JPH06306281A - Resin composition - Google Patents

Abstract

PURPOSE:To provide a resin composition comprising a polyamideimide copolymer having specific repeating units and a polyphenylene sulfide resin, excellent in heat resistance, mechanical strength and moldability, and suitable for the uses of molding materials for melt-molding. CONSTITUTION:The objective resin composition excellent in heat resistance, mechanical strength and moldability and suitable for the uses of molding materials comprises (A) a polyamideimide having copolymer structures of formula I (Ar is trivalent aromatic group containing at least a carbon six-membered ring; R is divalent aromatic group or aliphatic group) and formula II (Ar1 is divalent aromatic group containing at least a carbon six-membered ring) as repeating units and prepared by dissolving trimellitic acid anhydride, isophthalic acid, and 2,4-tolylene diisocyanate in N-methylpyrrolidone and subsequently polymerizing the compounds at 160 deg.C for 4hrs, and (B) a polyphenylene sulfide resin.

Description

Detailed Description of the Invention

[0001]

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 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 were difficult to injection mold. That is, the aromatic polyamide-imide resin is produced by a method of producing an aromatic tricarboxylic acid anhydride and diisocyanate in a solvent (Japanese Patent Publication No.
No. 74), a representative method is a method of producing from an aromatic tricarboxylic acid anhydride halide and a diamine in a solvent. Compared to the latter method, the former method makes it possible to obtain a polyamideimide having high heat resistance and toughness without post-treatment at high temperature for a long time, and halogen residues remain in the polyamideimide. Therefore, it is a suitable method for recent electronic and electrical applications. However, the polyamide-imide resin produced by these methods is suitable for applications such as varnishes and cast films, but is inferior in melt moldability and therefore unsuitable for melt molding.

A technique for improving melt moldability without impairing the heat resistance of the aromatic polyamide-imide resin is as follows:
An aromatic polyamideimide copolymer has already been proposed in which an aromatic dicarboxylic acid component such as isophthalic acid is used in combination with 20 to 80 mol% based on a total of 100 mol% of both the aromatic tricarboxylic acid component (US Patent 4,313,8
68). Although this copolymer has improved melt moldability as compared with mere aromatic polyamideimide, the flow start temperature during melt molding is still high at a temperature close to the decomposition temperature of the polyamideimide copolymer during melting. However, the actual situation is that good molding cannot be performed. Further, since the aromatic polyamideimide used in the same patent uses aromatic tricarboxylic acid chloride as a raw material, halogen atoms remain in the resin, which is an unsuitable method for electronic parts.

On the other hand, the polyphenylene sulfide resin is excellent in heat resistance, electrical characteristics and solvent resistance, and particularly excellent in melt fluidity. In particular, the crystalline polyphenylene sulfide resin has a high melting point and a high heat resistance derived therefrom. It is characterized by having excellent melt moldability, but it has a low glass transition temperature of about 100 ° C. and does not exhibit high heat resistance unless it is reinforced with a filler such as glass fiber. Further, when the polyphenylene sulfide resin is reinforced with glass fiber, the heat distortion temperature rises, but from the viewpoint of maintaining the mechanical properties at a high temperature of 150 ° C. or higher, the heat resistance is not sufficient. The glass fiber-reinforced elastic modulus of polyphenylene sulfide at room temperature is about 10 GPa or more,
At ℃, it will decrease to about 2 GPa. That is,
The polyphenylene sulfide resin has high flowability, that is, excellent melt moldability, but has a drawback that it is essentially inferior in heat resistance. As an attempt to solve this problem, a technique for improving heat resistance and melt moldability by blending an aromatic polyamideimide resin and a polyphenylene sulfide resin has been disclosed in Japanese Examined Patent Publication No. 9754/1982.
-9755, etc. However, according to these prior arts, although the molding processability of the aromatic polyamide-imide resin is improved to some extent, it is insufficient, and the mechanical strength is at a level requiring improvement.

