JPS61261351A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the titled resin compsn. having excellent impact resistance, mold release characteristics, etc. and suitable for use as a material for automotive parts, by blending a conjugated diene graft copolymer, a composite rubbery polymer, polyethylene wax, etc. with an arom. polycarbonate resin. CONSTITUTION:40-75wt% arom. polycarbonate resin (A), 55-15wt% mixture (B) of 100-10pts.wt. conjugated diene rubber/arom. vinyl compd./vinyl cyanide copolymer and 0-90pts.wt. arom, vinyl compd./vinyl cyanide copolymer, 1-15wt% composite rubbery polymer (C) selected from among MBS resin, acrylate ester copolymers and acrylate ester core/shell graft copolymer and 0.05-2pts.wt. (per 100pts.wt. of the combined quantity of components A, B and C) polyethylene wax (D) having an MW of 1,000-5,000 are mixed together to obtain the desired thermophastic resin compsn.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a thermoplastic resin composition that has excellent various mechanical properties, particularly impact resistance at low temperatures, and exhibits good mold release properties during molding. It provides a molding material suitable for automobile parts and the like.

[Conventional technology and its problems]

As is well known, aromatic polycarbonate resins are tough, have excellent impact resistance, electrical properties, and good dimensional stability, and are therefore widely used as useful engineering plastics. However, the range of its application is currently limited due to drawbacks such as high melt viscosity, poor moldability, and thickness dependence of impact resistance. For example, in the automobile industry, there is a strong demand for resins that have impact resistance at low temperatures due to safety needs, and aromatic polycarbonate resins are attracting attention for this reason. Due to its high viscosity, it is difficult to fill molds for large molded products such as automobile parts, resulting in short molds and crepe patterns, making it difficult to obtain good molded products.

Therefore, if the molding temperature is raised to a level that makes filling easy, problems such as thermal decomposition will occur, and p-propylphenol, bromophenol, pwtert-
Preferred are butylphenol and p-long chain alkyl substituted phenols. Typical aromatic polycarbonate resins include polycarbonates whose main raw material is bis(4-hydroxyphenyl)alkane dihydroxy compounds, particularly bisphenol A, which can be obtained by using two or more aromatic dihydroxy compounds in combination. Branched polycarbonate obtained by using a small amount of a polycarbonate copolymer and a trivalent phenol compound can also be mentioned. Aromatic polycarbonate resins may be used as a mixture of two or more types.

The conjugated diene rubber-aromatic vinyl-vinyl cyanide graft copolymer, which is one of the B components of the present invention, is usually A
It is known as BS resin, and is a graft polymer obtained by graft polymerizing an aromatic vinyl compound and vinyl cyanide as essential components to a rubbery polymer containing a conjugated diene as an essential component. The composition ratio of the conjugated diene rubber and the graft polymerization compound in the graft polymer is not particularly limited, but it is preferably 5 to 70 wt% of the conjugated diene rubber and 95 to 30 wt% of the graft polymerization compound. Further, the composition ratio of aromatic vinyl and cyanide vinyl in the graft polymerization compound is not particularly limited, but aromatic vinyl 50-80 wt% and cyanide vinyl 50-80 wt%.
Preferably, it is 20i1t%.

There is no particular restriction on the composition ratio of aromatic vinyl and vinyl cyanide in the aromatic vinyl-vinyl cyanide copolymer, but it may be 55 to 85 wt% of aromatic vinyl and 45 to 15 wt% of vinyl cyanide. Preferably, the viscosity is 0.60 to 0.60 at 30°C in dimethylformamide.
A range of 1.50 is preferred.

Examples of the conjugated diene rubber in the ABS resin include polybutadiene, butadiene-styrene copolymers, butadiene-acrylonitrile copolymers, and butadiene-acrylic acid ester copolymers. In addition, examples of aromatic vinyl include styrene,
Examples include halogenated styrene, vinyltoluene, α-methylstyrene, vinylnaphthalene, etc. Styrene is particularly good, and vinyl cyanide includes acrylonitrile,
Examples include methacrylonitrile and α-halogenated acrylonitrile, with acrylonitrile being particularly preferred. In addition,
Products in which aromatic vinyl or vinyl cyanide is partially replaced with other vinyl compounds, such as (meth)acrylic esters, vinyl acetate, vinyl chloride, etc., especially (meth)acrylic esters (= MABS resin) is also preferable.

