JP3199085B2 - Resin composition - Google Patents

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, mechanical strength and melt moldability.

[0002]

2. Description of the Related Art Aromatic polyamide-imide resin is a plastic material having excellent heat resistance, mechanical strength, electrical properties, and chemical resistance. It has been conventionally used as a varnish, a film, and the like. Inferior, most of them were difficult to injection mold. That is, a method of producing an aromatic polyamideimide resin from an aromatic tricarboxylic anhydride and a diisocyanate in a solvent, and a method of producing an aromatic tricarboxylic anhydride from a diamine and a diamine in a solvent are representative. However, the polyamideimide resins produced by these methods are suitable for applications such as varnishes and cast films, but are inferior in melt moldability, but are unsuitable for melt molding.

[0003] Techniques for improving the melt moldability without impairing the heat resistance of the aromatic polyamide-imide resin include:
An aromatic polyamide-imide copolymer in which an aromatic dicarboxylic acid component such as isophthalic acid and the like are used together in an amount of 20 to 80 mol% with respect to a total of 100 mol% of the aromatic tricarboxylic acid component (US Patent) 4,313,8
No. 68). Although this copolymer has improved melt moldability compared to mere aromatic polyamide-imide, the flow start temperature at the time of melt molding is still a high temperature close to the decomposition temperature at the time of melting of the polyamide-imide copolymer. In reality, good molding cannot be performed. In addition, since this method uses an aromatic tricarboxylic acid chloride as a raw material, a halogen atom remains in the resin and is not suitable for electronic parts.

On the other hand, polyester resins have a high melting point,
It is characterized by having excellent melt fluidity, but has a low glass transition temperature and low heat resistance. Incidentally, the heat distortion temperature of polybutylene terephthalate, which is a typical aromatic polyester, is as low as 50 to 60 ° C. Further, when the polyester resin is reinforced with glass fibers, the heat deformation temperature increases, but from the viewpoint of maintaining the mechanical properties at a high temperature of 100 ° C. or higher, the heat resistance is not sufficient. That is, the elastic modulus at room temperature of the glass fiber reinforced material of polybutylene terephthalate is about 10 GPa, but drops to 3 GPa at 100 ° C. That is, the polyester resin and the crystalline aromatic polyester resin have high fluidity and excellent moldability, but have a drawback that heat resistance is essentially inferior.

[0005] Therefore, it is desired to create a technique for supplementing the low heat resistance of the polyester resin with the excellent heat resistance of the aromatic polyamide-imide resin and at the same time improving the fluidity of the aromatic polyamide-imide resin. Attempts have been made so far, and a technique for improving the moldability of an aromatic polyamide-imide resin by blending it with a polyester resin having excellent fluidity has also been disclosed in JP-A-59-875.
No. 5 has been proposed. However, according to these prior arts, although the processability of the aromatic polyamide-imide resin is somewhat improved, the processability and heat resistance are not sufficiently improved, and further, the compatibility of the two resins is insufficient. However, only a material having poor mechanical strength was obtained.

[0006]

The problem to be solved by the present invention is that a resin composition of an aromatic polyamide-imide resin and a polyester resin has an aromatic polyamide-imide because of a low heat resistance of the polyester resin. The excellent heat resistance of the resin is not exhibited, and as a result, only a resin composition having low heat resistance is obtained, and the mechanical strength is reduced due to the lack of compatibility between the two resins. An object of the present invention is to provide a novel resin composition having excellent heat resistance, mechanical strength, and moldability.

[0007]

Means for Solving the Problems The present inventors have made intensive studies to solve the above problems. As a result, they have found that the problems of the present invention can be solved by a novel resin composition comprising an aromatic polyamide-imide copolymer having a specific structure as a repeating unit and a polyester resin, and have led to the present invention.

That is, the present invention relates to (A) the general formula (1)
And a polyamide-imide copolymer having the structure of (2) and (3) as a repeating unit, and (B) a polyester resin.

Embedded image [In the general formula (1), Ar represents at least one carbon 6
It represents a trivalent aromatic group containing a membered ring. In addition, the general formula (2)
In the formula, Ar ₁ represents a divalent aromatic group containing at least one carbon 6-membered 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. ]

The aromatic polyamide-imide copolymer used in the resin composition of the present invention has the general formulas (1) and (2)
And having the structure of (3) as a repeating unit,
(1) is at least 5 mol% and at most 95 mol%, and (2) is at most 1 mol%, based on a total of 100 mol% of each of the structures (1), (2) and (3).
Mol% or more and 94 mol% or less, (3) is 1 mol% or more and 94 mol% or less.
It is a resin composition having a structure consisting of at most 10 mol%, preferably at least 10 mol% and at most 70 mol%,
(2) is 1 mol% or more and 89 mol% or less, (3) is 1 mol% or more and 89 mol% or less, more preferably (1) is 10 mol% or less and 89 mol% or less.
Mol% or more and less than 50 mol%, (2) is 1 mol% or more and 89
Mol% or less, (3) is 1 mol% to 60 mol%, most preferably (1) is 10 mol% to less than 30 mol%, (2) is 1 mol% to 89 mol%, (3) Is 1
It is a resin composition having a structure consisting of at least 60 mol% and not more than 60 mol%. When the composition ratio of the structures (1) to (3) is out of the above-mentioned range, heat resistance and mechanical strength are impaired. The structural unit (1) is a polyamideimide structural unit containing an aromatic tricarbonyl group, the structural unit (2) is a polyamide structural unit containing an aromatic dicarbonyl group, and the structural unit (3) is an aliphatic dicarbonyl group. Containing polyamide structural units.

