JPH01123854A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the above composition excellent in impact resistance, moldability, heat resistance, chemical resistance and mold transferability, by melt-kneading an ABS resin with an aromatic polyester resin and a specified modified vinyl polymer. CONSTITUTION:1-98pts.wt. ABS resin which is a resin composition comprising a copolymer which comprises 5-85pts.wt. (1-60wt.%, based on the total composition) diene rubber (e.g., polybutadiene rubber), 5-50pts.wt. vinyl chanide (e.g., acrylonitrile), 10-90pts.wt. aromatic vinyl (e.g., styrene) and, optionally, other copolymerizable monomers (e.g., methyl methacrylate) and in which the respective monomers are grafted onto said diene rubber and copolymers of the remaining monomers is melt-mixed with 98-1pt.wt. aromatic polyester resin (e.g., polybutylene terephthalate) of a relative viscosity in a 0.5% o-chlorophenol solution of 1.15-3.0 at 25 deg.C and 1-70pts.wt. modified vinyl polymer comprising an aromatic vinyl (e.g., styrene), a vinyl cyanide (e.g., acrylonitrile) and 0.1-28wt.% alpha,beta-unsaturated carboxylic acid (e.g., acrylic acid) to obtain 100pts. wt. composition.

Description

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

<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 heat resistance, and its use is restricted under harsh conditions.

In addition, aromatic polyester resin (hereinafter abbreviated as polyester) has excellent mechanical properties, electrical properties, chemical resistance,
It has heat resistance, low moisture absorption, processability, etc., and is widely used as an engineering plastic, but it has the disadvantage of poor impact resistance.

In order to improve the impact resistance of polyester, blending it with ABS resin has been proposed (for example, JP-A-49-97
081, JP 56-14546, JP 57-117556, JP 57-137350
No. 1, JP-A-60-36558, JP-A-60-
123550, etc.).

In addition, a blend of a polyester and a graft copolymer obtained by graft copolymerizing an α,β-unsaturated dicarboxylic acid anhydride or an unsaturated carbonamide together with other monomers onto a rubber-like polymer has also been proposed ( For example, JP-A-49-97
081, JP 59-138256, JP 60-144349, JP 60-26284
7, JP-A-61-130366, etc.).

Additionally, a method has been proposed in which an epoxy resin is added to a mixture of polyester and diene polymer (Japanese Patent Application Laid-Open No. 59-1999).
-149951).

<Problems to be solved by the invention> However, the methods generally proposed so far have not yielded compositions that are fully satisfactory in terms of the total balance of compatibility, mechanical properties, fluidity, etc. .

For example, ABSf! A simple blend of F fat and polyester has poor compatibility and extremely low mechanical properties.

In addition, in the case of a blend of polyester and a graft copolymer obtained by graft copolymerizing a monomer having a functional group reactive or affinity with polyester together with other monomers onto a rubber-like polymer, the impact resistance is Although it can be improved, it is impractical because the compatibility is poor and the surface condition of the molded product is poor.

Furthermore, when an epoxy resin is added to a mixture of polyester and diene polymer, the epoxy resin is localized and hardened, resulting in essentially poor fluidity.

Therefore, the present invention aims to obtain a resin composition that has the chemical resistance, heat resistance, and mold transferability of polyester without impairing the moldability of ABS resin, and has impact resistance higher than that of ABS resin. It will be a section.

Means for Solving the Problems> The present inventors have conducted intensive studies to solve the above problems, and as a result, have arrived at the present invention.

That is, the present invention comprises 1 to 98 parts by weight of ABS resin (A), 98 to 1 part by weight of aromatic polyester resin (B), aromatic vinyl, vinyl cyanide, and α.

consisting of 1 to 70 parts by weight of a modified vinyl polymer (C) formed by copolymerizing β-unsaturated carboxylic acid, and (A),
The present invention provides a thermoplastic resin composition in which the total amount of (B) and (C) is 100 parts by weight.

The present invention will be explained in detail below.

