JPH0726140A - Polyamide-imide resin composition - Google Patents

Abstract

PURPOSE:To obtain a polyamide-imide resin composition useful as a molding material, etc., having excellent heat resistance, mechanical characteristics, etc., comprising an aromatic polyamide-imide copolymer having a repeating unit of a specific structure and a thermoplastic resin capable of forming an anisotropic melt phase. CONSTITUTION:The resin composition comprises (A) 5-95 pts.wt. of an aromatic polyamide-imide copolymer having structures of formula I (Ar is trifunctional aromatic group containing at least one six-membered carbon ring; R is bifunctional aromatic group or aliphatic group), formula II (Ar1 is bifunctional aromatic group containing at least one six-membered carbon ring) and formula III (R1 is bifunctional aliphatic group) as repeating units and (B) 95-5 pts.wt. of a thermoplastic resin (e.g. aromatic polyester or aromatic polyester-imide) capable of forming an anisotropic melt phase. The copolymer of the component A preferably comprises 5-95mol% of the repeating unit of formula I, 1-95mol% of the repeating unit of formula II and 0-70mol% of the repeating unit of formula III.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel resin composition having excellent heat resistance and mechanical properties as well as melt moldability.

[0002]

2. Description of the Related Art Aromatic polyamide-imide resin is a plastic material excellent in heat resistance, mechanical strength, electrical characteristics and chemical resistance, and has been used as a varnish, a film, etc. Inferiorly, most of them are currently molded by the compression molding method because injection molding is difficult. That is, the aromatic polyamide-imide resin is typically produced by a method in which a solvent is produced from an aromatic tricarboxylic acid anhydride and diisocyanate (Japanese Patent Publication No. 19274/44), and a method in which a solvent is produced from an aromatic tricarboxylic acid anhydride halide and a diamine. Target. However, the polyamideimides produced by these methods are suitable for applications such as varnishes and cast films, but are inferior in melt moldability and therefore unsuitable for melt molding. As a technique for improving the melt moldability without impairing the heat resistance of the aromatic polyamide-imide resin, an aromatic dicarboxylic acid component such as isophthalic acid has already been added to the aromatic tricarboxylic acid component and a total of 100 mol% of both. An aromatic polyamideimide copolymer in which 20 to 80 mol% is used in combination has been proposed (US Pat. No. 4,313,868). Although this copolymer has improved melt moldability as compared with aromatic polyamideimide, the flow start temperature during melt molding still requires a high temperature close to the decomposition temperature of the polyamideimide copolymer during melting. However, molding cannot be performed at a temperature at which sufficient moldability is obtained, and since aromatic tricarboxylic acid chloride is used as a raw material, halogen remains in the resin and high-temperature treatment is required for a long time.

On the other hand, a thermoplastic resin capable of forming an anisotropic molten phase is characterized by excellent heat resistance (hereinafter sometimes abbreviated as liquid crystal polymer) and mechanical properties, and particularly excellent melt fluidity. However, further improvement in mechanical strength, elastic modulus, heat resistance and the like is desired depending on the application, and it is also a fact that there is a big problem called anisotropy of physical properties. That is, there is a large difference in physical properties such as strength, elastic modulus, molding shrinkage, and linear expansion coefficient between the horizontal direction and the vertical direction with respect to the resin flow direction during injection molding, and the mechanical characteristics and dimensions in the direction perpendicular to the flow direction. Stability is low. Therefore, the high heat resistance and mechanical properties of the aromatic polyamide-imide resin improve the heat resistance and mechanical properties of the liquid crystal polymer, and further, the excellent melt moldability of the liquid crystal polymer improves the melt moldability of the aromatic polyamide-imide resin. It is desired to improve the heat resistance and mechanical properties, preferably to improve the anisotropy of physical properties and to create a novel material having easy melt moldability. Attempts have been made so far, for example, by blending the melt moldability of an aromatic polyamide-imide resin with a liquid crystal polymer having a fluidity superior to that of an aromatic polyamide-imide, heat resistance and melt moldability are excellent. Technology for creating materials
It is proposed in Japanese Patent Publication No. 181560. However, according to these prior arts, although the molding processability of the aromatic polyamide-imide resin is improved to some extent, the heat resistance and mechanical properties are still insufficient.

[0004]

The problems to be solved by the present invention are resin compositions having high mechanical properties, heat resistance and elastic modulus, excellent melt moldability, and improved anisotropy. It is to provide things.

[0005]

Means for Solving the Problems The inventors of the present invention have made extensive studies to improve the problems of a blend of an aromatic polyamideimide resin and a liquid crystal polymer of the prior art.
A novel resin composition comprising (A) an aromatic polyamideimide copolymer having the structures of the general formulas (1), (2) and (3) as repeating units and (B) a liquid crystal polymer provides a conventional aromatic composition. Heat resistance and mechanical properties of a resin composition comprising a group polyamide imide resin and a liquid crystal polymer,
The inventors have found that the anisotropy of physical properties is improved and have reached the present invention.

That is, the present invention is

[Chemical 2]

[In the general formula (1), Ar represents a trivalent aromatic group containing at least one carbon 6-membered ring. Also,
In the general formula (2), Ar ₁ represents a divalent aromatic group containing at least one 6-membered carbon ring. Further, in the general formula (3), R ₁ represents a divalent aliphatic group, and in the general formulas (1), (2) and (3), R represents a divalent aromatic group or an aliphatic group. ].

The aromatic polyamide-imide copolymer used in the resin composition of the present invention has the structures of the general formulas (1), (2) and (3) as repeating units, (1),
(2), (3) With respect to the total 100 mol% of each structure,
(1) has a structure of 5 mol% or more and 95 mol% or less, (2) has 1 mol% or more and 95 mol% or less, and (3) has a structure of 0 mol% or more and 70 mol% or less, and preferably (1 ) Is 10
Mol% to 90 mol%, (2) is 1 mol% to 90
Mol% or less, (3) has a structure consisting of 0 mol% or more and 50 mol% or less, and more preferably (1) is 10 mol%
Or more and 70 mol% or less, (2) is 1 mol% or more and 90 mol% or more
Hereinafter, (3) has a structure consisting of 0 mol% or more and 50 mol% or less, and most preferably (1) is 10 mol% or more and 5 mol% or less.
Less than 0 mol%, (2) 1 mol% or more and 90 mol% or less,
(3) has a structure consisting of 0 mol% or more and 50 mol% or less. When the composition ratio of the structures (1) to (3) deviates from the above amount range, heat resistance, melt moldability, mechanical properties, and anisotropy of physical properties are impaired.

The structural unit (1) is a poiamidoimide structural unit containing an aromatic tricarbonyl group. The structural unit (2) is a polyamide structural unit containing an aromatic dicarbonyl group. The structural unit (3) is a polyamide structural unit containing an aliphatic dicarbonyl group. Specific examples of Ar in the general formula (1) include those shown in the following chemical formula 3.

