JP3137549B2 - Polyimide - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel fluorine-containing containing polyimide <br/> de. More specifically, the present invention relates to a thermoplastic polyimide containing fluorine, which is excellent in colorless transparency, low dielectric property, and the like, a method for producing the same, and a novel aromatic diamino compound used for producing the polyimide. The novel aromatic diamino compound of the present invention is useful not only as a raw material for the polyimide of the present invention, but also as a raw material for other polyamides, polyimides, polyamideimides, bismaleimides, and epoxy resins.

[0002]

2. Description of the Related Art Conventionally, a polyimide resin obtained by the reaction of a tetracarboxylic dianhydride with a diamine has not only high heat resistance but also mechanical strength, dimensional stability, flame retardancy, electric insulation and the like. It is used as a material or as a heat-resistant adhesive in the fields of electrical and electronic equipment, aerospace equipment, transportation equipment and the like. For example, as one of the product forms of the polyimide resin, a polyimide film is expected to be widely used in fields where heat resistance is required due to its excellent physical properties. In recent years, polyimide resins having high levels of properties such as heat resistance and adhesiveness that can withstand use under more severe conditions have been developed. Many of these conventionally developed polyimides show excellent properties, but generally have low light transmittance,
Many have a dark yellow to brown color, and have a defect that the transmittance is particularly low in the visible region, and the color becomes deeper in space. On the other hand, polyester resins, polycarbonate films, and aliphatic polyimide films have been developed as resins having a colorless and transparent color or a color close thereto, but have poor long-term heat resistance and weather resistance.

However, in the field of space development in recent years, a film having little absorption of cosmic rays has been demanded as a coverlay of a solar cell or the like, and the development of a heat-resistant and colorless and transparent resin has been strongly desired. In addition, regarding coloring,
High heat resistance, high reliability optical communication cables and filters,
This is a very important issue in the development of optical materials such as liquid crystal display panels.

The transparency of commercially available polyimides is, specifically,
Yellowness index (hereinafter referred to as yellow index)
(Abbreviated as YI) as a parameter,
YI is 129 for a polyimide (trade name, Kapton) composed of diaminodiphenyl ether and pyromellitic dianhydride, and YI is 129 for a polyimide (trade name, Upilex-S) composed of p-phenylenediamine and biphenyltetracarboxylic dianhydride. 125I, 3,3′-diaminobenzophenone and benzophenone polyimide (LARC-TPI) composed of tetracarboxylic dianhydride have YI
Is 50, and both are very high. For use in the various optical material applications described above, YI should be 10 or less,
Desirably, a polyimide resin having a YI of 7 or less is desired because it is comparable to polycarbonate widely used for optical material applications at present.

[0005] As for the colorless and transparent polyimide,
General formula (A)

Embedded image A homopolymer having a repeating structural unit represented by
Alternatively, the repeating structural unit represented by the general formula (A) and the general formula (B)

Embedded image A copolymer having a repeating structural unit represented by the following formula is disclosed in JP-A-63-170420. Although these polyimides are remarkably excellent in transparency,
It does not fully satisfy the heat resistance inherent to polyimide.

On the other hand, in the recent electric and electronic fields,
The development of microelectronics is remarkable, especially in large computers, the adoption of a multilayer circuit board makes high-speed signal transmission indispensable.However, if the dielectric constant of the base material is high, signal transmission is delayed, and high-speed transmission becomes an obstacle. Become. Polyimide is used for an interlayer insulating film having a multilayer wiring structure. In addition to the above-mentioned characteristics of polyimide, the necessity of lowering the dielectric constant has been increasing.
Generally, Teflon, which is known as a fluorine-containing resin,
It has long been known as a resin having a low dielectric constant, and it is possible to reduce the dielectric constant of a polyimide resin by introducing fluorine and a fluoro group into a polyimide structure, for example, AKS.
t.Clair et.al., Polymeric Materials Science and Eng
ineering, 59, 28-32 (1988) and EP-029986.

However, the dielectric constant of currently commercialized polyimide resins is 3.5 / 1 MH at Kapton.
z, 3.5 / 1 MHz for Upilex-S, LAR
In C-TPI, it is 3.7 / 1 MHz. Conventional polyimides containing a large amount of fluorine do not produce polymers having a sufficient molecular weight, are very expensive, or are difficult to produce on an industrial level (see, for example, 182324, JP-A-2-60933, JP-A-2-281037, JP-A-4-122
729). Therefore, development of a polyimide having a high molecular weight and as low a cost as possible is desired.

All of these problems are caused by electron transfer in the resin. Discoloration is caused by cutting a conjugated system in the main chain, and dielectric constant is caused by electron transfer in the polymer main chain. Can be improved by constraining Specifically, it is known that it is effective to introduce an electron-withdrawing fluorine atom into a polyimide molecular unit. For example, an aromatic diamine containing a hexafluoroisopropylidene group has been disclosed as a polyimide monomer for a low dielectric material (Japanese Patent Application Laid-Open No. HEI 1-1990).
190652). However, these aromatic diamines
There are industrial and physical problems, such as the multi-step synthesis method, and insufficient melt fluidity when molding and processing the polyimide resin obtained therefrom.

Further, as the diamine having a trifluoromethyl group in the molecule, for example, 4,4 ′ represented by the formula (C)
-Bis (4-amino-5-trifluoromethylphenyloxy) biphenyl is known (WO840412).

Embedded image

However, this compound has a trifluoromethyl group, which is an electron-withdrawing group, at the terminal aromatic ring at which an amino group is present, and at an ortho position with respect to the amino group. It has been found that it is difficult to react and the degree of polymerization is hard to increase. In addition, since the amino group is at the para-position to the ether bond, the resulting polyimide has a rigid structure, and has a drawback that the molding process is difficult. In addition, improvement of adhesiveness is also a required subject.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to provide a melt-moldable thermoplastic polyimide which has not only the excellent thermal stability inherent in polyimide but also the properties of colorless transparency and low dielectric properties. That is. Another object of the present invention is to provide a novel aromatic diamino compound which is useful as a raw material for polyimide which has low dielectric constant, is colorless and transparent, and has excellent moldability and adhesiveness.

[0012]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above-mentioned object, and prepared 2,6-bis (3- or 4-aminophenoxy) -3 or 4-trifluoromethylpyridine. The inventors have found that a polyimide used as a diamine monomer can achieve the above object, and have completed the present invention.

That is, the present invention relates to (1) a general formula (1)

Embedded image (Wherein, Ar is a carbon atom having 6 to 27 carbon atoms, and is a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic ring in which aromatic groups are connected to each other directly or by a bridge member. Represents a tetravalent group which is an aromatic group of the formula, the substitution position of the trifluoromethyl group is 3 or 4 of the pyridine nucleus, and the bonding position of the imide nitrogen atom is 3 or 4 with respect to the ether bond.
Polyimide having at least one of the repeating structural units represented by

(2) General formula (1)

Embedded image (Wherein, the substitution position of Ar and trifluoromethyl group and the bonding position of imide nitrogen atom are the same as described above) as an essential structural unit, and the terminal of the polymer molecule is Polyimide which is essentially an aromatic ring which has no substituent or is substituted with a group having no reactivity with amine or dicarboxylic anhydride;

(3) General formula (1-1)

Embedded image (Wherein, Ar is the same as in the case of the general formula (1)) The polyimide of the above (1) or (2), which has at least one of the repeating structural units represented by the following as an essential structural unit:

(4) General formula (1-2)

Embedded image (Wherein, Ar is the same as in the case of the general formula (1)) The polyimide of the above (1) or (2), which has at least one of the repeating structural units represented by the following as an essential structural unit:

(5) General formula (1)

