JPS61261349A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the titled 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, a carboxylate ester, 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 graft 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 0.01-2pts.wt. (per 100pts.wt. of the combined quantity of components A, B and C) (partial) ester (D) derived from a 12-30C aliph. satd. monocarboxylic acid and a 20C or lower aliph. alcohol are mixed together to obtain the titled 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 forming temperature is raised to a level that makes filling easier,
Problems such as thermal decomposition occur, making it difficult to obtain molded products with good appearance and stable physical properties. On the other hand, there is a method of lowering the average molecular weight of polycarbonate resin to improve moldability.
There are drawbacks such as reduced impact resistance and difficulty in releasing from the mold.

In order to improve these drawbacks, proposals have been made to blend various resins into aromatic polycarbonate resins. For example, in Japanese Patent Publication No. 38-15225, ABS resin,
Japanese Patent Publication No. 39-71 shows MBS resin, Japanese Patent Publication No. 42-
Publication No. 11496 teaches incorporating MABS resin. However, polycarbonate resin has A
When BS resin or MABS resin is blended, the thickness dependence of impact resistance and moldability are somewhat improved, but the impact resistance at low temperatures is low, and the improvement is not necessarily sufficient to meet recent market demands. I can't say that. Furthermore, when MBS resin is blended with polycarbonate resin, the improvement in moldability is insufficient and it is difficult to mold large-sized molded products.

Furthermore, Japanese Patent Application Laid-Open No. 58-59258 discloses that aromatic polycarbonate resin is blended with ABS resin and MBS resin, and in Japanese Patent Application No. 59-19427, the present inventors disclose that aromatic polycarbonate resin is blended with ABS resin. It is proposed that a resin and an acrylic acid ester based core-shell graft copolymer be blended. Although these compositions have excellent moldability and impact resistance and are useful, they do not release well from the mold during injection molding, resulting in the molded product being deformed or falling out of the mold. There are disadvantages in that it takes time to take out the mold, and it is difficult to automate injection molding.

[Means for solving problems]

The present inventors have conducted intensive studies to improve the mold release properties of resin compositions made of polycarbonate resins, ABS resins, and composite rubber polymers. , fatty acid esters such as stearyl alcohol, and fatty acid amides such as stearyl amide tend to decompose aromatic polycarbonate resins, whereas aliphatic saturated monocarboxylic acids with 12 to 30 carbon atoms and fatty acid amides with 30 carbon atoms The present invention was completed based on the discovery that when the following esters or partial esters with aliphatic monohydric or polyhydric alcohols are blended, mold releasability is greatly improved, and the appearance and physical properties of molded products are also good. .

That is, the present invention comprises A, 40 to 75% by weight of aromatic polycarbonate resin, B, conjugated diene rubber-aromatic vinyl-vinyl cyanide graft copolymer 100 to 10-
1% and aromatic vinyl-vinyl cyanide copolymer θ~90
Mixture with waste t% 55-15% by weight, C, (a) MB
S resin, (b) acrylic ester copolymer and (C)
Resin composition consisting of 1 to 15% by weight of one or more composite rubbery polymers selected from the group consisting of acrylic acid ester-based core-shell graft copolymers 10
0 parts by weight, D, 0.01 to 2 esters or partial esters of aliphatic saturated monohydric carboxylic acid having 12 to 30 carbon atoms and aliphatic monohydric or polyhydric alcohol having 30 or less carbon atoms;
It is a thermoplastic resin composition consisting of parts by weight.

The present invention will be explained in detail below.

A, aromatic polycarbonate resin of the present invention is an optionally branched thermoplastic polycarbonate polymer made by reacting aromatic dihydroxy or a small amount of a polyhydroxy compound with a diester of phosgene or carbonic acid. An example of an aromatic dihydroxy compound is
2.2-bis(4-hydroxyphenyl)propane, bisphenol A), tetramethylbisphenol A1 tetrabromobisphenol A1 bis(4-hydroxyphenyl> -p-diisopropylbenzene, hydroquinone, resorcinol, 4.4-dihydroxydiphenyl, etc.) and bisphenol A is particularly preferred.In addition, to obtain a branched aromatic polycarbonate resin,
Phloroglucin, 4,6-dimethyl-2,4,6-tri(4-hydroxyphenyl)hebutene-2,4,6
-Simethyl-2.4.6- )li(4-hydroxyphenyl)hebutane, 2,6-cymethyl-2.4.6-
) li (4-hydroxyphenyl)hebutene-3,
4,6-dimethyl-2.4.6-toU (4-hydroxyphenyl)hebutane, 1.3.5-tri(4
-hydroxyphenyl)benzene, 1,1.1-tri
Polyhydroxy compounds exemplified by (4-hydroxyphenyl)ethane, 3,3-bis(4-hydroxyaryl)oxindole (= isatin bisphenol), 5-chloroisatin, 5,7-dichloroisatin, 5-bromiisatin A part of the dihydroxy compound, for example 0.1 to 2 mol %, is replaced with a polyhydroxy compound. Further, the monovalent aromatic hydroxy compound used to adjust the molecular weight is preferably t- and p-methylphenol, t- and p-propylphenol, p-bromophenol, pwter-butylphenol, p-long-chain alkyl-substituted phenol, etc. . 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 vinyl cyanide in the graft polymerization compound is not particularly limited, but aromatic vinyl 50-80% 1t% and vinyl cyanide 50-80%.
Preferably, it is 20 wt%.

