JPS61272266A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the titled composition of outstanding impact resistance, dimensional stability and compatibility, comprising amino group-contg. vinyl polymer and a modified resin composition prepared by reaction of unsaturated carboxylic acid (anhydride) with a blend of polyolefin and vinyl polymer. CONSTITUTION:The objective composition comprising (A) 5-95wt% of a modified resin composition with an average molecular weight 3,000-1,000,000 prepared by reaction of an unsaturated carboxylic acid (anhydride) with a blend of (i) a polyolefin (e.g., a (co)polymer consisting mainly of ethylene and 3-10C alpha-olefin) and (ii) a vinyl polymer (except those having, in the molecule, carboxyl group, epoxy group reactive with anhydride, hydroxyl group, etc.) and (B) 95-5wt% of a second vinyl polymer with a molecular weight 2,000-1,000,000 having amino group (pref. amino group-terminated polystyrene or amino group- terminated acrylic copolymer). Preferably, 100pts.wt. of said composition is farther incorporated with 10-2,000pts.wt. of a vinyl polymer and/or polyolefin.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a thermoplastic resin composition having excellent impact resistance, dimensional stability and compatibility. More specifically, the present invention relates to a composition comprising a modified resin composition obtained by reacting a mixture of a polyolefin and a vinyl polymer with an unsaturated carboxylic acid or its anhydride, and a vinyl polymer having an amino group.

[Conventional technology and problems]

Polyolefins are inexpensive and chemically stable, so they are widely used as general-purpose resins. However, its uses are limited because it has drawbacks such as poor dimensional stability, insufficient rigidity, and poor paintability and adhesion. In order to improve these drawbacks, a method of blending an amorphous vinyl polymer such as polystyrene or AS resin with polyolefin may be considered.

However, polyolefins and these vinyl polymers have poor compatibility, and simply blended resins suffer from significant layer peeling and are of no practical value. On the other hand, vinyl polymers such as styrene resin have low mold shrinkage, good dimensional stability of molded products, and high rigidity, so they are used in many fields.
It has the disadvantage of poor impact resistance. A method of blending rubber-like polyolefins may be considered to improve impact resistance, but as mentioned above, the compatibility between vinyl polymers and polyolefins is poor, so a simple blend has no practical value. do not have. As a method for improving the compatibility between polyolefins and vinyl polymers, it has been proposed to use a reaction product of an unsaturated carboxylic acid grafted polyolefin and a polar polymer containing an epoxy group or an amine group as a compatibility improver. (Unexamined Japanese Patent Publication No. 58-19852
(Refer to Japanese Patent Laid-Open No. 58-198530), this method does not have a sufficient effect of improving compatibility, and the impact resistance of the resulting composition cannot be said to be at a fully satisfactory level.

[Means for solving problems]

The present inventor believes that in order to solve the above problems, it is essential to increase the affinity between the vinyl polymer and the polyolefin, and for this purpose, a polymer that is compatible with both is used as a compatibilizer. As a result of intensive study, we found that a modified resin composition obtained by reacting a mixture of a polyolefin and a vinyl polymer with an unsaturated carboxylic acid or its anhydride was mixed with a vinyl polymer having an amino group. It has been found that a thermoplastic resin composition with excellent impact resistance, dimensional stability and compatibility can be obtained by doing so, and the present invention has been achieved.

The reason why the above effects are obtained in the present invention is that by reacting the mixture of polyolefin and vinyl polymer with an unsaturated carboxylic acid or its anhydride, both the polyolefin and the vinyl polymer have carboxyl groups or anhydride. an object is introduced, resulting in an increase in the affinity between the two;
Furthermore, it is thought that a polymer having an effect as a compatibilizer is produced by an entry-coupling reaction between the carboxyl group or anhydride of the polyolefin and the amino group of the vinyl polymer.

The present invention will be explained in detail below.

