JPS6195062A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide a good balanced composition of practical value, outstanding in mechanical properties especially low-temperature impact resistance with good appearance and molding processability, comprising aromatic polycarbonate resin, ABS resin, and specific ethylene-alpha-olefin copolymer. CONSTITUTION:The objective composition comprising (A) 40-80 pts. by wt. of an aromatic polycarbonate resin, (B) 20-60pts. by wt. of a blend of 1) 100-10wt% of conjugated diene rubber/aromatic vinyl/vinyl cyanide graft copolymer and 2) 0-90wt% of aromatic vinyl/vinyl cyanide copolymer and (C) 1-15 pts. by wt. of another copolymer with a melt index <=20g/10min a density 0.860-0.910g/cm<3>, a maximum peak temperature >=100 deg.C (measured by differential scanning calorimetry: DSC) and a boiling n-hexane insoluble >=10wt%, prepared by copolymerization between ethylene and alpha-olefin (of 3-12C) in the presence of Mg and Ti-contg. solid catalyst and organoaluminum catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention is applicable to various machines which are made by blending a novel ethylene/α-olefin copolymer into a composition of an aromatic polycarbonate resin and an ABS resin. The present invention relates to a thermoplastic resin composition that has excellent physical properties, particularly impact resistance at low temperatures, and exhibits good appearance and moldability.

[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, there are disadvantages such as high melt viscosity and poor moldability, thickness dependence of impact resistance, and problems with chemical resistance such as cranking when it comes into contact with aromatic solvents or gasoline. As a result, the scope of its application is actually limited. 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 occur, making it difficult to obtain a molded product with good appearance and stable physical properties. On the other hand, there is a method of improving the moldability by lowering the average molecular weight of the polycarbonate resin, but this method has drawbacks such as a decrease in impact resistance and difficulty in releasing the resin 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. 3B-15225, ABS resin,
Japanese Patent Publication No. 39-71 shows MBS resin, Japanese Patent Publication No. 42-
Publication No. 11496 teaches blending MABS resin. However, when ABS resin or MABS resin is blended with polycarbonate resin, although the thickness dependence of impact resistance and moldability are improved somewhat,
Impact resistance at low temperatures is low, and improvements cannot necessarily be said to be sufficient to meet recent market demands.Furthermore, when MBS resin is blended with polycarbonate resin, the improvement in moldability is insufficient. This makes it difficult to mold large molded products.

[Means for solving problems]

The present invention improves the moldability of polycarbonate resin and its impact resistance and impact resistance at low temperatures by further blending a novel ethylene/α-olefin copolymer into a composition of polycarbonate resin and ABS resin. The present inventors have discovered a thermoplastic resin composition that has improved thickness dependence and is well-balanced in various properties such as mechanical strength, heat resistance, and appearance. 9' That is, the present invention comprises A, 40 to 80 parts by weight of aromatic polycarbonate resin, B, 100 to 10% lt% of conjugated diene rubber-aromatic vinyl-vinyl cyanide graft copolymer and aromatic vinyl- Mixture with vinyl cyanide copolymer O~90 wt% 20
~60 parts by weight and C0 In the presence of a catalyst having the properties (1) to (4) below and consisting of a solid catalyst component containing at least magnesium and titanium and an organoaluminum compound, ethylene and α-olefin are co-coated. A thermoplastic resin composition containing 1 to 15 parts by weight of a polymerized copolymer and having excellent chemical resistance and impact resistance.

■Melt index 20g/10min or less■Density 0.860~0.910 g/cd■
Temperature of the maximum peak measured by differential scanning calorimetry (DSC): 100° C. or higher Boiling n-hexane insoluble content: 10-t% or higher The present invention will be described 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 A,
Tetrabromobisphenol A1 bis(4-hydroxyphenyl> -p-diisopropylbenzene, hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, etc., with bisphenol A being particularly preferred. Also, to obtain a branched aromatic polycarbonate resin is phloroglucin, 4.6-cymethyl-2.4.6-
) li (4-hydroxyphenyl)hebutene-2,4
, 6-dimethyl-2.4.6-)li(4-hydroxyphenyl)hebutane, 2.6-dimethyl-2.4.
6-tri(4-hydroxyphenyl)hebutene-3,
4,6-dimethy7L/-2,4,6-) IJ (4
-Hydroxyphenyl)hebutane, 1.3.5-1-
Li (4-hydroxyphenyl)benzene, 1,1.1
- polyhydroxy compounds such as tri(4-hydroxyphenyl)ethane, and 3゜3-bis(4-
Hydroxyaryl)oxindole (=isatin bisphenol), 5-chloroisatin, 5,7-dichloroisatin, 5-bromiisatin, etc. are substituted with a polyhydroxy compound for a portion of the dihydroxy compound, for example 0.1 to 2 mol%.

