JP3201826B2 - Liquid crystalline and low dielectric polyimide and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal and low dielectric polyimide. More specifically, the present invention relates to a thermoplastic polyimide having excellent liquid crystal properties and low dielectric properties, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, polyimide has excellent properties such as mechanical properties, chemical resistance, flame retardancy, and electrical properties in addition to its excellent heat resistance.
It is widely used in the fields of composite materials, electric / electronic parts and the like. However, even if it is excellent in heat resistance, it does not have a clear glass transition temperature, so when it is used as a molding material, it must be processed using a method such as sinter molding, and the workability is excellent. Has low and high glass transition temperatures, is soluble in halogenated hydrocarbon solvents, and is not satisfactory in terms of heat resistance and solvent resistance.

On the other hand, recently, a group of liquid crystalline polymers has attracted attention as highly functional engineering plastics.
Liquid crystalline polymers are classified into thermotropic liquid crystals and lyotropic liquid crystals due to their properties.Thermotropic liquid crystals show optical anisotropy when melted, and when a shear force is applied during melt molding, the molecular chain is Are widely used in the fields of molding materials, composite materials, and the like because they have properties such as improving the mechanical strength of the molded body and reducing the melt viscosity. Currently known liquid crystalline polymers are polyester, polyesteramide, polyazomethine (above thermotropic liquid crystal), polyamide,
Polybenzothiazole (the above is a lyotropic liquid crystal). Recently, liquid crystal polymers containing an imide group in the molecular skeleton such as polyesterimide and polyesteretherimide have been reported (for example, see
-4531, JP-A-4-33925, USP-4,38
3, 105, etc.), the portion of these polymers exhibiting liquid crystallinity is substantially an ester portion, and cannot be called a liquid crystalline polyimide. Further, since the glass transition temperature of these polymers is around 180 ° C. at the maximum, it cannot be said that they have sufficient heat resistance. That is, a polyimide exhibiting liquid crystal properties has not been known at all.

On the other hand, in the field of electric and electronic parts in recent years, microelectronics have been remarkably developed. In particular,
In a large computer, high-speed signal transmission is indispensable due to the adoption of a multilayer circuit board. However, if the dielectric constant of the substrate material is large, signal transmission is delayed, which is an obstacle to high-speed transmission. Polyimide is used for an interlayer insulating film having a multilayer wiring structure. For these reasons, the necessity of lowering the dielectric constant has been highlighted in addition to the excellent characteristics of the conventional polyimide.

[0005] Teflon resin has long been known as a resin having a low dielectric constant. However, the fact that a low dielectric constant can be achieved by introducing a fluoro group into a polyimide structure is known from AK.
St. Clair et.al., Polymeric Materials Science and En
gineering, 59 , 28-32 (1988) and EP 0299865.

However, a polyimide containing a large amount of fluorine cannot obtain a polymer having a sufficiently high molecular weight (for example, T. Ichino et al., J. Polym. Sci., Part A, Poly Che
m., 28 , 323 (1990) and Japanese Patent Application Laid-Open No. 01-182324), and the price is extremely high, so that production at an industrial level is difficult. Further, as represented by a Teflon resin, if a large amount of fluorine is contained, the adhesiveness is reduced, so that it is expected that the interlayer adhesion of the multilayer circuit board will be difficult.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a thermoplastic polyimide having excellent liquid crystallinity and low dielectric properties and good moldability in addition to excellent heat resistance inherent to polyimide.

[0008]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, a polyimide containing an aromatic diamine having a specific structure as a monomer component impairs various properties inherent to the polyimide. Without any problems, the present inventors have found out that this is a thermoplastic polyimide having excellent molding processability with liquid crystallinity and low dielectric properties, and completed the present invention. That is, the present invention provides a compound represented by the general formula (1):

[0009]

Embedded image (In the formula, R represents an aliphatic group having 2 to 27 carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group which are directly or mutually linked by a bridge member. A tetravalent group selected from the group consisting of non-fused polycyclic aromatic groups), a polyimide having a repeating structural unit represented by the formula: A polyimide which is an aromatic ring essentially having no substituent or substituted with a group having no reactivity with an amine or a dicarboxylic anhydride, and a polyamic acid which is a precursor of the present polyimide is converted into dimethylacetamide. After dissolving at a concentration of 0.5 g / dl, a polyimide having a logarithmic viscosity at 35 ° C. of 0.01 to 3.0 dl / g, or 9 parts by weight of the polyimide powder and 1 part by weight of p-chlorophenol In a mixed solvent of phenol 0.5
A polyimide having a logarithmic viscosity of 0.01 to 3.0 dl / g measured at 35 ° C. after heating and dissolving at a concentration of g / dl, and a method for producing them. More specifically, the present invention provides a compound represented by the general formula (1):

[0010]

Embedded image (In the formula, R represents an aliphatic group having 2 to 27 carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group which are directly or mutually linked by a bridge member. And a tetravalent group selected from the group consisting of non-condensed polycyclic aromatic groups), and a polyimide having a repeating structural unit represented by the formula (3):

[0011]

Embedded image 1,3-bis [4- (4-amino-6-trifluoromethylphenoxy) -α, α-dimethylbenzyl]
An aromatic diamine containing benzene as a main component and a compound represented by the general formula (4):

[0012]

Embedded image (In the formula, R represents an aliphatic group having 2 to 27 carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group which are directly or mutually linked by a bridge member. And a tetracarboxylic dianhydride represented by the formula (1), wherein the resulting polyamic acid is thermally or chemically imidized. It is a method of manufacturing. Further, an aromatic ring in which the terminal of the repeating structural unit represented by the general formula (1) has essentially no substituent or is substituted by a group having no reactivity with an amine or a dicarboxylic anhydride. Polyimide,
These polyimides are represented by the formula (3)
An aromatic diamine mainly composed of 3-bis [4- (4-amino-6-trifluoromethylphenoxy) -α, α-dimethylbenzyl] benzene and the above-mentioned general formula (4)
With a tetracarboxylic dianhydride represented by the formula (5)