There is no particular restriction on the composition ratio of aromatic vinyl and vinyl cyanide in the aromatic vinyl-vinyl cyanide copolymer, but it should be 55 to 85 wt% of aromatic vinyl and 45 to 15% of vinyl cyanide and 1 t% of vinyl cyanide. It is preferable that the viscosity is 0.60 to 1.0 at 30°C in dimethylformamide.
A range of 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, aromatic hinyl includes 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 (bl) 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, diacrylic acid 1.3
-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 5-1% is good, for example 1. Examples include those with a weight ratio of n-butyl acrylate to methyl methacrylate of 3:2. 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 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 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, monomers, 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.

Typical production examples of such acrylic acid ester-based core-shell graft copolymers include acrylic acid alkyl esters having an alkyl group of 2 to 12 carbon atoms, 70 to 95
parts by weight, butadiene 30-5 parts by weight, 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
Contains 50 to 75 parts by weight, and has an average particle diameter of O, OS to 0.
Average particle diameter obtained by adding a flocculant, such as a mineral acid such as hydrochloric acid or sulfuric acid, to latex in the range of 1 tea 0
．． Add 0.0 of a crosslinking agent to aggregated particles of 12 to 0.3 ta.
A mixture of 50 to 25 parts by weight of a monomer component consisting of 1 to 2.0 parts by weight of 10 to 90 parts by weight of styrene and 90 to IO of methyl methacrylate with methyl methacrylate containing styrene as a main component and containing a crosslinking agent. and methyl methacrylate containing a crosslinking agent, and the former is added and polymerized to the above-mentioned aggregated rubber latex, and then the latter is added and polymerized; 40 to 95 parts by weight of an acrylic acid alkyl ester having an alkyl group having 2 to 12 carbon atoms. , butadiene 40~
Crosslinked rubber obtained by emulsion polymerization of a mixed monomer consisting of 5 parts by weight, 0 to 30 parts by weight of methyl methacrylate) and 0.01 to 3 parts by weight, particularly 0.05 to 1.5 parts by weight of a crosslinking agent. Agglomerated particles having an average particle diameter of 0.12 to 0.5-0.1 mm are obtained by adding a flocculant, for example, a mineral acid such as hydrochloric acid or sulfuric acid, to a latex containing 50-80 parts by weight of the copolymer, and then acrylonitrile (10-10 mm) is first added to the agglomerated particles having an average particle diameter of 0.12-0.5 mm. 50% by weight and 90-50% by weight of styrene or methyl methacrylate and no crosslinking agent.
．． After addition polymerization of 45 to 10 parts by weight of a monomer containing 01 to 3.0 parts by weight, a methacrylic acid alkyl ester monomer 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 may be mentioned in which 5 to 25 parts by weight of the compound is further added and polymerized.

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.

Such an acrylic ester based core-shell graft copolymer is available from Isora Kagaku Kogyo under the trade name rHIA-15.
Resins commercially available as J, rHIA-28J or [HIA-304 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 aliphatic saturated monocarboxylic acid having 12 to 30 carbon atoms, and 30 carbon atoms are 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. Esters or partial esters with the following aliphatic monohydric or polyhydric alcohols from 0.01 to
2 parts by weight, preferably 0.05 to 2 parts by weight, especially 0.1
~2 parts by weight is blended, and the mold release resistance is 10~5
It has the effect of decreasing by 0%.

Most of the D components of the present invention are known as ester waxes contained in natural products such as plants, animals, insects, and minerals, and are obtained from compounds that are liquid or have a low melting point at room temperature, or mixtures thereof. Component D is easily soluble in the solvent of aromatic polycarbonate resin, such as methylene chloride, ethylene glycol, etc., so it can be used as a highly concentrated masterbatch powder by making a mixed solution of both and removing the solvent, etc. stabilizers, dyes/pigments, flame retardants, which are additives for the thermoplastic resin composition of the present invention;
It is prepared by mixing it with an inorganic filler such as glass fiber, or by simply adding it to raw material pellets and mixing, and usually pelletizes it.

