JP3405645B2 - Polyazole precursor composition, method for producing electronic component, and electronic component - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to various insulating members,
A protective film member, a polyazole precursor composition such as polyoxazole, polythiazole, polyimidazole, and polyoxadiazole, which is preferably used for forming a liquid crystal alignment film, and a polyazole resin obtained by curing the polyazole precursor composition. The present invention relates to an electronic component provided as an insulating film, a protective film, a liquid crystal alignment film, and a manufacturing method thereof.

[0002]

2. Description of the Related Art In recent years, electric appliances and electronic appliances tend to have larger capacities, smaller and lighter weights, higher reliability, and higher density, and accordingly, heat resistance as a material for multilayer substrates. Therefore, there is a demand for an organic polymer material which has high reliability, excellent through-hole adhesion reliability, dimensional stability, electrical characteristics, and flexibility. As a resin with excellent heat resistance, flexibility, and electrical characteristics,
Attention has been paid to polyazole resins such as polyoxazole, polythiazole, polyimidazole and polyoxadiazole. However, since the polyazole resin generally has a high glass transition temperature and is difficult to melt, and has a problem in workability such as low solubility in a solvent, when it is used as an insulating film or a protective film of an electric / electronic element, conventionally,
A precursor (polyamide or polyhydrazide) is applied onto a substrate, and the resulting coating film is heated under reduced pressure at a high temperature (250 to
By heating at 400 ° C. for a long time (3 to 30 hours), dehydration and cyclization is performed to form a polyazole film.

As described above, in order to cure the polyazole precursor to obtain the polyazole resin film, the polyazole film must be heated at an extremely high temperature, and the polyazole film cannot be used as an insulating film of a heat-sensitive electronic element or the like. . In addition, large-scale manufacturing equipment is required for decompression and heating,
In addition, there is a drawback that productivity is extremely low.

[0004]

As described above, although a polyazole film has excellent properties as an insulating film, a protective film, a liquid crystal alignment film, etc. for electronic parts, a precursor such as polyamide or polyhydrazide is used. In order to dehydrate and cyclize, it has conventionally been necessary to perform heat treatment at an extremely high temperature,
There were various problems associated with this.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a polyazole precursor composition capable of forming a polyazole film by heat treatment at a low temperature. Using this polyazole precursor composition, a polyazole film having no dielectric properties on the surface of a silicon substrate, a glass substrate, or the like and having excellent dielectric constant characteristics, moisture resistance, and environmental stability is used as an insulating member, a protective film member, or a heat-resistant structure. An object of the present invention is to provide an electronic component which is provided as a member or a liquid crystal alignment film member and which can realize high-speed operation and power saving and has high reliability.

[0006]

In order to solve the above-mentioned problems, the present invention provides a polyazole precursor having a repeating unit represented by the following general formula (1) with an acid dissociation index pKa of 0 to 0 in an aqueous solution. A substituted or unsubstituted nitrogen-containing heterocyclic compound (A1) which is 8, an amino acid compound and an N-acyl amino acid compound (A2), and a carboxyl group,
At least an aminocarbonyl group, a sulfonic acid group, an aminosulfonyl group, an acyl group, a carboxyalkyl group, a sulfoalkyl group, a hydroxyl group, a mercapto group, a substituted or unsubstituted amino group, and a substituted or unsubstituted aminoalkyl group. At least one curing accelerator selected from the group consisting of aromatic hydrocarbon compounds (A3) having two substituents introduced is used in an amount of 0.1 molar equivalent or more per 1 molar equivalent of the repeating unit of the polyazole precursor. Provided is a polyazole precursor composition characterized by being blended.

[0007]

[Chemical 3] (In the general formula (1), X is a tetravalent organic group, Y is a divalent organic group, R ¹ and R ² may be the same or different, and each is a hydroxy group or a mercapto group. , An amino group or a monosubstituted amino group.)

Further, according to the present invention, the solution of the above-mentioned polyazole precursor composition is applied to the surface of the substrate and heated at 100 to 300 ° C. in the atmosphere or an inert gas atmosphere to cure the polyazole precursor. Provided is a method for manufacturing an electronic component, which comprises depositing a polyazole resin film on the surface of a substrate.

Further, the present invention provides a polyazole resin film obtained by curing the above-mentioned polyazole precursor as an insulating member,
Provided is an electronic component comprising a protective film member or a liquid crystal alignment film.

The present invention will be described in detail below. The polyazole precursor used in the present invention is the polyamide represented by the general formula (1) or the polyhydrazide represented by the general formula (2). In the polyamide represented by the general formula (1), the tetravalent organic group X is an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group,
Aromatic hydrocarbon group and heterocyclic group, and polycyclic compound in which aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or heterocyclic group are directly or cross-linked with each other Selected from the group.

