JPH0453864A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition excellent in impact resistance, heat resistance and chemical resistance by mixing an ABS resin with a specified modified polyester resin and a specified vinyl polymer. CONSTITUTION:10-84 pts.wt. ABS resin (A) is mixed with 15-89 pts.wt. polyester resin (B) pared by modifying 100wt.% thermoplastic polyester prepared from an 8-20 C aromatic dicarboxylic acid or its lower alkyl ester and a 2-20 C diol with 0.01-20wt.% phenolic hydroxyl-containing organic sulfonic acid salt of the formula (wherein Ar is a 6-30 C aromatic ring; M is an alkali metal or an alkaline earth metal; m is 1 or 2; and n is 1-5) and 1-70 pts.wt. modified vinyl polymer (C) comprising an aromatic vinyl, vinyl cyanide and an epoxy vinyl monomer (the total of components A, B and C is 100 pts.wt.). In this way, a thermoplastic resin composition having both the impact resistance of the ABS resin and the heat resistance and chemical resistance of the polyester resin can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Field of Application> The present invention relates to a thermoplastic resin composition having excellent impact resistance, heat resistance 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 heat resistance, and its use is restricted under severe conditions.

In addition, polyester resin has excellent mechanical properties, electrical properties, chemical resistance, l1r1 heat resistance, etc., and is widely used as engineering plastics, but it has the disadvantage of poor impact resistance. Among them, some thermoplastic polyesters, such as polyethylene terephthalate, have particularly excellent properties, but their crystallization rate is slow, so they do not crystallize well in the low-temperature molds of 50 to 95 °C used for ordinary injection molding. At present, it is not widely applied to injection molding applications because it is difficult to obtain satisfactory molded products.

Therefore, in order to improve the impact resistance of polyester, blending it with ABS resin has been proposed (for example, JP-A-49-97081, JP-A-56-14546).
Publication No. 117556, Japanese Patent Publication No. 117556, Japanese Patent Application Laid-Open No. 1983
-137350, JP-A-60-36558, JP-A-60-123550, etc.).

Blends of polyesters 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 (e.g. Japanese Patent Publication No. 49-9708
Publication No. 1, JP-A-59-138256, JP-A-6
0144349, JP-A-60-26'2847, 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 Publication) 6 Next, as a method for improving the crystallization rate of thermoplastic polyester, for example, a sulfonic acid group with an alkali metal chloride on an aromatic ring selected from a benzene ring, a naphthalene ring, and an anthracene ring, and an alkali metal chloride with a sulfonic acid group A crystallization accelerator for polyester has been proposed which requires the bonding of phenolic hydroxyl groups (JP-A-56-57825).

In addition, a method for producing polyester for molding with improved crystallization rate has been proposed, which is characterized by adding an alkali metal salt of isethionic acid during polymerization of polyester (
(Japanese Unexamined Patent Publication No. 49-88993).

In addition, a high-speed crystallization polyester characterized by polymerizing polyester in the presence of a copolymer component or an alkali metal that converts the ends of polyester into metal salts has been proposed (Japanese Patent Laid-Open Publication No. 9291.8/1982).
.

<Problem to be solved by the invention> However, to date, the methods proposed for boat fishing have not yielded compositions that are fully satisfactory in terms of the total balance of compatibility, mechanical properties, and fluidity. First, there were problems in that not only the crystallization rate of polyester was not improved much, but also the mechanical properties of the molded product were deteriorated.

Therefore, the present inventors significantly improved the crystallization rate of thermoplastic polyester to obtain a polyester resin composition having good mechanical properties, and at the same time, the chemical resistance of polyester was improved without impairing the moldability of ABS resin. The object of the present invention is to obtain a resin composition that has both properties and heat resistance, and has impact resistance higher than that of ABS resin.

Means for Solving the Problems> The present inventors have conducted extensive studies to solve the above problems.
As a result, we have arrived at the present invention.