Specific examples of Ar in the general formula (1) include those shown in the following chemical formula (3).

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Among these, preferred are those shown in the following chemical formula 4.

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R in the general formulas (1), (2) and (3) is a divalent aromatic and / or aliphatic group, and specific examples thereof include those represented by the following chemical formulas (5) and (6). Is raised.

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Among these, preferred are those represented by Chemical Formula 7,

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Particularly preferred is a compound represented by Chemical formula 8.

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The most preferable one is represented by the following formula (9).

Embedded image 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.

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Preferred of these are the following:

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Particularly preferred are the following.

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R ₁ in the general formula (3) is a divalent aliphatic group, and specific examples thereof include those represented by the following chemical formula (13). Among the chemical formulas 13, more preferable ones are those of m = 2 to 12, and particularly preferable ones are
m = 4-12.

Embedded image {(CH ₂ ) _m } (where m = 2 to 20)

The aromatic polyamide-imide copolymer used in the resin composition of the present invention comprises (a) an amide-based or non-amide-based copolymer of an aromatic tricarboxylic anhydride, an aromatic dicarboxylic acid or an aliphatic dicarboxylic acid and a diisocyanate. A method of preparing in a solvent, a method of (b) an aromatic tricarboxylic anhydride halide, an aromatic dicarboxylic acid dihalide and an aliphatic dicarboxylic acid dihalide and a diamine in the solvent, and a method of (c) aromatic tricarboxylic acid It can be produced from any of anhydrides, aromatic dicarboxylic acids, aliphatic dicarboxylic acids and diamines in the above-mentioned solvents using a catalyst such as phosphoric acid or a phosphite ester. Of these methods, (b) has the above-mentioned problem of residual halogen, and further requires post-treatment at a high temperature for forming an imide ring, and (c) also requires post-treatment at a high temperature. , (A) are the most preferred production methods. In the present invention, an aromatic polyamide-imide copolymer that provides a resin composition having high heat resistance, mechanical strength, and good moldability is substantially a amide-imide structure and a random copolymer in which an amide structure is randomly arranged. And a block copolymer in which the amide imide structure and the amide structure are continuously bonded at a constant chain length, and an alternating copolymer in which the amide imide structure and the amide structure are bonded alternately,
Any of these structures may be used.

The aromatic triimide anhydride, aromatic dicarboxylic acid and aliphatic dicarboxylic acid used for producing the aromatic polyamideimide copolymer suitable for the resin composition of the present invention by the most preferred method (a). Acids and diisocyanates are the following chemical formulas 14, 15 and 16, respectively.
This is the compound represented by 7.

[0021]

Embedded image (In the formula, Ar has the same meaning as Ar in general formula (1).)

Embedded image (In the formula, Ar ₁ has the same meaning as Ar _{1 in} general formula (2).)

Embedded image (In the formula, R ₁ has the same meaning as R _{1 in} general formula (2).)

Embedded image O = C = N−R−N = C = 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 polyamideimide copolymer having 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 method of (1), when the number of moles of diisocyanate is P and the total number of moles of aromatic tricarboxylic anhydride, aromatic dicarboxylic acid and aliphatic dicarboxylic acid is Q, the molar ratio of both is 0.9 <Q / P <
1.1, preferably 0.99 <Q / P <
More preferably, it is maintained 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 formulas 13 to 16 in a solvent.
0 ° C to 200 ° C, more preferred polymerization temperature is 80 ° C to 18 ° C.
0 ° C. The most preferred polymerization temperature is between 80C and 170C. If it is lower than this range, the degree of polymerization does not increase, and if it is higher, only those having poor melt moldability can be obtained. Furthermore, during the polymerization reaction, the temperature is increased in multiple stages, preferably 2-3.
By raising the temperature in the step, a more preferable aromatic polyamideimide copolymer can be produced. That is, the polymerization temperature is set in multiple stages within the temperature range of 50 ° C. to 110 ° C. for the first stage and in the temperature range of 110 ° C. to 200 ° C. for the second and subsequent stages, whereby the amide group is substantially reduced An imide group is generated after the formation of the polyamideimide is completed, and a polyamideimide having excellent melt moldability and toughness is produced. The temperature in each stage may be set as long as it is within the temperature range. For example, the temperature may be raised, the temperature may be constant, or a combination of the temperature raising and the constant temperature may be used. Most preferably, the latter stage is higher by 20 to 80 ° C. than the former stage,
This is a method in which the temperature in each stage is made constant.