[0005]

The problem to be solved by the present invention is that even if a polyphenylene sulfide resin is added in order to improve the inferior melt moldability of the aromatic polyamideimide resin, a sufficient improvement effect is obtained. Therefore, it is not possible to create a new material having high heat resistance, excellent melt moldability, and high mechanical strength. An object of the present invention is to provide a novel resin composition having excellent heat resistance, mechanical strength and moldability.

[0006]

[Means for Solving the Problems] The present inventors have conducted extensive studies to solve the above problems. As a result, having a specific structure as a repeating unit, an aromatic polyamideimide copolymer, and a novel resin composition comprising a polyphenylene sulfide resin, melt moldability is improved without impairing the heat resistance of the resin composition, Furthermore, they have found that high mechanical strength is achieved, and have reached the present invention.

That is, the present invention provides (A) general formula (1)
And a resin composition comprising a polyamide-imide copolymer having the structure (2) as a repeating unit and (B) a polyphenylene sulfide resin.

[Chemical 2] [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. Furthermore, general formulas (1) and (2)
In, R represents a divalent aromatic group or an aliphatic group. ]
The structural unit (1) is a polyamideimide structural unit containing an aromatic tricarbonyl group, and the structural unit (2) is a polyamide structural unit containing an aromatic dicarbonyl group.

The aromatic polyamide-imide copolymer used in the resin composition of the present invention has the structures of the general formulas (1) and (2) as repeating units, (1),
(2) It is composed of a structure in which (1) is 5 mol% or more and 95 mol% or less and (2) is 1 mol% or more and 95 mol% or less with respect to 100 mol% in total of each structure, and preferably (1) Is 1
0 mol% or more and 70 mol% or less, (2) has a structure of 30 mol% or more and 90 mol% or less, and more preferably,
(1) is 10 mol% or more and less than 50 mol%, (2) is 50 mol%
It is composed of a structure having a mol% or more and 89 mol% or less, and most preferably (1) is 20 mol% or more and less than 40 mol%,
(2) is a resin composition having a structure of 60 mol% or more and 80 mol% or less. If the composition ratio of the structures (1) and (2) deviates from the above amount range, heat resistance and mechanical strength are impaired.

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) and (2) is a divalent aromatic and / or aliphatic group, and specific examples thereof include those shown in the following chemical formulas 5 and 6.

[Chemical 5]

[Chemical 6]

Among these, the compound of Chemical formula 7 is preferable.

[Chemical 7]

Further, as a particularly preferable one, there is a chemical formula (8).

[Chemical 8]

The most preferable one is the chemical formula (9).

[Chemical 9] Further, 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]

Of these, the preferable one is
I can give you one.

[Chemical 11]

Further, as a particularly preferable one, the compound of Chemical formula 12 is mentioned.

[Chemical 12]

Ar, A of the general formulas (1) and (2)
r ₁ and R are 1 selected from the above specific examples.
It may be one kind or a combination of two or more kinds.

The aromatic polyamideimide copolymer used in the resin composition of the present invention is produced from (a) aromatic tricarboxylic acid anhydride and aromatic dicarboxylic acid and diisocyanate in an amide-based or non-amide-based solvent. Method, (b) aromatic tricarboxylic acid anhydride halide and aromatic dicarboxylic acid, and a method for producing from diamine in the solvent, further, (c) aromatic tricarboxylic acid anhydride and aromatic dicarboxylic acid, and diamine Further, it can be produced by any method of producing using a catalyst such as phosphoric acid or phosphite ester in the above solvent.
Among these methods, (b) has the above-mentioned problem of residual halogen, and further requires post-treatment at high temperature for imide ring formation, and (c) also requires post-treatment at high temperature. (A) is the most preferable manufacturing method. In the present invention, the aromatic polyamide-imide copolymer that gives a resin composition having high heat resistance and mechanical strength and good moldability has a substantially amide imide structure and amide structure,
There are random copolymers randomly arranged, block copolymers in which amideimide structure and amide structure are continuously bonded with a constant chain length, and alternating copolymers in which amideimide structure and amide structure are alternately bonded. It does not matter even if it has the structure of.