Specifically, as the tetravalent organic group X, for example, benzene, naphthalene, anthracene, naphthacene, pentacene, hexacene, perylene, biphenyl,
Terphenyl, quaterphenyl, kinkphenyl, sexiphenyl, diphenylmethane, diphenylethane,
Diphenylpropane, diphenylbutane, diphenylpentane, diphenyldifluoromethane, diphenyltetrafluoroethane, diphenylhexafluoropropane, diphenyloctafluorobutane, diphenyldecafluoropentane, diphenylether, diphenylsulfide, diphenylsulfone, benzophenone, diphenyldimethylsilane, diphenyltetramethyl Disiloxane, bis (phenylmethyl) benzene, bis (phenylethyl) benzene, bis (phenylpropyl) benzene, diphenoxybenzene, bis (phenylthio) benzene, bis (phenylsulfonyl) benzene, diphenoxybiphenyl, bis (phenoxyphenyl) Methane, bis (phenoxyphenyl) ethane, bis (phenoxyphenyl) propa , Bis (phenoxyphenyl)
Difluoromethane, bis (phenoxyphenyl) tetrafluoroethane, bis (phenoxyphenyl) hexafluoropropane, bis (phenoxyphenyl) ether, bis (phenoxyphenyl) sulfide, bis (phenoxyphenyl) sulfone, bis (phenylpropylphenyl) ether, Bis (phenylhexafluoropropylphenyl) ether, bis (phenylpropylphenyl) sulfone, bis (phenylhexafluoropropylphenyl) sulfone, bis (phenoxyphenyl)
Dimethylsilane, bis (phenoxyphenyl) tetramethyldisiloxane, methane, ethane, propane, butane, pentane, dimethyl ether, diethyl ether,
Dipropyl ether, dibutyl ether, dipentyl ether, dialkyl permethyl polysiloxane, ethylene, cyclopentane, cyclohexane, bicyclohexyl, dicyclohexyl ketone, dicyclohexyl ether, dicyclohexylmethane, dicyclohexylethane, dicyclohexylpropane, dicyclohexyldifluoromethane, dicyclohexyltetrafluoroethane, Dicyclohexyl hexafluoropropane, 9-phenyl-9- (trifluoromethyl) xanthene, 9,
9-bis (trifluoromethyl) xanthene, bicyclo [2,2,2] oct-7-ene, pyridine, pyridazine, pyrimidine, pyrazine, triazine, quinoline, imidazole, pyrazole, thiazole, oxazole,
Examples thereof include a tetravalent organic group obtained by extracting four hydrogen atoms from a compound such as thiadiazole and oxadiazole. The tetravalent organic group as described above may be substituted with a characteristic group such as an alkyl group, a halogen group, and a polyfluoroalkyl group.

From the viewpoint of heat resistance and environmental resistance, X is benzene, naphthalene, anthracene, perylene, biphenyl, terphenyl, quaterphenyl, kinkphenyl, diphenylmethane, diphenylpropane, diphenylhexafluoropropane. , Diphenyl ether, diphenyl sulfone, benzophenone, diphenyltetramethyldisiloxane, bis (phenylpropyl) benzene, diphenoxybenzene, diphenoxybiphenyl, bis (phenoxyphenyl) propane, bis (phenoxyphenyl) hexafluoropropane, bis (phenoxyphenyl) A tetravalent organic group obtained by extracting four hydrogen atoms from a compound such as ether and bis (phenoxyphenyl) sulfone is particularly preferable.

The divalent organic groups Y and Z in the polyamide represented by the general formula (1) and the polyhydrazide represented by the general formula (2) have 1 to 30 carbon atoms.
An aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and a heterocyclic group, and an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group directly or It is a divalent organic group selected from the group consisting of polycyclic compounds interconnected by a bridging group.

Specifically, as the divalent organic groups Y and Z, for example, benzene, naphthalene, anthracene, naphthacene, pentacene, hexacene, perylene, biphenyl, terphenyl, quaterphenyl, kinkphenyl, sexiphenyl, diphenylmethane, Diphenylethane, diphenylpropane, diphenylbutane, diphenylpentane, diphenyldifluoromethane, diphenyltetrafluoroethane, diphenylhexafluoropropane, diphenyloctafluorobutane, diphenyldecafluoropentane, diphenylether, diphenylsulfide, diphenylsulfone, benzophenone,
Diphenyldimethylsilane, diphenyltetramethyldisiloxane, bis (phenylmethyl) benzene, bis (phenylethyl) benzene, bis (phenylpropyl) benzene, diphenoxybenzene, bis (phenylthio) benzene, bis (phenylsulfonyl) benzene, diphenoxy Biphenyl, bis (phenoxyphenyl) methane, bis (phenoxyphenyl) ethane, bis (phenoxyphenyl) propane, bis (phenoxyphenyl) difluoromethane, bis (phenoxyphenyl) tetrafluoroethane, bis (phenoxyphenyl) hexafluoropropane, bis (Phenoxyphenyl) ether, bis (phenoxyphenyl) sulfide, bis (phenoxyphenyl) sulfone, bis (phenylpropylphenyl) ether , Bis (phenylhexafluoropropylphenyl) ether, bis (phenylpropylphenyl) sulfone, bis (phenylhexafluoropropylphenyl) sulfone, bis (phenoxyphenyl) dimethylsilane, bis (phenoxyphenyl) tetramethyldisiloxane, methane, ethane , Propane, butane, pentane, dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, dipentyl ether, dialkyl permethyl polysiloxane, ethylene, cyclopentane, cyclohexane, bicyclohexyl, dicyclohexyl ketone, dicyclohexyl ether, dicyclohexyl methane, dicyclohexyl ethane, Dicyclohexyl propane, dicyclohexyl difluoromethane, dicyclohexyl tetra Ruoroetan, dicyclohexyl hexafluoropropane,
9-phenyl-9- (trifluoromethyl) xanthene, 9,9-bis (trifluoromethyl) xanthene,
Bicyclo [2,2,2] oct-7-ene, pyridine,
Examples thereof include divalent organic groups obtained by extracting two hydrogen atoms from a compound such as pyridazine, pyrimidine, pyrazine, triazine, quinoline, imidazole, pyrazole, thiazole, oxazole, oxadiazole, and thiadiazole. The divalent organic group as described above may be substituted with a characteristic group such as an alkyl group, a halogen group, and a polyfluoroalkyl group.

From the viewpoint of heat resistance and environmental stability, Y and Z are benzene, naphthalene, anthracene, perylene, biphenyl, terphenyl, quaterphenyl, kinkphenyl, diphenylmethane, diphenylpropane, diphenylhexa. Fluoropropane, diphenyl ether, diphenyl sulfone, benzophenone, diphenyltetramethyldisiloxane, bis (phenylpropyl) benzene, diphenoxybenzene, diphenoxybiphenyl, bis (phenoxyphenyl) propane, bis (phenoxyphenyl) hexafluoropropane, bis (phenoxy) A divalent organic group obtained by extracting two hydrogen atoms from a compound such as phenyl) ether and bis (phenoxyphenyl) sulfone is particularly preferable.