Furthermore, aromatic monohydroxy compounds suitable for adjusting the molecular weight include I- and p-methylphenol, ■- and p-propylphenol, p-bromophenol, p
Preferred are -tert-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, especially bisphenol A, and
Also included are polycarbonate copolymers obtained by using a combination of more than one type of aromatic dihydroxy compound, and branched polycarbonates obtained by using a small amount of a trivalent phenol compound. 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 a rubbery polymer containing a conjugated diene as an essential component, and an aromatic vinyl compound and vinyl cyanide. This is a graft polymer obtained by graft polymerization using the following as an essential component. The composition ratio of the conjugated diene rubber and the compound for graft polymerization 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 compound for graft polymerization. Further, the composition ratio of aromatic vinyl and vinyl cyanide in the compound for graft polymerization is not particularly limited, but aromatic vinyl 50 to 80 wt% and vinyl cyanide 5
It is preferably 0 to 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 is 55 to 85 wt% of aromatic vinyl and 45 to 15-t% of vinyl cyanide. It is preferable that the intrinsic viscosity is 0.60 to 1 at 30°C in dimethylformamide.
．． A range of 50 is preferred.

Examples of the conjugated diene rubber in the above graft copolymer or copolymer include polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, and butadiene-acrylic acid ester copolymer. Examples include rubber-like polymers. Further, examples of the aromatic vinyl include styrene, halogenated styrene, vinyltoluene, α-methylstyrene, vinylnaphthalene, etc., and styrene is particularly good.
Examples of vinyl cyanide include acrylonitrile, methacrylonitrile, and α-halogenated acrylonitrile, with acrylonitrile being particularly good. Those substituted with acrylic esters, vinyl acetate, vinyl chloride, etc., especially (meth)acrylic esters, are also preferable.

The C, ethylene/α-olefin copolymer used in the present invention is obtained by copolymerizing ethylene and α-olefin in the presence of a catalyst consisting of a solid catalyst component containing at least magnesium and titanium and an organoaluminum compound. It has the following properties (1) to (4).

0M I: 20g/10min or less, preferably 0
．． 05-5g/min, especially 0.2-4g/win
.

■Density: 0.860-0.910 g/c
ni.

■Temperature of the maximum peak measured by differential scanning calorimetry (DSC): 100°C or more, preferably 110°C to 124°C
.

(2) Boiling n-hexane insoluble matter: 10% 1t% or more, preferably 20-tχ to 94-tχ.

These conditions (1) to (4) are: (1) MI (JIS K 6760) is 20g/1
If it exceeds 0 min, the appearance of the molded product will deteriorate, which is not preferable.

■Density (JIS K 6760) is 0.860 g
/co! If it is less than that, the melting point will be lowered, so it cannot be used at high temperatures, and the mechanical strength will also be poor, which is not preferable.

(2) The maximum peak temperature (Tm) of DSC is a value that correlates with the crystal form, and if Tm is less than 100°C, the heat resistance and surface strength of the composition will be insufficient, and when the molded product is used at high temperatures, This is not preferable as it tends to cause plastic deformation.

■The insoluble matter in boiling n-hexane is a guideline for the proportion of amorphous parts and the content of low molecular weight components. This results in problems such as poor performance due to reduced strength and a sticky surface that attracts dust.

It is necessary to satisfy the following characteristics.

In addition, boiling n-hexane insoluble matter and DSC in the present invention
The measurement method is as follows.

[Boiling n-hexane insoluble matter]

2 from a heat press molded sheet with a thickness of 200 Irrn
Three sheets of ONX3Qmm are cut and each is extracted with boiling n-hexane for 5 hours using a Soxhlet extractor. After taking out the n-hexane insoluble matter and vacuum drying (7 hours, 50°C), it is calculated using the following formula.