[Chemical 3]

Of these, the preferable one is shown in the following chemical formula 4.

[Chemical 4]

R in the general formulas (1), (2) and (3) is a divalent aromatic and / or aliphatic group, specific examples of which are shown in the following chemical formulas 5 and 6. Can be given.

[Chemical 5]

[0012]

[Chemical 6]

Among these, the following are preferred.

[Chemical 7]

The following are particularly preferred.

[Chemical 8]

Most preferred are the following:

[Chemical 9]

Ar ₁ in the general formula (2) is a divalent aromatic group, and specific examples thereof include those shown in the following chemical formula 10.

[Chemical 10]

Among these, the following are preferred.

[Chemical 11]

The following are particularly preferred.

[Chemical 12]

R ₁ in the general formula (3) is a divalent aliphatic group, and specific examples thereof include m =
2 to 20 can be mentioned. Preferred is m = 2
˜12, and more preferably m = 4 to 12.

[Chemical Formula 13]-(CH2) _m-

The aromatic polyamide-imide copolymer used in the resin composition of the present invention is (a) an amide from a polycarboxylic acid component of aromatic tricarboxylic acid anhydride, aromatic dicarboxylic acid and aliphatic dicarboxylic acid and diisocyanate. System, a method for producing in a non-amide solvent, (b) an aromatic tricarboxylic acid anhydride halide, an aromatic dicarboxylic acid dihalide and an amide from an aliphatic dicarboxylic acid dihalide and a diamine, a method for producing in a non-amide solvent, Further, (c) a method for producing an aromatic tricarboxylic acid anhydride, an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid and a diamine using an amide-based or non-amide-based solvent in a phosphoric acid or phosphite ester-based catalyst, Can be manufactured by any of the above methods. Among these methods, (b) has the above-mentioned problem of residual halogen, and further requires a high-temperature post-treatment for forming an imide ring, and (c) also requires a high-temperature post-treatment. It's hard to say the preferred method,
(A) is the most preferable manufacturing method.

In the present invention, the aromatic polyamide-imide copolymer which gives a resin composition having high heat resistance, mechanical strength and good moldability is a random amide-imide structure and amide structure arranged at random. Copolymer, block copolymer in which amide imide structure and amide structure are continuously bonded with a constant chain length respectively, or alternating copolymer in which amide imide structure and amide structure are alternately bonded I do not care.

An aromatic tricarboxylic acid anhydride, an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, which is used for producing an aromatic polyamideimide copolymer suitable for the resin composition of the present invention by the method (a). The diisocyanate is a compound represented by the following general formula 14, chemical formula 15, chemical formula 16, and chemical formula 17.

[0023]

[Chemical 14] (In the formula, Ar has the same meaning as in the general formula (1).)

Embedded image HOOC—Ar ₁ —COOH (wherein Ar ₁ has the same meaning as Ar _{1 in} formula (2)).

Embedded image HOOC—R ₁ —COOH (wherein R ₁ has the same meaning as R _{1 in} formula (2)).

Embedded image O = N = C—R—C = N═O (wherein R has the same meaning as R in the general formulas (1) to (3)).

In the present invention, in order to produce an aromatic polyamide-imide copolymer with a high degree of polymerization and a high yield, which gives a resin composition having high heat resistance, mechanical strength and good moldability, (a) In the above method, when the number of moles of diisocyanate is P, the total number of moles of aromatic tricarboxylic acid anhydride, aromatic dicarboxylic acid and aliphatic dicarboxylic acid is Q, the molar ratio of both is 0.9 <Q. / P <
It is preferable to be maintained at 1.1, and 0.99 <Q / P <
More preferably, it is kept at 1.01.

The aromatic polyamide-imide copolymer used in the present invention is preferably obtained by polymerizing a predetermined amount of the components of Chemical formulas 13 to 16 in a solvent, and the preferable polymerization temperature is 5
0 ° C to 200 ° C, more preferable polymerization temperature is 80 ° C to 18 ° C.
It is 0 ° C. The most preferred polymerization temperature is 80 ° C to 170 ° C. If it is lower than this range, the degree of polymerization does not increase, and if it is higher than this range, only those having poor melt moldability can be obtained. Further, during the polymerization reaction, the temperature may be changed in multiple stages, preferably 2-3.
A more preferred aromatic polyamide-imide copolymer can be produced by increasing the number of steps. That is, the polymerization temperature is set in the temperature range of 50 ° C. to 110 ° C. in the first stage and in the temperature range of 110 ° C. to 200 ° C. in the second and subsequent stages, and the polymerization is carried out in a multi-stage manner, whereby the amide group is substantially formed. After completion of the formation of imide, an imide group is formed, and a tough polyamide imide having excellent melt moldability is produced. The temperature in each stage may be set to any value within the temperature range. For example, the temperature may be raised, the temperature may be constant, or a combination of the temperature rise and the constant temperature may be used. Most preferably, the latter stage is raised by 20 to 80 ° C. higher than the former stage,
This is a method in which the temperature in each stage is kept constant.

As a solvent used for producing the aromatic polyamideimide copolymer preferably used in the resin composition of the present invention, a solvent having solubility in the polyamideimide produced, specifically N-methylpyrrolidone. , Dimethylformamide, dimethylacetamide, dimethylsulfoxide, dimethylsulfolane, tetramethylenesulfone,
Diphenyl sulfone, γ-butyrolactone and the like are used, and polar solvents which are not soluble in polyamideimide, such as nitrobenzene, nitrotoluene, acetonitrile, benzonitrile, acetophenone, nitromethane, dichlorobenzene and anisole are also used. . It does not matter if a solvent having solubility in polyamideimide and a polar solvent having no solubility are mixed and used. Among the above, a preferable solvent is a solvent having solubility in polyamideimide. Further, these solvents are preferably used under the condition that the ratio of the monomer raw material to the solvent is 0.1 to 4 mol / liter.

Various catalysts described in the prior art can be used in the production of the aromatic polyamideimide copolymer preferably used in the resin composition of the present invention, but the melt moldability is impaired. In order not to use it, the amount used should be limited to the necessary minimum, and it is not necessary to use it.
Specific examples of the catalyst include pyridine, quinoline,
Isoquinoline, trimethylamine, triethylamine,
Tertiary amines such as tributylamine, N, N-diethylamine, γ-picoline, N-methylmorpholine, N-ethylmorpholine, triethylenediamine, 1,8-diazabicyclo [5,4,0] undecene-7, cobalt acetate, naphthene Examples thereof include metal salts of weak acids such as cobalt acid and sodium oleate, heavy metal salts, alkali metal salts and the like.

