JPS62218433A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition excellent in tear strength, tensile strength, moldability and flexibility, by mixing a specified polyether ester amide with a polyolefin elastomer. CONSTITUTION:A polyether ester amide (A) is obtained by reacting a 6C or higher aminocarboxylic acid or lactam or a salt of a 6C or higher diamine with a dicarboxylic acid (a) (e.g., 12-aminododecanoic acid) with a poly(alkylene oxide) glycol (b) of a number-average MW of 300-6,000 [e.g., poly(tetramethylene oxide)glycol] and a 4-20C dicarboxylic acid (c) (e.g., dodecanedioic acid). Separately, a polyolefin elastomer (B) is obtained by mixing 10-80wt% polyolefin resin (d) (e.g., PE) with 90-20wt% ethylene copolymer rubber (a) obtained from 20-90wt% ethylene, 80-10wt% alpha-olefin and, optionally, a nonconjugated diene. 1-99wt% component A is mixed with 99-1wt% component B.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Field of Application> The present invention relates to a thermoplastic resin composition having high tear strength and tensile strength, and excellent moldability and flexibility.

<Prior Art> Polyetheresteramides having polyamide repeating units, polyether repeating units and ester bonds in the polymer backbone are known (U.S. Pat. No. 3,044,9).
Specification No. 87). Polyolefin elastomers, which are compositions consisting of polyolefin resin and ethylene copolymer rubber, are also known (Japanese Patent Publication No. 53-21021, Japanese Patent Publication No. 53-34210, Japanese Unexamined Patent Publication No. 59-598).
8043, JP-A-59-91142).

<Problems to be solved by the invention> Polyether ester amide is used for various molding applications because it has poor flexibility, transparency, and mechanical properties, and is less likely to cause flashes or sink marks during molding. Sometimes, the solidification rate was slow and a long cooling time was required, which caused problems with productivity.

On the other hand, although polyolefin-based nidistomers are excellent in lightness and flexibility, they have problems in that molded products are prone to deformation such as sink marks during molding, and tear strength and tensile strength are low.

The present invention has been made to solve the above-mentioned problems and to provide a thermoplastic resin composition that has excellent tear strength, tensile strength, moldability, and flexibility at the same time.

As a result, the object of the present invention is to obtain a salt (a) of an aminocarboxylic acid or a lactam having 6 or more carbon atoms, or a diamine and a dicarboxylic acid having 6 or more carbon atoms, with a number average molecule i1300.
~6,000 poly(alkylene oxide) glycol (b) and a dicarboxylic acid having 4 to 20 carbon atoms (c
) Polyether ester amide (A) 1 derived from
~99% by weight of polyolefin resin and ethylene copolymer rubber ■9
It has been found that this can be achieved by creating a thermoplastic resin composition in which the ratio is 9 to 1% by weight.

The configuration of the present invention will be specifically described below.

Aminocarboxylic acid or tonic acid having 6 or more carbon atoms, ω-aminocaprylic acid, ω-aminopelargonic acid, ω-aminecapric acid, 11-aminoundecanoic acid, 12-aminododecane in the polyetheresteramide prisoner of the present invention Aminocarboxylic acids such as acids or lactams such as caprolactam, enantholactam, capryllactam, laurolactam, and hexamethylenediamine adipate, hexamethylenediamine sepacate, hexamethylenediamine isophthalate, undecamethylenediamine There are salts of diamine-dicarboxylic acids such as acyhinate and 4,4'-diaminodicyclohexylmethane-dodecanedioate, and caprolactam, 11-aminoundecanoic acid, and 12-aminododecanoic acid are particularly preferred.
These can also be used in combination depending on the purpose and use.

It is also permissible to use other amide-forming components as copolymerization components in small amounts for the purpose of lowering the melting point of polyether ester amide or increasing adhesiveness.

Examples of the poly(alkylene oxide) glycol having a number average molecular weight of 300 to 6,000 in the polyether ester amide (4) of the present invention include polyethylene glycol, poly(l, 2- and l).