Aromatic tricarboxylic acid anhydrides, aromatic dicarboxylic acids, and diisocyanates used for producing the aromatic polyamideimide copolymer suitable for the resin composition of the present invention by the most preferable method (a). Are compounds represented by the following chemical formulas 13, 14, and 15, respectively.

[0020]

[Chemical 13] (In the formula, Ar has the same meaning as Ar in the general formula (1).)

[Chemical 14] (Wherein Ar ₁ has the same meaning as Ar ₁ in formula (2).)

Embedded image O = C = N-R-N = C = O (wherein R has the same meaning as R in formulas (1) and (2)).

In the present invention, in order to produce an aromatic polyamide-imide 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 (2), when the number of moles of diisocyanate is P and the total number of moles of aromatic tricarboxylic acid anhydride and aromatic dicarboxylic acid is Q, the molar ratio of both is 0.9 <Q / P <1. It is preferable to keep 1 and more preferable to keep 0.99 <Q / P <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 15 in a solvent. 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.
The aromatic polyamideimide copolymer more preferable for the resin composition of the present invention can be produced by increasing the temperature in steps. That is, the polymerization temperature is 50 ° C to 1 in the first step.
Within the temperature range of 10 ℃, 110 ℃ ~ 200 after the second stage
By setting the polymerization temperature in the temperature range of ° C in multiple stages and carrying out polymerization, amide groups are formed after the formation of amide groups is substantially completed, and a polyamideimide having excellent melt moldability and toughness 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. The most preferable method is to increase the temperature of the latter stage by 20 to 80 ° C. with respect to the former stage, and make the temperature in each stage constant.

As a solvent used in the production of the aromatic polyamideimide copolymer preferably 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 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 for the production of the aromatic polyamideimide copolymer which is 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 polyamideimide 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.

The use of a small amount of the molecular weight modifier is not limited at all, and typical molecular weight modifiers include monocarboxylic acids such as benzoic acid, phthalic anhydride, succinic anhydride, and naphthalenedicarboxylic anhydride. Monofunctional compounds such as dicarboxylic acid anhydrides such as compounds, 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 / if it is represented by the reduced viscosity measured at a concentration of 1 g / dl at 30 ° C. in dimethylformamide. 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 polyphenylene sulfide resin which is the component (B) used in the resin composition of the present invention is
It is a polymer containing 70 mol% or more, more preferably 90 mol% or more, and most preferably substantially 100 mol% of the repeating unit represented by Chemical formula 16. The repeating unit is 7
If it is less than 0 mol%, it is difficult to obtain the resin composition of the present invention having unique properties. As a polymerization method for obtaining polyphenylene sulfide, various known methods can be adopted, but sodium sulfide and p-dichlorobenzene are mixed in an amide solvent such as N-methylpyrrolidone or dimethylacetamide or a sulfone solvent such as sulfolane. A method of reacting is preferable. At this time, it is a preferable method to add an alkali metal carboxylate such as sodium acetate or lithium acetate in order to control the degree of polymerization.

[Chemical 16]

The polyphenylene sulfide resin is a relatively low molecular weight compound (for example, Japanese Examined Patent Publication No. 45-3368), depending on the production method.
Gazette) and a linear high molecular weight compound (for example, Japanese Patent Publication No. 52-
No. 12240), however, those having a relatively low molecular weight can be used by increasing the molecular weight by heating in an oxygen atmosphere or in the presence of a crosslinking agent such as peroxide. Any polyphenylene sulfide resin may be used in the resin composition of the present invention. Further, the melt viscosity of the polyphenylene sulfide resin is 100 to 100,000 poise at 300 ° C.,
The preferred melt viscosity is 300 to 30,000 poise, more preferably 300 to 10,000 poise, and most preferably 500 to 8,000 poise.

