JPS59197458A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide a thermoplastic resin compsn. having good resistance to impact, heat and weather as well as excellent weld strength, by blending a specified rubber-reinforced thermoplastic resin and an unsaturated acid-modified olefin polymer with a polycarbonate. CONSTITUTION:A rubber-reinforced thermoplastic resin obtd. by polymerizing at least one compd. selected from an arom. vinyl compd. (e.g. styrene), a vinyl cyanide compd. (e.g. acrylonitrile) and an alkyl unsaturated carboxylate (e.g. methyl acrylate) in the presence of a rubber (e.g. polybutadiene, a butadiene/ styrene copolymer or an ethylene/vinyl acetate copolymer) is used. 0.1-40pts.wt. unsaturated carboxylic acid-modified olefin polymer is blended with 100pts.wt. compsn. consisting of 90-10wt% polycarbonate and 10-90wt% said resin.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel thermoplastic resin composition that is excellent in impact resistance, heat resistance, and moldability, and particularly has excellent low-temperature weld strength.

Previous efforts have been made to improve the moldability of polycarbonate resin by adding rubber-reinforced thermoplastic resins, such as ABS resin, to polycarbonate resin, and to further reduce the thickness dependence of impact strength. ．．
No. 39-71.42-11496.51-11142, etc., and all of the compositions have apparently good moldability,
For example, the outflow rate in Koka flow is improved.

However, in injection molding, which is the most common molding method, it is necessary to change the number of gates and the flow state of the resin depending on the shape and size of the molded product.
A so-called I-weld portion, which is a portion where resins flowing in different directions intersect, always occurs, but in conventional compositions, the strength of this weld portion (l-weld strength) is not sufficient. In particular, the weld strength at low temperatures is low, and at present it is difficult to say that it is a practically excellent material.

As a result of intensive research into improving the weld strength of such compositions made of polycarbonate resin and rubber-reinforced resin, the present inventors surprisingly found that a specific olefin polymer was added to the composition of polycarbonate resin and rubber-reinforced resin. It was discovered that by blending , the weld strength was significantly improved in addition to impact resistance, heat resistance, and moldability.
This has led to the present invention.

That is, the present invention provides impact resistance characterized by blending an unsaturated carboxylic acid-modified olefin polymer (C) into a composition consisting of a polycarbonate resin (6) and a rubber-reinforced thermoplastic resin (B), The object of the present invention is to provide a thermoplastic resin composition that has excellent heat-resistant body moldability and weld strength.

The thermoplastic resin composition of the present invention will be explained in detail below.

Examples of the polycarbonate resin (6) include aromatic polycarbonate, aliphatic polycarbonate, aliphatic-aromatic polycarbonate, and the like.

In general, 2,2-bis(4-oxyphenyl) argan, bis(4-oxyphenyl) ether, bis(4-oxyphenyl)
-oxyphenyl) sulfone, sulfide, or sulfoxide-based bisphenols, and is a polymer using bisphenols substituted with halogen depending on the purpose.

For the manufacturing method and types of polycarbonate, please refer to 1 Polycarbonate Resin # (゛Showa 4) published by Nikkan Kogyo Shimbun.
(Published September 30, 2014).

The rubber-reinforced thermoplastic resin (B) is produced by graft polymerization of one or more compounds selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds, and unsaturated carboxylic acid alkyl ester compounds in the presence of rubber. There are resin customers who do it.

In addition, such a resin is a (co)polymer produced during graft polymerization or a (co)polymer made of the above-mentioned compound produced separately.
Polymers may be included.

The composition ratio of rubber and compound in the rubber-reinforced thermoplastic resin (B) is not particularly limited, but it is preferably 3-70% by weight of rubber and 97-30% by weight of compound.

In addition, as a compound, an aromatic vinyl compound 40 to 80
% by weight and vinyl cyanide compound and/or unsaturated carboxylic acid alkyl ester compound 60-20% by weight
It is preferable to use a mixture consisting of: In addition, resin (B
Although there is no particular restriction on the particle size of ), it is preferably 0.05 to 5μ, particularly preferably 0.1 to 0.5μ.

