JPH0333141A - Compatibilizer for abs resin and polyolefin and thermoplastic resin composition containing same - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition excellent in impact resistance and mechanical properties especially flow, moldability, processability, etc., by mixing a mixture of an ABS resin with a polyolefin resin with a specified compatibilizer. CONSTITUTION:10-90wt.% modified polyolefin (obtained by grafting 0.1-2mol% alpha,beta-unsaturated carboxylic acid or its derivative onto a polyolefin) is blended with 10-90wt.% multicomponent copolymer [obtained from a mixture obtained by mixing 0.1-70wt.% hydroxylated vinyl monomer (a) (e.g. hydroxyalkyl acrylate) with 1-80wt.% aromatic vinyl monomer (b) and 1-80wt.% cyanated vinyl monomer (c) in a (b) to (c) weight ratio of 50:50-95:5] to obtain a compatibilizer for ABS resin and polyolefin. 5-20 pts.wt. this compatibilizer is mixed with 100 pts.wt. resin comprising 95-5wt.% ABS resin and 5-95wt.% polyolefin to obtain a thermoplastic resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to thermoplastic resin compositions. For details, see ABS
j! The present invention relates to a thermoplastic resin composition containing a polyolefin, a polyolefin, and a specific compatibilizing agent, and having excellent resistance, heat resistance, mechanical properties, and moldability.

(Problems to be solved by conventional technology/invention) Polyolefins, represented by polypropylene, are thermoplastic resins with excellent properties such as moldability and chemical resistance, and are inexpensive, so they can be used for various molding. Widely used in products. However, polyolefins have problems with impact resistance, paintability, heat resistance, adhesion, etc., and their uses are limited. Therefore, in order to improve the drawbacks of these polyolefins, such as their impact resistance, polymer blends (hereinafter referred to as polymer alloys), which are made by melt-mixing various thermoplastic resins, have been developed.

For example, slightly less weather resistant, but excellent hardness.

A polymer alloy of ABS resin and polyolefin, which has impact resistance and moldability, is considered. However, ABS resin and polyolefin have extremely poor compatibility due to their different chemical structures, and a polymer alloy that takes advantage of the advantages of each has not been obtained. In addition, a polymer alloy has been proposed that contains ABS resin and polyolefin as a compatibilizer, a thermoplastic resin obtained by graft polymerizing a vinyl monomer onto polyolefin (Japanese Patent Laid-Open No. 64-6965
Publication No. 1>, the impact resistance and the like are still unsatisfactory.

An object of the present invention is to provide a thermoplastic resin composition that has excellent impact resistance and mechanical properties, particularly fluidity and moldability, and has good processability.

(Means for Solving the Problems) The present inventors have solved the above problems (as a result of intensive studies on compatibilizers for ABS resins and polyolefins,
The present invention has been completed by discovering that the specific compatibilizing agent shown below can solve the above problem.

That is, the present invention provides: (1) 10 to 90% by weight of a modified polyolefin obtained by graft polymerizing 0.1 to 1.2 mol% of an α,β-unsaturated carboxylic acid or a derivative thereof to a polyolefin; and (2) Containing at least one hydroxy group. Multi-component copolymer 10 containing a vinyl monomer, at least one aromatic vinyl monomer, and at least one cyano group-containing vinyl monomer
ABS resin-polyolefin compatibilizer characterized by containing ~90% by weight, and 0 amino group-containing compound 41 with respect to a total of 100 parts by weight of the above-mentioned (1) modified polyolefin and (2) multi-component copolymer! A compatibilizer for ABS resin-polyolefin, characterized in that it contains less than a lit part, and (e) 5 to 95% by weight of polyolefin, (e) 95 to 5% by weight of ABS resin, and (i) polyolefin and 0ABS. The present invention relates to a thermoplastic resin composition containing 5 to 20 parts by weight of the compatibilizing agent based on a total of 100 parts by weight of the resin.

In the present invention, as described above, a thermoplastic resin consisting of a modified polyolefin (hereinafter referred to as component (1)) and a multi-component copolymer (hereinafter referred to as component (2)) is used as a compatibilizer for ABS resin and polyolefin.

The modified polyolefin of the present invention is a polyolefin containing α,
It refers to a product obtained by graft polymerization of β-unsaturated carboxylic acid or its derivative. In addition, the grafting rate of α, β-unsaturated carboxylic acid or its derivative is 0.1 to 1.2 mol%.
%, preferably 0.4 to 0.7 mol%. If the grafting rate is less than 0.1 mol%, impact resistance will not improve.

Here, polyolefin refers to a polymer obtained by independently polymerizing α-olefins such as ethylene or propylene, butene-1, hexene-1, decene-1,4-methylbutene-1,4-methylpentene-1, etc. Alternatively, there may be mentioned a copolymer obtained by copolymerizing two or more of these.