That is, the present invention is a thermoplastic polyester 100 using as starting materials 10 to 84 parts by weight of ABS resin FA), an aromatic dicarboxylic acid having 8- or -20 carbon atoms, or a lower alkyl ester thereof, and a diol having 2 to 20 carbon atoms. 15 to 89 parts by weight of a polyester resin (B) modified with 001 to 20% by weight of a phenolic hydroxyl group-containing organic sulfonate represented by the following general formula, aromatic vinyl, vinyl cyanide, and epoxy groups. modified vinyl polymer (C) consisting of a vinyl monomer having 1 to 70 parts by weight, and the total amount of FA>, (B) and (C) being 10
0 parts by weight of the thermoplastic resin composition.

HO-Ar-fsO3-4M)l/,)n--・-・■
(In the formula, Ar is an aromatic ring having 6 to 30 carbon atoms, M is an alkali or alkaline earth metal, m is 1 or 2, n
represents an integer from 1 to 5. ) Hereinafter, the present invention will be specifically explained.

The ABS resin (A) used in the present invention refers to diene rubber (
(a), vinyl cyanide monomer (b), aromatic vinyl monomer (viii), and if necessary, other copolymerizable monomers (
This is a resin composition consisting of a graft copolymer in which the entire 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 the 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-, β-carboxylic acids such as acrylic acid and methacrylic acid, methyl methacrylate, ethyl methacrylate, and methacrylic C-t-
α, β-, butyl, cyclohexyl methacrylate, etc.
β-carboxylic acid esters, α, β-unsaturated dinorphonic anhydrides such as maleic anhydride, itaconic anhydride, phenylmaleimide, N-methylmaleimide, N-t
-α such as butylmaleimide.

Examples include imide compounds of β-unsaturated dicarboxylic acids.

There is no particular restriction on the composition ratio of the ABS resin (^), but from the viewpoint of moldability and impact resistance of the resulting thermoplastic resin composition, the diene rubber (A) is used for 100 parts by weight of the 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 7 to 45 parts by weight, and more preferably 8 to 40 parts by weight. The aromatic vinyl (c) is preferably 10 to 90 parts by weight, particularly preferably 13 to 83 parts by weight, and further 1
It can be preferably used in a range of 7 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 (8), 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 thermoplastic polyester used in the present invention is a polymer or copolymer obtained by a polycondensation reaction containing a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof as main components.

Examples of such radical carboxylic acids 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'-diphenyl ether dicarboxylic acid, 4,4'-diphenylmethane dicarboxylic acid, 4,4'-diphenylsulfone dicarboxylic acid,
4,4'-diphenylisopropylidenedicarboxylic acid,
1.2-bis(phenoxy)ethane-4,4'-dicarboxylic acid, 2.5-anthracenedicarboxylic acid, 2.6-
Aromatic dicarboxylic acids such as anthracene dicarboxylic acid, 4.4'-p-terphenylene dicarboxylic acid, 2.5-pyridine dicarboxylic acid, adipic acid, azelaic acid,
These include aliphatic dicarboxylic acids such as dodecanedioic acid and sebacic acid, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, and terephthalic acid is preferably used.

Note that two or more of these dicarboxylic acids may be used in combination.

The diol components include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, and 2-methyl glycol.
1,3-Propanediol Diethylene glycol, aliphatic diol such as triethylene glycol, 1,4
-Alicyclic diols such as cyclohexane dimetatool, 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, polypropylene glycol, polytetramethylene glycol, etc., may be copolymerized.

Examples of cooperating thermoplastic polyesters include polyethylene terephthalate, polypropylene terephthalate,
In addition to polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polycyclohexane dimethylene terephthalate, and polyethylene 1,2-bis(phenoxy)ethane-4,4'-dicarboxylate, polyethylene isophthalate/terephthalate, Examples include copolymerized polyesters such as butylene terephthalate 2 isophthalate, polybutylene terephthalate 7·'decanedicarboxylate, and polycyclohexane dimethylene terephthalate/'isophthalate. Among these, polybutylene terephthalate, polycyclohexane dimethylene terephthalate, polyethylene naphthalate, and polyethylene terephthalate, which have well-balanced mechanical properties and moldability, can be preferably used.

