JPH02298541A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the title composition excellent in rigidity, coatability, heat resistance, molding processability, impact resistance and chemical resistance, comprising each specific modified polyolefin and maleimide copolymer. CONSTITUTION:The objective composition comprising (A) 10-90wt.% of a modified polyolefin having at least one functional group selected from amino, hydroxyl, epoxy and ester groups and (B) 90-10wt.% of a maleimide copolymer having (1) 30-70 (pref. 40-65) mol% of an aromatic vinyl monomer group, (2) 30-50 (pref. 30-45) mol% of a maleimide monomer group and (3) 1-20 (3-15) mol% of a unsaturated dicarboxylic anhydride monomer group.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a thermoplastic resin composition that has excellent rigidity, impact strength, heat resistance, paintability, and chemical resistance, and also has good moldability. More specifically, it is a composition comprising a modified polyolefin modified with one or more functional groups selected from the group consisting of an amino group, a hydroxyl group, an epoxy group, and an ester group, and a maleimide copolymer. The present invention relates to a thermoplastic resin composition having improved rigidity, paintability, heat resistance, molding processability, as well as impact strength and chemical resistance of a maleimide copolymer.

[Prior art] Although polyolefins have excellent toughness and resistance to environmental stress cracking, they have poor rigidity, heat resistance, and paintability.Furthermore, due to their crystallinity, they have a high molding shrinkage rate and are difficult to mold into molded products. It has the disadvantage that problems such as sink marks and warping are likely to occur. Usually, in order to eliminate such drawbacks, polyolefins are often used with the addition of an inorganic filler such as calcium carbonate. However, even if a filler is added, the degree of improvement of these drawbacks may not be sufficient depending on the application. Furthermore, compositions filled with inorganic fillers have the problem of abrasion of metals such as cylinders, screws, and molds of extruders or molding machines during production or molding of the compositions.

On the other hand, aromatic vinyl polymers are amorphous, so
Although polyolefins do not suffer from the defects that polyolefins have during molding, they have poor chemical resistance, and furthermore, because they are essentially brittle materials, their toughness and impact strength may be insufficient.

In order to improve these drawbacks of polyolefins or aromatic vinyl polymers, attempts have been made to add aromatic vinyl polymers such as polystyrene to polyolefins.
No. 9, No. 52-32990, No. 52-50390,
No. 52-89155, No. 57-174239, No. 5
No. 8-101142, No. 61-157551, No. 61
The technology can be seen in No.-285209. However, in these techniques, the elastic modulus or glass transition temperature of the aromatic vinyl polymer was not sufficiently high, and the degree of improvement of the drawbacks of polyolefins was insufficient.

[Problem to be solved by the invention]

As mentioned above, thermoplastic resin compositions consisting of polyolefins and aromatic vinyl polymers are known, but the resulting compositions have not sufficiently improved the drawbacks of polyolefins or aromatic vinyl polymers. There wasn't.

The object of the present invention is to provide a thermoplastic resin composition comprising a polyolefin and an aromatic vinyl polymer, which has excellent rigidity, impact strength, heat resistance, and chemical resistance, and has excellent moldability. It is about providing.

[Means to solve the problem]

That is, the present invention provides (A) an amino group, a hydroxyl group,
Modified polyolefins 10 to 9 having one or more functional groups selected from the group consisting of epoxy groups and ester groups
0% by weight, and (B) aromatic hinyl monomer group 30-7
0 mol% of maleimide monomer groups, 30 to 50 mol% of maleimide monomer groups, and 1 to 20 mol% of unsaturated dicarboxylic acid anhydride monomer groups. A resin composition, this resin composition is
Because maleimide copolymers have high rigidity and glass transition temperature, they are characterized by high rigidity and heat resistance, as well as excellent impact strength, moldability, paintability, and chemical resistance.

There are no particular limitations on the method for producing the maleimide copolymer used in the present invention. For example, in one method, aromatic vinyl monomers and maleimide monomers are mixed in the presence or absence of a rubbery polymer. It can be produced by radical copolymerization of unsaturated dicarboxylic anhydride monomers.

Specific examples of aromatic vinyl monomers include styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, etc. Specific examples of maleimide monomers include maleimide, N-methylmaleimide, and N-ethylmaleimide. , N
-Propylmaleimide, N-hexylmaleimide, N-
Cyclohexylmaleimide, N-phenylmaleimide,
N-tolylmaleimide, etc. Specific examples of unsaturated dicarboxylic anhydride monomers include maleic anhydride, methylmaleic anhydride, 1,2-dimethylmaleic anhydride, ethylmaleic anhydride, phenylmaleic anhydride, etc. There is.