Specific examples of α,β-unsaturated carboxylic acids or derivatives thereof include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, esters thereof, acid anhydrides, and imides thereof.

Such modified polyolefins can be produced according to conventional methods. For example, α,
A method in which β-unsaturated carboxylic acid or its derivative is added and melt-kneaded using a screw extruder etc. at 150 to 300°C, or an unmodified polyolefin is dissolved in an organic solvent, and α, β-unsaturated A method may be used in which a carboxylic acid or a derivative thereof is added and reacted. Also,
It is also optional to add a C1 organic peroxide catalyst to increase the efficiency of graft polymerization.

In the present invention, among these modified polyolefins, it is preferable to use maleic anhydride M-modified polypropylene, which is obtained by graft polymerizing maleic anhydride to polypropylene, in consideration of the moldability of the resulting thermoplastic resin composition.

The multi-component copolymer of the present invention is a multi-component copolymer containing at least one hydroxy group-containing vinyl monomer, at least one aromatic vinyl monomer, and at least one cyano group-containing vinyl monomer. It is.

Here, as the hydroxy group-containing vinyl monomer, 2-hydroxyethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (
Meta) acrylate.

2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxy-2-methylpropyl (meth)acrylate, polyethylene glycol mono(meth)acrylate (number of moles of ethylene oxide added: 2 to 10), polypropylene Examples include glycol sono(meth)acrylate (number of moles of propylene oxide added: 2 to 10), and one of these may be used alone or two or more may be used in combination.

In addition, aromatic vinyl monomers include styrene, α-methylstyrene, p-methylstyrene, etc. One of these may be used alone or two or more types may be used in combination. Among these, styrene is the most common. It is preferable to use

Examples of the cyano group-containing vinyl monomer include acrylonitrile and methacrylonitrile, and one of these may be used alone or two or more may be used in combination. Among these, acrylonitrile is preferably used.

The composition ratio of the hydroxy group-containing vinyl monomer, aromatic vinyl monomer, and cyano group-containing vinyl monomer is 0.1 to 70% by weight, preferably 1 to 50% by weight of the hydroxy group-containing vinyl monomer. Weight%. Further, the amount of aromatic vinyl monomer is 1 to 80% by weight, preferably 30 to 80% by weight. The amount of the cyano group-containing vinyl monomer is 1 to 80% by weight, preferably 10 to 35% by weight. Further, the weight ratio of the aromatic vinyl monomer and the cyano group-containing vinyl monomer is 50:50 to 95:5, preferably 65:35 to 8.
0:20. If the composition ratio and weight ratio of these monomers are outside the above range, the ABS resin-polyolefin compatibilization will be insufficient, and the impact resistance of the resulting thermoplastic resin composition will not be improved.

Further, the method for producing the multi-component copolymer of the monomers is not limited in any way, and any method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc. may be used.

The number average molecular weight of the multi-component copolymer thus obtained was 3.
000-1000000, preferably toooo-50
It is 0000. If it is less than 3,000, the impact resistance of the thermoplastic resin composition obtained decreases;
If it exceeds 0, the resulting thermoplastic resin composition will have poor fluidity.

The compatibilizer of the present invention consists of the above-mentioned component 0 and component
0% by weight, component (1) to 50% by weight, preferably 20 to 8%
It is 0% by weight. If the amount of component 0 is less than xoffiffi%, the molded product will be colored. On the other hand, 901ii1%
If it exceeds this amount, the compatibility between the ABS resin and the polyolefin deteriorates, and the impact resistance of the resulting thermoplastic resin composition decreases.

Further, in the present invention, the compatibilizer is an amino group-containing compound (
By using a compatibilizer containing component (hereinafter referred to as component 0), the compatibility between the ABS resin and the polyolefin is improved, and the impact resistance of the resulting thermoplastic resin composition can be further improved. Here, as the amino group-containing compound, a tertiary amine compound, a low molecular compound such as an imidazole compound, a (meth)acrylic acid ester containing a secondary or tertiary amino group, or a quaternary ammonium group-containing (
At least one selected from the group consisting of meth)acrylic acid ester, secondary and tertiary amino group-containing (meth)acrylamide, and quaternary ammonium group-containing (meth)acrylamide is added to the total amount of all monomers. ,1ffi
Examples include amine group-containing copolymers containing E in an amount of % or more.

Among these, amino group-containing copolymers containing the above monomers in an amount of 0.5 to 50% by weight based on the total of all monomers are preferred, and specifically, styrene-(meth)dimethylaminoethyl acrylate copolymers are preferred. In addition, the amount of the amino group-containing compound used is less than 4 parts by weight based on the total of 100 parts by weight of component 0 and component (2). This is because the impact resistance cannot be significantly improved compared to when less than one part by weight is used.