As the solvent used in the production of the aromatic polyamideimide copolymer suitably used in the resin composition of the present invention, a solvent having solubility in the produced polyamideimide, specifically, N-methylpyrrolidone , Dimethylformamide, dimethylacetamide, dimethylsulfoxide, dimethylsulfolane, tetramethylenesulfone,
Diphenyl sulfone, γ-butyrolactone and the like are used, and a polar solvent having no solubility with polyamideimide, specifically, nitrobenzene, nitrotoluene, acetonitrile, benzonitrile, acetophenone, nitromethane, dichlorobenzene, anisole and the like are also used. . A mixture of a solvent having solubility in polyamideimide and a polar solvent having no solubility may be used. Among the above, preferred solvents are those having solubility in polyamideimide. 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 / l.

For the production of the aromatic polyamideimide copolymer suitably used in the resin composition of the present invention, various catalysts described in the prior art can be used, but the melt molding processability is impaired. In order not to use it, its usage should be limited to a necessary minimum and may not be used.
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, and cobalt acetate and naphthene Metal salts, heavy metal salts, alkali metal salts and the like of weak acids such as cobalt acid and sodium oleate.

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 and the like is 500
It is preferable to keep the temperature below PPM, more preferably 1
00 PPM, most preferably kept below 50 PPM. If the amount of water contained in the system is larger than these, the melt formability is impaired.

The use of a small amount of the molecular weight modifier is not limited at all. Typical molecular weight regulators include monocarboxylic acids such as benzoic acid, phthalic anhydride, succinic anhydride, and naphthalenedicarboxylic anhydride. Monofunctional compounds such as dicarboxylic acid anhydrides, monoisocyanates such as phenyl isocyanate, and monohydric phenols.

Further, the degree of polymerization of the aromatic polyamideimide copolymer suitable for the resin composition of the present invention is 0.1 dl /, expressed as a 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, and most preferably 0.2 dl / g to 0.7 dl / g. .

The aromatic polyamideimide copolymer preferably used in the present invention includes 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. The polymer is recovered by precipitation and washing, but may be obtained by directly concentrating the polymerization solvent. Furthermore, a method of concentrating to a certain extent, removing the solvent under reduced pressure with an extruder or the like, and pelletizing is also preferable.

The polyester resin used in the resin composition of the present invention is a polyester resin having an ester bond in the main chain of the molecule.
A thermoplastic resin, specifically, a polycondensate obtained from a dicarboxylic acid or a derivative thereof and a dihydric alcohol or a divalent phenol compound; obtained from a dicarboxylic acid or a derivative thereof and a cyclic ether compound Polymers; polycondensates obtained from metal salts of dicarboxylic acids and dihalogen compounds; ring-opening polymers of cyclic ester compounds, and the like. The dicarboxylic acid derivative referred to here is
Acid anhydrides, esters, acid halides and the like. The dicarboxylic acids may be aliphatic or aromatic. Examples of the aromatic dicarboxylic acid include, for example, terephthalic acid, isophthalic acid, phthalic acid, chlorophthalic acid, nitrophthalic acid, p-carboxyphenylacetic acid, p-phenylenediacetic acid, m-phenylenediglycolic acid, and p-phenylenediglycolic acid , Diphenyldiacetate, diphenyl-p,
p'-dicarboxylic acid, diphenyl ether-p, p'-
Dicarboxylic acid, diphenyl-m, m'-dicarboxylic acid,
Diphenyl-4,4'-diacetic acid, diphenylmethane-
p, p'-dicarboxylic acid, diphenylethane-p, p '
Dicarboxylic acid-stilbene dicarboxylic acid, diphenylbutane-p, p-dicarboxylic acid, benzophenone-4,
4'-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-
2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, p-carboxyphenoxyacetic acid, p-carboxyphenoxybutyric acid, 1,2-diphenoxypropane-
p, p-dicarboxylic acid, 1,3-diphenoxypropane-p, p'-dicarboxylic acid, 1,4-diphenoxybutane-p, p'-dicarboxylic acid, 1,5-diphenoxypentane-p, p '-Dicarboxylic acid, 1,6-diphenoxyhexane-p, p'-dicarboxylic acid, p- (p-carboxyphenoxy) benzoic acid, 1,2-bis (2-methoxyphenoxy) -ethane-p, p' -Dicarboxylic acids,
1,3-bis (2-methoxyphenoxy) -propane-
p, p'-dicarboxylic acid and the like can be mentioned. Further, as the aliphatic dicarboxylic acid, for example, oxalic acid, succinic acid, adipic acid, coric acid, mazeleiic acid, sebacic acid, dodecanedicarboxylic acid, undecanedicarboxylic acid,
Maleic acid, fumaric acid and the like can be mentioned. Examples of preferred dicarboxylic acids are aromatic dicarboxylic acids, more preferably terephthalic acid, isophthalic acid, naphthalene-
2,6-dicarboxylic acid can be mentioned.