Measuring method using CD5C] Precisely weigh about 5 cm of a sample from a 100-unit film that has been heat-pressed, place it in a DSC device, and heat it at 170°C.
After increasing the temperature to 15 minutes and holding it at that temperature for 15 minutes, the temperature decrease rate was 2.
The sample is cooled to 0° C. at a rate of 5° C./min, and then heated from this state to 170° C. at a rate of 10° C./min for measurement. The temperature at the apex position of the maximum peak that appeared during the temperature increase from 0°C to 170°C is defined as Tm.

The above-mentioned ethylene/α-olefin copolymers are clearly distinguished from conventional ethylene/α-olefin copolymers obtained using vanadium-containing solid catalyst components. −・Low・
It is also distinguished from high-density polyethylene). That is, even if the monomer components constituting the copolymer of the present invention and the former are the same and the density is the same, the copolymer of the present invention has a higher Tm by DSC,
and the copolymer of the present invention has an n-hexane insoluble content of 10 wt.
% or more, whereas the conventional type is distinguished by the fact that there is no insoluble matter, or even if it exists, it is only in a very small amount. In addition, commercially available LLPE products usually have a density of 0.920g.
/co1 or more, it is distinguished, and the dynamic It of LLPE
Elasticity, D temperature dispersion. Behavior, yo, invention. Ega,
The temperature dispersion behavior of dynamic viscoelasticity is different from that of Z-N-α-olefin, and the chemical resistance improvement effect is also equivalent to that of ordinary high-density polyethylene, whereas the one of the present invention are greatly superior and distinct.

Next, the catalyst used for producing the ethylene/α-olefin copolymer of the present invention consists of a solid catalyst component containing at least magnesium and titanium and an organoaluminum compound.

As α-olefins, propylene, butene-1,4
-methylpentene-1, hexene-1, octene-1,
Examples thereof include α-olefins having C□ to CI□ such as 枦cene-1 and dodecene-1.

Here, the solid catalyst component is one in which a titanium compound is supported on an inorganic solid compound containing magnesium by a known method.

Inorganic solid compounds containing magnesium include metal magnesium, magnesium hydroxide, magnesium carbonate, magnesium oxide, magnesium chloride, etc., and double salts and complex oxides containing magnesium atoms and metals selected from silicon, aluminum, and calcium. Carbonates, chlorides or water! Oxides, substances, etc., as well as these inorganic solid compounds, water, organic oxygen-containing compounds such as allol, phenol, ketone, aldehyde, carboxylic acid, ester, polysiloxane, acid amide; metal alkoxide, metal oxyacid. Inorganic oxygen-containing compounds such as salts; organic sulfur-containing compounds such as thiols and thioethers; inorganic sulfur-containing compounds such as sulfur dioxide, sulfur trioxide, and sulfur; monocyclic compounds such as benzene, toluene, xylene, anthracene, and phenanthrene. Polycyclic aromatic hydrocarbon compounds; treated or reacted with halogen-containing compounds such as chlorine, hydrogen chloride, metal chlorides, and organic halides.

The titanium compounds supported on this inorganic solid compound include titanium halides, alkoxy halides,
These include alkoxides, halogenated M'4M, etc., and tetravalent or trivalent titanium compounds are preferred. Specifically, the tetravalent titanium compound has the general formula Ti (OR)
-X4□ (where R is an alkyl group having 1 to 20 carbon atoms,
It represents an aral group or an aralkyl group, X represents a halogen atom, and n satisfies 0≦n≦4. ) are preferred, and titanium tetrachloride, titanium tetrabromide, titanium tetraiodide,
Monomethoxytrichlorotitanium, dimethoxychlorotitanium, trimethoxymonochlorotitanium, tetramethoxytitanium, monoethoxytrichlorotitanium, jetoxydichlorotitanium, triethoxymonochlorotitanium, tetraethoxytitanium, monoisopropoxytrichlorotitanium,
Diisopropoxydichlorotitanium, triisopropoxymonochlorotitanium, tetraisopropoxytitanium, monobutoxytrichlorotitanium, dibutoxydichlorotitanium, monopentoxytrichlorotitanium, monophenoxytrichlorotitanium, diphenoxydichlorotitanium, triphenoxymonochlorotitanium, Examples include tetravalent titanium compounds such as tetraphenoxy titanium. In addition, trivalent titanium compounds include trivalent titanium compounds obtained by reducing titanium tetrahalides such as titanium tetrachloride and titanium tetrabromide with hydrogen, aluminum, titanium, or organometallic compounds of metals from groups I to II of the periodic table. titanium compound; general formula Ti(OR)-
A tetravalent halogen that is Examples include trivalent titanium compounds obtained by reducing valent alkoxytitanium with organometallic compounds of metals of groups I to II of the periodic table. Among these titanium compounds, tetravalent titanium compounds are particularly preferred. Specifically, as the components constituting the solid catalyst system of the present invention, Japanese Patent Publication No. 51-3514, Japanese Patent Publication No. 50-23864, Japanese Patent Publication No. 51-1
Publication No. 52, Japanese Patent Publication No. 15111/1983, Japanese Patent Application Publication No. 1973
9-106581, JP 52-11710, JP 51-153, JP 56-9590
Examples include those specifically exemplified in Publication No. 9 and the like.

