JPH07113043A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the composition, excellent in both thermal stability and chemical resistance, capable of suppressing foaming unique to the time of melt kneading and useful as daily subsistence stores, etc., by using a mixture of a resin having a specified epoxy equiv. with a phenoxy resin having a specified average molecular weight. CONSTITUTION:This thermoplastic resin composition contains (B) 1-50 pts.wt. mixture composed of (iii) 1-90wt.% resin having epoxy groups and an epoxy equiv. within the range of 500-8000(g/equiv.) and (iv) 1-90wt.% phenoxy resin having an average molecular weight within the range of 10000-50000, e.g. a compound expressed by the formula [(n) is 80-125] in (A) 100 pts.wt. resin composition composed of (i) a polycarbonate resin and (ii) a polyamide resin at (1/9) to (9/1) blending weight ratio.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition having excellent heat stability and chemical resistance.

[0002]

2. Description of the Related Art Polycarbonate resins are
It has excellent heat resistance and impact resistance, and is widely used in various machine parts such as daily life items, office equipment, and electrical and electronic parts. However, the polycarbonate resin has poor chemical resistance and has a drawback that cracks are likely to occur when it comes into contact with a certain solvent in the presence of stress.

[0003] In order to improve the chemical resistance of the polycarbonate resin, attempts are often made to melt mix the polyamide resin, but when the polycarbonate resin and the polyamide resin are melt mixed, the polycarbonate resin decomposes and melt molding is extremely difficult. However, even if a molded product is obtained, there is a problem that this resin composition cannot be used at all because the molded product is discolored and silver strips are generated in the molded product.

In order to solve the problem, some examples of adding a third component to a resin composition comprising a polyamide resin and a polycarbonate resin have been reported. For example, in JP-A-62-197448, a phenoxy resin containing a hydroxyl group is added, and in JP-A-62-187771, an effective amount of an effective epoxy-functional compatibilizer is added.
No. 28265 shows the combined use of an epoxy resin and a modified olefin. Addition to the resin composition composed of these polyamide resin and polycarbonate resin is effective for improving the thermal stability of the resin composition composed of the polyamide resin and polycarbonate resin, and particularly for suppressing foaming, however, the resin composition according to this proposal Improving the thermal stability or balance of physical properties of the product is not always sufficient, and there is a problem in that retention in the molten state causes problems such as thickening, gelation and coloring, or a remarkable decrease in physical properties when an additive is added.

[0005]

DISCLOSURE OF THE INVENTION As a result of investigations aimed at improving the chemical resistance of a polycarbonate resin, the present inventors have found that a melt blend of a polycarbonate resin and a polyamide resin has an epoxy group and an epoxy equivalent of 500.
To 6,000 (g / eq) in the range and a mixture of phenoxy resins having an average molecular weight in the range of 10,000 to 50,000 to improve the thermal stability of foaming, gelation and coloring. Solve the problem of
The present invention has been completed by finding that a resin composition having an excellent physical property balance can be obtained.

That is, according to the present invention, 100 parts by weight of a resin composition (A) having a weight compounding ratio of 1/9 to 9/1 of a polycarbonate resin and a polyamide resin has (B) an epoxy group and has an epoxy equivalent. 500-8,000 (g / eq)
1 to 90% by weight of a resin having a range of 1 to 90% by weight and (C) 1 to 90% by weight of a phenoxy resin having an average molecular weight in a range of 10,000 to 50,000. It is to provide a resin composition.

The polycarbonate resin used in the present invention has a viscosity average molecular weight of 10,000 to 100,000, preferably 15,000, derived from a dihydric phenol.
It is a polycarbonate of 0 to 60,000 and is usually produced from a dihydric phenol and a carbonate precursor by a solution method or a melting method.

As a typical example of the dihydric phenol, bisphenol A [2,2-bis (4-hydroxyphenyl)]
Propane], bis (4-hydroxyphenyl) methane,
Bis (4-hydroxyphenyl) ether, bis (4-
Hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl) ethane,
1,1-bis (hydroxyphenyl) cyclohexane,
2,2-bis (4-hydroxyphenyl) propane,
2,2-bis (4-hydroxyphenyl), 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propanebutane and the like can be mentioned. A preferred dihydric phenol is a bis (4-hydroxyphenyl) alkane compound, especially bisphenol A. The dihydric phenols can be used alone or in combination of two or more. Further, as the carbonate precursor, carbonyl halide,
Examples thereof include carbonates and haloformates. Representative examples include phosgene, diphenyl carbonate, dihaloformates of dihydric phenols, and mixtures thereof. In producing the polycarbonate resin, an appropriate molecular weight modifier, branching agent, catalyst, etc. can be used.