Examples include 3-propylene oxide) glycol, poly(tetramethylene oxide) glycol, poly(hexamethylene oxide) glycol, block or random copolymers of ethylene oxide and propylene oxide, block or random copolymers of ethylene oxide and tetrahydrofuran, etc. Due to the excellent physical properties of polyether esteramide, such as heat resistance, water resistance, mechanical strength, and elastic recovery, poly(tetramethylene oxide)
Glycols are preferably used. The number average molecular weight of poly(alkylene oxide) glycol is 300 to 6,0
00, but a molecule/layer region that does not cause coarse phase separation during polymerization and has excellent low-temperature properties and mechanical properties is selected, and this optimum molecular weight region is poly(alkylene = 4).
= Oxide) Varies depending on the type of glycol.

For example, in the case of polyethylene glycol, it is 300 to 6.00
0, particularly preferably 1,000 to 4,000, and 300 to 5 in the case of poly(propylene oxide) glycol
．． 0001, particularly preferably 500 to 3,000, and 50 in the case of poly(tetramethylene oxide) glycol
0 to 3,000, particularly preferably 500 to 2,500
Those having a molecular weight in the range of are preferably used.

The dicarboxylic acid (c) having 4 to 20 carbon atoms in the polyether ester amide prison of the present invention includes terephthalic acid,
Isophthalic acid, naphthalene-2゜6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4
′-dicarboxylic acid, diphenoxyethanedicarboxylic acid,
Aromatic dicarboxylic acids such as sodium 3-sulfoisophthalate, l, 4-cyclohexanedicarboxylic acid, l.

2-Cyclohexanedicarboxylic acid, dicyclohexyl-
Alicyclic dicarboxylic acids such as 4,4'-dicarboxylic acids,
and succinic acid, oxalic acid, adipic acid, sebacic acid,
Mention may be made of aliphatic dicarboxylic acids such as dodecanedioic acid (decanedicarboxylic acid). In particular, dicarboxylic acids such as terephthalic acid, iso7-esteric acid, l,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, and dodecanedioic acid are preferably used from the viewpoint of polymerizability, color tone, and physical properties of the polymer. .

Poly (alkylene oxide) glycol (b) and dicarboxylic acid (c) in polyether ester amide (4)
If the copolymerized amount of polyether ester units derived from is too small, flexibility and elastic recovery properties tend to be lost, whereas if it is too large, mechanical properties such as high temperature properties and strength tend to be impaired. Therefore, in order to obtain the effects of the present invention most significantly, the content is preferably 5 to 90% by weight.

The method for polymerizing the polyether ester amide () is not particularly limited, and any known method can be used. for example,
An aminocarboxylic acid or a lactam, or a salt of a diamine and a dicarboxylic acid (a) is reacted with a dicarboxylic acid (c) to produce a polyamide prepolymer with carboxylic acid groups at both ends, and this is injected with poly(alkylene oxide) glycol (
b) A method of reacting under vacuum, or the above (a),
The compounds (b) and (c) are charged into a reaction tank and reacted by heating at high temperature in the presence or absence of water to produce a carboxylic acid-terminated polyamide prepolymer, and then under normal pressure or reduced pressure. A method of proceeding with polymerization is known. There is also a method in which the compounds (a), (b), and (c) above are simultaneously charged into a reaction tank, melt-polymerized, and then polymerized all at once under high vacuum; this method actually causes less coloring of the polymer. preferable.

In the present invention, the polyolefin di-stomer) is a thermoplastic composition consisting of a polyolefin resin and an ethylene copolymer rubber. Here, polyolefin resin is a polymer consisting of α-olefin, such as polyethylene,
Polypropylene, polybutene-11 polypentene-1,
Examples include poly-4-methylpentene-1, among which polyethylene and polypropylene are preferably used.

In addition, ethylene copolymer rubber refers to ethylene and α-
It is a copolymer derived from a compound containing an olefin as an essential component and, in some cases, a non-conjugated diene.