The rubber constituting the rubber-reinforced thermoplastic resin (B) is as follows:
Conjugated diene rubbers such as polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, ethylene-propylene rubber such as ethylene-propylene copolymer, ethycine-propylene-nonconjugated die/copolymer, poly Acrylic ester rubbers such as butyl acrylate, butyl acrylate-styrene copolymer, chlorinated polyethylene, ethylene-vinyl acetate copolymer, etc.0 Aromatic bimo-methylstyrene, dimethylstyrene, vinyltoluene, etc. can. Examples of vinyl cyanide compounds include acrylonitrile, methacrylate trile, and the like.

Examples of the unsaturated carboxylic acid alkyl ester compound include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and the like.

Rubber-reinforced thermoneutral resin (methods for producing rice include emulsion polymerization, suspension polymerization, bulk polymerization, solution polymerization, emulsion-suspension polymerization, and bulk-suspension polymerization).

Polycarbonate resin (8) and rubber reinforced thermoplastic resin (B
), but there are no particular restrictions on the composition ratio of polycarbonate resin (10 to 90% by weight), rubber-reinforced thermoplastic resin (B
) It is preferably 90 to 10% by weight.

If the polycarbonate resin (A) is less than 10% by weight, the heat resistance will decrease and the weld strength will also be low, which is not preferable. Moreover, if it exceeds 90% by weight, processability decreases and the appearance further deteriorates, which is not preferable.

Unsaturated carboxylic acid-modified olefin polymer (Q is unsaturated carboxylic acid and/or its anhydride (1), inorganic and/or organometallic compound (11) Lera (1), (11), (m)
It is a polymer consisting of other ethylenically unsaturated monomers (V). There is no particular restriction on the composition ratio of the unsaturated carboxylic acid-modified olefin polymer Q, but the composition ratio of the unsaturated carboxylic acid and/or
or its anhydride (+) O, (j 1-20% by weight,
Inorganic and/or organometallic compound (II) 0.01
~80% by weight, 99.08
~5% by weight and other ethylenically unsaturated monomers 4v)0
-50% by weight is particularly preferred.

Unsaturated carboxylic acids and/or their anhydrides (+) include monocarboxylic acids such as acrylic acid and methacrylic acid;
dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid,
Examples include dicarboxylic anhydrides such as maleic anhydride and itaconic anhydride, with dicarboxylic acids being particularly preferred.

As the inorganic and/or organometallic compound (11),
Examples include metal oxides, carbonates, sulfides, hydroxides, etc. of magnesium, calcium, aluminum titanium, lithium, barium, etc., particularly magnesium oxide, magnesium hydroxide, calcium carbonate, and calcium sulfate.

As olefins, ethylene, propylene, butene
Examples include 1,4 methylpentene-1, with ethylene and propylene being particularly preferred.

In addition, as ethylenically unsaturated compounds, olefins,
Vinyl esters containing 02 to 6 in the saturated carboxylic acid component, acrylic and methacrylic esters and maleic esters containing C1 to 8 in the saturated alcohol component, norodanated vinyls, vinyl ethers, N-vinyl lactams, Examples include carboxylic acid amides.

The unsaturated carboxylic acid-modified olefin polymer (C) can be produced by various methods. For example, olefin (10 or orenzunsen) and other ethylenically unsaturated monomers 4v
) with an unsaturated carboxylic acid and/or its anhydride (1) and an inorganic and/or organometallic compound (
11) by mixing and heating.

There is no particular limit to the amount of the unsaturated carboxylic acid-modified olefin polymer (C), but the total amount of polycarbonate a fat (A) and rubber reinforced thermoplastic resin (B) is 100 parts by weight (#)
Particularly preferred is o, i to 40 parts by weight. 0,
If it is less than 1 part by weight, there is a problem with dispersibility, and if it exceeds 40 parts by weight, there is a tendency for layer peeling to occur in the molded product.

There is no restriction on the mixing order of the polycarbonate resin, rubber-reinforced thermoplastic resin, and unsaturated carboxylic acid-modified olefin polymer; only two of these three components are mixed in advance, and then the other component is added and mixed. Also,
``The three components may be mixed all at once.

Furthermore, the mixing method includes a known mixing method using a Banbury mixer, a single-screw extruder, a twin-screw extruder having a cross-wire block, and the like.

In addition, during mixing, polyolefin resins such as polyethylene, polypropylene, and ethylene-propylene copolymers, as well as known dyes and pigments, stabilizers, plasticizers, antistatic agents,
It is also possible to add ultraviolet absorbers, lubricants, fillers, etc.