The thermoplastic polyester used in the present invention is 0-
The intrinsic viscosity of a chlorophenol solution measured at 25°C is 0.
25-3.0 dl,/g, especially 04-2.25
A/g is preferred.

In the present invention, the compound added to polyester to modify it in order to improve the crystallization rate has the following structural formula.

HO-ArMo303 +M) l/jn””
"■ (In the formula, Ar represents an aromatic ring having 6 to 30 carbon atoms, M represents an alkali or alkaline earth metal, m represents 1 or 2, and n represents an integer from 1 to 5.) In 2〇, examples of the aromatic ring that forms the basic skeleton include hydrocarbon aromatic rings such as benzene, naphthalene, phenanthrene, an[・racene, and pyrene], pyridine, triazine, furan, N, noline, inquinoline, 1 .10-Phenanthrene and other heteroaromatic rings, as well as cyclic systems containing general aromatic rings such as indene, indole, benzofuran, fluorene, and dibenzofuran, are also used, and there are no particular limitations.

Here, it is essential that the aromatic ring has one hydroxyl group bonded to it, and if it does not have a hydroxyl group, it will hardly show any effect of improving the crystallization rate. Furthermore, the hydroxyl group must not be metal chlorinated with a metal such as an alkali metal. This is because when the hydroxyl group is converted into a metal salt, the compound itself tends to precipitate out of the polymerization system due to the strong gathering power of the salt, and often becomes a sludge, making the effect of improving the crystallization rate insufficient. Otherwise, the mechanical properties of the molded article made from the obtained thermoplastic polyester composition will be deteriorated.

Furthermore, one or more metal chlorinated sulfonic acid groups must be bonded to the aromatic ring, or it is desirable that the number of such groups be small. This is for the same reason as mentioned above. That is, if there are too many of these groups, they will not be uniformly dispersed in the polymerization system and will become solid, reducing the effect of improving the crystallization rate and deteriorating the mechanical properties of the molded product. Therefore, the number of metal chlorinated sulfonic acid groups is preferably 2.
A is also preferably one.

The aforementioned hydroxyl group and metal chlorinated sulfonic acid group can be bonded to any bondable position of the aromatic ring.

However, the degree of improvement in crystallization rate obtained differs depending on the position of the substituent. For example, in the case of sodium phenolsulfonate, there are three possible substituent positions: ortho, meta, and para, but the para position significantly improves the crystallization rate; The effect of improving crystallization rate tends to be smaller. Also,
In the case of phenol disulfonic acid disodium salt, the bonding positions of the sulfonic acid are 2.3; 2.4, 2,5
; 2, 6 ; 3.4 + 3.5, which are six,
Among these, the one with the largest improvement effect on crystallization rate is 2.6;
3.5, and the 3rd and 5th positions are particularly preferred.

As described in the examples above, those in which a substituent is bonded to the aromatic ring so as not to destroy the symmetry are particularly preferred because they have a large effect of improving the crystallization rate.

In addition, the additive of the present invention may be any W that does not inhibit the effects of the present invention other than hydroxyl groups and metal chlorinated sulfonic acid groups.
, may contain substituents. Such substituents include methyl groups, aliphatic groups such as ethyl groups, halogen groups such as chromium and bromine, cyanide groups, nitro groups, aral groups such as acetyl, propionyl, and pageyl, methylsulfonyl, ethylsulfonyl, and phenyl. Sulfonyl groups such as sulfonyl and tolylsulfonyl; carboxamide groups such as N-phenylcarboxamide, N-ethylcarboxamide and N-propylcarboxamide; 1. methoxy,
Examples thereof include alkoxy groups such as ethoxy and aromatic groups such as phenyl, among which aliphatic groups, halogen groups and alkoxy groups are preferred.

Specific examples of the compound represented by the above formula include compounds obtained by converting the sulfonic acid group of the following compound into a metal salt with an alkali metal or an alkaline earth metal.

