JPH0570643A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition having excellent impact resistance, chemical resistance, heat-resistance and rigidity by compounding a specific graft copolymer, a modified polyolefin, a modified vinyl copolymer and a polyamide resin. CONSTITUTION:The objective composition is produced by compounding (A) 5-85wt.% of a graft copolymer produced by the graftpolymerization of (i) 5-80 pts.wt. of a rubber polymer with (ii) 95-20 pts.wt. of a monomer mixture composed of an aromatic vinyl monomer, a vinyl cyanide monomer and/or an unsaturated carboxylic acid alkyl ester monomer and other vinyl monomer copolymerizable with the above monomers with (B) 95-15wt.% of a modified polyolefin produced by the grafting reaction of 0.05-10 pts.wt. of an alpha, beta-unsaturated carboxylic acid (derivative) to 100 pts.wt. of a polyolefin and compounding 100 pts.wt. of the obtained composition with (C) 3-70 pts.wt. of a modified vinyl polymer produced by copolymerizing an aromatic vinyl compound, vinyl cyanide and an alpha, beta-unsaturated carboxylic acid and (D) 1-50 pts.wt. of a polyamide resin.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thermoplastic resin composition having excellent heat resistance, chemical resistance, impact resistance and rigidity.

[0002]

2. Description of the Related Art Rubber-reinforced styrene resin (ABS, AE
(S, AAS, ACS, MBS resin) have high rigidity, good dimensional stability, and low hygroscopicity, and are widely used as general-purpose thermoplastic resins. However, its chemical resistance and heat resistance are not sufficient, and its use is limited under severe conditions.

Polyolefins generally have excellent heat resistance and chemical resistance and are characterized by low specific gravity, but on the other hand, they tend to lack rigidity and dimensional stability. In order to complement this characteristic, it has been attempted to melt-knead both to obtain a resin, but the compatibility is poor and it cannot be put to practical use. As a method for improving the compatibility of this resin composition, for example, a method of modifying a polyolefin with a functional group such as an epoxy group, an alkyl group or a phenyl group (JP-A-59-89346, JP-A-64-64).
69651 gazette), styrene-butadiene rubber,
A method of adding a rubber such as a styrene graft (ethylene-propylene) rubber (JP-A-59-217742, JP-A-64-31847, JP-A-2-173).
No. 140) and the like are known.

[0004]

However, the methods generally proposed so far have not yielded a composition which is sufficiently satisfactory in terms of total balance of compatibility, mechanical properties and fluidity. For example, the above method of modifying a polyolefin with a functional group such as an epoxy group, an alkyl group or a phenyl group is not practical because the compatibility is insufficient and the surface condition of the molded article is poor. Further, the above method of adding a rubber such as styrene-butadiene rubber or styrene graft (ethylene-propylene) rubber has a problem that surface hardness and rigidity are significantly reduced.

That is, the present invention has the chemical resistance and heat resistance of polyolefin without impairing the impact resistance of the graft copolymer such as ABS resin, and the graft copolymer such as ABS resin. An object is to obtain a thermoplastic resin composition having an average rigidity.

[0006]

The present invention has the following constitution in order to solve the above problems.

(A) 5 to 80 parts by weight of a rubbery polymer (b) 20 to 90% by weight of an aromatic vinyl monomer, a vinyl cyanide monomer and / or an unsaturated alkyl carboxylate Graft copolymer obtained by graft polymerizing 95 to 20 parts by weight of a monomer mixture consisting of 80 to 10% by weight of an ester monomer and 0 to 40% by weight of another vinyl monomer copolymerizable therewith. 5 to 85% by weight and (B) 100 parts by weight of polyolefin, 0.05 to
(C) Aromatic vinyl with respect to 100 parts by weight of a composition comprising 95 to 15% by weight of a modified polyolefin obtained by graft-reacting 10 parts by weight of an .alpha..beta.-unsaturated carboxylic acid and / or its derivative. Modified vinyl polymer obtained by copolymerizing vinyl cyanide and α / β-unsaturated carboxylic acid
It is achieved by a thermoplastic resin composition containing 3 to 70 parts by weight and (D) a polyamide resin of 1 to 50 parts by weight.

The present invention will be specifically described below.