In producing an aromatic polyamide-imide copolymer suitable for the resin composition of the present invention, a solvent,
The water content of the polymerization system composed of monomers etc. is 500
It is preferable to keep it at ppm or less, more preferably 1
It is kept at 00 ppm, most preferably below 50 ppm. This is because if the amount of water contained in the system is larger than these, the melt moldability is impaired. Further, the use of a small amount of the molecular weight modifier is not limited at all, as typical molecular weight modifiers, monocarboxylic acids such as benzoic acid, phthalic anhydride, succinic anhydride, naphthalenedicarboxylic acid anhydride and the like. Examples thereof include monofunctional compounds such as dicarboxylic acid anhydrides, monoisocyanates such as phenyl isocyanate, and monohydric phenols.

The degree of polymerization of the aromatic polyamide-imide copolymer suitable for the resin composition of the present invention is 0.1 dl / when it is expressed by the reduced viscosity measured in dimethylformamide at 30 ° C. at a concentration of 1 g / dl. g to 2.0 dl / g is preferably used, more preferably 0.1 dl / g to 1.0 dl / g, most preferably 0.2 dl / g to 0.7 dl / g. .

Aromatic polyamide-imide copolymers preferably used in the present invention include alcohols such as methanol and isopropyl alcohol, ketones such as acetone and methyl ethyl ketone, and aliphatic and aromatic hydrocarbons such as heptane and toluene. It is recovered by precipitating and washing with a solvent, but it may be obtained by directly concentrating the polymerization solvent. Further, a method in which the solvent is removed under reduced pressure by an extruder or the like and then pelletized after being concentrated to a certain extent is also preferable. Next, the thermoplastic resin (liquid crystal polymer) capable of forming an anisotropic melt phase (B) used in the resin composition of the present invention means an aromatic polyester (liquid crystal polyester) capable of forming an anisotropic melt phase, Aromatic polyester imide (liquid crystal polyester imide), aromatic polyester amide (liquid crystal polyester amide), polycarbonate (liquid crystal polycarbonate)
The following general formulas (8), (9) and (1
A typical one is one having a structure selected from the group of 0), (11), (12) and (13) as a repeating unit of the main component. The case where the structure alone in (8) is used as a main component, and the structure described in (8) is used as an essential component, and (9) to (1
1 or more kinds selected from the group of 1) and (12) to (1)
There are two cases in which one or more kinds selected from the group of 3), and a total of three or more kinds of structures are main components. In the latter case, it is substantially mol% and is (9) + (10) + (11) = (1
2) + (13) must be satisfied.

[0031]

Embedded image —X—Ar ₂ —CO— (8) [The general formula (8) represents an aromatic hydroxy acid and / or an aromatic amino acid residue, and therefore X is O or
Indicates NH. Ar ₂ represents a divalent aromatic group containing at least one 6-membered carbon ring. ]

Embedded image —OC—Ar ₁ —CO— (9) [The general formula (9) represents an aromatic dicarboxylic acid residue, and
r ₁ has the same meaning as in formula (2). ]

Embedded image —CO—Ar ₂ —O—R ₁ —O—Ar ₂ —CO— (10) [wherein the general formula (10) represents an aromatic dicarboxylic acid residue,
Ar ₂ and R ₁ have the same meanings as in general formulas (8) and (3), respectively. ]

[Chemical 21] [General formula (11) represents an aromatic dicarboxylic acid residue,
Ar and Ar ₁ have the same meaning as in general formulas (1) and (9), respectively. ]

[0032]

Embedded image —X—Ar ₃ —O— (12) [in the general formula (12), an aromatic dihydroxy compound and /
Or, it represents an aromatic aminohydroxy residue, and thus
X represents O or NH. Ar3 represents a divalent aromatic group containing at least one carbon 6-membered ring. ]

Embedded image —O—R ₁ —O— (13) [General formula (13) represents an aliphatic dihydroxy compound residue, and R ₁ has the same meaning as in general formula (3). ]

The liquid crystal polymer preferably used in the resin composition of the present invention is specifically the above-mentioned structural formulas (8) and (8).
/ (9) / (12), (8) / (9) / (13),
(8) / (9) / (10) / (12) or (8) /
This is due to the combination of (9) / (11) / (12). Here, (8) / (9) / (12) means a substantially liquid crystalline polyester or polyesteramide having the repeating units of the main components of the structures of the general formulas (8), (9) and (12). Means the structure of. When the liquid crystal polymer is a combination of the above three or four structural formulas, the general formula (8) is 5-8 based on the total 100 mol% of all structures.
0 mol%, preferably 10 to 70 mol%, and substantially (9) = (12), (9) = (13) in mol%,
(9) + (10) = (12), (9) + (11) = (1
There is a relationship of 2). Furthermore, when the structures of the formulas (17) and (18) are adopted, the structures of the general formulas (10) and (11) are respectively (9) + (10) and (9) + (11) in total of 10
1 to 90 mol% relative to 0 mol%, preferably 5 to 6
It accounts for 0 mol%. Further, Ar ₂ in the general formula (8) is 2
It is a valent aromatic group, and specific examples thereof include paraphenylene and 2,6-naphthalene structures.

When the liquid crystal polymer has the structure of the formula (14), Ar ₂ of the general formula (8) is paraphenylene and 2,
Taking both structures of 6-naphthalene is preferable to either paraphenylene or 2,6-naphthalene alone. In this case, the paraphenylene structure is 100 mol% in total of both.
Occupies 10 to 90 mol%. Ar ₁ in the general formula (9) is a divalent aromatic group and has the same meaning as Ar _{1 in the} general formula (2). The specific examples, preferable specific examples, and particularly preferable specific examples are as described above for Ar ₁ . Ar _{2 of the} general formula (10)
Also has the same meaning as in formula (8). Ar of the general formula (11) has exactly the same meaning as Ar of the general formula (1). Ar ₁ also has the same meaning as in the general formula (9). Further, Ar ₃ in the general formula (12) is a divalent aromatic group, and specific examples thereof include those obtained by removing the aliphatic group and the cycloaliphatic group from Chemical formula 5, and preferred examples Examples of the compound include those shown in the following chemical formula 24.

[Chemical formula 24]

The following are particularly preferred.

[Chemical 25] R ₁ in the general formula (13) is a divalent aliphatic group and has the same meaning as in the general formula (3).
Of m = 2-20. Preferred is m = 2 to 12, more preferred is m = 2
~ 6.

Preferred liquid crystal polymers for use in the resin composition of the present invention include liquid crystal polyester (when X in the general formulas (8) and (12) represents O), liquid crystal polyester amide (the general formula (8) and (12) when X represents NH), and a more preferable liquid crystal polymer is a liquid crystal polyester (when X in the general formulas (8) and (9) represents O). Among these liquid crystal polyesters and liquid crystal polyester amides, preferred are (8),
(8) / (9) / (13), (8) / (9) / (10)
/ (12) or (8) / (9) / (11) / (12)
And more preferably (8), (8)
/ (9) / (10) / (12) or (8) / (9) /
The structure of (11) / (12), particularly preferred is (8) / (9) / (10) / (12) or (8).
/ (9) / (11) / (12) structure, and the most preferable one is (8) / (9) / (11) / (1
It is the structure of 2). (8) / (9) / (11) / (1
In the structure of 2), Ar ₂ is a paraphenylene structure or a 2,6-naphthalene structure, Ar ₁ is a 2,6-naphthalene structure or a paraphenylene structure, and Ar ₃
Is more preferably a paraphenylene structure or a 4,4′-biphenyl structure, and Ar _{1 in the} general formula (11) is more preferably a 4,4′-diphenyl ether structure.