The polyamide resin used in the present invention is a ring-opening reaction of a lactam having three or more member rings, and a polymerizable ω-
It is produced by polycondensation reaction of amino acids and polycondensation of dibasic acid and diamine. For example, ε-caprolactam, aminocaproic acid, enanthlactam, 7-aminoheptanoic acid,
1,1-aminoundecanoic acid, 9-aminononanoic acid, α
-Pyrrolidone, polymers such as α-piperidone, further hexamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, diamines such as metaxylylenediamine and terephthalic acid, isophthalic acid, adipic acid, sebacic acid, Examples thereof include polymers and copolymers obtained by polycondensation with dicarboxylic acids such as dodecane dibasic acid and glutaric acid. Specific examples are nylon 4,6,7,8,11,12,6,6.
6, 9, 6, 10, 6, 11, 6, 12, 6/6, 6,
Examples include 6/12, 6 / 6T, 6I / 6T and the like. The molecular weight of these polyamides is generally 10,000 or more, preferably 13,000 to 50,000, particularly 15,000 to 3
50,000 is preferable, and the degree of polymerization is 100 or more, especially 13
0-500 is preferred. The polyamide resin of the present invention preferably contains no metal or amphoteric metal carbonate, and these are usually contained as components of the lubricant, mold release agent and crystal nucleating agent of the polyamide resin.

The compounding ratio of the resin composition (A) comprising the above polycarbonate and polyamide of the present invention is in the range of 1/9 to 9/1 in terms of polymerization ratio. If there is more polycarbonate than this, the chemical resistance of the polycarbonate will not be improved,
When the amount of polyamide is more than this, the heat resistance characteristic of polycarbonate is impaired.

As the resin having an epoxy group (B) used in the present invention, a resin having a glycidyl type epoxy which is already well known is preferably used. For example, polyphenols of diphenols such as monophenols and bisphenol and epichlorohydrin are polycondensed, or glycidyl methacrylate or acrylic glycidyl ether and methacrylic acid ester, methacrylic acid, vinyl acetate, vinyl alcohol, styrene, acrylic acid ester, ethylene, propylene, etc. Can be obtained by copolymerization with olefins or acrylonitrile.

The epoxy resin (B) has an epoxy equivalent of 500 to 8,000 (g / eq), more preferably 500 to 5,000 (g / eq). If the epoxy equivalent is less than this, the physical properties of the resin composition will be deteriorated, and if it is more than this, the epoxy group concentration in the resin will be too small and the effect will not be achieved.

Unlike the epoxy resin, the phenoxy resin (C) used in the present invention does not contain a highly reactive epoxy group in the molecular chain such as a molecular terminal.
The resin itself has excellent heat stability, ductility, and toughness. Specifically, hydroquinone, resorcin, 4,
Aromatic dihydroxy compounds such as 4'-bisphenol, 4,4'-dihydroxydiphenyl ether, bisphenol A and 2,6-dihydroxynaphthalene, or ethylene glycol diglycidyl ether propylene glycol diglycidyl ether, neopentyl glycol, neopentyl glycol diglycidyl Polyhydroxypolyether obtained by condensing glycerin and epichlorohydrin with one or more compounds selected from aliphatic dihydroxy compounds such as ether, polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether And so on.

In particular, the following formula (I)

[Chemical 1] The average molecular weight is 10,0.
00-50,000, preferably 10,000-40,0
A high molecular weight thermoplastic resin of 00 is preferably used. This phenoxy resin is formed by the condensation of bisphenol A and epichlorohydrin. Such a phenoxy resin may have PKHC, PKHH,
It is commercially available from Union Carbide Co., Ltd. under the name PKHJ or the like. The characteristics of these phenoxy resins are:
"Plastic Handbook" (published by Asakura Shoten, 1984)
Year edition) is detailed.