[0013]

Embedded image (In the formula, Z ₁ is an aliphatic group having 6 to 15 carbon atoms, a cyclic aliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group connected directly or by a crosslinking member. An aromatic dicarboxylic anhydride represented by the formula (6):

[0014]

Embedded image Z ₂ -NH ₂ (6) (wherein, Z ₂ represents an aliphatic group having from 6 to 15 carbon atoms, cycloaliphatic groups, monocyclic aromatic groups, condensed polycyclic aromatic group, An aromatic group represented by a monovalent group selected from the group consisting of non-condensed polycyclic aromatic groups which are connected to each other directly or by a bridging member) in the presence of an aromatic monoamine represented by the formula: A method for producing a polyimide, comprising thermally or chemically imidizing the obtained polyamic acid. The polyimide of the present invention has the general formula (1)

[0015]

Embedded image (Wherein, R is as defined above), and a polyimide having a repeating structural unit represented by the formula: Polyimide of this repeating structural unit as an aromatic diamine component,
The above formula (3)

[0016]

Embedded image 1,3-bis [4- (4-amino-6-trifluoromethylphenoxy) -α, α-dimethylbenzyl]
Benzene is used.

The method for producing 1,3-bis [4- (4-amino-6-trifluoromethylphenoxy) -α, α-dimethylbenzyl] benzene used as a raw material of the present invention is described in the following. 4- (4-nitro-6-trifluoromethylphenoxy) -α, α-dimethylbenzyl] benzene. 1,3-bis [4- (4
-Nitro-6-trifluoromethylphenoxy) -α,
α-Dimethylbenzyl] benzene can be prepared by, for example, converting 1,3-bis [(4-hydroxy) -α, α-dimethylbenzyl] benzene and 2-chloro-5-nitrotrifluoromethylbenzene in the presence of a base. It is produced by a method of reacting in an aprotic polar solvent. The method for reducing the dinitro compound is not particularly limited, and a method for reducing a nitro group to an amino group, for example, a method described in Shin-Jikken Kagaku Koza, Vol. 15, Oxidation and Reduction, Maruzen (1977) can be applied. Specifically, it can be produced by a catalytic reduction method using a metal catalyst such as a palladium catalyst.

The polyimide of the present invention uses the above-mentioned 1,3-bis [4- (4-amino-6-trifluoromethylphenoxy) -α, α-dimethylbenzyl] benzene as an essential monomer raw material of an aromatic diamine. However, other aromatic diamines can be mixed and used as long as the good physical properties of the polyimide are not impaired.

Examples of the diamines which can be used in combination are, for example, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, 4,4'-diaminodiphenyl ether, 3'-diaminodiphenyl ether, 3,
4'-diaminodiphenyl ether, bis (3-aminophenyl) sulfide, bis (4-aminophenyl) sulfide, (3-aminophenyl) (4-aminophenyl) sulfide, bis (3-aminophenyl) sulfoxide, bis (4 -Aminophenyl) sulfoxide, (3
-Aminophenyl) (4-aminophenyl) sulfoxide, bis (3-aminophenyl) sulfone, bis (4-
Aminophenyl) sulfone, (3-aminophenyl)
(4-aminophenyl) sulfone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4'-diaminodiphenylmethane, bis [4- (3-aminophenoxy)
Phenyl] methane, bis [4- (4-aminophenoxy)
Phenyl] methane, 1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 1,2-bis [4- (3-aminophenoxy) phenyl] ethane, 1,1-bis [4- (4 −
Aminophenoxy) phenyl] ethane, 1,2-bis [4
-(4-aminophenoxy) phenyl] ethane, 2,2 bis [4- (3-aminophenoxy) phenyl] propane, 2,
2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] butane, 2,2-bis [3- (3-aminophenoxy)
Phenyl] -1,1,1,3,3,3-hexafluoropropane,
2,2-bis [4- (4-aminophenoxy) phenyl]-
1,1,1,3,3,3-hexafluoropropane, 1,3-bis (3
-Aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,
4'-bis (3-aminophenoxy) biphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (3-
Aminophenoxy) phenyl] ketone, bis [4- (4-
Aminophenoxy) phenyl] ketone, bis [4- (3-
Aminophenoxy) phenyl] sulfide, bis [4-
(4-Aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfoxide, bis [4- (4-aminophenoxy) phenyl] sulfoxide, bis [4- (3-aminophenoxy) phenyl] Sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy)
Phenyl] ether, 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-
Aminophenoxy) benzoyl] benzene, 4,4'-bis [3- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4'-bis [3- (3-aminophenoxy) benzoyl] diphenyl ether, 4,4'- Screw [4- (4-
Amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] diphenylsulfone, bis [4- {4- (4-amino) Phenoxy) phenoxydiphenyl] sulfone, 1,4-bis [4- (4-aminophenoxy) phenoxy-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) phenoxy-α , α-dimethylbenzyl] benzene and the like, and these are used alone or in combination of two or more. The aromatic tetracarboxylic dianhydride is represented by the general formula (4):

[0020]

Embedded image The tetracarboxylic dianhydride represented by is used. In the general formula (4), R is an aliphatic group having 2 to 27 carbon atoms,
Cyclic aliphatic group, monocyclic aromatic group, fused polycyclic aromatic group,
And a tetravalent group selected from the group consisting of non-fused polycyclic aromatic groups in which the aromatic groups are connected to each other directly or by a bridging member. Specifically, R in the general formula (4) is 2 to 1 carbon atoms
0 aliphatic group, cycloaliphatic group having 4 to 10 carbon atoms, formula (a)