Suitable for use in the resin composition of the present invention,
The liquid crystal polyester can be produced by a known method. As a typical manufacturing method, for example, the following (d) to (e)
Can be given. The liquid crystal polyesteramide can be manufactured in the same manner. (D) A method of producing a dicarboxylic acid, an acetic acid ester of an aromatic dihydroxy compound and an acetic acid ester of an aromatic hydroxy acid by a deacetic acid polycondensation reaction. (E) A method for producing a dicarboxylic acid diphenyl ester, an aromatic dihydroxy compound and an aromatic hydroxy acid phenyl ester by a polycondensation reaction. Above all, the method (d) is a preferable method because the polycondensation reaction proceeds without a catalyst. Also, (8) / (9) /
The liquid crystal polyester of (13) can also be produced by transesterification of a polyester obtained by a polycondensation reaction of an aliphatic diol and an aromatic dicarboxylic acid, which is represented by polyethylene terephthalate, with an acetic acid ester of an aromatic hydroxy acid. it can.

Next, the component (A) of the resin composition of the present invention,
(B) is blended with 5 to 95% by weight of the aromatic polyamideimide copolymer as the component (A) with respect to 100% by weight of the total amount of both, preferably 10 to less than 80% by weight, more preferably , Less than 10-70% by weight, most preferably less than 10-50% by weight. If the amount of component (A) is greater than this amount, the mechanical properties will deteriorate, and if it is less, heat resistance will decrease and the anisotropy of physical properties will increase. The resin composition of the present invention is produced by melt-kneading each component, and the temperature of melt-kneading is 250 to 400 ° C., preferably 280 to 400 ° C., and the kneading method is an extruder, kneader, Banbury mixer, roll or the like. Can be done at. A preferred method is a twin-screw extruder method.

The resin composition of the present invention may optionally contain
Fillers, pigments, lubricants, plasticizers, stabilizers, UV absorbers,
Other components such as flame retardants, various additives of flame retardant aids, other resins, elastomers, etc. may be appropriately blended. Examples of fillers are glass beads, wollastonite, mica, talc, kaolin, silicon dioxide, clay, asbestos, calcium carbonate, magnesium hydroxide, silica, diatomaceous earth, graphite, carborundum, molybdenum disulfide. Mineral filler; inorganic fiber such as glass fiber, milled fiber, potassium titanate fiber, boron fiber, carbonized diatom fiber, metal fiber such as brass, aluminum and zinc; organic fiber represented by carbon fiber and aramid fiber;
Flake of aluminum or zinc can be mentioned.
The filler is preferably used in an amount of 1 to 70% by weight based on the whole composition. Preferred fillers are milled fiber, glass fiber and carbon fiber, which are epoxy-based, amino-based,
Those treated with a silane coupling agent such as a urethane type are also preferably used. Examples of the pigment include titanium oxide, zinc sulfide, zinc oxide and the like. Typical lubricants are mineral oil, silicone oil, ethylene wax, polypropylene wax, metal salts such as sodium stearate and lithium, metal salts such as sodium montanate, lithium and zinc, amides and esters of montanic acid, and the like. It is exemplified as

As examples of various additives, examples of flame retardants include phosphoric acid esters such as triphenyl phosphate and tricresyl phosphate; decabromobiphenyl, pentabromotoluene, decabromobiphenyl ether, Brominated compounds represented by hexabromobenzene, brominated polystyrene, brominated epoxy resins, brominated phenoxy resins, etc .; nitrogen-containing compounds such as melamine derivatives; nitrogen-containing phosphorus compounds such as cyclic phosphazene compounds and phosphazene polymers. You can Flame retardant aids may be used, examples of which include antimony, boron, zinc or iron compounds. Other additives include sterically hindered phenols, stabilizers such as phosphite compounds, oxalic acid diamide compounds, and ultraviolet absorbers exemplified by sterically hindered amine compounds.

Examples of the other resins mentioned above include epoxy resins, phenoxy resins; polyethylene terephthalate, polybutylene terephthalate, produced from dichlorophenol such as epichlorohydrin and 2,2-bis (4-hydroxyphenyl) propane. Polyesters such as polyethylene-2,6-naphthalate and polybutylene-2,6-naphthalate; nylon-6, nylon-10, nylon-12, nylon-6,6, nylon-MXD,
6, nylon-4,6, nylon-6, T, nylon-
6, I and other aliphatic and aromatic crystalline polyamides; aliphatic and aromatic amorphous polyamides; hydroquinone, resorcin, 4,4'-dihydroxydiphenyl, bis (4
-Hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, Bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 4-
Polycarbonates produced by using divalent phenols such as hydroxyphenyl 3-hydroxyphenyl ketone and phosgene or diphenyl carbonate or dimethyl carbonate as monomers; divalent phenols and phosgene or diphenyl carbonate, dimethyl carbonate and the above-mentioned dicarboxylic acids and their derivatives. Polyester carbonate produced by using as a monomer; polyphenylene ether obtained by oxidative coupling polymerization of 2,6-dimethylphenol; polysulfone, polyether sulfone, polyether imide,
Aromatic resins such as polythioether ketone, polyether ketone, and polyether ether ketone are exemplified.

Further, examples of the elastomer include a high-melting point hard segment mainly composed of an alkylene terephthalate unit, which is composed of the above-mentioned dihydric alcohol and terephthalic acid, and poly (ethylene oxide) glycol, poly (propylene oxide) glycol or the like. Ether glycol, or a polyester elastomer represented by a block copolymer of an aliphatic dicarboxylic acid and a soft segment made of an aliphatic polyester produced from a divalent alcohol (a typical product is Toyobo Co., Ltd. perprene, Examples include Hytrel manufactured by Dyupon); polyamide elastomers represented by block copolymers of hard segments such as nylon 11 and nylon 12 and polyether or soft segment of polyester (a typical quotient). Examples thereof include grill amides manufactured by EMS CHEMIE); various polyethylenes of low density, high density, ultra high molecular weight, linear low density, etc .; polypropylene; EP elastomers which are copolymers of ethylene and propylene; ethylene, propylene and norbornene. EPDM elastomers which are non-conjugated copolymers of bisphenols, cyclopentadiene, 1,4-hexadiene; α-olefins such as ethylene, propylene and butene-1 and α, β-unsaturation such as glycidyl acrylate and glycidyl methacrylate Copolymer elastomer with glycidyl ester of acid; Copolymer elastomer with α-olefin such as ethylene, propylene and butene-1 and unsaturated ester such as vinyl acetate, vinyl propionate, methyl acrylate and methyl methacrylate; More Polyethylene Grafting of α, β-unsaturated dicarboxylic acid anhydride represented by polypropylene, EP, EPDM, and maleic anhydride of α-olefin copolymer elastomer, or glycidyl ester of α, β-unsaturated acid such as glycidyl methacrylate. Modified product: A component of vinyl aromatic compound such as styrene and B of diene component such as butadiene and isoprene
A-B-A ', A-B type elastomeric block copolymer; A-B-A', B-component elastomeric block copolymer in which B component is hydrogenated, and further represented by maleic anhydride Α-β-unsaturated dicarboxylic acid anhydride, or AB-grafted with a glycidyl ester of an α, β-unsaturated acid such as glycidyl methacrylate
A ', AB type elastomeric block copolymer and graft-modified similarly AB with hydrogenated component B
Examples thereof include -A 'and AB type elastomeric block copolymers; polysulfide rubber, silicone rubber and the like.

