JPH01163243A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition outstanding in impact and chemical resistances, molding processability and mold transferability, suitable for molded articles with wide choice of gloss and good appearance, by blending ABS resin, aromatic polyester resin and modified vinyl polymer. CONSTITUTION:The objective composition can be obtained by homogeneously blending, using e.g., a high-speed agitator, (A) 1-98 pts.wt. of ABS resin produced by copolymerization between (i) a diene rubber such as polybutadiene, (ii) a vinyl cyanide monomer such as acrylonitrile, and (iii) an aromatic monomer (e.g., styrene), (B) 98-1 pts.wt. of an aromatic polyester resin such as polyethylene terephthalate and (C) 1-70 pts.wt. of a modified vinyl polymer produced by copolymerization between (i) an aromatic vinyl compound such as styrene, (ii) a vinyl cyanide such as acrylonitrile and (iii) a vinyl monomer with epoxy group such as glycidyl acrylate.

Description

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

<1 Original technology> 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 severe 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 WT impact resistance of polyester, blending it with ABS resin has been proposed (for example, JP-A-49-9
7081, JP 56-14546, JP 57-117556, JP 57-13735
Publication No. 0, 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, with the methods generally proposed so far, compositions that are fully satisfactory in terms of total balance of compatibility, mechanical properties, fluidity, etc. cannot be obtained. Not yet.

For example, a simple blend of ABS resin 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 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. Take it as a challenge.

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

That is, the present invention copolymerizes 1 to 98 parts by weight of ABS resin (A), 98 to 1 part by weight of aromatic polyester resin (B), and vinyl monomers having aromatic vinyl, vinyl cyanide, and epoxy groups. Modified vinyl polymer (C) 1
to 70 parts by weight, and the total amount of (A>, (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 monomer (b), aromatic vinyl monomer (c), and if necessary, other copolymerizable monomers (
This is a resin composition consisting of a graft copolymer in which the entire amount of the monomer is graft copolymerized with the diene rubber (i), and a copolymer in which the remaining monomer is copolymerized.

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.
More than one species can be used together.

In the present invention, 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 ρ-t-butylstyrene. Among them, styrene and/or α-methylstyrene are preferably used.

Other copolymerizable monomers (d) include α, β-unsaturated carboxylic acids such as acrylic acid and methacrylic acid, methyl methacrylate, ethyl methacrylate, and methacrylic acid-t-
α, β-unsaturated carboxylic acid esters such as butyl, cyclohexyl methacrylate, α such as maleic anhydride, itaconic anhydride, etc.

Examples include imide compounds of α,β-unsaturated dicarboxylic acids such as β-unsaturated dicarboxylic anhydride #)lJM, N-phenylmaleimide, N-methylmaleimide, and Nt-butylmaleimide.

There are no particular restrictions on the composition ratio of ABS resin (A>), but from the viewpoint of molding processability and impact resistance of the resulting thermoplastic resin composition, diene rubber should be used with respect to 100 parts by weight of ABS VA resin. (a) 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 7 to 45 parts by weight, and 8 to 40 parts by weight is preferred.

The aromatic vinyl (c) is preferably 10 to 90 parts by weight, particularly preferably 13 to 83 parts by weight, and more preferably 17 to 83 parts by weight.
~77 It can be preferably used in the foot part of the heavy background part.

Further, it is preferable that the content of the diene rubber (a) in the entire thermoplastic resin composition is 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. Furthermore, if the weight of the diene rubber in the resin composition is 15% by weight or more, especially 15 to 25% by weight, the impact resistance of the resin composition will be lower than that of the graft copolymer composition and the aromatic polyester resin. This is a dramatic improvement 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 ABS resin (A>), and commonly known methods such as bulk polymerization, solution polymerization, bulk suspension polymerization, suspension polymerization, and emulsion polymerization are used.
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-"biphenyl dicarboxylic acid, 4,4-monodiphenyl ether dicarboxylic acid, 4,4--diphenylmethane dicarboxylic acid, 4,4--diphenylsulfone dicarboxylic acid, 4,4--diphenylisopropylidene dicarboxylic acid, 1,2- Bis(phenoxy)ethane-4,4-monodicarboxylic acid, 2,5-anthracenedicarboxylic acid, 2
．． Examples include 6-anthracene dicarboxylic acid, 4,4-p-terphenylene dicarboxylic acid, 2,5- and lysine dicarboxylic 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. If the amount is small, one or more long-chain diols having a molecular weight of 400 to 6,000, such as polyethylene glycol, poly-1°3-propylene glycol, and polytetramethylene glycol, may be copolymerized.

Specific aromatic polyesters include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate-I, polyethylene-1,2-bis(phenoxy)ethane-4,4'-dicarboxy Examples include copolymerized polyesters such as polyethylene isophthalate/terephthalate, polybutylene terephthalate/isophthalate, and 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) (hereinafter referred to as copolymer (C)) used in the present invention is a vinyl monomer having aromatic vinyl (a), vinyl cyanide (b), and an epoxy group. ) 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 these, styrene and α'-methylstyrene are preferred. Examples of vinyl cyanide (b) include acrylonitrile and methacrylate trile. Among them, acrylonitrile is preferred. The vinyl monomer (c) having an epoxy group is a compound that shares both a radically polymerizable vinyl group and an epoxy group in one molecule, and specific examples include glycidyl acrylate, glycidyl methacrylate, and ethacrylic acid. Glycidyl, glycidyl esters of unsaturated organic acids such as glycidyl itaconate, glycidyl ethers such as allyl glycidyl ether, and bipedal derivatives such as 2-methylglycidyl methacrylate, among which glycidyl acrylate, Glycidyl methacrylate is preferably used for convenience. Further, these can be used alone or in combination of two or more.

The copolymerization amount occupied by the vinyl monomer having an epoxy group in the copolymerization K (C) composed of the above copolymerization components is preferably 0.001 to 14% by weight, more preferably 0.01 to 5% by weight. % range. Copolymerization amount is 0.00
If the amount is less than 1 part by weight, the impact strength of the composition will be low, and if it exceeds 14 parts by weight, the copolymer will tend to gel, making it impossible to obtain a molded product with a good surface condition.

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 α, β-unsaturated carboxylic acids such as acrylic acid and methacrylic acid, α, β-unsaturated carboxylic acids such as methyl methacrylate, ethyl methacrylate, tert-butyl methacrylate, and cyclohexyl methacrylate. - Unsaturated carboxylic acid esters, maleic anhydride, itaconic anhydride and other α, β-unsaturated dicarboxylic anhydrides - Phenylmaleimide, N-methylmaleimide, N-t-butylmaleimide and other α, β- , imide compounds of β-dicarboxylic acid, and the like.

In the thermoplastic resin composition of the present invention, AB S IM
The blending ratio of fat (A), polyester (B) and copolymer (C) is 1 to 98 parts by weight, preferably 2 to 9 parts by weight.
4 parts by weight, particularly preferably 5 to 90 parts by weight, (B) is 9
8 to 1 parts by weight, preferably 94 to 2 parts by weight, particularly preferably 90 to 5 parts by weight, and (C) is 1 to 70 parts by weight,
Preferably 2 to 65 heavy shadow parts, particularly preferably 5 to 60 heavy view parts, and the sum of (A>, (B) and (C) is 1
00 parts by weight. If ()\) 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, and (A
If > exceeds 98 parts by weight, if (B) is less than 1 part by weight, chemical resistance and mold transferability will be poor, and if (C) exceeds 70 parts by weight, moldability will be poor, which is not preferred.

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, A B S l; 31 The resin (A), polyester (B), and copolymer (C) are mixed uniformly in the form of pellets, powder, small pieces, etc. using a high-speed stirring machine, and then thoroughly kneaded. Various methods can be employed, such as melt-kneading in a capable single-screw or multi-screw 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 a predetermined composition is prepared. 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 7/acrylonitrile copolymer (SAN), Polymethyl methacrylate (PMMA), styrene/methyl methacrylate/acrylonitrile copolymer, α-methylstyrene/acrylonitrile copolymer, α-methylstyrene/styrene/acrylonitrile copolymer, α-methylstyrene/methyl methacrylate/ Acrylonitrile copolymer, p-methylstyrene/acrylonitrile copolymer, styrene/N-
Vinyl polymers such as phenylmaleimide copolymer, methacrylic acid-butadiene-styrene terpolymer ('M
BS) resin, ABS resin, AAS resin, polycarbonate, polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), etc. by appropriately mixing thermoplastic resins, polyethylene, polypropylene, ethylene/propylene copolymer. , ethylene/butene-1 copolymer, ethylene/propylene/dicyclopentadiene copolymer, ethylene/propylene 15-ethylidene-2-norbornene copolymer, ethylene/propylene/1,4-
By appropriately mixing polyolefin rubbers such as hexadiene copolymer, ethylene/vinyl acetate copolymer, and ethylene/butyl acrylate copolymer, it is also possible to adjust the physical properties and characteristics to more desirable ones. Depending on the purpose, pigments, dyes, reinforcing materials and fillers such as glass fibers, metal fibers, metal flakes, and carbon fibers, heat stabilizers,
Antioxidants, ultraviolet absorbers, light stabilizers, lubricants, plasticizers,
Antistatic agents, 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 flow tester at a resin temperature of 250 to 280°C and a load of 50°C.
The measurement was carried out under the condition of kg. As an evaluation of heat resistance, Vicat softening temperature was measured according to 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.

For mold transferability, a textured square plate was molded and its gloss was visually observed, and those with no gloss were expressed as ○, and those with gloss were expressed as ×.

Note that the following parts and percentages represent parts by weight and weight e6, 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
5μ, gel content 80%)) 40 parts of a monomer mixture consisting of 70% styrene and 30% acrylonitrile was emulsion polymerized in the presence of 60 parts (solid content equivalent).

The obtained Graph I 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: ;li liptadiene rubber (“diene” N F
After dissolving 20 parts of 35A manufactured by Asahi Kasei Co., Ltd. in 80 parts of styrene, bulk polymerization was performed to obtain a graft copolymer (A-4).
was prepared.

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 75 parts of styrene, 24 parts of acrylonitrile, and 1 part of glycidyl methacrylate.

C-2: Prepare bead-shaped modified vinyl copolymer (C-2>) by suspension polymerizing 60.8 parts of styrene, 24 parts of acrylonitrile, 0.2 parts of glycidyl acrylate, and 15 parts of methyl methacrylate. did.

C-3; 58 parts of styrene, 15 parts of α-methylstyrene,
Bead-shaped modified vinyl copolymer (C
-3) was prepared.

C-4: Bead-shaped modified vinyl copolymer (C
-4> was prepared.

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° using a 40 mmφ extruder.
After extrusion at C 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.

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 PBT-12 as polyester
0OL (polybutylene terephthalate manufactured by Toshiku Co., Ltd.) were mixed in a Henschel mixer at the compounding ratio shown in Table 1, and then extruded at 250°C using a 40-diameter 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 to 14 PET-J-135 (Mitsui Pets) as polyester
The experiments were carried out under the same conditions as in Examples 1 to 5, except that polyethylene terephthalate (manufactured by Resin Co., Ltd.) was used, 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 Example 6-10 Using PET-J-155 (polyethylene terephthalate 1- manufactured by Mitsui Pet Resin Co., Ltd.) as the polyester,
The conditions were the same as in Examples 1 to 5 except that 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 excellent in impact resistance, moldability, heat resistance, chemical resistance, and mold transferability. On the other hand, vinyl copolymers (C-5
) has poor E"A resistance, and modified vinyl copolymers containing no vinyl cyanide (C-3> have insufficient impact resistance, 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) having an epoxy group in a specific ratio. ,
In particular, the compatibility of (A> and (B)) is extremely good due to the presence of the epoxy group.

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 properties. can.

Claims (1)

[Claims] A modified vinyl type obtained by copolymerizing 1 to 98 parts by weight of ABS resin (A), 98 to 1 part by weight of aromatic polyester resin (B), and a vinyl monomer having aromatic vinyl, vinyl cyanide, and an epoxy group. A thermoplastic resin composition comprising 1 to 70 parts by weight of a polymer (C), and the total amount of (A), (B) and (C) is 100 parts by weight.