JPH0453862A - 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 modified vinyl polymer. CONSTITUTION:10-84 pts.wt. ABS resin is mixed with 15-89 pts.wt. polyester resin prepared by modifying 100wt.% thermoplastic polyester prepared from an 8-20C aromatic dicarboxylic acid or its lower alkyl ester and a 2-20C diol with 0.01-20wt.% phenolic hydroxyl-containing organic sulfonic acid salt of the formula (wherein Ar is a 6-30C 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 prepared by copolymerizing an aromatic vinyl with vinyl cyanide and an alpha,beta-unsaturated carboxylic acid (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, 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 good properties but have a slow crystallization rate, so they can be heated at temperatures between 50°C and 95°C, which are commonly used in injection molding.
At present, these low-temperature molds do not crystallize sufficiently and cannot produce satisfactory molded products, so they are not widely used in injection molding applications.

Therefore, in order to improve the impact resistance of polynisdel, binding with ABS resin has been proposed (for example, JP-A-49-97081, JP-A-56-145).
46, JP-A-57-117556, JP-A-57-137350, JP-A-60-36558, JP-A-60-123550, etc.).

In addition, a blend of polyester and a graft copolymer obtained by copolymerizing α, β-unsaturated dicarboxylic acid anhydride or unsaturated carbonamide with other monomers into a rubber-like polymer has also been proposed. (For example, JP-A-49-9
7081, JP-A-59-138256, JP-A-60-144349, JP-A-60-2628
47, 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).

Next, methods for improving the crystallization rate of thermoplastic polyester include, for example, benzene rings, naphthalene rings,
A crystallization accelerator for polyester has been proposed in which an alkali metal-chlorinated sulfonic acid group and an alkali metal-chlorinated phenolic hydroxyl group are bound to an aromatic ring selected from anthracene rings (Japanese Patent Laid-Open No. 5657825
Publication No.).

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 isethioni-Y phosphoric acid during polymerization of polyester (Japanese Patent Application Laid-Open No. 88993/1989). .

In addition, a copolymerization component that converts the terminal end of polyester into a metal salt, or a high-speed crystallization polyester characterized by polymerizing polyester in the presence of an alkali metal has been proposed (Japanese Patent Laid-Open No. 56-92918).
.

<Problem to be solved by the invention> 17 However, in the methods proposed for boat fishing so far, compatibility, I! A composition that is completely satisfactory in terms of the total balance of mechanical properties and fluidity has not been obtained, and not only has the crystallization rate of polyester not improved significantly,
There was a problem that the mechanical properties of the molded product deteriorated.

Therefore, the present inventors significantly improved the crystallization rate of thermoplastic polyester to obtain a polyester resin composition having good mtiti physical properties, while at the same time improving the chemical resistance of polyester 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 ABSII resin.

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

That is, the present invention provides 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 a lower alkyl ester thereof, and a diol having 2 to 20 carbon atoms. %, polyester resin fB) modified with 0.01 to 20% by weight of a phenolic hydroxyl group-containing organic sulfonate represented by the general 2〇 below, and 15 to 89 parts by weight of aromatic vinyl and vinyl cyanide. and a modified vinyl polymer (C) formed by copolymerizing α, β-unsaturated carboxylic acid from 1 to 70 parts by weight, and the total amount of (A), fB) and FC) is 100 parts by weight. A thermoplastic resin composition is applied thereto.

HOAr(E-3()3+M)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.

ABSI used in the present invention! F fat (A) refers to diene rubber (a), vinyl cyanide monomer (b), aromatic vinyl monomer (c), and if necessary, other copolymerized monomers (2). :), and the entire amount of the monomer is graft-copolymerized with the diene rubber (A), and the remaining monomer is copolymerized with the remaining monomer. .

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. Alternatively, 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, p-methylstyrene, and pt-butylstyrene. Among them, styrene and/or α-methylstyrene are preferably used.

Other copolymerizable monomers (:) include methyl methacrylate, ethyl methacrylate, and t-butyl methacrylate.1. α,β-unsaturated carboxylic acid esters such as cyclohexyl methacrylate, α,β-unsaturated dicarboxylic acid anhydrides such as hydromaleic acid and hydrothermal itaconic acid, N-phenylmaleimide, N-methylmaleimide, N- Examples include imide compounds of α, β-, and β-dicarboxylic acids such as t-butylmaleimide.

There is no particular restriction on the composition ratio of ABS resin (A), but diene rubber (() 5-85 parts by weight is preferred, <, more preferably 15-75 parts by weight, and similarly for vinyl cyanide (b), 5-50 parts by weight is preferred;
Particularly preferably 7 to 45 parts by weight, 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 more preferably 13 to 83 parts by weight.
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, particularly in the range of 3 to 55% by weight, and more preferably in the range of 5 to 50% by weight. It is preferable that there be.