A resin composition comprising the aromatic polyamide-imide copolymer of the present invention and a thermoplastic resin capable of forming an anisotropic melt phase forms an anisotropic melt phase with the prior art aromatic polyamide-imide resin. Thermoplastic resin (liquid crystal polymer)
It realizes high mechanical properties and high heat resistance, which are not achieved by the resin composition comprising, and also improves anisotropy. It is considered that this excellent property is mainly due to the fact that the novel resin composition comprising the specific aromatic polyamide-imide copolymer of the present invention and the liquid crystal polymer improves the compatibility of both resins, which are inferior to the resin composition of the prior art. . However, the aromatic polyamide-imide copolymer of the present invention has a lower imide structure than the aromatic polyamide-imide resin of the prior art and has a low heat resistance (glass transition point), but the heat resistance of the resin composition of the prior art is low. To improve the mechanical properties, in particular,
The elastic modulus of the aromatic polyamide-imide copolymer / liquid crystal polymer was changed specifically, and therefore, the addition of a small amount of the liquid crystal polymer enabled a great improvement in the elastic modulus of the aromatic polyamide-imide copolymer. It can be said that it is specific.

[0044]

The resin composition comprising the aromatic polyamide-imide copolymer of the present invention and a thermoplastic resin capable of forming an anisotropic molten phase has a conventional aromatic polyamide-imide resin and an anisotropic molten phase. High mechanical properties and heat resistance, which were not achieved by a resin composition composed of a thermoplastic resin (liquid crystal polymer) that can be formed, are realized, and anisotropy is also improved. The resin composition of the present invention is suitably used for molding material applications that require high heat resistance, high mechanical strength and elastic modulus, and further excellent melt moldability.

Reference Examples 1 to 9 below show production examples of aromatic polyamideimide copolymerization. Further, Reference Examples 10 to 14 show production examples of liquid crystalline polyester. The liquid crystalline polyesters produced here all formed an anisotropic molten phase in the molten state and exhibited optical anisotropy. Furthermore, the resin composition of the present invention will be described in more detail with reference to Examples and Comparative Examples. The results of the reference examples are shown in Table 1, and the results of the examples and comparative examples are shown in Tables 2, 3, 4, and 5. Reference Example 1 3 liters of N-methylpyrrolidone having a water content of 40 ppm was charged into a reactor equipped with a 5 liter stirrer, a thermometer, and a reflux condenser equipped with a drying tube filled with calcium chloride at the tip. Here, trimellitic anhydride 222.
1 g (20 mol%), isophthalic acid 192.1 g (2
0 mol%), adipic acid 84.4 g (10 mol%),
Then 2,4-tolylene diisocyanate 503.3
g (50 mol%) was added. The water content in the system was 50 ppm when trimellitic anhydride, isophthalic acid, and adipic acid were added. Initially, it takes 20 minutes from room temperature to set the content temperature to 1
The temperature was set to 00 ° C., and polymerization was carried out at this temperature for 4 hours. After 15 minutes, the temperature was raised to 160 ° C., and the polymerization was continued for 4 hours while maintaining this temperature. After completion of the polymerization, add the polymer solution to N
-Dripping into methanol twice the volume of methylpyrrolidone with vigorous stirring. The precipitated polymer is filtered off with suction, redispersed in methanol, washed thoroughly, and separated after washing.
It was dried under reduced pressure at 0 ° C. for 10 hours to obtain a polyamideimide powder. Dimethylformamide solution (concentration 1.0 g / d
When the reduced viscosity of this product at 30 ° C. was measured in 1), it was 0.40 dl / g. Further, the glass transition temperature was measured by a differential scanning calorimetry (DSC) method. The results are shown in Table 1 together with other reference examples.

Reference Example 2 3 liters of N-methylpyrrolidone having a water content of 20 ppm was charged into a reactor equipped with a 5 liter stirrer, a thermometer, and a reflux condenser equipped with a drying tube filled with calcium chloride at the tip. It is. 210.6 g (20 mol%) of trimellitic anhydride chloride, 203.0 g (20 mol%) of isophthalic acid dichloride, and 91.6 g (10 mol%) of adipic acid dichloride were added to a 5 liter stirrer, thermometer, and tip. The reactor was equipped with a reflux condenser equipped with a drying tube filled with calcium chloride. Then 305.4 g (50 mol%) of m-toluylene diamine
Was added. First, polymerization was performed at room temperature to 40 ° C. for 15 hours. After that, the temperature was raised to 150 ° C., and the polymerization was continued for 7 hours while maintaining this temperature. After the polymerization was completed, the polymer solution was diluted twice by adding N-methylpyrrolidone, and this was twice as much as N-methylpyrrolidone. In a volume of methanol with vigorous stirring. The precipitated polymer was filtered by suction, redispersed in methanol, washed thoroughly, separated after washing, and dried under reduced pressure at 200 ° C. to obtain a polyamideimide powder. When the reduced viscosity at 30 ° C. of this product was measured with a dimethylformamide solution (concentration 1.0 g / dl), it was 0.30 dl
/ G.

Reference Example 3 3 liters of N-methylpyrrolidone having a water content of 40 ppm was charged in the same reactor as in Example 1. To this, 222.1 g (20 mol%) of trimellitic anhydride, 288.1 g (30 mol%) of isophthalic acid, and then 503.3 g (50 mol%) of 2,4-tolylene diisocyanate were added. Thereafter, polymerization and treatment were carried out in the same manner as in Reference Example 1 to obtain polyamideimide powder. Dimethylformamide solution (concentration 1.0 g / dl)
When the reduced viscosity at 0 ° C was measured, it was 0.40 dl / g
Met.

