JPH02218738A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition which is suitable for parts of electric or electronic appliances and of automobiles, because of its excellent mechanical properties, chemical resistance, and heat resistance by using a polyamide resin, a thermoplastic polyester and a specific condensate in a specific proportion. CONSTITUTION:(A) 100 pts.wt. of a resin which is composed of A1: 95 to 5wt.%, preferably 40 to 90wt.% of a polyamide resin and A2: 5 to 95wt.%, preferably 40 to 90wt.% of a thermoplastic polyester containing alkylene terephthalate as a main structural unit such as polyethylene terephthalate are combined with (B) 0.001 to 30 pts.wt., preferably 0.05 to 20 pts.wt. of a condensate of 11 or more polymerization degree from a bisphenol and epichlorohydrin of the formula (n is 11 or higher).

Description

Detailed Description of the Invention [Industrial Field of Application] The resin composition of the present invention has excellent mechanical properties, chemical resistance, and heat resistance, and has good moldability. , automobile parts, household goods, equipment housings, mechanical parts, etc., extrusion molded sheets, films, etc.
Applicable to a wide range of fields such as blow molding.

[Conventional technology]

Polyamide resin or thermoplastic polyester resin is
Despite having excellent physical and chemical properties, there are several drawbacks when these resins are used alone. For example, polyamide resins have drawbacks such as reduced rigidity due to moisture absorption and large dimensional changes in molded products, while thermoplastic polyester resins have drawbacks such as poor impact resistance and hot water resistance. . Therefore, in order to obtain a resin that compensates for the above-mentioned drawbacks, research is being carried out on blending thermoplastic polyester resin with polyamide resin.
03/9/ issue or JP-A-Sho! r/-10!3! ! r
Compositions described in, for example, No. 1, are known.

However, polyamide resins and thermoplastic polyester resins have poor compatibility, resulting in decreased mechanical properties, especially tensile properties and impact properties, and phase separation, which deteriorates the appearance. However, the actual situation is that a composition that can be put to practical use cannot be obtained using this method.

[Purpose of the invention]

The present invention is a condensate of polyamide resin, thermoplastic polyester resin, bisphenols, and epichlorohydrin, which has a degree of polymerization of substantially 11 or more. It has excellent impact and tensile properties due to an improved processing method, preferably by melt-kneading the three components simultaneously, without using disadvantageous methods,
It is possible to obtain a resin composition that has a good appearance without delamination in the molded product when injection molded.

[Structure of the invention]

The present invention will be specifically explained below.

As the polyamide used in the present invention, polyamides obtained by polycondensation of lactams having three or more membered rings, polymerizable ω-amino acids, dibasic acids, diamines, etc. can be used.

Specifically, ε-caglodictam, aminocaproic acid,
Polymers such as enantholactam, 7-aminehebutanoic acid, 11-aminoundecanoic acid, aminononanoic acid, α-pyrrolidone, α-piperidone, hexamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, Polymers obtained by polycondensing diamines such as metaxylylene diamine with dicarboxylic acids such as terephthalic acid, inphthalic acid, adipic acid, sepathic acid, dodecane dibasic acid, and geltaric acid, or copolymers thereof, such as nylon Q, A, 7,
11.

/2, Otsu, A, i? ,6. / 0. A, / /, i/
Ko, 6T14/i A, 6112, A/A T, A
Examples include I/A T.

The thermoplastic polyester resin used in the present invention is a polyalkylene terephthalate obtained by a polycondensation reaction of terephthalic acid or its dialkyl ester and an aliphatic glycol, or a copolymer mainly composed of the polyalkylene terephthalate,
Typical examples include polyethylene terephthalate,
Examples include polybutylene terephthalate.

Examples of the aliphatic glycols include ethylene glycol, propylene glycol, tetramethylene glycol,
Examples include hexamethylene glycol, but together with these aliphatic glycols, other diols or polyhydric alcohols, such as cyclohexanediol, cyclohexane dimetatool, xylylene glycol, etc. in an amount of 30% by weight or less based on the aliphatic glycols, Ko, Corbis (4
=-hydroxyphenyl)furopane, λ, 2-upper 2-4
t-hydroxy-3,3-dibromphenyl)propane, co,2-bis(lI-hydroxyethoxyphenyl)
Propane, 2,2-bis(11-hydroxyethoxyl 3.tadibromphenyl)propane, 19-serine,
Pentaerythritol or the like may be used in combination.