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

Examples of the diene rubber (a) include polybutadiene rubber, acrylonitrile-butadiene copolymer rubber, and styrene-based rubber.
Examples include butadiene copolymer rubber and polyisoprene rubber, and these can be used alone or in combination of two or more. In particular, polybutadiene and/or styrene-butadiene copolymer rubber is preferably used.

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

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

Other copolymerizable monomers (d) include α, β-unsaturated carboxylic acid esters such as methyl methacrylate, ethyl methacrylate, t-butyl methacrylate, and cyclohexyl methacrylate, maleic anhydride, and anhydride. Itaconic acid, α, β-unsaturated dicarboxylic acid anhydride, α, β-, β-dicarboxylic acid imide compounds such as phenylmaleimide, N-methylmaleimide, N-t-butylmaleimide, etc. 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, vinyl cyanide (b) is preferably 5 to 50 parts by weight, particularly preferably 7 to 45 parts by weight, and more preferably 8 to 40 parts by weight.

Regarding the aromatic vinyl (c), 10 to 90 folds are preferable, 13 to 83 folds are particularly preferable, and 17 to 83 folds are particularly preferable.
It can be preferably used in the range of 77 to 77 heavy background areas.

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% heavy background, and more preferably 5 to 50% heavy background. Furthermore, if the diene rubber in the resin composition of the present invention is 15% by weight or more, especially 15 to 25% by weight, the impact resistance of the resin composition is lower than that of the graft copolymer composition and the aromatic polyester resin. are dramatically improved compared to each alone. In this case, particularly significant effects occur when polybutadiene terephthalate is selected as the aromatic polyester.

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 aromatic polyester (B) used in the present invention is a polyester having an aromatic ring in the chain unit of the polymer, and is obtained by a polycondensation reaction with an aromatic dicarboxylic acid (or its ester-forming derivative) as the main component. It is a polymer or copolymer.

The aromatic dicarboxylic acids mentioned here include terephthalic acid, isophthalic acid, orthophthalic acid, 1°5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,
6-naphthalenedicarboxylic acid, 2.2°-biphenyldicarboxylic acid, 3.3-biphenyldicarboxylic acid, 4,
4″-biphenyldicarboxylic acid, 4,4″-diphenyl ether dicarboxylic acid, 4.4°-diphenylmethanedicarboxylic acid, 4.4″-diphenylsulfonedicarboxylic acid, 4.4-monodiphenylisopropylidenedicarboxylic acid, 1.2- Bis(phenoxy)ethane-4,4-monodicarboxylic acid, 2,5-anthracenedicarboxylic acid, 2
．． Examples include 6-anthracenedicarboxylic acid, 4.4-p-terphenylenedicarboxylic acid, 2.5-pyridinedicarboxylic acid, and terephthalic acid is preferably used.

Two or more of these aromatic dicarboxylic acids may be used in combination. In addition, if the amount is small, one or more types of aliphatic dicarboxylic acids such as adipic acid, azelaic acid, dodecanedioic acid, and sebacic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid may be used in combination with these aromatic dicarboxylic acids. can do.

In addition, as diol components, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, 2-methyl-1
, 3-propanediol, diethylene glycol, aliphatic diols such as triethylene glycol, alicyclic diols such as 1,4-cyclohexane dimetatool, etc.
and mixtures thereof. In addition, if it is a small amount, a long chain diol with a molecular weight of 400 to 6,000, that is, 1. One or more types of polyethylene glycol, poly-1°3-propylene glycol, polytetramethylene glycol, etc. may be copolymerized.

Specific aromatic polyesters include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene-1,2-bis(phenoxy)ethane-4,4''-dicarboxylate, and the like. In addition, polyethylene isophthalate/terephthalate, polybutylene terephthalate/isophthalate,
Examples include copolymerized polyesters such as polybutylene terephthalate/decanedicarboxylate.

Among these, polybutylene terephthalate and polyethylene terephthalate can be preferably used.

The aromatic polyester used in the present invention is 0.5
% 0-chlorophenol solution at 25° C. is preferably 1.15 to 3.0, particularly 1°3 to 2.5. If the relative viscosity is less than 1.15, the impact strength of the resulting molded product will be low, and if it is greater than 3.0, the surface gloss of the molded product will be poor, which is not preferred.

The modified vinyl polymer (C) used in the present invention (hereinafter referred to as copolymer (C)) consists of aromatic vinyl (a), vinyl cyanide (b), and α, β-, β-carboxylic acid (ha). ) is a copolymer formed by copolymerizing a monomer mixture consisting of:

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. α, β−, β
- Specific examples of carboxylic acid (c) include acrylic acid and methacrylic acid, and these can be used alone or in combination of two or more.

The copolymerization amount occupied by α, β-, β-carboxylic acid in the copolymer (C) composed of the above copolymerized components is preferably 0.1 to 28% by weight, more preferably 0.1 to 10% by weight.
% by weight. If the copolymerization amount is less than 0.1% by weight, the impact strength of the composition will be low, and if it exceeds 28% by weight, the copolymer will tend to gel, resulting in a molded product with a good surface condition. I can't.

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 charging (a), (b), and (c), and they may be charged 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 the monomers (a), (b), and (c).

Other copolymerizable monomers include methyl methacrylate,
α of ethyl methacrylate, 71-butyl methacrylate, cyclohexyl methacrylate, etc.

β-unsaturated carboxylic acid esters, maleic anhydride, α, β-unsaturated dicarboxylic acid anhydride such as itaconic anhydride, phenylmaleimide, N-methylmaleimide,
Examples include imide compounds of α, β-, and β-dicarboxylic acids such as N-t-butylmaleimide.

ABS resin (A) in the thermoplastic resin composition of the present invention
The blending ratio of polyester (B) and copolymer (C) is preferably 5 to 90 parts by weight per 1 to 98 parts by weight or 2 to 94 parts by weight, and (B) 98-1 parts by weight, preferably 94-2 parts by weight, particularly preferably 90 parts by weight
~5 parts by weight, and (C) is 1 to 70 parts by weight, preferably 2 to 65 parts by weight, particularly preferably 5 to 60 parts by weight,
And the total amount of (A), (B) and (C) is 100 parts by weight. If (A> is less than 1 part by weight and (B) is more than 98 parts by weight, if (C) is less than 1 part by weight, the resulting resin composition will have poor impact resistance; If (B) exceeds 1 part by weight, the chemical resistance and mold transferability will be poor, and if (C) exceeds 70 parts by weight, the molding processability will be poor, which is not preferable.

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), polyester (B), and copolymer (C) in the form of pellets, powder, or small pieces using a high-speed stirrer or the like, Various methods can be employed, such as a method of melt-kneading with a shaft extruder. In addition, ABS resin (A> and polyester (B), polyester (B) and copolymer (C), ABS resin (A) and copolymer (C), etc. are pre-kneaded in advance, and then the predetermined blending is performed. A method of kneading by adjusting the ratio is also possible.

In addition to ABS resin (A), polyester (B), and copolymer (C), the thermoplastic resin composition of the present invention may optionally contain polystyrene (PS), styrene/acrylonitrile copolymer (SAN), and polyester. Methyl methacrylate (
PMMA), styrene/methyl methacrylate/acrylonitrile copolymer, α-methylstyrene/acrylonitrile copolymer, α-methylstyrene/styrene/acrylonitrile copolymer, α-methylstyrene/methyl methacrylate/acrylonitrile copolymer, Vinyl polymers such as p-methylstyrene/acrylonitrile copolymer, styrene/N-phenylmaleimide copolymer, methacrylic acid-butadiene-styrene terpolymer (MBS
＞Resin, AES resin, AAS resin, polycarbonate,
Thermoplastic resins such as polycaproamide (nylon 6) and polyhexamethylene adipamide (nylon 66) may be mixed as appropriate, or 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/vinyl acetate copolymer and ethylene/vinyl acetate copolymer By appropriately mixing polyolefin rubber such as butyl acrylate copolymer, it is also possible to adjust the physical properties and characteristics to more desirable values. 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 according to ASTM D256-56.

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 and a load of 50 kg.

ASTM D
-1525.

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.

Mold transferability was determined by molding a textured square plate and visually observing its glossiness, and marking a matte board with a Q mark and a glossy board with an x mark.

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 (A-2> was prepared in the same manner as A-1).

A-3: After dissolving 20 parts of polybutadiene rubber (Diene NF35A manufactured by Asahi Kasei Corporation) in 70 parts of styrene and 10 parts of acrylonitrile, bulk polymerization was performed to prepare a graft copolymer (A-3>). did.

A-4: Polybutadiene rubber (° “Diene” NF35A
A graft copolymer (A-4) was prepared by dissolving 20 parts of Asahi Kasei Co., Ltd. in 80 parts of styrene and carrying out bulk polymerization.

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, 20 parts of acrylonitrile, and 10 parts of methacrylic acid.

C-2: A bead-shaped modified vinyl copolymer (C-2) was prepared by suspension polymerization of 60 parts of styrene, 20 parts of acrylonitrile, 5 parts of acrylic acid, and 15 parts of methyl methacrylate.

C-3 = 58 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 2 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: Bead-shaped modified vinyl copolymer (C-5
> was prepared.

Examples 1 to 7 A-1 to A-3 produced in Reference Example 1, C-1 to C-3 produced in Reference Example 2, and PBT-1 as polyester
20OL (polybutylene terephthalate manufactured by Toshiku Co., Ltd.)
were mixed in a Henschel mixer at the mixing ratio shown in Table 1, and then extruded at 250°C using a 40ml 1φ extruder.
After extruding and pelletizing each pellet, 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 shown in Table-1.

Specifications 1 to 5 A-1 to A-4 produced in Reference Example 1 C-1 to C-5 produced in Reference Example 2 and PBT-12 as polyester
0OL (polybutylene terephthalate manufactured by Toshiku Co., Ltd.) were mixed using a Henschel mixer in the proportions shown in Table 1, and then extruded at 250°C using a 40 mφ extruder.
After extruding and pelletizing each pellet, 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 8-14 The same conditions as Examples 1-5 except that PET-J-135 (polyethylene terephthalate manufactured by Mitsui Pet Resin Co., Ltd.) was used as the polyester, the extrusion temperature was 280°C, and the molding temperature was 280°C. I did it. The blending ratio and measurement results of physical properties are shown in Table-2.

Comparative Examples 6-10 Same conditions as Examples 1-5 except that PET-J-135 (polyethylene terephthalate manufactured by Mitsui Pet Resin Co., Ltd.) was used as the polyester, the extrusion temperature was 280°C, and the molding temperature was 280°C. I did it. 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 excellent in @ impact resistance, moldability, heat resistance, chemical resistance, and mold transferability. On the other hand, vinyl copolymers (C-5) which do not contain α,β-unsaturated carboxylic acids as a copolymerization component have poor impact resistance, and modified vinyl copolymers (C-3) which do not contain vinyl cyanide have poor impact resistance. >, the impact resistance is insufficient,
High melt viscosity and poor moldability.

<Effects of the Invention> The thermoplastic resin composition of the present invention contains ABS resin (A), polyester (B), and a specific modified vinyl copolymer (C
) are blended in a specific ratio, but (A) and (B)
The compatibility is extremely good.

Furthermore, the thermoplastic resin composition of the present invention has impact resistance and moldability equivalent to that of ABS resin, heat resistance of aromatic polyester,
In addition to having chemical resistance and mold transferability, it itself has high gloss, so it is possible to obtain molded products with a desired appearance ranging from low gloss to high gloss.

Furthermore, the thermoplastic resin composition of the present invention has moldability and impact resistance equivalent to that of ABS resin, and heat resistance and chemical resistance of polyester, so it can be used in various molded products that take advantage of these characteristics. Can be done.

Claims (1)

[Claims] A modified vinyl polymer obtained by copolymerizing 1 to 98 parts by weight of ABS resin (A), 98 to 1 part by weight of aromatic polyester resin (B), aromatic vinyl, vinyl cyanide, and α,β-unsaturated carboxylic acid. Consisting of 1 to 70 parts by weight of combined (C),
and a thermoplastic resin composition in which the total amount of (A), (B) and (C) is 100 parts by weight.