Reference Example 4 3 liters of N-methylpyrrolidone having a water content of 40 ppm was charged into the same reactor as in Example 1. Here, trimellitic anhydride 333.1 g (30 mol%), isophthalic acid 144.0 g (15 mol%), adipic acid 4
2.2 g (5 mol%) were added, followed by 503.3 g (50 mol%) 2,4-tolylene diisocyanate. Thereafter, polymerization and treatment were carried out in the same manner as in Reference Example 1 to obtain polyamideimide powder. The reduced viscosity of this product at 30 ° C. measured with a dimethylformamide solution (concentration 1.0 g / dl) was 0.35 dl / g.

Reference Example 5 3 liters of N-methylpyrrolidone having a water content of 30 ppm was charged in the same reactor as in Example 1. To this, 333.1 g (30 mol%) of trimellitic anhydride, 192.0 g (20 mol%) of isophthalic acid, and then 503.3 g (50 mol%) of 2,4-tolylene diisocyanate were added. Thereafter, polymerization and treatment were carried out in the same manner as in Reference Example 1 to obtain polyamideimide powder. Dimethylformamide solution (concentration 1.0 g / dl)
The reduced viscosity at 0 ° C was measured to be 0.33 dl / g
Met.

Reference Example 6 3 L of N-methylpyrrolidone having a water content of 40 ppm was charged in the same reactor as in Example 1. Here, trimellitic anhydride 166.6 g (15 mol%), isophthalic acid 48.0 g (5 mol%), adipic acid 25
3.2 g (30 mol%), then 503.3 g (50 mol%) of 2,4-tolylene diisocyanate were added.
Thereafter, polymerization and treatment were carried out in the same manner as in Reference Example 1 to obtain polyamideimide powder. The reduced viscosity of this product at 30 ° C. measured with a dimethylformamide solution (concentration 1.0 g / dl) was 0.35 dl / g.

Reference Example 7 3 L of N-methylpyrrolidone having a water content of 30 ppm was charged in the same reactor as in Reference Example 1. 555.3 g (50 mol%) of trimellitic anhydride was added thereto, and then 503.3 g (5 of 2,4-tolylene diisocyanate).
0 mol%) was added. The water content in the system when trimellitic anhydride was added was 25 ppm. First, it took 20 minutes from room temperature to bring the content temperature to 90 ° C., and polymerization was carried out at this temperature for 50 minutes. After 15 minutes, the temperature was raised to 115 ° C., and the polymerization was continued for 4 hours while maintaining this temperature. After the completion of the polymerization, the polymer solution was added dropwise to methanol having twice the volume of N-methylpyrrolidone under strong stirring. The precipitated polymer was separated by suction filtration, redispersed in methanol, washed thoroughly, separated after washing, and dried under reduced pressure at 200 ° C. for 15 hours to obtain a polyamideimide powder. When the reduced viscosity of this product at 30 ° C. was measured with a dimethylformamide solution (concentration: 1.0 g / dl), it was 0.27 dl / g.

Reference Example 8 3 L of N-methylpyrrolidone having a water content of 15 ppm was charged in the same reactor as in Reference Example 1. Isophthalic acid 480.1 g (50 mol%), then 2,4
503.3 g (50 mol%) of tolylene diisocyanate was added. Water content in the system is 50p when isophthalic acid is added
It was pm. First, it took 20 minutes from room temperature to bring the content temperature to 100 ° C., and polymerization was carried out at this temperature for 70 minutes.
After 15 minutes, the temperature was raised to 115 ° C., and the polymerization was continued for 4 hours while maintaining this temperature. After the completion of the polymerization, the polymer solution was added dropwise to methanol having twice the volume of N-methylpyrrolidone under strong stirring. The precipitated polymer was filtered by suction, redispersed in methanol, washed thoroughly, separated after washing, and dried under reduced pressure at 200 ° C. to obtain a polyamide powder. Dimethylformamide solution (concentration 1.0 g / dl)
The reduced viscosity of this product at 30 ° C. was 0.30 dl / g.

Reference Example 9 3 liters of N-methylpyrrolidone having a water content of 15 ppm was charged in the same reactor as in Reference Example 1. To this, 422.3 g (50 mol%) of adipic acid and then 503.3 g (50 mol%) of 2,4-tolylene diisocyanate were added. Water content in the system when adipic acid is added is 50 pp
It was m. First, it took 20 minutes from room temperature to bring the content temperature to 100 ° C., and polymerization was carried out at this temperature for 70 minutes. After 15 minutes, the temperature was raised to 145 ° C., and the polymerization was continued for 4 hours while maintaining this temperature. After the completion of the polymerization, the polymer solution was added dropwise to methanol having twice the volume of N-methylpyrrolidone under strong stirring. The precipitated polymer is filtered off with suction,
Furthermore, redisperse in methanol, wash well, separate after washing,
Vacuum drying was performed at 200 ° C. to obtain polyamide powder. When the reduced viscosity of this product at 30 ° C. was measured with a dimethylformamide solution (concentration 1.0 g / dl), it was 0.3.
It was 5 dl / g.

Reference Example 10 p-acetoxybenzoic acid 1081 g (60 mol%),
1,4-diacetoxybenzene 388 g (20 mol%), 4,4′-diphenyl ether-bis (N-trimellitimide) 110 g (2 mol%) and 2,6
-Preparing 389 g (18 mol%) of naphthalene dicarboxylic acid into a 5 liter reactor equipped with a stirrer, thermometer, pressure gauge, nitrogen gas introducing pipe, distillation head, etc., purging with nitrogen gas 3 times, and then gently stirring. Meanwhile, the temperature was raised to 200 ° C. while flowing a small amount of nitrogen gas into the reactor. 200 ° C
After reaching, the stirring speed was increased to 240 ° C. for 1 hour, 260
The reaction was carried out at 1 ° C for 1 hour, 280 ° C for 1 hour, and 300 ° C for 2 hours. Next, the pressure inside the reactor is gradually reduced to 0.5T.
Polymerization was completed by stirring at 300 ° C. for 1 hour, 320 ° C. for 30 minutes, and 340 ° C. for 30 minutes while maintaining a vacuum of orr.
The logarithmic viscosity measured at 60 ° C. at a concentration of 0.16 g / dl in pentafluorophenol was 3.99 dl / g.

Reference Example 11 p-acetoxybenzoic acid 1080 g (60 mol%),
1,4-diacetoxybenzene 388 g (20 mol%), 1,6-bis (phenoxy) hexane-4,4 ′
-Dicarboxylic acid 358 g (10 mol%) and 2,6
-Naphthalenedicarboxylic acid 216 g (10 mol%) was charged into the same 5 l reactor as in Reference Example 9, and in the same manner as in Reference Example 9, 240 ° C for 3.5 hours, 260 ° C for 2 hours,
The reaction was carried out at 280 ° C for 1.5 hours. Then, the pressure inside the reactor is gradually reduced to 28 Torr while maintaining a vacuum of 0.5 Torr.
Polymerization was completed by stirring at 0 ° C. for 3.5 hours and at 300 ° C. for 3 hours. 0.16 g / dl in pentafluorophenol
The logarithmic viscosity measured at 60 ° C. at a concentration of 2.56 dl /
It was g.

