylene] bis [2,6-dimethylphenol], 4,4 ′-[(4-hydroxyphenyl) methylene] bis [2,6-dimethylphenol], 2,2 ′ -[(4-hydroxyphenyl) methylene] bis [3,5-dimethylphenol], 4,4 '-[(4-hydroxy-3-methoxyphenyl) methylene] bis [2,6-dimethylphenol], 2, 2 ′-[(2-hydroxyphenyl) methylene] bis [2,3,5-trimethylphenol], 4,4 ′-[(4-hydroxyphenyl) methylene Bis [2,3,6-trimethylphenol], 4,4 ′-[(2-hydroxyphenyl) methylene] bis [2-cyclohexyl-5-methylphenol], 4,4 ′-[(3-hydroxyphenyl) Methylene] bis [2-cyclohexyl-5-methylphenol], 4,4 ′-[(4-hydroxyphenyl) methylene] bis [2-cyclohexyl-5-methylphenol], 4,4 ′-[(3-methoxy -4-hydroxyphenyl) methylene] bis [2-cyclohexyl-5-methylphenol], 4,4 '-[(3,4-dihydroxyphenyl) methylene] bis [2-methylphenol], 4,4'-[ (3,4-dihydroxyphenyl) methylene] bis [2,6-dimethylphenol], 4,4 ′-[(3,4-dihydroxyphenyl) Methylene] bis [2,3,6-trimethylphenol], 4- [bis (3-cyclohexyl-4-hydroxy-6-methylphenyl) methyl] -1,2-benzenediol, 4,4 ′, 4 ″, 4 "'-(1,2-ethanediylidene) tetrakisphenol, 4,4', 4", 4 "'-(1,2-ethanediylidene) tetrakis [2-methylphenol], 4,4', 4", 4 ""-(1,2-ethanediylidene) tetrakis [2,6-dimethylphenol], 4,4 ', 4 ", 4"'-(1,4-phenylenedimethylidene) tetrakisphenol, 4,4 ', 4 ", 4" '-(1,4-phenylenedimethylidene) tetrakis (2,6-dimethylphenol), 4,4'-[(2-hydroxyphenyl) methylene] bis [3-methylphenol 2,2 ′-[(3-hydroxyphenyl) methylene] bis [3,5-dimethylphenol], 4,4 ′-[(2-hydroxy-3-methoxyphenyl) methylene] bis [2,5-dimethyl Phenol], 4,4 '-[(2-hydroxy-3-methoxyphenyl) methylene] bis [2,6-dimethylphenol], 2,2'-[(2-hydroxy-3-methoxyphenyl) methylene] bis [3,5-dimethylphenol], 2,2 '-[(3-hydroxy-4-methoxyphenyl) methylene] bis [3,5-dimethylphenol], 4,4'-[(2-hydroxyphenyl) methylene ] Bis [2-methylethylphenol], 4,4 ′-[(3-hydroxyphenyl) methylene] bis [2-methylethylphenol], 4,4 ′-[(4- Droxyphenyl) methylene] bis [2-methylethylphenol], 2,2 ′-[(3-hydroxyphenyl) methylene] bis [3,5,6-trimethylphenol], 2,2 ′-[(4- Hydroxyphenyl) methylene] bis [3,5,6-trimethylphenol], 2,2 ′-[(4-hydroxy-3-ethoxyphenyl) methylene] bis [3,5-dimethylphenol], 4,4′- [(2-hydroxy-3-methoxyphenyl) methylene] bis [2- (methylethyl) phenol], 4,4 ′-[(3-hydroxy-4-methoxyphenyl) methylene] bis [2- (methylethyl) Phenol], 4,4 ′-[(4-hydroxy-3-methoxyphenyl) methylene] bis [2- (methylethyl) phenol], 2,2 ′-[(2- Hydroxy-3-methoxyphenyl) methylene] bis [3,5,6-trimethylphenol], 2,2 ′-[(3-hydroxy-4-methoxyphenyl) methylene] bis [3,5,6-trimethylphenol] 2,2 ′-[(4-hydroxy-3-methoxyphenyl) methylene] bis [3,5,6-trimethylphenol], 4,4 ′-[(4-hydroxy-3-ethoxyphenyl) methylene] bis [2- (methylethyl) phenol], 2,2 ′-[(4-hydroxy-3-ethoxyphenyl) methylene] bis [3,5,6-trimethylphenol], 4,4 ′-[(4-hydroxy -3-Ethoxyphenyl) methylene] bis [2,3,6-trimethylphenol], 4,4 ′-[(4-hydroxy-3-methoxyphenyl) methylene] [2- (1,1-dimethylethyl) -5-methylphenol], 4,4 ′-[(2-hydroxyphenyl) methylene] bis [2-cyclohexylphenol], 4,4 ′-[(3- Hydroxyphenyl) methylene] bis [2-cyclohexylphenol], 4,4 ′-[(4-hydroxyphenyl) methylene] bis [2-cyclohexylphenol], 4,4 ′-[(2-hydroxy-3-methoxyphenyl) ) Methylene] bis [2-cyclohexylphenol], 4,4 ′-[(3-hydroxy-4-methoxyphenyl) methylene] bis [2-cyclohexylphenol], 4,4 ′-[(4-hydroxy-3-) Ethoxyphenyl) methylene] bis [2- (1,1-dimethylethyl) -6-methylphenol], 4,4 ′-[(4-hydrido Xyl-3-ethoxyphenyl) methylene] bis [2-cyclohexyl-5-methylphenol], 4,4 ', 4 "-methylidenetris [2-cyclohexyl-5-methylphenol], 2,2'-[(3 4-dihydroxyphenyl) methylene] bis [3,5-dimethylphenol], 4,4 ′-[(3,4-dihydroxyphenyl) methylene] bis [2- (methylethyl) phenol], 2,2 ′-[ (3,4-dihydroxyphenyl) methylene] bis [3,5,6-trimethylphenol], 4,4 ′-[(3,4-dihydroxyphenyl) methylene] bis [2-cyclohexylphenol], 3,3 ′ -[(2-hydroxyphenyl) methylene] bis [5-methylbenzene-1,2-diol], 4,4 '-[4-[[bis (4-hydride) Roxy-2,5-dimethylphenyl) methyl] phenyl] methylene] bis [1,3-benzenediol], 4,4′-methylenebis [2- [di (4-hydroxy-3-methylphenyl)] methyl] phenol 4,4′-methylenebis [2- [di (4-hydroxy-2,5-dimethylphenyl)] methyl] phenol, 4,4′-methylenebis [2- [di (4-hydroxy-3,5-dimethyl) Phenyl)] methyl] phenol, 4,4′-methylenebis [2- [di (3-cyclohexyl-4-hydroxy-6-methylphenyl)] methyl] phenol, 4,4 ′-(3,5-dimethyl-4 -Hydroxyphenylmethylene) -bis (2,6-dimethylphenol), 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide 3,6-bis (dimethylamino) fluorane-γ- (4′-nitro) -aminolactam, 2- (2-chloroanilino) -6-diethylaminofluorane, 2- (2-chloroanilino) -6-dibutylaminofluor Oran, 2-N, N-dibenzylamino-6-diethylaminofluorane, 6-diethylamino-benzo [a] -fluorane, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5 ′ -Tetraphenyl-1,2'-bi (imidazole), 1,3-dimethyl-6-diethylaminofluorane, 2-anilino-3-methyl-6-dibutylaminofluorane, 3,7-bis (dimethylamino) -10-benzoylphenothiazine, 3-diethylamino-6-chloro-7- (β-ethoxyethylamino) fluorane, 3-diethylamino 6-methyl-7-anilinofluoran, 3-triethyl-6-methyl-7-anilinofluoran, 3-cyclohexylamino-6-methyl-7-anilinofluoran, and the like.