The polyphenylene sulfide resin of the present invention contains a meta-sulfide bond, an ether bond, a sulphone bond, and a poly-phenylene sulfide resin within a range that does not significantly affect the crystallinity of the polymer.
Biphenyl bond, amino group-substituted phenyl sulfide bond, carboxyl group-substituted phenyl sulfide bond, other alkyl, nitro, phenyl, alkoxy group-substituted phenyl sulfide bond, trifunctional phenyl sulfide bond,
You may contain the copolymerization component which has etc. The copolymerization component should be less than 30 mol%, preferably less than 10 mol%.

Further, S of polyphenylene sulfide resin is used.
The present invention also includes those adjusted for the H terminal group concentration. Depending on the composition of the composition, the kneading conditions, etc., a polyphenylene sulfide resin having an SH terminal group concentration of 10 mg / equivalent or more per kg of the resin gives a preferable result, and further, 20 mg / equivalent or more may give a more preferable result. Various methods can be considered as the method for introducing the SH group, but if there is no particular limitation, for example, the polyphenylene sulfide resin treated with hydrochloric acid, acetic acid or the like at the final stage of the production of the polyphenylene sulfide resin or purified The SH group can be easily introduced to the terminal by treating the compound with a solvent such as hydrochloric acid or acetic acid such as acetone.

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 of the component (A) based on 100% by weight of the total amount of both, but the aromatic polyamideimide copolymer is represented by the general formula (1) When the structure contains 50 mol% or more of (1) with respect to 100 mol% of the total of each structure of (2), the aromatic polyamideimide of the component (A) is used with respect to 100 wt% of both. It is preferable to add 10 to less than 70% by weight of the polymer, and in the case of a structure containing less than 50 mol% of (1), add 5 to 95% by weight of the aromatic polyamideimide copolymer as the component (A). It is preferable to add 10 to less than 70% by weight of the aromatic polyamideimide copolymer as the component (A) to 100% by weight of both, regardless of the structure of the aromatic polyamideimide copolymer. More preferred, most Mashiku the blending less than 20 to 50% by weight. If the amount of component (A) is greater than this amount, the fluidity during melting will decrease, and if it is less, heat resistance will decrease.

The resin composition of the present invention is produced by melt-kneading the respective components. The melt-kneading temperature is 250 to 400 ° C.
The temperature is preferably 280 to 400 ° C., and the kneading method can be performed using an extruder, a kneader, a Banbury mixer, a roll or the like. A preferred method is a twin-screw extruder method.

The resin composition of the present invention, if desired,
Fillers, pigments, lubricants, plasticizers, stabilizers, UV absorbers,
Various additives such as flame retardants and flame retardant aids, other resins, and components such as elastomers may be appropriately blended. Examples of fillers are mineral beads such as glass beads, wollastonite, mica, talc, clay, asbestos, calcium carbonate, magnesium hydroxide, silica, diatomaceous earth, graphite, carborundum, molybdenum disulfide; Inorganic fibers such as glass fibers, milled fibers, potassium titanate fibers, boron fibers, silicon carbide fibers, metal fibers such as brass, aluminum and zinc; organic fibers such as carbon fibers and aramid fibers; aluminum and zinc flakes I can give you. The filler is preferably used in an amount of 1 to 70% by weight based on the whole composition. Preferred fillers are milled fibers and glass fibers, and those obtained by treating these with silane coupling agents such as epoxy type and amino type are also suitably used.

Examples of the pigment include titanium oxide, zinc sulfide, zinc oxide and the like. As a lubricant, mineral oil, silicone oil, ethylene wax, polypropylene wax,
Metal salts of sodium stearate, lithium, etc., Metal salts of sodium montanate, lithium, zinc, etc.,
Typical examples are montanic acid amides and esters.

Examples of various additives include, as examples of flame retardants, 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.