The MBS resin of C and (a) used in the present invention is a butadiene-based rubbery polymer such as polybutadiene or butadiene-styrene copolymer, and one or more of methacrylic acid ester, aromatic monovinyl compound, and vinyl cyanide compound. It is obtained by graft polymerization using methods such as bulk polymerization, suspension polymerization, bulk suspension polymerization, solution polymerization, or emulsion polymerization, especially emulsion polymerization. Here, the amount of butadiene polymer used is 10 to 85% by weight, preferably 30 to 7% by weight.
When the butadiene-based polymer is a copolymer, it is preferable to use a copolymer in which the butadiene component is 50% by weight or more. Usage amount is 10% by weight
If it is less than 85% by weight, the resulting composition will have low impact resistance.
Exceeding the above range is undesirable because the moldability of the composition deteriorates. In addition, as methacrylic ester, carbon number 1 to
Alkyl esters of No. 4, particularly methyl methacrylate, are preferred. Examples of the aromatic monovinyl compound include styrene, halogenated styrene, vinyltoluene, α-methylstyrene, and vinylnaphthalene, with styrene being particularly preferred. Examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile, and α-halogenated acrylonitrile, with acrylonitrile being particularly preferred.

The acrylic ester copolymer of C and (b) used in the present invention is an acrylic ester having a saturated or unsaturated linear or branched aliphatic hydrocarbon group having 1 to 5 carbon atoms; It is a copolymer with a methacrylic acid ester having 1 to 5 saturated or unsaturated linear or branched aliphatic hydrocarbon groups.

Here, (ii) the acrylic ester having a saturated or unsaturated linear or branched aliphatic hydrocarbon group having 1 to 5 carbon atoms is preferably methyl acrylate, ethyl acrylate, isobutyl acrylate, diacrylic acid 1 , 4-butanediol, n-butyl acrylate, 1,3 diacrylate
-butylene is exemplified, and (1) methacrylic acid esters having a saturated or unsaturated linear or branched aliphatic hydrocarbon group having 1 to 5 carbon atoms are preferably methyl methacrylate, ethyl methacrylate, or methacrylic acid. isobutyl,
Examples include 1,3-butylene methacrylate and n-butyl methacrylate. In the present invention, the acrylic ester moiety in the acrylic ester copolymer is about 50 to 8
A range of 5 wt% is preferred, such as a 3:2 weight ratio of n-butyl acrylate to methyl methacrylate. As such an acrylic ester copolymer, one commercially available from Rohm & Haas under the trade name "Paraloid KM330 J" is suitably used.

The C, (c) acrylic acid ester based core-shell graft copolymer used in the present invention is a conjugated diene type double ester represented by an alkyl ester of acrylic acid having 2 to 12 carbon atoms in the alkyl group and butadiene. A core consisting of a crosslinked rubber copolymer obtained by copolymerizing a polyfunctional polymerizable monomer with a bond as an essential component and adding a small amount of a crosslinking agent,
One or more vinyl compounds are an essential component,
Refers to a core-shell graft copolymer formed by adding a small amount of cross-linking agent and graft-polymerizing it to form a shell consisting of a resin layer. ) is 50 to 80% by weight, and the shell is 50 to 20% by weight.

As the acrylic acid alkyl ester in which the alkyl group has 2 to 12 carbon atoms to be used to form the crosslinked rubber copolymer core, n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferred. Further, as the conjugated diene, in addition to the above-mentioned butadiene, 1-methyl-2-vinyl-4,6-hebutadien-1-ol, 7-methyl-
Examples include 3-methylene-1,6-octadiene and 1,3.7-octatriene.

Furthermore, the crosslinking agent used should be selected to be one that copolymerizes well with the mixed monomers in each polymerization step. For example, aromatic polyfunctional vinyl compounds such as divinylbenzene and divinyltoluene, and ethylene glycol Dimethacrylates such as methacrylate, diethylene glycol dimethacrylate, and triethylene glycol dimethacrylate, and diacrylates such as engineered ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, and 1,3-butanediol diacrylate are preferred.

In addition, when copolymerizing an alkyl ester of acrylic acid with a polyfunctional polymerizable monomer having a conjugated diene type double bond, an aromatic vinyl compound such as styrene or methyl methacrylate may be used as desired. A short-functional polymerizable monomer appropriately selected from methacrylic acid esters, vinyl cyanide compounds represented by acrylonitrile, vinyl ether compounds represented by methyl vinyl ether, and halogenated vinyl compounds represented by vinyl chloride,
In particular, a methacrylic acid ester represented by methyl methacrylate can also be used as a part of an acrylic acid alkyl ester in which the alkyl group has 2 to 12 carbon atoms.

Next, the vinyl compounds used for graft polymerization to the crosslinked rubber copolymer (core) include methacrylic acid esters represented by methyl methacrylate, aromatic vinyl compounds represented by styrene, and acrylonitrile. Examples include polymerizable monomers selected from the group consisting of vinyl cyanide compounds and halogenated vinyl compounds represented by vinyl chloride, and two or more of these may be used as a mixture. Furthermore, the above-mentioned crosslinking agent may be used in combination during graft polymerization.