Reference Example 12 p-acetoxybenzoic acid 1081 g (50 mol%),
1380 g (50 mol%) of 6-acetoxy-2-naphthoic acid was charged into the same 5 l reactor as in Reference Example 9 and reacted in the same manner as in Reference Example 9 to complete the polymerization.

Reference Example 13 p-acetoxybenzoic acid 1081 g (60 mol%),
1,4-diacetoxybenzene 388 g (20 mol%), 2,6-naphthalenedicarboxylic acid 432 g (20
(Mol%) was charged into the same 5 l reactor as in Reference Example 9 and reacted in the same manner as in Reference Example 9 to complete the polymerization. 60 ° C at a concentration of 0.16 g / dl in pentafluorophenol
The logarithmic viscosity measured at 5.42 dl / g.

Reference Example 14 p-acetoxybenzoic acid 1081 g (60 mol%),
768 g (40 mol%) of polyethylene terephthalate was charged into the same 5 l reactor as in Reference Example 9 and reacted in the same manner as in Reference Example 9 to complete the polymerization.

[0059]

【Example】

Example 1 Aromatic polyamide-imide copolymer 2 produced in Reference Example 1
Liquid crystal polyester 75 manufactured in Reference Example 10 with 5% by weight
The weight% was melt-kneaded and pelletized at 320 ° C. using a twin-screw extruder. A test piece having a thickness of 1/8 inch was injection-molded from the obtained pellet. From this test piece, the heat deformation temperature of 18.6 kg / cm ² stress was measured for the purpose of heat resistance evaluation, and the flexural modulus and strength of mechanical properties were measured. Further, the melt moldability was measured at 310 ° C. under a 20 kg / cm ² stress melt flow value by a Koka type flow tester. The results are shown in Table 2.

Examples 2-5 Example 1 was repeated with the composition of Table 2. The results are shown in Table 2. Comparative Example 1 The aromatic polyamideimide copolymer of Reference Example 1 was heated to 350 ° C.
Was compression-molded and the flexural modulus was measured. The results are shown in Table 2. Comparative Example 2 The liquid crystal polyester of Reference Example 10 was injection-molded and the flexural modulus, strength, heat distortion temperature, and melt flow value were measured in the same manner as in Example 1. The results are shown in Table 2. Comparative Examples 3 to 7 Examples 1 to 5 were repeated except that the aromatic polyamideimide copolymer of Reference Example 7 was used. The results are shown in Table 2.

Example 6 Example 2 was repeated using the aromatic polyamideimide copolymer of Reference Example 2. The results are shown in Table 3. Example 7 Example 2 was repeated using the aromatic polyamideimide copolymer of Reference Example 3. The results are shown in Table 3. Example 8 Example 2 was repeated using the aromatic polyamideimide copolymer of Reference Example 4. The results are shown in Table 3. Example 9 Example 2 was repeated using the aromatic polyamideimide copolymer of Reference Example 5. The results are shown in Table 3. Comparative Examples 8 to 10 Example 2 was repeated except that the aromatic polyamides of Reference Examples 6, 8 and 9 were replaced. The results are shown in Table 3.

Example 10 Example 2 was repeated using the liquid crystalline polyester of Reference Example 11. The results are shown in Table 4. Example 11 Example 2 was repeated using the liquid crystalline polyester of Reference Example 12. The results are shown in Table 4. Example 12 Example 2 was repeated using the liquid crystalline polyester of Reference Example 13. The results are shown in Table 4. Example 13 Example 2 was repeated using the liquid crystalline polyester of Reference Example 14. The results are shown in Table 4. Comparative Example 11 Example 10 was repeated except that the aromatic polyamide of Reference Example 7 was replaced. The results are shown in Table 4. Comparative Example 12 Example 11 was repeated except that the aromatic polyamide of Reference Example 7 was replaced. The results are shown in Table 4. Comparative Example 13 Example 12 was repeated except that the aromatic polyamide of Reference Example 7 was replaced. The results are shown in Table 4. Comparative Example 14 Example 13 was repeated except that the aromatic polyamide of Reference Example 7 was replaced. The results are shown in Table 4.

Example 14 Aromatic Polyamideimide Copolymer 4 Produced in Reference Example 1
0 wt% and the liquid crystal polyester 60 produced in Reference Example 10
The weight% was melt-kneaded and pelletized at 320 ° C. using a twin-screw extruder. From the pellets obtained, length 10 cm, width 1
A 0 cm, 3 mm thick square specimen was injection molded. From this test piece, a test piece in the flow direction of the resin and a direction perpendicular to the flow were cut out, and the flexural modulus in both directions was measured for the purpose of anisotropic evaluation. The results are shown in Table 5. Comparative Example 15 Example 14 was repeated except that the aromatic polyamide of Reference Example 7 was replaced. The results are shown in Table 5.

[0064]

[Table 1] Reference example Acid component composition Diisocyanate Glass transition point (mol%) (mol%) (° C) TMA / IPA / ADA TDI 1 20/20 / 1050 50 250 2 (20/25/5) (50) 250 (Acid black) (m-TDA) 3 20/30/0 50 290 4 30/15/5 5 50 295 5 30/20/0 50 305 6 15 / 5/30 50 173 7 50/0/0 50 326 8 0/50/0 50 260 260 0/0/50 50 155 TMA; trimellitic anhydride IPA; isophthalic acid ADA; adipic acid TDI; 2,4-tolylene diisocyanate m-TDA; metatoluylene diamine acid chloride; anhydrous Trimellitic acid chloride / isophthalic acid dichloride / adipic acid dichloride

[0065]

Table 2 Example PAI LCP Elastic modulus Strength HDT Q value / Comparative example (wt%) (wt%) (GPa) (MPa) (° C) (cc / sec) Example 1 25 75 5.2 110 110 20 80 0.03 (Reference Example 1) (Reference Example 10) Example 2 40 60 5.2 110 215 0.03 (Reference Example 1) (Reference Example 10) Example 3 50 50 4.9 100 218 0.02 (Reference Example 1) (Reference Example 10) Example 4 60 40 4.8 100 100 222 0.002 (Reference Example 1) (Reference Example 10) Example 5 75 25 4.5 4.5 90 232 0.001 (Reference Example 1) ( Reference Example 10) Comparative Example 1 100 3.6 (Reference Example 1) Comparative Example 2-100 4.2 4.2 110 167 0.18 (Reference Example 10) Comparative Example 3 25 75 4.2 4.2 80 180 0.03 (Reference Example) 7) (Reference Example 10) Comparative Example 4 40 60 4.2 80 184 .02 (Reference example 7) (Reference example 10) Comparative example 5 50 50 4.0 80 80 200 0.02 (Reference example 7) (Reference example 10) Comparative example 6 60 40 3.7 70 70 202 0.003 (Reference) Example 7) (Reference Example 10) Comparative Example 7 75 25 4.5 60 60 204 0.001 (Reference Example 7) (Reference Example 10)