Examples of the dihydric alcohol include ethylene glycol, propane-1,2-diol, and propane-1,3.
-Diol, butane-1,3-diol, butane-1,
4-diol, 2,2-dimethylpropane-1,3-diol, cis-2-butene-1,4-diol, tr
and ans-2-butene-1,4-diol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, heptamethylene glycol, octamethylene glycol, decamethylene glycol and the like. Examples of preferred dihydric alcohols are ethylene glycol, propane-1,2-diol, propane-1,
3-diol, butane-1,3-diol, butane-
1,4-diol can be mentioned, and more preferably, ethylene glycol and butane-1,4-diol can be mentioned. As the dihydric phenol compound,
Hydroquinone, resorcinol, 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, -Hydroxyphenyl 3-hydroxyphenyl ketone and the like. Examples of the cyclic ether compound include ethylene oxide and propylene oxide. Examples of the cyclic ester compound include ε-caprolactone and δ-
Valerolaclon can be mentioned. The dihalogen compound to be reacted with the metal dicarboxylate refers to a compound obtained by replacing the hydroxyl group of the dihydric alcohol or the dihydric phenol compound with a halogen atom such as chlorine or bromine. The polyester used in the resin composition of the present invention is produced by a known method using the above raw materials, for example, a transesterification method, a direct dehydration condensation, a dehalogenated metal by interfacial polycondensation, or the like.

In order to suitably maintain the balance between the melt moldability and the heat resistance of the resin composition of the present invention, preferred polyester resins are aromatic dicarboxylic acids and derivatives thereof and crystalline aromatic compounds prepared from dihydric alcohols. Polyesters derived from terephthalic acid such as polyethylene terephthalate and polybutylene terephthalate or derivatives thereof; naphthalene dicarboxylic acids such as polyethylene naphthalate and polybutylene naphthalate;
Particularly, polyesters using naphthalene-2,6-dicarboxylic acid or a derivative thereof as a raw material can be exemplified. More preferred are terephthalic acids such as polyethylene terephthalate and polybutylene terephthalate, or polyesters derived from derivatives thereof and dihydric alcohols, and the most preferred are polyethylene terephthalate and polybutylene terephthalate.

Next, the component (A) of the resin composition of the present invention,
(B) is 5 to 95% by weight, preferably 10 to 70% by weight, more preferably 10 to 65% by weight of the aromatic polyamideimide copolymer of the component (A) based on 100% by weight of the total.
%, Most preferably 10 to 50% by weight. When the amount of the component (A) is more than the above range, the fluidity at the time of melting decreases, and when the amount is less, the heat resistance decreases.

The resin composition of the present invention is produced by melt-kneading each component. The melt-kneading temperature is 200 to 400 ° C.
Preferably at 230 to 380 ° C., the kneading method can be performed by an extruder, a kneader, a Banbury mixer, a roll or the like. A preferred method is a method using a twin screw extruder.

The resin composition of the present invention may contain, if desired,
Fillers, pigments, lubricants, plasticizers, stabilizers, UV absorbers,
Other components such as a flame retardant, various additives of a flame retardant auxiliary, other resins, and elastomers can be appropriately compounded. Examples of fillers include mineral fillers represented by glass beads, wollastonite, mica, talc, clay, asbestos, charcoal, magnesium hydroxide, silica, diatomaceous earth, graphite, carborundum, molybdenum disulfide;
Glass fiber, milled fiber, potassium titanate fiber, boron fiber, cesium carbide fiber, inorganic fiber such as metal fiber such as brass, aluminum and zinc; organic fiber represented by carbon fiber and aramid fiber; flakes of aluminum and zinc I can give it. The filler is preferably used in an amount of 1 to 70% by weight of the whole composition. Preferred fillers are milled fibers and glass fibers, and those obtained by treating them with an epoxy-based, amino-based, or other silane coupling agent are also suitably used.

Examples of the pigment include titanium oxide, zinc sulfide, zinc oxide and the like. Lubricants include mineral oil, silicone oil, ethylene wax, polypropylene wax,
Metal salts such as sodium and lithium stearates, metal salts such as sodium, lithium and zinc montanates,
Representative examples include montanic acid amides and esters.

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

Examples of other resins mentioned above include epoxy resins and phenoxy resins produced from epichlorohydrin and dihydric phenols such as 2,2-bis (4-hydroxyphenyl) propane; nylon-6, nylon-10 ,
Nylon-12, Nylon-6,6, Nylon-MX
Aliphatic, aromatic crystalline polyamides such as D, 6, nylon-4,6, nylon-6, T, nylon-6, I; aliphatic, aromatic amorphous polyamides; hydroquinone, resorcinol, 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 dihydric phenol such as hydroxyphenyl 3-hydroxyphenyl ketone and phosgene or diphenyl carbonate or dimethyl carbonate as monomers; dihydric phenol and phosgene or diphenyl carbonate, dimethyl carbonate and the above-mentioned dicarboxylic acids and derivatives thereof Polyester carbonates produced by using as a monomer: polyphenylene ether obtained by oxidative coupling polymerization of 2,6-dimethylphenol; polysulfone, polyethersulfone, polyetherimide;
Examples thereof include aromatic resins such as polythioetherketone, polyetherketone, and polyetheretherketone. Preferred among these are polycarbonates, particularly polycarbonates using 2,2-bis (4-hydroxyphenyl) propane as the dihydric phenol.