Here, the α-olefins include propylene, butene-1
, pentene-114-methylpentene-I, among which propylene and butene-1 are preferably used.

In addition, as the non-conjugated diene, dicyclopentadiene (DCPD), 5-(2-me, chiru-2-7'7
-nyl)-2-norbornene, 5-methylene-2-norbornene (MNB), 5-x-f lithine-2-norbornene (ENB), methyltetrahydroindene (MT
HI),! , 4-hexadiene (1,4-f(D), etc., among which DCPolENB, 1.4-HD
is preferably used.

~10% by weight, and in the case of copolymerizing a non-conjugated diene, it is preferably 10 parts by weight or less per 100 parts by weight of ethylene and α-olefin. The polyolefin elastomer (B) is a composition consisting of the above-mentioned polyolefin resin and ethylene copolymer rubber, but the blending ratio is such that if the polyolefin resin is too small, the moldability will be poor, and if the polyolefin resin is too large, the flexibility will be insufficient. 10 to 80% by weight of polyolefin resin and ethylene copolymer rubber 9
A proportion of 0 to 20% by weight is preferred.

This composition is manufactured by a known method.

That is, a method of melt blending polyolefin NEW and ethylene copolymer rubber, a method of melt blending a partially vulcanized product of ethylene copolymer rubber and polyolefin resin (Japanese Patent Publication No. 53-21021), and a method of melt blending polyolefin resin and polyolefin resin. A method of dynamically curing a mixture of ethylene copolymer rubber to obtain a partially vulcanized product (Japanese Patent Publication No. 53-34210), a method of dynamically vulcanizing a mixture of polyolefin resin and ethylene copolymer rubber at high shear rates. There are methods such as dynamically vulcanizing the ethylene copolymer rubber and finely dispersing the vulcanizate of the ethylene copolymer rubber in the polyolefin resin (Japanese Patent Laid-Open No. 59-58043, Japanese Patent Laid-Open No. 59-91142). Can be mentioned.

As a vulcanizing agent, organic peroxide, sulfur, phenol ml
MN, phenylene bismaleimide, urethane vulcanizing agent,
Diamine vulcanizing agents are preferred and can be used in combination with vulcanization aids.

Here, the ethylene copolymer rubber is preferably vulcanized. If unvulcanized, mechanical properties tend to be poor.

In the present invention, the blending ratio of polyether ester amide and polyolefin elastomer is 1 to 99% by weight, preferably 5 to 95% by weight, and preferably 10% by weight.
to 90% by weight, 99 to 1% by weight, preferably 9
The proportion should be 5 to 5% by weight, particularly preferably 90-10 M%. If (2) is less than 1% by weight, the tear strength, tensile strength, and moldability of the present invention are insufficient, and if it exceeds 99% by weight, there are problems with moldability.

The resin composition of the present invention is preferably melt-kneaded, and a known method can be used for the melt-kneading method. For example, the resin composition can be prepared by melt-kneading the resin composition using a Banbury mixer, a rubber roll machine, a screw-screw or twin-screw extruder, etc., usually at a temperature of 100 to 300°C.

The resin composition of the present invention also contains known antioxidants, thermal decomposition inhibitors, ultraviolet absorbers, hydrolysis resistance improvers, colorants (
pigments, dyes), antistatic agents, conductive agents, flame retardants, reinforcing agents,
Fillers, lubricants, nucleating agents, mold release agents, plasticizers, process oils, adhesion aids, adhesives, and the like can be optionally contained.

These additives can be added at any time.

For example, a method of adding to polyether ester amide and blending with a polyolefin-based nidistomer, a method of adding to a polyolefin-based elastomer and blending with polyether ester amide, or a method of adding polyether ester amide, a polyolefin-based nidistomer, and additives. Examples include a method of simultaneously blending. Further, these blending methods may be used in combination.

II - <Examples> Unless otherwise specified in the examples, parts mean parts by weight.

Reference Example [Manufacture of Polyetheresteramide] The polymerization of the polyetheresteramide used in the Examples and Comparative Examples is as follows.