Embedded image (Wherein the substitution position of Ar and trifluoromethyl group and the bonding position of imide nitrogen atom are the same as described above), and 1 to 100 mol% of the repeating structural unit represented by the general formula (2)

Embedded image (Wherein, n represents an integer of 0 to 6, Q is a direct bond, -O-, -S-
, -CO-, -SO _2- , -CH _2- , -C (CH ₃ ) ₂ -or -C (CF ₃ ) _2-
In the case where there are a plurality of bonding groups Q connecting the aromatic rings, the bonding groups may be the same or different, and Ar ′ has 6 to 27 carbon atoms and is a monocyclic aromatic Group, a condensed polycyclic aromatic group, or a tetravalent group which is a non-condensed polycyclic aromatic group wherein the aromatic groups are directly or mutually linked by a bridging member) Polyimide or polyimide copolymer containing 0 mol% as an essential structural unit, or the terminal of the polymer molecule has essentially no substituent, or has no reactivity with amine and / or dicarboxylic anhydride. Group-substituted polyimide or polyimide copolymer,

(6) The general formula (3)

Embedded image (Wherein the substitution position of the trifluoromethyl group is at the 3- or 4-position of the pyridine nucleus, and the substitution position of the amino group is at the 3- or 4-position with respect to the ether bond); Equation (4)

Embedded image (Wherein, Ar is a monocyclic aromatic group having 6 to 27 carbon atoms, a condensed polycyclic aromatic group, or a non-condensed polycyclic aromatic group in which aromatic groups are directly or mutually linked by a bridge member. Wherein a tetracarboxylic dianhydride represented by the following formula: is reacted, and the resulting polyamic acid is thermally or chemically imidized.

Embedded image (Wherein, the substitution position of Ar and the trifluoromethyl group and the bonding position of the imide nitrogen atom are the same as those described above), a method for producing a polyimide having at least one of the repeating structural units as an essential structural unit,

(7) General formula (3)

Embedded image (Wherein the substitution position of the trifluoromethyl group and the substitution position of the amino group are the same as those described above), and mainly the general formula (4)

Embedded image (Wherein Ar is the same as described above) represented by the general formula (5)

Embedded image (Wherein Z has 6 to 15 carbon atoms, and is a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic aromatic group in which aromatic groups are connected to each other directly or by a bridge member. An aromatic dicarboxylic acid anhydride represented by a divalent group that is an aromatic group) or a general formula (6) Z ₁ —NH ₂ (6) (wherein Z ₁ has 6 to 15 carbon atoms, and A aromatic group represented by a cyclic aromatic group, a condensed polycyclic aromatic group, or a monovalent group which is a non-condensed polycyclic aromatic group in which the aromatic groups are connected to each other directly or by a bridging member) A general formula characterized by reacting in the presence of an aromatic monoamine to thermally or chemically imidize the resulting polyamic acid
(1)

Embedded image (Wherein the substitution position of Ar and trifluoromethyl group and the bonding position of imide nitrogen atom are the same as those described above) as an essential structural unit, and the terminal of the polymer molecule A method for producing a polyimide, which has essentially no substituents or is an aromatic ring substituted with a group having no reactivity with an amine or dicarboxylic anhydride,

(8) General formula (3)

Embedded image (Wherein the substitution position of the trifluoromethyl group and the substitution position of the amino group are the same as described above), and 1 to 0.01 mol part of the aromatic diamine represented by the general formula (4)

Embedded image (Wherein Ar is the same as described above) 1 to 0.01 mol part of tetracarboxylic dianhydride represented by the following general formula (9)

Embedded image (Where n is an integer of 0 to 6, Q is directly connected, -O-, -S-, -C
O-, -SO _2- , -CH ₂ , -C (CH ₃ ) ₂ -or -C (CF ₃ ) _2- , and when there are a plurality of bonding groups Q connecting the aromatic rings, At least one kind of aromatic diamine 0 represented by the following formula:
0.99 mol part and general formula (10)

Embedded image (Wherein, Ar ′ has 6 to 27 carbon atoms, and is a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic ring in which aromatic groups are connected to each other directly or by a bridge member. (5) a method for producing a polyimide or a polyimide copolymer according to the above (5), wherein the tetracarboxylic dianhydride represented by the formula (4) is a tetravalent dianhydride represented by the formula:

(9) The above reaction is further carried out based on the general formula (5) based on 1 mole of the total amount of aromatic diamine.

Embedded image (In the formula, Z has 6 to 15 carbon atoms, and is a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic group in which aromatic groups are connected to each other directly or by a bridge member. The aromatic dicarboxylic acid anhydride represented by a divalent group which is an aromatic group) of 0.001 to 1.0 mol or the total amount of aromatic tetracarboxylic dianhydride of 1 mol is represented by the general formula (6) Z ₁ —NH ₂ (6) (wherein, Z ₁ has 6 to 15 carbon atoms, and a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group is mutually connected directly or by a bridge member. A monovalent group which is a non-fused polycyclic aromatic group)
Reacting in the presence of 0.001 to 1.0 mol, and thermally or chemically imidizing the resulting polyamic acid, the method for producing a polyimide or a polyimide copolymer according to the above (8),

(10) Further, the present invention relates to a novel aromatic diamino compound used as a monomer of the polyimide of the present invention, which has a general formula (3)

Embedded image (Wherein the substitution position of the trifluoromethyl group and the substitution position of the amino group are the same as described above),

(11) Formula (3-1) as a particularly preferred diamine compound

Embedded image

(12) or equation (3-2)

Embedded image An aromatic diamino compound represented by

(13) 2,3-dichloro-3 or 4-trifluoromethylpyridine and 3- or 4-aminophenol are condensed in an aprotic polar solvent in the presence of a base. (10) The method for producing an aromatic diamino compound.

(14) 100 parts by weight of the polyimide or polyimide copolymer described in (5) above and 5 to 70 parts by weight of a fibrous reinforcing material selected from carbon fibers, glass fibers, aromatic polyamide fibers and potassium titanate fibers. Containing polyimide-based resin composition,

(15) An injection molded product obtained from the polyimide resin composition,

(16) A polyimide film containing the polyimide or the polyimide copolymer of the present invention.

The polyimide or the polyimide copolymer of the present invention is characterized in that the 2,6-bis (3-aminophenoxy) trifluoromethylpyridine of the present invention is used as a diamine component. Polyimide which is excellent in melt flow stability, has greatly improved moldability, and has excellent colorless transparency and low dielectric properties. From these characteristics, it can be expected to be used in fields such as electric / electronic materials and optical materials.

The polyimide of the present invention has the general formula (1)

Embedded image (Wherein the substitution position of Ar and trifluoromethyl group and the bonding position of imide nitrogen atom are the same as those described above), which is a polyimide having at least one of the repeating structural units as an essential structural unit.

In particular, a preferred polyimide is a compound represented by the general formula (1) among the repeating structural units represented by the general formula (1).
-1)

Embedded image Wherein Ar is as defined above, and / or general formula (1-2)

Embedded image (Wherein Ar is the same as described above), which is a polyimide having at least one of the repeating structural units as an essential structural unit.

Further, 1 to 100 mol% of the repeating structural unit represented by the general formula (1) and the general formula (2)

Embedded image (Wherein, n, Q and Ar ′ are the same as described above). The polyimide or the polyimide copolymer contains 99 to 0 mol% of repeating structural units as essential structural units. As the polyimide copolymer, a repeating structural unit represented by the general formula (1) in the polyimide copolymer includes:
Preferably, it is a polyimide copolymer containing 50 mol% or more, more preferably 70 mol% or more. These polyimides or polyimide copolymers are polyimides in which the terminal of the polymer molecule is an aromatic ring substituted essentially with no substituent or a group having no reactivity with amine or dicarboxylic anhydride. It may be.