Examples of the elastomer include a high melting point hard segment mainly composed of an alkylene terephthalate unit composed of the above-mentioned dihydric alcohol and terephthalic acid, and a poly (ethylene oxide) glycol, poly (propylene oxide) glycol or the like. Polyester elastomers represented by ether glycol or a block copolymer of a soft segment composed of an aliphatic polyester produced from an aliphatic dicarboxylic acid and a dihydric alcohol (for example, Perprene manufactured by Toyobo Co., Ltd., manufactured by DuPont) Hytrel); polyamide elastomers represented by block copolymers of hard segments such as nylon 11 and nylon 12 and polyether or soft segment of polyester (for example, EMS Various types of polyethylene such as low-density, high-density, ultra-high-molecular-weight, linear low-density; polypropylene; ethylene;
EP elastomer which is a copolymer of propylene; EPDM elastomer which is a non-conjugated copolymer such as ethylene, propylene and norbornenes, cyclopentadiene, and 1,4-hexadiene; α-elastomer such as ethylene, propylene and butene-1 Copolymer elastomer of olefin and glycidyl acrylate, α, β-unsaturated acid glycidyl ester such as glycidyl methacrylate; ethylene, propylene, butene-1 and other α-olefin and vinyl acetate, vinyl propionate, methyl acrylate, Copolymer elastomers with unsaturated esters such as methyl methacrylate; above-mentioned polyethylene, polypropylene, EP, E
PDM, α, β-unsaturated dicarboxylic anhydride typified by maleic anhydride of α-olefin copolymer elastomer, or α, β- such as glycidyl methacrylate
A graft modified form of a glycidyl ester of an unsaturated acid; A-B-A 'comprising A component of a vinyl aromatic compound such as styrene and B of a diene component such as butadiene and isoprene;
AB type elastomeric block copolymer; ABA ′ in which the B component is hydrogenated, AB type elastomeric block copolymer, and α represented by maleic anhydride,
ABA ', AB type elastomeric block copolymer graft-modified with a glycidyl ester of an α, β-unsaturated acid such as β-unsaturated dicarboxylic anhydride or glycidyl methacrylate, and likewise ABA ′, AB graft-modified, hydrogenated B component
Type elastomeric block copolymer; polysulfide rubber, silicone rubber and the like.

The resin composition of the present invention comprising an aromatic polyamide-imide copolymer and a polyester resin has improved the heat resistance and mechanical strength of the conventional resin composition comprising an aromatic polyamide-imide resin and a polyester resin. It is considered that this excellent property is mainly because the novel resin composition of the specific aromatic polyamideimide copolymer of the present invention and the polyester resin has improved the compatibility of both resins, which is inferior to the resin composition of the prior art, Moreover, it is unique that the aromatic polyamide-imide copolymer of the present invention has heat resistance higher than that of the conventional resin composition, although the imide structure is smaller than that of the conventional aromatic polyamide-imide resin. This is a phenomenon that is both predictable and unpredictable.

Hereinafter, the resin composition of the present invention will be described in more detail with reference to Reference Examples, Examples and Comparative Examples. Also,
Table 1 shows the aromatic polyamide-imide copolymers produced in Reference Examples, and Tables 2, 3, and 4 show the results of Examples and Comparative Examples.

REFERENCE EXAMPLE 1 3 liters of N-methylpyrrolidone having a water content of 15 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. Here, trimellitic anhydride 222.
1 g (20 mol% based on the total number of moles of all monomer components), isophthalic acid 240.1 g (25 mol%),
42.2 g of adipic acid (5 mol% of the same), followed by 2,4
Toluylene diisocyanate (503.3 g, 50 mol%) was added. Trimellitic anhydride and isophthalic acid,
The water content in the system when adding adipic acid was 30 ppm. First, the temperature of the contents was set to 100 ° C. over 20 minutes from room temperature, and polymerization was carried out at this temperature for 4 hours. Thereafter, the temperature was raised to 115 ° C. in 15 minutes, and polymerization was continued for 4 minutes while maintaining the temperature.
The polymerization was continued at 160 ° C. for 2 hours. After the completion of the polymerization, the polymer solution was dropped into methanol twice the volume of N-methylpyrrolidone with vigorous stirring. The precipitated polymer was filtered off with suction, further redispersed in methanol, washed well and separated, and dried under reduced pressure at 200 ° C. for 10 hours to obtain a polyamideimide powder. The reduced viscosity at 30 ° C. of the dimethylformamide solution (concentration: 1.0 g / dl) was 0.43 dl / g. The glass transition point 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 L of N-methylpyrrolidone having a water content of 20 ppm was charged into a reactor equipped with a 5 L stirrer, a thermometer and a reflux condenser equipped with a drying tube filled with calcium chloride at the tip. It is. Here, 210.6 g of trimellitic anhydride chloride (20 mol% based on the total number of moles of all monomer components) and 253.isophthalic dichloride.
8 g (25 mol%), adipic acid dichloride
8 g (5 mol% of the same) in a 5 liter stirrer, thermometer and
And a reflux condenser equipped with a drying tube filled with calcium chloride at the tip. Then, 305.4 g (50 mol% of the same) of m-toluylenediamine was added. First, polymerization was performed at room temperature to 40 ° C. for 15 hours. Thereafter, the temperature was raised to 150 ° C., and polymerization was continued for 7 minutes at this temperature.
After the completion of the polymerization, which was continued for a period of time, the polymer solution was diluted twice by adding N-methylpyrrolidone, and added dropwise to methanol twice as much as N-methylpyrrolidone with vigorous stirring. The precipitated polymer was filtered off with suction, further redispersed in methanol, washed well, separated and dried at 200 ° C. under reduced pressure to obtain a polyamideimide powder. Polya obtained
The midimide powder was heat treated at 250 ° C. for 24 hours. The reduced viscosity at 30 ° C. of a dimethylformamide solution (concentration: 1.0 g / dl) was measured to be 0.28.
dl / g.

