JP2001264715A - Nonlinear optical material, method for manufacturing the same and nonlinear optical device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a nonlinear optical material having high heat resistance and excellent nonlinear optical characteristics. SOLUTION: The nonlinear optical material consists of a thin film containing polyimide, a nonlinear optical substance and a low-temperature curing accelerator. At least one kind selected from the group consisting of (AC1) a substituted or unsubstituted nitrogenous heterocyclic compound of 0 to 8 in acid dissociation index pKa of the proton complex in an aqueous solution, (AC2) a substituted or unsubstituted amino acid component and (AC3) an aromatic hydrocarbon compound or aromatic heterocyclic compound of a molecular weight of <=1,000 having at least >=2 pieces of hydroxy groups may be used as the low- temperature curing accelerator.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a nonlinear optical material,
The present invention relates to a manufacturing method thereof and a nonlinear optical device using the same.

[0002]

2. Description of the Related Art In recent years, in the field of communication technology such as optical data link and optical-wireless fusion technology, and in the field of optical information processing such as optical switching, optical computer, and optical interconnection, the phase intensity of light is controlled by electric signals. Optical modulators and optical switches are becoming indispensable. In the field of recording technology such as holographic optical memory, a highly efficient photorefractive recording medium is indispensable. Non-linear optical materials having an effect of changing the refractive index by an electric field are used for devices utilizing these electro-optical effects.

As a nonlinear optical material used for a high-speed response device represented by an optical modulator, conventionally, inorganic dielectrics such as LiNbO ₃ , LiTaO ₃ , and PLZT have been used. However, these materials have many problems. For example, such an inorganic dielectric shows deliquescent and has a low destruction threshold. Furthermore, it is difficult to improve the response speed due to the high dielectric constant, and the frequency band is limited. In addition, a high-temperature process is required in manufacturing. In the case of using the electric field absorption effect of a compound semiconductor quantum well structure device, an optical amplifier is used in combination because of a large light propagation loss, but there is a problem that the operation band is limited.

On the other hand, a nonlinear optical material made of an organic polymer material has a low dielectric constant, so that there is no speed mismatch between a microwave / millimeter wave region and a light wave region, and the response speed can be greatly improved. There is. In addition, since the nonlinear optical characteristics are high over a wide wavelength range and resistant to optical damage, nonlinear optical materials made of organic polymer materials are expected as high-performance optical device materials. Furthermore, a thin film can be easily formed by spin coating, etc.
Since it is excellent in workability such as microfabrication and molding, there is a great advantage that elements can be formed at extremely low cost as compared with inorganic material devices.

On the other hand, since a second-order nonlinear optical effect such as an electro-optical effect is exhibited only by a substance having no inversion symmetry, a polymer is subjected to a polarization orientation treatment called poling treatment for orienting molecules in one direction. Need to be applied. In general, the poling process is performed by applying an electric field in a temperature region near the glass transition temperature (Tg), and the inversion symmetry is obtained by returning to room temperature while the electric field is applied. However, in the polymer in which the non-linear molecules are oriented in this way, since the base polymer or the polymer serving as the main chain has a low Tg, an orientation relaxation phenomenon in which the orientation is gradually lost due to the thermal motion of the molecular chain occurs, and the non-linearity is increased. There is a problem that the optical effect is reduced. Conventionally, polymethyl methacrylate (PM), which has been energetically studied as a polymer waveguide material,
It has been reported that in a nonlinear optical material to which MA) is applied, the nonlinearity developed by the poling treatment is quickly lost at room temperature because the glass transition temperature of PMMA is as low as about 100 ° C.

[0006] Nonlinear optical materials using polymers are roughly classified into three types. The first is a dispersion polymer in which a nonlinear optical material is dispersed in a polymer, the second is a side-chain polymer in which a nonlinear optical material is chemically bonded to a side chain, and the third is a nonlinear optical material is incorporated in the main chain. It is a main chain type polymer. Although dispersed polymers are advantageous in that they can easily form nonlinear optical materials, in many cases,
Due to the low solubility of the nonlinear optical material in the polymer matrix, it is difficult to obtain high nonlinear optical characteristics. Moreover,
When a large amount of nonlinear optical material is introduced, microcrystals precipitate due to phase separation, and there is a problem that light propagation loss due to light scattering increases. Materials that can basically reduce such disadvantages include side-chain polymers and main-chain polymers. In the main chain type polymer, when the orientation of the nonlinear optical material is controlled by the poling process, the main chain of the entire polymer must be reoriented. Therefore, there is a problem that the processing temperature is inevitably increased or the processing time is lengthened, but the stability is very high. On the other hand, the side-chain type polymer has the advantage that the molecular design and synthesis are diverse and the poling treatment is relatively easy.However, compared with the main-chain type polymer, there is a problem that the orientation is easily relaxed. is there. For these reasons, many studies have been made on main-chain and side-chain polymers in addition to dispersion-type polymers.

Further, it is known that it is effective to use a polymer having a high glass transition temperature as a common measure for reducing the orientation relaxation in these polymer material systems. Applications such as have attracted attention. Wu et al. Disperse molecules having a large nonlinear optical effect in a polyamic acid and perform imidization while performing a poling treatment to obtain a dispersion type nonlinear optical polymer using a polyimide as a host (JW Wu).
et al, Appl. Phys. Lett. 58,2
25 (1991)). This dispersion type nonlinear optical polymer is
Although the heat treatment at 150 ° C. for 10 hours or longer does not show a decrease in nonlinear optical response due to orientation relaxation,
The electro-optic constant was as small as several pm / V, which was not practical.

One of the reasons for the low nonlinear optical performance is that the imidization temperature of polyimide is usually 300 ° C.
As described above, it is mentioned that the nonlinear optical material is sublimated or decomposed under such a high temperature condition. As a means for increasing the electro-optic constant, it has been studied to use a molecule having an extremely high nonlinear susceptibility.
Generally, a molecule having a higher nonlinear susceptibility tends to have a lower thermal decomposition temperature. Therefore, high nonlinear optical characteristics have not been obtained with a polymer material such as polyimide which requires a high-temperature heat treatment.

As a technique for curing polyimide at a low temperature, a method of treating with a mixture of an aliphatic carboxylic dianhydride and a tertiary amine is known, and there is also an application example to a polyimide nonlinear optical material (Appl. Phys.Let
t. , 59, 2213 (1991)). However,
This method has many problems, such as difficulty in application to insoluble polyimide, and the necessity of heat treatment at around 300 ° C. for complete imidization. Even when applied to an actual nonlinear optical material, only an extremely low electro-optic constant is obtained.

[0010]

In order to obtain a high-performance nonlinear optical device using a polymer, it is necessary to develop a nonlinear optical material having high heat resistance and high nonlinear optical characteristics. At present, no material has been obtained yet.

Accordingly, an object of the present invention is to provide a nonlinear optical material having high heat resistance and excellent nonlinear optical characteristics.

Another object of the present invention is to provide a method for producing a nonlinear optical material having high heat resistance and excellent nonlinear optical characteristics.

Another object of the present invention is to provide a high-performance nonlinear optical device using a polymer.

[0014]

According to the present invention, there is provided a nonlinear optical material comprising a thin film containing a polyimide, a nonlinear optical material, and a low-temperature curing accelerator. I do.

Further, the present invention provides a step of forming a thin film containing a polyimide precursor containing a polyamic acid having a nonlinear optical material dispersed or chemically bonded thereto and a low-temperature curing accelerator, and forming the thin film from 60 to 300 And b. Curing the polyimide precursor by heat treatment at a temperature in the range of ° C.

Further, the present invention provides a channel waveguide made of a nonlinear optical material, means for applying a voltage to the nonlinear optical material, an inlet for introducing light into the nonlinear optical material, and a light guide for extracting light. Wherein the nonlinear optical material is the above-mentioned nonlinear material.

In the thin film constituting the nonlinear optical material of the present invention, the nonlinear optical substance can be dispersed in polyimide as a base polymer. Alternatively, the nonlinear optical material may be chemically bonded to the polyimide backbone or side chain.

The low-temperature curing accelerator in the nonlinear optical material of the present invention includes (AC1) a substituted or unsubstituted nitrogen-containing heterocyclic compound having an acid dissociation index pKa of 0 to 8 in an aqueous solution of (AC1); A) a substituted or unsubstituted amino acid compound, and (AC3) having a molecular weight of 1000
And at least one selected from the group consisting of aromatic hydrocarbon compounds or aromatic heterocyclic compounds having at least two or more hydroxyl groups is preferred.

Alternatively, as the low-temperature curing accelerator, at least one selected from the group consisting of compounds represented by the following general formulas (1) to (10) and derivatives thereof can be used.

[0020]

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(In the above formula (2), R ²¹ has 1 to 10 carbon atoms.
Alkylene group, ethynylene group, or -CH ₂ CO-
It is. )

[0022]

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(In the above formula (5), X^{twenty one}Is -C (= O)-
O- or -C (= O) -NH-, R ^{twenty two}Is 1 to 4 carbon atoms
An alkylene group of R^{twenty three}And R^{twenty four}Is a methyl group or ethyl
Group. )

[0024]

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(In the above formula (8), R ²⁵ is a direct bond, —O
_{-, - SO 2 -, -} CH 2 -, - C (CH 3) 2 - or -
C (CF _{3) 2} - a. )

[0026]

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Further, as the low-temperature curing accelerator, at least one selected from the group consisting of compounds represented by the following general formulas (1) to (4) and (6) to (10) and derivatives thereof: And a tertiary amine compound.

[0028]

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(In the above formula (2), R ²¹ has 1 to 10 carbon atoms.
Alkylene group, ethynylene group, or -CH ₂ CO-
It is. )

[0030]

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[0031]

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(In the above formula (8), R ²⁵ is a direct bond, —O
_{-, - SO 2 -, -} CH 2 -, - C (CH 3) 2 - or -
C (CF _{3) 2} - a. )

[0033]

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The content of such a low-temperature curing accelerator is 1 p
It is preferable to be in the range of pm to 1 wt%.

In the method of the present invention, a polyamic acid having a repeating unit represented by the following general formula (PA) can be used.

[0036]

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(In the above formula, φ is a tetravalent organic group, Ψ is a divalent organic group, R is a substituted or specific substituted hydrocarbon group, an organosilicon group, or a hydrogen atom.) Will be described in detail.

In the present invention, a low-temperature curing accelerator is further added to a non-linear optical material in which a non-linear optical material is dispersed or chemically bonded using polyimide, which has been conventionally used as a non-linear optical material, as a base polymer. It is characterized by containing a small amount. One reason for including such a low-temperature curing accelerator is in the method for producing the same. That is, conventionally, a polyimide requires a very high temperature of generally 300 ° C. or higher in the imidization process, which makes it difficult to apply the polyimide to a nonlinear optical material including a nonlinear optical material having low heat resistance.

The inventors of the present invention have proposed a technique for curing polyimide at a low temperature (Japanese Patent Application Laid-Open Nos. 9-30225 and 7-13-13).
No. 8479) has already been developed. As a result of intensive studies on the application of this low-temperature curing technique of polyimide to nonlinear optical materials, the present invention has been achieved.

According to the present invention, it is possible to take advantage of the fact that imidization of polyimide can be performed at a low temperature of 200 ° C. or less as in the conventional results. In addition, it has been found that a small amount of the low-temperature curing accelerator remains in the cured polyimide, so that further advantages can be obtained. That is, when the non-linear optical material or the non-linear optical device is exposed to normal or high temperature conditions, the remaining low-temperature curing accelerator promotes imidization of the incompletely imidized portion. Thereby, it functions to remarkably suppress the orientation relaxation phenomenon. As a result, it has been clarified that the degradation of the nonlinear optical characteristics due to the relaxation of the orientation of the nonlinear optical material under normal temperature or high temperature conditions, which was a problem in the past, can be significantly reduced.

The appropriate content of the low-temperature curing accelerator in the polyimide varies depending on the material system, but if at least about 1 ppm is present, the above-mentioned effects can be obtained. On the other hand, if the content of the low-temperature curing accelerator is too large, the plasticization of the polyimide may occur or an interaction with the nonlinear optical material may be observed. It is desired to keep it below the level. Therefore, the content of the curing accelerator in the nonlinear optical material of the present invention is appropriately from 1 ppm to 1 wt%. A more preferable content range is 1 ppm to 100 ppm.
It is 0 ppm. The content of such a curing accelerator can be evaluated by mass spectrometry or the like.

In the past, there has been no technique in which a curing accelerator is contained in the cured polyimide so that the action remains even after a polyimide material or a device using the same is obtained. It was obtained for the first time by those.

[0043]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail.

The first compound incorporated in the nonlinear optical material of the present invention
(AC1) a substituted or unsubstituted nitrogen-containing heterocyclic compound having an acid dissociation index pKa of 0 to 8 in an aqueous solution of (AC1), (AC2) a substituted or unsubstituted amino acid compound, and (AC3) molecular weight 10
And at least one selected from the group consisting of aromatic hydrocarbon compounds and aromatic heterocyclic compounds having at least two hydroxyl groups.

First, an acid dissociation index pK of a proton complex in an aqueous solution, which is used as a curing accelerator in the present invention, is used.
The substituted or unsubstituted nitrogen-containing heterocyclic compound (AC1) wherein a is 0 to 8 will be described. Where the acid dissociation index p
Ka is the logarithm (−log K) of the reciprocal of the acid dissociation constant Ka.
a). The nitrogen-containing heterocyclic compound used as a low-temperature curing accelerator in the present invention has an acid dissociation index of a proton complex in an aqueous solution of from 0 to 8, more preferably from 2.5 to 7. The reason for this is that if the acid dissociation index of the proton complex of the nitrogen-containing heterocyclic compound is too small, it is difficult to sufficiently promote the curing reaction of the polyamic acid at a low temperature. This is because the gelation of the polyimide precursor is apt to progress and the storage stability of the polyimide precursor composition tends to decrease.

Examples of the unsubstituted nitrogen-containing heterocyclic compound contained in (AC1) include, for example, imidazole, pyrazole,
Triazole, tetrazole, benzimidazole, naphthimidazole, indazole, benzotriazole, purine, imidazoline, pyrazoline, pyridine, quinoline, isoquinoline, dipyridyl, diquinolyl, pyridazine, pyrimidine, pyrazine, phthalazine, quinoxaline, quinazoline, cinnoline, naphthyridine, acridine, acridine Nantridine, benzoquinoline, benzoisoquinoline, benzocinnoline, benzophthalazine, benzoquinoxaline, benzoquinazoline, phenanthroline, phenazine, carboline, perimidine, triazine, tetrazine, pteridine, oxazole, benzoxazole, isoxazole, benzisoxazole, thiazole, benzo Thiazole, isothiazole,
Benzoisothiazole, oxadiazole, thiadiazole, pyrroledione, isoindoledione, pyrrolidinedione, benzoisoquinolinedione, triethylenediamine, and hexamethylenetetramine. These compounds may be N-oxide compounds.

Examples of the substituents introduced into these nitrogen-containing heterocyclic compounds and constituting the substituted nitrogen-containing heterocyclic compounds include disubstituted amino groups (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, propylamino, isopropylamino, tert-butylamino, anilino, anisidino, phenetidino, toluidino, xylidino, pyridylamino, thiazolylamino, benzylamino, benzylideneamino, 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, methylsulfamoylamino group, sulfanylamino group, acetylsulfanylamino group, etc.), amino group, hydroxyamino group, ureido group, semicarbazide group, carbazide group, disubstituted hydrazino group (dim Ruhydrazino group, diphenylhydrazino group, methylphenylhydrazino group, etc.), monosubstituted 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.), hydroxyalkyl group (hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, etc.), Hydroxyaryl group (hydroxyphenyl group, hydroxynaphthyl group, dihydroxyphenyl group, etc.), alkoxyalkyl group (methoxymethyl group, methoxyethyl group,
Ethoxyethyl group), 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, Thiazolyloxy 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 thereof, oxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, pyridyloxycarbonyl group, etc.), aminocarbonyl group (carbamoyl group, methylcarbamoyl group, phenylcarbamoyl group,
Pyridylcarbamoyl group, carbazoyl group, allophanoyl group, oxamoyl group, succinamoyl group, etc.),
Thiocarboxyl group and its salt, dithiocarboxyl group and its salt, thiocarbonyl group (methoxythiocarbonyl group, methylthiocarbonyl group, methylthiothiocarbonyl group, etc.), acyl group (formyl group, acetyl group, propionyl group, acryloyl group, benzoyl Group,
Cinnamoyl group, pyridinecarbonyl group, thiazolecarbonyl 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, sulfanyl 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, 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, Trimethylsili Group, triphenylsilyl group) characteristic groups such as. In addition, among these, a hydroxyl group, an oxy group, an oxime group, a carboxyl group, an aminocarbonyl group, a hydroxyalkyl group,
Hydroxyaryl group, di-substituted amino group, mono-substituted amino group, cyclic amino group, acylamino group, amino group, hydroxyamino group, ureido group, mercapto group, nitro group, cyano group, acyl group, sulfonic acid group, acylsulfonyl group , An azo group and a thio group are particularly preferred.