The compounding ratios of the above-mentioned components A, B and C of the present invention are most effective as shown below.

100 parts by weight of the A composition, 1 to 90 parts of the B component
A mixture of 1% to 90% by weight of C component and 1% to 90% by weight of C component is in the range of 1 to 50 parts by weight. Even more preferably, it is 1 to 30 parts by weight. If the mixture of the B component and the C component is less than 1 part by weight, the effect is not sufficient, and if it exceeds 50 parts by weight, the physical properties of the thermoplastic resin composition are deteriorated.

The composition of the present invention may contain, for example, an antioxidant, a flame retardant, an antistatic agent, an ultraviolet absorber, etc., in addition to the above-mentioned composition, within the range of not impairing the properties of the resin composition. .

The resin composition of the present invention can be produced by mixing the mixed components with a mixer such as a tumbler / blender, a Nauter mixer, a Banbury mixer, a kneading roll and an extruder.

The composition of the present invention can be applied to any molding method such as injection molding, extrusion molding, compression molding, rotational molding,
The thermal stability during molding and the chemical resistance of the obtained molded product are extremely good.

[0020]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples. In the examples,% and parts are based on weight unless otherwise specified.

Raw material Aromatic polycarbonate resin (trade name: Europylon S
3,000, manufactured by Mitsubishi Gas Chemical Co., Ltd., nylon 6 (trade name: Ube 1013B, manufactured by Ube Industries), and (B) as a resin having an epoxy group, an ethylene-glycidyl methacrylate copolymer, Rexpearl J3700 (epoxy). Equivalent 560 (g / eq), manufactured by Nippon Petrochemical Co., Ltd., Epotote Y of diglycidyl ether of bisphenol A
D-7020 (Epoxy equivalent 3,800 g / eq, manufactured by Tohto Kasei Co., Ltd.), and ethylene-vinyl acetate-glycidyl methacrylate copolymer bond fast 7B (epoxy equivalent 610 (g / eq), Sumitomo Chemical Co., Ltd.) Made),
(C) PKHH as phenoxy resin (number average molecular weight 3
50,000, manufactured by Union Carbide Co., Ltd. was used.

In addition, as a hindered phenolic antioxidant, Irganox 1010 (Ciba Geigy Co., Ltd.)
Manufactured by ADEKA STAB 1178 as a phosphorus-based antioxidant
(Asahi Denka Co., Ltd.) was used.

Examples 1 to 6 and Comparative Examples 1 to 6 Melt kneading was carried out with the compounding amounts shown in Table 1. All kneading is TEM35 manufactured by Toshiba Machine Plastic Engineering Co., Ltd.
Using a B twin-screw extruder, the mixture was melt-kneaded at 250 to 260 ° C into pellets.

The resin composition thus obtained was injection-molded into test pieces. Physical properties were measured using the obtained test piece. The results are shown in Table 1.

(1) Evaluation of Foaming and Coloring The pellets obtained in Examples 1 to 7 and Comparative Examples 1 to 8 were melt-kneaded again, and after replacing the resin in the extruder, the feeder and screw were stopped and the mixture was allowed to stay for 15 minutes. . With respect to the stayed strands, those with foaming were visually evaluated as x, those without foaming were evaluated as o, those with coloring were evaluated as x, and those without were evaluated as o.

(2) Tensile test According to ASTM standard D-638.

(3) Impact resistance test (with Izod notch) According to ASTM standard D-256.

[0028]

[Table 1]

[0029]

As shown in Table 1 and Examples, the present invention provides a resin composition having a well-balanced physical property in which peculiar foaming during melt-kneading of a polycarbonate resin and a polyamide resin is considerably suppressed. You can see that

Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display area C08L 71:10)

Claims (1)

[Claims] 1. A resin composition (A) having 100 parts by weight of a polycarbonate resin and a polyamide resin and having a weight compounding ratio of 1/9 to 9/1 has (B) an epoxy group and an epoxy equivalent of 500 to 8. 1 to 90% by weight of resin in the range of 1,000 (g / eq) and (C) average molecular weight of 10,
Phenoxy resin 1 in the range of 000 to 50,000
A thermoplastic resin composition containing 1 to 50 parts by weight of a mixture of 90% by weight.