The modified thermoplastic resin composition (hereinafter referred to as component (A)) used in the present invention is obtained by reacting a mixture of a polyolefin and a vinyl polymer with an unsaturated carboxylic acid or its anhydride. It will be done. This polyolefin is a polymer or copolymer whose main components are ethylene and α-olefin having 3 to 10 carbon atoms, and specific examples thereof include polyethylene, polypropylene, poly-1-butene, poly-4- Methyl-1-pentene.

Examples include ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-1-hexene copolymer, propylene-1-butene copolymer, and ethylene-propylene-diene terpolymer.

Vinyl polymers to be mixed with this polyolefin include vinyl monomers, such as styrene monomers such as styrene, methylstyrene, edylstyrene, and chlorostyrene, acrylic acid, methacrylic acid, ethyl acrylate, and methyl methacrylate. , acrylamide, methacrylic acid amide.

Unsaturated carboxylic acids and their derivatives such as maleic anhydride, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, vinyl esters such as vinyl acetate,
Examples include polymers or copolymers obtained by vinyl polymerization using unsaturated halides such as vinyl chloride and vinylidene chloride. However, within the molecule or at the end of the molecule, a functional group that is reactive with a carboxyl group or anhydride,
For example, those having epoxy groups, hydroxyl groups, amino groups, etc. are excluded.

The mixing ratio of the polyolefin and vinyl polymer is appropriately selected depending on the type and molecular weight of the polyolefin or vinyl polymer used, but usually, the mixing ratio of the vinyl polymer is 5 to 9.
It is preferable to mix in a range of 5% by weight.

The unsaturated carboxylic acid or its anhydride to be grafted onto the mixture of polyolefin and vinyl polymer includes:
α,β-unsaturated carboxylic acids or their anhydrides such as maleic acid, maleic anhydride, acrylic acid, methacrylic acid, citraconic acid, citraconic anhydride, itaconic acid, itaconic anhydride, cis-4-cyclohexene-1,2 -Dicarboxylic acid.

Cis-4-cyclohexene-1,2-dicarboxylic anhydride, endo-bicyclo-(2,2,1)-5-hebutene-
2,3-dicarboxylic acid, endo-bicyclo-(2,2,
1) Alicyclic dicarboxylic acids having a cis-type non-conjugated double bond such as -5-hebutene-2,3-dicarboxylic anhydride or anhydrides thereof. The grafting reaction is carried out by various known methods. Examples include a method in which the reaction is carried out in a molten state using a Banbury mixer 2 extruder or the like in the presence or absence of a reaction initiator, or a method in which the reaction is carried out in a solution state. Obtained in this way (A>
The average molecular weight of the ingredients is 3000 to 1, ooo, oo
o is preferably 5,000 to 500,000, and has 1 to 100, preferably 1 to 50 carboxyl groups or anhydrides grafted within the molecule.

Vinyl polymers having amino groups (hereinafter referred to as component (B)) include vinyl monomers such as styrene, methylstyrene, and ethylstyrene.

Styrene monomers such as chlorstyrene, acrylic acid,
Unsaturated carboxylic acids and their IC forms such as methacrylic acid, acrylic esters, methacrylic esters, acrylic amide, methacrylic amide, maleic anhydride, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, vinyl acetate, etc. Polymers or co-car bodies obtained by vinyl polymerization using vinyl esters, vinyl chloride, unsaturated halides such as vinylidene chloride, etc., and examples include those having the above amine groups in the molecule and/or at the terminals. . Specific examples of such polymers include compounds having an amine group in the molecule and acting as a chain transfer agent for radical reactions, such as di-p-7.
Those with an amino group introduced at the end of the molecule using minophenyl disulfide or the like, or monohung vinyl bodies having an amino group in the molecule, such as p-aminostyrene, styrene, methylstyrene, α-methylstyrene, Aromatic compounds such as vinylstyrene, (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, (
Propyl meth)acrylate.

1so-butyl (meth)acrylate, n-butyl (meth)acrylate, hexyl methacrylate.

Acrylic acid and its derivatives such as 2-ethylhexyl acrylate and (meth)acrylonitrile.

Vinyl halides such as vinyl chloride, vinyl acetate.