  Among these, a hydroxyl group-containing compound having a triarylmethane skeleton is particularly preferable because it has a high thermochromic temperature and excellent heat resistance. These may be used alone or in combination. The hydroxyl group-containing compound having a triarylmethane skeleton may be used as a quinonediazide compound by esterifying a sulfonic acid of naphthoquinonediazide to the compound.

  The amount of the colorant (e) used in the present invention is preferably 1 to 300 parts by weight with respect to 100 parts by weight of the polymer whose main component is the structural unit represented by (a) the general formula (1). The use of 10 to 200 parts by weight is preferred. (A) When the amount of (e) the colorant used is greater than 300 parts by weight relative to 100 parts by weight of the polymer having the structural unit represented by the general formula (1) as a main component, the resin ratio decreases, and the photosensitive resin film And the adhesion strength of the substrate decreases.

  When the component (e) is used in the composition of the present invention, it may be at least one selected from (e1) to (e4). For example, a method using one dye or an organic pigment, two or more dyes Or a method using a mixture of organic pigments, a method using a combination of one or more dyes and one or more organic pigments, a method using a combination of one or more thermochromic compounds and one or more dyes, and one type Examples thereof include a method using a combination of the above inorganic pigments and one or more thermochromic compounds.

Solvents used in the present invention are polar aprotic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dioxane, propylene Ethers such as glycol monomethyl ether, ketones such as acetone, methyl ethyl ketone, diisobutyl ketone and diacetone alcohol, esters such as ethyl acetate, propylene glycol monomethyl ether acetate and ethyl lactate, and aromatic hydrocarbons such as toluene and xylene These solvents can be used alone or in combination.
The amount of the solvent used in the present invention is preferably 50 to 2000 parts by weight, particularly 100 to 1500 parts per 100 parts by weight of the polymer having (a) the structural unit represented by the general formula (1) as a main component. Part by weight is preferred.