The present invention will be specifically explained below using Examples, but the present invention is not limited to these in any way.

A polycarbonate resin, a rubber-reinforced thermoplastic resin, and an unsaturated carboxylic acid-modified olefin polymer were mixed at once based on the blending ratio shown in Table 1 to obtain various compositions.

Table 2 shows the physical properties of the obtained composition.

The rubber-reinforced thermoplastic resin and unsaturated carboxylic acid-modified olefin polymer used were obtained by the following formulation, and the polycarbonate resin was a commercially available product.

O polycarbonate resin (A) Manufactured by Teijin Chemicals! Panrai) L-1250W #0 Rubber reinforced thermoplastic resin (B) -A B S m (fat - Styrene-butadiene copolymer latex (5/95
, 50 parts by weight of gel (90%), 35% by weight of styrene and 15% by weight of acrylonitrile were polymerized based on a known emulsion graft polymerization method in the presence of a redox initiator, and then separately polymerized styrene-acrylonitrile (70/30
) 1:1 with copolymer latex (ABS-1) and 1
:2 (ABS-2).

After salting out and drying, ABS resins (ABS-1 and ABS-2) having graft particles with an average particle size of 0.35 μm were obtained.

-AESIfB resin- Ethylene-propylene-ethylidene norbornene copolymer (45150/'s) 30 parts by weight, styrene 50
Parts by weight and 2 parts by weight of acrylonitrile were polymerized in the presence of benzoyl peroxide based on a known solution polymerization method to obtain a polymer.The obtained polymer was mixed with separately produced styrene-acrylonitrile (70/30). Copolymer and 1=IC
AE8-1) and 1:2 (AES-2) at a ratio of ABS resin (AEtS-1 and ABS-2).
2) was obtained.

0.5 parts by weight of maleic anhydride and 3 parts by weight of magnesium oxide were added to 100 parts by weight of rubonic acid-modified olefin polymer polyethylene powder, and after mixing, 20 parts by weight
The mixture was kneaded for about 3 minutes using two rolls heated to 0°C to obtain a modified olefin polymer sheet. After cooling, it was crushed into 3W square dice.

＼ ) -Weld strength- Two gates with a gate spacing of 100m (each 2.5 x 2,
Inject the molten resin (260℃),
A test piece with a thickness of 3 fins and 150 tIrIn in the vertical and horizontal directions is prepared.

Place the test piece in a jig (height 80Wn, inner diameter 120mm, outer diameter 12mm)
6).

A 1 kg steel ball is dropped onto the center of the test piece in a cold room adjusted to -30°C, and the maximum energy value (vs crn) at which the test piece does not break is determined.

patent applicant Sumitomo Naugatuck Co., Ltd.

Claims (1)

[Scope of Claims] 1) A thermoplastic characterized by blending an unsaturated carboxylic acid-modified olefin polymer (C) into a composition consisting of a polycarbonate resin (4) and a rubber-reinforced thermoplastic resin ω). Resin composition. 2) The rubber-reinforced thermoplastic resin (B) is a resin obtained by polymerizing an aromatic vinyl compound, a vinyl cyanide compound, and/or an unsaturated carboxylic acid alkyl ester compound in the presence of rubber. The thermoplastic resin composition described in . 3) The thermoplastic resin composition according to claim 1, wherein the polycarbonate resin (base) is 10 to 90% by weight and the rubber reinforced thermoplastic resin (B) is 90 to 10% by weight. 4) Composition The thermoplastic resin composition according to claim 1, which contains 100 parts by weight of the unsaturated carboxylic acid-modified olefin polymer (C). 5) A patent claim in which the unsaturated carboxylic acid-modified olefin polymer (C) is a polymer consisting of an unsaturated carboxylic acid and/or its anhydride (1), an organic and/or inorganic metal compound (11), and an olefin polymer. 6) Unsaturated carboxylic acid-modified olefin polymer (Q is unsaturated carboxylic acid and/or its anhydride (1), organic and/or inorganic metal compound (11)) , olefin (i
ff) and another ethylenically unsaturated monomer (V). 7) The composition according to claim 5 or 6, wherein the olefin is one or more compounds selected from ethylene and α-olefin. 8) The composition according to claim 7, wherein the α-olefin is propylene.