[0021]

Embedded image A monocyclic aromatic group represented by the formula (b):

[0022]

Embedded image A condensed polycyclic aromatic group represented by the formula (c):
3]

[0023]

Embedded image (Wherein X is a direct bond, -CO-, -O-, -S-,-
SO ₂ —, —CH ₂ —, —C (CH ₃ ) ₂ —, —C (CF
₃ ) _2- , Formula (d) [Formula 24], Formula (e) [Formula 24]

[0024]

Embedded image Or the formula (f)

[0025]

Embedded image (Where Y is a direct bond, -CO-, -O-, -S-,
—SO ₂ —, —CH ₂ —, —C (CH ₃ ) ₂ —, —C (C
Tetracarboxylic acid, which is a tetravalent group selected from the group consisting of non-condensed polycyclic aromatic groups in which the aromatic groups represented by F ₃ ) ₂ — are interconnected directly or by a bridging member Dianhydride is used.

The tetracarboxylic dianhydride represented by the general formula (4) used in the present invention includes, for example, ethylene tetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, pyromellitic dianhydride. Anhydride, 3,
3 ', 4,4'-benzophenonetetracarboxylic dianhydride,
2,2 ', 3,3'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic acid Dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone Anhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride Product, 2,2-bis (3,4-dicarboxyphenyl)-
1,1,1,3,3,3-hexafluoropropane dianhydride, 2,
3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,
8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-
Naphthalenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7, -anthracene Examples thereof include tetracarboxylic dianhydride, 1,2,7,8-phenanthrene tetracarboxylic dianhydride and the like. These may be used alone or in combination of two or more.

The polyimide obtained by using the aromatic diamine component and the aromatic tetracarboxylic dianhydride component as monomer components is mainly a polyimide having a repeating structural unit represented by the general formula (1), and is mainly a polyimide having the general formula (1) Or a polyimide having an aromatic ring substituted with a group having no substituent at the polymer molecule terminal or having no reaction with an amine or dicarboxylic anhydride, or a polyimide having the same. A composition containing a polyimide is also included.

The polyimide having an aromatic ring substituted at the terminal without a substituent or with a group having no reactivity with an amine or a dicarboxylic anhydride can be obtained by preparing the 1,3-bis-formula of the above formula (3). [4- (4-amino-6-trifluoromethylphenoxy) -α, α-dimethylbenzyl] aromatic amine mainly composed of benzene and tetracarboxylic dianhydride mainly represented by the general formula (4) With the formula (5)

[0029]

Embedded image (In the formula, Z ₁ is an aliphatic group having 6 to 15 carbon atoms, a cyclic aliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group connected directly or by a crosslinking member. Or a divalent group selected from the group consisting of non-condensed polycyclic aromatic groups described above) or an aromatic dicarboxylic anhydride represented by the formula (6):

[0030]

Embedded image Z ₂ -NH ₂ (6) (wherein, Z ₂ represents an aliphatic group having from 6 to 15 carbon atoms, cycloaliphatic groups, monocyclic aromatic groups, condensed polycyclic aromatic group, An aromatic group represented by a monovalent group selected from the group consisting of non-condensed polycyclic aromatic groups which are connected to each other directly or by a bridging member) in the presence of an aromatic monoamine represented by the formula: It is obtained by thermally or chemically imidizing the resulting polyamic acid.

Here, Z ₁ and Z ₂ in the formulas (5) and (6) include those having the same definition as R in the polyimide formula represented by the formula (1). The dicarboxylic anhydrides used in these methods include phthalic anhydride, 2,3
-Benzophenone dicarboxylic anhydride, 3,4-benzophenone dicarboxylic anhydride, 2,3-dicarboxyphenyl phenyl ether anhydride, 3,4-dicarboxyphenyl phenyl ether anhydride, 2,3-biphenyl dicarboxylic anhydride , 3,4-biphenyldicarboxylic anhydride, 2,
3-dicarboxyphenylphenylsulfone anhydride, 3,
4-dicarboxyphenylphenylsulfone anhydride, 2,
3-dicarboxyphenylphenyl sulfide anhydride,
3,4-dicarboxyphenylphenyl sulfide anhydride, 1,2-naphthalenedicarboxylic anhydride, 2,3-naphthalenedicarboxylic anhydride, 1,8-naphthalenedicarboxylic anhydride, 1,2-anthracenedicarboxylic anhydride object,
Examples thereof include 2,3-anthracene dicarboxylic anhydride and 1,9-anthracene dicarboxylic anhydride. These dicarboxylic anhydrides may be substituted with a group having no reactivity with amine or dicarboxylic anhydride.

Of these dicarboxylic anhydrides, phthalic anhydride is most preferred from the viewpoint of properties and practical use of the polyimide from which phthalic anhydride can be obtained. That is, it is a polyimide excellent in molding stability at the time of high-temperature molding, has excellent chemical resistance, and considering the excellent workability, for example,
Polyimide is extremely useful as a base material for spacecraft and as an electric / electronic component.

When phthalic anhydride is used, there is no problem in using a part of it with another dicarboxylic anhydride as long as the good physical properties of polyimide are not impaired. The amount of the dicarboxylic anhydride to be used is per 1 mol of 1,3-bis [4- (4-amino-6-trifluoromethylphenoxy) -α, α-dimethylbenzyl] benzene represented by the formula (3). The molar ratio is 0.001 to 1.0. If the amount is less than 0.001 mol, the viscosity is increased during high-temperature molding, which causes a reduction in molding processability. Also, 1.0
If the molar ratio is exceeded, the mechanical properties deteriorate. The preferred amount is 0.01 to 0.5 mol.