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

  The photosensitive resin precursor composition is applied onto the substrate. As the substrate, a silicon wafer, ceramics, gallium arsenide, metal, glass, metal oxide insulating film, silicon nitride, ITO, or the like is used, but not limited thereto. Examples of the coating method include spin coating using a spinner, spray coating, roll coating, and slit die coating. 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 precursor composition is dried to obtain a photosensitive resin precursor 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 precursor 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. .

  The formation of the heat-resistant resin pattern from the photosensitive resin precursor composition film is accomplished by removing the exposed portion using a developer after exposure. The developer is an aqueous solution of tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylamino An aqueous solution of a compound exhibiting alkalinity such as ethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine and the like is preferable. In some cases, these alkaline aqueous solutions may contain polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, dimethylacrylamide, methanol, ethanol, 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. After development, rinse with water. Here, alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water for rinsing treatment.

  After development, a temperature of 200 ° C. to 500 ° C. is applied to convert it to a heat resistant resin 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 heat-resistant resin film formed from the photosensitive heat-resistant precursor composition according to the present invention includes a semiconductor passivation film, a protective film for semiconductor elements, an interlayer insulating film for multilayer wiring for high-density mounting, an insulating layer for organic electroluminescent elements, etc. Used for

Hereinafter, the present invention will be described with reference to examples and the like, but the present invention is not limited to these examples. In addition, evaluation of the photosensitive resin precursor composition in an Example is the following method.
(1) Evaluation of pattern processability Production of photosensitive resin precursor film A photosensitive resin precursor composition (hereinafter referred to as varnish) was applied on a 6-inch silicon wafer so that the film thickness after pre-baking was 7 μm. Subsequently, the photosensitive resin precursor film | membrane was obtained by prebaking for 3 minutes at 120 degreeC using the hotplate (Tokyo Electron Co., Ltd. coating development apparatus Mark-7).

Film thickness measurement method Using Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd., the film after pre-baking and development is measured at a refractive index of 1.629, and the cured film is measured at a refractive index of 1.773. did.

Exposure The reticle from which the pattern was cut was set in an exposure machine (i-line stepper DSW-8000 manufactured by GCA), and the photosensitive resin precursor film was exposed with i-line by changing the exposure time at an intensity of 365 nm.

Development Using a developing device of Mark-7 manufactured by Tokyo Electron Ltd., a 2.38% aqueous solution of tetramethylammonium hydroxide was sprayed on the exposed film for 10 seconds at 50 revolutions. Then, it was allowed to stand for 60 seconds at 0 rotation, rinsed with water at 400 rotation, and shaken and dried for 10 seconds at 3000 rotation.

Calculation of Sensitivity After exposure and development, an exposure time for forming a 50 μm line and space pattern (1L / 1S) in a one-to-one width (hereinafter referred to as an optimal exposure time) was determined.

Calculation of resolution After exposure and development, the minimum pattern size in the optimum exposure time in which a 50 μm line-and-space pattern (1L / 1S) is formed in a one-to-one width was defined as the resolution.

Cure Using the inert oven INH-21CD manufactured by Koyo Thermo System Co., Ltd., nitrogen atmosphere (oxygen concentration 20 ppm or less) at 140 ° C. for 30 minutes, and then to 350 ° C. for 1 hour. Was heated at 350 ° C. for 1 hour to prepare a cured film (heat-resistant resin film).

Calculation of shrinkage rate After producing a cured film, the shrinkage rate was calculated according to the following equation.
Shrinkage rate (%) = (film thickness after pre-baking−film thickness after curing) / film thickness after pre-baking × 100
(2) Evaluation of standing stability after exposure The film was developed after being left in a yellow room (23 ° C., 45% RH) for 48 hours after exposure, and the sensitivity, shrinkage rate, and resolution of the varnish were evaluated as described above.
(3) Adhesion evaluation with substrate Substrate-like cuts of 10 rows and 10 columns at 2 mm intervals are made in the cured film, and after 100 hours of pressure cooker test (PCT) treatment, peeling with cello tape (registered trademark) Tested. In the peeling test, the number of peeling was less than 10 as good and 10 or more as bad. The PCT treatment was performed under a saturation condition of 121 ° C. and 2 atm.

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 gamma butyrolactone and cooled to −15 ° C. To this, 22.1 g (0.11 mol) of trimellitic anhydride chloride dissolved in 50 g of gamma 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 Hydroxyl Group-Containing Diamine (d) 2-Amino-4-nitrophenol 15.4 g (0.1 mol) was dissolved in acetone 100 mL and propylene oxide 17.4 g (0.3 mol), and −15 Cooled to ° C. A solution prepared by dissolving 20.4 g (0.11 mol) of 4-nitrobenzoyl chloride in 100 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. Thereafter, the target compound crystal was obtained in the same manner as in Synthesis Example 2.