Next, a substituted or unsubstituted amino acid compound (AC) used as a curing accelerator in the present invention
2) will be described.

Examples of the unsubstituted amino acid compound contained in (AC2) include glycine, sarcosine, dimethylglycine, betaine, alanine, β-alanine, α-aminobutyric acid, β-aminobutyric acid, γ-aminobutyric acid, and γ-aminobutyric acid. 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, homoserine, threonine, o-methylthreonine,
Allothreonine, o-methyl allothreonine, roseonin, 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-S-oxide, cysteic acid, homocysteine, homocystine, methionine, penicillamine, taurine, α, β-diaminopropionic acid, ornithine, lysine, arginine, canalin, canavanine, δ
-Hydroxylysine, aspartic acid, asparagine,
Isoasparagine, glutamic acid, glutamine, isoglutamine, α-methylglutamic acid, β-hydroxyglutamic acid, γ-hydroxyglutamic acid, α-aminoadipate, citrulline, lanthionine, cystathionine, phenylalanine, α-methylphenylalanine,
o-chlorophenylalanine, m-chlorophenylalanine, p-chlorophenylalanine, o-fluorophenylalanine, m-fluorophenylalanine, p-fluorophenylalanine, β- (2-pyridyl) alanine, tyrosine, tyrosine, dichlorotyrosine, dibromothiocin, Diiodotyrosine, 3,4-dihydroxyphenylalanine, α-methyl-3,4-dihydroxyphenylalanine, phenylglycine, tryptophan,
Abrin, histidine, 1-methylhistidine, 2-mercaptohistidine, proline, hydroxyproline,
Examples include anthranilic acid and paraminol. The substituents introduced into these amino acid compounds and constituting the substituted amino acid compounds include the characteristic groups described above.

Examples of the curing accelerator comprising the above-mentioned substituted or unsubstituted amino acid compound (AC2) include N-substituted amino acid compounds in which the amino group is substituted with an acyl group.
Acyl amino acid compounds and N-aryl (or heteroaryl) amino acid compounds in which the amino group of the amino acid compound is substituted with an aromatic hydrocarbon group or an aromatic heterocyclic group are particularly preferred.

Examples of the acyl group introduced into the N-acylamino acid compound include formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, pivaloyl, lauroyl, myristoyl, and palmitoyl groups. , 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, imidazolecarbonyl group, benzimidazolecarbonyl group, thiazolecarbonyl group,
Benzothiazolecarbonyl group, oxazolecarbonyl group, benzoxazolecarbonyl group, oxalyl group, malonyl group, succinyl group, glutaryl group, adipoyl group, pimeloyl group, suberoyl group, azelaoil group, sebacoil group, maleoyl group, fumaroyl group, citraconoyl group, Mesaconoyl group, mesoxalyl group, oxalacetyl group, camphoroyl group, phthaloyl group, isophthaloyl group, terephthaloyl group, oxalo group, methoxalyl group, ethoxalyl group, glyoxyloyl group, pyrvoyl group, acetoacetyl group, mesooxalo group, oxalaceto group, Cysteinyl group, homocysteinyl group, tryptofil group, alanyl group, β-alanyl group, arginyl group, cystathionyl group, cistyl 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, seryl group, threonyl group, thyronyl group, tyrosyl group, valyl group Is mentioned.

The aromatic hydrocarbon group or aromatic heterocyclic group introduced into the N-aryl (or heteroaryl) amino acid compound includes, for example, a benzene ring group, a naphthalene ring group, an anthracene ring group, a phenanthrene ring group, tetralin Ring group, azulene ring group, biphenylene ring group, acenaphthylene ring group, acenaphthene ring group, fluorene ring group, triphenylene ring group, pyrene ring group, chrysene ring group, picene ring group, perylene ring group, benzopyrene ring group, rubicene ring group , Coronene ring group, ovalene ring group, indene ring group, pentalene ring group, heptalene ring group, indacene ring group, phenalene ring group, fluoranthene ring group, acephenanthrylene ring group, aceanthrylene ring group, naphthacene ring group, Preyaden ring group, pentaphene ring group, pentacene ring group, tetraphenylene ring group, Xaphene ring group, hexacene ring group, trinaphthylene ring group, heptaphen ring group, heptacene ring group, pyranthrene ring group, pyrrole ring group, indole ring group, isoindole ring group, carbazole ring group, carboline ring group, furan ring group, cumarone Ring group, isobenzofuran ring group, thiophene ring group, benzothiophene ring group, dibenzothiophene ring group, pyrazole ring group, indazole ring group, imidazole ring group, benzimidazole ring group, oxazole ring group, benzoxazole ring group, benzoxazoline Ring group, isoxazole ring group, benzoisoxazole ring group, thiazole ring group, benzothiazole ring group,
Benzothiazoline ring group, isothiazole ring group, benzoisothiazole ring group, triazole ring group, benzotriazole ring group, oxadiazole ring group, thiadiazole ring group, benzooxadiazole ring group, benzothiadiazole ring group, tetrazole ring group , Purine ring group, pyridine ring group, quinoline ring group, isoquinoline ring group, acridine ring group, phenanthridine ring group, benzoquinoline ring group, benzoisoquinoline ring group, naphthyridine ring group, phenanthroline ring group, pyridazine ring group, pyrimidine Ring group, pyrazine ring group, phthalazine ring group, quinoxaline ring group, quinazoline ring group, cinnoline ring group, phenazine ring group, perimidine ring group, triazine ring group, tetrazine ring group, pteridine ring group, benzoxazine ring group, phenoxazine Ring group, benzothiazine ring group, phenothi Unsubstituted aromatic groups such as gin ring group, oxadiazine ring group, thiadiazine ring group, benzodioxole ring group, benzodioxane ring group, pyran ring group, chromene ring group, xanthene ring group, chroman ring group, and isochroman ring group Examples include a hydrocarbon group and an unsubstituted heterocyclic group. These unsubstituted aromatic hydrocarbon groups and unsubstituted heterocyclic groups may be substituted with the various characteristic groups described above.

Next, the aromatic hydrocarbon compound or aromatic heterocyclic compound (AC3) having a molecular weight of 1,000 or less and having at least two hydroxyl groups, which is used as a curing accelerator in the present invention, will be described.

If the molecular weight of the compound contained in (AC3) is too large, the vaporization point (boiling point, sublimation point or decomposition point) becomes high, and a large amount may remain in the film. For this reason, the molecular weight of the compound contained in (AC3) was specified in the range of 1000 or less. Further, in order to obtain good curing properties, two or more hydroxyl groups in (AC3) are required.

Examples of (AC3) include a polyhydroxy compound represented by the following chemical formula (PHD).

[0056]

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(Here, Ar in the general formula (PHD)
¹ and Ar ² may be the same or different and each represents a substituted or unsubstituted aromatic hydrocarbon group or an aromatic heterocyclic group; X ¹ may be the same or different, and Represents a group or a single bond, u represents 0 or 1, v and w are 0 to satisfy v + w ≧ 2
It is an integer of 5. In the formula (PHD), examples of the unsubstituted aromatic hydrocarbon group introduced as Ar ¹ and Ar ² include a benzene ring group, a naphthalene ring group, an anthracene ring group, a phenanthrene ring group, a tetralin ring group, Azulene ring group, biphenylene ring group, acenaphthylene ring group, acenaphthene ring group, fluorene ring group, triphenylene ring group, pyrene ring group, chrysene ring group, picene ring group, perylene ring group, benzopyrene ring group, rubicene ring group, coronene ring Group, ovalene ring group, indene ring group, pentalene ring group, heptalene ring group,
Indacene ring group, phenalene ring group, fluoranthene ring group, acephenanthrylene ring group, aceanthrylene ring group, naphthacene ring group, pleiaden ring group, pentaphene ring group, pentacene ring group, tetraphenylene ring group, hexaphene ring group , A hexacene ring group, a trinaphthylene ring group, a heptaphen ring group, a heptacene ring, and a pyranthrene ring group.

Examples of the substituent which is introduced into these unsubstituted aromatic hydrocarbon groups to constitute a substituted aromatic hydrocarbon group include a cyano group, a cyanato group, a thiocyanato group, a nitro group,
Nitroso group, oxy group (methoxy group, ethoxy group, propoxy group, butoxy group, hydroxyethoxy group, phenoxy group, naphthoxy group, pyridyloxy group, thiazolyloxy group, acetoxy group, etc.), thio group (methylthio group, ethylthio group, phenylthio group) Group, pyridylthio group,
Thiazolylthio group, etc.), mercapto group, halogen group (fluoro group, chloro group, bromo group, iodo group), carboxyl group and salts thereof, oxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, pyridyloxycarbonyl group) An aminocarbonyl group (carbamoyl group, methylcarbamoyl group, phenylcarbamoyl group, pyridylcarbamoyl group, carbazoyl group, allophanoyl group, oxamoyl group, succinamoyl group, etc.), thiocarboxyl group and its salt, dithiocarboxyl group and its salt, Thiocarbonyl group (methoxythiocarbonyl group, methylthiocarbonyl group, methylthiothiocarbonyl group, etc.), acyl group (formyl group, acetyl group, propionyl group, acryloyl group, benzoyl group Cinnamoyl group, pyridinecarbonyl group, thiazolecarbonyl 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, sulfanylyl group, acetylsulfanylyl group, etc., oxysulfonyl group (methoxysulfonyl group, ethoxysulfonyl group) Group, phenoxysulfonyl group, acetaminophenoxysulfonyl group, pyridyloxysulfonyl group, etc.), thiosulfonyl group (methylthiosulfonyl group, ethylthiosulfonyl group, phenylthiosulfonyl group, acetaminophenylthiosulfonyl group, pyridylthiosulfonyl group, etc.) An aminosulfonyl group (sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, phenylsulfamoyl group) Group, acetaminophenylsulfamoyl group, pyridylsulfamoyl group, etc.), ammonium 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 groups (chloromethyl, bromomethyl, fluoromethyl, dichloromethyl, dibromomethyl, difluoromethyl, trifluoromethyl,
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) And the like).

In the general formula (PHD), A
Examples of the unsubstituted aromatic heterocyclic group introduced as r ¹ and Ar ² include a pyrrole ring group, an indole ring group, an isoindole ring group, a carbazole ring group, a furan ring group, a coumarone ring group, and an isobenzofuran ring group. , Thiophene ring group, benzothiophene group, dibenzothiophene ring group, oxazine ring group, benzoxazine ring group, phenoxazine ring group,
Thiazine ring group, benzothiazine ring group, phenothiazine ring group, oxadiazine ring group, thiadiazine ring group, benzodioxole ring group, benzodioxane ring group, pyran ring group,
Examples thereof include a chromene ring group, a xanthene ring group, a chroman ring group, and an isochroman ring group. These heterocyclic groups may be substituted with the various characteristic groups described above.

In the general formula (PHD), X
Examples of the divalent organic group introduced as ¹ include a divalent oxy group, a thio group, a sulfinyl group, a sulfonyl group, a carbonyl group, a carbonyloxy group, an oxycarbonyloxy group, a peralkylpolysiloxanediyl group (1,1 ,
3,3-tetramethyldisiloxane-1,3-diyl group, 1,1,3,3,5,5-hexamethyltrisiloxane-1,5-diyl group, 1,1,3,3,5 5,
7,7-octamethyltetrasiloxane-1,7-diyl group, etc., substituted or unsubstituted imino group (imino group, methylimino group, ethylimino group, propylimino group, phenylimino group, etc.), substituted or unsubstituted Aliphatic hydrocarbon group (methylene group, ethylene group, propylene group, butylene group, pentylene group, ethylidene group, propylidene group, butylidene group, pentylidene group, vinylene group, difluoromethylene group, tetrafluoroethylene group, hexafluoropropylene group, Octafluorobutylene group, decafluoropentylene group, tetrafluoroethylidene group, hexafluoropropylidene group, octafluorobutylidene group, decafluoropentylidene group, etc., substituted or unsubstituted alkylenedioxy group (methylenedioxy group) , Echire Dioxy group, propylenedioxy group, butylenedioxy group, pentylene dioxy group, ethylidene group, pro pyridinium Denji group,
Butylidenedioxy group, pentylidenedioxy group, etc.), azo group, azoxy group, azomethine group and the like.

Examples of the curing accelerator comprising an aromatic hydrocarbon compound or an aromatic heterocyclic compound (AC3) having at least two hydroxyl groups having a molecular weight of 1,000 or less as described above include, for example, benzene, naphthalene, anthracene , Anthraquinone, phenanthrene,
Phenanthrenequinone, fluorene, fluorenone, pyrrole, indole, isoindole, carbazole,
Furan, coumarone, isobenzofuran, thiophene, benzothiophene, dibenzothiophene, benzodioxole, benzodioxane, biphenyl, acetophenone, propiophenone, butyrophenone, benzophenone, benzoate, benzenedicarboxylate diester, benzamide, benznitrile, benzaldehyde , Alkoxybenzene, benzyl alcohol, nitrobenzene, benzenesulfonic acid, aniline, diphenyl ether, diphenylsulfone, diphenylmethane, diphenylethane, diphenylpropane, diphenyldifluoromethane, diphenyltetrafluoroethane, diphenylhexafluoropropane, diphenylamine, diphenylmethylamine, triphenyl Amine, triphenylmethane, triphe Le methanol, and compounds the aromatic ring compound substituted with at least two or more hydroxyl groups such as fuchsone is particularly preferred.

The above (AC1) to (AC3)
May be used alone or in combination of two or more.