The rubbery polymer (a) which is a constituent of the graft copolymer (A) used in the present invention is preferably one having a glass transition temperature of 0 ° C. or lower, and specifically, polybutadiene. , Poly (styrene-butadiene),
Diene rubbers such as poly (acrylonitrile-butadiene), acrylic rubbers such as polyisoprene, polychloroprene, and polybutyl acrylate, and rubbery polymers such as ethylene-propylene-diene monomer terpolymer can be used. Particularly preferred is butadiene or a butadiene copolymer.

Examples of the aromatic vinyl-based monomer used as the monomer mixture (b) include styrene, α-methylstyrene, vinyltoluene, o-ethylstyrene, op-dichlorostyrene, and the like. Styrene is preferred, and one or more of these can be used.

Examples of vinyl cyanide-based monomers include acrylonitrile, methacrylonitrile, and ethacrylonitrile.

Examples of unsaturated carboxylic acid alkyl ester monomers include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, cyclohexyl acrylate, chloromethyl acrylate. , Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, chloromethyl methacrylate, acrylate-2-
Hydroxyethyl, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, glycidyl acrylate,
Examples thereof include α, β-unsaturated carboxylic acid alkyl esters such as glycidyl methacrylate, with methyl methacrylate, ethyl methacrylate and n-butyl methacrylate being particularly preferred.

Other copolymerizable vinyl monomers include (meth) acrylamides such as acrylamide, methacrylamide, N-methylacrylamide, N, N-dimethylacrylamide, maleic anhydride, and itaconic anhydride. Α, β-unsaturated dicarboxylic acid anhydrides, N-methylmaleimide, Nt-butylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-o-chlorophenylmaleimide, and the like,
Imido compounds of β-unsaturated carboxylic acid, vinyl acetate,
Examples thereof include carboxylic acid vinyl esters such as vinyl propionate.

Further, the (A) graft copolymer is (a)
5 to 80 parts by weight of the rubbery polymer, preferably 5 to 75 parts by weight, more preferably 5 to 70 parts by weight, and the monomer mixture 95.
˜20 parts by weight, preferably 93 to 25 parts by weight, more preferably 90 to 30 parts by weight by a known polymerization method, for example, in the presence of a rubbery polymer latex, the above-mentioned ratio of the monomer mixture and the polymerization initiator are added. It can be obtained by a method such as continuous supply and emulsion graft polymerization.

If the proportion of the rubbery polymer (a) in the graft copolymer is less than 5 parts by weight, the impact resistance of the resulting resin will be poor, and if it exceeds 80 parts by weight, the rubbery polymer will be poorly dispersed, resulting in molding. Not practical because it damages the appearance of the product.

The proportion of the aromatic vinyl monomer in the monomer mixture (b) is 20 to 90% by weight, preferably 30.
If it is less than 20% by weight, moldability is poor, and if it exceeds 90% by weight, impact resistance and chemical resistance of the obtained resin are deteriorated, which is not preferable.

The proportion of vinyl cyanide-based monomer and / or unsaturated carboxylic acid alkyl ester-based monomer is 80 to 10% by weight, preferably 70 to 15% by weight. The impact resistance of the resulting resin is poor, which is not preferable. On the other hand, when it exceeds 80% by weight, the thermal stability of the copolymer is remarkably lowered, resulting in a molded product having a poor color tone.

The blending amount of the other vinyl monomer is 0 to
40% by weight.

The content of (a) in the total thermoplastic resin composition is preferably in the range of 1 to 60% by weight,
In particular, it is preferably in the range of 3 to 55% by weight, more preferably 5 to 50% by weight. Further, when the weight of the diene rubber in the resin composition is 15% by weight or more, particularly 15 to 25% by weight, the impact resistance of the resin composition is higher than that of the graft copolymer composition and the polyolefin alone. Dramatically improved in comparison.

(B) which can be used in the present invention
The modified polyolefin is obtained by graft-reacting 0.05 to 10 parts by weight of .alpha..beta.-unsaturated carboxylic acid and / or its derivative with respect to 100 parts by weight of polyolefin. As the polyolefin used here, generally commercially available polypropylene, polyethylene, ethylene / propylene copolymer,
Examples thereof include ethylene / butene-1 copolymers and mixtures thereof, and polypropylene and polyethylene are particularly preferably used.