Synthesis Example 5 Synthesis of quinonediazide compound (e) Under a dry nitrogen stream, BisP-RS (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 16.10 g (0.05 mol) and 5-naphthoquinonediazidesulfonyl acid chloride 26.86 g (0.1 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 10.12 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature in the system would not be 35 ° C. or higher. It stirred at 30 degreeC after dripping for 2 hours. 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 (e).

Synthesis Example 6 Synthesis of quinonediazide compound (f) 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 (f) was obtained in the same manner as in Synthesis Example 5 using 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane.

Synthesis Example 7 Synthesis of quinonediazide compound (g) TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), 21.22 g (0.05 mol) and 5-naphthoquinonediazidesulfonyl chloride 26. 86 g (0.10 mol) and 13.43 g (0.05 mol) of 4-naphthoquinone diazide sulfonyl chloride were dissolved in 450 g of 1,4-dioxane and brought to room temperature. A quinonediazide compound (g) was obtained in the same manner as in Synthesis Example 5 using 12.65 g of triethylamine mixed with 50 g of 1,4-dioxane.

Synthesis Example 8 Synthesis of quinonediazide compound (h) In a dry nitrogen stream, 11.41 g (0.05 mol) of bisphenol A and 26.86 g (0.1 mol) of 4-naphthoquinonediazidesulfonyl acid chloride were added to 1,4-dioxane. Dissolved in 450 g and brought to room temperature. A quinonediazide compound (h) was obtained in the same manner as in Synthesis Example 5 using 10.12 g of triethylamine mixed with 50 g of 1,4-dioxane.

  The compounds having a phenolic hydroxyl group, the photoacid generator, and the thermally crosslinkable compound used in each Example and Comparative Example are shown below.

Example 1
Under a dry nitrogen stream, 5.01 g (0.025 mol) of 4,4′-diaminophenyl ether and 1.24 g (0.005 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane were added to N—. It was dissolved in 50 g of methyl-2-pyrrolidone (NMP). To this, 21.4 g (0.03 mol) of the hydroxy group-containing acid anhydride (a) obtained in Synthesis Example 1 was added together with 14 g of NMP and reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 4 hours. . Thereafter, a solution obtained 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 polymer solution A.

  2 g of the quinonediazide compound (e) obtained in Synthesis Example 5 and 0.01 g of WPAG-314 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.) were added to 40 g of the obtained polymer solution A, and Nicalac MX-270 was used as a thermally crosslinkable compound. (Product name, manufactured by Sanwa Chemical Co., Ltd.) 1.2 g and 0.1 g of vinyltrimethoxysilane as an adhesion improving component were added to obtain a varnish A of a photosensitive polyimide precursor composition. Using the obtained varnish, pattern workability evaluation, post-exposure standing stability evaluation, and adhesion evaluation with a substrate were performed as described above.

Example 2
Under a dry nitrogen stream, 15.1 g (0.025 mol) of the hydroxyl group-containing diamine (b) obtained in Synthesis Example 2 was dissolved in 50 g of N-methyl-2-pyrrolidone (NMP). 17.5 g (0.025 mol) of the hydroxy group-containing acid anhydride (a) obtained in Synthesis Example 1 was added thereto together with 30 g of pyridine, and reacted at 60 ° C. for 6 hours. After completion of the reaction, the solution was poured into 2 L of water, and a polymer solid precipitate was collected by filtration. The polymer solid was dried with a vacuum dryer at 80 ° C. for 20 hours to obtain polymer B.

  10 g of the polymer B solid thus obtained was weighed, 2 g of the quinonediazide compound (f) obtained in Synthesis Example 6, 0.1 g of WPAG-505 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.), thermal crosslinking 2 g of the chemical compound TMOM-BP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), 1.5 g of Bis-Z (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), and 0.2 g of m-aminophenyltrimethoxysilane. It was made to melt | dissolve in GBL30g and the varnish B of the photosensitive polyimide precursor composition was obtained. Using the obtained varnish, pattern workability evaluation, post-exposure standing stability evaluation, and adhesion evaluation with a substrate were performed as described above.

Example 3
Under a dry nitrogen stream, 17 g (0.045 mol) of the hydroxyl group-containing diamine compound (c) obtained in Synthesis Example 3 and 1.24 g (0.005) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane. Mol) was dissolved in 50 g of NMP. To this, 12.4 g (0.04 mol) of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid anhydride (ODPA) was added together with 21 g of NMP, reacted at 20 ° C. for 1 hour, and then at 50 ° C. for 2 hours. Reacted. To this, 0.98 g (0.01 mol) of maleic anhydride was added, stirred for 2 hours at 50 ° C., and then a solution obtained by diluting 14.7 g (0.1 mol) of N, N-dimethylformamide diethyl acetal with 5 g of NMP was added. It was added dropwise over a period of minutes. After dropping, the mixture was stirred at 50 ° C. for 3 hours to obtain a polymer solution C.