A typical production example of such an acrylic ester-based core-shell graft copolymer is an alkyl esternyl acrylate having an alkyl group of 2 to 12 carbon atoms, 70 to 9
5 parts by weight, butadiene 30-5 parts by weight, and crosslinking agent o
, contains 50 to 75 parts by weight of a crosslinked rubber copolymer obtained by emulsion polymerization of mixed monomers consisting of oi to 3 parts by weight, especially 0.05 to 1.5 parts by weight, and has an average particle size of 0.05 to 1.5 parts by weight. 0
．． A flocculant, such as hydrochloric acid, is added to the latex in the range of 1-
Average particle size obtained by adding mineral acids such as sulfuric acid: 0.1
0.01 to 2.0 of the crosslinking agent is added to the aggregated particles of 2 to 0.3
Monomer component consisting of 10 to 90% by weight of styrene and 90 to 10% by weight of methyl methacrylate 50
~25 parts by weight was first divided into a mixture of styrene-based methyl methacrylate containing a cross-linking agent and methyl methacrylate containing a cross-linking agent, the former was added and polymerized to the agglomerated rubber latex, and then the latter was added and polymerized. Method: 40 to 95 parts by weight of an acrylic acid alkyl ester having an alkyl group having 2 to 12 carbon atoms, 40 to 5 parts by weight of butadiene,
0 to 30 parts by weight of methyl methacrylate and crosslinking agent 0.
Crosslinked rubber copolymer obtained by emulsion polymerization of mixed monomers consisting of 01 to 3 parts by weight, especially 0.05 to 1.5 parts by weight
Average particle diameter obtained by adding a flocculant, for example, a mineral acid such as hydrochloric acid or sulfuric acid, to latex containing 50 to 80 parts by weight 0
．． First, 10 to 50% by weight of acrylonitrile and 90 to 50% by weight of styrene or methyl methacrylate are added to 12 to 0.5% of agglomerated particles, and 0.01 to 0.5% of a crosslinking agent is added to the aggregated particles.
After adding and polymerizing 45 to 10 parts by weight of a monomer containing 3.0 parts by weight, a methacrylic acid alkyl ester monomer 5 having an alkyl group having 1 to 4 carbon atoms and containing 0.01 to 3.0 parts by weight of a crosslinking agent. A method of further adding and polymerizing up to 25 parts by weight is mentioned.

These graft polymerizations may be carried out in one stage, or may be carried out in multiple stages by changing the components of the graft component monomer in multiple stages. Although a typical production example is shown using an emulsion polymerization method, the desired acrylic acid ester core-shell graft copolymer can be produced by other known polymerization methods as well. is unpaid.

As such an acrylic ester-based core-shell graft copolymer, Isora Kagaku Kogyo has released the product name rHIA-15.
Resins commercially available as HIA-28J, rHIA-28J, or HIA-30J are preferably used.

In the thermoplastic resin composition of the present invention, the blending ratio of components A, B, and C is 40 to 75% by weight for component A and 55 to 75% by weight for component B.
15% by weight, and 1 to 15% by weight of component C.

If the A component is less than 40% by weight, the heat resistance will not reach the level required for engineering plastics, and the dimensional stability will be poor, and if the B component is less than 15% by weight, the effects of improving moldability, impact resistance, etc. will be insufficient. If it exceeds 55% by weight, the heat resistance will be insufficient, and if the C component exceeds 1% by weight,
If it is less than 15% by weight, no improvement in impact resistance will be achieved, and if it exceeds 15% by weight, it will cause poor heat resistance.

In the present invention, D, an average molecular weight of 1,000 to 5.000 is added to 100 parts by weight of the resin composition consisting of the above aromatic polycarbonate resin A, ABS resin B, and composite rubbery polymer C.
0.05 to 2 parts by weight, preferably 0.2 to 1 part by weight, especially 0.1 to 2 parts by weight of polyethylene wax, which has the effect of reducing mold release resistance by 10 to 80%. have

In addition to polyethylene wax, typical long-chain hydrocarbons used as mold release agents include liquid paraffin, microwax, and the like. The present inventors blended various long-chain hydrocarbons into compositions of aromatic polycarbonate resin, ABS resin, and composite rubber copolymer and examined their mold release properties, and found that the mold release properties of the composition of the present invention were We have found that molecular weight is an extremely important factor in increasing the properties of It is effective as a mold release agent even if the average molecular weight is less than 1,000 or 5.00.
Even if it is higher than 0, it is insufficient. Such polyethylene waxes suitable for the present invention include “Hoechstwax PA
520J (manufactured by Hoechst Chemical ■), "Mitsui Hiwax 410P J" and "Mitsui Hiwax 320P" (
Examples include Mitsui Petrochemical (manufactured by Mitsui Petrochemical Corporation).