Specific examples of the .alpha..beta.-unsaturated carboxylic acid or its derivative used as the graft reaction component on the polyolefin include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, maleic anhydride and itacone. Acid, glutaconic anhydride, citraconic anhydride, anicotic anhydride, maleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, acrylamide, glycidyl acrylate, glycidyl methacrylate, etc., and these compounds are Each can be used alone or in the form of a mixture of two or more kinds. The graft amount of the α / β-unsaturated carboxylic acid or its derivative is in the range of 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the polyolefin. If the graft amount is less than 0.05 parts by weight, the resulting thermoplastic resin composition has a poor surface appearance due to insufficient affinity for the modified vinyl polymer and polyamide of the modified polyolefin to be produced, which is not preferable because it causes delamination. On the contrary, if the graft amount exceeds 10 parts by weight, the fluidity of the obtained thermoplastic resin composition will be deteriorated, which is not preferable.

As a preferable example of the method (B) for producing a modified polyolefin, a mixture obtained by mixing polyolefin, an .alpha..beta.-unsaturated carboxylic acid derivative and a small amount of an organic peroxide using a Henschel mixer or the like is uniaxially or The method of supplying to a twin-screw extruder and melt-kneading at a temperature of 180 to 250 ° C. can be mentioned, but the method for producing the modified polyolefin is not limited to this. For example, the polyolefin is dissolved in a suitable solvent. However, it is also possible to add a .alpha..beta.-unsaturated carboxylic acid derivative and an organic peroxide to the resulting solution and carry out a graft reaction in a solution state.

(C) which can be used in the present invention
The modified vinyl polymer is a copolymer obtained by copolymerizing a monomer mixture of aromatic vinyl, vinyl cyanide and α · β-unsaturated carboxylic acid. Examples of aromatic vinyl include styrene, α-methylstyrene, pt-butylstyrene and the like. Among them, styrene, α
-Methylstyrene is preferred. Examples of vinyl cyanide include acrylonitrile and methacrylonitrile. Of these, acrylonitrile is preferred. Examples of the α / β-unsaturated carboxylic acid include acrylic acid and methacrylic acid, and two or more kinds of them can be used in combination.

The copolymerization ratio of the modified vinyl polymer (C) is
Aromatic vinyl 50 to 90% by weight, vinyl cyanide 9 to 5
It is preferably 1 to 70% by weight of a monomer mixture consisting of 0% by weight and an α-β-unsaturated carboxylic acid.

There are no particular restrictions on the method for producing the (C) modified vinyl polymer, including bulk polymerization, solution polymerization, and bulk polymerization.
Known methods such as suspension polymerization, suspension polymerization and emulsion polymerization are used.

(D) which can be used in the present invention
Polyamide resins include polyamides obtained by ring-opening polymerization of lactams such as ε-caprolactam and ω-dodecalactam, polyamides derived from amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid, Ethylenediamine, tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine,
Aliphatic, alicyclic and aromatic diamines such as 1,3- and 1,4-bis (aminomethyl) cyclohexane, bis (4,4-aminocyclohexyl) methane, meta and paraxylylenediamine, and adipic acid, suberin Acid, sebacic acid, dodecanedioic acid, 1,3- and 1,4-cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid,
A polyamide resin derived from an aliphatic, alicyclic or aromatic dicarboxylic acid such as dimer acid, a copolyamide resin of these, or a mixed polyamide resin. Of these, polycaproamide (nylon 6), polyundecane amide (nylon 11), polydodecane amide (nylon 12), polyhexamethylene adipamide (nylon 66) and copolyamides containing these as the main components are usually used. Resins are usefully used.

The above polyamide resins can be used alone or in combination of two or more.

As the method for polymerizing the polyamide resin, generally known melt polymerization, solid phase polymerization and a combination thereof can be adopted. The degree of polymerization of the polyamide resin is not particularly limited, and a polyamide resin having a relative viscosity (measured at 25 ° C. by dissolving 1 g of polymer in 100 ml of 98% concentrated sulfuric acid at 25 ° C.) in the range of 2.0 to 5.0 is used depending on the purpose. Can be selected arbitrarily.

In the present invention, the blending ratio of the (A) graft copolymer and the (B) modified polyolefin is 5 for the (A) component.
-85% by weight, preferably 10-80% by weight, particularly preferably 10-65% by weight, the component (B) is 95-15% by weight, preferably 90-20% by weight, particularly preferably 90%.
~ 35% by weight. (B) Modified polyolefin is 15
If it is less than wt%, the chemical resistance of the resin composition will be insufficient, and if it exceeds 95 wt%, the impact resistance of the resin composition will be poor, such being undesirable.