In addition, as other solid catalyst components, for example, reaction products of Grignard compounds and titanium compounds can be used, such as those disclosed in Japanese Patent Publication No. 50-39470 and Japanese Patent Publication No. 54-1'1953.
Publication No. 12954/1983, Japanese Patent Application Publication No. 1987-12954
790'+09, etc., and in addition, JP-A No. 56-474.
A solid catalyst component in which an inorganic oxide is used together with an optionally used organic carboxylic acid ester described in Japanese Patent Application Laid-Open No. 07-187305, Japanese Patent Application Laid-open No. 58-21405, etc. can also be used.

The organoaluminum compound of the present invention has the general formula R
3Al, IhAIX, RAIXZ, RZAIOR, RA
I (OR) Preferred are compounds such as triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum,
Examples include diethylaluminum chloride, diethylaluminum ethoxide, ethylaluminum sesquichloride, and mixtures thereof. The amount of the organoaluminum compound to be used is not particularly limited, but it can usually be used in an amount of 0.1 to 1000 times the mole of the titanium compound.

The ethylene/α-olefin copolymer of the present invention is synthesized using the above catalyst system.

Prior to the polymerization reaction of the present invention, carrying out the polymerization reaction after contacting the α-olefin with the catalyst system of the present invention greatly improves the polymerization activity and allows the polymerization reaction to be performed more stably than in the case of no treatment. It is something that can be done. As for the pretreatment conditions, the contact time and temperature between the catalyst system and the α-olefin are not particularly limited.
The amount of α-olefin is about 1 to 50,000 g, preferably about 5 to 30,000 g.

The polymerization reaction is similar to the polymerization reaction of olefins using ordinary Ziegler-type catalysts (in the absence of oxygen, water, etc., in the gas phase, in the presence of an inert solvent, or by using the monomer itself as a solvent). As, temperature 20~300℃, preferably 40~200℃, pressure normal pressure~70kg/cn!・
G, preferably 2 to 60 kg/CrA.G. Although the molecular weight can be controlled to some extent by changing polymerization conditions such as polymerization temperature and catalyst molar ratio, it is usually effectively carried out by adding hydrogen to the polymerization system. Of course, a two-step or more multi-step polymerization reaction with different polymerization conditions such as hydrogen concentration and polymerization temperature can also be carried out without any problem.

The copolymerization ratio of α-olefin in the ethylene/α-olefin copolymer produced by the above method is 5 to 40 mol%.
A range of is preferred.

The blending ratio of the above-mentioned components in the thermoplastic resin composition of the present invention is A, and the aromatic polycarbonate resin is 40%.
~80 parts by weight, B, conjugated diene rubber - aromatic vinyl -
Vinyl cyanide graft copolymer 100-10 wt% and aromatic vinyl-vinyl cyanide graft copolymer 0-9
It is a mixture of 20 to 60 parts by weight with 0-t% and 1 to 15 parts by weight of C, ethylene/α-olefin copolymer.

If the aromatic polycarbonate resin is less than 40 parts by weight, the heat resistance will not reach the level required for engineering plastics, and the dimensional stability will also be poor. If the amount of the graft copolymer or the mixture thereof is less than 20 parts by weight, the effect of improving moldability, impact resistance, etc. will be insufficient;
If it exceeds 0 parts by weight, heat resistance will be insufficient. Also, C,
If the ethylene-α-olefin copolymer is less than 1 part by weight, no improvement in impact resistance will be achieved, and if it exceeds 15 parts by weight, it will cause poor heat resistance.

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,
Extrusion is possible as long as conventionally known methods are adopted 3)
A method of kneading with a machine, a Banbury mixer, a roll, etc. is appropriately selected.

〔Example〕

In the following description, "%", "molecular weight" and "part" are based on weight unless otherwise specified.