  To the obtained polymer solution C30 g, quinonediazide compound (g) 1.6 g obtained in Synthesis Example 7, WPAG-567 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.) 0.05 g, thermally crosslinkable compound DMOM-PTBP 1 g (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 0.5 g of p-aminophenyltrimethoxysilane were dissolved to obtain a varnish C of a photosensitive polyimide precursor composition. Using the obtained varnish, pattern workability evaluation, post-exposure standing stability evaluation, and adhesion evaluation with a substrate were performed as described above.

Example 4
Under a dry nitrogen stream, 6.08 g (0.025 mol) of the hydroxyl group-containing diamine compound (d) obtained in Synthesis Example 4 and 4.51 g (0.0225 mol) of 4,4′-diaminodiphenyl ether and 1,3 -0.62 g (0.0025 mol) of bis (3-aminopropyl) tetramethyldisiloxane was dissolved in 70 g of NMP. Hydroxyl group-containing acid anhydride (a) 24.99 g (0.035 mol), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride 4.41 g (0.015 mol) together with NMP 25 g at room temperature In addition, the mixture was stirred at room temperature for 1 hour and then at 50 ° C. for 2 hours. Next, a solution obtained by diluting 17.6 g (0.2 mol) of glycidyl methyl ether with 10 g of NMP was added and stirred at 70 ° C. for 6 hours to obtain a polymer solution D.

  To the polymer solution D40g, quinonediazide compound (h) 2.5g obtained in Synthesis Example 8, 0.2g WPAG-350 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.) 0.2g, thermally crosslinkable compound Nicalak MX-290 ( Trade name, Sanwa Chemical Co., Ltd. (1.5 g) and m-acetylaminophenyltrimethoxysilane (0.5 g) were dissolved to obtain a varnish D of a photosensitive polyimide precursor composition. Using the obtained varnish, pattern workability evaluation, post-exposure standing stability evaluation, and adhesion evaluation with a substrate were performed as described above.

Example 5
Under a dry nitrogen stream, 13.60 g (0.018 mol) of hydroxyl group-containing diamine (b) and 0.50 g (0.002 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane are dissolved in 50 g of NMP. I let you. To this, 17.86 g (0.025 mol) of a hydroxy group-containing acid anhydride (a) was added together with 30 g of pyridine, and reacted at 60 ° C. for 2 hours. Next, 0.59 g (0.005 mol) of 4-ethynylaniline was added as a terminal blocking agent, and the mixture was further reacted at 60 ° C. for 2 hours. After completion of the reaction, the solution was poured into 2 L of water, and a polymer solid precipitate was collected by filtration. The polymer solid was dried with a vacuum dryer at 80 ° C. for 20 hours to obtain polymer E.

  10 g of the polymer E solid thus obtained was weighed, 2 g of quinonediazide compound (e), WPAG-360 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.) 0.01 g, thermally crosslinkable compound DMOM-PC (product) Name, Honshu Chemical Industry Co., Ltd. 2 g, TPPA (trade name, Honshu Chemical Industry Co., Ltd.) 1.5 g, 3,3′-diaminodiphenyltetramethoxydisiloxane 0.5 g were dissolved in GBL 30 g. The varnish E of the photosensitive polyimide precursor composition was obtained. Using the obtained varnish, pattern workability evaluation, post-exposure standing stability evaluation, and adhesion evaluation with a substrate were performed as described above.

Example 6
Polymer F was obtained in the same manner as in Example 5 except that 0.59 g of 4-ethynylaniline as the end-capping agent in Example 5 was changed to 0.54 g (0.005 mol) of 3-aminophenol. 10 g of the polymer F solid thus obtained was weighed, 2 g of the quinonediazide compound (f), WPAG-372 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.) 0.005 g, the heat-crosslinkable compound Nicalac MX-280 ( Product name, Sanwa Chemical Co., Ltd. 2 g, BIR-PC (trade name, Honshu Chemical Industry Co., Ltd.) 1.5 g, 3,3′-diacetylaminodiphenyltetramethoxydisiloxane 0.5 g and GBL 30 g The varnish F of the photosensitive polyimide precursor composition was obtained. Using the obtained varnish, pattern workability evaluation, post-exposure standing stability evaluation, and adhesion evaluation with a substrate were performed as described above.

Example 7
10 g of the polymer B solid obtained in Example 2 was weighed, 2 g of the quinonediazide compound (g), WPAG-314 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.) 0.01 g, and the thermally crosslinkable compound Nicalak MX-270. 1 g of DMMO-PC, 0.5 g of vinyltriethoxysilane and 0.5 g of 3,3′-diacetylaminodiphenyltetramethoxydisiloxane were dissolved in 30 g of GBL to prepare a varnish for a photosensitive polyimide precursor composition. G was obtained. Using the obtained varnish, pattern workability evaluation, post-exposure standing stability evaluation, and adhesion evaluation with a substrate were performed as described above.