Reference Example 3 3 liters of N-methylpyrrolidone having a water content of 15 ppm was charged into the same reactor as in Reference Example 1. Here, 222.1 g of trimellitic anhydride (20 mol% based on the total number of moles of all monomer components) and 192.1 g of isophthalic acid were used.
g (20% by mole), 84.4 g of adipic acid (10% by mole)
Mol%), followed by 2,4-tolylene diisocyanate
503.3 g (50 mol% of the same) were added. Thereafter, polymerization and treatment were performed in the same manner as in Reference Example 1 to obtain a polyamideimide powder. Dimethylformamide solution (concentration 1.0g
/ Dl) was 30.degree. C., and the reduced viscosity was 0.40 dl / g.

Reference Example 4 3 liters of N-methylpyrrolidone having a water content of 15 ppm was charged into the same reactor as in Example 1. Here, 222.1 g of trimellitic anhydride (20 mol% based on the total number of moles of all monomer components) and 96.0 g of isophthalic acid
(10 mol%), 168.9 g of adipic acid (20
Mol%), followed by 2,4-tolylene diisocyanate
503.3 g (50 mol% of the same) were added. Thereafter, polymerization and treatment were performed in the same manner as in Reference Example 1 to obtain a polyamideimide powder. Dimethylformamide solution (concentration 1.0g
/ Dl), the measured reduced viscosity at 30 ° C. was 0.36 d / g.

Reference Example 5 3 liters of N-methylpyrrolidone having a water content of 15 ppm was charged into the same reactor as in Example 1. Here, 138.8 g of trimellitic anhydride (12.5 mol% based on the total number of moles of all monomer components) and 28 of isophthalic acid
8.1 g (30 mol%), adipic acid 63.3 g
(7.5 mol%) and 503.3 g of 2,4-toluylene diisocyanate (50 mol%) were added.
Thereafter, polymerization and treatment were performed in the same manner as in Reference Example 1 to obtain a polyamideimide powder. The reduced viscosity of the dimethylformamide solution (at a concentration of 1.0 g / dl) at 30 ° C. was 0.39 dl / g.

Reference Example 6 3 liters of N-methylpyrrolidone having a water content of 15 ppm was charged into the same reactor as in Example 1. Here, 55.3 g of trimellitic anhydride (5 mol% based on the total number of moles of all monomer components), 336.1 g of isophthalic acid
(35 mol%), adipic acid 84.4 g (10 mol%), and then 2,4-tolylene diisocyanate 5
03.3 g (50 mol% of the same) were added. Thereafter, polymerization and treatment were performed in the same manner as in Reference Example 1 to obtain a polyamideimide powder. Dimethylformamide solution (concentration 1.0 g /
It was 0.36 dl / g as measured by dl) at 30 ° C.

Reference Example 7 3 L of N-methylpyrrolidone having a water content of 15 ppm was charged into the same reactor as in Example 1. Here, 333.1 g of trimellitic anhydride (30 mol% based on the total number of moles of all monomer components), 144.0 g of isophthalic acid
g (15 mol%), adipic acid 42.2 g (5 mol%), and then 2,4-tolylene diisocyanate 5
03.3 g (50 mol% of the same) were added. Thereafter, polymerization and treatment were performed in the same manner as in Reference Example 1 to obtain a polyamideimide powder. Dimethylformamide solution (concentration 1.0 g /
It was 0.35 dl / g when the reduced viscosity at 30 ° C. was measured by dl).

Reference Example 8 3 liters of N-methylpyrrolidone having a water content of 15 ppm was charged into the same reactor as in Example 1. Here, 444.2 g of trimellitic anhydride (40 mol% based on the total number of moles of all monomer components) and 48.0 g of isophthalic acid
(5 mol%), 42.2 g of adipic acid (5 mol%), and then 2,4-tolylene diisocyanate 50
3.3 g (50 mol% of the same) were added. Then, Reference Example 1
Polymerization and treatment were carried out in the same manner as in the above to obtain a polyamideimide powder. Dimethylformamide solution (concentration 1.0 g / d
The reduced viscosity of this product at 30 ° C. was measured in 1) and found to be 0.35 dl / g.