R ¹ and R ² in the above general formula (1)
Are the same or different and each is a monosubstituted amino group substituted with a hydroxyl group, a mercapto group, an amino group, an alkyl group, an aryl group or the like.

The polyamide and polyhydrazide as described above have an intrinsic viscosity of 0.5 (dL) of a 0.5 wt% N-methyl-2-pyrrolidone solution at 30 ° C.
/ G) or more, further 0.3 (dL / g) or more 2.0
It is preferably (dL / g) or less. The reason for this is
Either polymer has an intrinsic viscosity that is too low, that is, if the degree of polymerization is too low, it may not be possible to obtain a highly heat-resistant polyazole, while the intrinsic viscosity is too high, that is, if the degree of polymerization is too high. Is difficult to handle.

The polyamide and the polyhydrazide may be used alone or in combination of two or more kinds. In preparing the polyazole precursor composition, these polyazole precursors are dissolved in an organic solvent in advance to prepare a polyamide solution. Alternatively, prepare a polyhydrazide solution.

The organic solvent used here is, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide,
N, N-dimethoxyacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone,
M-methylcaprolactam, 1,2-dimethoxyethane, 1,2-diethoxyethane, bis (2-methoxyethyl) ether, bis (2-ethoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane Bis [2- (2-methoxyethoxy) ethyl] ether,
1-acetoxy-2-methoxyethane, 1-acetoxy-2-ethoxyethane, (2-acetoxyethyl) (2
-Methoxyethyl) ether, (2-acetoxyethyl) (2-ethoxyethyl) ether, methyl 3-methoxypropionate, tetrahydrofuran, 1,3-dioxane, 1,3-dioxolane, 1.4-dioxane,
Pyroline, pyridine, picoline, dimethyl sulfoxide, sulfolane, γ-butyrolactone, propylene carbonate, phenol, cresol, cyclohexanone, acetonylacetone and the like can be mentioned. These organic solvents may be used alone or in combination of two or more.

(A1) used in the present invention,
The organic compounds selected from (A2) and (A3) are both low-temperature curing accelerators having an action of promoting the curing reaction of polyamide or polyhydrazide at low temperatures.

First, the substituted or unsubstituted nitrogen-containing heterocyclic compound (A1) having an acid dissociation index pKa in an aqueous solution of 0 to 8 which is used as a curing accelerator in the present invention will be described. Here, the acid dissociation index pKa is the logarithm of the reciprocal of the acid dissociation constant Ka. The nitrogen-containing heterocyclic compound used as the low temperature curing accelerator in the present invention has an acid dissociation index of 0 to 8, more preferably 2.5 to 6. The reason for this is that if the acid dissociation index of the nitrogen-containing heterocyclic compound is too small, it is difficult to sufficiently accelerate the curing reaction of the polyamide or polyhydrazide at low temperatures, and conversely, if the acid dissociation index is too large, the polyamide solution or poly This is because the gelation of the hydrazide solution is likely to proceed and the storage stability of the polyazole precursor composition tends to decrease.

Examples of the unsubstituted nitrogen-containing heterocyclic compound contained in (A1) include imidazole, pyrazole, triazole, tetrazole, benzimidazole, indazole, benzotriazole, purine, imidazoline, pyrazoline, pyridine, quinoline, isoquinoline,
Dipyridyl, diquinolyl, pyridazine, pyrimidine, pyrazine, phthalazine, quinoxaline, quinazoline, cinnoline, naphthyridine, acridine, phenanthridine, benzoquinoline, phenanthroline, phenazine,
Triazine, tetrazine, pteridine, oxazole,
Examples thereof include benzoxazole, isoxazole, benzisoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, oxadiazole, thiadiazole, triethylenediamine and hexamethylenetetramine.