Example 8
To 30 g of the polymer solution C obtained in Example 3, 1.6 g of quinonediazide compound (g), 0.01 g of BDS-109 (trade name, manufactured by Midori Chemical Co., Ltd.), WPAG-567 (trade name, Wako Pure Chemical Industries, Ltd.) Co., Ltd.) 0.01 g, thermally crosslinkable compound DMOM-PTBP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 1 g, m-acetylaminophenyltrimethoxysilane 0.5 g was dissolved to form a photosensitive polyimide precursor composition. A product varnish H was obtained. Using the obtained varnish, pattern workability evaluation, post-exposure standing stability evaluation, and adhesion evaluation with a substrate were performed as described above.

Reference example 1
Under a dry nitrogen stream, 18.3 g (0.05 mol) of BAHF was dissolved in 50 g of NMP and 26.4 g (0.3 mol) of glycidyl methyl ether, and the temperature of the solution was cooled to −15 ° C. A solution prepared by dissolving 14.7 g (0.050 mol) of diphenyl ether dicarboxylic acid dichloride in 25 g of GBL was added dropwise so that the internal temperature did not exceed 0 ° C. After completion of the dropwise addition, stirring was continued for 6 hours at -15 ° C. After completion of the reaction, the 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 to obtain polymer G.

  30 g of GBL, 10 g of the obtained polymer G solid, 2 g of quinonediazide compound (f), WPAG-314 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.) 0.01 g, thermally crosslinkable compound DMOM-PC (trade name, Honshu Chemical Industry Co., Ltd. (1 g) and p-aminophenyltrimethoxysilane (0.5 g) were dissolved to obtain a varnish I of a photosensitive polybenzoxazole precursor composition. Using the obtained varnish, pattern workability evaluation, post-exposure standing stability evaluation, and adhesion evaluation with a substrate were performed as described above.

Comparative Example 1
Varnish J of the photosensitive polyimide precursor composition was obtained in the same manner as in Example 1 except that WPAG-314 of Example 1 and vinyltrimethoxysilane were not used. Using the obtained varnish, pattern workability evaluation, post-exposure standing stability evaluation, and adhesion evaluation with a substrate were performed as described above.

Comparative Example 2
Varnish K of the photosensitive polyimide precursor composition was obtained in the same manner as in Example 2 except that WPAG-505 and m-aminophenyltrimethoxysilane of Example 2 were not used. Using the obtained varnish, pattern workability evaluation, post-exposure standing stability evaluation, and adhesion evaluation with a substrate were performed as described above.

Comparative Example 3
Except for using WPAG-567 of Example 3 and using DML-PTBP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) instead of the thermally crosslinkable compound DMOM-PTBP, the same procedure as in Example 3 was carried out. The varnish L of the conductive polyimide precursor composition was obtained. Using the obtained varnish, pattern workability evaluation, post-exposure standing stability evaluation, and adhesion evaluation with a substrate were performed as described above.

Comparative Example 4
Under a dry nitrogen flow, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride 24.82 g (0.08 mol), n-butyl alcohol 11.86 g (0.16 mol), triethylamine 0.4 g (0.004 mol) and 110 g of NMP were charged, and the mixture was stirred and reacted at room temperature for 8 hours to obtain an NMP solution of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid di-n-butyl ester.

  Then, after cooling the flask to 0 ° C., 17.13 g (0.144 mol) of thionyl chloride was added dropwise to react for 1 hour, and di-n-butyl 3,3 ′, 4,4′-diphenyl ether tetracarboxylate. A solution of ester dichloride was obtained. Subsequently, 105 g of N-methylpyrrolidone was charged into a 0.5 liter flask equipped with a stirrer and a thermometer, and 26.37 g (0.072 mol) of BAHF was added and dissolved by stirring. Then, 22.78 g (0 .288 mol) was added and the solution of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid di-n-butyl ester dichloride was added dropwise over 20 minutes while maintaining the temperature at 0 to 5 ° C. Stirring was continued for 1 hour at 30 ° C. The solution was poured into 3 liters of water, and the precipitate was collected and washed, and then the polymer solid was dried with an 80 ° C. vacuum dryer for 20 hours to obtain polymer H.

  10 g of the obtained polymer H solid, 2 g of quinonediazide compound (g), 0.10 g of diphenyliodonium nitrate, and 1 g of Epicoat 828 of bisphenol A type epoxy resin (trade name, manufactured by Japan Epoxy Resin Co., Ltd.) are dissolved in 30 g of NMP. The varnish M of the photosensitive polyimide precursor composition was obtained. Using the obtained varnish, pattern workability evaluation, post-exposure standing stability evaluation, and adhesion evaluation with a substrate were performed as described above.