When an aromatic monoamine is used,
Examples of the aromatic monoamine include aniline, o-toluidine, m-toluidine, p-toluidine, 2,3-xylidine, 2,6-xylidine, 3,4-xylidine, 3,5-
Xylidine, o-chloroaniline, m-chloroaniline, p-chloroaniline, o-bromoaniline, m-bromoaniline, p-bromoaniline, o-nitroaniline, m-nitroaniline, p-nitroaniline, o-amino Phenol, m-aminophenol, p-aminophenol, o-anisidine, m-anisidine, p-anisidine, o-phenezine, m-phenezine, p-phenezine, o-aminobenzaldehyde, m-aminobenzaldehyde, p- Aminobenzaldehyde, o-aminobenzonitrile, m-aminobenzonitrile, p-aminobenzonitrile, 2-aminobiphenyl, 3-aminobiphenyl, 4-aminobiphenyl, 2-aminophenylphenyl ether, 3-aminophenylphenyl ether , 4-aminop Alkenyl phenyl ether, 2-aminobenzophenone, 3-aminobenzophenone, 4-aminobenzophenone, 2-aminophenyl phenyl sulfide, 3-aminophenyl phenyl sulfide, 4
Aminophenylphenyl sulfide, 2-aminophenylphenylsulfone, 3-aminophenylphenylsulfone, 4-aminophenylphenylsulfone, α-naphthylamine, β-naphthylamine, 1-amino-2-naphthol, 2-amino-1-naphthol, 4-amino-
1-naphthol, 5-amino-1-naphthol, 5-amino-2-naphthol, 7-amino-2-naphthol,
Examples thereof include 8-amino-1-naphthol, 8-amino-2-naphthol, 1-aminoanthracene, 2-aminoanthracene, and 9-aminoanthracene. These aromatic monoamines may be substituted with a group having no reactivity with amine or dicarboxylic anhydride.

The amount of the aromatic monoamine used is 0.001 to 1.0 mole ratio per mole of the tetracarboxylic dianhydride represented by the general formula (4). If the amount is less than 0.001 mol, the viscosity is increased at the time of high-temperature molding, which causes a reduction in moldability. If the molar ratio exceeds 1.0, the mechanical properties deteriorate. The preferred amount is 0.01 to 0.1.
5 mole ratio.

As described above, when the polyimide of the present invention having no substituent at the terminal or a substituted aromatic ring is produced, tetracarboxylic dianhydride, aromatic diamine, and dicarboxylic anhydride or The molar ratio of the aromatic monoamine is 0.9 to 1.0 mol of the aromatic diamine, and 0.001 to 1.0 mol of the dicarboxylic anhydride or the aromatic monoamine per 1 mol of the tetracarboxylic dianhydride.
Is a mole. In the production of polyimide, it is customary to adjust the ratio of tetracarboxylic dianhydride to aromatic diamine in order to adjust the molecular weight of the resulting polyimide. In the method of the present invention, an appropriate molar ratio of aromatic diamine to tetracarboxylic dianhydride to obtain a polyimide having good melt flowability is 0.9 to 1.0.
Range.

The method for producing the polyimide of the present invention includes:
Although all methods capable of producing polyimide can be applied including known methods, it is particularly preferable to carry out the reaction in an organic solvent. The solvent used in such a reaction is preferably N, N-dimethylacetamide, but other usable solvents include, for example,
N, N-dimethylformamide, N, N-diethylacetamide, N, N-dimethoxyacetamide, N-methyl-2
-Pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2
-Methoxyethoxy) ethane, bis [2- (2-methoxyethoxy) ethyl] ether, tetrahydrofuran,
3-dioxane, 1,4-dioxane, pyrroline, picoline, dimethylsulfoxide, dimethylsulfone, tetramethylurea, hexamethylphosphoramide, phenol, o-cresol, m-cresol, p-cresol, m-cresolic acid, p -Chlorophenol, anisole, benzene, toluene, xylene and the like.
These organic solvents may be used alone or as a mixture of two or more.

In the method of the present invention, 1,3-bis [4
-(4-amino-6-trifluoromethylphenoxy)-
[α, α-dimethylbenzyl] benzene, tetracarboxylic dianhydride, aromatic dicarboxylic anhydride or aromatic monoamine can be added and reacted by (a) tetracarboxylic dianhydride and 1,3-bis [4- (4-amino-
6-trifluoromethylphenoxy) -α, α-dimethylbenzyl] benzene, followed by addition of an aromatic dicarboxylic anhydride or an aromatic monoamine to continue the reaction, (b) 1,3-bis [ 4- (4-amino-6-
(Trifluoromethylphenoxy) -α, α-dimethylbenzyl] benzene, to which an aromatic dicarboxylic anhydride is added and reacted, tetracarboxylic dianhydride is added, and the reaction is further continued. After reacting the acid dianhydride with an aromatic monoamine, 1,3-bis [4- (4-amino-6-trifluoromethylphenoxy) -α, α-dimethylbenzyl] benzene is added,
A method of continuing the reaction, (d) tetracarboxylic dianhydride, 1,3-bis [4- (4-amino-6-trifluoromethylphenoxy) -α, α-dimethylbenzyl] benzene, aromatic dicarboxylic acid Examples include a method in which an anhydride or an aromatic monoamine is simultaneously added and reacted, and any addition method may be used.