Examples of the substituent introduced into these nitrogen-containing heterocyclic compounds to form the substituted nitrogen-containing heterocyclic compound include di-substituted amino (dimethylamino group, diethylamino group, dibutylamino group, ethylmethylamino group, butyl). Methylamino group, diamylamino group, dibenzylamino group, diphenethylamino group, diphenylamino group, ditolylamino group, dixylylamino group, methylphenylamino group, benzylmethylamino group, etc., mono-substituted amino group (methylamino group, Ethylamino group, propylamino group, isopropylamino group, tert-butylamino group, anilino group, anisidino group, phenetidino group, toluidino group, xylidino group, pyridylamino group, thiazolylamino group, benzylamino group, benzylideneamino group, etc., cyclic Ami Group (pyrrolidino group, piperidino group,
Piperazino group, morpholino group, 1-pyrrolyl group, 1-pyrazolyl group, 1-imidazolyl group, 1-triazolyl group, etc., acylamino group (formylamino group, acetylamino group, benzoylamino group, cinnamoylamino group, pyridinecarbonyl) Amino group, trifluoroacetylamino group, etc., sulfonylamino group (mesylamino group, ethylsulfonylamino group, phenylsulfonylamino group, pyridylsulfonylamino group, tosylamino group, taurylamino group, trifluoromethylsulfonylamino group, sulfamoylamino group Groups, methylsulfamoylamino groups, sulfanylamino groups, acetylsulfanylamino groups, etc.), amino groups, hydroxyamino groups, ureido groups, semicarbazide groups, carbazide groups, disubstituted hydrazino groups (dimes Luhydrazino group, diphenylhydrazino group, methylphenylhydrazino group, etc.), mono-substituted hydrazino group (methylhydrazino group, phenylhydrazino group, pyridylhydrazino group, benzylidenehydrazino group, etc.), hydrazino group, amidino group, hydroxyl Group, oxime group (hydroxyiminomethyl group, methoxyiminomethyl group, ethoxyiminomethyl group, hydroxyiminoethyl group, hydroxyiminopropyl group, etc.), alkoxyalkyl group (hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, etc.), Cyano group, cyanato group, thiocyanato group, nitro group, nitroso group, oxy group (methoxy group, ethoxy group, propoxy group, butoxy group, hydroxyethoxy group, phenoxy group, naphthoxy group, pyridyloxy group, thiazo Luoxy group, acetoxy group, etc.), thio group (methylthio group, ethylthio group, phenylthio group, pyridylthio group, thiazolylthio group, etc.), mercapto group, halogen group (fluoro group, chloro group, bromo group, iodo group), carboxyl group and Salts, oxycarbonyl groups (methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, pyridyloxycarbonyl group, etc.), aminocarbonyl groups (carbamoyl group, methylcarbamoyl group, phenylcarbamoyl group, pyridylcarbamoyl group, carbazoyl group, allofanoyl group , Oxamoyl group, succiamoyl group, etc.), thiocarboxyl group and its salt, dithiocarboxyl group and its salt, thiocarbonyl group (methoxythiocarbonyl group, methylthiocarbonyl group, methyl Thiothiocarbonyl group etc.), acyl group (formyl group, acetyl group, propionyl group, acryloyl group, benzoyl group, cinnamoyl group, pyridine carbonyl group, thiazole carbonyl group, trifluoroacetyl group etc.), thioacyl group (thioformyl group, thioacetyl Group, thiobenzoyl group, pyridinethiocarbonyl group, etc.), sulfinic acid group and its salt, sulfonic acid group and its salt, sulfinyl group (methylsulfinyl group, ethylsulfinyl group, phenylsulfinyl group, etc.), sulfonyl group (mesyl group, Ethylsulfonyl group,
Phenylsulfonyl group, pyridylsulfonyl group, tosyl group, tauryl group, trifluoromethylsulfonyl group, sulfamoyl group, methylsulfamoyl group, sulfanilyl group, acetylsulfanylyl group, etc., oxysulfonyl group (methoxysulfonyl group, ethoxysulfonyl) Group, phenoxysulfonyl group, acetaminophenoxysulfonyl group, pyridyloxysulfonyl group, etc.), thiosulfonyl group (methylthiosulfonyl group, ethylthiosulfonyl group, phenylthiosulfonyl group, acetaminophenylthiosulfonyl group, pyridylthiosulfonyl group, etc.) , Aminosulfonyl group (sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, phenylsulfamoyl group Group, acetaminophenylsulfamoyl group, pyridylsulfamoyl group, etc.), ammonio group (trimethylammonio group, ethyldimethylammonio group, dimethylphenylammonio group, pyridinio group, quinolinio group, etc.), azo group ( Phenylazo group, pyridylazo group, thiazolylazo group, etc.), azoxy group,
Halogenated alkyl group (chloromethyl group, bromomethyl group, fluoromethyl group, dichloromethyl group, dibromomethyl group, difluoromethyl group, trifluoromethyl group,
Pentafluoroethyl group, heptafluoropropyl group, etc.), hydrocarbon group (alkyl group, aryl group, alkenyl group, alkynyl group, etc.), heterocyclic group, organosilicon group (silyl group, disilanyl group, trimethylsilyl group, triphenylsilyl group) Groups and the like). Among these, hydroxyl group, oxy group, oxime group, aminocarbonyl group, alkoxyalkyl group, disubstituted amino group, monosubstituted amino group, cyclic amino group, acylamino group, amino group, ureido group, mercapto group, thio group. Groups are particularly desirable.

Next, the amino acid compound or N-acyl amino acid compound (A2) used as the curing accelerator in the present invention will be explained. Examples of the amino acid compound contained in (A2) include glycine, sarcosine, dimethylglycine, betaine, alanine, β-alanine,
α-aminobutyric acid, β-aminobutyric acid, γ-aminobutyric acid, γ
-Amino-β-oxobutyric acid, valine, β-aminoisovaleric acid, γ-aminoisovaleric acid, norvaline, β-aminovaleric acid, γ-aminovaleric acid, δ-aminovaleric acid, leucine, isoleucine, norleucine, serine, α-methylserine, isoserine, α-methylisoserine, cycloserine, threonine, o-methylthreonine, alothreonine, o-methylalothreonine, roseonine, trans-3-aminocyclohexanecarboxylic acid, cis-3-
Aminocyclohexanecarboxylic acid, ε-aminecaproic acid, ω-aminododecanoic acid, β-hydroxyvaline, β
-Hydroxyisoleucine, α-hydroxy-β-aminoisovaleric acid, ε-diazo-δ-oxonorleucine,
α-amino-ε-hydroxyaminocaproic acid, cysteine, cystine, S-methylcysteine, S-methylcysteine sulfoxide, cysteic acid, homocysteine, homocystine, methionine, penicillamine, taurine, α, β-diaminopropionic acid, ornithine, lysine , Arginine, kanaline, canavanine, δ-hydroxylysine, aspartic acid, asparagine, isoasparagine, glutamic acid, glutamine, isoglutamine,
α-methylglutamic acid, β-hydroxyglutamic acid, γ-hydroxyglutamic acid, α-aminoadipic acid, citrulline, cystathionine, phenylalanine,
α-methylphenylalanine, o-chlorophenylalanine, m-chlorophenylalanine, p-chlorophenylalanine, o-fluorophenylalanine, m-fluorophenylalanine, p-fluorophenylalanine, β- (2-pyridyl) alanine, tyrosine, dichlorotyrosine, dibromo Thiocin, diiodotyrosine,
3,4-dihydroxyphenylalanine, α-methyl-
Examples include 3,4-dihydroxyphenylalanine, phenylglycine, anilinoacetic acid, 2-pyridylglycine, tryptophan, histidine, 1-methylhistidine, 2-thiolhistidine, proline and hydroxyproline.