Comparative Example 5
In 30 g of NMP, 10 g of the polymer H solid obtained in Comparative Example 4, 2 g of the quinonediazide compound (h), 0.10 g of diphenyliodonium nitrate, and 0.50 g of dimethylolurea were dissolved to make varnish N of the photosensitive polyimide precursor composition. Got. Using the obtained varnish, pattern workability evaluation, post-exposure standing stability evaluation, and adhesion evaluation with a substrate were performed as described above.

Comparative Example 6
Varnish O of the photosensitive polyimide precursor composition was obtained in the same manner as in Comparative Example 5, except that 1,4-bis (methoxyphenoxy) benzene was used instead of dimethylolurea in Comparative Example 5. Using the obtained varnish, pattern workability evaluation, post-exposure standing stability evaluation, and adhesion evaluation with a substrate were performed as described above.

Comparative Example 7
Except not using the epicoat 828 of the comparative example 4, it carried out similarly to the comparative example 4, and obtained the varnish P of the photosensitive polyimide precursor composition. Using the obtained varnish, pattern workability evaluation, post-exposure standing stability evaluation, and adhesion evaluation with a substrate were performed as described above.

Comparative Example 8
Under a dry nitrogen stream, 32.2 g (0.1 mol) of benzophenonetetracarboxylic dianhydride, 200 g of NMP and 26.06 g (0.21 mol) of p-hydroxybenzyl alcohol were added and stirred, followed by 21.2 g of triethylamine. (0.21 mol) was added dropwise over 30 minutes. This state was allowed to stand for 3 hours, and after completion of the reaction, 20.02 g (0.1 mol) of 4,4'-diaminodiphenyl ether was added and stirred for 30 minutes to dissolve. Next, 0.21 mol of diphenyl (2,3-dihydro-2-thioxo-3-benzoxazole) phosphonate was added in 5 portions, and a condensation reaction was performed in that state for 5 hours. The obtained slurry-like mixture was poured into a large amount of methanol and washed, and the polymer solid was dried with a vacuum dryer at 80 ° C. for 20 hours to obtain polymer I of general formula (1) where p + q = 0. .

  Varnish Q of the photosensitive polyimide precursor composition was obtained by dissolving 10 g of the obtained polymer I solid, 2 g of the quinonediazide compound (g), and 5 g of triethylene glycol divinyl ether in 30 g of NMP. Using the obtained varnish, pattern workability evaluation, post-exposure standing stability evaluation, and adhesion evaluation with a substrate were performed as described above.

Comparative Example 9
Under a dry nitrogen stream, 3.44 g (0.0117 mol) of 1,4-bis (4-aminophenoxy) benzene, 9.42 g (0.0470 mol) of 4,4′-diaminodiphenyl ether and 140 g of NMP were gradually added. After completely dissolved by stirring, 1.24 g (0.0056 mol) of pyromellitic dianhydride and 15.92 g (0.0513 mol) of ODPA were gradually added and stirred while maintaining at room temperature. After stirring for 2 hours, 0.49 g (0.0029 mol) of 5-norbornene-2,3-dicarboxylic anhydride was gradually added and stirred at room temperature for 16 hours. Thereafter, while maintaining the temperature of the solution at −25 ° C., 50 g of NMP was added to reduce the concentration of the mixed solution, and 7.26 g (0.0717 mol) of triethylamine was diluted to 30 g of NMP while maintaining the room temperature. The mixture was stirred while gradually adding. Further, 7.18 g (0.0759 mol) of chloromethyl ethyl ether was diluted with 30 g of NMP and gradually added. After stirring for 2 hours, the triethylammonium chloride salt is removed by filtration while maintaining a low temperature, and the filtrate is gradually poured into a mixture of 1 L of methanol and 2 L of distilled water to precipitate into a white fine solid. It was. Filtration, washing with about 5 L of distilled water, and drying for 20 hours in a vacuum dryer at 80 ° C. gave a polymer J of general formula (1) where p + q = 0.

  In 10 g of NMP, 10 g of the obtained polymer J solid, 2 g of the quinonediazide compound (h), and 0.01 g of WPAG-314 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved to prepare a photosensitive polyimide precursor composition. Varnish R was obtained. Using the obtained varnish, pattern workability evaluation, post-exposure standing stability evaluation, and adhesion evaluation with a substrate were performed as described above.

Comparative Example 10
In the same manner as in Example 1 except that ODPA was used in place of the hydroxy group-containing acid anhydride (a) of polymer A synthesized in Example 1, a polymer solution K of general formula (1) where p + q = 0 was obtained. Obtained. The varnish S of the photosensitive polyimide precursor composition was obtained like Example 3 except having used the obtained polymer solution K instead of the polymer solution C. Using the obtained varnish, pattern workability evaluation, post-exposure standing stability evaluation, and adhesion evaluation with a substrate were performed as described above.