Reference Example 9 3 liters of N-methylpyrrolidone having a water content of 15 ppm was charged into the same reactor as in Reference Example 1. To this was added 555.3 g of trimellitic anhydride (50 mol% based on the total number of moles of all monomer components), and then 503.3 g of 2,4-tolylene diisocyanate (50 mol%). 25 ppm of water in the system when trimellitic anhydride is added
Met. First, the temperature of the contents was set to 90 ° C. over 20 minutes from room temperature, and polymerization was performed at this temperature for 70 minutes. Thereafter, the temperature was raised to 115 ° C. in 15 minutes, and the polymerization was continued for 4 hours while maintaining the temperature. After polymerization is completed, the polymer solution is
-Methylpyrrolidone was added dropwise under vigorous stirring to twice the volume of methanol. The precipitated polymer was filtered off with suction, re-dispersed in methanol, washed well and separated.
Vacuum drying was performed at 0 ° C. for 15 hours to obtain a polyamideimide powder. Dimethylformamide solution (concentration 1.0 g / d
The reduced viscosity of this product at 30 ° C. was measured in 1) and found to be 0.30 dl / g.

Reference Example 10 3 liters of N-methylpyrrolidone having a water content of 15 ppm was charged into the same reactor as in Reference Example 1. To this were added 480.1 g of isophthalic acid (50 mol% based on the total number of moles of all monomer components), and then 503.3 g (50 mol% of 2,4-tolylene diisocyanate). The water content in the system when adding isophthalic acid was 50 ppm. Thereafter, polymerization and treatment were carried out in the same manner as in Reference Example to obtain a polyamide powder. Dimethylformamide solution (concentration 1.0 g /
It was 0.30 dl / g when the reduced viscosity at 30 ° C. was measured by dl).

REFERENCE EXAMPLE 11 3 L of N-methylpyrrolidone having a water content of 15 ppm was charged into the same reactor as in Reference Example 1. To this were added 422.3 g of adipic acid (50 mol% based on the total number of moles of all monomer components), and then 503.3 g of 2,4-tolylene diisocyanate (50 mol%). The water content in the system when adding adipic acid was 50 ppm. Thereafter, polymerization and treatment were performed in the same manner as in Reference Example 1 to obtain a polyamide powder. Dimethylformamide solution (concentration 1.0 g /
It was 0.35 dl / g when the reduced viscosity at 30 ° C. was measured by dl).

[0053]

【Example】

Example 1 Aromatic polyamideimide copolymer 5 produced in Reference Example 1
0% by weight and 50% by weight of polybutylene terephthalate (hereinafter referred to as PBT, N1100C manufactured by Mitsubishi Rayon Co., Ltd.)
Was melt-kneaded at 280 ° C. using a twin-screw extruder to form pellets. From the obtained pellets, a test piece having a thickness of 1/8 inch was injection molded. For the purpose of heat resistance evaluation, the heat deformation temperature of 18.6 kg / cm ² stress was measured from this test piece, and the bending strength was measured for mechanical strength. Furthermore, melt moldability is 2
The melt flow value at 70 ° C. under a stress of 30 kg / cm ² was measured by a Koka flow tester. The results are shown in Table 2.

Examples 2 to 8 Example 1 was repeated, except that the aromatic polyamideimide copolymers of Reference Examples 2 to 8 were used. The results are shown in Table 2.

Comparative Examples 1 to 3 Example 1 was repeated with the aromatic polyamide-imide copolymer or aromatic polyamide of Reference Examples 9 to 11.
The results are shown in Table 2.

Example 9 Aromatic polyamideimide copolymer 4 produced in Reference Example 3
0% by weight and 50% by weight of polybutylene terephthalate (hereinafter referred to as PBT, N1100C manufactured by Mitsubishi Rayon Co., Ltd.)
And bisphenol A type polycarbonate (hereinafter referred to as P
Abbreviated as C, Iupilon E200 manufactured by Mitsubishi Gas Chemical Co., Ltd.
0) 10 wt% was melt-kneaded at 280 ° C. using a twin-screw extruder and pelletized. From the obtained pellets, a test piece having a thickness of 1/8 inch was injection molded. For the purpose of heat resistance evaluation, the heat deformation temperature of 18.6 kg / cm ² stress was measured from this test piece, and the bending strength was measured for mechanical strength. further,
The melt moldability was measured at 270 ° C. and a melt flow value under a stress of 60 kg / cm ² using a Koka flow tester. The results are shown in Table 3.

Comparative Example 9 Example 9 was repeated, except that the aromatic polyamideimide copolymer of Reference Example 9 was used. The results are shown in Table 3.