The above-mentioned low-temperature curing accelerator preferably has a low vaporization point (boiling point, sublimation point or decomposition point), and has good curing acceleration effect and good solubility in a polyamic acid solution. In this respect, particularly preferred low-temperature curing accelerators include imidazole, 1,2,4-triazole, benzimidazole, naphthimidazole, purine, quinoline, isoquinoline, pyridazine, phthalazine, quinazoline, cinnoline, naphthyridine, acridine, phenanthridine. , Benzoquinoline, benzoisoquinoline, benzocinnoline, benzophthalazine, benzoquinazoline, phenanthroline, phenazine, carboline, perimidine, 2,2'-dipyridyl, 2,4'-dipyridyl, 4,4'-dipyridyl, 2,2'- Diquinolyl, 2
-Hydroxypyridine, 3-hydroxypyridine, 4-
Hydroxypyridine, 2-hydroxyquinoline, 3-hydroxyquinoline, 4-hydroxyquinoline, 5-hydroxyquinoline, 6-hydroxyquinoline, 7-hydroxyquinoline, 8-hydroxyquinoline, picolinamide, nicotinamide, isonicotinamide, N, N-dimethylnicotinamide, N, N-diethylnicotinamide, N, N-dimethylisonicotinamide, N, N-diethylisonicotinamide, hydroxynicotinic acid, picolinic acid ester, nicotinic acid ester, isonicotinic acid ester, 2 -Pyridinesulfonamide, 3-pyridinesulfonamide, 4-pyridinesulfonamide, picolinaldehyde, nicotinaldehyde, isonicotinaldehyde, 3-nitropyridine, 3-acetoxypyridine, 2-aminopi Gin, 3-aminopyridine, 4-aminopyridine, picoline aldoxime, nicotine aldoxime, isonicotine aldoxime, 2- (hydroxymethyl) pyridine, 3- (hydroxymethyl) pyridine, 4- (hydroxymethyl) pyridine, -(Hydroxyethyl) pyridine, 3- (hydroxyethyl) pyridine, 4- (hydroxyethyl) pyridine, 3-hydroxypyridine-N-oxide, 4-hydroxypyridine-N-oxide, 4-hydroxyquinoline-N-oxide, N-hydroxypyrrole-2,5-dione, N-hydroxyisoindole-1,3-dione, N-hydroxypyrrolidine-2,5-dione, N-hydroxybenzo [de] isoquinoline-1,3-dione, tri Ethylenediamine, hexamethylenetetrami , Hydantoin, histidine, uracil, barbituric acid, diallylic acid, cytosine, anilinoacetic acid, 2- (pyridyl) glycine, 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-benzoylvaline, N-picolinoylvaline,
N-nicotinoyl valine, N-isonicotinoyl valine, benzenetriol, dihydroxyacetophenone, trihydroxyacetophenone, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dihydroxybenzoate, trihydroxybenzoate, dihydroxybenzamide, trihydroxy Benzamide, dihydroxybenzyl alcohol, trihydroxybenzyl alcohol, alkoxybenzenediol, alkoxybenzenetriol, dihydroxybenzaldehyde, trihydroxybenzaldehyde, nitrobenzenediol,
Dihydroxy-N, N-dimethylaniline, dihydroxydiphenylamine, trihydroxydiphenylamine, tetrahydroxydiphenylamine, dihydroxytriphenylamine, trihydroxytriphenylamine, tetrahydroxytriphenylamine, dihydroxybiphenyl, trihydroxybiphenyl, tetrahydroxybiphenyl, dihydroxydiphenyl ether ,
Trihydroxydiphenyl ether, tetrahydroxydiphenylether, dihydroxydiphenylsulfone, trihydroxydiphenylsulfone, tetrahydroxydiphenylsulfone, dihydroxydiphenylmethane, trihydroxydiphenylmethane, tetrahydroxydiphenylmethane, dihydroxydiphenylethane,
Trihydroxydiphenylethane, tetrahydroxydiphenylethane, dihydroxydiphenylpropane, trihydroxydiphenylpropane, tetrahydroxydiphenylpropane, dihydroxydiphenylhexafluoropropane, trihydroxydiphenylhexafluoropropane, tetrahydroxydiphenylhexafluoropropane, triphenylmethanetriol, dihydroxy Examples include fuchsone, naphthalene diol, naphthalene triol, naphthalene tetraol, anthracene diol, anthracentriol, anthracene tetraol, fluorenediol, fluorene triol, fluoren tetraol, fluorenone diol, fluorenone triol, and fluorenone tetraol.

These low-temperature curing accelerators are used in an amount of 0.1 mol equivalent or more per 1 mol equivalent of the repeating unit of the polyamic acid.
Preferably it is used in the range of 0.2 to 4.0 molar equivalents, most preferably in the range of 0.5 to 2.5 molar equivalents. The reason for this is that if the blending amount of the low-temperature curing accelerator is too small, the imidization of the polyamic acid is insufficient at a low-temperature heat treatment to obtain a good polyimide, and the blending amount of the low-temperature curing accelerator is too large. This is because the storage stability of the polyimide precursor composition may be degraded, or the residual amount of the low-temperature curing accelerator after heat curing may increase to adversely affect various properties.

The second compound incorporated in the nonlinear optical material of the present invention
Is at least one selected from the group consisting of compounds represented by the following general formulas (1) to (10) and derivatives thereof.

[0066]

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(In the above formula (2), R ²¹ has 1 to 10 carbon atoms.
Alkylene group, ethynylene group, or -CH ₂ CO-
It is. )

[0068]

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(X in the above formula (5)^{twenty one}Is -C (= O)-
O- or -C (= O) -NH-, R ^{twenty two}Is 1 to 4 carbon atoms
An alkylene group of R^{twenty three}And R^{twenty four}Is a methyl group or ethyl
Group. )

[0070]

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(In the above formula (8), R ²⁵ is a direct bond, —O
_{-, - SO 2 -, -} CH 2 -, - C (CH 3) 2 - or -
C (CF _{3) 2} - a. )

[0072]

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The carboxylic acid compound represented by the general formula (1) includes, for example, hydroxybenzoic acid. Examples of the carboxylic acid compound represented by the general formula (2) include hydroxyphenylacetic acid, hydroxyphenylpyruvic acid, and hydroxycinnamic acid. Examples of the carboxylic acid compounds represented by the general formulas (3) and (4) include hydroxynaphthoic acid. Examples of the carboxylic acid ester or carboxylic acid amide represented by the general formula (5) include -N, N-dimethylaminomethyl hydroxybenzoate, -N, N-diethylaminomethyl hydroxybenzoate, and 2-N, N-hydroxybenzoic acid. Dimethylaminoethyl, 2-N, N-diethylaminoethyl hydroxybenzoate, 3-N, N-hydroxybenzoic acid
Dimethylaminopropyl, hydroxybenzoic acid 3-N,
N-diethylaminopropyl, hydroxybenzoic acid 2-
N, N-dimethylaminopropyl, 2-N, N-diethylaminopropyl hydroxybenzoate, 1-methyl-2-N, N-dimethylaminoethyl hydroxybenzoate,
1-methyl-2-N, N-diethylaminoethyl hydroxybenzoate, 4-N, N-dimethylaminobutyl hydroxybenzoate, 4-N, N-diethylaminobutyl hydroxybenzoate, 3-methyl-3 hydroxybenzoate
-N, N-dimethylaminopropyl, 3-methyl-3-N, N-diethylaminopropyl hydroxybenzoate,
2-N, N-dimethylaminoethylhydroxybenzoic acid amide, 2-N, N-diethylaminoethylhydroxybenzoic acid amide, 3-N, N-dimethylaminopropylhydroxybenzoic acid amide, 3-N, N-diethylaminopropylhydroxy Benzoic acid amide, 2-N, N-dimethylaminopropylhydroxybenzoic acid amide, 2-
N, N-diethylaminopropylhydroxybenzoic acid amide and the like. In the compounds having a phenolic hydroxyl group represented by the general formulas (1) to (5), the hydroxyl group may be bonded to any site of the aromatic ring, such as the ortho, meta, and para positions. In addition, the derivatives of the compounds represented by the general formulas (1) to (5) mean that the hydrogen atom of the aromatic ring of these compounds further includes a hydroxyl group, a carboxyl group, a halogen atom, a cyano group, a nitro group, a methyl group, an ethyl group. A compound substituted with a methoxy group or an amino group.

The method for synthesizing the carboxylic acid ester or carboxylic acid amide represented by the general formula (5) is not particularly limited. For example, a method of heating a carboxylic acid represented by the general formula (1) and a tertiary amine represented by the following general formula (11) in the presence of a catalyst can be employed. At this time, the mixing ratio of the tertiary amine to the carboxylic acid is in the range of 1: 1 to 6 and more preferably 1: 1 to 3 in terms of molar ratio from the viewpoint of yield. As the catalyst used, sulfuric acid, phosphoric acid, hydrochloric acid or p-toluenesulfonic acid,
And boron trifluoride diethyl ether complex. The heating temperature is set to a temperature at which the tertiary amine refluxes. The heating time is 1 to 10 hours, more preferably 2 to 7 hours.

[0075]

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(Wherein R ²² is an alkylene group having 1 to 4 carbon atoms, R ²³ and R ²⁴ are a methyl group or an ethyl group,
²¹ is -OH or -NH _2. The compounding amount of the compound having a phenolic hydroxyl group represented by the general formulas (1) to (5) is preferably 0.05 to 3.0 equivalents based on the carboxyl group of the polyamic acid. If the amount is less than 0.05 equivalent, the photosensitive performance may be insufficient. Conversely, the compounding amount is 3.
If it exceeds 0 equivalents, the viscosity stability during storage becomes worse,
Further, film loss during development of the obtained coating film increases. Further, the compounding amount of these compounds is more preferably 0.1 to 2.0 equivalents. When a polyimide is blended, a compound having a phenolic hydroxyl group may be further blended up to 20% by weight with respect to the polyimide in addition to the amount specified above.

The compounds represented by formulas (6) to (10) will be described. Examples of the compound represented by the general formula (6) include aminobenzoic acid. Examples of the compounds represented by the general formulas (7) and (8) include aminophenol. Examples of the compound represented by the general formula (9) include phenolsulfonic acid. Examples of the compound represented by the general formula (10) include hydroxybenzaldehyde. Among these compounds, the compound represented by the general formula (9) is particularly preferable because it greatly lowers the temperature of the imidization reaction. In the compounds represented by the general formulas (6) to (10), the hydroxyl group or the amino group may be an ortho-position, a meta-position,
It may be bonded to any of the para-positions, but is preferably bonded to the meta- or para-position. In addition, the derivatives of the compounds represented by the general formulas (6) to (10) mean that the hydrogen atom of the aromatic ring of these compounds further includes a hydroxyl group, a halogen atom, a cyano group, a nitro group, a nitro group, a methyl group, an ethyl group, and a methoxy group. Refers to a compound substituted with a group or an amino group.

It is preferable that the compounding amounts of the compounds represented by the general formulas (1) to (10) and the derivatives thereof are 0.05 to 3.0 equivalents to the carboxyl group of the polyamic acid. When the compounding amount of these compounds is less than 0.05 equivalent, a polyimide film cannot be obtained by low-temperature heat treatment.
Conversely, if the compounding amount of these compounds exceeds 3.0 equivalents, the viscosity stability during storage will be poor. Further, the compounding amount of these compounds is more preferably 0.1 to 2.0 equivalents.

When the carboxylic acid ester or carboxylic acid amide represented by the general formula (5) is blended, a part or the whole thereof may be decomposed into a carboxylic acid and a tertiary amine.

The third compound incorporated in the nonlinear optical material of the present invention
The low-temperature curing accelerator of the following general formulas (1) to (4),
It is composed of a combination of at least one selected from the group consisting of the compounds represented by (6) to (10) and derivatives thereof and a tertiary amine compound.

[0081]

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(In the above formula (2), R ²¹ has 1 to 10 carbon atoms.
Alkylene group, ethynylene group, or -CH ₂ CO-
It is. )

[0083]

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[0084]

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(In the above formula (8), R ²⁵ is a direct bond, —O
_{-, - SO 2 -, -} CH 2 -, - C (CH 3) 2 - or -
C (CF _{3) 2} - a. )

[0086]

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The tertiary amine used here is not particularly limited, and trimethylamine, triethylamine, pyridine, picoline and the like can be used in addition to those represented by the general formula (11). These tertiary amines have an effect of further lowering the temperature of the imidization reaction when used in combination with the compounds represented by the general formulas (1) to (4) and (6) to (10).

The preferred amount of the tertiary amine is 0.05 to 0.3 equivalent based on the carboxyl group of the polyamic acid.
More preferably, it is 0.05 to 1.0 equivalent. When the compounding amount of the tertiary amine is less than 0.05 equivalent, the tertiary amine is compared with the case where only the compounds represented by the general formulas (1) to (4) and (6) to (10) are used. In addition, the temperature of the heat treatment for obtaining the polyimide film does not change so much. Conversely, if the blending amount of the tertiary amine exceeds 3.0 equivalents, the residual amount of the tertiary amine in the polyimide film increases, and the tertiary amine is mixed into the liquid crystal to cause the liquid crystal display device to fail. There is a possibility that the display function of the display may be deteriorated.

By using such a low-temperature curing accelerator, it becomes possible to obtain a polyimide film by heat treatment at a lower temperature than in the case of the second low-temperature curing accelerator.

Next, the polyimide used in the present invention will be described in detail. As the polyimide, a polyimide basically composed of the following tetracarboxylic dianhydride and a diamine compound can be used. Further, in the present invention, a molecule in which a nonlinear optical substance is chemically bonded to such a polyamic acid may be used. The following method can be employed to chemically bond the nonlinear optical material. For example, there is a method of synthesizing a chemically modified polyimide using a molecule in which a nonlinear optical substance is previously bound to either a tetracarboxylic dianhydride or a diamine compound which is a starting material of a polyamic acid. Alternatively, a method of synthesizing a polyimide using a tetracarboxylic dianhydride or a diamine compound having a site to be reacted with a nonlinear optical material later, and then reacting the nonlinear optical material with the above-described reaction site and bonding the same. . Polyamide acid obtained by chemically bonding the nonlinear optical substance thus obtained can easily increase its concentration while preventing aggregation and phase separation of the nonlinear optical substance because the nonlinear optical substance is fixed to the polyimide main chain. become.
Moreover, it is preferable in that the orientation relaxation phenomenon after the polarization orientation treatment is significantly reduced.

The polyamic acid used in the present invention is represented by the following general formula (DA1): 0.8 to 1.2 molar equivalents of a tetracarboxylic dianhydride component represented by the following general formula (DAH1). Diamine compound component 0.8-
What polymerized 1.2 molar equivalents is mentioned.

[0092]

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(However, φ in the general formula (DAH1)
Is a tetravalent organic group, and in the general formula (DA1) is a divalent organic group. In the present invention, in order to adjust the molecular weight of the polyamic acid, a dicarboxylic anhydride or a monoamine compound may be added as necessary in the synthesis thereof.

The polyamic acid is obtained in principle by the polymerization of 1 molar equivalent of a tetracarboxylic dianhydride component and 1 molar equivalent of a diamine compound component. The compounding ratio of 0.8 to 1.2 mole equivalent of the diamine compound component to the equivalent, or the compounding ratio of 0.8 to 1.2 mole equivalent of the tetracarboxylic dianhydride component to 1 mole equivalent of the diamine compound component. Within this range, the desired polyamic acid can be obtained.

In the tetracarboxylic dianhydride represented by the general formula (DAH1), the tetravalent organic group φ has 1 carbon atom.
To 30 aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups and heterocyclic groups, and aliphatic hydrocarbon groups;
An alicyclic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group is selected from the group consisting of a polycyclic compound group directly or interconnected by a bridging group.