In addition, together with terephthalic acid or its dialkyl ester, other dibasic acids, polybasic acids, or their alkyl esters, such as phthalic acid, isophthalic acid, naphthalene dicarboxylic acid, diphenyl, in an amount of JO14 or less with respect to terephthalic acid or its dialkyl ester. dicarboxylic acid,
Adipic acid, sebacic acid, trimesic acid, trimellitic acid, alkyl esters thereof, and the like may be used in combination.

Here, regarding the blending ratio of polyamide resin and thermoplastic polyester resin, one is compared to qs-r weight % of the other! -9j Jukei Chi, and the total amount is 100% by weight. If it deviates from either of these ranges, the properties of both polymers cannot be maintained. Preferably, the blending ratio is 170-90% by weight of polyamide resin and 10-60% by weight of thermoplastic polyester resin. A condensate with phosphorus, for example, in the case of bisphenol A, it is a condensate consisting of repeating units represented by the following formula and whose degree of polymerization n is substantially 71 or more, preferably 75 or more.

Specific examples of bisphenols include: bisphenol A1 bisphenol F1 bisphenol C1 tetramethyl-bisphenol A1 tetramethyl-bisphenol F1 di-isopropyl-bisphenol A1 di-5ec-butyl-bisphenol A1 tetra-t-butyl-bisphenol A1f tra-t-butyl -Bisphenol F1
Tetra-t-butyl-bisphenol, he/-ethylidene-bisphenol, /,/-imbutylizo/-bisphenol, methyl-ethyl-methylene-bisphenol, methyl-isobutyl-methylene-bisphenol, methyl-hexyl-methylene-bisphenol, methyl- 7enyl methylene-bisphenol, bisphenol Z1 P, P'-bisphenol, methylene-bis(ko, Hiro-DTB-, ?CR), 0, P
'-bisphenol A1, tetramethyl-bisphenol S, and the like.

It is also possible to use more than one type of specific condensate in the present invention.

In this case, when the degree of polymerization is relatively low, such as 11 to SO, preferably 75 to Da θ, a bisphenol-based high molecular weight epoxy compound whose terminal group is an epoxy group as shown by the following formula is preferred.

(n=11~SO) Also, the degree of polymerization (,) is 5θ or more, preferably go~/jθ
If it is relatively high, the terminal group is not particularly limited, and hydroxyl group,
The amount of the condensate added is 0.07 parts by weight per 100 parts by weight of the mixture of polyamide resin and thermoplastic polyester resin.
-30 parts by weight, but if it is less than 0.07 parts by weight, no effect of improving compatibility will be observed, and if it exceeds 30 parts by weight, mechanical properties will deteriorate. Preferably, the range is 5-20 parts by weight of O,O. Especially in the case of condensates with a high degree of polymerization, O
, S to -0 parts by weight are preferred.

The composition of the present invention is blended by a melt mixing method well known to those skilled in the art, and there are no particular restrictions on kneading temperature or time, but a temperature of 750 to 330°C is generally recommended, and specifically,
Examples include an extruder, a Banbury mixer roll, and a kneader.

When blending polyamide resin, polyester resin, and specific condensate, it is preferable to melt-knead these three components at the same time, but in some cases, after blending one of the co-components and melt-kneading, the remaining components may be blended. Furthermore, it may be melt-kneaded.

In the present invention, in addition to the above three components, an appropriate amount of a rubber-like substance such as a rubber-like polymer or a rubber-modified styrene resin can be added in order to further improve the impact strength. Specific examples of the rubbery polymer include polybutadiene, butadiene-styrene copolymer, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, polyinfrene, ethylene-α-olefin copolymer, polyisobutylene, Examples include polyacrylic esters, polyesters, polyurethanes, and various modified polymers thereof.