The other resin mentioned above is an epoxy resin produced from epichlorohydrin and a dihydric phenol such as 2,2-bis (4-hydroxyphenyl) propane.
Phenoxy resin; 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)
Polycarbonate produced by using divalent phenol such as sulfone, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, and 4-hydroxyphenyl-3-hydroxyphenylketone and phosgene or diphenyl carbonate or dimethyl carbonate as monomers. Polyesters produced by using dihydric phenol and phosgene or diphenyl carbonate, dimethyl carbonate and the aforementioned dicarboxylic acids and their derivatives as monomers; polyphenylene obtained by oxidative coupling polymerization of dimethylphenol and / or trimethylphenol Ether; polysulfone, polyether sulfone, polyetherimide, polythioether ketone,
Aromatic resins such as polyetherketone and polyetheretherketone are exemplified. Among these, polyphenylene ether obtained by oxidative coupling polymerization of 2,6-dimethylphenol and a maleic acid-modified product thereof are preferable.

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 a poly (ethylene oxide) glycol, poly (propylene oxide) glycol or the like. A polyester elastomer represented by a block copolymer of ether glycol or a soft segment made of an aliphatic polyester produced from an aliphatic dicarboxylic acid and a dihydric alcohol (for example, Toyobo Co., Ltd., Perprene, manufactured by Deyupon) Hytrel); polyamide elastomers represented by block copolymers of hard segments such as nylon 11 and nylon 12 and polyether or soft segment of polyester (eg, EMS). CHEMIE's grill amide); low density, high density, ultra high molecular weight, linear low density polyethylene, etc .; polypropylene; ethylene,
EP elastomer, which is a copolymer of propylene; EPDM elastomer, which is a non-conjugated copolymer of ethylene, propylene and norbornenes, cyclopentadiene, 1,4-hexadiene; α-, such as ethylene, propylene and butene-1 Copolymer elastomers of olefins with α, β-unsaturated glycidyl esters of glycidyl acrylate, glycidyl methacrylate and the like; α-olefins such as ethylene, propylene and butene-1 and vinyl acetate, vinyl propionate, methyl acrylate, Copolymer elastomer with unsaturated ester such as methyl methacrylate; the above-mentioned polyethylene, polypropylene, EP, E
PDM, α-β-unsaturated dicarboxylic acid anhydride represented by maleic anhydride of α-olefin copolymer elastomer, or α, β-such as glycidyl methacrylate.
Graft-modified glycidyl ester of unsaturated acid; A-B-A 'consisting of A component of vinyl aromatic compound such as styrene and B of diene component such as butadiene and isoprene
AB type elastomeric block copolymer; A-B-A 'in which the B component is hydrogenated, AB type elastomeric block copolymer, and α represented by maleic anhydride,
ABA-A ', AB type elastomeric block copolymers graft-modified with β-unsaturated dicarboxylic acid anhydrides or glycidyl esters of α, β-unsaturated acids such as glycidyl methacrylate and the like. Graft-modified A-B-A 'and A-B with hydrogenated component B
Elastomeric block copolymers; polysulfide rubber, silicone rubber and the like are exemplified.

The resin composition comprising the aromatic polyamide-imide copolymer of the present invention and the polyphenylene sulfide resin is melt-molded without impairing the heat resistance of the prior art resin composition comprising the aromatic polyamide-imide resin and the polyphenylene sulfide resin. The properties and mechanical strength were improved.
It is considered that this excellent property is mainly due to the fact that the novel resin composition of the specific aromatic polyamideimide copolymer and the polyester resin of the present invention improves the compatibility of both resins, which are inferior to the resin composition of the prior art, Moreover, although the aromatic polyamide-imide copolymer of the present invention has less imide structure than the aromatic polyamide-imide resin of the prior art, it has a heat resistance higher than that of the resin composition of the prior art. It is a phenomenon that is both objective 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,
The aromatic polyamide-imide copolymer produced in Reference Example is shown in Table 1, and the results of Examples and Comparative Examples are shown in Tables 2, 3, and 4.