The compounding amount of the (C) modified vinyl polymer is 3 to 70 parts by weight, preferably 5 to 50 parts by weight, relative to 100 parts by weight of the composition comprising the (A) graft copolymer and the (B) modified polyolefin. Parts, particularly preferably 7 to 35 parts by weight. If the amount of the modified vinyl polymer (C) is less than 3 parts by weight, the impact resistance of the resin composition is poor, and if it exceeds 70 parts by weight, the moldability of the resin composition is poor, which is not preferable.

The blending amount of the (D) polyamide resin is 1 to 50 parts by weight, preferably 2 to 45 parts by weight, particularly 100 parts by weight of the composition comprising the (A) graft copolymer and the (B) modified polyolefin. It is preferably 5 to 35 parts by weight. If the amount of the (D) polyamide resin is less than 1 part by weight, the affinity for the modified polyolefin is insufficient, so that the surface appearance of the obtained thermoplastic resin composition is poor and further layered peeling occurs, which is not preferable. When the amount exceeds 50 parts by weight, the physical properties of the resin composition are deteriorated due to the deterioration of the physical properties of the polyamide resin when absorbing water, which is not preferable.

There is no particular limitation on the method for producing the thermoplastic resin composition of the present invention. For example, (A) graft copolymer, (B) modified polyolefin, (C) modified vinyl polymer and (D) polyamide resin. The mixture is melted and kneaded with a Banbury mixer, a roll, an extruder or the like to obtain a product.

The thermoplastic resin composition of the present invention comprises other thermoplastic polymers such as styrene / acrylonitrile copolymer, α-methylstyrene / acrylonitrile copolymer, α-methylstyrene / styrene / acrylonitrile copolymer. , Styrene / acrylamide copolymer, styrene / acrylonitrile / methyl methacrylate copolymer,
By mixing polymethylmethacrylate etc.,
It is possible to further improve the balance between melt flowability, heat resistance, and impact resistance.

For example, when the rubber polymer concentration in the (A) graft copolymer is high, one or more of the above copolymers such as styrene / acrylonitrile / methyl methacrylate copolymer are added.

Further, depending on the purpose, reinforcing agents and fillers such as pigments and dyes, glass fibers, metal fibers, metal flakes and carbon fibers, heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, lubricants, plasticizers. Agents, antistatic agents, flame retardants and the like can also be added.

The molding method of the resin composition of the present invention is not particularly limited, and injection molding, extrusion molding (tube, pipe, sheet, etc.), blow molding (direct blow, injection blow, multi-layer blow, etc.), vacuum molding. Various parts and products can be made by molding processing methods such as compression molding.

Further, adhesion, labeling, printing, painting,
Post-processing treatments such as welding and cutting can be applied.

The application is also not particularly limited, but it can be used as parts and materials for automobiles, chemical plants, aviation, space, machines, electricity and electronics.

[0039]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples.

As an evaluation of impact resistance, 1/2 "Izod impact strength was measured according to ASTM D256-56. As an evaluation of rigidity, flexural modulus was determined according to ASTM D79.
It was measured according to 0. As an evaluation of heat resistance, the Vicat softening temperature was measured according to ASTM D-1525.
For chemical resistance, the injection-molded square plate was immersed in methanol and gasoline at 23 ° C. for 24 hours, and the square plate surface was visually observed.

The following parts and% represent parts by weight and% by weight, respectively.

Reference Example (1) Preparation of Graft Copolymer A-1: Polybutadiene Latex (Rubber Particle Diameter 0.2
40 parts of a monomer mixture consisting of 70% styrene and 30% acrylonitrile was emulsion-polymerized in the presence of 60 parts (solid content) of 5 μ, gel content 80%.

The obtained graft copolymer was coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered and dried to prepare a powdery graft copolymer (A-1).

A-2: 60 parts of a monomer mixture consisting of 15% of methyl methacrylate, 65% of styrene and 20% of acrylonitrile was emulsified in the presence of 40 parts (as solid content) of the polybutadiene latex used in A-1. After polymerization
Powder-like graft copolymer (A
-2) was prepared.

A-3: Polybutadiene rubber ("diene")
After 20 parts of NF35A, manufactured by Asahi Kasei Co., Ltd. was dissolved in 70 parts of styrene and 10 parts of acrylonitrile, bulk polymerization was carried out to prepare a graft copolymer (A-3).