Example 10 Aromatic polyamide-imide copolymer 2 prepared in Reference Example 3
0% by weight, 30% by weight of polyethylene terephthalate (hereinafter abbreviated as PET, RT543 manufactured by Nihon Unipet Co., Ltd.) and 10% by weight of PC, and further glass fiber (hereinafter abbreviated as glass fiber or GF, Asahi Fiber Glass Co., Ltd.)
40 wt% of chopped strand (03JAFT540) was melt-kneaded at 280 ° C. using a twin-screw extruder to form pellets. From the obtained pellets, test pieces were injection-molded in the same manner as in Example 9, the heat deformation temperature and the bending strength were measured, and the melt flow value was measured. The results are shown in Table 3.

Comparative Example 10 Example 10 was repeated, except that the aromatic polyamideimide copolymer of Reference Example 9 was used. The results are shown in Table 3.

Example 11 Aromatic polyamide-imide copolymer 3 prepared in Reference Example 3
0% by weight, 30% by weight of PBT and 40% by weight of glass fiber were melt-kneaded at 280 ° C. using a twin-screw extruder to form pellets. From the obtained pellets, test pieces were injection-molded in the same manner as in Example 9, the heat deformation temperature and the bending strength were measured, and the melt flow value was measured. The results are shown in Table 3.

Comparative Example 11 Example 11 was repeated, except that the aromatic polyamideimide copolymer of Reference Example 9 was used. The results are shown in Table 3.

Example 12 Example 11 was repeated, except that PBT was replaced with PET. The results are shown in Table 3.

Examples 13 and 14 Example 12 was repeated, except that the aromatic polyamideimide copolymers of Reference Examples 4 and 5 were used. The results are shown in Table 3.

Comparative Example 12 Example 12 was repeated, except that the aromatic polyamideimide copolymer of Reference Example 9 was used. The results are shown in Table 3.

[0065]

The resin composition of the present invention has improved heat resistance and mechanical strength of the conventional resin composition comprising an aromatic polyamideimide resin and a polyester resin. The resin composition of the present invention is suitably used for molding materials that require high heat resistance, high mechanical strength, and excellent melt moldability.

[0066]

Table 1 Acid component composition Diisocyanate Reference example TMA / IPA / ADA TDI Glass transition point (mol%) (mol%) (° C) 120/25/550 280 2 (20/25/5) (50) ) 280 (acid chromato) (m-TDA) 3 20/20/10 50 250 4 20/10/20 50 230 5 12.5 / 30 / 7.5 50 280 65/35/10 50 280 7 30/15 / 550 295 840/5/550 50 305 950/0/050 326 100/50/050 50 260 110/0/5050155 TMA; trimellitic anhydride IPA; isophthalic acid ADA; adipic acid TDI 2,4-tolylenediisocyanate m-TDA; metatoluylenediamine acid chloride; trimellitic anhydride chloride / isophthalic acid Le acid dichloride / adipic acid dichloride

[0067]

Table 2 Example 2 Amidoimide polyester Thermal deformation Bending Melting Comparative example Type Type Temperature strength Flow value (% by weight) (% by weight) (° C) (MPa) (cc / sec) Example 1 Reference example 1 PBT 200 93 0.08 50 50 Example 2 Reference Example 2 PBT 197 100 0.09 50 50 Example 3 Reference Example 3 PBT 203 98 0.07 50 50 Example 4 Reference Example 4 PBT 200 90 0.08 50 50 Example 5 Reference Example 5 PBT 204 98 0.10 50 50 Example 6 Reference Example 6 PBT 190 85 0.08 50 50 Example 7 Reference Example 7 PBT 184 82 0.09 50 50 Example 8 Reference Example 8 PBT 180 73 0. 09 50 50 Comparative Example 1 Reference Example 9 PBT 180 48 0.13 50 50 Comparative Example 2 Reference Example 10 PBT 192 43 0.11 50 50 Comparative Example 3 Reference Example 11 PBT 159 38 0.09 50 50

[0068]

[Table 3]

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-59-135253 (JP, A) JP-A-59-8755 (JP, A) JP-A-3-166260 (JP, A) JP-A-62 39629 (JP, A) JP-A-6-145282 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 73/00-73/26 C08L 79/00-79/08 C08L 67/00-67/08

Claims (3)

(57) [Claims] 1. A resin composition comprising (A) a polyamideimide copolymer having the general formula (1), (2) and (3) as repeating units, and (B) a polyester resin. Embedded image [In the general formula (1), Ar represents at least one carbon 6
It represents a trivalent aromatic group containing a membered ring. In addition, the general formula (2)
In the formula, Ar ₁ represents a divalent aromatic group containing at least one carbon 6-membered 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 structure of the polyamide-imide copolymer (A) is such that (1) is 5 mol% or more and 95 mol% or less, and (2) is 1 mol% or less.
Mol% or more and 94 mol% or less, (3) is 1 mol% or more and 94 mol% or less.
The resin composition according to claim 1, which is at most mol%. 3. The method according to claim 1, wherein (A) is the total amount of (A) and (B).
The resin composition according to claim 1, wherein the proportion of the polyamideimide copolymer is 5 to 95% by weight.