The polyimide having a repeating structural unit represented by the above general formula (1) can be obtained by the following general formula (3)

Embedded image (Wherein the substitution position of the trifluoromethyl group is at the 3- or 4-position of the pyridine nucleus, and the substitution position of the amino group is at the 3- or 4-position with respect to the ether bond). With an aromatic diamine mainly composed of

Embedded image (Wherein, Ar is a monocyclic aromatic group having 6 to 27 carbon atoms, a condensed polycyclic aromatic group, or a non-condensed polycyclic aromatic group in which aromatic groups are directly or mutually linked by a bridge member. The tetracarboxylic dianhydride represented by the following formula: is reacted, and the resulting polyamic acid is thermally or chemically imidized.

The aromatic diamino compound of the present invention used for the production of the polyimide of the present invention has the general formula (3)

Embedded image (Wherein the substitution position of the trifluoromethyl group and the substitution position of the amino group are the same as described above), preferably an aromatic diamine represented by the formula (3-1):

Embedded image Or equation (3-2)

Embedded image Is an aromatic diamino compound represented by the formula:

The aromatic diamino compound of the present invention has structural features such as having a trifluoromethyl group and a pyridine ring in the molecule, and substituting the amino group at the meta position with respect to the ether bond group. It is a nitrogen-containing diamine compound.

Hereinafter, the method for producing 2,6-bis (3- or 4-aminophenoxy) -3 or 4-trifluoromethylpyridine according to the present invention will be specifically described. The 2,6-bis (3-
Or 4-aminophenoxy) -3 or 4-trifluoromethylpyridine is 2,6-dichloro-3-trifluoromethylpyridine or 2,6-dichloro-4-trifluoromethylpyridine and 3- or 4-amino Phenol can be produced in high yield by reacting in the presence of a base in an aprotic polar solvent. In the reaction of the present invention, 3- or 4-aminophenol is used in an amount of at least twice equivalent to 2,6-dichloro-3-trifluoromethylpyridine or 2,6-dichloro-4-trifluoromethylpyridine. Considering the complexity of post-processing, cost, etc., 2-2.5 equivalents is preferable.

The base used in the present invention is an alkali metal carbonate, hydrogencarbonate, hydroxide or alkoxide, and includes potassium carbonate, potassium hydrogencarbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, hydrogencarbonate. Sodium, lithium carbonate, lithium hydroxide, sodium methoxide, potassium isopropoxide and the like can be mentioned. The amount of these bases used may be at least equivalent to the hydroxyl group of the raw material 3- or 4-aminophenol.
~ 2 equivalents are preferred. The aprotic polar solvent used in the present invention includes formamide, N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-
Methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethylsulfoxide, sulfolane and the like. The amount of these solvents used is not particularly limited,
Usually, 1 to 10 times the weight of the raw material is sufficient. The reaction temperature is usually in the range of 40 to 250 ° C, preferably 80 to 250 ° C.
In the range of ~ 180 ° C.

In the method of the present invention, as a catalyst for accelerating the reaction, a copper powder and a copper-based compound, or a phase transfer catalyst such as crown ether, polyethylene glycol, quaternary ammonium salt and quaternary phosphonium salt are used. There is nothing wrong with using.

As a general reaction method of the present invention, a predetermined amount of 3- or 4-aminophenol, a base and a solvent are charged, and the 3- or 4-aminophenol is converted into an alkali metal salt. 6-Dichloro-3-trifluoromethylpyridine or 2,6-dichloro-4-trifluoromethylpyridine is added and reacted, or 2,6-dichloro-3-trifluoromethylpyridine or 2,6-dichloro-3-trifluoromethylpyridine is added in advance. Any method may be used, in which all the raw materials including 6-dichloro-4-trifluoromethylpyridine are added at the same time, and the mixture is heated and reacted as it is. Also,
The present invention is not limited to these, and can be appropriately implemented by other methods. Further, when water is present in the reaction system, there is a method of removing the water outside the system by passing nitrogen gas or the like during the reaction, but generally, benzene, toluene, xylene, chlorobenzene, or the like is used. Use a small amount,
A method of removing azeotropically out of the system is often used.

The end point of the reaction can be determined by thin-layer chromatography or high-performance liquid chromatography while observing the reduction of the raw materials. After completion of the reaction, the reaction solvent is distilled off to obtain 2,6-bis (3
-Or 4-aminophenoxy) 3- or 4-trifluoromethylpyridine is obtained. The resulting product is
Further, it can be purified by a commonly used purification method such as purification as a hydrochloride. The polyimide of the present invention uses the aromatic diamine obtained as described above as an essential monomer, alone or as a mixture, but uses a mixture of other aromatic diamines within a range that does not impair the good physical properties of the polyimide. You can also.

The aromatic tetracarboxylic dianhydride used for producing the polyimide of the present invention is represented by the general formula (4)

Embedded image (In the formula, Ar is the same as described above.) At least one tetracarboxylic dianhydride is used.

Specifically, in the general formula (4), Ar represents the formula (a)

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

Embedded image A condensed polycyclic aromatic group represented by the formula:

Embedded image Wherein X ′ is a direct bond, —CO—, —O—, —S—,
SO ₂ —, —CH ₂ —, —C (CH ₃ ) ₂ —, —C (C
F ₃ ) ₂ −

Embedded image (Where Y 'is a direct bond, -CO-, -O-, -S-,
—SO ₂ —, —CH ₂ —, —C (CH ₃ ) ₂ —, —C
Represents a divalent group represented by (CF ₃ ) _2- ), or a tetravalent group such as a non-condensed polycyclic aromatic group wherein the aromatic groups represented by The tetracarboxylic dianhydride is used.

The tetracarboxylic dianhydride represented by the general formula (4) used in the present invention includes, for example,
Pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3
3′-benzophenonetetracarboxylic dianhydride, 3,
3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride Anhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4
-Dicarboxyphenyl) sulfone dianhydride, 1,1-
Bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 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-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride and the like. These may be used alone or in combination of two or more.

In the production of polyimide, it is customary to control the amount ratio of aromatic tetracarboxylic dianhydride to aromatic diamine in order to control the molecular weight of the resulting polyimide. In the method of the present invention, a suitable molar ratio of aromatic tetracarboxylic dianhydride to aromatic diamine is 0.2 to obtain a polyimide having good melt flowability.
It is in the range of 9 to 1.0.

The polyimide of the present invention obtained by using the above aromatic diamine and aromatic tetracarboxylic dianhydride as monomer components is mainly a polyimide having an essential structural unit having a repeating structural unit represented by the general formula (1). It is. Further, a mixture of the aromatic diamine of the present invention and one or more other aromatic diamines and one or more aromatic tetracarboxylic dianhydrides as monomers is used as a repeating unit represented by the general formula (1). A polyimide copolymer having a structural unit and a repeating structural unit represented by the general formula (2) is obtained.

The polyimide copolymer composed of the repeating structural unit represented by the general formula (1) and the repeating structural unit represented by the general formula (2) has the general formula (3)

Embedded image (Wherein the substitution position of the trifluoromethyl group and the substitution position of the amino group are the same as those described above) and a general formula (9)

Embedded image (Where n is an integer of 0 to 6, Q is directly connected, -O-, -S-, -C
O-, -SO _2- , -CH ₂ , -C (CH ₃ ) ₂ -or -C (CF ₃ ) _2- , and when there are a plurality of bonding groups Q connecting the aromatic rings, The bonding group may be the same or different) in the presence of at least one aromatic diamine represented by the general formula (10):

Embedded image (Wherein, Ar ′ is the same as described above), and is reacted with at least one kind of aromatic tetracarboxylic dianhydride.

