JPS63170455A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition outstanding in mechanical strength, dimensional stability, heat resistance, etc., suitable for various automobile parts, etc., by blending a thermoplastic polyester and a polyamide of specific structure in specified proportion. CONSTITUTION:The objective composition can be obtained by blending (A) 5-95pts.wt. of a thermoplastic polyester resin (e.g., polyethylene terephthalate) and (B) 95-5pts.wt. of a polyamide resin prepared by (co)polymerization of (between) B1: 100-80pts.wt. of a polyamide-forming component consisting of aliphatic diamine and isophthalic acid and/or terephthalic acid and B2: 0-20pts. wt. of a second polyamide-forming component consisting of lactam and/or aliphatic diamine and aliphatic dicarboxylic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel thermoplastic resin composition comprising a thermoplastic polyester resin and a polyamide resin having a specific structure. More specifically, it relates to a thermoplastic resin composition that is obtained by uniformly melting and intermixing a thermoplastic polyester resin and a polyamide resin having a specific structure in a specific amount in a specific amount to have mechanical strength, dimensional stability, heat resistance, etc. at ℃.

[Conventional technology]

Thermoplastic polyesters such as polyethylene terephthalate and polybutylene terephthalate have excellent mechanical properties and are widely used as useful engineering plastics. On the other hand, polyamide resin is widely used as an engineering plastic useful in the field of molded products, which is different from polyester, due to its excellent toughness, abrasion resistance, and chemical resistance.

Both polyester and polyamide have excellent performance as described above, but each also has drawbacks.

In other words, molded products made of polyester resin are extremely susceptible to warping.

On the other hand, polyamide resin has very poor physical properties and dimensional changes due to moisture absorption. Therefore, attempts have been made since ancient times to improve the shortcomings of straw and to combine the two to create a well-balanced material.

However, due to the poor compatibility between the two, the composition undergoes phase separation due to aggregation during molding, resulting in a molded product with extremely poor mechanical properties.

[Purpose of the invention]

Therefore, the present inventors sought to find a polyamide resin that is highly compatible with polyester resins and exhibits excellent mechanical properties when used as a composition (the present invention was arrived at after intensive study). Therefore, an object of the present invention is to provide a resin composition having excellent mechanical properties, which is composed of a polyester resin and a specific polyamide resin.

That is, the present invention comprises (a) a thermoplastic polyester resin, (b) an aliphatic diamine, ioo to 10 parts by weight of a polyamide forming component from isophthalic acid and/or terephthalic acid, a lactam and/or an aliphatic diamine, and an aliphatic dicarboxylic acid. A resin composition comprising a polyamide resin obtained by polymerizing or copolymerizing 0 to 20 parts by weight of a polyamide-forming component from an acid.

[Structure of the invention]

The present invention will be explained in detail below.

The thermoplastic polyester resin which is component (a) used in the present invention is a polymer obtained by a condensation reaction whose main components are dicarboxylic acid or its ester-forming star conductor and diol or its ester-forming fermented conductor. .

Examples of dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, ↓6-naphthalenedicarbone m, 1.5
-naphthalene dicarboxylic acid, succinic acid, adipic acid, sebacic acid, 7.3-cyclohexa/dicarboxylic acid, /,
Examples include tercyclohexane dicarbonate modified or ester-forming conductors thereof, alone or in mixtures. Diol components include ethylene glycol, propylene glycol, /, a-butanediol, /, J-
Examples include butanediol, neopentyl glycol, 7.5-pentanedio-v,i,t-hexanediol, tecamethylene glycol, cyclohexane dimetatool, cyclohexanediol, and long chain glycols with a molecular weight of 4AOO-^000, singly or in mixtures. It will be done. Specific examples of thermoplastic polyesters include polyethylene terephthalate, polyethylene naphthalate, polyglobylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexane dimethylene terephthalate, and poly(ethylene terephthalate/ethylene isophthalate). copolymers, poly(butylene terephthalate/butylene dodecadiate) copolymers, etc., and those particularly useful in the present invention are polyethylene terephthalate and polybutylene terephthalate.

The molecular weight of the polyester used in the present invention is not particularly limited, but it is preferable to use a mixed solvent of phenol and tetrachloroethane in a weight ratio of 1:1, and the intrinsic viscosity [η] measured at 30° C. at a concentration of /i/di. is 17. jnaishi/
, 3 is desirable.

Next, the polyamide resin with a specific chemical structure which is the (original) component used in the present invention is a semi-aromatic polyamide component (component a) made from aliphatic diamine and isophthalic acid and/or terephthalic acid.Ioo to 10 parts by weight It is obtained by polymerizing or copolymerizing an aliphatic polyamide component (component b) of 0 to 01 parts of and lactam or aliphatic diamide/and aliphatic dicarboxylic acid.

Aliphatic diamines that can be used in the present invention specifically include linear aliphatic diamines such as ethylene diamine, tetramethylene diamine, hexamethylene diamine, octamethylene diamine, and decamethylene diamine, and their methylated, ethylated, and halogenated compounds. It contains visiting conductors such as, and the temperature during polymerization is /1! At least one kind can be used.