[0066]

Table 3 Example PAI LCP Elastic modulus Strength HDT Q value / Comparative example (wt%) (wt%) (GPa) (MPa) (° C) (cc / sec) Example 6 40 60 5.2 100 100 207 0 .05 (reference example 2) (reference example 10) Example 7 40 60 5.1 100 210 210 0.02 (reference example 3) (reference example 10) Example 8 40 60 4.9 90 90 212 0.02 (reference Example 4) (Reference example 10) Example 9 40 60 5.0 5.0 90 213 0.02 (Reference example 5) (Reference example 10) Comparative example 8 40 60 3.2 50 167 0.02 (Reference example 6) ( Reference Example 10) Comparative Example 9 40 60 3.7 60 180 180 0.02 (Reference Example 8) (Reference Example 10) Comparative Example 10 40 60 60 3.0 40 40 163 0.03 (Reference Example 9) (Reference Example 10)

[0067]

Table 4 Example PAI LCP Elastic modulus Strength HDT Q value / Comparative example (wt%) (wt%) (GPa) (MPa) (° C) (cc / sec) Example 10 40 60 4.7 70 70 255 0 .04 (Reference Example 1) (Reference Example 11) Example 11 40 60 5.3 80 203 0.03 (Reference Example 1) (Reference Example 12) Example 12 40 60 5.2 5.2 70 258 0.007 (Reference) Example 1) (Reference Example 13) Example 13 40 60 5.2 80 80 116 0.04 (Reference Example 1) (Reference Example 14) Comparative Example 11 40 60 60 3.5 40 233 0.03 (Reference Example 7) ( Reference Example 11) Comparative Example 12 40 60 4.3 50 182 0.02 (Reference Example 7) (Reference Example 12) Comparative Example 13 40 60 60 4.2 50 237 0.004 (Reference Example 7) (Reference Example 13) Comparative example 14 40 60 4.3 40 87 0.02 (example 7 (Reference Example 14)

[0068]

Table 5 Examples Elastic modulus (GPa) / Comparative example Flow direction Direction perpendicular to flow Example 14 5.1 4.2 Comparative example 15 4.2 2.5

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] May 13, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0046

[Correction method] Change

[Correction content]

Reference Example 2 3 liters of N-methylpyrrolidone having a water content of 20 ppm was charged into a reactor equipped with a 5 liter stirrer, a thermometer and a reflux condenser equipped with a drying tube filled with calcium chloride at the tip. It is. 210.6 g (20 mol%) of trimellitic anhydride chloride, 203.0 g (20 mol%) of isophthalic acid dichloride, and 91.6 g (10 mol%) of adipic acid dichloride were added to a 5 liter stirrer, thermometer and tip. The reactor was equipped with a reflux condenser equipped with a drying tube filled with calcium chloride.
Then, 305.4 g (50 mol%) of m-toluylenediamine was added. First, polymerization was performed at room temperature to 40 ° C. for 15 hours. After that, the temperature was raised to 150 ° C., and the polymerization was continued for 7 hours while maintaining this temperature. After the completion of the polymerization, the polymer solution was diluted to 2 times with N-methylpyrrolidone.
-Dripping into methanol twice the volume of methylpyrrolidone with vigorous stirring. The precipitated polymer is filtered off with suction, redispersed in methanol, washed thoroughly, and separated after washing.
It was dried under reduced pressure at 0 ° C. to obtain a polyamideimide powder. Profit
The obtained polyamide-imide powder is heat-treated at 240 ° C. for 24 hours.
I understood Dimethylformamide solution (concentration 1.0 g / d
When the reduced viscosity of this product at 30 ° C. was measured in 1), it was 0.30 dl / g. ─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] July 4, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0025

[Correction method] Change

[Correction content]

The aromatic polyamideimide copolymer used in the present invention is preferably obtained by polymerizing a predetermined amount of the components of Chemical formulas 13 to 16 in a solvent, and the preferable polymerization temperature is 50.
℃ ~ 200 ℃, more suitable polymerization temperature 80 ℃ ~ 180 ℃
And the most preferable polymerization temperature is 80 ° C to 170 ° C. If it is lower than this range, the degree of polymerization does not increase, and if it is higher than this range, only those having poor melt moldability can be obtained. Further, during the polymerization reaction, the temperature may be changed in multiple stages, preferably 2-3.
A more preferred aromatic polyamide-imide copolymer can be produced by increasing the number of steps. That is, the polymerization temperature is set in the temperature range of 50 ° C. to 110 ° C. in the first stage and in the temperature range of 110 ° C. to 200 ° C. in the second and subsequent stages, and the polymerization is carried out in a multi-stage manner, whereby the amide group After completion of the formation of imide, an imide group is formed, and a tough polyamide imide having excellent melt moldability is produced. The temperature in each stage may be set to any value within the temperature range. For example, the temperature may be raised, the temperature may be constant, or a combination of the temperature rise and the constant temperature may be used. Most preferably, the latter stage is raised by 20 to 80 ° C. higher than the former stage,
This is a step temperature raising method in which the temperature in each stage is constant.
The polymerization time of the first step is usually 30 minutes to 5 hours, preferably 30 minutes to 3 hours, and the second step and thereafter is usually 30 minutes to 10 hours.
It is preferably 1 to 8 hours.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Koji Yamamoto 5-6-2 Higashi-Hachiman, Hiratsuka-shi, Kanagawa Sanryo Gas Chemical Co., Ltd. Plastics Center

Claims (3)

[Claims] (A) General formulas (1), (2) and (3)
A resin composition comprising 5 to 95 parts by weight of an aromatic polyamideimide copolymer having the structure of (1) as a repeating unit and 95 to 5 parts by weight of a thermoplastic resin (B) capable of forming an anisotropic melt phase. [Chemical 1] [In the general formula (1), Ar is at least one carbon 6
A trivalent aromatic group containing a member ring is shown. In addition, the general formula (2)
In, Ar ₁ represents a divalent aromatic group containing at least one 6-membered carbon ring. Further, in the general formula (3), R ₁ represents a divalent aliphatic group,
In (2) and (3), R represents a divalent aromatic group or an aliphatic group. ] 2. The (A) polyamide-imide copolymer comprises:
The copolymer having a structure in which (1) is 5 mol% or more and 95 mol% or less, (2) is 1 mol% or more and 95 mol% or less, and (3) is 0 mol% or more and 70 mol% or less. The resin composition described. 3. A group (B) in which the thermoplastic resin capable of forming an anisotropic melt phase comprises an aromatic polyester, an aromatic polyesterimide, an aromatic polyesteramide, or a polycarbonate capable of forming an anisotropic melt phase. The resin composition according to claim 1, which is at least one selected from the group consisting of: