JPS63179957A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition having impact resistance, molding and processing properties and chemical resistance, by blending ABS resin with a polyamide resin and a specific modified vinyl polymer. CONSTITUTION:A resin composition consisting of (A) 10-84pts.wt. ABS resin consisting of preferably 5-85pts.wt. diene rubber, 8-50pts.wt. vinyl cyanide, 10-90pts.wt. aromatic vinyl and, if necessary, another copolymerizable monomer, (B) 15-89pts.wt. polyamide resin, preferably nylon 6 of nylon 66 and (C) 1-70pts.wt. modified vinyl polymer obtained by copolymerizing an aromatic vinyl (preferably styrene or alpha-styrene) with a vinyl cyanide (preferably acrylonitrile), an alpha,beta-unsaturated carboxylic acid [e.g. (meth)acrylic acid] and, if necessary, another copolymerizable monomer having 100pts.wt. in sum of the components A, B and C.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a thermoplastic resin composition having excellent impact resistance, moldability and chemical resistance.

<Prior art> Acrylonitrile-butadiene-styrene copolymer resin (ABS resin) has excellent impact resistance and moldability,
Widely used as a general-purpose thermoplastic resin. but,
It does not have sufficient chemical resistance or abrasion resistance, and its use is restricted under harsh conditions.

Furthermore, polyamide resins have excellent chemical resistance and abrasion resistance, and are widely used as engineering plastics, but they have the disadvantage of poor impact resistance.

In order to improve the impact resistance of polyamide, blending it with ABS resin has been proposed (Japanese Patent Publication No. 38-2347
Publication No. 6).

Blends of polyamide resins and graft copolymers obtained by graft copolymerizing α,β-unsaturated dicarboxylic acid anhydrides or unsaturated carbonamides with other monomers onto rubber-like polymers have also been proposed.

(Unexamined Japanese Patent Publication No. 56-112957, Unexamined Japanese Patent Publication No. 58-93
Publication No. 745).

<Problems to be Solved by the Invention> However, a simple blend of ABS resin and polyamide resin has poor compatibility and extremely low mechanical properties.

In addition, in the case of a blend of the graft copolymer and polyamide resin, in which a monomer having a functional group reactive with the amide group of the polyamide resin is graft-copolymerized with other monomers to a rubber-like polymer, the polyamide resin Although the compatibility with the material can be improved, the impact resistance is insufficient.
Furthermore, the melt viscosity was high and the moldability was poor.

The object of the present invention is to have the chemical resistance of polyamide resin without impairing the moldability of ABS resin, and to
An object of the present invention is to provide a resin composition having impact resistance higher than that of resins.

<Means for Solving the Problems> According to studies by the present inventors, a composition comprising a copolymer obtained by copolymerizing ABS resin, polyamide resin, and a specific monomer mixture solves the problem of the present invention. I found a solution.

That is, the present invention is a modified vinyl copolymer consisting of 10 to 84 parts by weight of ABS resin (A), 15 to 89 parts by weight of polyamide resin (B), aromatic vinyl, vinyl cyanide, and α,β-unsaturated carboxylic acid. The present invention provides a thermoplastic resin composition comprising 1 to 70 parts by weight of a combined (C), and the total amount of (A), (B) and (C) being 100 parts by weight.

The characteristics of the present invention are aromatic vinyl, cyanide vinyl and α
, a modified vinyl copolymer (C) (hereinafter referred to as copolymer (C)) which is a copolymer essentially containing β-unsaturated carboxylic acid. By adding the copolymer (C>), the miscibility of ABS resin and polyamide resin is improved, and there is no increase in the melt viscosity of the composition, and moldability is good, and impact resistance is also sufficiently high. The present invention has been achieved based on the discovery that the following results can be obtained.

The present invention will be explained in detail below.

The ABS resin (8) used in the present invention refers to diene rubber (
a), vinyl cyanide monomer (b), aromatic vinyl monomer (c), and if necessary, other copolymerizable monomers (
A graft copolymer consisting of (d), in which the entire amount of the monomer is graft copolymerized with the diene rubber (a), or a graft copolymer in which a part of the monomer is graft copolymerized with the diene rubber (a). It is a resin composition of a copolymer obtained by copolymerizing a polymer and the remaining monomers.

-31 Examples of the diene rubber (a) used in the present invention include polybutadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, polyisoprene rubber, etc. Or two or more types can be used in combination.

In the present invention, polybutadiene and/or styrene-butadiene copolymer rubber is preferably used.

Examples of the vinyl cyanide (b) include acrylonitrile and methacrylonitrile, with acrylonitrile being particularly preferred.

Examples of the aromatic vinyl (c) include styrene, α-methylstyrene, methylstyrene, and pt-butylstyrene. Among them, styrene and/or α
- Methylstyrene is preferably used.

Other copolymerizable monomers (d) include α, β-unsaturated carboxylic acid esters such as methyl methacrylate, ethyl methacrylate, 1-butyl methacrylate, and cyclohexyl methacrylate, maleic anhydride, and anhydride. Examples include α,β-unsaturated dicarboxylic acid anhydrides such as itaconic acid, and imide compounds of α,β-unsaturated dicarboxylic acids such as N-phenylmaleimide, N-methylmaleimide, and N-1-butylmaleimide. be able to.

There is no particular restriction on the composition ratio of ABS resin (A), but from the viewpoint of moldability and impact resistance of the resulting thermoplastic resin composition, diene rubber (A) is used for 100 parts by weight of ABS resin. It is preferably 5 to 85 parts by weight, more preferably 15 to 75 parts by weight.

Similarly, for vinyl cyanide (b), 5 to 50
Parts by weight are preferred, especially 7 to 45 parts by weight, more preferably 8 to 4 parts by weight.
0 parts by weight is preferred. Regarding aromatic vinyl (c),
It is preferably used in an amount of 10 to 90 parts by weight, particularly preferably 13 to 83 parts by weight, and more preferably in a range of 17 to 77 parts by weight.

Further, it is preferable that the content of the diene rubber (a) in the entire thermoplastic resin composition is 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.

There are no particular restrictions on the method for producing the ABS resin (A), and commonly known methods such as bulk polymerization, solution polymerization, bulk suspension polymerization, suspension polymerization, and emulsion polymerization can be used. Also, separately (
It is also possible to obtain the above composition by blending copolymerized resins (graft).

The polyamide resin (B) used in the present invention includes polyamide obtained by ring-opening polymerization of lactams such as ε-cabrolactam and ω-dodecalactam, 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, etc. Polyamides derived from the amino acids ethylenediamine, tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2.2.4-/2,2.4-trimethylhexamethylenediamine, 1.3- and Aliphatic, alicyclic, and aromatic diamines such as 1,4-bis(aminomethyl)cyclohexane, bis(4,4'-aminocyclohexyl)methane, meta- and para-xylylene diamine, and adipic acid, speric acid, and sebacic acid. , dodecanionic acid, 1.3- and 1.A-cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid, dimer acid and other aliphatic and alicyclic acids,
These include polyamide resins derived from aromatic dicarboxylic acids, copolymerized polyamide resins thereof, and mixed polyamide resins. Among these, polycaproamide (nylon 6), polyundecaneamide (nylon 11), polydodecanamide (nylon 12), polyhexamethylene adipamide (nylon 66) and copolyamide resins containing these as main components are usually used. is useful.

As the method for polymerizing the polyamide resin, generally known melt polymerization, solid phase polymerization, or a combination of these methods can be employed. There are no particular restrictions on the degree of polymerization of the polyamide resin, and polyamide resins with a relative viscosity (measured at 25°C by dissolving 1 g of polymer in 100 ml of 98% concentrated sulfuric acid) within the range of 2.0 to 5°C can be used depending on the purpose. can be selected arbitrarily.

Nylon 6 and nylon 66 are preferably used from the viewpoint of compatibility with ABS resin (A) and cost.

-7 The copolymer (C) used in the present invention is an aromatic vinyl (A)
and vinyl cyanide (b) and α,β-unsaturated carboxylic acid (
This is a copolymer obtained by copolymerizing a monomer mixture consisting of (c).

Examples of the aromatic vinyl (a) include styrene, α-methylstyrene, p-methylstyrene, and pt-butylstyrene. Among them, styrene and α-methylstyrene are preferred. Examples of vinyl cyanide (b) include acrylonitrile and methacrylonitrile. Among them, acrylonitrile is preferred. Examples of the α,β-unsaturated carboxylic acid (iii) include acrylic acid and methacrylic acid, and two or more of these can also be used in combination.

There are no particular limitations on the method for producing the copolymer (C), and commonly known methods such as bulk polymerization, solution polymerization, bulk-suspension polymerization, suspension polymerization, and emulsion polymerization can be used. There are no particular restrictions on the method of preparing (a), (b), and (c), and they may be added all at once at the initial stage. Polymerization may be carried out while part or all of the mixture is continuously or dividedly charged.

It is also possible to copolymerize 0 to 70 parts by weight of other copolymerizable monomers with respect to 100 parts by weight of monomers (a), (i), and (c).

Other copolymerizable monomers include methyl methacrylate,
α of ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, etc.

β-unsaturated carboxylic acid esters, α,β-unsaturated dicarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride, N-phenylmaleimide, N-methylmaleimide,
α such as N-t-butylmaleimide.

Examples include imide compounds of β-unsaturated dicarboxylic acids.

ABS resin (A) in the thermoplastic resin composition of the present invention
The blending ratio of polyamide resin (B) and copolymer (C) is 10 to 84 parts by weight, preferably 12 to 80 parts by weight of (A).
parts by weight, particularly preferably 14 to 75 parts by weight, (B) is 1
5 to 89 parts by weight, preferably 18 to 86 parts by weight, particularly preferably 20 to 81 parts by weight, and (C) is 1 to 70 parts by weight, preferably 2 to 65 parts by weight, particularly preferably 5 to 65 parts by weight.
60 parts by weight, and the total amount of (A), (B) and (C) is 100 parts by weight. If (A) is less than 10 parts by weight and (B) is more than 89 parts by weight, if (C) is less than 1 part by weight, the resulting resin composition will have poor impact resistance; If the amount exceeds 15 parts by weight (B), the chemical resistance will be poor, and if the amount (C) exceeds 70 parts by weight, the moldability will be poor, which is not preferable.

The content of α,β-unsaturated carboxylic acid in the resin composition of the present invention is not particularly limited, but from the viewpoint of miscibility between ABS resin and polyamide resin and moldability of the resulting resin composition,
．． α of the copolymer (C) so that the amount is 07 to 10 parts by weight,
It is preferable to select the amount of β-unsaturated carboxylic acid and the amount of copolymer (C) blended in the resin composition.

There are no particular limitations on the method for producing the thermoplastic resin composition of the present invention, and generally known methods can be employed.

That is, after uniformly mixing ABS resin (A), polyamide resin ([1), and copolymer (e) in the form of pellets, powder, or small pieces using a high-speed mixer, etc., a uniaxial mixer with sufficient kneading capacity is used. Alternatively, various methods can be employed, such as a method of melt-kneading using a multi-screw extruder, a method of melt-kneading using a Banbury mixer or a rubber roll machine, and the like.

In addition, ABS resin (A) and polyamide resin (B), polyamide resin (B) and copolymer (C), ABS resin (A)
It is also possible to pre-knead the copolymer (C) and the like, and then adjust the blending ratio to a predetermined ratio and knead.

In addition to ABS resin (8), polyamide resin (B), and copolymer (C), the thermoplastic resin composition of the present invention may optionally contain polystyrene (PS), styrene/acrylonitrile copolymer (SAN), Polymethyl methacrylate (P
MMA), styrene/methyl methacrylate/acrylonitrile copolymer, α-methylstyrene/acrylonitrile copolymer, α-methylstyrene/styrene/acrylonitrile copolymer, α-methylstyrene/methyl methacrylate/acrylonitrile Copolymer, Kano methylstyrene/
Vinyl polymers such as acrylonitrile copolymer, styrene/N-phenylmaleimide copolymer, methacrylic acid resin-butadiene-styrene terpolymer (MBS) resin, ABS resin, AAS resin, polycarbonate, polybutylene terephthalate, By appropriately mixing thermoplastic resins such as polyethylene terephthalate, polyethylene, polypropylene, ethylene/propylene copolymer, ethylene/butene-1 copolymer, ethylene/propylene/dicyclopentadiene copolymer, ethylene/propylene 15
-ethylidene 2-norbornene copolymer, ethylene/propylene/1,4-hexadiene copolymer, ethylene/
Further desirable physical properties and characteristics can be adjusted by appropriately mixing polyolefin rubber such as vinyl acetate copolymer and ethylene/butyl acrylate copolymer. Depending on the purpose, reinforcing materials and fillers such as pigments, dyes, glass fibers, metal fibers, metal flakes, and carbon fibers, heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, lubricants, plasticizers, and electrostatic charges are also added. Inhibitors, flame retardants, etc. can be added.

<Examples> Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples. As an evaluation of impact resistance, 1/2° Izot impact strength was measured in accordance with ASTH 0256-56. As an evaluation of moldability, the melt viscosity was measured using a Koka type flow tester at a resin temperature of 250 to 280°C. Chemical resistance was determined by immersing an injection-molded square plate in methanol and gasoline at 23°C for 24 hours and visually observing the surface of the square plate.

Note that the following parts and percentages represent parts by weight and percentages by weight, respectively.

Reference Example 1 ABS resins A-1 to A-3 and graft copolymer A-4 were manufactured according to the following formulations.

A-1 = Polybutadiene latex (rubber particle size 0.2
40 parts of a monomer mixture consisting of 70% styrene and 30% acrylonitrile was emulsion polymerized in the presence of 60 parts (in terms of solid content) (5μ, 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: Polybutadiene latex 4 used in A-1
Methyl methacrylate in the presence of 0 parts (based on solids) 15
After emulsion polymerization of 60 parts of a monomer mixture consisting of 65% styrene and 20% acrylonitrile, a powdery graft copolymer (8-2) was prepared in the same manner as A-1.

A-3=Polybutadiene rubber (“diene”’NF35A
A graft copolymer (A-3) was prepared by dissolving 20 parts of Asahi Kasei Co., Ltd. in 70 parts of styrene and 10 parts of acrylonitrile, followed by bulk polymerization.

A-4 = Polybutadiene rubber (°゛diene゜NF35
A graft copolymer (A-4) was prepared by dissolving 20 parts of Yaasahi Kasei Co., Ltd. in 80 parts of styrene and bulk polymerizing the mixture.

Reference Example 2 Modified vinyl copolymers C-1 to C-4 and vinyl copolymer C-5 were prepared according to the following formulations.

C-1: A bead-shaped modified vinyl copolymer (C-1) was prepared by suspension polymerization of 70 parts of styrene, 25 parts of acrylonitrile, and 5 parts of methacrylic acid.

C-2=60 parts of styrene, 23 parts of acrylonitrile, 2 parts of acrylic acid, and 15 parts of methyl methacrylate were subjected to suspension polymerization to prepare a bead-shaped modified vinyl copolymer (c-2).

C-3: 53 parts of styrene, 15 parts of α-methylstyrene,
A bead-shaped modified vinyl copolymer (C-3) was prepared by suspension polymerization of 25 parts of acrylonitrile and 7 parts of methacrylic acid.

C-4: A bead-shaped modified vinyl copolymer (C-4) was prepared by suspension polymerization of 95 parts of styrene and 5 parts of methacrylic acid.

C-5: A bead-shaped vinyl copolymer (C-5) was prepared by suspension polymerization of 72 parts of styrene and 28 parts of acrylonitrile.

-15 A-1 to A-3 produced in Example 1 to Reference Example 1 and C-1 to C-3 produced in Reference Example 2 and C)11 as polyamide resin
017 Nylon 6) manufactured by Toshiku Co., Ltd. was mixed in a Henschel mixer at the mixing ratio shown in Table 1, and then a 40 mφ
After extruding with an extruder at an extrusion temperature of 250°C and pelletizing each pellet, each pellet was molded at a molding temperature of 250°C.
Each test piece was prepared by injection molding at a mold temperature of 60° C., and its physical properties were evaluated. These results are shown in Table-1.

Comparative Examples 1 to 5 A-1 to A-4 produced in Reference Example 1, C-1 to C-5 produced in Reference Example 2, and CM10 as the polyamide resin
17 Nylon 6) manufactured by Toshiku Co., Ltd. was mixed in a Henschel mixer at the blending ratio shown in Table 1, and then extruded using a 40φ extruder at an extrusion temperature of 250°C, and each was pelletized. Each pellet was subjected to injection molding at a molding temperature of 250° C. and a mold temperature of 60° C. to prepare each test piece, and its physical properties were evaluated. These results are also shown in Table-1.

Examples 6 to 10 The same conditions as Examples 1 to 5 were carried out except that CM3001N (Nylon 66 manufactured by Toshiku Co., Ltd.) was used as the polyamide resin, the extrusion temperature was 280°C, and the molding temperature was 280°C. The blending ratio and measurement results of physical properties are shown in Table-2.

Comparative Examples 6 to 10 Comparative Examples 1 to 5 were conducted under the same conditions as in Comparative Examples 1 to 5, except that CM3001N (Nylon 66 manufactured by Toshiku Co., Ltd.) was used as the polyamide resin, the extrusion temperature was 280°C, and the molding temperature was 280°C. The blending ratio and measurement results of physical properties are also shown in Table-2.

The following is clear from the Examples and Comparative Examples.

That is, the products obtained according to the present invention are all excellent in impact resistance, moldability, and chemical resistance. On the other hand, the vinyl copolymer (C-5) that does not contain α,β-unsaturated carboxylic acid has poor impact resistance, and the modified vinyl copolymer (C-3) that does not contain vinyl cyanide has Impact resistance is insufficient, melt viscosity is high, and moldability is poor.

<Effects of the Invention> As explained above, the resin composition of the present invention is a resin composition that has both the impact resistance and moldability of ABS resin and the chemical resistance of polyamide resin.
A), a polyamide resin (B), and a modified vinyl copolymer (C) are blended together to achieve this effect.

Claims (1)

[Claims] 10 to 84 parts by weight of ABS resin (A) and polyamide resin (
B) 15 to 89 parts by weight and (A) 1 to 70 parts by weight of a modified vinyl polymer (C) consisting of aromatic vinyl, vinyl cyanide, and α,β-unsaturated carboxylic acid;
A thermoplastic resin composition in which the total amount of (B) and (C) is 100 parts by weight.