The aromatic diamine of the general formula (9) used herein includes m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, benzidine,

3,3'-diaminodiphenyl ether, 3,4'-
Diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide,
4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminobenzophenone ,
3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 2,2-bis (4-aminophenyl ) Propane, 2,2-bis
(3-aminophenyl) propane, 2- (3-aminophenyl)-
2- (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (3-aminophenyl)- 1,1,1,3,3,3-hexafluoropropane, 2- (3-aminophenyl) -2- (4-aminophenyl)-
1,1,1,3,3,3-hexafluoropropane,

1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4- Aminophenoxy) benzene, 1,3-bis (3-aminobenzoyl) benzene, 1,4-bis (3-aminobenzoyl) benzene, 1,3-bis (4-aminobenzoyl) benzene, 1,4-bis ( 4-aminobenzoyl) benzene, 3,3'-diamino-4-
Phenoxybenzophenone, 4,4'-diamino-5-phenoxybenzophenone, 3,4'-diamino-4-phenoxybenzophenone, 3,4'-diamino-5'-phenoxybenzophenone,

4,4'-bis (4-aminophenoxy) biphenyl, 3,3'-bis (4-aminophenoxy) biphenyl,
4'-bis (3-aminophenoxy) biphenyl, bis [4- (4
-Aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] ketone, bis [3- (4-aminophenoxy) phenyl] ketone, bis [3- (3-aminophenoxy) phenyl] ketone, 3,3'-diamino-4,4'-
Diphenoxybenzophenone, 4,4'-diamino-5,5'-diphenoxybenzophenone, 3,4'-diamino-4,5'-diphenoxybenzophenone, bis [4- (4-aminophenoxy) phenyl] sulfide, Bis [4- (3-aminophenoxy) phenyl] sulfide, bis [3- (4-aminophenoxy) phenyl] sulfide, bis [3- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-amino Phenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [3- (4-aminophenoxy) phenyl] sulfone, bis [3- (3-aminophenoxy) phenyl] sulfone, bis [ 4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, bis [3- (3-aminophenoxy) phenyl] ether, bis [3- (4-aminophenoxy) C) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] methane, bis [3- (3-aminophenoxy) phenyl] methane, bis [ 3- (4-aminophenoxy) phenyl] methane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2-bis [3- (3-aminophenoxy) phenyl] propane, 2,2-bis [3- (4
-Aminophenoxy) phenyl] propane, 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, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,
1,1,3,3,3-hexafluoropropane, 2,2-bis [3- (4-
Aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane,

1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy)
Benzoyl] benzene, 1,3-bis (3-amino-4-phenoxybenzoyl) benzene, 1,4-bis (3-amino-4-phenoxybenzoyl) benzene, 1,3-bis (4-amino-5- Phenoxybenzoyl) benzene, 1,4-bis (4-amino-5-
Phenoxybenzoyl) benzene,

4,4'-bis [3- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4'-bis [3- (3-aminophenoxy) benzoyl] diphenyl ether, 4,4'-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4′-bis [4- (4-amino-α, α
-Dimethylbenzyl) phenoxy] diphenylsulfone, bis [4-4- (4-aminophenoxy) phenoxyphenyl] sulfone, 3,3′-diamino-4,4′-dibiphenoxybenzophenone, 4,4′-diamino-5 , 5'-dibiphenoxybenzophenone, 3,4'-diamino-4,5'-dibiphenoxybenzophenone,

1,3-bis (3-amino-4-biphenoxybenzoyl) benzene, 1,4-bis (3-amino-4-biphenoxybenzoyl) benzene, 1,3-bis (4-amino-5 -Biphenoxybenzoyl) benzene, 1,4-bis (4-amino-5-biphenoxybenzoyl) benzene, 1,4-bis [4- (4-aminophenoxy) phenoxy-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) phenoxy-α,
α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-trifluoromethylphenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino- 6-fluorophenoxy) -α, α-dimethylbenzyl] benzene,
3-bis [4- (4-amino-6-methylphenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-cyanophenoxy) -α, α-dimethyl Benzyl] benzene,
1,3-bis (3-amino-4-biphenoxybenzoyl) benzene, 1,4-bis (3-amino-4-biphenoxybenzoyl) benzene, 1,3-bis (4-amino-5-biphenoxy) Benzoyl) benzene, 1,4-bis (4-amino-5-biphenoxybenzoyl) benzene, and the like. These may be used alone or in combination of two or more.

As the tetracarboxylic dianhydride of the general formula (10) used as one monomer, any of the compounds listed as specific examples of the general formula (4) can be used. The tetracarboxylic dianhydride of the general formula (10) may be the same as or different from the tetracarboxylic dianhydride of the general formula (4), and the tetracarboxylic dianhydride used in the production of the polyimide copolymer may be used. The acid dianhydrides may be used alone or in combination of two or more.

In the production of the polyimide or the polyimide copolymer, the amounts of the aromatic diamine component and the aromatic tetracarboxylic dianhydride used are from 1 to 0.01 mol part of the aromatic diamine represented by the general formula (3) and from the general formula (3). 1 to 0.01 mol part of an aromatic tetracarboxylic dianhydride represented by (4), and 0 to 0.99 of an aromatic diamine represented by the general formula (9)
It is a molar part and 0 to 0.99 molar part of the aromatic tetracarboxylic dianhydride represented by the general formula (10). In the case of the polyimide copolymer, the amount of the aromatic diamine represented by the general formula (3) in the aromatic diamine component is preferably 0.5 mol part or more, more preferably 0.7 mol part or more. further,
The polyimide of the present invention contains a polyimide or a polyimide copolymer having an aromatic ring substituted at its polymer molecular terminal unsubstituted or substituted with a group having no reactivity with amine or dicarboxylic anhydride, or contains these polyimides. Compositions are also included, and these polyimides may exhibit better performance.

A polyimide or a polyimide copolymer having an aromatic ring at the terminal of the polymer molecule which is unsubstituted or substituted with a group having no reactivity with an amine or a dicarboxylic anhydride is mainly represented by the general formula (3): A mixture of an aromatic diamine or another diamine with one or more tetracarboxylic dianhydrides represented by the general formula (4) is represented by the general formula (5)

Embedded image (In the formula, Z has 6 to 15 carbon atoms, and is a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic group in which aromatic groups are connected to each other directly or by a bridge member. An aromatic dicarboxylic acid anhydride represented by a divalent group which is an aromatic group) or a formula (6) Z ₁ -NH ₂ (6) (wherein, Z ₁ has 6 to 15 carbon atoms; A monocyclic aromatic group, a condensed polycyclic aromatic group, or a monovalent group which is a non-condensed polycyclic aromatic group in which the aromatic groups are connected to each other directly or by a bridging member) A polyimide obtained by sealing with an aromatic monoamine, preferably phthalic anhydride or aniline.

This polyimide is prepared by combining an aromatic diamine component and an aromatic tetracarboxylic dianhydride in the presence of an aromatic dicarboxylic anhydride represented by the general formula (5) or an aromatic monoamine represented by the general formula (6). And the resulting polyamic acid is thermally or chemically imidized.