Further, other copolymerizable monomer groups can also be contained in the maleimide copolymer. Specific examples of other copolymerizable monomers include methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate.
Acrylic monomers such as acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, decyl (meth)acrylate, octadecyl (meth)acrylate, hydroxyethyl (meth)acrylate, methoxyethyl (meth)acrylate, glycidyl (meth)acrylate, etc. There are vinyl cyanide monomers such as acrylonitrile, methacrylonitrile, etc., and these can be used alone or in combination. However, here, for example, methyl (meth)acrylate refers to methyl acrylate or methyl methacrylate.

There is no particular restriction on the method of radical copolymerization of these monomers, and any known method of radical copolymerization can be applied.

In the present invention, a rubber-like polymer can be included in the maleimide copolymer for the purpose of further increasing the impact strength of the resin composition of the present invention. A rubbery polymer is a polymer of a conjugated diene monomer such as butadiene, isoprene, or chloroprene, or a copolymerizable monomer such as a conjugated diene monomer and an aromatic vinyl monomer and/or an acrylic monomer. It is a copolymer with a polymer.

Another method for producing the maleimide copolymer used in the present invention is to copolymerize aromatic vinyl monomers, unsaturated dicarboxylic acid anhydride monomers, and other copolymers in the presence or absence of a rubbery polymer. An example of the method is to react a copolymer obtained by copolymerizing a monomer with ammonia or a primary amine to imidize the acid anhydride residue.

The imidization reaction between a polymeric substance having an acid anhydride residue in its polymer chain and an amine compound is known, for example, according to the method disclosed in Japanese Patent Publication No. 61-26936 or No. 62-8456. A desired maleimide copolymer having an imide group can be produced by reacting a molecular substance with an amine compound.

Examples of primary amines used in imidization reactions −
Examples include methylamine, ethylamine, propylamine, butylamine, hexylamine, cyclohexylamine, decylamine, aniline, toluidine, naphthylamine, chlorophenylamine, dichlorophenylamine, bromophenylamine, dibromophenylamine, and the like.

The imidization reaction can be carried out in any manner, and the reaction can be carried out in an autoclave in a solution state, a bulk molten state, or a suspension state. It is also possible to carry out the reaction in a molten state using a melt kneading device such as a screw extruder.

Any solvent can be used in the solution reaction, such as acetone, methyl ethyl ketone, methyl isobutyl ketone,
Ketones such as cyclohexanone, tetrahydrofuran,
Ethers such as 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and the like are disclosed.

The imidization reaction temperature is preferably in the range of 50 to 350°C, particularly preferably in the range of 100 to 300°C.

Although the imidization reaction does not necessarily require the presence of a catalyst,
If used, trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N,N-
Tertiary amines such as diethylaniline are preferred.

The maleimide copolymer used in the present invention contains aromatic vinyl mono[1[-30 to 70 mol%, maleimide monomer group 30 to 50 mol%, unsaturated dicarboxylic anhydride monomer group 1 to 20 mol % of other copolymerizable monomer groups and a rubbery polymer added as necessary. More preferred ranges are 40 to 65 mol% of aromatic vinyl monomer groups, 30 to 45 mol% of maleimide monomer groups, and 3 to 15 mol% of unsaturated dicarboxylic anhydride monomer groups.

If the maleimide monomer group is less than 30 mol%, the resulting composition will have poor heat resistance, and if it exceeds 50 mol%, moldability will be poor. If the unsaturated dicarboxylic anhydride monomer group is less than 1 mol %, the mechanical properties of the resin composition obtained by mixing with the modified polyolefin will be poor, and if it exceeds 20 mol %, the thermal stability will be poor.

The polyolefins used in the present invention include ethylene, propylene, butene-1, pentene-1, hexene-13
-Methylbutene-A homopolymer of α-olefin monomers such as 1,4-methylpentene-1, heptene-1, and octene-1, or a random or block copolymer of these monomers. Furthermore, a mixture of these polymers may be used.

There are no particular restrictions on the method for producing these polyolefins, and known techniques can be applied as they are.

Furthermore, the polyolefin used in the present invention has amino groups,
It is a functional group-modified polyolefin having one or more functional groups selected from the group consisting of hydroxyl group, epoxy group, and ester group. Furthermore, it may be a mixture of the functional group-modified polyolefin and unmodified polyolefin.