(2) Preparation of modified polyolefin B-1: polypropylene 10 having MFR of 1.5 g / 10 min
Pellets of modified polyolefin (B-1) were produced by dry blending 0 part with 3 parts of maleic anhydride with a Henschel mixer, and melt-kneading and extruding this mixture with a vented 40 mmφ extruder at a resin temperature of 240 ° C. .

B-2: 100 parts by weight of polyethylene having an MFR of 0.5 g / 10 min was dry-blended with 3 parts by weight of maleic anhydride using a Henschel mixer, and this mixture was mixed with B-1.
Pellets of the modified polyolefin (B-2) were produced in the same manner as in.

(3) Preparation of modified vinyl polymer C-1: 70 parts of styrene, 25 parts of acrylonitrile, and 5 parts of methacrylic acid were subjected to suspension polymerization to obtain a modified vinyl polymer (C-1) in the form of beads. Prepared.

C-2: 60 parts of styrene, 23 parts of acrylonitrile, 2 parts of acrylic acid and 15 parts of methyl methacrylate are subjected to suspension polymerization to give a bead-like modified vinyl polymer (C-
2) was prepared.

(4) Preparation of polyamide resin D-1: CM1017 (nylon 6 manufactured by Toray Industries, Inc.) was used.

Examples 1 to 7 The (A) graft copolymer, (B) modified polyolefin, (C) modified vinyl polymer and (D) polyamide resin prepared in Reference Examples were used at the compounding ratios shown in Table 1. Mix and
Pellets were produced by melt-kneading and extruding at a resin temperature of 240 ° C. with a vented 40 mmφ extruder.

Then, a test piece was molded with an injection molding machine at a cylinder temperature of 240 ° C. and a mold temperature of 60 ° C., and the physical properties were measured.

Comparative Examples 1 to 5 The (A) graft copolymer, (B) modified polyolefin, (C) modified vinyl polymer and (D) polyamide resin prepared in Reference Examples were mixed at the compounding ratios shown in Table 1. Melt kneading and molding were carried out in the same manner as in the examples, and the physical properties were measured.

The measurement results are shown in Table 2.

[0055]

[Table 1]

[0056]

[Table 2]

From the examples and comparative examples, the following is clear.

That is, all of the products obtained by the present invention are excellent in impact resistance, rigidity, heat resistance and chemical resistance.

On the other hand, those containing a small amount of the graft copolymer (Comparative Examples 1 and 5) are inferior in impact resistance and therefore not preferable. Further, those having a small amount of the modified polyolefin (Comparative Examples 2 and 4) are inferior in chemical resistance and inferior in heat resistance. Further, the one having a small amount of the modified vinyl copolymer (Comparative Example 3) is inferior in impact resistance, and the one having a large amount of the modified vinyl copolymer is inferior in molding processability. Not preferable.

[0060]

According to the present invention, a thermoplastic resin composition having excellent impact resistance, chemical resistance, heat resistance and rigidity can be obtained.

Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08L 51/04 LKY 7142-4J 51/06 LLE 7142-4J 55/02 LME 7142-4J LMF 7142-4J 77 / 00 LQS 9286-4J // (C08L 55/02 51:06 25:08 9166-4J 77:00) 9286-4J

Claims (1)

[Claims] 1. A rubber polymer of 5 to 80 parts by weight of (A) (a), 20 to 90% by weight of (b) an aromatic vinyl monomer, a vinyl cyanide monomer and / or an unsaturated carvone. Graft copolymer obtained by graft-polymerizing 95 to 20 parts by weight of a monomer mixture consisting of 80 to 10% by weight of an acid alkyl ester monomer and 0 to 40% by weight of another vinyl monomer copolymerizable therewith. The polymer is 5 to 85% by weight and (B) 100 parts by weight of the polyolefin, 0.05 to
(C) Aromatic vinyl with respect to 100 parts by weight of a composition consisting of 95 to 15% by weight of a modified polyolefin obtained by graft-reacting 10 parts by weight of α-β-unsaturated carboxylic acid and / or its derivative. Modified vinyl polymer obtained by copolymerizing vinyl cyanide and α / β-unsaturated carboxylic acid
A thermoplastic resin composition containing 3 to 70 parts by weight and (D) a polyamide resin of 1 to 50 parts by weight.