Reference Example-1 Ethylene and butene-1 are copolymerized using a solid catalyst component obtained from substantially anhydrous magnesium chloride, 1,2-dichloroethane, and titanium tetrachloride, and a catalyst consisting of triethylaluminum to produce ethylene-butene. -1 copolymer was obtained (hereinafter referred to as EB).

The ethylene content of this ethylene-butene-1 copolymer is 91.5 mol%, MI 0.5 g/10 min, density 0.904 g/cni, maximum peak temperature of D SC is 120.5 °C, boiling n-hexane insoluble matter 94-t
%Met.

Reference Example-2 Ethylene-propylene copolymer was obtained by copolymerizing ethylene and propylene using a solid catalyst component obtained from substantially anhydrous magnesium chloride, anthracene, and titanium tetrachloride and a catalyst consisting of triethylaluminum. Ta(
(hereinafter referred to as EP).

The ethylene content of this ethylene-propylene copolymer is 81.5 mol%, M I 1.0 g/10 min,
Density 0.890 g/d, maximum peak temperature of D SC 121.6°C, boiling n-hexane insoluble content 58 wt%
Met.

Examples 1 to 5 and Comparative Examples 1 to 7 Aromatic polycarbonate resin made from bisphenol A (manufactured by Mitsubishi Gas Chemical, trade name Newpiron S-2000, molecular weight 2
4.000), ABS resin (manufactured by Japan Synthetic Rubber, product name: JSRABS 35, manufactured by Japan Synthetic Rubber,
Product name: JSRABS 42) and ethylene-α-olefin copolymer (EB; Reference Example-1, EP; Reference Example-
2) in the proportions shown in Table 1, add 30
Mixed for a minute.

The resulting mixture was fed to a 401 Otori vented extruder,
The pellets were melted and kneaded at a cylinder temperature of 250°C to form pellets. After drying this pellet in a hot air dryer at 120° C. for 5 hours or more, a test piece for measuring physical properties was molded by injection molding.

The test results are shown in Table 1.

For comparison, aromatic polycarbonate resin alone (comparative example -
1), Composition of aromatic polycarbonate resin and AB, S resin (Comparative Example-2), Composition of aromatic polycarbonate resin and EB of Reference Example-1 (Comparative Example-3), Aromatic polycarbonate resin and High-density polyethylene (manufactured by Nippon Petrochemical ■, product name: Stafrene E707, MI
0.7g/10min, density 0.950g/cJ) (Comparative Example-4), aromatic polycarbonate resin and MBS resin (Japan Synthetic Rubber Placement Type, product name: JS
RMBS 67) (Comparative Example-5), aromatic polycarbonate resin and MAS resin (manufactured by Mitsubishi Rayon,
Product name: Metablen W 529) composition (comparative example)
6) and a composition (Comparative Example 7) in which ABS resin was added to the composition of Comparative Example 6, pellets and test pieces were prepared in the same manner as in the Examples, and physical properties were measured. The test results are shown in Table 1.

Note 1. Q value is elevated flow tester, load 160Kg
/cd, the amount of resin flowing out from a nozzle of 1 dragon φ x 10 wmL at a temperature of 280° C. is expressed in cc/sec.

[Operation and effects of the invention]

It is clear from the above detailed description, Examples, and Comparative Examples.

As can be seen, the composition of the present invention has significantly better impact resistance than polycarbonate resin-ABSm compositions, and has moldability that is equal to or better than that of polycarbonate resin-ABSm compositions, making it extremely well-balanced and practical. I understand.

l′! Inside the hall

Claims (1)

[Scope of Claims] 1. A, 40 to 80 parts by weight of aromatic polycarbonate resin, B, 100 to 10 wt% of conjugated diene rubber-aromatic vinyl-vinyl cyanide graft copolymer and aromatic vinyl-vinyl cyanide. Mixture 2 with copolymer 0-90wt%
Ethylene and α
- A thermoplastic resin composition containing 1 to 15 parts by weight of a copolymer copolymerized with an olefin and having excellent chemical resistance and impact resistance. (1) Melt index 20g/10min or less (2
) Density: 0.860 to 0.910 g/cm^3 (3) Temperature of its maximum peak measured by differential scanning calorimetry (DSC): 100° C. or higher (4) Boiling n-hexane insoluble content: 10 wt% or higher. 2. The composition according to claim 1, wherein the α-olefin in the ethylene/α-olefin copolymer has 3 to 12 carbon atoms.