The N-acyl amino acid compound contained in (A2) is obtained by substituting the amino group of the above amino acid compound with an acyl group. Examples of the acyl group introduced into the N-acylamino acid compound include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristoyl group, palmitoyl group, stearoyl group. , Acryloyl group, propioloyl group, methacryloyl group, crotonoyl group, isocrotonoyl group, oleoyl group, cyclopentanecarbonyl group, cyclohexanecarbonyl group, benzoyl group, naphthoyl group, toluoyl group, hydroatropoyl group, atropoyl group, cinnamoyl group, Furoyl group, thenoyl group, picolinoyl group, nicotinoyl group, isonicotinoyl group, quinolinecarbonyl group, pyridazinecarbonyl group, pyrimidinecarbonyl group, pyrazinecarbonyl group, imidazole Rubonyl group, benzimidazole carbonyl group, thiazole carbonyl group, benzothiazole carbonyl group, oxazole carbonyl group, benzoxazole carbonyl group, oxalyl group, malonyl group, succinyl group, glutaryl group, adipoyl group, pimeloyl group, suberoyl group, azela oil group, Sebacoyl group, maleoyl group, fumaroyl group, citraconoyl group, mesaconoyl group, mesooxalyl group, oxalacetyl group, camphoroyl group, phthaloyl group, isophthaloyl group, terephthaloyl group, oxalo group, methoxalyl group, ethoxalyl group, glyoxyloyl group, pyruvoyl Group, acetoacetyl group, mesoxalo group, oxalaceto group, cysteinyl group, homocysteinyl group, tryptophyll group, alanyl group, β-alanyl group, arginyl group Group, cystathionyl group, cystyl group, glycyl group, histidyl group, homoseryl group, isoleucyl group, lanthionyl group, leucyl group, lysyl group, methionyl group, norleucyl group, norvalyl group, ornithyl group,
Prolyl group, sarcosyl group, ceryl group, threonyl group,
Examples thereof include tyronyl group, tyrosyl group and valyl group.

Next, the aromatic hydrocarbon compound (A3) substituted with at least two specific substituents, which is used as the curing accelerator in the present invention, will be described. Examples of the aromatic hydrocarbon compound contained in (A3) include benzene, naphthalene, anthracene, phenanthrene, tetralin, azulene, biphenylene,
Acenaphthylene, acenaphthene, fluorene, triphenylene, pyrene, chrysene, picene, perylene, benzopyrene, rubisene, coronene, ovalen, indene, pentalene, heptalen, indacene, phenalene, fluoranthene, acephenanthrylene, aceanthrylene, naphthacene, pleiaden, Pentaphene, pentacene, tetraphenylene, hexaphene, hexacene,
Trinaphthylene, heptaphene, heptacene, pyrantrene, biphenyl, terphenyl, quaterphenyl,
Examples include kink phenyl and sexiphenyl.

In addition to the aromatic hydrocarbon compounds described above,
Carboxyl group, aminocarbonyl group, sulfonic acid group,
The same or different selected from the group consisting of an aminosulfonyl group, an acyl group, a carboxyalkyl group, a sulfoalkyl group, a hydroxyl group, a mercapto group, a substituted or unsubstituted amino group, and a substituted or unsubstituted aminoalkyl group, The curing accelerator (A3) is constituted by introducing at least two substituents which are In terms of curing acceleration effect, aromatic hydrocarbon compounds such as benzene, naphthalene, and biphenyl may be substituted with one substituent selected from a carboxyl group, a sulfonic acid group, a carboxyalkyl group, an acyl group, and a sulfoalkyl group, Further, a disubstituted aromatic hydrocarbon compound having a substituent selected from a hydroxyl group, a mercapto group, a substituted or unsubstituted amino group, and a substituted or unsubstituted aminoalkyl group is particularly preferable.

The above-mentioned low temperature curing accelerators (A1) to (A3) may be used alone or in combination of two or more. It is preferable that the above-mentioned low temperature curing accelerator has a low vaporization point (boiling point, sublimation point or decomposition point), and has a good curing acceleration effect and good solubility in a polyamide solution or a polyhydrazide solution. From this point of view, particularly preferable low temperature curing accelerators include imidazole, 1,2,
4-triazole, benzimidazole, purine, quinoline, isoquinoline, pyridazine, phthalazine, quinazoline, cinnoline, naphthyridine, acridine, phenanthridine, benzoquinoline, phenanthroline, phenazine, 2,2'-dipyridyl, 2,4'-dipyridyl, 4,4'-dipyridyl, 2,2'-diquinolyl, 2
-Hydroxypyridine, 3-hydroxypyridine, 4-
Hydroxypyridine, 8-hydroxyquinoline, picolinic acid amide, nicotinic acid amide, isonicotinic acid amide, hydroxynicotinic acid, picolinic acid ester, nicotinic acid ester, isonicotinic acid ester, 2-cyanopyridine, 3-cyanopyridine, 4- Cyanopyridine,
Picolinaldehyde, nicotinaldehyde, isonicotinaldehyde, 3-nitropyridine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-
(Hydroxymethyl) pyridine, 3- (hydroxymethyl) pyridine, 4- (hydroxymethyl) pyridine, 2
-(Hydroxyethyl) pyridine, 3- (hydroxyethyl) pyridine, 4- (hydroxyethyl) pyridine,
Picoline aldoxime, nicotine aldoxime, isonicotine aldoxime, hydantoin, histidine, uracil, barbituric acid, dialuric acid, cytosine, anilinoacetic acid, 2-pyridylglycine, tryptophan, proline, N-acetylglycine, hippuric acid, N- Picolinoylglycine, N-nicotinoylglycine, N-isonicotinoylglycine, N-acetylalanine, N-benzoylalanine, N-picolinoylalanine, N-nicotinoylalanine, N-isonicotinoylalanine, α-
(Acetylamino) butyric acid, α- (benzoylamino) butyric acid, α- (picolinoylamino) butyric acid, α- (nicotinoylamino) butyric acid, α- (isonicotinoylamino) butyric acid, N-acetylvaline, N-benzoyl Valine, N-
Picolinoyl valine, N-nicotinoyl valine, N-isonicotinoyl valine, 2-hydroxybenzoic acid, 3-
Hydroxybenzoic acid, 4-hydroxybenzoic acid, 2,4
-Dihydroxybenzoic acid, (2-hydroxyphenyl)
Acetic acid, (3-hydroxyphenyl) acetic acid, (4-hydroxyphenyl) acetic acid, 3- (4-hydroxyphenyl)
Propionic acid, 2- (4-hydroxyphenyl) isovaleric acid, 2-phenolsulfonic acid, 3-phenolsulfonic acid, 4-phenolsulfonic acid, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-amino Benzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-hydroxybenzaldehyde, 3-
Examples thereof include hydroxybenzaldehyde and 4-hydroxybenzaldehyde.