There are no particular limitations on the method for producing the ABS resin (A), and commonly known methods such as continuous 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.

The cicaflebonic acid referred to in 2 above includes terephthalic acid,
Isophthalic acid, orthophthalic acid, 1,5 naphthalene dicarboxylic acid, 2,5-naphthalene dicarboxylic 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'-diphenyliso10pylidene dicarboxylic 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=tuterenylene 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.

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, the molecular weight is 400 to 6. One or more OOO long chain diols, such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc., may be copolymerized.

Specific examples of 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, polybutylene Examples include copolymerized polyesters such as terephthalate/'isophthalate, polybutylene terephthalate/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 the chlorophenol bath solution measured at 25°C is 0.
．． 25-3. Oa/g, especially 04~2.25al
t 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-Ar+SO3+M)l/, 1 n ------
-■ (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,
Examples of aromatic rings that form the basic skeleton include hydrocarbon aromatic rings such as benzene, naphthalene, phenanthrene, anthracene, and pyrene, and heteroaromatic rings such as pyridine, triazine, furan, quinoline, inquinoline, and 1,10-phenanthrene. Furthermore, cyclic systems containing general aromatic rings such as indene, indole, benzofuran, fluorene, and dibendifuran can also be used, and are not particularly limited.

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. must not be metal chlorinated. 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 concentrating force of the salt, often becoming foreign matter and not only making the effect of improving the crystallization rate insufficient. This is because the mechanical properties of the molded article made from the obtained thermoplastic resin composition are 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 is too much of this group, it will not be uniformly dispersed in the polymerization system and will become foreign matter, reducing the effect of improving the crystallization rate and deteriorating the mechanical properties of the molded article. Therefore, the number of metal chlorinated sulfonic acid groups is preferably 2.
It is no more than two, and most 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 rose; however, it is the rose position that 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, and 3.5, but among these, the ones that have the greatest effect on improving the crystallization rate are 2,6; 3,
5, and 3.5 is particularly preferred.

As described in the examples above, those in which a substituent is bonded to the aromatic ring without breaking the symmetry are particularly preferred because they have a large effect of improving the crystallization rate.

Further, the additive of the present invention may contain other substituents other than the hydroxyl group and the metal-chlorinated sulfonic acid group as long as the effects of the present invention are not impaired. Such substituents include methyl groups, aliphatic groups such as ethyl groups, chromium,
Halogen groups such as bromine, cyan groups, nitro groups, aral groups such as acetyl, propionyl, pageyl, methylsulfonyl, ethylsulfonyl, phenylsulfonyl,
These include sulfonyl groups such as tolylsulfonyl, carboxamide groups such as N-phenylcarboxamide, N-ethylcarboxamide, and N-propylcarboxamide, alkoxy groups such as methoxy and ethoxy, and aromatic groups such as phenyl. Group 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 alkaline earth metal.

That is, the base compounds include Q-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,
1-Hydroxy-3,4-benzenedisulfonic acid, 2-
Examples include naphthol-6-sulfonic acid, 1-naphthol-5-sulfonic acid, 1-naphthol-4-sulfonic acid, 9-hydroxy-10-anthracenesulfonic acid, and phenolsulfonic acid, especially p-phenolsulfonic acid. Most preferable 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.・Rium is preferred.

The amount of the sulfonic acid metal salt compound added in the present invention is from 0.01 to 100% by weight based on 100% by weight of the thermoplastic polyester.
20% by weight, preferably 0.005 to 10% by weight, more preferably 0.01 to 5% by weight. Added amount is 0.01% by weight
If it is less than 20 parts by weight, the effect of improving the crystallinity of the thermoplastic polyester will not be sufficient, and if it exceeds 20 parts by weight, the melt viscosity will increase, the fluidity of the resin will deteriorate, and the mechanical properties will 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 has a polyester component having a molecular weight of 2.000 or less based on the polystyrene unit molecular weight, and a sulfur concentration of 0.005% by weight or more.
It is desirable that the polymerization be carried out so that the content is 20% by weight.

Molecular weight2. The content of oligomers below OOO can be determined by conventional gel permeation chromatography methods. The solvent used was Q-chlorophenol/chloroform-1/4 (vol/v).

), a differential refractometer can be used as the detector.

In other words, the column was calibrated using commercially available polystyrene with a narrow molecular weight distribution, and the ratio of the area after the retention time corresponding to the molecular weight of polystyrene of 2.000 to the entire area narrowed by the polyester output curve and baseline was calculated. and calculate the oligomer content.