Further, the polyolefin (hereinafter referred to as component (1)) which is a component of the thermoplastic resin composition of the present invention includes the same polyolefins as described above.

Among these polyolefins, polypropylene obtained by polymerizing propylene is preferred in view of the moldability of the thermoplastic resin composition obtained by melt-mixing.

In addition, various known ABS resins (hereinafter referred to as component 0), which are components of the other thermoplastic resin of the present invention, can be used, and generally aromatic vinyl monomers are added in the presence of a diene rubber component. and graft copolymers obtained by bulk polymerization, suspension polymerization, or emulsion polymerization of mixed monomers consisting of cyano group-containing vinyl monomers, and other aromatic vinyl monomers and cyano group-containing vinyl monomers. Examples include a blend of a copolymer obtained from a diene monomer and a copolymer obtained from a cyano group-containing vinyl monomer.

Examples of the diene rubber component include polybutadiene, polyisoprene, and various synthetic rubbers or natural rubbers such as copolymers of these diene monomers with styrene, acrylonitrile, and the like. In addition, aromatic vinyl monomers include styrene, α-methylstyrene, p
Examples of the cyan group-containing vinyl monomer include acrylonitrile and methacrylonitrile.

The method for producing the thermoplastic resin composition of the present invention includes:
A compatibilizer consisting of the ■component and the ■component, or 0 component,
This is carried out by melt-mixing the component (1) and the compatibilizer consisting of Of&, the component (2) and the component (2). Melt mixing may be performed by a known method, usually at 160 to 260°C.
Any device such as an extruder, kneader, or Banbury mixer may be used for melt mixing.
In addition, the order of the melt-mixing is also arbitrary, such as a method of melt-mixing the ■component, ■component, ■component, ■component and 0 component at once, ■component and ■component or [phase] component, ■component and 0 component. Any other method may be used, such as a method of melt-mixing the components (1) and (2) and then mixing the component (0).

The amount of each component used is 5 to 95% by weight, preferably 20 to 80 parts by weight. If it is less than 5% by weight, the weather resistance will deteriorate, and if it exceeds 95% by weight, the impact resistance will not improve. The content of component (1) is 5 to 95% by weight, preferably 20 to 80% by weight. If it is less than 5% by weight, the impact resistance will not improve, and if it exceeds 95% by weight, the weather resistance will deteriorate. Further, the amount of the compatibilizer is 5 to 20 parts by weight based on a total of 100 parts by weight of the @ component and the 0 component. If it is less than 5% by weight, the IJ impact resistance will not be improved, and even if it exceeds 20% by weight, it will not improve the IJ impact resistance.
Impact resistance cannot be significantly improved compared to when using 91 parts of i.

The dispersed particle size of the thermoplastic resin composition thus obtained was 6.
It is preferable that it is less than μm. Preferably it is 5 μm or less.

The thermoplastic resin composition of the present invention eliminates problems such as processability and fluidity during molding, and also has improved impact resistance.

Therefore, the thermoplastic resin composition of the present invention can be used not only in the fields in which it has been conventionally used, but also in electrical, electromechanical parts,
Vines are used in a wide variety of fields such as automobile parts.

The excellent performance of the thermoplastic resin composition of the present invention is due to the compatibilizer of the present invention;
The hydroxyl groups in the components react to form ester bonds, producing a kind of polymer-to-polymer graft, in which component 0 and component ■ of the graft are compatible, and on the other hand, component
The components and component (1) are compatible with each other, the whole is mixed uniformly, and the dispersion state of the thermoplastic resin composition is extremely fine.
It is considered that a thermoplastic resin composition having excellent properties as described above was obtained. In addition, by adding component (1), the reaction between carboxyl groups and/or derivatives and hydroxyl groups can be promoted, and a thermoplastic resin composition with even better performance can be obtained.

The present invention will be explained in detail below with reference to production examples, working examples, and comparative examples, but the present invention is not limited to these examples. and @indicate amount%.

Production Example 1 In a 5-volume flask equipped with a reflux condenser, stirrer, thermometer, dropping funnel, and nitrogen inlet tube, 2900 parts of xylene and polypropylene (trade name Ace Polypro M1600) were added.
, manufactured by Ace Polymer Co., Ltd.) and 50 parts of maleic anhydride were charged and dissolved by heating at 120° C. for 1 hour while blowing nitrogen. Furthermore, 13.3 parts of benzoyl peroxide (g5) was dissolved in 200 parts of xylene and added dropwise for 30 minutes using a dropping funnel.
After the reaction was completed, it was cooled to 80°C, filtered, washed with xylene,
It was dried to obtain modified polypropylene with a graft ratio of 0.5 mol%. Hereinafter, this modified polypropylene will be referred to as modified product A.