These low-temperature curing accelerators are used in an amount of 0.1 molar equivalent or more, preferably 1 to 4 molar equivalents, and most preferably 1.5 to 2.5 molar equivalents per 1 molar equivalent of the repeating unit of the polyazole precursor. Used in the range of. The reason for this is that when the amount of the low-temperature curing accelerator is too small, a good polyazole cannot be obtained because of insufficient cyclization of the polyazole in the low-temperature heat treatment, and when the amount of the low-temperature curing accelerator is too large. This is because the storage stability of the polyazole precursor composition may be poor, and the residual amount of the low temperature curing accelerator after heat curing may be large, which may adversely affect various properties.

The polyazole precursor composition of the present invention comprises, for example, a solution obtained by dissolving the above-mentioned polyazole precursor in an organic solvent and adding at least one curing accelerator of (A1) to (A3). It can be prepared by adding.

In the present invention, in order to manufacture an electronic component, a solution of the above-mentioned polyazole precursor composition is applied on the surface of a substrate, and the temperature is 100 to 300 ° C., preferably 150 to 300, in the air or an inert gas atmosphere. Heating in the temperature range of ℃ (direct heating) or 60 to 250 ℃
After heating (prebaking) in the temperature range of 100 to 250
The polyazole precursor composition is cured by heating in vacuum at 0 ° C. to deposit the polyazole resin film on the substrate surface. As for the heating time, 5 minutes to 3 hours is sufficient, though it depends on the types of polyamide and polyhydrazide and the curing accelerator used, the heating temperature, the film thickness, and the like. This heat treatment volatilizes the solvent component remaining in the coating film, changes the azole structure to the azole structure by cyclization of the polyazole precursor, and further volatilizes, sublimates and decomposes the low temperature curing accelerator to volatilize the polyazole film. Is formed.

Compared with the case where the conventional polyazole precursor solution was used for heat curing at about 300 ° C. or higher, in the present invention, heat curing at a low temperature of 200 ° C. or lower in many cases is preferable. A polyazole film having physical properties can be obtained. The heat curing temperature can be appropriately selected according to the application of polyazole. For example, the heating temperature or vacuum heating temperature is set relatively high in applications where the curing accelerator does not remain well, but 150 ° C or less in applications where the curing accelerator does not have much effect, such as in a liquid crystal alignment film. It may be heat-cured at a relatively low temperature.

The polyazole film obtained by curing the polyazole precursor composition of the present invention is used for various electronic parts such as semiconductor devices, high density printed wiring boards, thin film magnetic heads,
It can be applied to a magnetic bubble memory, a solar cell, and a thermal head as a protective film such as an interlayer insulating film between conductors or semiconductors, a passivation film, and a high heat resistant coating film. In this case, since the polyazole film is formed using the solution of the polyazole precursor composition, the surface can be flattened after the wiring of the electronic component is formed. Also, since the heat curing temperature is low,
For example, it can be applied to an electronic element such as a plastic substrate or a glass substrate which is weak against heat, and can prevent thermal stress from being generated in an electronic component. Therefore, in addition to the heat resistance, flexibility, and electric characteristics of the polyazole itself, the reliability of the electronic component can be improved.

The polyazole film obtained by curing the polyazole precursor composition of the present invention has electrodes and a liquid crystal alignment film formed on the surfaces of a pair of transparent substrates, respectively, and the liquid crystal alignment film is placed inside to face each other. It can be applied as a liquid crystal alignment film in a liquid crystal element in which liquid crystal is sealed in the gap. In this case as well, the heat curing temperature can be made much lower than in the past, so that the deterioration of display characteristics can be suppressed.

[0035]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples. (1) Preparation of Polyazole Precursor Composition First, the polyamide solution and the polyhydrazide solution shown in Tables 1 and 2 were dissolved in N, N-dimethylacetamide (DMAC) as a solvent to prepare 6 kinds of varnish (PA).
Z1), (PAZ2), (PAZ3), (PAZ4),
(PAZ5) and (PAZ6) were obtained.

[0036]

[Table 1]

[0037]

[Table 2]

Next, as shown in Tables 3 to 5, a curing accelerator was added at a predetermined compounding ratio to prepare polyazole precursor composition solutions of Examples (1 to 30). In addition, Tables 3-5
In the above, the addition amount is shown as a molar equivalent to 1 molar equivalent of the polyamide and the polyhydrazide repeating unit.

For comparison, as shown in Table 6, a polyamide solution and a polyhydrazide solution (varnish) containing no curing accelerator were prepared. Here, Tables 3 to 6
The abbreviations of the curing accelerators described in 1 above indicate the following compounds. BIM: benzimidazole IQN: isoquinoline INA: isonicotinic acid amide PNT: 1,10-phenanthroline 4HP: 4-hydroxypyridine AGL: N-acetylglycine BGL: hippuric acid 3HB: 3-hydroxybenzoic acid 4HA: 4-hydroxyphenylacetic acid (2) Formation of polyazole film and measurement of physical properties Tables 3 to 6 show the results of forming a polyazole film and measuring the azole formation rate as follows.

A polyazole precursor composition solution was applied onto a 2 cm square silicon wafer by a spin coating method so that the film thickness after curing would be 0.5 to 2 μm, and then on a hot plate at 80 ° C. for 10 minutes. Prebaked for a minute. Then, the polyazole film was formed by heating on another hot plate at 150 ° C. for 1 hour. The IR spectrum of each obtained polyazole film was measured.