The reaction temperature is usually 250 ° C. or lower, preferably 50 ° C. or lower. The reaction pressure is not particularly limited, and the reaction can be sufficiently performed at normal pressure. The reaction time varies depending on the type of tetracarboxylic dianhydride, the type of solvent and the reaction temperature, and usually 4 to 24 hours is sufficient. Further, by heating the obtained polyamic acid to 100 to 400 ° C. to imidize or chemically imidizing using an imidizing agent such as acetic anhydride, a polyimide having a repeating structural unit corresponding to the polyamic acid is obtained. can get.

After dissolving polyamic acid as a precursor of the present polyimide in N, N-dimethylacetamide at a concentration of 0.5 g / dl, the value of logarithmic viscosity measured at 35 ° C. is 0.01.
After further dissolving the polyimide powder by heating in a mixed solvent of 9 parts by weight of p-chlorophenol and 1 part by weight of phenol at a concentration of 0.5 g / dl, 35
The value of the logarithmic viscosity measured in ° C is 0.01 to 3.0 d.
1 / g.

Further, 1,3-bis [4- (4-amino-6-
Trifluoromethylphenoxy) -α, α-dimethylbenzyl] benzene and tetracarboxylic dianhydride, and further, when the terminal of the polyimide has an aromatic ring, an aromatic dicarboxylic anhydride or an aromatic monoamine in an organic solvent. After heating or suspending or dissolving in water, the desired polyimide can be obtained by imidation simultaneously with the production of the polyamic acid, which is a precursor of the polyimide.

Further, as a method for producing a polyimide film in the present patent, a varnish of a polyamic acid, which is a precursor of the present polyimide, is applied on a glass plate and then heated to imidize, or a polyimide powder is directly used. A method of forming a film by heating and pressing is possible. That is, a film-like or powder-like polyimide can be obtained by using a conventionally known technique.

When the polyimide of the present invention is subjected to melt molding, other thermoplastic resins such as polyethylene, polypropylene, polycarbonate, polyarylate, polyamide, polysulfone, polyethersulfone, and the like can be used without impairing the object of the present invention. It is also possible to mix appropriate amounts of polyether ketone, polyphenyl sulfide, polyamide imide, polyether imide, modified polyphenylene oxide, polyimide other than the present invention, etc. according to the purpose. Further, the following fillers and the like used in ordinary resin compositions may be used as long as the object of the invention is not impaired. That is, graphite, carborundum,
Abrasion resistance improvers such as silica stone powder, molybdenum disulfide, and fluororesin; reinforcing agents such as glass fiber and carbon fiber; flame retardant improvers such as antimony trioxide, magnesium carbonate and calcium carbonate; clays and mica Electric property improver, tracking resistance improver such as asbestos, silica, graphite, etc., acid resistance improver such as barium sulfate, silica, calcium metasilicate, etc., heat conductivity improvement of iron powder, zinc powder, aluminum powder, copper powder, etc. Agent, other glass beads, glass spheres, talc, diatomaceous, alumina, shirasubarun,
Hydrated alumina, metal oxides, coloring agents and the like.

Since the polyimide of the present invention has liquid crystallinity, when it is blended with the above-mentioned thermoplastic resin,
It is possible to reduce the melt viscosity of the thermoplastic resin. In addition, the polyimide of the present invention may be in the form of fibers in addition to various molding materials and films. Furthermore,
The present invention is also used as a composite material obtained by impregnating a fiber cloth made of fibers such as carbon fibers with polyimide. Further, taking advantage of the low dielectric property of the present polyimide, the polyimide can be used as a substrate for a copper-clad circuit coated on a metal foil or a metal plate of copper or the like.

[0045]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to embodiments. In addition, the physical property of the polyimide in an Example was measured by the following methods. Tg, Tc, Tm; DSC (Shimadzu DT-40 series,
DSC-41M). Melt viscosity; Shimadzu Koka type flow tester (CFT500
Measured with a load of 100 kg according to A). Dielectric constant; measured according to ASTM D150-87. Logarithmic viscosity; polyamic acid in N, N-dimethylacetamide, polyimide in p-chlorophenol / phenol (9/1 by weight) mixed solvent, 0.5 g / 10 each
Measured at 35 ° C. after dissolving at a concentration of 0 ml.

Synthesis Example 1 (Synthesis of 1,3-bis [4- (4-nitro-6-trifluoromethylphenoxy) -α, α-dimethylbenzyl] benzene) A thermometer, a reflux condenser and a stirrer were provided. Container
700 ml of N, N-dimethylformamide (DMF), 30 ml of toluene, 87 g (0.386 mol) of 2-chloro-5-nitrobenzotrifluoride, 1,3-bis (4
-Hydroxycumyl) benzene 63.6 g (0.184)
mol), 53.3 g of potassium carbonate (0.386 mol)
l) was charged, and the mixture was heated to 110 ° C under stirring, and then aged at 110 ° C for 4 hours.

After the completion of the reaction, the mixture was cooled to 80 ° C. and filtered to remove inorganic salts. 30 ml of water was added to the filtrate, and the mixture was cooled to room temperature to crystallize the desired product. The precipitated crystals were separated by filtration, and further sludged with isopropyl alcohol to give the target product, 1,3-bis [4- (4-
Nitro-6-trifluoromethylphenoxy) -α, α
[Dimethylbenzyl] benzene was obtained. Melting point 127.4-128.4 ° C. Yield 120 g Yield 90% 1H-NMR δ (CDC13, ppm) 1.69 (s, 6H) 6.90 (d, 4H) 6.94-7.34 (m, 4H) 7.26 (d, 4H) 7.18 (d, 2H) 8.28 (dd, 2H) 8.58 (d, 2H) Elemental analysis (C38H30N2O6F6) CHNF計算 Calculated value (%) 62.98 4.17 3.87 15.73 Actual value (%) 89 4.29 3.70 15.66─────────────────────────────────