Specific examples of the tetracarboxylic dianhydride represented by the general formula (DAH1) include, for example, pyromellitic dianhydride, 3-fluoropyromellitic dianhydride, 3,6
-Difluoropyromellitic dianhydride, 3- (trifluoromethyl) pyromellitic dianhydride, 3,6-bis (trifluoromethyl) pyromellitic dianhydride, 1,2,3
4-benzenetetracarboxylic dianhydride, 3,3 ′,
4,4′-benzophenonetetracarboxylic dianhydride,
2,2 ', 3,3'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 3,3 ", 4,4" -terphenyltetracarboxylic Acid dianhydride, 3,3 ′ ″, 4,4 ″ ′-quaterphenyltetracarboxylic dianhydride, 3,
3 ″ ″, 4,4 ″ ″-quinkphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, methylene-4,4′-diphthalic acid Dianhydride, 1,1-ethylidene-4,4'-diphthalic dianhydride, 2,2-propylidene-4,4'-diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic Acid dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4,4 '-Diphthalic anhydride, 1,1,1,3,3,3-hexafluoro-2,2-propylidene-4,4'-diphthalic anhydride, difluoromethylene-4,4'-diphthalic acid Dianhydride, 1,1,2,2-tetrafluoro-1,2-ethylene-4,4'-diphthalic dianhydride , 1,1,2,
2,3,3-hexafluoro-1,3-trimethylene-
4,4'-diphthalic dianhydride, 1,1,2,2,3
3,4,4-octafluoro-1,4-tetramethylene-4,4′-diphthalic dianhydride, 1,1,2,2
3,3,4,4,5,5-decafluoro-1,5-pentamethylene-4,4′-diphthalic dianhydride, oxy-
4,4'-diphthalic dianhydride, thio-4,4'-diphthalic dianhydride, sulfonyl-4,4'-diphthalic dianhydride, 1,3-bis (3,4-dicarboxyphenyl ) -1,1,3,3-Tetramethylsiloxane dianhydride, 1,3-bis (3,4-dicarboxyphenyl) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenyl) Benzene dianhydride, 1,3-bis (3,4-
Dicarboxyphenoxy) benzene dianhydride, 1,4-
Bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,3-bis [2- (3,4-dicarboxyphenyl) -2-propyl] benzene dianhydride, 1,4-bis [2- (3,4-dicarboxyphenyl) -2-propyl] benzene dianhydride, bis [3- (3,4-dicarboxyphenoxy) phenyl] methane dianhydride, bis [4- (3,4-dicarboxy) Phenoxy) phenyl]
Methane dianhydride, 2,2-bis [3- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,
2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,2-bis [3- (3
4-dicarboxyphenoxy) phenyl] -1,1,
1,3,3,3-hexafluoropropane dianhydride,
2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane dianhydride, bis (3,4-dicarboxyphenoxy) dimethyl Silane dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-
Tetramethyldisiloxane dianhydride, 2,3,6,7-
Naphthalenetetracarboxylic dianhydride, 1,4,5,8
-Naphthalenetetracarboxylic dianhydride, 1,2,5
6-naphthalenetetracarboxylic dianhydride, 3,4
9,10-perylenetetracarboxylic dianhydride, 2,
3,6,7-anthracenetetracarboxylic dianhydride,
1,2,7,8-phenanthrenetetracarboxylic dianhydride, 1,3-bis (3,4-dicarboxyphenyl)
-1,1,3,3-tetramethyldisiloxane dianhydride, ethylene tetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexane-1,
2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,
3 ', 4,4'-bicyclohexyltetracarboxylic dianhydride, carbonyl-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,
4'-bis (cyclohexane-1,2-dicarboxylic acid)
Dianhydride, 1,2-ethylene-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-
Ethylidene-4,4'-bis (cyclohexane-1,2
-Dicarboxylic acid) dianhydride, 2,2-propylidene-
4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-propylidene-4,4'-bis (cyclohexane- 1,2-dicarboxylic acid) dianhydride, oxy-
4,4′-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4′-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfonyl-4,
4'-bis (cyclohexane-1,2-dicarboxylic acid)
Dianhydride, 2,2'-difluoro-3,3 ', 4,4'
-Biphenyltetracarboxylic dianhydride, 5,5'-difluoro-3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 6,6'-difluoro-3,3',
4,4′-biphenyltetracarboxylic dianhydride, 2,
2 ', 5,5', 6,6'-hexafluoro-3,
3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2′-bis (trifluoromethyl) -3,
3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 5,5′-bis (trifluoromethyl) -3,
3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 6,6′-bis (trifluoromethyl) -3,
3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 5,5'-tetrakis (trifluoromethyl) -3,3 ', 4,4'-biphenyltetracarboxylic dianhydride , 2,2 ', 6,6'-tetrakis (trifluoromethyl) -3,3', 4,4'-biphenyltetracarboxylic dianhydride, 5,5 ', 6,6'-tetrakis (trifluoro Methyl) -3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 5
5 ', 6,6'-Hexakis (trifluoromethyl)-
3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3′-difluoro-oxy-4,4′-diphthalic dianhydride, 5,5′-difluoro-oxy-4,
4′-diphthalic dianhydride, 6,6′-difluoro-oxy-4,4′-diphthalic dianhydride, 3,3 ′, 5
5 ', 6,6'-hexafluoro-oxy-4,4'-
Diphthalic dianhydride, 3,3'-bis (trifluoromethyl) -oxy-4,4'-diphthalic dianhydride, 5,
5'-bis (trifluoromethyl) -oxy-4,4 '
-Diphthalic dianhydride, 6,6'-bis (trifluoromethyl) -oxy-4,4'-diphthalic dianhydride,
3,3 ′, 5,5′-tetrakis (trifluoromethyl) -oxy-4,4′-diphthalic dianhydride, 3,
3 ', 6,6'-tetrakis (trifluoromethyl)-
Oxy-4,4'-diphthalic dianhydride, 5,5 ',
6,6′-tetrakis (trifluoromethyl) -oxy-4,4′-diphthalic dianhydride, 3,3 ′, 5
5 ', 6,6'-Hexakis (trifluoromethyl)-
Oxy-4,4'-diphthalic dianhydride, 3,3'-difluoro-sulfonyl-4,4'-diphthalic dianhydride, 5,5'-difluoro-sulfonyl-4,4'-diphthalic dianhydride Anhydride, 6,6′-difluoro-sulfonyl-4,4′-diphthalic dianhydride, 3,3 ′, 5
5 ', 6,6'-hexafluoro-sulfonyl-4,
4′-diphthalic dianhydride, 3,3′-bis (trifluoromethyl) -sulfonyl-4,4′-diphthalic dianhydride, 5,5′-bis (trifluoromethyl) -sulfonyl-4, 4'-diphthalic dianhydride, 6,6'-bis (trifluoromethyl) -sulfonyl-4,4'-diphthalic dianhydride, 3,3 ', 5,5'-tetrakis (trifluoromethyl) -Sulfonyl-4,4'-diphthalic dianhydride, 3,3 ', 6,6'-tetrakis (trifluoromethyl) -sulfonyl-4,4'-diphthalic dianhydride, 5,5', 6 , 6′-Tetrakis (trifluoromethyl) -sulfonyl-4,4′-diphthalic dianhydride, 3,3 ′, 5,5 ′, 6,6′-hexakis (trifluoromethyl) -sulfonyl-4, 4'-diphthalic dianhydride, 3,3'-difluoro-2,2-par Le Oro propylidene-4,4'-diphthalic dianhydride, 5,
5'-difluoro-2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 6,6'-difluoro-2,2-perfluoropropylidene-4,4'-diphthalic dianhydride 3,3 ', 5,5', 6,6'-hexafluoro-2,2-perfluoropropylidene-
4,4'-diphthalic dianhydride, 3,3'-bis (trifluoromethyl) -2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 5,5'-bis ( (Trifluoromethyl) -2,2-perfluoropropylidene-4,4′-diphthalic anhydride, 6,6′-bis (trifluoromethyl) -2,2-perfluoropropylidene-4,4 ′ -Diphthalic dianhydride, 3,3 ',
5,5'-tetrakis (trifluoromethyl) -2,2
-Perfluoropropylidene-4,4'-diphthalic dianhydride, 3,3 ', 6,6'-tetrakis (trifluoromethyl) -2,2-perfluoropropylidene-4,
4'-diphthalic anhydride, 5,5 ', 6,6'-tetrakis (trifluoromethyl) -2,2-perfluoropropylidene-4,4'-diphthalic anhydride and 3,3' , 5,5 ', 6,6'-Hexakis (trifluoromethyl) -2,2-perfluoropropylidene-
4,4'-diphthalic dianhydride, 9-phenyl-9-
(Trifluoromethyl) xanthene-2,3,6,7-
Tetracarboxylic dianhydride, 9,9-bis (trifluoromethyl) xanthene-2,3,6,7-tetracarboxylic dianhydride and bicyclo [2,2,2] oct-7
-Ene-2,3,5,6-tetracarboxylic dianhydride.

These tetracarboxylic dianhydrides may be used alone or in combination of two or more. Tetracarboxylic dianhydride is 0.1% of the total anhydride components.
It is used in an amount of at least 8 molar equivalents, preferably at least 0.9 molar equivalents. The reason for this is that if the amount of the tetracarboxylic dianhydride is too small, the heat resistance of the obtained polyimide is reduced.

In the diamine compound represented by formula (DA1), the divalent organic group Ψ is an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, The ring group is selected from the group consisting of a polycyclic compound group in which an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic group is connected to each other directly or by a bridging group.

Specific examples of the diamine compound represented by the general formula (DA1) include, for example, 1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, 3,3′-diaminobiphenyl, 3,4'-
Diaminobiphenyl, 4,4′-diaminobiphenyl,
3,3 ″ -diaminoterphenyl, 4,4 ″ -diaminoterphenyl, 3,3 ′ ″-diaminoquaterphenyl, 4,4 ′ ″-diaminoquaterphenyl, oxy-
3,3'-dianiline, oxy-4,4'-dianiline, thio-3,3'-dianiline, thio-4,4'-dianiline, sulfonyl-3,3'-dianiline, sulfonyl-4,4'- Dianiline, methylene-3,3'-dianiline, methylene-4,4'-dianiline, 1,2-
Ethylene-3,3'-dianiline, 1,2-ethylene-
4,4′-dianiline, 2,2-propylidene-3,
3'-dianiline, 2,2-propylidene-4,4'-
Dianiline, 1,1,1,3,3,3-hexafluoro-2,2-propylidene-3,3′-dianiline, 1,
1,1,3,3,3-hexafluoro-2,2-propylidene-4,4′-dianiline, 1,1,2,2,3,
3-hexafluoro-1,3-propylene-3,3'-
Dianiline, 1,1,2,2,3,3-hexafluoro-1,3-propylene-4,4′-dianiline, 1,3
-Bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenylthio) benzene, 1,3-bis (4-aminophenylthio) benzene , 1,3-bis (3-aminophenylsulfonyl) benzene, 1,3-
Bis (4-aminophenylsulfonyl) benzene, 1,
3-bis [2- (3-aminophenyl) -2-propyl] benzene, 1,3-bis [2- (4-aminophenyl) -2-propyl] benzene, 1,3-bis [2-
(3-aminophenyl) -1,1,1,3,3,3-hexafluoro-2-propyl] benzene, 1,3-bis [2- (4-aminophenyl) -1,1,1,3 , 3,
3-hexafluoro-2-propyl] benzene, 1,4
-Bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenylthio) benzene, 1,4-bis (4-aminophenylthio) benzene , 1,4-bis (3-aminophenylsulfonyl) benzene, 1,4-
Bis (4-aminophenylsulfonyl) benzene, 1,
4-bis [2- (3-aminophenyl) -2-propyl] benzene, 1,4-bis [2- (4-aminophenyl) -2-propyl] benzene, 1,4-bis [2-
(3-aminophenyl) -1,1,1,3,3,3-hexafluoro-2-propyl] benzene, 1,4-bis [2- (4-aminophenyl) -1,1,1,3 , 3,
3-hexafluoro-2-propyl] benzene, 2,2
-Bis [4- (3-aminophenoxy) phenyl]-
1,1,1,3,3,3-hexafluoropropane,
2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 5-fluoro-1,3-phenylenediamine, 2-
Fluoro-1,4-phenylenediamine, 2,5-difluoro-1,4-phenylenediamine, 2,4,5,6
-Hexafluoro-1,3-phenylenediamine, 2,
3,5,6-hexafluoro-1,4-phenylenediamine, 3,3′-diamino-5,5′-difluorobiphenyl, 4,4′-diamino-2,2′-difluorobiphenyl, 4,4 ′ -Diamino-3,3'-difluorobiphenyl, 3,3'-diamino-2,2 ', 4
4 ′, 5,5 ′, 6,6′-octafluorobiphenyl, 4,4′-diamino-2,2 ′, 3,3 ′, 5
5 ', 6,6'-octafluorobiphenyl, oxy-
5,5'-bis (3-fluoroaniline), oxy-
4,4'-bis (2-fluoroaniline), oxy-
4,4'-bis (3-fluoroaniline), sulfonyl-5,5'-bis (3-fluoroaniline), sulfonyl-4,4'-bis (2-fluoroaniline), sulfonyl-4,4'- Bis (3-fluoroaniline), 1,
3-bis (3-aminophenoxy) -5-fluorobenzene, 1,3-bis (3-amino-5-fluorophenoxy) benzene, 1,3-bis (3-amino-5-fluorophenoxy) -5- Fluorobenzene, 5- (trifluoromethyl) -1,3-phenylenediamine, 2-
(Trifluoromethyl) -1,4-phenylenediamine, 2,5-bis (trifluoromethyl) -1,4-phenylenediamine, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl , 3,3'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, oxy-5,5'-bis [3- (trifluoromethyl) aniline], oxy-4,4'-bis [2 -(Trifluoromethyl) aniline], oxy-4,4'-bis [3- (trifluoromethyl) aniline], sulfonyl-5,5'-bis [3- (trifluoromethyl) aniline], sulfonyl-4 , 4'-bis [2- (trifluoromethyl) aniline], sulfonyl-4,4'-bis [3- (trifluoromethyl) aniline], 1,3-bis (3-aminophenoxy) -5- ( (Trifluoromethyl) benzene, 1,3-bis [3-amino-5- (trifluoromethyl) phenoxy] benzene, 1,3-bis [3-amino-5- (trifluoromethyl) phenoxy] -5- ( Trifluoromethyl) benzene, 3,3 '
-Bis (trifluoromethyl) -5,5'-diaminobiphenyl, bis (3-aminophenoxy) dimethylsilane, bis (4-aminophenoxy) dimethylsilane,
1,3-bis (3-aminophenyl) -1,1,3,3
-Tetramethyldisiloxane, 1,3-bis (4-aminophenyl) -1,1,3,3-tetramethyldisiloxane, methylenediamine, 1,2-ethanediamine,
1,3-propanediamine, 1,4-butanediamine,
1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,2-bis (3-amino Propoxy) ethane,
1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis (3-aminocyclohexyl) methane, bis (4-aminocyclohexyl) methane, 1,2
-Bis (3-aminocyclohexyl) ethane, 1,2-
Bis (4-aminocyclohexyl) ethane, 2,2-bis (3-aminocyclohexyl) propane, 2,2-bis (4-aminocyclohexyl) propane, bis (3-
Aminocyclohexyl) ether, bis (4-aminocyclohexyl) ether, bis (3-aminocyclohexyl) sulfone, bis (4-aminocyclohexyl) sulfone, 2,2-bis (3-aminocyclohexyl)-
1,1,1,3,3,3-hexafluoropropane,
2,2-bis (4-aminocyclohexyl) -1,1,1
1,3,3,3-hexafluoropropane, 1,3-xylylenediamine, 1,4-xylylenediamine, 1,
8-Diaminonaphthalene, 2,7-diaminonaphthalene, 2,6-diaminonaphthalene, 2,5-diaminopyridine, 2,6-diaminopyridine, 2,5-diaminopyrazine and 2,4-diamino-s-triazine No.

These diamine compounds may be used alone or in combination of two or more. Diamine compound is 0.8 mole equivalent or more of all amine compound components,
Preferably, it is used in an amount of 0.9 molar equivalent or more. The reason for this is that if the amount of the diamine compound is too small, the heat resistance of the obtained polyimide is reduced.

Next, the tetracarboxylic dianhydride component represented by the above general formula (DAH1) and the above general formula (DAH1)
Among the diamine compound components represented by 1), particularly preferred ones will be described.

Among the tetracarboxylic dianhydride components represented by the above general formula (DAH1), particularly preferred are the following general formulas (DAH2), (DAH3) and (DH3).
AH4) is an aromatic tetracarboxylic dianhydride.