Reference Example 1 3 L of N-methylpyrrolidone having a water content of 40 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, trimellitic anhydride 222.
1 g (20 mol% based on the total number of moles of all monomer components), isophthalic acid 288.1 g (30 mol%),
Then 2,4-tolylene diisocyanate 503.3
g (50 mol% of the same) was added. The water content in the system when trimellitic anhydride and isophthalic acid were added was 30 ppm. 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 4 hours. Then, the temperature was raised to 160 ° C. over 15 minutes, 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, redispersed in methanol, washed thoroughly, separated after washing, and kept at 200 ° C. for 1 hour.
It was dried under reduced pressure for 0 hours to obtain a polyamide-imide powder.
When the reduced viscosity at 30 ° C. of this product was measured with a dimethylformamide solution (concentration 1.0 g / dl), it was found to be 0.
It was 40 dl / g. Moreover, the glass transition temperature is measured by differential scanning calorimetry (DSC).
It was measured by the 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 in the same reactor as in Reference Example 1. 210.6 g of trimellitic anhydride chloride (20 mol% based on the total number of moles of all monomer components) and 304.5 g of isophthalic acid dichloride (30 mol%) were added thereto. Then, 305.4 g of m-toluylenediamine (50 mol% in the same amount) 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 twice by adding N-methylpyrrolidone, and this was diluted with N
-Methylpyrrolidone was added dropwise to methanol in a volume of 2 times 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. When the reduced viscosity at 30 ° C. of this product was measured with a dimethylformamide solution (concentration 1.0 g / dl), it was 0.2.
It was 6 dl / g.

Reference Example 3 3 L of N-methylpyrrolidone having a water content of 40 ppm was charged in the same reactor as in Reference Example 1. Here, 333.1 g of trimellitic anhydride (30 mol% based on the total number of moles of all monomer components), isophthalic acid 192.0
g (20 mol% in the same amount), and then 503.3 g (50 mol% in the same amount) 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 4 3 L of N-methylpyrrolidone having a water content of 30 ppm was charged in the same reactor as in Example 1. Here, 444.2 g of trimellitic anhydride (40 mol% with respect to the sum of the number of moles of all monomer components), 96.0 g of isophthalic acid
(10 mol% in the same amount), and then 503.3 g (50 mol% in the same amount) 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 0.30 d / g.

Reference Example 5 3 L of N-methylpyrrolidone having a water content of 30 ppm was charged in 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 toluylene diisocyanate (50 mol%). The water content in the system is 25 pp when trimellitic anhydride is added.
It was m. 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. Then, the temperature was raised to 115 ° C. over 15 minutes, 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,
It was dried under reduced pressure at 200 ° C. for 10 hours to obtain a polyamideimide powder. Dimethylformamide solution (concentration 1.0g
The reduced viscosity of this product at 30 ° C. was 0.27 dl / g.

Reference Example 6 3 L of N-methylpyrrolidone having a water content of 15 ppm was charged in the same reactor as in Reference Example 1. To this, 480.1 g of isophthalic 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%) were added. The water content in the system when isophthalic acid was added was 50 ppm. 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. Then, the temperature was raised to 115 ° C. over 15 minutes, 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 10 hours to obtain a polyamideimide powder. Dimethylformamide solution (concentration 1.0 g / dl)
The reduced viscosity of this product at 30 ° C. was 0.30 dl / g.

[0048]

【Example】

 Example 1 Aromatic Polyamide-imide Copolymer 3 Produced in Reference Example 1
0 parts by weight and polyphenylene sulfide resin (hereinafter PPS
Abbreviated as T-4 manufactured by Topren Co., Ltd. at 300 ° C.
70 parts by weight of twin screw extruder
Was melt-kneaded at 340 ° C. and pelletized. Obtained
Injection molded 1/4 inch thick test pieces from the pellets
It was 18.6k for heat resistance evaluation from this test piece
g / cm ²The heat distortion temperature of stress, and the mechanical strength of bending
The strength was measured. Furthermore, melt moldability is 350 ° C., 60
kg / cm²Higher flow tester for increasing melt flow under stress
The results are shown in Table 2.

Examples 2 to 4 Example 1 was repeated except that the compounding ratio was changed. The results are shown in Table 2.
It was shown to.