Examples include polymers with at least one monomer such as fatty acid vinyl esters such as vinyl propionate. Among these vinyl polymers having amino groups, amino-terminated polystyrene and amino-terminated acrylic copolymers are preferred.

Such a vinyl polymer having an amino group has a molecule M of 2000 to 1,000,000, preferably s, ooo
~1,000,000, particularly preferably ~10,000
500,000, and the number of intramolecular and/or terminal amine groups is 1 to 100, preferably 1 to 10.

If this molecular can is less than 2,000, the vinyl polymer molecule m
is small, and the effect of improving compatibility in mixing polyolefin and vinyl polymer is insufficient.
．． If it exceeds 000.000, moldability will deteriorate. In addition, if the number of amino groups per molecule is less than 1, the reaction rate is slow and there will be a large amount of unreacted substances, whereas if it exceeds 100, the polymer reaction will proceed significantly and crosslinking gelation will occur, which is undesirable. .

The thermoplastic resin composition of the present invention comprises the above (A),
It is obtained by mixing the components (B) in amounts of 5 to 95% and 95 to 5%, respectively. If the content of component (8) is less than 5% by weight, the effect of improving impact resistance will be low, and if it exceeds 95 times, the vinyl polymer component will decrease and the properties of the vinyl polymer will not be fully utilized, resulting in disadvantages. Examples of the mixing method include a known melt mixing method such as a Banbury mixer 2 extruder, or a method of mixing in a solution.

At this time, stabilizers, plasticizers, antistatic agents, lubricants, dyes and pigments,
It is also possible to add fillers and the like. (A), (B) of the present invention
) The two-component thermoplastic resin composition is a compatibilized composition of a polyolefin and a vinyl polymer, and is a polyolefin composition with improved dimensional stability, rigidity, paintability, and adhesion, as well as impact resistance. Provides an excellent vinyl polymer composition. Furthermore, since it has both a polar component and a non-polar component, it has good compatibility with many resins and is effective as a compatibility improver.

In the present invention, a sufficiently useful thermoplastic resin composition can be obtained using the two components (8) and (B) as described above, but in addition to this, a vinyl m combination (hereinafter referred to as the (C) component) is obtained.

) and/or a polyolefin (hereinafter referred to as component (D)), a thermoplastic resin composition with better properties can be obtained.

The vinyl polymer used as component (C) is one obtained by polymerizing or copolymerizing the above-mentioned vinyl monomers, and is other than component (8). Specific examples thereof include polystyrene, styrene-acrylonitrile copolymer, styrene-methyl methacrylate copolymer, polymethyl methacrylate, and methyl methacrylate-acrylonitrile copolymer.

The polyolefin used as component (D) is a polymer or copolymer whose main components are ethylene and an α-olefin having 3 to 10 carbon atoms, and a specific example thereof is polyethylene.

Polypropylene, poly-1-butene, poly-4-methyl-1-pentene, ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-1-hexene copolymer, propylene-1-butene copolymer Coalescence, ethylene-
Examples include propylene-diene terpolymer.

The mixing ratio of these components (C) and (D) is as follows: per 100 ffii of a composition consisting of (8) component 5 to 95% by weight, and (B) component 95 to 1%, at least 10-2000 parts by weight of one kind. that time(
Although the order of addition of components A), (B), (C) and (D) is not limited, it is preferable to add (C) and/or (D) after the addition of components (^) and (B). As a result, for example, high-impact polystyrene (HIPS), a polystyrene resin with significantly improved fim resistance, is used.
), it is also possible to produce so-called AES resins, which were developed for the purpose of improving the weather resistance of ABS resins.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.

In addition, the test method was performed according to the following method.

(1) Molding shrinkage rate A flat plate (with a marker) was prepared using a 10 oz injection molding machine, and its shrinkage rate was measured.

(2) Presence of layer peeling A 3m test piece was created using a 3.5oz injection molding machine.
The test piece was bent and visually observed for the presence or absence of layer peeling.

(3) Izod Impact Measured according to ASTM D256-73.