Specific examples of rubber-modified styrenic resins include, for example:
Butadiene rubber-modified polystyrene, butadiene rubber-modified styrene-acrylonitrile copolymer, acrylic rubber-modified polystyrene, acrylic rubber-modified styrene-acrylonitrile copolymer, ethylene-propylene copolymer-modified polystyrene, ethylene-methyl methacrylate copolymer-modified polystyrene, etc. can be mentioned.

In addition to the above-mentioned formulations, the composition of the present invention may contain various well-known additives, such as glass fibers, carbon fibers, reinforcing agents such as metal whiskers, silica, alumina-silica-alumina clay minerals, and silica-magnesium clay minerals. It may contain fillers such as minerals, calcium silicate, calcium carbonate, asbestos, and carbon black, as well as flooring agents, nucleating agents, antioxidants, flame retardants, antistatic agents, weathering agents, and the like.

〔Example〕

Hereinafter, the method of the present invention will be explained in detail with reference to Examples.
The present invention is not limited to these.

The measurement conditions are as follows.

(1) Tensile strength and elongation Compliant with ASTM D-43g (2) Tensile impact value Compliant with ASTM D-7g22 (3) Izod impact value 11 inch thick test piece, ASTM [)-,2
Example based on JIS K-1, GLO, as a copolyamide, nylon 6 with a relative viscosity of 2.5 measured by Ostwald viscosity tube according to JIS K-1, GLO.
Polybutylene terephthalate (manufactured by Mitsubishi Chemical Industries, Ltd., trademark, Novad Wool 5o10) with a limiting viscosity of
After melt-mixing at a temperature of ~3°C, the resulting composition was injection molded under the conditions shown in Table 2.

Examples 3 to g Instead of the polybutylene terephthalate described in Example 2, polyethylene terephthalate having an intrinsic viscosity of 0.6 and a melting point of 260°C was used and blended to have the composition shown in Table 2, and Example 2 was prepared. The same operation as in λ was performed, and the resulting composition was injection molded under the conditions shown in Table 2.

Comparative Example/-44 A composition was obtained by melt-mixing in an extruder in the same manner as the compositions of Examples/--g, except that no high molecular weight bisphenol-based epoxy compound was added, and injection molding was performed.

Comparative Examples 5 to g A bisphenol-based epoxy compound with a degree of polymerization (,) of 1
Using materials with relatively low molecular weights of 0 or less, they were blended to have the composition shown in Table 7, melted and mixed in an extruder in the same manner as in Examples/~g to obtain a composition, and injection molded. I did it.

Comparative Examples 9 to 11 Epoxy compounds other than specific wire hardware were blended to have the composition shown in Table -/, and the compositions were melted and mixed in an extruder in the same manner as Examples/~g, and injection molding was performed. Ta.

The tensile strength, tensile elongation, tensile impact value, and Izod impact value of the injection molded products of the resin compositions of Examples/~g1 Comparative Examples/~/l thus obtained were measured. The measurement results are shown in Table C.

Examples 9~/q High polymerization degree (n≧SO) shown in Table 3 as a specific condensate
A composition was obtained by melt-mixing in an extruder and injection molding in the same manner as in Examples/-g except that the resin of Example 1 was used. The results of measuring the mechanical properties of the obtained fine products are also listed in Table 3.

〔Effect of the invention〕

As described above, even when the composition of the present invention is produced by a conventional method, it does not undergo phase separation and has excellent mechanical properties.

wish Reason Mitsubishi Chemical Industries, Ltd.

Claims (4)

[Claims] (1) A condensate of bisphenols and epichlorohydrin is added to 100 parts by weight of a resin consisting of 95 to 5% by weight of a polyamide resin and 5 to 95% by weight of a thermoplastic polyester whose main constituent units are alkylene terephthalate units. , the degree of polymerization is 0.001 to 11 or more.
A resin composition containing 30 parts by weight. (2) The resin composition according to claim 1, wherein the condensate has a repeating unit represented by the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (n is an integer of 11 or more, and the benzene ring may have a substituent.) (3) The condensate has epoxy groups at both ends, and the degree of polymerization is 1.
The resin composition according to claim 1 or 2, wherein the resin composition has a molecular weight of 1 to 40. (4) The resin composition according to claim 1 or 2, wherein the degree of polymerization of the condensate is substantially 50 or more.