Specific examples of the aromatic dicarboxylic anhydride represented by the general formula (5) include phthalic anhydride, 2,3-
Benzophenone dicarboxylic anhydride, 3,4-benzophenone dicarboxylic anhydride, 2,3-dicarboxyphenyl ether anhydride, 3,4-dicarboxyphenyl phenyl ether anhydride, 2,3-biphenyl dicarboxylic anhydride, 3 2,4-biphenyldicarboxylic anhydride, 2,3-dicarboxyphenylphenylsulfone anhydride, 3,4-dicarboxyphenylphenylsulfone anhydride, 2,3-dicarboxyphenylphenylsulfide anhydride, 3,4-di Carboxyphenylphenyl sulfide anhydride, 1,2-naphthalenedicarboxylic anhydride, 2,3-naphthalenedicarboxylic anhydride, 1,8-naphthalenedicarboxylic anhydride, 1,2-anthracenedicarboxylic anhydride, 2,3 -Anthracene dicarboxylic anhydride, 1,
9-anthracene dicarboxylic anhydride and the like. 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 obtained. That is, it is a polyimide having excellent molding stability at the time of high-temperature molding, has excellent heat resistance, and considering the excellent workability, for example, structural materials, base materials for spacecraft, It is a very useful polyimide as an electronic component or adhesive. In the case of using phthalic anhydride, there is no problem if a part of the phthalic anhydride is replaced with another dicarboxylic anhydride as long as the good physical properties of the polyimide are not impaired. The amount of dicarboxylic anhydride used is between 0.001 and 1.0 mole per mole of aromatic diamine used. If the amount is less than 0.001 mol, an increase in viscosity is observed during high-temperature molding, which causes a reduction in moldability. On the other hand, if it exceeds 1.0 mol, the mechanical properties are lowered. The preferred amount is 0.01 to 0.5 mol.

When an aromatic monoamine is used,
As aromatic monoamines, for example, 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-aminophenol, 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-aminophenylphenyl ether, 2-aminobenzophenone, 3-aminobenzophenone, 4-aminobenzophenone, 2-aminophenylphenyl sulfide, 3-aminophenyl Aminophenylphenyl sulfide, 4-aminophenylphenyl sulfide, 2-aminophenylphenyl sulfone, 3-aminophenylphenyl sulfone, 4-aminophenylphenyl sulfone, 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, 8-amino-1
-Naphthol, 8-amino-2-naphthol, 1-aminoanthracene, 2-aminoanthracene, 9-aminoanthracene and the like. These aromatic monoamines may be substituted with a group having no reactivity with amine or dicarboxylic anhydride.

The amount of the aromatic monoamine to be used is 0.001 to 1.0 per mol of the tetracarboxylic dianhydride used.
0 moles. When the molar ratio is less than 0.001, the viscosity is increased at the time of high-temperature molding, which causes a reduction in moldability. Also,
If the molar ratio exceeds 1.0, the mechanical properties deteriorate. Preferred amounts are from 0.01 to 0.5 mol.

As described above, a suitable molar ratio of aromatic tetracarboxylic dianhydride to aromatic diamine in order to obtain a polyimide having good melt flowability is in the range of 0.9 to 1.0. Therefore, when producing a polyimide in which the terminal of the polyimide of the present invention is an unsubstituted or substituted aromatic ring, an aromatic tetracarboxylic dianhydride,
The molar ratio of the aromatic diamine and the dicarboxylic anhydride or the aromatic monoamine is one mole of tetracarboxylic dianhydride.
Per mole, the aromatic diamine is from 0.9 to 1.0 mole and the dicarboxylic anhydride or aromatic monoamine is from 0.001 to 1.0 mole. As the method for producing polyimide of the present invention, any method capable of producing polyimide, including known methods, can be applied. Among them, 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,
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, 1,3-dioxane, 1,4-dioxane, pyridine, picoline, dimethylsulfoxide, dimethylsulfone, tetramethylurea, hexamethylphosphoramide,
Examples include phenol, o-cresol, m-cresol, p-cresol, m-cresylic acid, p-chlorophenol, anisole and the like. These organic solvents may be used alone or
More than one kind may be mixed and used.

In the method of the present invention, the method of adding and reacting an aromatic diamine, an aromatic tetracarboxylic dianhydride, an aromatic dicarboxylic anhydride or an aromatic monoamine with an organic solvent includes the following steps: After reacting the aromatic tetracarboxylic dianhydride, a method of continuing the reaction by adding the aromatic dicarboxylic anhydride, (b) reacting the aromatic diamine by adding the aromatic dicarboxylic anhydride, A method of adding an aromatic tetracarboxylic dianhydride and continuing the reaction, (c) a method of simultaneously adding an aromatic tetracarboxylic dianhydride and an aromatic dicarboxylic anhydride to an aromatic diamine and reacting them, A) reacting an aromatic tetracarboxylic dianhydride with an aromatic diamine and then adding an aromatic monoamine to continue the reaction; After reacting by adding an aromatic monoamine to the product, a method of continuing the reaction by adding an aromatic diamine, (f) simultaneously adding an aromatic diamine and an aromatic monoamine to an aromatic tetracarboxylic dianhydride, A reaction method may be used, and any method may be used.

The reaction temperature is usually 250 ° C. or lower, preferably 60 ° C. or lower. The reaction pressure is not particularly limited, and the reaction can be sufficiently performed at normal pressure. Reaction time is aromatic diamine, aromatic tetracarboxylic dianhydride, aromatic dicarboxylic anhydride,
Depending on the aromatic monoamine, the type of solvent and the reaction temperature, usually 4 to 24 hours are sufficient.

According to such a method, the general formula (1-3)

Embedded image (Wherein, Ar is a carbon atom having 6 to 27 carbon atoms, and is a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic ring in which aromatic groups are connected to each other directly or by a bridge member. Represents a tetravalent group which is an aromatic group of formula, and the substitution position of the trifluoromethyl group is at the 3 or 4 position of the pyridine nucleus, and the substitution position of the amide bond is at the 3 or 4 position with respect to the ether bond. A polyamic acid having at least one of the repeating structural units represented by the following as an essential structural unit is obtained.

The polyamic acid is dehydrated by heating to 100 to 400 ° C. or a commonly used imidizing agent such as, for example,
By performing chemical imidization using triethylamine, acetic anhydride, or the like, a polyimide having, as a basic skeleton, a repeating structural unit of the general formula (1) corresponding to polyamic acid can be obtained. Generally, after the polyamic acid is formed at a low temperature, the above-mentioned method for thermally or chemically imidizing the polyamic acid is further performed. At a temperature of 60 to 250 ° C., the polyimide can be obtained by simultaneously performing the polyamic acid generation and the thermal imidization reaction. That is,
Aromatic diamine, tetracarboxylic dianhydride, and
After suspending or dissolving an aromatic dicarboxylic anhydride or an aromatic monoamine in an organic solvent, the reaction is carried out under heating, and the formation of polyamic acid and the dehydration / imidization are simultaneously carried out, whereby the above-mentioned general formula (1) A polyimide having a repeating structural unit as a basic skeleton can also be obtained.

After dissolving polyamic acid, which is a precursor of the polyimide of the present invention, in N, N-dimethylacetamide at a concentration of 0.5 g / dl, the logarithmic viscosity measured at 35 ° C. is 0.01 to 3.
0 dl / g, and this polyimide powder was mixed with 9 parts by weight of p-chlorophenol and 1 part by weight of phenol in a mixed solvent of 0.1 part by weight.
After heating and dissolving at a concentration of 5 g / dl, the value of the logarithmic viscosity measured at 35 ° C. is 0.01 to 3.0 dl / g. As a method for producing a polyimide film in the present invention, a method of applying a varnish of polyamic acid, which is a precursor of the present polyimide, on a glass plate and then heating and imidizing the film, directly heating and pressing the polyimide powder, Or a method of dissolving in an organic solvent and removing the solvent to form a film. That is, a film-like or powder-like polyimide can be obtained by using a conventionally known technique.

The polyimide resin composition of the present invention comprises a polyimide resin such as the polyimide or polyimide copolymer of the present invention and carbon fiber, glass fiber, aromatic polyamide fiber or titanic acid based on 100 parts by weight of the resin. 5 to 70 parts by weight of fibrous reinforcing material such as potassium fiber, preferably
It contains 10 to 50 parts by weight. If the content of the fibrous reinforcing material is less than 5 parts by weight, a sufficient reinforcing effect cannot be obtained. On the other hand, if it exceeds 70 parts by weight, it is difficult to obtain a good molded product by melt molding such as injection molding.