In addition, the amount of sulfur contained in the oligomer has a molecular weight of 2
．． It can be determined by separating a polyester component of 000 or less 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 the polyester. It also varies depending on the time of addition and the method of addition (powder, solution, suspension) of the sulfonate compound with . 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, there are various additives known as moldability improvers for thermoplastic polyesters, typified by polyethylene terephthalate. It is also preferable to use an acid salt or an inorganic compound in combination 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, talc, and salicylanilides. Examples include sodium salts of substituted phenols, such as sodium salts of salicylaldehyde, sodium salts of salicylaldehyde, and sodium salts of nitrophenol.

The modified vinyl polymer (C) (hereinafter referred to as copolymer (C)) used in the present invention is aromatic vinyl (a), vinyl cyanide (b), and α,β-unsaturated unsaturated norboxic acid. This is a copolymer obtained 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. Specific examples of the α,β unsaturated carboxylic acid (c) include acrylic acid and methacrylic acid, and these can be used alone or in combination of two or more.

In the copolymer (C) composed of the above copolymerized components, the copolymerization amount occupied by α, β-, β-carboxylic acid is preferably 0.1 to 28% by weight, more preferably 0.1-1% by weight.
It is in the range of 0% by weight.

When the copolymerization amount is less than 0.1% by weight, the impact strength of the composition is low, and when it exceeds 28% by weight, the copolymer tends to gel, making it difficult to obtain a molded product with a good surface condition. do not have.

There are no particular restrictions on the method for producing the copolymer (C),
Generally known methods such as bulk polymerization, solution polymerization, bulk-suspension polymerization, suspension polymerization, and emulsion polymerization are used. ((), f
There are no particular restrictions on the method of charging (8) and (8), and the charging may be carried out all at once at the initial stage, or some or all of the monomers may be added in order to prevent the formation of a compositional distribution of the copolymer. Polymerization may be carried out by continuous charging or divided charging.

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 ((), f) and (c).

Other copolymerizable monomers include methyl methacrylate,
α, β-, β-carboxylic acid esters such as ethyl methacrylate, monobutyl methacrylate, cyclohexyl methacrylate, α-carboxylic acid esters such as maleic anhydride, itaconic anhydride, etc.
, β-unsaturated dicarbonate #! i anhydrides, imide compounds of α, β-, and β-dicarboxylic acids such as N-phenylmaleimide, N-methylmaleimide, N-t-butylmaleimide, and the like.

ABS resin (8) in the thermoplastic resin composition of the present invention
, polyester resin (B) and modified vinyl polymer [
The blending ratio of C) is 10 to 84 parts by weight of (A), preferably 12 to 80 parts by weight, particularly preferably 14 to 75 parts by weight, and 15 to 89 parts by weight of (B), preferably 18 to 86 parts by weight. , particularly preferably from 20 to 81 parts by weight, fc)
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), FB) and (C) is 100 parts by weight. (
If A) is less than 10 parts by weight and (B) exceeds 89 parts by weight, if (C) is less than 1 part by weight, the resulting resin composition will have poor impact resistance, and if (A) exceeds 84 parts by weight. If fB
) is less than 15 parts by weight, the chemical resistance is poor, and (C) is less than 70 parts by weight.
If the amount exceeds 1 part by weight, the molding processability will be poor, which is not preferable.

Furthermore, by adding a crystallization promoter commonly used for thermoplastic polyesters to the thermoplastic resin composition of the present invention, moldability and mechanical properties 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. Benzoic acid ester compounds such as α,ω dialkyl etherified polypolyalkylene glycol opentyl glycol dibenzoate and aliphatic polyesters such as polycaprolactone and polyethylene adipate can be preferably used.

Further, by further adding a filler and/or reinforcing material to the thermoplastic resin composition of the present invention, the properties 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, Examples include barium sulfate, titanium oxide, and aluminum oxide, among which chopped 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, mold release agents, etc. within the range that does not impair the purpose of the present invention. Additives and common additives such as colorants including dyes and pigments to 1
More than one species can be added.

Further, the thermoplastic resin composition of the present invention is made of ABS resin (A
), polyester resin (B) and modified vinyl polymer (C), as required, polystyrene (PS), styrene/acrylonitrile copolymer (SAN), polymethyl methacrylate (PMMA), styrene/methacrylic acid Methyl/acrylonitrile copolymer, α-methylstyrene, /acrylonitrile copolymer, α-methylstyrene/styrene/acrylonitrile copolymer, α-methylstyrene/methyl methacrylate/acrylonide-lyl copolymer, p-methylstyrene Vinyl polymers such as /acrylonitrile copolymer, styrene/N-phenylmaleimide copolymer, methacrylic acid-butadiene-styrene terpolymer (MBS) fit resin, ABS resin, AAS
l! I fat, polycarbonate, polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 6)
6), or by appropriately mixing thermoplastic resins such as 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/butyl acrylate copolymer By appropriately mixing a polyolefin rubber such as a polymer, it is also possible to adjust the physical properties and characteristics to more desirable values.

There are no particular restrictions on the method for producing the thermoplastic resin composition of the present invention and the method for adding fillers and/or reinforcing materials, as well as additives, and generally known methods can be employed. That is, after uniformly mixing ABS@resin (A), polyester resin CB), modified vinyl polymer (C), and/or fillers, reinforcing materials, and additives in the form of pellets, powder, or small pieces, thorough kneading is performed. Various methods can be employed, such as melt-kneading in a capable single-screw or multi-screw extruder.

<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” Izotsu impact strength was A.
Measured according to STM D256-56. ASTM D-152 Vicat softening temperature was used to evaluate heat resistance.
Measured according to 5.

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 were manufactured using 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 (solid content:

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
1 part of methyl methacrylate in the presence of 0 parts (based on solid content)
After emulsion polymerization of 60 parts of a monomer mixture consisting of 5% styrene, 65% styrene, and 20% acrylonitrile, a powdery graft copolymer (A-2) was prepared in the same manner as A-1.

A-3: Polybutadiene latex 4 used in A-1
After emulsion polymerizing 60 parts of styrene in the presence of 0 parts (solid content), a powdery graft copolymer (A-3
) was adjusted 6 Reference Example 2 Polyester resins B-1 to B-5 were manufactured by the following method.

To a mixture of 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, a predetermined amount of the additive compound shown in Table 1 was added. Added. After the temperature was raised to 140°C and dimethyl terephthalate was melted, stirring was started and the temperature was raised to 140°C.
The transesterification reaction was carried out by raising the temperature from 245° C. to 245° C. over 3.5 hours, and most of the methanol was distilled off. Next, while raising the temperature from 245° C. to 280° C. over 3 hours, the mixture was gradually evacuated and polymerization was carried out under a vacuum of 0.6 mHg.

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 rises and the lower the heating crystallization temperature, the better the crystal quality. 8T at that time was used as a measure of crystallinity.

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

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

C-1 = Bead-shaped modified vinyl copolymer (C-1) was prepared by suspension polymerization of 0 parts of styrene, 20 parts of acrylonitrile, and 10 parts of methacrylic acid.

C-2 = Bead-shaped modified vinyl copolymer ((, -2>) was prepared by suspension polymerization of 0 parts of styrene, 20 parts of acrylonitrile, 5 parts of acrylic acid, and 15 parts of methyl methacrylate.

C-3: Bead-shaped modified vinyl copolymer (C-3) was prepared by suspension polymerization of 95 parts of styrene and 5 parts of methacrylic acid.

C-4 = Bead-shaped vinyl copolymer (C-4) was prepared by suspension polymerization of 2 parts of styrene and 28 parts of acrylonitrile.

Examples 1 to 7 A-1 and A-2 produced in Reference Example 1, B-1 and B-2 produced in Reference Example 2, and C-I C produced in Reference Example 3
-2 were mixed in a Henschel mixer at the mixing ratio shown in Table 2, and then extruded at a temperature of 260℃ using a 40mm diameter extrusion.
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 shown in Table 2.

Comparative Examples 1 to 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 3
-4 were mixed in a Henschel mixer at the compounding ratio shown in Table 2, and then extruded at a temperature of 26 mm using a 40wφ extruder.
After extrusion at 0°C and forming pellets, 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. In contrast, a vinyl polymer (C4) that does not contain α, β-unsaturated carboxylic acid as a copolymerization component, a modified vinyl polymer (C-3) that does not contain vinyl cyanide, and a modified vinyl polymer are further blended. If the amount of the modified vinyl polymer is not included or the amount of the modified vinyl polymer is outside the specified amount, the impact resistance will be poor.

In addition, polyester resin (B-3) is a polyester resin with no additives added, a polyester resin composition (B-4) in which the additive amount of sodium P-phenolsulfonate is less than the specified amount, and Polyester resins (B-5) containing disodium p-phenolsulfonate, those containing no polyester resin, and those containing less polyester resin than the specified amount have poor heat resistance and chemical resistance.

In addition, ABS resin that does not contain vinyl cyanide (A-3
> and those that do not contain ABS resin have poor impact resistance.

<Effects of the Invention> As explained above, the resin composition of the present invention has an ABS of 1!
It is a resin composition that has both the impact resistance of lubricant and the heat resistance and chemical resistance of polyester resin, and this effect is achieved by combining ABS resin (A), polyester resin with excellent crystallinity (B), and modified vinyl polymer. (C) is an essential component and is achieved by blending it.

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
15 to 89 parts by weight of a modified vinyl polymer (C) formed by copolymerizing aromatic vinyl, vinyl cyanide, and α,β-unsaturated carboxylic acid, and (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.)