Synthesis Example 2 (Synthesis of 1,3-bis [4- (4-amino-6-trifluoromethylphenoxy) -α, α-dimethylbenzyl] benzene) A thermometer, a reflux condenser and a stirrer were installed. 90 g (0.124 mol) of 1,3-bis [4- (4-nitro-6-trifluoromethylphenoxy) -α, α-dimethylbenzyl] benzene, 500 ml of methyl cellosolve and 5% -Pd / C5g (50% water content)
And reacted under a hydrogen atmosphere at 70 to 80 ° C. for 4 hours. After completion of the reaction, the catalyst was filtered off, and the filtrate was concentrated under reduced pressure.
Light yellow crystals of 1,3-bis [4- (4-amino-6-trifluoromethylphenoxy) -α, α-dimethylbenzyl] benzene were obtained. Melting point 118.5-119.2 ° C Yield 73.4 g Yield 89% 1H-NMR δ (CDC13, ppm) 1.86 (s, 6H) 3.71 (s, 4H) 6.76 to 7.45 ( m, 10H) 6.95 (d, 4H) 7.29 (d, 4H) Elemental analysis (C38H34N2O2F6) CHNF} ────────────Calculated value (%) 68.67 5.16 4.21 17.15 Actual value (%) 68.78 5.22 4.15 17.01０１ ─────────────────────────────

Example 1 1,3-bis [4- (4-amino-6-trifluoromethylphenoxy) -α, α was added to a vessel equipped with a stirrer, a reflux condenser, a water separator, and a nitrogen inlet tube. -Dimethylbenzyl] benzene 66.47 g (0.1 mol), pyromellitic dianhydride 21.38 g (0.098 mol), phthalic anhydride 0.592 g (0.004 mol), γ-picoline 1.40 g And 351.4 g of m-cresol, and heated to 150 ° C. while stirring under a nitrogen atmosphere. Then, it reacted at 150 degreeC for 4 hours. During this time, distillation of about 3.6 ml of water was confirmed.

After the completion of the reaction, cool to room temperature
After discharge into methyl ethyl ketone, the polyimide powder was separated by filtration. After washing the polyimide powder with methyl ethyl ketone, the powder was dried in air at 50 ° C for 24 hours and under reduced pressure at 180 ° C for 4 hours.
After drying for an hour, 83.22 g (yield 98.1%) of polyimide powder was obtained. The logarithmic viscosity of the polyimide powder thus obtained was 0.45 dl / g, and the glass transition temperature was 196 ° C. FIG. 1 shows the infrared absorption spectrum of this polyimide powder. From this spectrum diagram, it can be seen that the imide characteristic absorption band 1
Absorption around 780 and 1720 cm ^-1 was remarkably observed. The elemental analysis values of the polyimide powder were as follows. Elemental analysis value CHNF calculated value (%) 68.08 3.82 3.31 13.46 Measured value (%) 67.86 3.75 3.40 13.02 The obtained polyimide powder was subjected to pressure. By pressing and heating under the conditions of 300 psi and 350 ° C.
μm polyimide film. The dielectric constant was measured using this polyimide film.
It was 2.99 at 02 and 3 KHz, and 2.96 at 1 MHz.

Further, the molding processing stability of this polyimide was measured using a Koka type flow tester with a load of 100 kg and an orifice having a diameter of 0.1 cm and a length of 1 cm. 300 ° C, 320 ° C, 350 ° C, residence time 5
The melt viscosity per minute is 13100 poise and 49
10 poise and 1860 poise. 320 ° C
2 shows the results of measuring the melt viscosity while changing the residence time in the cylinder. Even if the residence time in the cylinder becomes longer, the melt viscosity hardly changes, indicating that the thermal stability is good.

Further, the polyimide powder was prepared by using commercially available polyether sulfone (trade name: VICTR, manufactured by ICI).
EX PES 4100P) (weight ratio: polyether sulfone / the present polyimide = 7/3), and the melt viscosity at 350 ° C. and 370 ° C. was measured (residence time 5).
Minutes). The results are shown below.

(Measurement value of melt viscosity: unit poise) {350 ° C. 370 ° C.} ───────────────────────────── Polyethersulfone 12000 5700 Polyethersulfone / Polyimide 5250 3350 , The melt viscosity was greatly reduced, and the resulting strands were oriented in the extrusion direction and fibrous fibrils were observed.

Comparative Example 1 82.33 g of polyimide powder (97.6% yield) in exactly the same manner as in Example 1 except that phthalic anhydride was not used.
I got The logarithmic viscosity of the polyimide powder thus obtained was 0.47 dl / g, and the glass transition temperature was 197 ° C. The molding processing stability of this polyimide was measured in the same manner as in Example 1 using a flow tester. The results are shown in FIG. 2 together with the results of Example 1. It can be seen that the polyimide obtained in this comparative example has an increased melt viscosity as the residence time in the cylinder becomes longer, and has poorer molding stability than the polyimide obtained in Example 1.

Example 2 A container equipped with a stirrer, a reflux condenser, and a nitrogen inlet tube was charged with 1,3-bis [4- (4-amino-6-trifluoromethylphenoxy) -α, α-dimethylbenzyl]. 66.47 g (0.1 mol) of benzene and 353.1 g of N, N-dimethylacetamide were charged, and 21.81 g (0.1 mol) of pyromellitic dianhydride was added under a nitrogen atmosphere to raise the solution temperature. Carefully add in portions and add about 3 at room temperature.
Stir for 0 hours. The logarithmic viscosity of the polyamic acid thus obtained was 0.77 dl / g. After taking a part of this polyamic acid solution and casting it on a glass plate,
The film was heated at 0 ° C., 200 ° C., and 300 ° C. for 1 hour each to obtain a film having a thickness of about 50 μm. The glass transition temperature of this polyimide film was 198 ° C. The film has a tensile strength of 9.59 kg / mm ² and a tensile modulus of 240.
kg / mm ² , and the elongation percentage was 8.4% (the measuring method is based on ASTM D-822). When the dielectric constant was measured using this polyimide film, the frequency was 60 Hz.
At 3.01, 2.98 at 3 KHz, 2.94 at 1 MHz
Met.