On the other hand, each polyazole precursor varnish to which no curing accelerator was added was applied to the same film thickness as above, and 8
After prebaking at 0 ° C. for 10 minutes, it was heat-cured in vacuum at 300 ° C. for 5 hours to form a polyazole film. The azotization rates of the polyazole films of the present invention and the comparative examples were shown as relative ratios, with the azotization rate of each of the polyazole films thus obtained as 100%.

[0042]

[Table 3]

[0043]

[Table 4]

[0044]

[Table 5]

[0045]

[Table 6]

Comparing the azotization rates in Tables 3 to 6,
In the polyazole precursor varnishes of Comparative Examples 1 to 6 to which the curing accelerator was not added, the azole formation rate was 10% or less. On the other hand, in the polyazole precursor composition of the present invention (Examples 1 to 30), the azole conversion rate is almost 100%. As described above, the polyazole precursor composition solution of the present invention has excellent low temperature curing characteristics.

The polyazole film obtained by curing the polyazole precursor composition of the present invention by heating at low temperature as described above is a polyazole original property such as heat resistance, flexibility and electrical characteristics. It was confirmed by the dielectric constant measurement and the thermal property (TG / DTA) measurement.

Further, a polyazole film obtained by curing the polyazole precursor composition of the present invention is used, and FIGS.
The various electronic components and liquid crystal display elements shown in Figure 3 were prototyped.
FIG. 1 is a cross-sectional view of a semiconductor device having a multilayer wiring structure having an interlayer insulating film made of a polyazole film according to the present invention. Here, using the polyazole precursor composition of Example 11,
After prebaking at 80 ° C. for 10 minutes, heating at 180 ° C. for 1 hour to cure the polyazole film was used as an interlayer insulating film.

In FIG. 1, a thermal oxide film 12 is formed on the surface of the silicon substrate 11. A contact hole is opened in a part of the thermal oxide film 12, and a first layer A is formed on the contact hole.
The l wiring 13 is formed. An interlayer insulating film 14 made of a polyazole film is formed on the Al wiring 13. A contact hole is opened in a part of the interlayer insulating film 14, and a second-layer Al wiring 15 connected to the first-layer Al wiring 13 is formed thereon. This Al wiring 15
An interlayer insulating film 16 made of a polyazole film is further formed thereon.

Since the above-mentioned interlayer insulating film 14 is formed by spin-coating the polyazole precursor composition solution and then hardening it, the step A on the surface is alleviated and the multi-layered A film is formed.
The l wiring can be formed, and a highly reliable wiring structure can be obtained. Also, if you select the appropriate monomer,
The polyazole film obtained from the polyazole precursor composition of the present invention exhibits low thermal expansion. Moreover, since it is cured by the low temperature curing process, the polyazole film can be formed in a temperature range where the thermal expansion is small. Therefore, the thermal stress applied to the semiconductor element can be reduced, and the occurrence of cracks in the element can be suppressed even when subjected to a heat cycle.

FIG. 2 is a sectional view of a semiconductor device having a passivation film made of a polyazole film according to the present invention. Here, the polyazole precursor composition of Example 3 was used, prebaked at 80 ° C. for 10 minutes, and then at 180 ° C. for 1 minute.
A polyazole film which was heated and cured for a period of time was used as a passivation film.

In FIG. 2, an n-type base region 22 and a p-type emitter region 23 are formed on the surface of the p-type silicon substrate 21.
Are formed to form a pnp-type transistor.
A thermal oxide film 24 is formed on the silicon substrate 21. A contact hole is opened in the thermal oxide film 24,
A base electrode 25 and an emitter electrode 26 made of Al are formed thereon. Further, a passivation film 27 made of a polyazole film is formed on the entire surface.

When the polyazole film obtained from the polyazole precursor composition of the present invention is used as the passivation film 27, a highly reliable semiconductor device can be obtained and there are few defects in the manufacturing process.

FIG. 3 is a sectional view of a thin film magnetic head having an interlayer insulating film made of a polyazole film according to the present invention.
Here, the polyazole precursor composition of Example 12 was used, prebaked at 80 ° C. for 10 minutes, and then at 180 ° C. for 1 minute.
A polyazole film which was heated and cured for a period of time was used as a passivation film.

In FIG. 3, the lower magnetic material 32 and the gap alumina 33 are sequentially formed on the lower alumina 31 provided on the surface of the AlTiC substrate 30. On the gap alumina 33, a first conductor coil 35 and a second conductor coil 36 are formed so as to be insulated from each other while being embedded in an interlayer insulating film 34 made of a polyazole film. Further, an upper magnetic body 37 is formed on the outermost layer, and the lower magnetic body 32 is sandwiched between the head end faces with the gap alumina 33 interposed therebetween.
And the upper magnetic body 37 is arranged.

Since the above-mentioned interlayer insulating film 34 is formed by spin-coating the polyazole precursor composition solution and then curing it, the step formed by the first and second conductor coils 35 and 36 is relaxed. In addition, the interlayer insulating film 34
Etching back is performed to flatten the film, but since the step is relaxed, the amount of etching back can be halved as compared with the conventional method, and the manufacturing process can be shortened, and the interlayer insulating film 34 can be shortened.
The film thickness accuracy of is also improved.

FIG. 4 is a sectional view of a multi-chip module having an interlayer insulating film made of a polyazole film according to the present invention. Here, the polyazole precursor composition of Example 7 was used, prebaked at 80 ° C. for 10 minutes, and then 180
A polyazole film that was heated and cured at 1 ° C. for 1 hour was used as an interlayer insulating film.

In FIG. 4, a thermal oxide film 42 is formed on a silicon substrate 41. On the thermal oxide film 42, a copper wiring 43 and an interlayer insulating film 4 made of a polyazole film are formed.
4, a copper wiring 45, and an interlayer insulating film 46 made of a polyazole film are sequentially formed. Further, a contact hole is opened in a part of the upper interlayer insulating film 46, and the copper wiring 4
Pb / Sn electrode 47 and BLM (Ball Li
A miting metallization) 48 is formed.