Examples 5 to 7 The aromatic polyamideimide copolymer of Example 2 was used as a reference example 2.
Repeated with an aromatic polyamideimide copolymer of ~ 4. The results are shown in Table 2.

Comparative Examples 1 to 6 Examples 1 to 3 were repeated except that the aromatic polyamideimide copolymers of Reference Examples 5 to 6 were used. The results are shown in Table 3.

Example 8 Aromatic Polyamideimide Copolymer 2 Prepared in Reference Example 1
5 parts by weight and 35 parts by weight of PPS and glass fiber (hereinafter, abbreviated as glass fiber or GF, chopped strand manufactured by Asahi Fiber Glass Co., Ltd. 03JAFT540)
40 parts by weight were melt-kneaded and pelletized at 350 ° C. using a twin-screw extruder. A 1/4 inch thick test piece was injection-molded from the obtained pellet. From this test piece, the heat deformation temperature of 18.6 kg / cm ² stress and the flexural modulus at 200 ° C. were measured for the purpose of evaluating heat resistance. Further, the melt moldability was measured at 350 ° C. and the melt flow value under stress of 60 kg / cm ² with a Koka type flow tester. The results are shown in Table 4.

Examples 9-10 Example 8 was repeated except that the aromatic polyamideimide copolymers of Reference Examples 3-4 were replaced. The results are shown in Table 4.

Comparative Examples 7-8 Example 8 was repeated except that the aromatic polyamideimide copolymers of Reference Examples 5-6 were used. The results are shown in Table 4.

[0055]

The resin composition of the present invention has improved heat resistance and mechanical strength of the prior art resin composition comprising an aromatic polyamideimide resin and a polyphenylene sulfide resin. The resin composition of the present invention is suitably used for molding material applications that require high heat resistance, high mechanical strength, and excellent melt moldability.

[0056]

Table 1 Acid component composition Diisocyanate Reference example TMA / IPA TDI Glass transition point (mol%) (mol%) (° C) 1 20/30 50 50 290 2 (20/30) (50) 290 (acid chloride) (m -TDA) 3 30/20 50 50 305 4 40/10 50 50 310 5 50/0 50 326 660/50 50 260 260 TMA; trimellitic anhydride IPA; isophthalic acid TDI; 2,4-tolylene diisocyanate m-TDA; Metatoluylenediamine acid chloride; trimellitic anhydride chloride / isophthalic acid dichloride

[0057]

[Table 2] Example Amidoimide PPS Thermal deformation Bending Melt flow value / Comparative example Type Temperature Strength × 10 ⁻¹ (wt%) (wt%) (° C.) (MPa) (cc / sec) Example 1 Reference Example 1 70 168 130> 10 30 Example 2 Reference Example 1 50 230 230 160 6.2 50 Example 3 Reference Example 1 30 252 150 150 1.0 70 Example 4 Reference Example 1 25 253 135 0.05 0.05 75 Example 5 Reference Example 2 50 230 155 6.8 50 Example 6 Reference example 3 50 230 157 4.7 50 Example 7 Reference example 4 50 230 150 150 3.8 50

[Table 3] Example Amidoimide PPS Thermal deformation Bending Melt flow value / Comparative example Type Temperature Strength × 10 ⁻¹ (wt%) (wt%) (° C) (MPa) (cc / sec) Comparative Example 1 Reference Example 5 70 170 120 7.0 30 Comparative Example 2 Reference Example 5 50 230 230 140 3.0 50 Comparative Example 3 Reference Example 5 30 248 130 130 0.6 70 Comparative Example 4 Reference Example 6 70 140 120 120 7.4 30 Comparative Example 5 Reference Example 6 50 207 100 3.8 50 Comparative example 6 Reference example 6 30 220 80 0.8 70

[0058]

[Table 4] Example Amidoimide PPS GF Thermal deformation Bending Melt flow value / Comparative example Type Temperature elastic modulus x 10 ^-1 (wt%) (wt%) (wt%) (° C) (GPa) (cc / sec) Example 8 Reference Example 1 35 40 274 5.6 2.3 25 Example 9 Reference Example 3 35 40 275 5.5 1.8 25 25 Example 10 Reference Example 4 35 40 275 5.2 1.3 25 Comparative Example 7 Reference example 5 35 40 275 5.0 0.8 25 25 Comparative example 8 Reference example 6 35 40 260 3.2 2.1 25 Note) The flexural modulus was measured at 200 ° C.