Example 3 21.38 g of pyromellitic dianhydride in Example 1
(0.098 mol) was changed to 30.40 g (0.098 mol) of 3,3 ′, 4,4′-diphenylethertetracarboxylic dianhydride to obtain a polyimide powder 92.0 mol. 12 g (yield 98.1%) were obtained. The logarithmic viscosity of the polyimide powder thus obtained was 0.47 dl / g, and the glass transition temperature was 184 ° C. Using this polyimide powder, a polyimide film having a thickness of about 50 μm was obtained in the same manner as in Example 1. When the dielectric constant was measured using this polyimide film, it was 2.9 at a frequency of 60 Hz.
It was 2.95 at 8, 3 KHz and 2.92 at 1 MHz.

Example 4 21.81 g of pyromellitic dianhydride in Example 2
(0.1 mol) was changed to 31.02 g (0.1 mol) of 3,3 ′, 4,4′-diphenylethertetracarboxylic dianhydride to carry out polyamic acid in the same manner as in Example 2. Obtained. The logarithmic viscosity of the polyamic acid thus obtained is 0.1.
It was 68 g / dl. Using this polyamic acid, a polyimide film having a thickness of about 50 μm was obtained in the same manner as in Example 2.

The polyimide film had a glass transition temperature of 190 ° C., a tensile strength of 8.56 kg / mm ² , a tensile modulus of 236 kg / mm ² and an elongation of 9.1%.
Furthermore, when the dielectric constant was measured using this polyimide film, it was 3.00 at a frequency of 60 Hz and 2.0 at a frequency of 3 KHz.
96 and 1.92 at 1 MHz.

Example 5 21.38 g of pyromellitic dianhydride in Example 1
(0.098 mol) to 43.54 g (0.098 mol) of 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride Except having changed, it carried out exactly like Example 1 and 104.68g of polyimide powders
(Yield 97.8%). The logarithmic viscosity of the polyimide powder thus obtained was 0.44 g / dl, and the glass transition temperature was 196 ° C. Example 1 using this polyimide powder
A polyimide film having a thickness of about 50 μm was prepared in exactly the same manner as described above, and the dielectric constant was measured. As a result, it was 2.88 at a frequency of 60 Hz, 2.85 at 3 KHz, and 2.80 at 1 MHz.

Example 6 21.81 g of pyromellitic dianhydride in Example 2
(0.1 mol) to 44.43 g (0.1 mol) of 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride Except having changed, it carried out exactly like Example 2 and obtained the polyamic acid. The logarithmic viscosity of the polyamic acid thus obtained was 0.69 dl / g. Using this polyamic acid, a polyimide film having a thickness of about 50 μm was obtained in the same manner as in Example 2. The glass transition temperature of this polyimide film is 199 ° C., the tensile strength is 10.28 kg / mm ² , and the tensile modulus is 266 kg.
/ Mm ² , and the elongation percentage was 6.0%. Further, the dielectric constant of the polyimide film measured was 2.86 at a frequency of 60 Hz, 2.82 at 3 KHz, and 2.78 at 1 MHz.

Comparative Example 2 66.47 g (0.1 mol) of 1,3-bis [4- (4-amino-6-trifluoromethylphenoxy) -α, α-dimethylbenzyl] benzene in Example 2 was added to 1 Polyamide acid was obtained in the same manner as in Example 2 except that the amount was changed to 52.87 g (0.1 mol) of 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene. . The logarithmic viscosity of the polyamic acid thus obtained is 0.7.
It was 2 dl / g. Using this polyamic acid, a polyimide film having a thickness of about 50 μm was obtained in the same manner as in Example 2. The glass transition temperature of this polyimide film was 200 ° C. When the dielectric constant of the obtained polyimide film was measured, it was 3.4 at a frequency of 60 Hz.
It was 3.40 at 6, 3 KHz and 3.36 at 1 MHz.

The dielectric constants of the polyimide films measured in Examples 1 to 6 and Comparative Example 2 are summarized in Table 1 [Table 1].

[0063]

[Table 1] * 1) In the film forming method, A indicates a method of pressing and heating polyimide powder, and B indicates a method of casting polyamic acid. * 2) 1,3-bis [4- (4-amino-6-trifluoromethylphenoxy) -α, α-dimethylbenzyl] benzene * 3) pyromellitic dianhydride * 4) 3,3 ', 4 , 4'-diphenylethertetracarboxylic dianhydride * 5) 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,
3,3,3-hexafluoropropane dianhydride * 6) 1,3-bis [4- (4-aminophenoxy) -α, α
-Dimethylbenzyl] benzene

[0064]

The polyimide of the present invention comprises 1,3-bis [4
-(4-amino-6-trifluoromethylphenoxy)-
It is characterized by using [α, α-dimethylbenzyl] benzene as an aromatic diamine component, and is a polyimide having excellent low dielectric properties, workability, heat resistance and liquid crystallinity. This polyimide has the same heat resistance as conventional polyimides, but exhibits particularly excellent low dielectric properties.Moreover, since it has thermoplasticity and liquid crystallinity, it has good molding workability, so it is industrially particularly a molding material. It can be greatly expected to be used in the field or in the field of electric and electronic materials.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum of a polyimide powder obtained in Example 1 of the present invention.