That is, the base compounds include 0-phenolsulfonic acid, m-phenolsulfonic acid, P-phenolsulfonic acid, 1-hydroxy-3,5-benzenedisulfonic acid, 1-hydroxy-2,6-benzenedisulfonic acid, 1 -hydroxy-2,4-benzenedisulfonic acid,
Examples include 1-hydroxy-3,4-benzenedisulfonic acid, 2-naphthol-6-sulfonic acid, 1-naphthol-5-sulfonic acid and 1-naphthol-4-sulfonic acid, 9-droxy-10-anthracenesulfonic acid, etc. ,
Among them, phenolsulfonic acid, particularly P-phenolsulfonic acid, is most preferred from the viewpoint of performance and economy.

The metal of the metal salt of the sulfonic acid compound used in the present invention is preferably an alkali metal such as lithium, sodium, potassium, rubidium, or cesium, or an alkaline earth metal such as calcium or barium. Among the alkali metals, lithium and sodium are particularly preferred. preferable.

The amount of the sulfonic acid metal salt compound added in the present invention is from 0.01 to 100 parts by weight of the thermoplastic polyester.
When the amount added is less than 20 parts by weight, preferably 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, or less than 0.01 parts by weight, the effect of improving the crystallinity of the thermoplastic polyester is If the amount exceeds 20 parts by weight, the melt viscosity increases, the fluidity of the resin deteriorates, and the mechanical properties tend to deteriorate, which is not preferable.

In order for the sulfonic acid metal salt compound of the present invention to exhibit the most excellent crystallization rate improvement effect, the polymerization conditions must be devised,
The obtained polyester composition contains 1 to 2 polyester components having a molecular weight of 2,000 or less in polystyrene Wx molecular weight and a sulfur concentration of 0,005% by weight or more.
It is desirable to polymerize to contain 0% by weight of 9 molecular weight 2
．． The content of oligomers below 0.000 can be determined by conventional gel permeation chromatography methods. As a solvent, Q-triphenol/chloroform-1/
4 (vol/v.

1) A differential refractometer can be used as the detector. That is, the column was calibrated using commercially available polystyrene with a narrow molecular weight distribution, and the molecular weight of polystyrene was 2. The proportion of the area after the retention time corresponding to OOO is determined, and the oligomer content is calculated.

In addition, the amount of sulfur contained in the oligomer has a molecular weight of 2
,000 or less of the polyester component and quantifying it by elemental analysis.

As a method for modifying a polyester resin modified with a phenolic hydroxyl group-containing organic sulfonate, it is preferable to add the phenolic hydroxyl group-containing organic sulfonate during polycondensation of polyester. It also varies depending on the time of addition of the sulfonate compound and the method of addition (powder, solution, suspension).

It is also greatly influenced by the reaction conditions of the esterification reaction, transesterification reaction, or polymerization reaction (type of catalyst, amount of catalyst, temperature, speed of temperature increase, degree of pressure reduction, speed of pressure reduction, etc.). The optimal conditions depend on the sulfonate compound having a phenolic hydroxyl group to be added, and although it is difficult to generalize, in general, the timing of addition of the sulfonate compound having a phenolic hydroxyl group is during the transesterification reaction. , addition at the initial stage of the esterification reaction, or even before the reaction, often gives desirable results.

For the polyester resin of the present invention, various m-acid salts known as moldability improvers for thermoplastic polyesters, such as polyethylene terephthalate, and 41! ! It is also preferable to use organic compounds together from the viewpoint of improving moldability. Specific examples of these compounds include stearates such as sodium stearate and barium stearate;
Sodium salts of partially saponified montanic acid esters, barium salts, ionomers, sodium salts of β-diketones, sodium salts of talc and salicylanilide, sodium salts of salicylaldehyde, sodium salts of substituted phenols, such as sodium salts of nitrophenol. Examples include.