Examples 1 to 7 and Comparative Examples 1 to 5 (Preparation of modified thermoplastic resin composition (component (A))] (A
-1) Copolymer of ethylene and propylene (propylene content 135% by weight, MFI = 6.0>80% by weight
and polystyrene resin (Showa Denko Varnish Bright 9M>
2 parts by weight of maleic anhydride and 0.2 parts by weight of benzoyl peroxide were mixed for 10 minutes with a Henschel mixer. Then, a reaction was carried out using a 50 sφ vented extruder at a cylinder temperature of 170° C. to obtain a modified thermoplastic resin composition (A-1) grafted with 5 sets of anhydrous maleic IQ (fit%).

(A=2) Copolymer of ethylene and propylene 60
A modified thermoplastic resin composition (A-1) was prepared in the same manner as in (A-1) except that a mixture of 40% by weight of polystyrene and
2> was obtained. Maleic anhydride grafting ratio is 0.6%
Met.

(A-3) As resin (
Daicel Chemical, CS grade) was used (A-1
) A modified thermoplastic resin composition (A-3) was obtained in the same manner as in Example 1.

The amount of maleic anhydride grafted was 0.6% by weight.

(A-4) A modified thermoplastic resin composition (A-4>) was obtained in the same manner as in (A-1) except that a polypropylene resin (Show Aroma-3A510) was used instead of the ethylene-propylene copolymer. The amount of maleic anhydride grafted is 0.4
%.

(A-5) A maleic anhydride grafted ethylene-propylene copolymer was obtained in the same manner as (A-1) except that the polystyrene resin was not used. The amount of maleic anhydride grafted was 0.6% by weight.

[Preparation of amino group-containing vinyl polymer (component (B))] (
B-1) 40 kg of styrene, 4000 azobisisobutyro-nitrile, and 3 kg of p-aminophenyl disulfide were charged into a 100J autoclave substituted with Nz, and a polymerization reaction was carried out at 80°C for 5 hours. By contacting the obtained polymerization solution with a large excess of methanol, polystyrene containing terminal amino groups was precipitated and separated and dried. This product had an average of 2 amino groups per molecule and a weight average molecular stiffness of about 60,000.

(B-2) A terminal amino group-containing styrene-acrylonitrile copolymer was obtained in the same manner as in (B-1) except that 30 Ky of styrene and 1 ON g of acrylonitrile were used as monomers. This product had an average of 2 amino groups per molecule, and the weight average molecular group was about 50,000.

[Preparation of thermoplastic resin composition]

A modified thermoplastic resin composition (component (A)), an amino group-containing vinyl polymer (component (8)), and optionally a vinyl polymer and/or a polyolefin are mixed in Banbury at the m ratios shown in Table 1. A thermoplastic resin composition was obtained by kneading using a mixer. Its dimensional stability, compatibility and resistance! i51 properties are shown in Table 1.

〔Effect of the invention〕

As explained above, the thermoplastic resin composition of the present invention is
Since it consists of a modified thermoplastic resin composition obtained by reacting a mixture of a polyolefin and a vinyl polymer with an unsaturated carboxylic acid or its anhydride, and a vinyl polymer having an amine group, the polyolefin and The compatibility with vinyl polymers is increased, and the compatibility is also increased by reaction with vinyl polymers having amino groups, so that layer peeling and phase separation do not occur, and the impact resistance of polyolefins and the high compatibility of vinyl polymers are improved. It takes full advantage of dimensional stability, high rigidity, and good adhesion, and has excellent properties with a balance J:<.

Therefore, according to this resin composition, each component's fil
By changing the ratio, a wide range of properties can be obtained, and molded products etc. that can be applied to various uses can be obtained.

Claims (1)

[Claims] 5 to 95% by weight of a modified thermoplastic resin composition obtained by reacting a mixture of a polyolefin and a vinyl polymer with an unsaturated carboxylic acid or its anhydride, and 95 to 5% by weight of a vinyl polymer having an amino group. A thermoplastic resin composition consisting of %.