FIG. 2 shows the results of measuring the relationship between the residence time of a polyimide powder obtained in Example 1 and Comparative Example 1 in a cylinder of a flow tester and a change in melt viscosity.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Tadashi Asanuma 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Akihiro Yamaguchi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Examiner in the company Hiroki Amano (56) References JP-A-5-320100 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 73/00-73/26 C08L 79 / 00-79/08 CAPLUS (STN)

Claims (15)

(57) [Claims] 1. A compound of the general formula (1) (In the formula, R represents an aliphatic group having 2 to 27 carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group which are directly or mutually linked by a bridge member. A liquid crystalline and low dielectric polyimide having a repeating structural unit represented by the following formula (4): a tetravalent group selected from the group consisting of non-fused polycyclic aromatic groups. 2. A compound of the general formula (1) (In the formula, R represents an aliphatic group having 2 to 27 carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group which are directly or mutually linked by a bridge member. Represents a tetravalent group selected from the group consisting of non-condensed polycyclic aromatic groups), and whether the terminal of the polymer molecule has essentially no substituent, Alternatively, a liquid crystalline and low dielectric polyimide which is an aromatic ring substituted with a group having no reactivity with an amine or a dicarboxylic anhydride. 3. The following formula (2), which is a precursor of a polyimide having a repeating structural unit represented by the formula (1): (Wherein R is the same as described above).
After dissolving in N, N-dimethylacetamide at a concentration of 0.5 g / dl, the value of the logarithmic viscosity measured at 35 ° C. is 0.
3. The liquid crystalline and low dielectric polyimide according to claim 1, wherein the amount is from 0.1 to 3.0 dl / g. 4. A mixed solvent consisting of 0.5 g of a polyimide having a repeating structural unit represented by the formula (1) and 9 parts by weight of p-chlorophenol and 1 part by weight of phenol.
The liquid crystalline and low dielectric polyimide according to claim 1 or 2, wherein the value of the logarithmic viscosity measured at 35 ° C after dissolution is 0.01 to 3.0 dl / g. 5. A compound of the formula (3) 1,3-bis [4- (4-amino-6-trifluoromethylphenoxy) -α, α-dimethylbenzyl]
An aromatic diamine mainly composed of benzene, and mainly represented by the general formula (4): (In the formula, R represents an aliphatic group having 2 to 27 carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group which are directly or mutually linked by a bridge member. A tetravalent dianhydride selected from the group consisting of non-condensed polycyclic aromatic groups), and thermally or chemically imidizing the resulting polyamic acid. The method for producing a liquid crystalline and low dielectric polyimide according to claim 1, wherein 6. A compound of the formula (3) 1,3-bis [4- (4-amino-6-trifluoromethylphenoxy) -α, α-dimethylbenzyl]
Aromatic diamine mainly composed of benzene, and mainly represented by general formula (4) (In the formula, R represents an aliphatic group having 2 to 27 carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group which are directly or mutually linked by a bridge member. A tetravalent dianhydride selected from the group consisting of non-condensed polycyclic aromatic groups). (In the formula, Z ₁ is an aliphatic group having 6 to 15 carbon atoms, a cyclic aliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group connected directly or by a crosslinking member. Represents a divalent group selected from the group consisting of a non-fused polycyclic aromatic group), is reacted in the presence of an aromatic dicarboxylic anhydride represented by
The method for producing a liquid crystalline and low dielectric polyimide according to claim 2, wherein the obtained polyamic acid is thermally or chemically imidized. 7. A compound of the formula (3) 1,3-bis [4- (4-amino-6-trifluoromethylphenoxy) -α, α-dimethylbenzyl]
Aromatic diamine mainly composed of benzene, and mainly represented by general formula (4) (In the formula, R represents an aliphatic group having 2 to 27 carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group which are directly or mutually linked by a bridge member. Represents a tetravalent group selected from the group consisting of non-condensed polycyclic aromatic groups) with a tetracarboxylic dianhydride represented by the formula (6):
1] Z ₂ —NH ₂ (6) (wherein Z ₂ is an aliphatic group having 6 to 15 carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group) A monovalent group selected from the group consisting of non-condensed polycyclic aromatic groups in which a group or an aromatic group is directly or interconnected by a bridging member) in the presence of an aromatic monoamine represented by the formula: 3. The method for producing a liquid crystalline and low dielectric polyimide according to claim 2, wherein the resulting polyamic acid is thermally or chemically imidized. 8. The method according to claim 6, wherein the aromatic dicarboxylic anhydride is phthalic anhydride. 9. The method for producing a liquid crystalline and low dielectric polyimide according to claim 7, wherein the aromatic monoamine is aniline. 10. The liquid crystal according to claim 6, wherein the amount of the aromatic dicarboxylic anhydride is 0.001 to 1.0 mol per 1 mol of the aromatic diamine represented by the formula (3). For producing conductive and low dielectric polyimide. 11. The amount of phthalic anhydride used is 0.001 to 1 mol per mole of the aromatic diamine represented by the formula (3).
7. The method for producing a liquid crystalline and low dielectric polyimide according to claim 6, wherein the ratio is 1.0 mol. 12. The liquid crystal according to claim 7, wherein the amount of the aromatic monoamine is 0.001 to 1.0 mol based on 1 mol of the tetracarboxylic anhydride represented by the formula (4). And a method for producing a low dielectric polyimide. 13. The amount of aniline used is 0.001 to 1 mol of tetracarboxylic anhydride represented by the formula (4).
The method for producing a liquid crystalline and low dielectric polyimide according to claim 7, wherein the ratio is from 1.0 to 1.0 mol. 14. A composition containing the polyimide according to claim 1 or 2. 15. A polyimide film containing the polyimide according to claim 1.