Since the above-mentioned interlayer insulating film 44 is formed by spin-coating the polyazole precursor composition solution and then hardening it, the step due to the copper wiring can be largely alleviated and flattened.
A highly reliable wiring structure can be obtained.

FIG. 5 is a sectional view of a liquid crystal display device having a liquid crystal alignment film made of a polyazole film according to the present invention. Here, using the polyazole precursor composition of Example 1, 8
A polyazole film which was prebaked at 0 ° C. for 10 minutes and then heated at 150 ° C. for 1 hour to be cured was used as an interlayer insulating film.

A pair of glass substrates 51 each have a transparent electrode 52 and a polyazole film having a thickness of 20 to 2 on the surface thereof.
A liquid crystal alignment film 53 having a thickness of about 00 nm is formed. The liquid crystal alignment film 53 is rubbed by a conventional method. Further, the pair of glass substrates 5 are arranged so that the liquid crystal alignment films 53 face each other.
1 are arranged at a predetermined interval, and a liquid crystal 54 is injected between the glass substrates 51, 51 to form a liquid crystal cell.

When the polyazole precursor composition of the present invention is used, the curing temperature (150 to 250 ° C.) is lower than the curing temperature (300 ° C. or higher) when the conventional polyazole precursor composition is used, It is possible to form the liquid crystal alignment film 53 having a high azole formation rate with a curing time of 0.5 to 10 hours, which is the same as the conventional one. Therefore, according to the present invention, it is possible to prevent the problem that the display function of the liquid crystal display device is deteriorated by the high temperature heat treatment.

[0063]

As described above in detail, the polyazole precursor composition of the present invention can be azole-ized at a low temperature of 100 to 250 ° C., and the polyazole film obtained by curing this can be a dielectric layer. Rate and hygroscopicity are low, and it is excellent in heat resistance and environmental stability (hygroscopic decomposition resistance). Furthermore, if the polyazole precursor composition of the present invention is used, it has an insulating film, a protective film or a liquid crystal alignment film made of polyazole having excellent dielectric constant characteristics, moisture resistance, heat resistance and environmental stability, and high-speed operation and Power saving can be realized,
Moreover, it is possible to provide highly reliable electronic components. In particular, I
C, LSI carrier frame, flat cable, flexible printed circuit board, LSI wiring insulation film, LSI
Moisture-resistant protective film, LSI α-ray blocking film, film insulating coil, semiconductor passivation film, metal core printed board with polyazole insulating film, thin film magnetic head interlayer insulating film, magnetic bubble memory device interlayer insulating film, glass cloth laminated plate It is also useful as a highly heat-resistant coating film for thermal heads and a liquid crystal alignment film for liquid crystal display devices.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of a semiconductor device having a multilayer wiring structure having an interlayer insulating film made of a polyazole film according to the present invention.

FIG. 2 is a cross-sectional view of a semiconductor device having a multilayer wiring structure having a passivation film made of a polyazole film according to the present invention.

FIG. 3 is a sectional view of a thin film magnetic head having an interlayer insulating film made of a polyazole film according to the present invention.

FIG. 4 is a cross-sectional view of a multi-chip module having an interlayer insulating film made of a polyazole film according to the present invention.

FIG. 5 is a sectional view of a liquid crystal display device having a liquid crystal alignment film made of a polyazole film according to the present invention.

[Explanation of symbols]

11 ... Silicon substrate 12 ... Thermal oxide film 13, 15 ... Al wiring 14, 16 ... Interlayer insulating film made of polyazole film 21 ... Silicon substrate 22 ... n-type base region 23 ... p-type emitter region 24 ... Thermal oxide film 25 ... Base electrode 26 ... Emitter electrode 27 ... Passivation film 30 ... Altic substrate 31 ... Lower alumina 32 ... Lower magnetic body 33 ... Gap alumina 34 ... Interlayer insulating film made of polyazole film 35 ... First conductor coil 36 ... Second conductor coil 37 ... Upper magnetic body 41 ... Silicon substrate 42 ... Thermal oxide film 43, 45 ... Copper wiring 44, 46 ... Interlayer insulating film made of polyazole film 47 ... Pb / Sn electrode 48 ... BLM (Ball Limiting Metallization) 51 ... Glass substrate 52 ... Transparent electrode 53 ... Liquid crystal alignment film composed of polyazole film 54 ... Liquid crystal

Claims (3)

(57) [Claims] 1. A substituted or unsubstituted nitrogen-containing heterocyclic compound (A1) having an acid dissociation index pKa in an aqueous solution of 0 to 8 with respect to a polyazole precursor having a repeating unit represented by the following general formula (1). An amino acid compound and an N-acyl amino acid compound (A2); and a carboxyl group,
At least an aminocarbonyl group, a sulfonic acid group, an aminosulfonyl group, an acyl group, a carboxyalkyl group, a sulfoalkyl group, a hydroxyl group, a mercapto group, a substituted or unsubstituted amino group, and a substituted or unsubstituted aminoalkyl group. At least one curing accelerator selected from the group consisting of aromatic hydrocarbon compounds (A3) having two substituents introduced is used in an amount of 0.1 molar equivalent or more per 1 molar equivalent of the repeating unit of the polyazole precursor. A polyazole precursor composition characterized by being blended. [Chemical 1] (In the general formula (1), X is a tetravalent organic group, Y is a divalent organic group, R ¹ and R ² may be the same or different, and each is a hydroxy group or a mercapto group. , An amino group or a monosubstituted amino group.) 2. A substrate is prepared by applying the polyazole precursor composition according to claim 1 on a substrate surface and heating the substrate at 100 to 300 ° C. in the atmosphere or an inert gas atmosphere to cure the polyazole precursor. A method for manufacturing an electronic component, which comprises depositing a polyazole resin film on the surface. 3. An electronic component comprising the polyazole resin film obtained by curing the polyazole precursor according to claim 1 as an insulating member, a protective film member or a liquid crystal alignment film.