Example 9
A photosensitive polyimide precursor was prepared in the same manner as in Example 1 except that the thermally crosslinkable compound DMOM-PTBP was used in place of the thermally crosslinkable compound Nicalac MX-270 in Example 1 and the adhesion improving component vinyltrimethoxysilane was removed. A varnish T of the body composition was obtained. Using the obtained varnish, pattern workability evaluation, post-exposure standing stability evaluation, and adhesion evaluation with a substrate were performed as described above.

Example 10
Except that WPAG-567 and thermally crosslinkable compound DMOM-PC were used in place of WPAG-505 and thermally crosslinkable compound TMOM-BP of Example 2, except that m-aminophenyltrimethoxysilane as an adhesion improving component was removed. It carried out like 2 and obtained the varnish U of the photosensitive polyimide precursor composition. Using the obtained varnish, pattern workability evaluation, post-exposure standing stability evaluation, and adhesion evaluation with a substrate were performed as described above.

Example 11
It carried out similarly to Example 1 except having used WPAG-315 instead of WPAG-314 of Example 1, and obtained the varnish V of the photosensitive polyimide precursor composition. Using the obtained varnish, pattern workability evaluation, post-exposure standing stability evaluation, and adhesion evaluation with a substrate were performed as described above.

Example 12
A photosensitive polyimide precursor composition was prepared in the same manner as in Example 2 except that WPAG-419 and thermally crosslinkable compound Nicalak MX-280 were used instead of WPAG-505 and thermally crosslinkable compound TMOM-BP of Example 2. Varnish W was obtained. Using the obtained varnish, pattern workability evaluation, post-exposure standing stability evaluation, and adhesion evaluation with a substrate were performed as described above.

Example 13
Varnish X of the photosensitive polyimide precursor composition was obtained in the same manner as in Example 4 except that WPAG-461 was used instead of WPAG-350 in Example 4. Using the obtained varnish, pattern workability evaluation, post-exposure standing stability evaluation, and adhesion evaluation with a substrate were performed as described above.

Reference example 2
Except for using WPAG-422 instead of WPAG-314 of Reference Example 1 was conducted in the same manner as in Reference Example 1, to obtain a varnish Y of a photosensitive polybenzoxazole precursor composition. Using the obtained varnish, pattern workability evaluation, post-exposure standing stability evaluation, and adhesion evaluation with a substrate were performed as described above.

The varnish compositions of Examples 1 to 13, Reference Examples 1 to 2 and Comparative Examples 1 to 10 are shown in Table 1 below, and the evaluation results are shown in Table 2 below.

Claims (3)

(A) a polymer containing the structural unit represented by the general formula (1) as a main component, (b) two or more photoacid generators, (c) an alkoxymethyl group-containing compound, and (b) two types Among the above photoacid generators, at least one is a quinonediazide compound, and at least one is a triarylsulfonium salt, a photosensitive resin precursor composition.

(Wherein R ¹ is a divalent to octavalent organic group having 2 or more carbon atoms, R ² is a divalent to hexavalent organic group having 2 or more carbon atoms, and R ³ is hydrogen or carbon. Any one of organic groups having a number of 1 to 20 , which is a mixture of hydrogen or a hydrogen atom and an organic group having 1 to 20 carbon atoms, n is in the range of 10 to 100,000, and m is 1 Or 2 , p and q are integers from 0 to 4, provided that p + q> 0. (C) alkoxymethyl group-containing compound, No placement claim 1 Symbol characterized in that it is a compound containing a urea organic group represented by the compound containing a phenolic hydroxyl group and / or the general formula (2) Photosensitive resin precursor composition.

(In the formula, R ⁴ represents an alkyl group having 1 to 20 carbon atoms.) The photosensitive material according to claim 1 or 2 , comprising at least one compound selected from (d) a compound represented by the general formula (3), a compound represented by the general formula (4), and a vinylsilane compound. Resin precursor composition.

(Ar ¹ and Ar ² represent an aromatic ring having 6 or more carbon atoms or an aromatic heterocyclic structure having 2 or more carbon atoms. R ⁵ , R ⁶ , R ¹² , R ¹⁴ , R ²¹ , R ²² may be the same or different and each represents hydrogen or an organic group having 1 to 4 carbon atoms, and R ⁷ , R ¹⁵ , and R ²⁰ may be the same or different and each have 1 to 6 carbon atoms. Represents an organic group, and R ^{8 to} R ¹² and R ^{16 to} R ¹⁹ may be the same or different and are selected from a hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenyl group. And at least one of R ^{8 to} R ¹² and R ^{16 to} R ¹⁹ is an alkoxy group having 1 to 6 carbon atoms, a, d, f, and h are integers of 1 or more, and b, c, e, and g are Represents an integer greater than or equal to 0. 1 ≦ a + b ≦ 4, 1 ≦ d + e ≦ 4, A ≦ g + h ≦ 4.)