There are no particular restrictions on the method for producing the functional group-modified polyolefin, and it is produced, for example, by copolymerization of a monomer having a functional group and an α-olefin monomer. Monomers having functional groups used here include, for example, monomers having ester groups such as acrylic monomers used in the production of maleimide copolymers, vinyl formate, vinyl acetate, vinyl propionate, etc. Monomers with epoxy groups include glycidyl compounds such as glycidyl (meth)acrylate and allyl glycidyl ether, and monomers with amino groups include allylamine, aminoethyl ( There are meth)acrylates, aminopropyl(meth)acrylates, aminostyrenes, etc. Monomers with hydroxyl groups include allyl alcohol, hydroxyethyl(meth)acrylates, hydroxystyrenes, hydroxyphenylmaleimides, etc.
Ru.

Another method for producing functional group-modified polyolefins is
A method can be proposed in which the aforementioned monomers having a functional group and a radical initiator are mixed together with an unmodified polyolefin in the molten state to add the monomer to the polyolefin chain. This method is known as an active processing method, and the reaction can be carried out using a known melt-kneading device such as a screw extruder or co-kneader. Examples of radical initiators used in the iron include peroxides such as hensyl peroxide, lauroyl peroxide, dicumyl peroxide, and di-t-butyl peroxide; azo compounds such as azobisisobutyronitrile; ．．
3-',;pheny)Lt-2,3-dimethylbutane,
3,4-diphenyl-3,4-dimethylhexane and the like can be used.

The resin composition of the present invention has a modified polyolefin of 10 to 90%
% by weight and 90 to 10% by weight of the maleimide copolymer. If the modified polyolefin is less than 10% by weight, the resulting resin composition will have poor impact strength and chemical resistance. If the maleimide copolymer content is less than 10% by weight, the resulting resin composition will have poor heat resistance, rigidity, paintability, and dimensional stability.

In order to produce the resin composition of the present invention, a modified polyolefin and a maleimide copolymer are melt-kneaded to form a composition, and there are no particular restrictions on the melt-kneading method, including a screw extruder, Banbury mixer, Any known melt-kneading device such as a co-kneader or mixing roll can be used.

In the present invention, in addition to the modified polyolefin and the maleimide copolymer, other polymers can be mixed to form a composition. Examples of such polymers include polyolefins such as polypropylene and polyethylene, polystyrene, Styrenic resins such as acrylonitrile-styrene resin, ABS resin, MBS resin, methacrylic resin, polyamide,
Examples include polycarbonate resin, vinyl chloride resin, polyethylene terephthalate, polybutylene terephthalate, and particularly polyolefin, styrene resin, and polyamide are preferably used.

Furthermore, the resin composition of the present invention can contain an inorganic filler if necessary. Examples of inorganic fillers used include reinforcing fibers such as glass fiber, alumina fiber, and carbon fiber, talc, clay, silica, mica,
Fillers include calcium carbonate, barium sulfate, titanium oxide, zinc oxide, wollastonite, glass flakes, and the like.

〔Example〕

The present invention will be explained in more detail with reference to examples below, and all parts and percentages used in the examples and comparative examples are based on weight.

[Sample] (1) Functional group-modified polyolefin (A) 100 parts of polypropylene J-340P manufactured by Mitsui Petrochemical Industries, Ltd., 1 part of Oriru Mitsu, and 0.2 part of 3,4-diphenyl-3,4-dimethylhexane were mixed in a Henschel mixer. After mixing with
A pellet was obtained by melt-kneading at °C. The obtained pellet is referred to as (A-1).

Except that allylamine was changed to other monomers shown below (A
(A-2), (A-3) and (A-4) were obtained by operating in the same manner as in -1).

(A-2) = 4-hydroxyphenylmaleimide (A-
3): Methyl acrylate (A-4) nigericidyl methacrylate Also, as an unmodified polyolefin, polypropylene JH manufactured by Mitsui Toatsu Co., Ltd.
G (A-5) was used.

(2) Maleimide-based copolymer (B) 100 parts of styrene was charged into an autoclave equipped with a stirrer, and after purging the inside of the system with nitrogen gas, it was heated to a temperature of 80°C. A solution of 67 parts of maleic anhydride and 0.2 parts of benzoyl peroxide dissolved in 300 parts of methyl ethyl ketone was added to this over 8 hours. Further temperature 8 after addition
The mixture was stirred at 0°C for 4 hours to obtain a styrene-maleic anhydride copolymer.