Production Example 2 In a 52-capacity flask equipped with a reflux condenser, a stirrer, a thermometer, and a 9 element inlet tube, 2333 parts of ion-exchanged water and polyvinyl alcohol (trade name Poval 224 (saponification degree 88 mol%)/trade name Poval 124 were added. (Saponification degree 98.
5 mol %) = 8/2 4 parts (manufactured by Kuraray ■) were charged and dissolved by heating while blowing nitrogen. After cooling, 686 parts of styrene, 294 parts of acrylonitrile, 20 parts of 2-hydroxypropyl methacrylate, and 10 m of azobisisobutyronitrile were added, and a polymerization reaction was carried out at 75°C for 3 hours with vigorous stirring, resulting in Mn=9. OXl 0', Mw=3.
3X 10', hydroxyl value 6.9m g/K OH
A copolymer of Hereinafter, this copolymer will be referred to as copolymer B.

Examples 1 to 6 As shown in Table 1, polypropylene (trade name Ace Polypro M1600, manufactured by Ace Polymer ■) and ABS resin (
(trade name Denka GR-2000, made by Denki Kagaku ■) and modified product A, copolymer B and/or amino group-containing copolymer obtained in the production example (trade name Lunavell 9!2, amine value 100, Arayo Kagaku) After mixing Copolymer C (manufactured by Copolymer C), 21
The mixture was kneaded and pelletized at 0 to 230°C. This pellet was molded into a 5" x (1/2)" x (1/8)" molded product using an injection molding machine, and the following physical properties were evaluated. The results are shown in Table 1.

Comparative Examples 1 to 5 As shown in Table 2, polypropylene (trade name Ace Polypro Ml 600, manufactured by Nisborimer) and ABS resin were used.
After mixing <trade name Denka GR-2000, manufactured by Denki Kagaku ■) or the modified product A or copolymer B obtained in the production example, the following physical properties were evaluated in the same manner as in the example. The results are shown in Table 2.

(1) Dispersibility A sample was prepared by cutting out a part of the molded product.

The dispersed particle diameter (μm) of the obtained sample was observed using a field emission scanning electron microscope (S-800, manufactured by Hitachi Seisakusho).

(2) Izot impact strength The value was measured at 23° C. using an Izot Nangun tester manufactured by Toyo Seiki Seisakusho in accordance with the notched Izot impact test method of JIS 7110.

(Effects of the Invention) The ABS resin-polyolefin containing the compatibilizer of the present invention provides a thermoplastic resin composition with excellent impact resistance, mechanical properties, especially fluidity and moldability, and good processability. It can be used not only in the fields in which it has traditionally been used, but also in electrical and electromechanical parts.

Vines are used in a wide variety of fields such as automobile parts.

Procedural amendment (sealed) Case description 1999 Patent Application No. 169239 Name of the invention ABS resin-polyolefin compatibilizer and thermoplastic resin composition containing the compatibilizer Arakawa Chemical Industry Co., Ltd.

Claims (1)

[Scope of Claims] 1. (a) 10 to 90% by weight of a modified polyolefin obtained by graft polymerizing 0.1 to 1.2 mol% of α,β-unsaturated carboxylic acid or a derivative thereof to a polyolefin, and (b) Contains 10 to 90% by weight of a multicomponent copolymer containing at least one hydroxy group-containing vinyl monomer, at least one aromatic vinyl monomer, and at least one cyano group-containing vinyl monomer. A compatibilizing agent for ABS resin-polyolefin, which is characterized by: 2. (a) modified polyolefin according to claim 1 and (
b) For a total of 100 parts by weight of the multi-component copolymer, (c)
A compatibilizing agent for ABS resin-polyolefin, characterized in that it contains less than 4 parts by weight of an amino group-containing compound. 3. The multi-component copolymer contains 0.0 hydroxy group-containing vinyl monomers.
1-70% by weight, aromatic vinyl monomer 1-80% by weight
and 1 to 80% by weight of the cyano group-containing vinyl monomer, and the weight ratio of the aromatic vinyl monomer to the cyano group-containing vinyl monomer is 50:50 to 95:5. Compatibilizer as described. 4. The compatibilizing agent according to claim 1, 2 or 3, wherein the hydroxy group-containing vinyl monomer of the multi-element copolymer is hydroxyalkyl acrylate or hydroxyalkyl methacrylate. 5, (d) polyolefin 5-95% by weight, (e) AB
S resin is 95 to 5% by weight, and the total of (d) polyolefin and (e) ABS resin is 100%.
A thermoplastic resin composition comprising 5 to 20 parts by weight of the compatibilizer according to claim 1, 2, 3, or 4, based on parts by weight.