The thermoplastic resin composite acid of the present invention as described above includes:
Various additives such as stabilizers, pigments, dyes, flame retardants, and lubricants, reinforcing materials such as inorganic or organic fiber substances, and various fillers such as glass beads can be added as desired.
Furthermore, other resin components may be blended within a range that does not impair the characteristics of the present invention. For example, polycarbonate from bisphenol A or tetrabromobisphenol A.
Examples include adding oligomers to improve moldability, flame retardancy, and surface properties, and adding heat-resistant polyesters such as polyester carbonate and polyarylate (for example, product name: U Polymer, Unitika ■) to improve heat resistance. .

In preparing the thermoplastic resin composition of the present invention,
Any conventionally known method may be used, and methods of kneading using an extruder, Banbury mixer, rolls, etc. may be selected as appropriate.

〔Example〕

Hereinafter, it will be explained by examples and comparative examples, but "%"
and "molecular weight" are based on weight unless otherwise specified.

Examples 1 to 5 and Comparative Examples 1 to 4 Aromatic polycarbonate resin made from bisphenol A (manufactured by Mitsubishi Gas Chemical, trade name Newpiron S-20)
00, molecular weight 25,000, written as S-2000),
ABS resin, which is a mixture of conjugated diene rubber-aromatic vinyl-vinyl cyanide graft copolymer and aromatic vinyl-vinyl cyanide copolymer (manufactured by Japan Synthetic Rubber, product name: JSRABS op4, DP-35) ), composite rubber polymers include ABS resin (manufactured by Japan Synthetic Rubber ■, product name: JSR Mon BS 67, written as MBS-67), acrylic ester copolymer (manufactured by Rohm & Haas ■, product name; Paraloid KM 330, KM-330), acrylic acid ester based core-shell graft copolymer (manufactured by Isora Kagaku ■, product name: HIA-15 and old)
28, referred to as HIA-15 and HIA-28, respectively), polyethylene wax with a molecular weight of 1.000 to 4.000 (manufactured by Mitsui Petrochemicals, trade name: Mitsui Hiwax 2102, molecular weight 2.000.310P, molecular weight 3゜0
00 and 410P molecular weight 4,000, respectively ■, ■, ■
), liquid paraffin (molecular weight 230-280, ■
), natural paraffin (molecular weight 250-450, ■
) and low density polyethylene (molecular weight 24°000
, 0.5 part of a lubricant (denoted as ■) was added and mixed.

The resulting mixture was L/D. The mixture was supplied to a No. 25 4On+ vented extruder and melted and kneaded at a cylinder temperature of 240°C to form pellets. This pellet is dried in a hot air dryer at 110℃.
After drying for more than 5 hours, injection molding (Sumitomo Nestal Cycap, in-line screw complete molding machine) was carried out at a molding temperature of 260°C to form a piece of 70mm long x 70mm wide x 60mm deep with a wall thickness of 3fi. A box-shaped molded product was molded, and the mold internal pressure and mold release resistance were measured using a sensor connected to the ejector pin.

The test results are shown in Table 1.

Table 1 *1, Unit: kg/crl, *2, Unit: k.

Examples 6 to 10 Using pellets obtained in the same manner as Examples 1 to 5,
A specimen for physical property testing was prepared and the physical properties were measured. The results are shown in Table 3.

Table 2 Note) YF: Flexural Modulus [Function and Effects of the Invention] As is clear from the above detailed description, Examples, and Comparative Examples, the composition of the present invention contains a polyethylene wax having a specific molecular weight range. It is clear that its use results in a composition with significantly superior mold release properties compared to those outside the scope of the present invention. Therefore, the present invention can provide an extremely well-balanced and practical resin composition whose molding process can be easily automated.

Claims (1)

[Claims] A, aromatic polycarbonate resin 40-75% by weight, B
, a mixture of conjugated diene rubber-aromatic vinyl-vinyl cyanide graft copolymer 100-10 wt% and aromatic vinyl-vinyl cyanide copolymer 0-90 wt% 55-55 wt%
15% by weight, and C, one or more selected from the group consisting of (a) MBS resin, (b) acrylic ester copolymer, and (c) acrylic ester core-shell graft copolymer. Composite rubbery polymers 1 to 15
To 100 parts by weight of a resin composition consisting of
A thermoplastic resin composition containing 5 to 2 parts by weight.