[0103]

Embedded image

(However, R in the general formula (DAH2)
¹ may be the same or different and each represents a fluoro group or an unsubstituted or substituted aliphatic hydrocarbon group with a fluorine atom, a is an integer of 0 to 2, and represented by the general formula (DAH3) X represents a divalent oxy group, a thio group, a sulfonyl group, a carbonyl group, a peralkylpolysiloxanylene group, an unsubstituted or substituted with a fluorine atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group or a single bond. And R ² and R ³ may be the same or different, and each represents a fluoro group or an unsubstituted or substituted aliphatic hydrocarbon group with a fluorine atom, and b and c are integers of 0 to 3 R ⁴ in the general formula (DAH4)
To R ⁷ may be the same or different,
It represents a fluoro group or an unsubstituted or substituted with a fluorine atom an aliphatic hydrocarbon group, and d and e are integers of 0 to 2. Examples of the aromatic tetracarboxylic dianhydride represented by the general formula (DAH2) include pyromellitic dianhydride,
Fluoropyromellitic dianhydride, 3,6-difluoropyromellitic dianhydride, 3- (trifluoromethyl) pyromellitic dianhydride and 3,6-bis (trifluoromethyl) pyromellitic dianhydride Can be

As the aromatic tetracarboxylic dianhydride represented by the general formula (DAH3), for example, 3,3 ′, 4,
4'-benzophenonetetracarboxylic dianhydride, 3,
3 ', 4,4'-biphenyltetracarboxylic dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1
-Ethylidene-4,4'-diphthalic dianhydride, 2,2
-Propylidene-4,4'-diphthalic dianhydride, 1,
2-ethylene-4,4'-diphthalic dianhydride, 1,3
-Trimethylene-4,4'-diphthalic dianhydride, 1,
4-tetramethylene-4,4'-diphthalic dianhydride,
1,5-pentamethylene-4,4′-diphthalic dianhydride, 3,3 ″, 4,4 ″ -terphenyltetracarboxylic dianhydride, 3,3 ′ ″, 4,4 ′ ″ -Quaterphenyltetracarboxylic dianhydride, 3,3 "", 4,4 ""
-Kink phenyltetracarboxylic dianhydride, 1,1,
1,3,3,3-hexafluoro-2,2-propylidene-4,4′-diphthalic dianhydride, difluoromethylene-4,4′-diphthalic dianhydride, 1,1,2,2-
Tetrafluoro-1,2-ethylene-4,4′-diphthalic dianhydride, 1,1,2,2,3,3-hexafluoro-1,3-trimethylene-4,4′-diphthalic dianhydride 1,1,2,2,3,3,4,4-octafluoro-1,4-tetramethylene-4,4′-diphthalic dianhydride, 1,1,2,2,3,3 , 4,4,5,5-decafluoro-1,5-pentamethylene-4,4'-diphthalic dianhydride, oxy-4,4'-diphthalic dianhydride, thio-4,4'- Diphthalic dianhydride, sulfonyl-4,4'-diphthalic dianhydride, 1,3-bis (3,
4-dicarboxyphenyl) -1,1,3,3-tetramethylsiloxane dianhydride, 2,2′-difluoro-
3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 5,5′-difluoro-3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 6,6′-difluoro- 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 5,5 ', 6,6'-hexafluoro-3,3', 4,4'-biphenyltetracarboxylic acid Dianhydride, 2,2'-bis (trifluoromethyl)
-3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 5,5'-bis (trifluoromethyl) -3,
3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 6,6′-bis (trifluoromethyl) -3,
3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 5,5'-tetrakis (trifluoromethyl) -3,3 ', 4,4'-biphenyltetracarboxylic dianhydride , 2,2 ', 6,6'-tetrakis (trifluoromethyl) -3,3', 4,4'-biphenyltetracarboxylic dianhydride, 5,5 ', 6,6'-tetrakis (trifluoro Methyl) -3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 5
5 ', 6,6'-Hexakis (trifluoromethyl)-
3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3′-difluoro-oxy-4,4′-diphthalic dianhydride, 5,5′-difluoro-oxy-4,
4′-diphthalic dianhydride, 6,6′-difluoro-oxy-4,4′-diphthalic dianhydride, 3,3 ′, 5
5 ', 6,6'-hexafluoro-oxy-4,4'-
Diphthalic dianhydride, 3,3'-bis (trifluoromethyl) -oxy-4,4'-diphthalic dianhydride, 5,
5'-bis (trifluoromethyl) -oxy-4,4 '
-Diphthalic dianhydride, 6,6'-bis (trifluoromethyl) -oxy-4,4'-diphthalic dianhydride,
3,3 ′, 5,5′-tetrakis (trifluoromethyl) -oxy-4,4′-diphthalic dianhydride, 3,
3 ', 6,6'-tetrakis (trifluoromethyl)-
Oxy-4,4'-diphthalic dianhydride, 5,5 ',
6,6′-tetrakis (trifluoromethyl) -oxy-4,4′-diphthalic dianhydride, 3,3 ′, 5
5 ', 6,6'-Hexakis (trifluoromethyl)-
Oxy-4,4'-diphthalic dianhydride, 3,3'-difluoro-sulfonyl-4,4'-diphthalic dianhydride, 5,5'-difluoro-sulfonyl-4,4'-diphthalic dianhydride Anhydride, 6,6′-difluoro-sulfonyl-4,4′-diphthalic dianhydride, 3,3 ′, 5
5 ', 6,6'-hexafluoro-sulfonyl-4,
4′-diphthalic dianhydride, 3,3′-bis (trifluoromethyl) -sulfonyl-4,4′-diphthalic dianhydride, 5,5′-bis (trifluoromethyl) -sulfonyl-4, 4'-diphthalic dianhydride, 6,6'-bis (trifluoromethyl) -sulfonyl-4,4'-diphthalic dianhydride, 3,3 ', 5,5'-tetrakis (trifluoromethyl) -Sulfonyl-4,4'-diphthalic dianhydride, 3,3 ', 6,6'-tetrakis (trifluoromethyl) -sulfonyl-4,4'-diphthalic dianhydride, 5,5', 6 , 6′-Tetrakis (trifluoromethyl) -sulfonyl-4,4′-diphthalic dianhydride, 3,3 ′, 5,5 ′, 6,6′-hexakis (trifluoromethyl) -sulfonyl-4, 4'-diphthalic dianhydride, 3,3'-difluoro-2,2-par Le Oro propylidene-4,4'-diphthalic dianhydride, 5,
5'-difluoro-2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 6,6'-difluoro-2,2-perfluoropropylidene-4,4'-diphthalic dianhydride 3,3 ', 5,5', 6,6'-hexafluoro-2,2-perfluoropropylidene-
4,4'-diphthalic dianhydride, 3,3'-bis (trifluoromethyl) -2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 5,5'-bis ( (Trifluoromethyl) -2,2-perfluoropropylidene-4,4′-diphthalic anhydride, 6,6′-bis (trifluoromethyl) -2,2-perfluoropropylidene-4,4 ′ -Diphthalic dianhydride, 3,3 ',
5,5'-tetrakis (trifluoromethyl) -2,2
-Perfluoropropylidene-4,4'-diphthalic dianhydride, 3,3 ', 6,6'-tetrakis (trifluoromethyl) -2,2-perfluoropropylidene-4,
4'-diphthalic anhydride, 5,5 ', 6,6'-tetrakis (trifluoromethyl) -2,2-perfluoropropylidene-4,4'-diphthalic anhydride and 3,3' , 5,5 ', 6,6'-Hexakis (trifluoromethyl) -2,2-perfluoropropylidene-
4,4'-diphthalic dianhydride is mentioned.

As the aromatic tetracarboxylic dianhydride represented by the general formula (DAH4), for example, 9-phenyl-
9- (trifluoromethyl) xanthene-2,3,6
Examples include 7-tetracarboxylic dianhydride and 9,9-bis (trifluoromethyl) xanthene-2,3,6,7-tetracarboxylic dianhydride.

These aromatic tetracarboxylic dianhydrides may be used alone or as a mixture of two or more. When the aromatic tetracarboxylic dianhydride represented by any of the general formulas (DAH2) to (DAH4) is used, the resulting polyimide has a high glass transition point and a high decomposition temperature, and thus has high heat resistance. These aromatic tetracarboxylic dianhydrides are preferably used in an amount of at least 0.8 molar equivalent, more preferably at least 0.9 equivalent, among all the anhydride components. The reason for this is that if the amount of the aromatic tetracarboxylic dianhydride is too small, the heat resistance of the resulting polyimide may be reduced.

Further, from the viewpoints of heat resistance, environmental stability and low dielectric constant, the above-mentioned formulas (DAH2) to (DAH2)
Particularly preferred among the aromatic tetracarboxylic dianhydrides represented by 4) are pyromellitic dianhydride, 3
-(Trifluoromethyl) pyromellitic dianhydride, 3,
6-bis (trifluoromethyl) pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ″, 4,4 ″ -terphenyltetracarboxylic dianhydride, 3,3 ′ ″, 4,4 ′ ″
-Quaterphenyltetracarboxylic dianhydride, 1,
1,1,3,3,3-hexafluoro-2,2-propylidene-4,4′-diphthalic dianhydride, oxy-4,
4'-diphthalic dianhydride, -2,2-sulfonyl-
4,4'-diphthalic dianhydride, 1,3-bis (3,4
-Dicarboxyphenyl) -1,1,3,3-tetramethylsiloxane dianhydride, 9-phenyl-9- (trifluoromethyl) xanthene-2,3,6,7-tetracarboxylic dianhydride and 9 , 9-bis (trifluoromethyl) xanthene-2,3,6,7-tetracarboxylic dianhydride.

Among the diamine compounds represented by formula (DA1), preferred are aromatic diamine compounds represented by the following formula (DA2).

[0110]

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(Where Y in the general formula (DA2) is a divalent oxy group, thio group, sulfonyl group, carbonyl group, peralkylpolysiloxanylene group, unsubstituted or substituted by a fluorine atom, an aliphatic hydrocarbon) R ⁸ and R ⁹ may be the same or different and each represents a fluoro group or an unsubstituted or substituted by a fluorine atom, a hydrocarbon group; and f and g
Is an integer of 0 to 4, and h is an integer of 0 to 6. As specific examples of the aromatic diamine compound represented by the general formula (DA2), for example, 1,2-phenylenediamine,
1,3-phenylenediamine, 1,4-phenylenediamine, 3,3′-diaminobiphenyl, 3,4′-diaminobiphenyl, 4,4′-diaminobiphenyl, 1,
3-phenylene-3,3'-dianiline, 1,3-phenylene-4,4'-dianiline, 1,4-phenylene-
3,3′-dianiline, 1,4-phenylene-4,4 ′
-Dianiline, oxy-3,3'-dianiline, oxy-4,4'-dianiline, thio-3,3'-dianiline, thio-4,4'-dianiline, sulfonyl-3,
3'-dianiline, sulfonyl-4,4'-dianiline, methylene-3,3'-dianiline, methylene-4,
4′-dianiline, 1,2-ethylene-3,3′-dianiline, 1,2-ethylene-4,4′-dianiline,
2,2-propylidene-3,3'-dianiline, 2,2
-Propylidene-4,4'-dianiline, 1,1,1,
3,3,3-hexafluoro-2,2-propylidene-
3,3′-dianiline, 1,1,1,3,3,3-hexafluoro-2,2-propylidene-4,4′-dianiline, 1,1,2,2,3,3-hexafluoro- 1,
3-propylene-3,3'-dianiline, 1,1,2,2
2,3,3-hexafluoro-1,3-propylene-
4,4′-dianiline, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenylthio) benzene, 1,3 -Bis (4-aminophenylthio) benzene, 1,3-bis (3-aminophenylsulfonyl) benzene, 1,3-bis (4-aminophenylsulfonyl) benzene, 1,3-bis [2- (3- Aminophenyl) -2-propyl] benzene, 1,3-bis [2- (4-aminophenyl) -2-propyl] benzene, 1,3-bis [2- (3-aminophenyl) -1,
1,1,3,3,3-hexafluoro-2-propyl]
Benzene, 1,3-bis [2- (4-aminophenyl)
-1,1,1,3,3,3-hexafluoro-2-propyl] benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy)
Benzene, 1,4-bis (3-aminophenylthio) benzene, 1,4-bis (4-aminophenylthio) benzene, 1,4-bis (3-aminophenylsulfonyl)
Benzene, 1,4-bis (4-aminophenylsulfonyl) benzene, 1,4-bis [2- (3-aminophenyl) -2-propyl] benzene, 1,4-bis [2-
(4-aminophenyl) -2-propyl] benzene,
1,4-bis [2- (3-aminophenyl) -1,1,1
1,3,3,3-hexafluoro-2-propyl] benzene, 1,4-bis [2- (4-aminophenyl)-
1,1,1,3,3,3-hexafluoro-2-propyl] benzene, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3,3,3- Hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 5-fluoro-1,3-phenylenediamine, 2- Fluoro-1,4-phenylenediamine, 2,5-difluoro-1,4-phenylenediamine, 2,4,5,6-hexafluoro-1,3-phenylenediamine, 2,3,5,6-hexafluoro -1,
4-phenylenediamine, 3,3′-diamino-5
5'-difluorobiphenyl, 4,4'-diamino-
2,2'-difluorobiphenyl, 4,4'-diamino-3,3'-difluorobiphenyl, 3,3'-diamino-2,2 ', 4,4', 5,5 ', 6,6'- Octafluorobiphenyl, 4,4'-diamino-2,2 ',
3,3 ′, 5,5 ′, 6,6′-octafluorobiphenyl, oxy-5,5′-bis (3-fluoroaniline), oxy-4,4′-bis (2-fluoroaniline), oxy -4,4'-bis (3-fluoroaniline), sulfonyl-5,5'-bis (3-fluoroaniline), sulfonyl-4,4'-bis (2-fluoroaniline), sulfonyl-4,4 ' -Bis (3-fluoroaniline), 1,3-bis (3-aminophenoxy)-
5-fluorobenzene, 1,3-bis (3-amino-5
-Fluorophenoxy) benzene, 1,3-bis (3-
Amino-5-fluorophenoxy) -5-fluorobenzene, 5- (trifluoromethyl) -1,3-phenylenediamine, 2- (trifluoromethyl) -1,4-phenylenediamine, 2,5-bis (tri (Fluoromethyl) -1,4-phenylenediamine, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 3,3′-bis (trifluoromethyl) -4,4 ′
-Diaminobiphenyl, oxy-5,5'-bis [3-
(Trifluoromethyl) aniline], oxy-4,4 '
-Bis [2- (trifluoromethyl) aniline], oxy-4,4'-bis [3- (trifluoromethyl) aniline], sulfonyl-5,5'-bis [3- (trifluoromethyl) aniline] , Sulfonyl-4,4'-bis [2- (trifluoromethyl) aniline], sulfonyl-4,4'-bis [3- (trifluoromethyl) aniline], 1,3-bis (3-aminophenoxy) −5-
(Trifluoromethyl) benzene, 1,3-bis [3-
Amino-5- (trifluoromethyl) phenoxy] benzene, 1,3-bis [3-amino-5- (trifluoromethyl) phenoxy] -5- (trifluoromethyl) benzene, 3,3′-bis (tri Fluoromethyl) -5
5'-diaminobiphenyl, bis (3-aminophenoxy) dimethylsilane, bis (4-aminophenoxy) dimethylsilane, 1,3-bis (3-aminophenyl)-
1,1,3,3-tetramethyldisiloxane, 1,3-
Bis (4-aminophenyl) -1,1,3,3-tetramethyldisiloxane and the like can be mentioned.

These diamine compounds may be used alone or in combination of two or more. General formula (DA
When the aromatic diamine compound represented by the formula 2) is used, the resulting polyimide has a high glass transition point and a high decomposition temperature, and thus exhibits high heat resistance. These aromatic diamine compounds are preferably at least 0.8 molar equivalent, more preferably 0.9 mole equivalent, of all amine compound components.
It is used in an equivalent amount or more. The reason for this is that if the amount of the aromatic diamine compound is too small, the heat resistance of the obtained polyimide may be reduced.