The polyimide resin composition of the present invention can be prepared by various methods. Usually, it can be prepared by adding a fibrous reinforcing material to a polyimide resin by various known methods. For example, after preliminarily kneading the polyimide resin powder and the fibrous reinforcing material using a mortar, Henschel mixer, drum blender, tumbler blender, ball mill, ribbon blender, etc., use a melt mixer, a hot roll or the like to pellet or powder. The most common method is to obtain a mixture. The polyimide-based resin composition of the present invention thus obtained is molded by a known molding method such as an injection molding method, an extrusion molding method, a compression molding method, a rotational molding method, and put into practical use. Since the polyimide resin composition of the present invention has excellent fluidity, the injection molding method is most preferable in terms of working efficiency.

When the polyimide resin composition of the present invention is subjected to melt molding, other thermoplastic resin resins such as polyethylene, polypropylene, polycarbonate, polyarylate, polyamide and the like may be used within a range not to impair the object of the present invention. An appropriate amount of polysulfone, polyether sulfone, polyether ketone, polyether ether ketone, polyphenyl sulfide, polyamide imide, polyether imide, modified polyenylene oxide, polyimide other than the present invention, etc. depending on the purpose of the present invention. You may mix.

Further, the following fillers and the like used in ordinary resin compositions may be used as long as the object of the present invention is not impaired. That is, graphite, carborundum, silica stone powder, molybdenum disulfide, an abrasion resistance improver such as a fluorine-based resin, a flame retardant improver such as antimony trioxide, magnesium carbonate, calcium carbonate, an electrical property such as clay and mica Improver, asbestos, silica, cracking improver such as graphite, barium sulfate, silica,
Acid resistance improver such as calcium metasilicate, thermal conductivity improver such as iron powder, zinc powder, aluminum powder, and copper powder, other glass beads, glass spheres, talc, diatomaceous earth, alumina, silasbarn, hydrated alumina, metal oxide Materials, coloring agents and the like.

Hereinafter, the present invention will be described in detail with reference to examples. In addition, the physical properties of the polyimide in the examples were measured by the following methods. In the examples, various physical properties were measured by the following methods. Logarithmic viscosity: polyamic acid 0.5 g of polyamic acid in 100 ml of N, N-dimethylacetamide
And measured at 35 ° C. Polyimide powder 0.5 g of polyimide powder is added to p-chlorophenol / phenol
(Weight ratio 9/1) After heating and dissolving in 100 ml of mixed solvent, 35
Measured in ° C. Glass transition temperature (Tg): DSC (Shimadzu DT-40 series, DSC-
A1M). 5% weight loss temperature (Td5): DTA-TG in air (Shimadzu DT-40)
Series, DTG-40 M). Yellowness Index (YI): JIS K-71 by SM color computer (SM-6-IS-2B manufactured by Suga Test Instruments Co., Ltd.)
Measured by transmission method according to 03. Light transmittance: measured by Shimadzu UV160. Dielectric constant: Measured according to ASTM-D-150-87. Infrared absorption spectrum: Measured by JASCO FT / IR-300. Flow start temperature: Shimadzu Koka type flow tester (CFT500A)
Measured at a load of 100 kg and a heating rate of 5 ° C / min. Melt viscosity: Measured with a load of 100 kg using a Shimadzu Koka flow tester (CFT500A). Thermal expansion coefficient: Measured according to ASTM-696-79.

Reference Example 1 400 g of N, N-dimethylformamide (DMF) was placed in a four-necked flask equipped with a thermometer, a reflux condenser, and a stirrer.
40 g of toluene, 45.3 g (0.21 mol) of 2,6-dichloro-4-trifluoromethylpyridine, 48.1 g (0.441 mol) of m-aminophenol, potassium carbonate 3
After 1.9 g (0.231 mol) of each was charged, the temperature was increased to 130 ° C. with stirring, and the mixture was aged at 130 ° C. for 5 hours. After completion of the reaction, the resultant was cooled to room temperature and filtered to remove inorganic salts. After adding 480 g of water to the filtrate and separating the organic layer, 1 L of water was added to the organic layer to obtain a crude crystal. This was recrystallized from isopropanol (IPA) to obtain 50.4 g (yield: 66%) of 2,6-bis (3-aminophenoxy) -4-trifluoromethylpyridine, which was a target substance. Mp 112.8 to 113.2 ° C. Elemental analysis _{(C 18 H 14 N 3 O} 2 F 3) C H N F Calculated (%) 59.84 3.91 11.63 15.77 Found (%) 59 .79 3.95 11.61 15.74 ¹ H-NMR δ (CDCl ₃ , ppm) 3.68 (4H (1), s), 6.38 to 6.53 (6H (2), m), 6.63 (1H (3), s), 6.95 to 7.46 (2H (4), m), (1) to (4) indicate positions in the following formula.

Embedded image

Reference Example 2 400 g of N, N-dimethylformamide (DMF) was placed in a four-necked flask equipped with a thermometer, a reflux condenser, and a stirrer.
Toluene 40 g, 2,6-dichloro-3-trifluoromethylpyridine 45.3 g (0.21 mol), m-aminophenol 48.1 g (0.44 mol), potassium carbonate
After charging 9 g (0.231 mol) of each and heating to 130 ° C. with stirring, the mixture was aged at 130 ° C. for 6 hours.
After completion of the reaction, the resultant was cooled to room temperature and filtered to remove inorganic salts. DMF was distilled off under reduced pressure, and 300 g of isopiranol (IPA) was added to and dissolved in the residue, and 184 g of 36% HCl was added to the solution to precipitate the desired product as a hydrochloride. The obtained hydrochloride is dissolved in 200 g of water, and 2
The solution was neutralized with 8% aqueous ammonia, the solution was extracted with 1,2-dichloroethane (EDC), the EDC layer was washed with water, the solvent was distilled off, and the target product, 2,6-bis (3-aminophenoxy) was removed. ) -3-
33.1 g of trifluoromethylpyridine (44% yield)
I got Mp from 103.0 to 104.2 ° C. Elemental analysis _{(C 18 H 14 N 3 O} 2 F 3) C H N F Calculated (%) 59.84 3.91 11.63 15.77 Found (%) 59 .80 3.93 11.59 15.71 ¹ H-NMR δ (CDCl ₃ , ppm) 3.66 (4H (1), s), 6.37-6.60 (7H (2), m) 6 0.88 to 7.08 (2H (3), m), 7.85 (1H (4)), d) Note that (1) to (4) indicate positions in the following formula.

Embedded image

Example 1 7.2264 g (0.02 mol) of 2,6-bis (3-aminophenoxy) -4-trifluoromethylpyridine was placed in a vessel equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet tube. ) And N, N
Dimethylacetamide (64.09 g) was charged and 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride was added at room temperature under a nitrogen atmosphere.
8.7961 g (0.0198 mol) were added in portions while paying attention to the rise in solution temperature, and the mixture was stirred at room temperature for 4 hours.
Thereafter, 0.0592 g (0.0004 mol) of phthalic anhydride was charged, and the mixture was stirred at room temperature for 24 hours. The logarithmic viscosity of the polyamic acid thus obtained is 0.61 dl / g,
It had a good varnish shape. A part of the above polyamic acid is taken, cast on a glass plate, and then heated to 100 ° C and 20 ° C.
The temperature was raised to 0 ° C. and 250 ° C. over 1 hour, respectively, and maintained at each temperature for 1 hour. However, the holding time at 250 ° C. is 4 hours. Thus, a polyimide film having a thickness of 49.8 μm was obtained. The glass transition temperature of this polyimide film is 194 ° C., and the 5% weight loss temperature is 505 ° C.
Met. The yellowness index is 6, the light transmittance at 500 nm is 86%, and the dielectric constant is 2.94 at a frequency of 60 Hz, 2.92 at 3 kHz, and 1 MH.
Z was 2.90. FIG. 1 shows an infrared absorption spectrum of this polyimide film. In this spectrum diagram, the imide characteristic absorption bands of 1780 cm ⁻¹ and 172
Absorption near 0 cm ^-1 was remarkably observed.