Specifically, the lactam that can be used in the present invention includes caprolactam, lauryllactam, etc., and seven or more of them can be used in the polymerization.

Specifically, the aliphatic dicarboxylic acids that can be used in the present invention include succinic acid, glutaric acid, adipic acid, pimelic acid, superric acid, azelaic acid, heptanosic acid, and their methylation, ethylation, and It contains a conductor such as a compound, and one or more of them can be used in the polymerization.

Isophthalic acid and terephthalic acid may be used alone or in combination, and in that case, the ratio of isophthalic acid and terephthalic acid used is arbitrary, but preferably isophthalic acid: terephthalic acid = - 0:za 0~80:2
It is 0.

In addition, the semi-aromatic polyamide of the a component is ``cgo% by weight or more based on the total polyamide component. That is, the a component is 8% by weight or more.
If it is less than 0% by weight, the heat resistance will be significantly lowered and the strength will be significantly lowered due to water absorption.

The polyamide used in the present invention is usually produced by the so-called melt polymerization method by adding a lactam to a nylon salt consisting of diamine and dicarboxylic acid or an aqueous solution thereof as required. It is also produced by a solution method or an interfacial polymerization method. When polymerizing as necessary, polymerization terminal terminators substituted for monocarboxylic acids and monoamines, heat stabilizers such as phosphoric acid esters, surfactants, antifoaming agents, antioxidants, etc. Gluing agents, pigments, etc. can be added.

The molecular weight of the polyamide used in the present invention is not particularly limited, but preferably 11% concentrated sulfuric acid is used, and the concentration/g/
It is desirable that the relative viscosity ηred measured at 5° C. is between /,t and 3.0.

The composition of the present invention is produced by melt-mixing a thermoplastic polyester resin and a polyamide resin at °C.

Melt mixing is done using an extruder, plastic bender, etc. according to the usual method1.
can be done.

The blending ratio of both resins can be varied over a wide range of degrees Celsius, but usually thermoplastic polyester resin: polyamide resin =
qs:r-z:tz (weight ratio).

If the ratio of the polyamide resin boiled to the whole is less than SZ amount %, the composition is likely to warp, and if it exceeds 95% by weight, the physical properties will deteriorate due to water absorption, and in either case, the advantage of using the composition is Not demonstrated.

The resin composition obtained by the present invention can be used depending on the purpose.In addition to the above ingredients, the resin composition may be used in addition to inorganic fillers, reinforcing agents and fillers such as glass fibers and carbon fibers, pigments, dyes, heat resistant agents, antioxidants, weathering agents, lubricants, crystals, etc. Nucleating agent, anti-blocking agent, mold release agent,
Plasticizers, flame retardants, antistatic agents, and other additives can be added.

The resin composition of the present invention can be molded into ordinary thermoplastic resins such as injection molding, extrusion molding, blow molding, and compression molding, and these molded products can be used for various automobile parts, mechanical parts, electrical/electronic parts, general miscellaneous goods, etc. It is useful.

〔Example〕

The present invention will be explained in more detail with reference to Examples below.

The characteristics of the resins and compositions described in Examples and Comparative Examples were evaluated by the following method.

(1) Relative viscosity of polyamide 9t% @ measured using sulfuric acid at a concentration of 9/di at -5°C (2) Intrinsic viscosity of thermoplastic polyester Using a mixed solvent of phenol and tetrachloroethane in a weight ratio of 12/2 Concentration/g/d7! Measured at 30°C (3) Tensile properties Based on ASTM D 63g (4
) Bending properties Compliant with ASTM D-90 (5)
Izotsu impact strength Compliant with ASTM Dco36 (6)
Heat distortion temperature Compliant with AsTM D 44 (7)
Soli / Ocm X /
Measurement Reference Example 1 Production of polyamide/Hexamethylenediamine θ% water bath liquid Co, Coj
kg/water
De, o
H. Isophthal#/,
DeAkg・Terephthalic acid Q, Det
Acetic acid/1.0/l was added to a salt aqueous solution consisting of 1.0 kg, and the mixture was charged into a reaction tank equipped with a stirrer and sufficiently N! After replacing /Iψ−
The mixture was heated and pressurized until the pressure within the system reached 11 kg7-, and the polymerization reaction was started by stirring while releasing the pressure so that the pressure within the system became /I'9/cd. During that time, the internal temperature rose more slowly than the temperature at which almost no water was distilled out in the j-hour layer, and at this point the internal temperature indicated 0°C. Further pressure is released, and the final system pressure is 70011XHg.
After reducing the pressure until the pressure was reduced to , the pressure was returned and the molten polymer was extracted from the bottom of the reaction tank.

This polymer was a polyamide resin containing 100% by weight of polyamide components consisting of aliphatic diamine, iso-7-thalic acid and terephthalic acid, and had a relative viscosity of 0.5%.