Further, from the viewpoints of heat resistance, environmental stability and low dielectric constant, preferred among the aromatic diamine compounds represented by the above general formula (DA2) are 1,3-
Phenylenediamine, 1,4-phenylenediamine,
3,3′-diaminobiphenyl, 4,4′-diaminobiphenyl, 3,3 ″ -diaminoterphenyl, 4,4 ″
-Diaminoterphenyl, 3,3 '''-diaminoquaterphenyl,4,4'''-diaminoquaterphenyl,
Oxy-3,3'-dianiline, oxy-4,4'-dianiline, sulfonyl-3,3'-dianiline, sulfonyl-4,4'-dianiline, methylene-3,3'-dianiline, methylene-4,4 '-Dianiline, 2,2-
Propylidene-3,3'-dianiline, 2,2-propylidene-4,4'-dianiline, 1,1,1,3,3
3-hexafluoro-2,2-propylidene-3,3 '
-Dianiline, 1,1,1,3,3,3-hexafluoro-2,2-propylidene-4,4′-dianiline,
1,3-bis (3-aminophenoxy) benzene, 1,
3-bis (4-aminophenoxy) benzene, 1,3-
Bis [2- (3-aminophenyl) -2-propyl] benzene, 1,3-bis [2- (4-aminophenyl)-
2-propyl] benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis [2- (3-aminophenyl) -2-propyl Benzene, 1,4-bis [2-
(4-aminophenyl) -2-propyl] benzene,
2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl]- 1,1,1,3,3,3-hexafluoropropane, 5-fluoro-1,3-phenylenediamine, 2
-Fluoro-1,4-phenylenediamine, 2,5-difluoro-1,4-phenylenediamine, 2,4,5
6-hexafluoro-1,3-phenylenediamine,
2,3,5,6-hexafluoro-1,4-phenylenediamine, 3,3′-diamino-5,5′-difluorobiphenyl, 4,4′-diamino-2,2′-difluorobiphenyl, 4, 4'-diamino-3,3'-difluorobiphenyl, 3,3'-diamino-2,2 ', 4
4 ′, 5,5 ′, 6,6′-octafluorobiphenyl, 4,4′-diamino-2,2 ′, 3,3 ′, 5
5 ', 6,6'-octafluorobiphenyl, 5- (trifluoromethyl) -1,3-phenylenediamine, 2
-(Trifluoromethyl) -1,4-phenylenediamine, 2,5-bis (trifluoromethyl) -1,4-phenylenediamine, 2,2′-bis (trifluoromethyl) -4,4′-diamino Biphenyl, 3,3'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, oxy-5,5'-bis [3- (trifluoromethyl) aniline], oxy-4,4'-bis [ 2- (trifluoromethyl) aniline], oxy-4,4'-bis [3- (trifluoromethyl) aniline], sulfonyl-5,5'-bis [3- (trifluoromethyl) aniline], sulfonyl- 4,4'-bis [2- (trifluoromethyl) aniline], sulfonyl-4,4'-bis [3- (trifluoromethyl) aniline], 1,3-bis (3-aminophenoxy) -5 (Trifluoromethyl) benzene, 1,3-bis [3-amino-5- (trifluoromethyl) phenoxy] benzene, 1,3-bis [3-amino-5- (trifluoromethyl) phenoxy] -5- (Trifluoromethyl) benzene, 3,3 '
-Bis (trifluoromethyl) -5,5'-diaminobiphenyl.

Further, among the diamine compounds represented by the general formula (DA2), an aromatic diamine compound represented by the following general formula (DA3) is particularly preferable.

[0115]

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(Where Z in the general formula (DA3) is a divalent oxy group, thio group, sulfonyl group, carbonyl group, peralkylpolysiloxanylene group, aliphatic hydrocarbon unsubstituted or substituted with a fluorine atom) R ^{10 to} R ¹² may be the same or different and each represents a fluoro group or an unsubstituted or substituted by a fluorine atom, an aliphatic hydrocarbon group;
J is an integer of 0 to 4, k is 0 or 1, l, m and n are integers of 0 to 4. The aromatic diamine compound represented by the general formula (DA3)
(1) an aromatic diamine compound having a structure in which one benzene ring has two amino groups bonded to the benzene ring at the meta position, and (2) an aromatic diamine compound having two or more benzene rings. An aromatic diamine compound having a structure in which two amino groups are respectively bonded to a terminal benzene ring at a meta position as viewed from a bonding site of the terminal benzene ring to another benzene ring is included.

Specific examples of the aromatic diamine compound having an amino group at the meta position represented by the general formula (DA3) include, for example, 1,3-phenylenediamine, 3,3′-
Diaminobiphenyl, 1,3-phenylene-3,3'-
Dianiline, 1,4-phenylene-3,3'-dianiline, oxy-3,3'-dianiline, thio-3,3'-
Dianiline, sulfonyl-3,3′-dianiline, methylene-3,3′-dianiline, 1,2-ethylene-3,
3'-dianiline, 2,2-propylidene-3,3'-
Dianiline, 1,1,1,3,3,3-hexafluoro-2,2-propylidene-3,3′-dianiline, 1,
1,2,2,3,3-hexafluoro-1,3-propylene-3,3′-dianiline, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (3-aminophenylthio ) Benzene, 1,3-bis (3-aminophenylsulfonyl) benzene, 1,3-bis [2- (3-
Aminophenyl) -2-propyl] benzene, 1,3-
Bis [2- (3-aminophenyl) -1,1,1,3,
3,3-hexafluoro-2-propyl] benzene,
1,4-bis (3-aminophenoxy) benzene, 1,
4-bis (3-aminophenylthio) benzene, 1,4
-Bis (3-aminophenylsulfonyl) benzene,
1,4-bis [2- (3-aminophenyl) -2-propyl] benzene, 1,4-bis [2- (3-aminophenyl) -1,1,1,3,3,3-hexafluoro -2
-Propyl] benzene, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-
Hexafluoropropane, 5-fluoro-1,3-phenylenediamine, 2,4,5,6-hexafluoro-
1,3-phenylenediamine, 3,3′-diamino-
5,5'-difluorobiphenyl, 3,3'-diamino-2,2 ', 4,4', 5,5 ', 6,6'-octafluorobiphenyl, oxy-5,5'-bis (3- Fluoroaniline), sulfonyl-5,5′-bis (3-fluoroaniline), 1,3-bis (3-aminophenoxy) -5-fluorobenzene, 1,3-bis (3-amino-5-fluorophenoxy) ) Benzene, 1,3-bis (3-amino-5-fluorophenoxy) -5-fluorobenzene, 5- (trifluoromethyl) -1,3-phenylenediamine, oxy-5,5'-bis [3- (Trifluoromethyl) aniline], sulfonyl-5,5 '
-Bis [3- (trifluoromethyl) aniline], 1,
3-bis (3-aminophenoxy) -5- (trifluoromethyl) benzene, 1,3-bis [3-amino-5
(Trifluoromethyl) phenoxy] benzene, 1,3
-Bis [3-amino-5- (trifluoromethyl) phenoxy] -5- (trifluoromethyl) benzene, 3,
3′-bis (trifluoromethyl) -5,5′-diaminobiphenyl, bis (3-aminophenoxy) dimethylsilane, 1,3-bis (3-aminophenyl) -1,
1,3,3-tetramethyldisiloxane and the like can be mentioned.

These diamine compounds may be used alone or in combination of two or more. When an aromatic diamine compound having an amino group at the meta position represented by the general formula (DA3) is used, the resulting polyimide hardly undergoes moisture absorption decomposition even when left in the air, and is particularly excellent in environmental stability. I have. The aromatic diamine compound having an amino group at the meta position is preferably used in an amount of at least 0.4 molar equivalent, more preferably at least 0.6 molar equivalent among all the diamine compound components. The reason for this is that when the amount of the aromatic diamine compound having an amino group at the meta position is too small, the environmental stability (resistance to hygroscopic decomposition) of the obtained polyimide may be reduced.

Further, from the viewpoints of heat resistance, environmental stability and low dielectric constant, particularly preferred aromatic diamine compounds having an amino group at the meta position represented by the above general formula (DA3) include: For example, 1,3-phenylenediamine, 3,3′-diaminobiphenyl, 1,3-phenylene-3,3′-dianiline, 1,4-phenylene-
3,3′-dianiline, oxy-3,3′-dianiline, sulfonyl-3,3′-dianiline, 2,2-propylidene-3,3′-dianiline, 1,1,1,3,
3,3-hexafluoro-2,2-propylidene-3,
3'-dianiline, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy)
Benzene, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 5-fluoro-1,3-phenylenediamine, 2,4 5,6-hexafluoro-1,3-phenylenediamine, 3,3′-diamino-5,5′-difluorobiphenyl, 3,3′-diamino-2,2 ′,
4,4 ′, 5,5 ′, 6,6′-octafluorobiphenyl, 5- (trifluoromethyl) -1,3-phenylenediamine, oxy-5,5′-bis [3- (trifluoromethyl) Aniline], sulfonyl-5,5′-bis [3- (trifluoromethyl) aniline], 1,3-bis (3-aminophenoxy) -5- (trifluoromethyl) benzene, 1,3-bis [3 -Amino-5- (trifluoromethyl) phenoxy] benzene, 1,3-bis [3-amino-5- (trifluoromethyl) phenoxy] -5- (trifluoromethyl) benzene, 3,3 ′
-Bis (trifluoromethyl) -5,5'-diaminobiphenyl.

In the present invention, a diamine compound represented by the following formula (DA4), that is, a bis (aminoalkyl) peralkylpolysiloxane compound may be used in combination with the above-described diamine compound.

[0121]

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(However, in the general formula (DA4), R ¹³
To R ¹⁶ may be the same or different and each represents an alkyl group having 1 to 5 carbon atoms, q and r are integers of 1 to 10, and p is a positive integer. As specific examples of the bis (aminoalkyl) peralkylpolysiloxane compound represented by the general formula (DA4), for example, 1,3-bis (aminomethyl) -1,1,1
3,3-tetramethyldisiloxane, 1,3-bis (2
-Aminoethyl) -1,1,3,3-tetramethyldisiloxane, 1,3-bis (3-aminopropyl) -1,
1,3,3-tetramethyldisiloxane, 1,3-bis (4-aminobutyl) -1,1,3,3-tetramethyldisiloxane, 1,3-bis (5-aminopentyl)-
1,1,3,3-tetramethyldisiloxane, 1,3-
Bis (6-aminohexyl) -1,1,3,3-tetramethyldisiloxane, 1,3-bis (7-aminoheptyl) -1,1,3,3-tetramethyldisiloxane,
1,3-bis (8-aminooctyl) -1,1,3,3
-Tetramethyldisiloxane, 1,3-bis (10-aminodecyl) -1,1,3,3-tetramethyldisiloxane, 1,5-bis (3-aminopropyl) -1,1,1
3,3,5,5-hexamethyltrisiloxane, 1,7
-Bis (3-aminopropyl) -1,1,3,3,5
5,7,7-octamethyltetrasiloxane, 1,11
-Bis (3-aminopropyl) -1,1,3,3,5
5,7,7,9,9,11,11-Dodecamethylhexasiloxane, 1,15-bis (3-aminopropyl)-
1,1,3,3,5,5,7,7,9,9,11,1
1,13,13,15,15-hexadecamethyloctasiloxane, 1,19-bis (3-aminopropyl)-
1,1,3,3,5,5,7,7,9,9,11,1
1,13,13,15,15,17,17,19,19
-Eicosamethyldecasiloxane.

The bis (aminoalkyl) peralkylpolysiloxane compound represented by the general formula (DA4) is
For example, it has an effect of improving the adhesion and adhesion of polyimide formed on a semiconductor substrate such as a glass substrate or silicon. These compounds are preferably used in a mixture of 0.02 to 0.1 molar equivalent of all the diamine compound components. This is because, although the adhesion and adhesion of the polyimide obtained by adding such a compound to a substrate are improved, excessive mixing may cause a decrease in the heat resistance of the polyimide.

In the present invention, the dicarboxylic anhydride which is added as necessary in the synthesis of polyamic acid is represented by the following general formula (AH1).

[0125]

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(However, in the general formula (AH1), α represents a divalent organic group.) When the dicarboxylic anhydride represented by the general formula (AH1) is used, the tetracarboxylic acid represented by the general formula (DAH1) is used. Carboxylic anhydride (1-m / 2) molar equivalent, general formula (AH1)
M molar equivalent of the dicarboxylic anhydride represented by
Is preferably in the ratio of 0.97 to 1.03 molar equivalents of the diamine compound component represented by the general formula (DA1).

In the present invention, the monoamine compound added as necessary in the synthesis of polyamic acid is represented by the following general formula (MA1).

[0128]

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(However, in the general formula (MA1), β represents a monovalent organic group.) When a monoamine compound represented by the general formula (MA1) is used, a tetracarboxylic acid represented by the general formula (DAH1) 0.97 to 1.03 molar equivalents of dianhydride, a compound represented by the general formula (DA
The diamine compound component (1-n / 2) molar equivalent represented by 1) and the monoamine compound n molar equivalent (where n is 0 to 0.4) represented by the general formula (MA1) are compounded at a compounding ratio. Is preferred.

The method for synthesizing the polyamic acid used in the present invention is not particularly limited, but a method in which polymerization is carried out in an organic polar solvent in an inert gas atmosphere under anhydrous conditions is preferred.

The organic polar solvent used in this reaction includes, for example, N, N-dimethylformamide, N, N-
Dimethylacetamide, N, N-diethylacetamide, N, N-dimethoxyacetamide, N-methyl-2
-Pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-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-dioxolan, 1,4-dioxane,
Examples include pyrroline, pyridine, picoline, dimethyl sulfoxide, sulfolane, γ-butyrolactone, propylene carbonate, phenol, cresol, cyclohexanone, and acetonylacetone. These organic solvents may be used alone or as a mixture of two or more.

The reaction temperature is usually -20 to 100 ° C, preferably -5 to 30 ° C. The reaction pressure is not particularly limited,
It can be carried out at normal pressure. The reaction time varies depending on the type of the tetracarboxylic dianhydride and the type of the reaction solvent.
~ 24 hours is sufficient. The polyamic acid obtained at this time is 0.5 wt% -N-methyl-2-at 30 ° C.
The inherent viscosity (logarithmic viscosity number) of the pyrrolidone solution is 0.3 (dL / g) or more, further 0.3 (dL / g)
It is preferably at least 3 (dL / g) or less. The reason for this is that the inherent viscosity of the polyamic acid is too low,
That is, if the degree of polymerization of the polyamic acid is too low, it may not be possible to obtain a polyimide having high heat resistance, the inherent viscosity of the polyamic acid is too high,
That is, if the degree of polymerization of the polyamic acid is too high, it becomes difficult to handle the polyamic acid.

In the method for producing a nonlinear optical material according to the present invention, first, a nonlinear optical substance is dispersed in such a polyamic acid solution, and a low-temperature curing accelerator is further blended to prepare a raw material solution. Alternatively, a nonlinear optical substance may be chemically bonded to polyamic acid.

As the nonlinear optical substance that can be used, a molecule having a large supramolecular polarizability β and a large dipole moment μ corresponds to increase the electro-optic constant of the nonlinear optical material.
It is generally said that those having a molecular structure in which a donor group and an acceptor group are provided at both ends of a π-conjugated chain are good. Such molecules include 4- (dimethylamino) -4′-nitrostilbene (DANS), 4 [N-ethyl-N- (2
-Hydroxyethyl)] amino-4'-nitrostilbene (DR1), DR19, DR13, DO1, DO3,
4- (dicyanovinyl) -4- (dialkylamino) azobenzene (DCV), 4- (dicyanomethylene) -2
-Methyl-6- [p- (dimethylamino) styryl]-
4H-pyran (DCM), 4-tricyanovinyl-4 '
-(Diethylamino) azobenzene (TCV), p-N
A, p-NMDA, MNA, 1- (4-nitrophenyl) -4- [4- (dimethylamino) phenyl] -1,
3-butadiene, di- [2-hydroxyethyl] aminohexanylsulfonylazostilbene, and 2 ', 5
-Diamino-4- (dimethylamino) -4'-nitrostilbene (DDANS) and the like;
It is not limited to these.

As described above, these nonlinear optical materials are incorporated into the nonlinear optical material of the present invention in the form of being dispersed in a polymer host or in the form of being chemically bonded to a polymer side chain or main chain. Further, the content can be appropriately determined according to the type and form of the components used.

In the production of the nonlinear optical material, a solution of the above-described polyimide precursor composition containing the nonlinear optical substance and the low-temperature curing accelerator is applied onto a desired substrate by a spin coating method or the like, and then necessary. Is dried by a method such as heating according to the above. Thereafter, the polyimide precursor composition is cured by heating in a temperature range of 60 to 300 ° C. When the heating temperature is lower than 60 ° C., the solvent cannot be sufficiently volatilized. On the other hand, when the heating temperature exceeds 300 ° C., the nonlinear optical material is adversely affected. Therefore, in the present invention, the heat treatment temperature is limited to the range of 60 to 300 ° C. To form a polyimide film at a low temperature, after applying a solution of the above-described polyimide precursor composition to the substrate surface, drying at a temperature of 200 ° C. or lower as necessary, and in air or an inert gas atmosphere. 100-300
° C, preferably 120-300 ° C, more preferably 15 ° C.
By heating in a temperature range of 0 to 250 ° C (direct heating) or heating in a temperature range of 60 to 250 ° C (prebaking) and then heating in vacuum at 60 to 250 ° C, preferably 100 to 250 ° C, polyimide Curing the precursor composition. The heating time varies depending on the kind of the polyamic acid and the curing accelerator used, the heating temperature, the film thickness and the like, but 5 minutes to 3 hours is sufficient. The solvent component remaining in the coating film is volatilized by this heat treatment, and a change to an imide structure is caused by imidization of the polyamic acid.
A nonlinear optical material made of a polyimide film is formed.