Polymerization of polyether ester amide (A-1) 81.9 parts of ω-aminododecanoic acid, 6.8 parts of dodecanedioic acid, and poly(tetramethylene oxide) with a number average molecular weight of 650.
19.3 parts of glycol “Irganox” 109
8 Pour 0.5 parts (antioxidant) into a reaction vessel equipped with a helical ribbon stirring blade, purge with nitrogen, and boil to 260 ml.
After heating and stirring at ℃ for 1 hour to obtain a homogeneous transparent solution, 0.015 parts of antimony trioxide catalyst, 0.015 parts of monobutyl monohydroxytin oxide catalyst, and 0.005 parts of phosphoric acid (
A color inhibitor) was added and the polymerization conditions were brought to below lffHg in 1 hour according to a vacuum program. When the reaction was carried out under these conditions for 2.5 hours, a viscous colorless and transparent molten polymer was obtained, and when this polymer was discharged into water as a gut, it crystallized and turned white. The obtained polyether ester amide (A-1) had a relative viscosity (ηr) of 181 when measured in orthochlorophenol at 25°C at a concentration of 0.5%, and a crystal melting point of 167°C by DSC.

Polymerization of polyether ester amide (A-2) 49.1 parts of ω-aminododecanoic acid, 7.9 parts of terephthalic acid, poly(tetramethylene oxide) with a number average molecular weight of 1020
Glycol 48.8 parts, Irganox” 109
8, 0.015 m of antimony trioxide, 0.015 part of motuputyl monohydroxytin oxide, and 0.005 part of phosphoric acid under the same conditions as for polymer (A-1), and the relative viscosity was 1. 93, a polyether ester amide (A-2) having a melting point of 154°C was obtained.

Polymerization of polyether ester amide (A-3) 27.3 parts of ω-aminododecanoic acid, 5.7 parts of terephthalic acid, poly(tetramethylene oxide) with a number average molecular weight of 2060
Glycol 70.5 parts, "Irganox" 109
8 0.5 parts, antimony trioxide 0.015 parts, motuputyl monohydroxytin oxide 0.015 parts, and phosphoric acid 0.005 parts under the same conditions as Polymer (A-1), and the relative viscosity was 1. A polyether ester amide (A-3) having a melting point of 145° C. and a melting point of 145° C. was obtained.

[Manufacture of polyolefin-based nidistomer] The polyolefin-based nidistomer (B) used in the Examples and Comparative Examples was manufactured as follows.

Manufacturing melting index of polyolefin elastomer (13-1) (230°C, 2160 f tij &) F3
．． 0 720 parts of Noholipropylene, copolymerization ratio of ethylene/
Propylene 15-ethylidene-2-norbornene = 65
/3015 and a Mooney viscosity (ML++4.100°C) of 40 ethylene copolymer rubber (EPDM) 8 (1) and 0.8 part of dicumyl peroxide as an organic peroxide vulcanizing agent were placed in a Banbury mixer with a volume of 31. Pour and heat to 190℃, 3
The mixture was kneaded at 0 rpm for 10 minutes to obtain a polyolefin elastomer (B-1).

Production of (B-2) 30 parts of the same polypropylene used in the production of (B-1), 70 parts of EPDM, and 0.7 parts of dicumyl peroxide were kneaded under the same conditions as in (B-1). A polyolefin-based didistomer (B-2) was obtained.

Production of (B-3) 40 parts of the same polypropylene used in the production of (B-1), 60 parts of EPDM, and 0.6 part of dicumyl peroxide were kneaded under the same conditions as in (B-1). A polyolefin elastomer (B-3) was obtained.

Production of (B-4) Same EPDM as used in production of (B-1)
100 parts of clay, 30 parts of clay, 100 parts of paraffinic process oil with a flash point of 310°C, and 5 parts of titanium dioxide were placed in a Banbury mixer with a capacity of 101°C, and the mixture was heated at 100°C at 30°C.
A masterbatch was obtained by kneading at rpm for 30 minutes. 235 parts of master pan f (m), 33 parts of the same polypropylene used in the production of (B-1), 5 parts of zinc oxide, 1 m of stearic acid/acid and 10 parts of brominated alkylphenol formaldehyde resin curing agent in a volume of 3 I! into a Banbury mixer and mix at 200°C and 50 rpm.
After kneading for 0 minutes, the polyolefin elastomer (B-
4) was obtained.