Reference example Co. Production of polyamide/Hexamethylene diamide 790% water bath solution Co, = tk
g. Water
De, 0 Yu/ Isophthal ell
i, zoroyu・tele 7rikm,
o, yprIq・ Caprolactam O
, Vinegar rR/l in an aqueous solution consisting of kukuyu,! 9 was added and charged into a reaction tank equipped with a stirrer, and after replacing with sufficient N, heating and pressurizing was carried out until the system pressure reached /1 &/d. The mixture was stirred while releasing the pressure so that the polymerization reaction started. During that time, the internal temperature was ko1
The temperature was gradually raised from 0°C, and almost no water was distilled out in the 5-hour layer, and at this point the internal temperature indicated 150°C. The pressure was further released, and after the system pressure was finally reduced to 700° C. mH9, the pressure was returned and the molten polymer was extracted from the bottom of the reaction tank.

This polymer was a polyamide resin in which the polyamide component from aliphatic diamine, iso-7 tar acid and terephthalic acid was t5% by weight, and the polyamide component from lactam was 7j% by weight, and the relative viscosity ηrel was 0.

Reference example 3 Production of polyamide (comparative example) - Hexamethylene diamide 770% water bath liquid
De, o kli
l. Isophthalic acid / Zoroyukai
Terephthalic acid 0. Add J4 fl of acetic acid to an aqueous solution consisting of 3.7 kg of caprolactam, charge it to a reactor with a stirrer, and add enough N! After the substitution, the temperature was raised while adjusting the system internal pressure to J kg/ffl, and then water was distilled out. When the amount of distillate reached z, okg, the -carrying valve was closed. The temperature was further increased and water was distilled off. Thereafter, the pressure was released, and the pressure was finally reduced to 700 uHH, and this pressure was maintained for 1 hour. Thereafter, the molten polymer at the bottom of the reactor was pressurized with N and was extracted and made into chips.

This polymer is a polyamide resin containing 10% by weight of a polyamide component made from aliphatic diamide/isophthalic acid and terephthalic acid, and 0% by weight of a polyamide component made from caprolactam, and has a relative viscosity of ? r・1 was ko, os.

Example 1 Parts by weight of the polyamide resin go obtained in Reference Example 1 and polybutylene terephthalate resin (manufactured by Mitsubishi Kasei@, Novado Wool Zoto, [η]=/, 01) were pellet-blended and then mixed in a twin-screw kneading extruder (Ikegai Tekko's). em'RPCM-JO”/
The mixture was melt-kneaded at a resin temperature of -10° C. and then pelletized to obtain a fatty acid compound.

This composition is processed into a j ounce injection molding machine (manufactured by Toshiba Machine).
Temperature: 80℃, injection/cooling = io seconds/ko 0 seconds cycle,
Various test pieces were obtained by molding at a resin temperature of -10°C.

Mechanical properties, heat distortion temperature, and
The water absorption rate, etc. will be recorded in Clothing I below.

Example λ The same procedure as in Example 1 was carried out except that the polyamide@FacoQ heavy dobe obtained in Reference Example 1 and 10** parts of polybutylene terephthalate resin were used. The physical property measurement results are listed below.

Example 3 The results of measuring the physical properties of a composition obtained in the same manner as in Example 1 except that 10 parts by weight of the polyamide resin obtained in Reference Example 1 were used are described in Section 1 below.

Comparative Example/The results of measuring the physical properties of a composition obtained by the same procedure as in Example 1 except that 10H parts of the polyamide resin obtained in Reference Example 3 were used are described in Clothing 1 below.

Comparative example = 3, DA6 nylon (Tsubamitsudo 1010J manufactured by Mitsubishi Kasei Corporation)
The physical properties of the polyamide resin and polybutylene terephthalate resin obtained in Reference Example 1 obtained by obtaining test pieces in the same manner as in Example 1 are described in Clothing 1 below.

〔Effect of the invention〕

As described above, the resin composition of the present invention maintains the excellent mechanical properties possessed by polyamide resins and thermoplastic polyester resins, while at the same time avoiding the deterioration of physical properties and warping during water absorption, which are the drawbacks of each. It has been improved in temperature and can provide extremely useful materials for various automobile parts, mechanical parts, electrical/electronic parts, and other fields.

Claims (2)

[Claims] (1) 100 to 80 parts by weight of a polyamide-forming component made from (a) a thermoplastic polyester resin and (b) an aliphatic diamine, isophthalic acid and/or terephthalic acid, and a lactam and/or aliphatic diamine and an aliphatic dicarboxylic acid. A thermoplastic resin composition comprising a polyamide resin obtained by polymerizing or copolymerizing 0 to 20 parts by weight of polyamide-forming components. (2) (a) 5 to 95 parts by weight of a thermoplastic polyester resin and (b) 100 to 80 parts by weight of a polyamide-forming component from an aliphatic diamine and isophthalic acid and/or terephthalic acid, and a lactam and/or aliphatic diamine. The thermoplastic resin composition according to claim 1, comprising 95 to 5 parts by weight of a polyamide resin obtained by polymerizing or copolymerizing 0 to 20 parts by weight of a polyamide-forming component from an aliphatic dicarboxylic acid.