Compared to the case where the conventional polyamic acid solution was used for heat curing at about 300 ° C.,
In the present invention, a non-linear optical material having good physical properties can be obtained by heat curing at a low temperature of 200 ° C. or less in many cases. Note that the heat curing temperature can be appropriately set according to the use of the nonlinear optical material.

It is to be noted that the compounds represented by the above formulas (1) to (5) and derivatives thereof are used as a low-temperature curing accelerator, and a photosensitive agent such as a diazide compound is further blended to form a photosensitive pattern. Can also. Specifically, examples of the diazide compound include a diazide compound such as an o-quinonediazide compound having at least one o-quinonediazide group in a molecule or a naphthoquinonediazide compound having at least one naphthoquinonediazide group in a molecule. . Specifically, at least one compound selected from the group consisting of compounds (P-1) to (P-29) represented by the following structural formulas can be used.

[0139]

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[0140]

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[0141]

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A raw material solution containing these components is applied on a substrate and, if necessary, dried by heating or the like to form a thin film. Furthermore, after irradiating exposure light through a mask having a desired pattern and then performing development processing, a patterned nonlinear optical material is obtained. As the exposure light, for example, X-ray, visible light, infrared light, ultraviolet light,
Energy rays such as excimer laser light;
Examples of the developer include an aqueous solution of an inorganic alkali such as potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate, potassium hydrogen carbonate, ammonium phosphate, ammonia, or propylamine, butylamine, Organic alkali aqueous solutions such as monoethanolamine, ethylenediamine, trimethylenediamine, trimethylammonium hydroxide, hydrazine, tetramethylammonium hydroxide, and trimethylhydroxyethylammonium hydroxide can be used. Further, methanol, ethanol, 2-propanol, ethylene glycol, ethyl cellosolve, butyl cellosolve, diethylene glycol, ethyl carbitol, N-methylpyrrolidone, N,
A mixture of organic solvents such as N-dimethylformamide, N, N-dimethylacetamide and dimethylsulfoxide can also be used.

In the case of producing a patterned non-linear optical material, it is preferable that the heat treatment at 60 to 300 ° C. is performed after the coating film is formed, dried and exposed, and then developed with an alkali developing solution. In this method, the condition of the heat treatment applied to the resin layer after exposure is a temperature of about 90 to 200.
C., preferably at 90-140.degree. C. for about 5 seconds to 60 minutes.

By employing such a method, it is possible to easily manufacture a channel waveguide structure.

The nonlinear optical device of the present invention can be obtained by using the nonlinear optical material manufactured by the method as described above.

A typical example of the nonlinear optical device is a Mach-Zehnder type optical modulator. However, the same applies to other channel waveguides such as a directional coupler, a Y-branch type, and an X-branch type. Can be. Further, the present invention can be applied to an optical modulator or an optical switch configured by combining a plurality of these. Further, in addition to intensity modulation by combination with a polarization optical element, it can be used as a birefringence modulation element.

Further, application to other nonlinear optical devices utilizing the same electro-optic effect as the optical modulator is also possible. For example, by using the nonlinear optical material of the present invention, it is possible to provide a nonlinear optical device having an electro-optic effect and a carrier transporting property and exhibiting a photorefractive effect.

[0148]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to specific examples.

(Example 1) Pyromellitic dianhydride, oxy-4,4'-dianiline, 1,3-bis- (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane were mixed with 1 : 0.95: 0.05 polyamic acid was dissolved in N, N-dimethylacetamide as a solvent. To the obtained polyamic acid solution, benzimidazole as a low-temperature curing accelerator was added at a ratio of 2 molar equivalents to 1 molar equivalent of the repeating unit of the polyamic acid to prepare a mixed solution. Further, Disperse Red 1 as a nonlinear optical material was added at a ratio of 20% by weight to the mixture to prepare a raw material solution of the nonlinear optical material of the present example.

This raw material solution was treated with Si having a SiO ₂ layer formed thereon.
A coating film was formed by spin coating on the wafer, and heated on a hot plate at 160 ° C. for 30 minutes to obtain a polyimide non-linear optical material almost imidized by 100%. As a result of mass spectrometry, the content of benzimidazole in the obtained polyimide was about 10 ppm.

Next, the same raw material solution as described above was applied onto an ITO substrate by spin coating, and dried by heating at 90 ° C. to form a thin film having a thickness of 5 μm. An Al electrode was deposited on this thin film, and heated at 160 ° C. for 30 minutes while applying an electric field of 50 V / μm to prepare a sample.

As a result of measuring the electro-optic constant at a wavelength of 1300 nm using a Mach-Zehnder interference optical system, a high value of r ₃₃ = 35 pm / V was obtained.

Further, when this sample was heated at 100 ° C. in the atmosphere, the initial electro-optic constant was maintained even after lapse of 2000 hours, and it was confirmed that an extremely stable nonlinear optical material was obtained.

(Comparative Example) A raw material solution was prepared by using the same polyamic acid as in Example 1 and adding 20% by weight of Disperse Red 1 as a nonlinear optical material without blending a low-temperature curing accelerator.

This raw material solution was treated with Si having a SiO ₂ layer formed thereon.
A coating film was formed by spin coating on a wafer, and heated on a hot plate at 300 ° C. for 30 minutes in a nitrogen atmosphere to obtain a polyimide non-linear optical material almost imidized by 100%.

Next, the same raw material solution as described above was applied onto an ITO substrate by spin coating, and dried by heating at 90 ° C. to form a thin film having a thickness of 5 μm. An Al electrode is deposited on this thin film, and 160 ° C. while applying an electric field of 50 V / μm.
For 30 minutes to produce a sample.

With respect to the obtained sample, the wavelength was 1300 nm.
Was measured in the same manner as in Example 1 above, and as a result, only a low value of r ₃₃ = 3 pm / V was obtained.

When this sample was heated at 100 ° C. in the air, the nonlinear optical characteristics almost disappeared 10 hours after the start.

(Example 2) Pyromellitic dianhydride, oxy-4,4'-dianiline, 1,3-bis- (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane were mixed with 1 : 0.95: 0.05 polyamic acid was dissolved in N, N-dimethylacetamide as a solvent. To the obtained polyamic acid solution, N-acetylglycine as a low-temperature curing accelerator was added at a ratio of 2 mol equivalent to 1 mol equivalent of the repeating unit of polyamic acid to prepare a mixed solution. Furthermore, Disperse Red 1 as a nonlinear optical material was added to the mixture at 20% by weight.
, A raw material solution of the nonlinear optical material of this example was prepared.

This raw material solution was treated with Si having a SiO ₂ layer formed thereon.
After spin coating on the wafer to form a coating film and heating on a hot plate at 120 ° C. for 60 minutes, further heating in a vacuum oven at 100 ° C. for 60 minutes,
A polyimide non-linear optical material that was almost 90% imidized was obtained.

As a result of mass spectrometry, the content of N-acetylglycine in the obtained polyimide was about 20 ppm.

Next, the same raw material solution as described above was applied on an ITO substrate by spin coating, and dried by heating at 90 ° C. to form a thin film having a thickness of 5 μm. An Al electrode is deposited on this thin film, and is applied at 120 ° C. while applying an electric field of 50 V / μm.
After heating for 60 minutes in a vacuum oven,
A sample was prepared by heating at 60 ° C. for 60 minutes.

As a result of measuring the electro-optic constant at a wavelength of 1300 nm using a Mach-Zehnder interference optical system, a high value of r ₃₃ = 25 pm / V was obtained.

When this sample was heated at 100 ° C. in the air, the initial electro-optical constant was maintained after 1500 hours, and it was confirmed that an extremely stable nonlinear optical material was obtained.

Example 3 Pyromellitic dianhydride, oxy-4,4'-dianiline, 1,3-bis- (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane : 0.95: 0.05 polyamic acid was dissolved in N, N-dimethylacetamide as a solvent. To the obtained polyamic acid solution, 3 ′, 5′-dihydroxyacetophenone as a low-temperature curing accelerator was added in an amount of 2 mol per 1 mol equivalent of the polyamic acid repeating unit.
A mixture was prepared by adding at a molar equivalent ratio. further,
Disperse Red 1 as a nonlinear optical material was added at a ratio of 20% by weight to the mixture to prepare a raw material solution of the nonlinear optical material of the present example.

This raw material solution was treated with Si having a SiO ₂ layer formed thereon.
After spin coating on the wafer to form a coating film and heating on a hot plate at 120 ° C. for 60 minutes, further heating in a vacuum oven at 100 ° C. for 60 minutes,
A polyimide non-linear optical material imidized by 90% or more was obtained.

As a result of mass spectrometry, the content of 3 ′, 5′-dihydroxyacetophenone in the obtained polyimide was
It was about 10 ppm.

Next, the same raw material solution as described above was applied on an ITO substrate by spin coating, and dried by heating at 90 ° C. to form a thin film having a thickness of 5 μm. An Al electrode is deposited on this thin film, and is applied at 120 ° C. while applying an electric field of 50 V / μm.
After heating for 60 minutes in a vacuum oven,
A sample was prepared by heating at 60 ° C. for 60 minutes.

The electrooptic constant was measured at a wavelength of 1300 nm using a Mach-Zehnder interference optical system. As a result, a high value of r ₃₃ = 20 pm / V was obtained.

When this sample was heated at 100 ° C. in the atmosphere, the initial electro-optic constant was maintained after 1300 hours, and it was confirmed that an extremely stable nonlinear optical material was obtained.

Example 4 Pyromellitic dianhydride, 4,
4'-diaminodiphenyl ether, 1,3-bis-
Polyamic acid in which (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane was mixed at a ratio of 1: 0.94: 0.06 was dissolved in N-methyl-2-pyrrolidone as a solvent. . To the obtained polyamic acid solution, 4-hydroxyphenylacetic acid as a low-temperature curing accelerator was added at a ratio of 1.2 g to 10 g of the polyamic acid composition to prepare a mixed solution. Furthermore, Disperse Red 1 as a nonlinear optical material was added to the mixture at 20% by weight.
, A raw material solution of the nonlinear optical material of this example was prepared.

[0172] This raw material solution was treated with Si having a SiO ₂ layer formed thereon.
A coating film was formed by spin coating on the wafer, and heated on a hot plate at 100 ° C. for 60 minutes to obtain a polyimide non-linear optical material which was imidized by about 98%.

As a result of mass spectrometry, the content of 4-hydroxyphenylacetic acid in the obtained polyimide was about 30 ppm.
Met.

Next, the same raw material solution as described above was applied onto an ITO substrate by spin coating, and dried by heating at 90 ° C. to form a thin film having a thickness of 5 μm. An Al electrode is vapor-deposited on this thin film, and 100 ° C. while applying an electric field of 50 V / μm.
For 60 minutes to produce a sample.

As a result of measuring the electro-optic constant at a wavelength of 1300 nm using a Mach-Zehnder interference optical system, a high value of r ₃₃ = 27 pm / V was obtained.

When this sample was heated at 100 ° C. in the air, the initial electro-optic constant was maintained after 1800 hours, and it was confirmed that an extremely stable nonlinear optical material was obtained.

Example 5 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride,
2,2-bis (4-aminophenyl) hexafluoropropane, 1,3-bis- (3-aminopropyl) -1,
1: 0.9 1,3,3-tetramethyldisiloxane
Polyamic acid blended at a ratio of 4: 0.06 was dissolved in N-methyl-2-pyrrolidone as a solvent. To the obtained polyamic acid solution, p-hydroxybenzaldehyde and triethylamine as low-temperature curing accelerators were added to prepare a mixed solution. The addition amounts of p-hydroxybenzaldehyde and triethylamine were 0.6 g and 0.4 g, respectively, for 10 g of the polyamic acid composition. Further, Disperse Red 1 as a nonlinear optical material was added at a ratio of 20% by weight to the mixture to prepare a raw material solution of the nonlinear optical material of the present example.

This raw material solution was treated with Si having a SiO ₂ layer formed thereon.
The coating film was formed by spin coating on the wafer, and heated on a hot plate at 100 ° C. for 90 minutes to obtain a polyimide non-linear optical material imidized by about 92%.

As a result of mass spectrometry, the content of triethylamine in the obtained polyimide was about 5 ppm.

Next, the same raw material solution as described above was applied onto an ITO substrate by spin coating, and dried by heating at 90 ° C. to form a thin film having a thickness of 5 μm. An Al electrode is vapor-deposited on this thin film, and 100 ° C while applying an electric field of 50 V / μm.
For 90 minutes to produce a sample.

As a result of measuring the electro-optic constant at a wavelength of 1300 nm using a Mach-Zehnder interference optical system, a high value of r ₃₃ = ₃₃ pm / V was obtained.

Further, when this sample was heated at 100 ° C. in the atmosphere, the value after 1500 hours maintained the initial electro-optical constant, and it was confirmed that an extremely stable nonlinear optical material was obtained.

(Example 6) Polyamic acid in which a diamine compound obtained by chemically modifying nonlinear optical material Disperse Red 1 and pyromellitic dianhydride were mixed at a ratio of 1: 1 was mixed with N, N- Dissolved in dimethylacetamide. To the obtained polyamic acid solution, benzimidazole as a low-temperature curing accelerator was added at a ratio of 2 mol equivalent to 1 mol equivalent of the repeating unit of polyamic acid, and the raw material of the nonlinear optical material of this example was added. A solution was prepared.

This raw material solution was treated with Si having a SiO ₂ layer formed thereon.
A coating film was formed by spin coating on the wafer, and heated on a hot plate at 160 ° C. for 30 minutes to obtain a polyimide non-linear optical material almost imidized by 100%. The polyimide obtained here is a so-called side chain type nonlinear optical polymer.

As a result of mass spectrometry, the content of benzimidazole in the obtained polyimide was about 13 ppm.

Next, the same raw material solution as described above was applied on an ITO substrate by spin coating, and dried by heating at 90 ° C. to form a thin film having a thickness of 5 μm. An Al electrode was deposited on this thin film, and heated at 160 ° C. for 30 minutes while applying an electric field of 50 V / μm to prepare a sample.

As a result of measuring the electro-optic constant at a wavelength of 1300 nm using a Mach-Zehnder interference optical system, a high value of r ₃₃ = 45 pm / V was obtained.

Further, when this sample was heated at 100 ° C. in the air, the initial electro-optical constant was maintained even after lapse of 5000 hours, and it was confirmed that an extremely stable nonlinear optical material was obtained.

Example 7 A carboxylic dianhydride obtained by reacting a diamine compound obtained by chemically modifying a nonlinear optical material Disperse Red 1 with trimellitic chloride anhydride, and oxy-4,4 ' -Dianiline:
The polyamic acid blended in a ratio of 1 was mixed with N, N-
Dissolved in dimethylacetamide. To the obtained polyamic acid solution, benzimidazole as a low-temperature curing accelerator was added at a ratio of 2 mol equivalent to 1 mol equivalent of the repeating unit of polyamic acid, and the raw material of the nonlinear optical material of this example was added. A solution was prepared.

This raw material solution was treated with Si having a SiO ₂ layer formed thereon.
A coating film was formed by spin coating on the wafer, and heated on a hot plate at 160 ° C. for 30 minutes to obtain a polyimide non-linear optical material almost imidized by 100%. The polyimide obtained here is a so-called side chain type nonlinear optical polymer.

As a result of mass spectrometry, the content of benzimidazole in the obtained polyimide was about 10 ppm.

Next, the same raw material solution as described above was applied on an ITO substrate by spin coating, and dried by heating at 90 ° C. to form a thin film having a thickness of 5 μm. An Al electrode was deposited on this thin film, and heated at 160 ° C. for 30 minutes while applying an electric field of 50 V / μm to prepare a sample.