Production of (B-5) 235 parts of the same masterbatch (m) used in the production of (B-4), 67 parts of polypropylene, 5 parts of zinc oxide, 1 part of stearic acid, and brominated alkylphenol formaldehyde resin curing agent From 10 parts, knead under the same conditions as (B-4) to obtain a polyolefin-based disstomer (B-4).
-5) Got it:.

Production of (B-6) The same master buyer as that used for production of (B-4)
From 235 parts of f (m), 150 parts of polypropylene, 5 parts of zinc oxide, 1 part of stearic acid and 10 parts of brominated alkylphenol formaldehyde resin hardener (B
A polyolefin elastomer (B-6) was obtained by kneading under the same conditions as in -4).

Production of (B-7) The same master pie as that used for production of (B-4)
f (m) 235 parts, (B-6) 160 parts, zinc oxide 5 parts, stearic acid 1 part and brominated alkylphenol formaldehyde! Fat hardening agent t.

A polyolefin elastomer (B-7) is obtained by kneading the parts under the same conditions as (B-4).

Examples 1 to 13 Polyether ester amides (A-1), (A-2), and (A-3) were mixed with the polyolefin elastomers shown in the table, and mixed in a 30mm extruder heated to 200°C. After melting and kneading, the mixture was pelletized. The obtained pellets are
A JIS No. 2 tensile test piece and a tear test piece (thickness: 2 m + 11 mm) were molded at a molding temperature of 200° C. and a mold temperature of 40° C. using an injection molding machine having an injection capacity of 1 oz. Shore hardness is ASTM D-2240, tensile strength is ASTM D
-638 and tear strength were measured according to JIS K6301. The molding cycle was set to a holding pressure time and a cooling time to obtain a good JIS No. 2 tensile test piece. In addition, the presence or absence of sink marks at the gate opening of the molded test piece was visually determined. The results are shown in the table.

Comparative Examples 1 to 10 Polyetheresteramide (A-1), (A-2)
and (A-3), polyolefin elastomer -
(B-1), (B-2), (B-3
), (B-4), (B-5), (B-6)
Regarding (B-7), JI as in Example 1-13.
S No. 2 tensile test pieces and tear test pieces were molded, and Shore hardness, tensile strength, tear strength, and molding cycle were measured. The presence or absence of sink marks on the molded pieces was also determined. The results are shown in the table.

The following can be seen from the results in the table.

As seen in Examples 1 to 13, the resin compositions of the present invention have excellent tear strength, tensile strength, moldability, and flexibility at the same time.

As seen in Comparative Examples 1 to 3, polyether ester amide has a long molding cycle and does not have sufficient moldability.

As seen in Comparative Examples 4 to 10, the polyolefin-based nidistomers had sink marks on the molded pieces and had low tear strength and low tensile strength.

<Effects of the Invention> In the present invention, a thermoplastic resin composition having excellent tear strength, tensile strength, moldability, and flexibility at the same time can be obtained by blending a polyolefin-based nidistomer with a polyether ester amide.

Patent application Daitoshi Co., Ltd.

Claims (1)

[Claims] Aminocarboxylic acids or lactams having 6 or more carbon atoms,
Or a salt of diamine and dicarboxylic acid having 6 or more carbon atoms (
a), poly(alkylene oxide) glycol (b) having a number average molecular weight of 300 to 6,000, and having 4 carbon atoms
1 to 99% by weight of a polyether ester amide (A) derived from a dicarboxylic acid (c) of ~20, and 99 to 1% by weight of a polyolefin elastomer (B) consisting of a polyolefin resin and an ethylene copolymer rubber. A thermoplastic resin composition formed by blending the proportions.