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 them, styrene and α-methylstyrene are preferred, and examples of the 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, glucidyl methacrylate, and ethacrylic acid. Unsaturated compounds such as glycidyl and glycidyl itaconate! Examples include glycidyl esters of acid A, glycidyl ethers such as allyl glycidyl ether, and the above-mentioned derivatives such as 2-methylglycidyl methacrylate, among which glycidyl acrylate and glycidyl methacrylate are preferably used. 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 copolymer (C) composed of the above copolymerization components is preferably 0.001 to 10% by weight, more preferably 0.01 to 5% by weight. % range. Copolymerization amount is 0.00
When the amount is less than 1% by weight, the impact strength of the composition is low, and when it is more than 10% by weight, the copolymer tends to gel, making it impossible to obtain a molded article 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. +41f mouth)
There are no particular restrictions on the preparation method for and (c).
The monomers may be charged all at once at the initial stage, or part or all of the monomers may be continuously or dividedly charged in order to prevent the formation of a compositional distribution of the copolymer.

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 (() 1) and (c).

Other copolymerizable monomers include α, β-unsaturated carboxylic acids such as acrylic acid and methacrylic acid, α, such as methyl methacrylate, ethyl methacrylate, t-butyl methacrylate, and cyclohexyl methacrylate. β-unsaturated carboxylic acid esters, monohydric acid, α-β-unsaturated dicarboxylic anhydrides such as itaconic anhydride, N-phenylmaleimide, N-methylmaleimide, N-t-butylmaleimide, etc. Examples include imide compounds of α,β-unsaturated dicarboxylic acids.

ABS resin (A) in the thermoplastic resin composition of the present invention
Polyester resin FB) and modified vinyl polymer (C
) The blending ratio of (A) is 10 to 84 parts by weight, preferably 12 to 80 parts by weight, particularly preferably 14 to 75 parts by weight,
(B) is 15 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 60 parts by weight and fA), FB> and (
The ratio is such that the total amount of C) is 100 parts by weight. fA>
is less than 1 part by weight, fB) 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, and if (^) is more than 84 parts by weight. ,(B)
If the amount is less than 15 parts by weight, chemical resistance will be poor, and (C) will be 70!
Exceeding this amount is undesirable because the moldability is poor.6 Furthermore, by adding a crystallization accelerator commonly used for thermoplastic polyesters to the thermoplastic resin composition of the present invention, moldability and mechanical properties can be improved. This can be further improved. Specific examples of such crystallization promoters include polyalkylene glycols such as polyethylene glycol and polypropylene glycol, their carboxylic acid diesters, α,ω-dialkyl etherified polyethylene glycol, α,ω-dialkyl etherified polypropylene glycol, etc. α.

ω-dialkyl etherified polyalkylene glycol,
Benzoic acid ester compounds such as neopentyl glycol dibenzoate and aliphatic polyesters such as polycabrolactone and polyethylene adipate can be preferably used.

Further, by further adding a filler and/or a reinforcing material to the thermoplastic resin composition of the present invention, the regularity can be significantly improved. Such fillers and/or reinforcements include glass fibers, carbon fibers,
Metal fibers, aramid fibers, asbestos, potassium titanate whiskers, wollastenite, crow flakes, glass peas, talc, mica, clay, calcium carbonate, barium sulfate, titanium oxide and aluminum oxide are among the most commonly found. Strand type glass fiber is preferably used. The amount of these additives is preferably 120 parts by weight or less based on 100 parts by weight of the thermoplastic resin composition.

Furthermore, the thermoplastic resin composition of the present invention may contain antioxidants, heat stabilizers, light stabilizers, antistatic agents, flame retardants, ultraviolet absorbers, lubricants, and mold release agents within a range that does not impair the purpose of the present invention. and usual additives such as colorants including dyes and pigments.
More than one species can be added.

The thermoplastic resin composition of the present invention also includes ABS resin (^),
Polyester resin (B) and modified vinyl polymer (C
), as necessary, polystyrene (PS), styrene/acrylonitrile copolymer <5AN), polymethyl methacrylate (PMMA), styrene/'methyl methacrylate/acrylonitrile copolymer, α-methylstyrene/ Acrylonitrile copolymer, α-methylstyrene styrene/acryloni 1-helyl copolymer, α-methylstyrene/methyl methacrylate/acrylonitrile copolymer, p-methylstyrene/acrylonitrile copolymer,
Vinyl polymers such as styrene/N-phenylmaleimide copolymer, methacrylic acid-butadiene-styrene copolymer (MBS) resin, AES resin, AAS resin, polycarbonate, polycaproamide (nylon 6), polyhexane By appropriately mixing thermoplastic resins such as methylene adipamide (Nairon 66), polyethylene, polypropylene, ethylene/propylene copolymer, ethylene/butene-1 copolymer, ethylene/propylene/dicyclopentadiene copolymer. , ethylene/brobi17/・5-
Ethylidene-2-norbornene copolymer, ethylene 7.
By appropriately mixing polyolefin rubbers such as 'propylene/1,4-hexadiene copolymer, ethyne' vinyl acetate copolymer, and ethylene/butyl acrylate copolymer, more desirable physical properties and characteristics can be adjusted. It is also possible to do so.

'Ij! of the thermoplastic resin composition of the present invention! There are no particular restrictions on the method of adding the filler, the reinforcing material, and the additives, and generally known methods can be employed. In other words, ABSt! ! J fat (^
), polyester resin (B), modified vinyl polymer (C
) and/or fillers, reinforcing materials, and additives.
-Various methods can be employed, such as a method in which the mixture is uniformly mixed in the form of powder or pieces, and then melt-kneaded using a single-screw or multi-screw extruder with sufficient kneading capacity.

<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 y'2'' isot impact strength was measured according to ASTM D256-56. 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.

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

Reference Example 1 ABSlij fats A-1 to A-3 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) (gel content 80%).

The obtained graft copolymer was coagulated with sulfuric acid. Neutralize with hardened caustic soda, wash, filter, Graft copolymerization in dry powder form The body (A-1) was prepared.

A-2: Polybutadiene latex 4 used in A-1
After emulsion polymerizing 60 parts of a monomer mixture consisting of 15% methyl methacrylate, 65% styrene, and 20% acrylonitrile in the presence of 0 parts (solid content), a powdery graft copolymer was prepared in the same manner as A-1. A polymer (A-2) was prepared.

A-32 Polybutadiene latex 4 used in A-1
After emulsion polymerizing 60 parts of styrene in the presence of 0 parts (in terms of solid content), a powdery graft copolymer (A-3) was prepared in the same manner as A-1.

Reference Example 2 Polyester resins B-1 to B-5 were manufactured by the following method.

100 parts by weight of dimethyl terephthalate, 62 parts by weight of ethylene glycol, 0.16 parts by weight of lithium acetate, 0.04 parts by weight of antimony dioxide, and 0.02 parts by weight of manganese acetate.
Further, predetermined amounts of additive compounds shown in Table 1 were added to each part by weight of the mixture. After raising the temperature to 140°C and melting dimethyl terephthalate, stirring was started and 1
The temperature was raised from 40°C to 245°C over 35 hours to carry out the transesterification reaction, and most of the methanol was distilled off. Next, while raising the temperature from 245°C to 280°C over 3 hours, the vacuum was gradually drawn down to 06+m+1l (under a vacuum of 06+m+1l).
Polymerization was performed.

Regarding the obtained polyethylene terephthalate composition,
Differential thermal analysis was performed using a differential scanning calorimeter manufactured by PerkinElmer, and crystallinity was evaluated by measuring the heating-up crystallization temperature and cooling-down crystallization temperature. As is generally known,
The higher the cooling crystallization temperature is, the lower the heating crystallization temperature is, the better the crystal quality is.△T=
The ΔT obtained by (cooling down crystallization temperature) - (heating up crystallization temperature) was used as a measure of crystallinity.

Moreover, the intrinsic viscosity of the Q-chlorophenol solution at 25°C was measured for each sample. These results are shown in Table 1.

Table Reference Example 3 Modified vinyl polymers C-1 to C-3 and vinyl polymer C-4 were prepared according to the following formulations.