To this were added 1.2 parts of tri'ethylamine and 52 parts of aniline, and the reaction was carried out at 130°C for 7 hours. The reaction solution was cooled to room temperature, poured into 300 parts of vigorously stirred methanol, and the precipitated polymer was filtered off and dried to obtain a maleimide copolymer CB-1).

The reaction was carried out in the same manner as in (B-1) except that the amount of aniline added was changed to 64 parts to obtain ('B-2).

The compositions of (B-1) and (B-2) were determined by I3CNMR. Here, St represents a styrene group, PMI represents an N-phenylmaleimide group, and MAR represents a maleic anhydride group.

(B-1) Stj59.5mol% PMI: 33.0 mol% MAH: 7.5 mol% (B-2) St: 59.5 mol% PMI: 40.5 mol% (3) Other Polymer (C) (C-1”) Olefin elastomer Tafmer P-0680 manufactured by Nimitsui Petrochemicals (4) Inorganic filler (D) (D-1) Calcium carbonate: Whiten SB G manufactured by Shiraishi Calcium Co., Ltd. 1 to 7 and 611 to 3 (A) component, (B) component, (C) component and (D) component are mixed in a Henschel mixer in the proportions shown in Table-1,
Furthermore, it is fed to a PCM-30 type twin screw extruder and heated to 280°C.
The mixture was melted and kneaded. A molded article was manufactured by injection molding using the obtained pellet, and the molded article was subjected to physical property evaluation.

The physical property evaluation method is as follows.

(1) Heat Resistance In accordance with ASTM D-648, the heating deformation temperature was measured using an injection molded product having a thickness of 1 part and 4 inches under a load of 18.6 kg/cd. However, there is no annealing.

(2) Impact Strength According to ASTM D-256, the notched isot impact strength was measured using an injection molded product having a thickness of 1 part and 4 inches. The ambient temperature was 23° C.9(3).The bending modulus of elasticity was measured according to ASTM D'-790. The ambient temperature was 23° C0 (4) Dimensional stability ASTM-1 dumbbells were molded and the molding shrinkage rate in the longitudinal direction was measured. However, molding temperature 260°C1 mold temperature 60
It was set to °C.

(5) Paintability: Form a square plate of 120x120x2mm at a temperature of 23°C.
1. After being left in an atmosphere with a relative humidity of 55% for 24 hours, it was painted using a spray gun. The paint used was Crack #72M manufactured by Fujikura Kasei ■, and the thinner used was #702. After painting, it was left for another 24 hours, and base marks were drawn at 1 mm intervals to conduct a base mark test.

The results were evaluated as the percentage of detached eyes.

(6) Chemical-resistant ASTM-1 dumbbells were molded and fixed in a bow shape on a two-point support jig so that the maximum deflection was 50 mm and the maximum strain was 5%. Genuine Yamaha brake oil was applied to a dumbbell test piece, and the time required for the test piece to break was measured at an ambient temperature of 23°C.

(7) Appearance A molded product having ribs and bosses on the back side and an opening was molded using a 5-ounce injection molding machine, and the appearance of the molded product was visually measured. Those with no practical problems were rated as Δ, those requiring O1 improvement were rated as Δ, and those with layer peeling were rated as ×.

The test results are shown in Table-1.

! [Effects of the Invention] As shown in Table 1, the resin composition according to the example of the present invention is a mixture of a functional group-modified polyolefin and a specific maleimide copolymer having an unsaturated dicarboxylic anhydride monomer group. As a result, compatibility is improved, and as a result, strength, rigidity, dimensional stability, paintability, chemical resistance, and appearance are significantly improved compared to the compositions of Comparative Example 1 and Comparative Example 2. I understand that. Furthermore, it can be seen that the resin composition of the present invention is superior in heat resistance, strength, rigidity, dimensional stability, and paintability, even when compared with the resin composition of Comparative Example 3, which does not use a maleimide-based copolymer. Moreover, as shown in Example 7, it is seen that even when an inorganic filler such as calcium carbonate is added to the resin composition of the present invention, its properties are not impaired.

Patent applicant Denki Kagaku Kogyo Co., Ltd. ,1

Claims (1)

[Claims] (1) (A) 10 to 90% by weight of a modified polyolefin having one or more functional groups selected from the group consisting of amino groups, hydroxyl groups, epoxy groups, and ester groups, and (B) aromatic vinyl monomer groups 30 to 70 mol%, 90 to 10% by weight of a maleimide copolymer containing 30 to 50 mol% of maleimide monomer groups, and 1 to 20 mol% of unsaturated dicarboxylic anhydride monomer groups. Thermoplastic resin composition.