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

[Procedure amendment]

[Submission date] May 13, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0032

[Correction method] Change

[Correction content]

Further, S of polyphenylene sulfide resin is used.
The present invention also includes those adjusted for the H terminal group concentration. Composition of the composition, gave a result polyphenylene sulfide resin preferably has a 10 milligram equivalents or more SH terminal group concentration per resin 1Kg by kneading conditions and the like,
Furthermore have a SH terminal group concentration of more than 20 milli-gram equivalent
The polyphenylene sulfide resin may give more preferable results. As a method of introducing the SH group,
Stated without are conceivable various methods of specifically limited, manufacturing, for example, polyphenylene sulfide resin
Treated with hydrochloric acid, acetic acid, etc. at the final stage of production or purified polyphenylene sulfide resin is treated with hydrochloric acid, acetic acid.
SH can be easily processed by treating with acetone solution of
Groups can be introduced at the ends.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0043

[Correction method] Change

[Correction content]

Reference Example 2 3 L of N-methylpyrrolidone having a water content of 20 ppm was charged in the same reactor as in Reference Example 1. 210.6 g of trimellitic anhydride chloride (20 mol% based on the total number of moles of all monomer components) and 304.5 g of isophthalic acid dichloride (30 mol%) were added thereto. Then, 305.4 g of m-toluylenediamine (50 mol% in the same amount) 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 twice by adding N-methylpyrrolidone, and this was diluted with N
-Methylpyrrolidone was added dropwise to methanol in a volume of 2 times 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 250 ° 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 0.26 dl / g. ─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] July 4, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0022

[Correction method] Change

[Correction content]

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 15 in a solvent. 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.
The aromatic polyamideimide copolymer more preferable for the resin composition of the present invention can be produced by increasing the temperature in steps. That is, the polymerization temperature is 50 ° C to 1 in the first step.
Within the temperature range of 10 ℃, 110 ℃ ~ 200 after the second stage
By setting the polymerization temperature in the temperature range of ° C in multiple stages and carrying out polymerization, amide groups are formed after the formation of amide groups is substantially completed, and a polyamideimide having excellent melt moldability and toughness 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 preferred is the step temperature increasing method in which the temperature of each stage is set to a constant temperature by increasing the temperature of the latter stage by 20 to 80 ° C. with respect to the former stage. Regarding the polymerization time, the first stage is usually 30 minutes to 5 hours, preferably 30 minutes to 3 hours, and the second stage and thereafter are usually 30 minutes to 10 hours, preferably 1 hour to 8 hours.

Front page continued (72) Inventor Hidefumi Harada 22 Wadai, Tsukuba City, Ibaraki Prefecture, Mitsubishi Gas Chemical Co., Ltd. (72) Inventor Banichi 22 Wadai, Tsukuba City, Ibaraki Prefecture, Mitsubishi Gas Chemical Co., Ltd.

Claims (3)

[Claims] 1. A resin composition comprising (A) a polyamide-imide copolymer having the structures of the general formulas (1) and (2) as repeating units, and (B) a polyphenylene sulfide resin. [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. Furthermore, general formulas (1) and (2)
In, R represents a divalent aromatic group or an aliphatic group. ] 2. The structure of the (A) polyamide-imide copolymer is such that (1) is 5 mol% or more and 95 mol% or less, and (2) is 1
The resin composition according to claim 1, which is in the range of mol% to 95 mol%. 3. With respect to the total amount of (A) and (B), (A)
The resin composition according to claim 1, wherein the ratio of the polyamide-imide copolymer is 5 to 95% by weight.