Examples 2 to 4 and Comparative Examples 1 and 2 Various polyimides were prepared in exactly the same manner as in Example 1 by using a diamine component and a tetracarboxylic dianhydride component as shown in Table 1 (Table 1). A film was obtained. Table 1 (Table 1) shows diamine component, tetracarboxylic dianhydride component, logarithmic viscosity of amic acid, glass transition temperature (Tg), 5
The% weight loss temperature (Td5), yellowness index (YI), light transmittance at 500 nm, and dielectric constant are shown together with the results of Example 1.

[0078]

[Table 1]

Example 5 2,6-bis (3-aminophenoxy)-was placed in a vessel equipped with a stirrer, a thermometer, a reflux condenser, a water fractionator and a nitrogen inlet tube.
7.2264 g of 4-trifluoromethylpyridine (0.
002 mol), 2,2-bis (3,4-dicarboxyphenyl)-
1,1,1,3,3,3-hexafluoropropane dianhydride 8.52
96 g (0.0192 mol), phthalic anhydride 0.237
Then, 0 g (0.0016 mol), 20 g of toluene and 63.02 g of m-cresol were charged and heated to 150 ° C. while stirring under a nitrogen atmosphere. Thereafter, the reaction was performed at 150 ° C. for 4 hours. During this time, distilling of about 0.7 ml of water was confirmed. After completion of the reaction, the mixture was cooled to room temperature, discharged into about 1 L of methanol, and then the polyimide powder was separated by filtration. This polyimide powder was washed with methanol and dried under reduced pressure to obtain 15.4.
g (96.3%) of polyimide powder was obtained. The logarithmic viscosity of the polyimide powder thus obtained was 0.48 dl / g. The glass transition temperature of this polyimide powder is 185 ° C, 5
The% weight loss temperature was 505 ° C. The melt flow temperature of this polyimide powder at 280 ° C. and 340 ° C. was 3520 poise.

Comparative Example 3 15.3 g (95.7%) of a polyimide powder was obtained in exactly the same manner as in Example 5 except that phthalic anhydride was not used. The logarithmic viscosity of the polyimide powder thus obtained is 0.4
It was 9 dl / g. The glass transition temperature of this polyimide powder was 191 ° C, and the 5% weight loss temperature was 508 ° C. Further, the melt flow starting temperature of this polyimide powder is 285 ° C.
The melt viscosity at 340 ° C. was 3920 poise. The weight loss rate of the polyimide powder obtained in this comparative example was 350 ° C,
The measurement was performed while changing the holding time in the air. FIG. 2 shows the results together with the results of Example 5. From the results shown in FIG. 2, it can be seen that the weight loss rate of the obtained polyimide powder increases as the holding time becomes longer, and the thermal oxidation stability is inferior to that of the polyimide powder obtained in Example 5.

Examples 6 to 8 By exactly the same method as in Example 5, various polyimide powders were obtained using a diamine component and a tetracarboxylic dianhydride component as shown in Table 2 (Table 2). Table 2 (Table 2) shows diamine component, tetracarboxylic dianhydride component, yield, logarithmic viscosity of polyimide powder, glass transition temperature (T
g) 5% weight loss temperature (Td5), melt flow starting temperature, and melt viscosity at 340 ° C. are shown together with the results of Example 5.

[0082]

[Table 2]

Example 9 The 2,6-bis (3-aminophenoxy) -4- obtained in Reference Example 2 was placed in a vessel equipped with a stirrer, a reflux condenser, and a nitrogen inlet tube.
5.0589 g of trifluoromethylpyridine (0.0
14 mol) and 3,3'-diaminodiphenyl ether 1.2
016 g (0.006 mol) and 60.23 g of N, N-dimethylacetamide were charged and 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3, 3,3
-8.7962 g of hexafluoropropane dianhydride
(0.0198 mol) was added in portions while paying attention to the rise in temperature, and the mixture was stirred at room temperature for 4 hours. Thereafter, 0.0592 g (0.0004 mol) of phthalic anhydride was charged and the mixture was stirred at room temperature for 24 hours. The logarithmic viscosity of the polyamic acid thus obtained was 0.66 dl / g. After taking a part of the above polyamic acid and casting it on a glass plate, 100
The temperature was raised to 200 ° C., 200 ° C., and 250 ° C. over 1 hour, respectively, and maintained at each temperature for 1 hour. However, the holding time at 250 ° C. is 4 hours. Thus, thickness 52.
A 3 μm polyimide film was obtained. The glass transition temperature of this polyimide film was 206 ° C., and the 5% weight loss temperature was 518 ° C. The yellowness index is 8, the light transmittance at 500 nm is 85%, and the dielectric constant is 2.98 at a frequency of 60 Hz, 2.93 at 3 kHz, and 1M.
It was 2.91 in Hz.

Examples 10 to 18 By the same method as in Example 9, various polyimide films were obtained using a diamine component and a tetracarboxylic dianhydride component as shown in Table 3 (Table 3). Table-3
Table 3 shows the logarithmic viscosity of the diamine component, the tetracarboxylic dianhydride component, the polyamic acid, and the glass transition temperature (T
g) 5% weight loss temperature, yellowness index
(YI), the light transmittance at 500 nm (T%), and the dielectric constant are shown together with the results of Example 9.

[0085]

[Table 3]

Examples 19 to 28 To each of the polyamic acid varnishes obtained in the above Examples, a fiber length of 3 mm was used with respect to 100 parts by weight of polyimide.
Table 4 (Table 4) shows a silane-treated glass fiber having a fiber diameter of 13 μm (trade name: Nitto Boseki Co., Ltd .: CS-3PE-467S).
And the respective amounts shown in Table 5) were added, sufficiently stirred and homogenized, and a polyimide film was prepared in the same manner as in Example 9. Table 4 (Tables 4 and 5) shows the dielectric constant and the coefficient of linear expansion (according to ASTM-696-76).

Comparative Examples 4 to 7 The same operations as in Examples 19 to 22 were carried out except that glass fibers in amounts outside the range of the present invention were used, and the respective physical properties were measured.
The results are shown in Table 4 (Tables 4 and 5) together with the results of Examples 19 to 28.

Comparative Examples 8 to 9 Glass fibers were added to the polyamic acid varnishes obtained in Comparative Examples 1 and 2 in the same manner as in Examples 19 to 22, and the respective physical properties were measured. The results are shown in Table 4 (Tables 4 and 5) together with the results of Examples 19 to 28.

[0089]

[Table 4]

[0090]

[Table 5]

Examples 29 to 38 Each of the polyamic acid varnishes obtained in the above Examples was added with an average fiber length of 3 m based on 100 parts by weight of polyimide.
Table 5 shows silane-treated aromatic polyamide fibers (trade name: Kevlar, manufactured by DuPont) having a diameter of 13 m and a fiber diameter of 13 m.
The respective amounts shown in (Table 6 and Table 7) were added, sufficiently stirred and homogenized, and a polyimide film was prepared in the same manner as in Example 1. Table 5 (continuation of Table 6 and Table 7)
Has a dielectric constant and a coefficient of linear expansion (ASTM-696-76).
).