As a result of measuring the electro-optic constant at a wavelength of 1300 nm using a Mach-Zehnder interference optical system, a high value of r ₃₃ = 39 pm / V was obtained.

When this sample was heated at 100 ° C. in the atmosphere, the initial electro-optic constant was maintained even after 5000 hours, and it was confirmed that an extremely stable nonlinear optical material was obtained.

(Example 8) A polyamic acid in which a diamine compound obtained by chemically modifying a nonlinear optical material Disperse Red 1 and pyromellitic dianhydride were mixed at a 1: 1 ratio was mixed with N, N- Dissolved in dimethylacetamide. To the obtained polyamic acid solution, N-acetylglycine as a low-temperature curing accelerator was added at a ratio of 2 mol equivalent to 1 mol equivalent of the repeating unit of polyamic acid, and the nonlinear optical material of this example was added. Was prepared.

This raw material solution was treated with Si having a SiO ₂ layer formed thereon.
A coating film was formed by spin coating on the wafer, and heated on a hot plate at 160 ° C. for 30 minutes to obtain a polyimide non-linear optical material almost imidized by 100%. The polyimide obtained here is a so-called side chain type nonlinear optical polymer.

As a result of mass spectrometry, the content of N-acetylglycine in the obtained polyimide was about 28 ppm.

Next, the same raw material solution as described above was applied onto an ITO substrate by spin coating, and dried by heating at 90 ° C. to form a thin film having a thickness of 5 μm. An Al electrode was deposited on this thin film, and heated at 160 ° C. for 30 minutes while applying an electric field of 50 V / μm to prepare a sample.

As a result of measuring the electro-optic constant at a wavelength of 1300 nm using a Mach-Zehnder interference optical system, a high value of r ₃₃ = 35 pm / V was obtained.

When this sample was heated at 100 ° C. in the atmosphere, the initial electro-optic constant was maintained after 3000 hours, and it was confirmed that an extremely stable nonlinear optical material was obtained.

Example 9 A polyamic acid prepared by mixing a diamine compound obtained by chemically modifying a nonlinear optical material Disperse Red 1 and pyromellitic dianhydride in a 1: 1 ratio was mixed with N, N- as a solvent. Dissolved in dimethylacetamide. 3 ′, 5′-dihydroxyacetophenone as a low-temperature curing accelerator was added to the obtained polyamic acid solution,
A raw material solution of the nonlinear optical material of this example was prepared by adding 2 mol equivalents to 1 mol equivalent of the repeating unit of polyamic acid.

[0202] This raw material solution was treated with Si having a SiO ₂ layer formed thereon.
By spin coating on a wafer to form a coating film and heating on a hot plate at 160 ° C. for 30 minutes, 9
A polyimide nonlinear optical material imidized by 0% or more was obtained. The polyimide obtained here is a so-called side chain type nonlinear optical polymer.

As a result of mass spectrometry, the content of 3 ′, 5′-dihydroxyacetophenone in the obtained polyimide was
It was about 33 ppm.

Next, the same raw material solution as described above was applied onto an ITO substrate by spin coating, and dried by heating at 90 ° C. to form a thin film having a thickness of 5 μm. An Al electrode was deposited on this thin film, and heated at 160 ° C. for 30 minutes while applying an electric field of 50 V / μm to prepare a sample.

As a result of measuring the electro-optic constant at a wavelength of 1300 nm using a Mach-Zehnder interference optical system, a high value of r ₃₃ = ₃₃ pm / V was obtained.

Further, when this sample was heated at 100 ° C. in the atmosphere, the initial electro-optical constant was maintained even after lapse of 2000 hours, and it was confirmed that an extremely stable nonlinear optical material was obtained.

Example 10 A polyamic acid obtained by chemically modifying a non-linear optical substance Disperse Red 1 with a diamine compound and pyromellitic dianhydride in a ratio of 1: 1 was mixed with N-methyl-as a solvent. Dissolved in 2-pyrrolidone. To the obtained polyamic acid solution, 4-hydroxyphenylacetic acid as a low-temperature curing accelerator was added at a ratio of 1.2 g to 10 g of the polyamic acid composition, and the raw material solution of the nonlinear optical material of this example was added. Prepared.

This raw material solution was treated with Si having a SiO ₂ layer formed thereon.
A coating film was formed by spin coating on the wafer, and heated on a hot plate at 160 ° C. for 30 minutes to obtain a polyimide non-linear optical material almost imidized by 100%. The polyimide obtained here is a so-called side chain type nonlinear optical polymer.

As a result of mass spectrometry, the content of 4-hydroxyphenylacetic acid in the obtained polyimide was about 18 ppm.
Met.

Next, the same raw material solution as described above was applied on an ITO substrate by spin coating, and dried by heating at 90 ° C. to form a thin film having a thickness of 5 μm. An Al electrode was deposited on this thin film, and heated at 160 ° C. for 30 minutes while applying an electric field of 50 V / μm to prepare a sample.

As a result of measuring the electro-optic constant at a wavelength of 1300 nm using a Mach-Zehnder interference optical system, a high value of r ₃₃ = 47 pm / V was obtained.

Further, when this sample was heated at 100 ° C. in the atmosphere, the initial electro-optic constant was maintained even after 5000 hours, and it was confirmed that an extremely stable nonlinear optical material was obtained.

Example 11 A polyamic acid obtained by chemically modifying a non-linear optical material Disperse Red 1 with a diamine compound and pyromellitic dianhydride in a 1: 1 ratio was mixed with N, N- Dissolved in dimethylacetamide. To the obtained polyamic acid solution, p-hydroxybenzaldehyde and triethylamine as low-temperature curing accelerators were added to prepare a raw material solution of the nonlinear optical material of this example. The addition amounts of p-hydroxybenzaldehyde and triethylamine were 0.6 g and 0.4 g, respectively, for 10 g of the polyamic acid composition.

[0214] This raw material solution was mixed with Si having a SiO ₂ layer formed thereon.
A coating film was formed by spin coating on a wafer, and heated on a hot plate at 160 ° C. for 30 minutes to obtain a polyimide non-linear optical material which was almost imidized at 95%. The polyimide obtained here is a so-called side chain type nonlinear optical polymer.

As a result of mass spectrometry, the content of triethylamine in the obtained polyimide was about 5 ppm.

Next, the same raw material solution as described above was applied onto an ITO substrate by spin coating, and dried by heating at 90 ° C. to form a thin film having a thickness of 5 μm. An Al electrode was deposited on this thin film, and heated at 160 ° C. for 30 minutes while applying an electric field of 50 V / μm to prepare a sample.

As a result of measuring the electro-optic constant at a wavelength of 1300 nm using a Mach-Zehnder interference optical system, a high value of r ₃₃ = 40 pm / V was obtained.

Further, when this sample was heated at 100 ° C. in the atmosphere, the initial electro-optic constant was maintained even after lapse of 5000 hours, and it was confirmed that an extremely stable nonlinear optical material was obtained.

(Example 12) As shown in FIG.
_On a silicon substrate 1 having _two films, Al
After forming the deposited film, a low refractive index epoxy resin
The lower clad layer 3 was formed by applying a thickness of 0 μm. After forming a core layer 4 of a non-linear optical material thin film (thickness: 6 μm) made of the same polyimide as in Example 1, a Mach-Zehnder type as shown in FIG. 2 is formed by photolithography and RIE. A channel waveguide was formed. Further, an epoxy resin layer similar to the lower
The upper clad layer 5 was formed with a thickness of m. The relative refractive index difference between the upper and lower cladding layers 3 and 5 and the core layer 4 was adjusted to be 0.5%. The width 2 of Au is overlapped on one arm of the Mach-Zehnder type channel waveguide.
A microstrip electrode 6 having a thickness of 5 μm and a thickness of 10 μm was formed on the upper cladding layer 5 by a plating method. The length of the microstrip electrode 6 overlapping the channel waveguide 4 is 10 mm.

This is adjusted to 50 V by polarization between parallel plate electrodes.
The poling treatment of the core layer was performed by heating (160 ° C.) while applying an electric field of / μm. Through the above steps, a waveguide-type light modulation element was manufactured.

From the end face of the obtained waveguide device, the wavelength 131
When the measurement was performed by inputting a laser beam of 0 nm, the electro-optic constant of the core layer was 35 pm / V, which was sufficiently higher than that of the conventional one, and the waveguide propagation loss was 1 dB / cm, which was sufficient. The half-wavelength voltage was 5 V, and when microwaves were input using a coaxial cable, the response frequency characteristics showed a flat light modulation characteristic up to 60 GHz.
Further, even in an accelerated test environment at a temperature of 80 ° C. and a relative humidity of 75%, no deterioration of the light modulation characteristics was observed.

(Example 13) Pyromellitic dianhydride,
Polyamic acid obtained by blending 4,4′-diaminodiphenyl ether and 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisisiloxane at a ratio of 1: 0.94: 0.06, It was dissolved in N-methyl-2-pyrrolidone as a solvent. 20 g of the obtained polyamic acid solution
4-hydroxybenzoic acid 2 as a carboxylic acid derivative
3 g of -N, N dimethylaminoethyl and 0.8 g of 1,2-naphthoquinonediazidosulfonic acid ester as a photosensitizing agent, and Disperse Red 1 as a non-linear optical substance at a ratio of 20% by weight to prepare a raw material solution Prepared.

This raw material solution was spin-coated on an ITO substrate and heated at 90 ° C. to form a thin film having a thickness of 5 μm.
Thereafter, ultraviolet rays (11 mW / cm ² , 405 nm) were irradiated through a waveguide mask pattern for 30 seconds using an exposure machine. This was heat-treated at 140 ° C. for 30 minutes and then developed with an aqueous solution of tetramethylammonium hydroxide to obtain a predetermined waveguide pattern.

A channel waveguide was formed in the same manner as in Example 12, and after performing a poling treatment, the electro-optic constant was measured. As a result, 28 pm / V at 1310 nm was obtained.
And high values were obtained. The temperature is 80 ° C. and the relative humidity is 75
% Under the accelerated test environment, no deterioration of the characteristics was observed.

(Embodiment 14) A continuous wave laser light source, a laser driving circuit, an electric signal generator, means for injecting a laser into an optical modulator, an optical modulator, An optical signal generation device was constructed by combining the means for extracting the output light from the light source, the light propagation path, and the photodetector.

The continuous light emitted from the laser is analog- or digital-modulated in accordance with the electric signal given to the optical modulator, and can be taken out as an optical signal. Optical signal could be transmitted to the location at

Also, by using an optical multiplexing circuit by combining a plurality of similarly configured optical signal generators,
A time multiplexed optical signal or a wavelength multiplexed optical signal was synthesized and transmitted.

(Embodiment 15) A continuous wave laser light source, a laser driving circuit, a radio wave receiving mechanism, means for injecting laser light into an optical modulator, an optical modulator A radio-to-optical signal converter was constructed by combining the means for extracting the output light from the device and the photodetector.

The continuous light emitted from the laser was analog-modulated according to the radio wave reception signal given to the optical modulator, and could be extracted as an optical signal. This optical signal could be transmitted to a location remote from the radio wave receiving position by using the optical propagation path.

It is also possible to convert the output light from the optical modulator to an electric signal by inputting it to a photodetector, and obtain an intermediate frequency by mixing with an electric signal having a frequency close to the received radio wave. After that, processing as an electric signal using an A / D converter was also possible.

[0231]

As described in detail above, according to the present invention,
A non-linear optical material having high heat resistance and excellent non-linear optical characteristics and a method for manufacturing the same are provided. Further, according to the present invention, a high-performance nonlinear optical device using a polymer is provided.

According to the present invention, it is possible to realize an imidization treatment at about 200 ° C. or lower while using polyimide as a base polymer. By using the high Tg polymer in this way, while suppressing the orientation relaxation of the nonlinear optical material,
Deterioration of nonlinear optical characteristics due to a high-temperature process can be prevented. As a result, a nonlinear optical device excellent in both the orientation relaxation lifetime and the nonlinear optical constant can be realized, and its industrial value is enormous.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of an optical modulator having an optical waveguide structure according to the present invention.

FIG. 2 is a schematic diagram of a Mach-Zehnder optical modulator according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Substrate 2 ... Lower electrode 3 ... Lower clad layer 4 ... Core layer 5 ... Upper clad layer 6, 6 '... Upper electrode 7, 7' ... Electric signal source

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C08L 79/08 C08L 79/08 A G02B 6/12 G02F 1/065 G02F 1/065 G02B 6/12 NF term (reference) 2H047 KA04 LA11 NA08 QA05 TA05 TA11 TA41 2H079 AA02 AA12 BA01 DA07 EA05 HA11 4J002 CM041 EJ016 EJ036 EJ066 EN036 EN106 ER007 ES007 EU006 EU026 EU046 EU056 EU116 EU126 EU136 EU146 EU166 EU186 EU216 EU226 EV217 EV236

Claims (8)

[Claims] 1. A nonlinear optical material comprising a thin film containing a polyimide, a nonlinear optical substance, and a low-temperature curing accelerator. 2. A low-temperature curing accelerator comprising: (AC1) a substituted or unsubstituted nitrogen-containing heterocyclic compound having an acid dissociation exponent pKa of 0 to 8 in an aqueous solution of (AC1);
2) a substituted or unsubstituted amino acid compound, and (A)
The nonlinear optical material according to claim 1, wherein C3) has a molecular weight of 1,000 or less and is at least one selected from the group consisting of an aromatic hydrocarbon compound or an aromatic heterocyclic compound having at least two or more hydroxyl groups. . 3. The low-temperature curing accelerator has the following general formula:
Compounds represented by (1) to (10) and derivatives thereof
At least one member selected from the group consisting of
2. The nonlinear optical material according to 1. Embedded image(In the above formula (2), R^{twenty one}Is alkylene having 1 to 10 carbon atoms
Group, ethynylene group, or -CH_TwoCO-. )(In the above formula (5), X^{twenty one}Is -C (= O) -O- or-
C (= O) -NH-, R ^{twenty two}Is alkylene having 1 to 4 carbon atoms
Group, R^{twenty three}And R^{twenty four}Is a methyl or ethyl group
You. )(In the above formula (8), R^{twenty five}Is a direct bond, -O-, -SO_Two
-, -CH_Two-, -C (CH_Three)_Two-Or -C (CF_Three)
_Two-. ) 4. The low-temperature curing accelerator is at least one selected from the group consisting of compounds represented by the following general formulas (1) to (4) and (6) to (10) and derivatives thereof.
The nonlinear optical material according to claim 1, comprising a seed and a tertiary amine compound. Embedded image (In the above formula (2), R ²¹ is an alkylene group having 1 to 10 carbon atoms, an ethynylene group, or —CH ₂ CO—.) Embedded image (In the above formula (8), R ²⁵ is a direct bond, —O—, —SO _{2
-, - CH 2 -, -} C (CH 3) 2 - or -C (CF _3)
2- . ) 5. The content of the low-temperature curing accelerator is 1 pp.
The nonlinear optical material according to any one of claims 1 to 4, wherein the content is from m to 1 wt%. 6. A step of forming a thin film containing a polyimide precursor containing a polyamic acid having a non-linear optical material dispersed or chemically bonded and a low-temperature curing accelerator, and forming the thin film in a temperature range of 60 to 300 ° C. Heating the polyimide precursor by heating at a temperature to cure the polyimide precursor. 7. The polyamic acid has the following general formula (P
The method for producing a nonlinear optical material according to claim 6, which has a repeating unit represented by A). Embedded image (In the above general formula, φ is a tetravalent organic group, Ψ is a divalent organic group, R is a substituted or specific substituted hydrocarbon group, an organosilicon group, or a hydrogen atom.) 8. A channel waveguide made of a non-linear optical material, means for applying a voltage to said non-linear optical material,
An optical modulator device having an inlet for introducing light into the nonlinear optical material and an outlet for extracting light, wherein the nonlinear optical material is the nonlinear material according to any one of claims 1 to 5. Nonlinear optical device characterized by the above-mentioned.