C-1: Prepare a bead-shaped modified vinyl polymer (C-1>) by suspension polymerizing 75 parts of styrene, 24 parts of acrylonitrile, and 1 part of glycidyl methacrylate.

C-2: A bead-shaped modified vinyl polymer (C-2) was prepared by suspension polymerization of 60.8 parts of styrene, 24 parts of acrylonitrile, 0.2 parts of glycidyl acrylate, and 15 parts of methyl methacrylate.

C-3=Bead-shaped modified vinyl polymer (C-3) was prepared by suspension polymerization with 5 parts of styrene and 5 parts of glycidyl methacrylate.

C-4=2 parts of styrene and 28 parts of acrylonitrile were subjected to suspension polymerization to prepare a bead-shaped vinyl polymer (C-4).

Examples 1 to 7 A-1, A-2 produced in Reference Example 1, B-1, B-2 produced in Reference Example 2, and C-1, C produced in Reference Example 3
-2 were mixed in a Henschel mixer at the compounding ratio shown in Table 2, and then extruded using a 40 mm diameter extruder at an extrusion temperature of 260°C to form pellets I~.For each pellet, the molding temperature was 260°C and the mold temperature was 80°C. Each test piece was prepared by injection molding at ℃, and its physical properties were evaluated. These results are shown in Table 2.

Comparative Example 1-10 A-1 to A-3 produced in Reference Example 1, B-1 to B-5 produced in Reference Example 2, and C-1 to C- produced in Reference Example
4 were mixed in a Henschel mixer at the mixing ratio shown in Table 2, and then extruded at 260°C using a 40 mm diameter extruder.
After extruding and forming each pellet into a pellet, each pellet was subjected to injection molding at a molding temperature of 260° C. and a mold temperature of 80° C. to prepare each test piece, and its physical properties were evaluated. These results are also shown in Table 2.

The following is clear from the Examples and Comparative Examples.

That is, all of the products obtained according to the present invention have excellent impact resistance, heat resistance, and chemical resistance. On the other hand, a vinyl polymer (C-4) which does not contain a vinyl monomer having an epoxy group as a copolymerization component, a modified vinyl polymer (C-3) which does not contain vinyl cyanide, and a modified vinyl polymer (C-3) which does not contain vinyl cyanide. If the polymer is not blended or if the amount of the modified vinyl polymer is deviated from the specified amount, the impact resistance will be poor.

In addition, a polyester resin composition (B-3) in which no additive is added to the polyester resin composition, and a polyester resin composition (B-4) in which the additive amount of sodium p-phenolsulfonate is less than the specified amount. , a polyester resin composition containing disodium p-phenolsulfonate as an additive (B-5), and a polyester resin composition containing no polyester resin composition and a polyester resin composition containing less than the specified amount have poor heat resistance, Poor chemical resistance.

In addition, ABS resin that does not contain vinyl cyanide (A-3
) and those without ABS resin have poor impact resistance.

<Effects of the Invention> As explained above, the resin composition of the present invention is a resin composition that has both the impact resistance of ABS resin and the heat resistance and chemical resistance of polyester resin, and this effect is ABSt! I fat (
^), a polyester resin CB) with excellent crystallinity and a modified vinyl polymer (C) are blended as essential components.

Claims (1)

[Claims] 100 parts by weight of a thermoplastic polyester starting from 10 to 84 parts by weight of ABS resin (A), an aromatic dicarboxylic acid having 8 to 20 carbon atoms or its lower alkyl ester, and a diol having 2 to 20 carbon atoms. %, the following general formula (I)
Phenolic hydroxyl group-containing organic sulfonate represented by 0
．． Polyester resin (B) modified with 01 to 20% by weight
(A
), (B) and (C) in a total amount of 100 parts by weight. HO-Ar■SO_3■M)_1_/_m]n...(
I) (In the formula, Ar represents an aromatic ring having 6 to 30 carbon atoms, M represents an alkali or alkaline earth metal, m represents 1 or 2, and n represents an integer from 1 to 5.)