The thermoplastic resin composition of the present invention as described above may contain various additives such as stabilizers, pigments, dyes, flame retardants, and lubricants, reinforcing materials such as inorganic or organic fiber substances, glass beads, etc., as desired. Various fillers may be blended, and other resin components may also be blended within a range that does not impair the characteristics of the present invention. For example, polycarbonate oligomers made from bisphenol A or tetrabromobisphenol A can be used to improve moldability, flame retardancy, and surface properties, and heat-resistant polyesters such as polyester carbonates and polyarylates (e.g., trade names: U Polymer, Unitika ■) For improving heat resistance, it is possible to incorporate

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 4 and Comparative Examples-1 to 5 Aromatic polycarbonate resin made from bisphenol A (manufactured by Mitsubishi Gas Chemical, trade name Newpiron S-20)
00, molecular weight 25,000, hereinafter referred to 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 ( Made of Japanese synthetic rubber,
Product name: JSRABS DP-35, hereinafter DP-3
5), ABS resin (manufactured by Japan Synthetic Rubber ■, product name: JSRMBS 'a7, hereinafter referred to as MBS-67), an acrylic acid ester core-shell graft copolymer (hereinafter referred to as MBS-67), Manufactured by layer chemistry ■, product name:
HrA-15 and former A-28, hereinafter referred to as HIA-1 respectively
5, former A-28), a mixture containing butyl stearate and myricyl palmitate as main components (beeswax, hereinafter referred to as ■), and a mixture containing cetyl palmitate as main components (NOF ■ (manufactured by Hoechst Co., Ltd., trade name: Nispalm acetate, hereinafter referred to as ■), ethylene glycol ester of montanic acid (manufactured by Hoechst, trade name: Hoechstwax E, hereinafter referred to as ■), and butyl stearate (hereinafter referred to as ■),
For comparison, stearic acid (hereinafter referred to as ■),
A mixture containing stearyl alcohol as the main component (hereinafter referred to as ■), a lubricant of stearylamide (hereinafter referred to as ■), laurylamide (hereinafter referred to as ■), and ethylene bisstearamide (hereinafter referred to as ■) at 0.5 part was added and mixed.

The obtained mixture was supplied to a 40 m vented extruder with L/D 25, and melt-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 (
Inline screw complete molding machine manufactured by Meiki Seisakusho, 5J
-45B), the appearance of the test piece was observed, and the thermal stability was investigated.

The test results are shown in Table 1.

Table 1 Examples-5 to 10 and Comparative Examples-6 to 11 Examples-1 to
The same resin components and acrylic acid ester copolymer (manufactured by Rohm & Haas) as used in 4 and Comparative Examples 1 to 5 were
Product name: Paraloid KM330 (hereinafter referred to as KM-330), lubricant (■, ■, ■), liquid paraffin (hereinafter referred to as [phase]) and polyethylene wax (manufactured by Mitsui Petrochemical ■, product). Name: Mitsui Hiwax 22
Add and mix 0.5 part of a lubricant of 35H (hereinafter referred to as ■),
Similarly, after extrusion, pelletization, drying, injection molding (resident nester) at a molding temperature of 260℃,
70 mm vertically using an in-line screw molding machine)
A box-shaped molded product of mm x width 7 ON x depth 60 mm and wall thickness of 3 fl is molded, and a sensor connected to the ejecting pin measures the internal pressure of the mold.
The mold release resistance was measured.

The test results are shown in Table 2.

2nd table ratio 1, unit kg/cd, *2, unit kg Examples-11 to 14 Using the pellets obtained in the same manner as Examples-5 to 10, test pieces for physical property tests were prepared and physical properties were measured. Did. The results are shown in Table 3.

[Operation and effects of the invention]

As is clear from the above detailed description, Examples, and Comparative Examples, the composition of the present invention has higher thermal stability than a composition containing the same resin component and a lubricant other than that of the present invention. It has excellent physical properties and mold releasability compared to additive-free compositions, is significantly superior in mold releasability, is easy to automate the molding process, and is extremely well-balanced. It can be seen that this is a practical product.

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
D, an ester or partial ester of an aliphatic saturated monohydric carboxylic acid having 12 to 30 carbon atoms and an aliphatic monohydric or polyhydric alcohol having 30 or less carbon atoms is added to 100 parts by weight of a resin composition consisting of 0.0% by weight. A thermoplastic resin composition containing 01 to 2 parts by weight.