Comparative Examples 10 to 13 The same operations as in Examples 29 to 38 were carried out except that the amount of the aromatic polyamide fiber outside the range of the present invention was used, and the respective physical properties were measured. The results are shown in Table 1 together with the results of Examples 29 to 38.
5 (Tables 6 and 7).

Comparative Examples 14 and 15 The polyamic acid varnishes obtained in Comparative Examples 1 and 2 were used in Example 2.
Aromatic polyamide fibers were added in the same manner as in Examples 9 to 38, and each physical property was measured. The results are shown in Table 5 (Tables 6 and 7) together with the results of Examples 29 to 38.

[0094]

[Table 6]

[0095]

[Table 7]

[Brief description of the drawings]

FIG. 1 is a diagram of an infrared absorption spectrum of a polyimide powder obtained in Example 1.

FIG. 2 is a diagram showing the weight loss rate of the polyimide powders obtained in Example 5 and Comparative Example 3 in air at 350 ° C.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Shoji Tamai 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Tsutomu Ishida 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Inside (72) Inventor Mitsuru Matsuo 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside (72) Keisaburo Yamaguchi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Akihiro Yamaguchi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemicals Co., Ltd. (58) Field surveyed (Int.Cl. ⁷ , DB name) C08G 73/10 C08J 5/06 CFG C08J 5/08 CFG C08J 5/18 CFG CA (STN) REGISTRY (STN)

Claims (12)

(57) [Claims] 1. A compound of the general formula (1) (In the formula, Ar has 6 to 27 carbon atoms, and is a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic ring in which aromatic groups are connected to each other directly or by a bridge member. Represents a tetravalent group which is an aromatic group of the formula. The substitution position of the trifluoromethyl group is at the 3 or 4 position of the pyridine nucleus, and the bonding position of the imide nitrogen atom is at the 3 or 4 position with respect to the ether bond. A polyimide having at least one of the repeating structural units represented by the formula (1) as an essential structural unit. 2. A compound of the general formula (1) (Wherein, the substitution position of Ar and trifluoromethyl group and the bonding position of imide nitrogen atom are the same as described above) as an essential structural unit, and the terminal of the polymer molecule is 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. 3. A compound represented by the general formula (1-1): 3. The polyimide according to claim 1, having at least one of the repeating structural units represented by the formula (where Ar is the same as in the case of the general formula (1)) as an essential structural unit. 4. 4. A compound of the general formula (1-2) 3. The polyimide according to claim 1, having at least one of the repeating structural units represented by the formula (where Ar is the same as in the general formula (1)) as an essential structural unit. 4. 5. A compound of the general formula (1) (Wherein the substitution position of Ar and trifluoromethyl group and the bonding position of imide nitrogen atom are the same as described above), and 1 to 100 mol% of a repeating structural unit represented by the following general formula (2): (Wherein, n represents an integer of 0 to 6, Q is a direct bond, -O-,
_{-S -, - CO -, -} SO 2 -, - CH 2 -, - C (C
H ₃ ) ₂ — or —C (CF ₃ ) ₂ —, and when there are a plurality of bonding groups Q connecting the aromatic rings, the bonding groups may be the same or different, and Ar is a carbon atom. A tetravalent aromatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic aromatic group in which the aromatic groups are connected to each other directly or by a bridging member; A polyimide or a polyimide copolymer containing 99 to 0 mol% of a repeating structural unit represented by the formula (1) as an essential structural unit, or a terminal of the polymer molecule having essentially no substituent, or A polyimide or a polyimide copolymer substituted with a group having no reactivity with an amine or a dicarboxylic anhydride. 6. A compound of the general formula (3) (Wherein the substitution position of the trifluoromethyl group is at the 3- or 4-position of the pyridine nucleus, and the substitution position of the amino group is at the 3- or 4-position with respect to the ether bond); Formula (4) (Wherein, Ar is a monocyclic aromatic group having 6 to 27 carbon atoms, a condensed polycyclic aromatic group, or a non-condensed polycyclic aromatic group in which aromatic groups are directly or mutually connected by a bridge member. Is 4
Wherein the resulting polyamic acid is thermally or chemically imidized by reacting a tetracarboxylic dianhydride represented by the formula (1): (Wherein, the substitution position of Ar and trifluoromethyl group and the bonding position of imide nitrogen atom are the same as those described above). 7. A compound of the general formula (3) (Wherein the substitution position of the trifluoromethyl group and the substitution position of the amino group are the same as those described above), and mainly the general formula (4) (Where Ar is the same as described above), and a tetracarboxylic dianhydride represented by the following general formula (5): (In the formula, Z has 6 to 15 carbon atoms, and is a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic group in which aromatic groups are connected to each other directly or by a bridge member. An aromatic dicarboxylic acid anhydride represented by a divalent group which is an aromatic group) or a general formula (6) Z ₁ -NH ₂ (6) (wherein, Z ₁ has 6 to 15 carbon atoms; A monocyclic aromatic group, a condensed polycyclic aromatic group, or a monovalent group which is a non-condensed polycyclic aromatic group in which aromatic groups are connected to each other directly or by a bridging member) A polyamic acid obtained by reacting in the presence of an aromatic monoamine to thermally or chemically imidize the resulting polyamic acid; (Wherein the substitution position of Ar and trifluoromethyl group and the bonding position of imide nitrogen atom are the same as those described above) as an essential structural unit, and the terminal of the polymer molecule A method for producing 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. 8. A compound of the general formula (3) (Wherein the substitution position of the trifluoromethyl group and the substitution position of the amino group are the same as described above), and 1 to 0.01 mol part of the aromatic diamine represented by the general formula (4): (Wherein Ar is the same as described above) in an amount of 1 to 0.01 mol part of a tetracarboxylic dianhydride represented by the following general formula (9): (Where n is an integer of 0 to 6, Q is directly connected, -O-, -S
_{-, - CO -, - SO} 2 -, - CH 2 -, - C (C
H ₃ ) ₂ — or —C (CF ₃ ) ₂ —, and when there are a plurality of bonding groups Q connecting the aromatic rings, the bonding groups may be the same or different. 0 to 0.99 mol part of one kind of aromatic diamine and general formula (10) (Wherein, Ar ′ has 6 to 27 carbon atoms, and is a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic ring in which aromatic groups are connected to each other directly or by a bridge member. The method for producing a polyimide or a polyimide copolymer according to claim 4, wherein 0 to 0.99 mol parts of a tetracarboxylic dianhydride represented by a formula (4) representing a tetravalent group which is an aromatic group is reacted. 9. The above reaction is further carried out by reacting the compound of the general formula (5) with respect to 1 mol of the total amount of the aromatic diamine. (In the formula, Z has 6 to 15 carbon atoms, and is a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic group in which aromatic groups are directly or mutually linked by a bridge member The aromatic dicarboxylic acid anhydride represented by a divalent group which is an aromatic group) is represented by the general formula:
(6) Z ₁ -NH ₂ (6) (wherein, Z ₁ has 6 to 15 carbon atoms, and a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group is directly or Represents a monovalent group which is a non-condensed polycyclic aromatic group linked to each other), and reacts the resulting polyamic acid by thermal reaction in the presence of 0.001 to 1.0 mol of an aromatic monoamine. 9. The method for producing a polyimide or a polyimide copolymer according to claim 8, wherein the polyimide or the polyimide copolymer is chemically imidized. 10. The polyimide or poly according to claim 5,
100 parts by weight of imide copolymer and carbon fiber, glass fiber,
From aromatic polyamide fiber and potassium titanate fiber
PO containing 5 to 70 parts by weight of selected fibrous reinforcing material
Liimide resin composition. 11. The polyimide resin set according to claim 10,
An injection molded product obtained from a product. 12. The polyimide or poly according to claim 5,
A polyimide film containing an imide copolymer.