JPH06329852A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the subject resin composition comprising a saturated polyester and a copolymer comprising aromatic vinylic compound units, hydroxyl group-containing unsaturated carboxylic acid units, vinyl cyanate compound units, etc., and good in resistances to heat impact, and chemicals. CONSTITUTION:The objective thermoplastic resin composition comprising (A) a saturated polyester (e.g. polyethylene terephthalate) and (B) a hydroxyl group- containing modified aromatic vinylic random copolymer comprising (i) 50-99.9wt.% of the units of an aromatic vinyl compound (e.g. styrene), (ii) 0.1-20wt.% of the units of a hydroxyl group-containing alpha,beta-unsaturated carboxylate ester compound (e.g. 2-hydroxyethyl methacrylate), (iii) 0-50wt.% of the units of a vinyl cyanate compound (e.g. acrylonitrile), and (iv) 0-40wt.% of the units of a copolymerizable vinylic compound (e.g. methyl methacrylate) excluding the components i-iii, excellent in the compatibility between both the resins and good in the balance between the rigidity and the mechanical strength.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thermoplastic resin composition having excellent heat resistance, impact resistance, water absorption resistance, chemical resistance and molding processability.

This resin belongs to engineering plastics and is useful for automobile wheel caps, instrument panels, handles, door trims, etc., as well as electronic and electronic device housings, knob dials and the like.

[0003]

2. Description of the Related Art Saturated polyesters represented by polybutylene terephthalate and polyethylene terephthalate are
It is known as an engineering plastic with excellent heat resistance, chemical resistance, electrical properties, etc., but it has poor water absorption resistance and is used during molding processing such as injection molding and extrusion molding, and when used under high temperature and high humidity conditions. It has the drawbacks that it is easily deteriorated and that physical properties such as impact strength are deteriorated.

On the other hand, A containing styrene, α-methylstyrene, acrylonitrile, rubber-like polymer and the like as a copolymerization component
Aromatic hydrocarbon copolymers such as BS, SAN, AAS, AES and HIPS are amorphous and have excellent impact resistance,
Widely used in wheel caps, instrument panels, etc. as a general-purpose thermoplastic resin that has moldability and paintability. However, heat resistance and chemical resistance are not sufficient,
Limited use under harsh conditions. Therefore, various compositions have been proposed for the purpose of providing a molding material that complements the drawbacks without impairing the advantages of both resins.

For example, JP-A-1-123854 discloses a modified vinyl obtained by copolymerizing an aromatic vinyl monomer, a vinyl cyanide monomer and an α, β-unsaturated carboxylic acid monomer. A method of blending a system copolymer has been proposed.
However, this composition does not have sufficient compatibility, and the effect of improving mechanical strength such as impact resistance is not yet sufficient. Further, in JP-A-3-88842, an epoxy-modified copolymer obtained by copolymerizing an aromatic vinyl monomer, a vinyl cyanide monomer and an ethylenically unsaturated epoxy group-containing monomer is blended. The method of doing is proposed. However, although the compatibility of this composition is improved to some extent, in the case of melt kneading with an extruder or the like, the fluidity is lowered due to the formation of a part of a gelled product, and the extruded strand cannot be stably taken out. Also, there are problems that the surface appearance of the injection-molded product is deteriorated and mechanical strength such as impact resistance is reduced.

[0006]

In order to solve the above problems, the present invention provides a thermoplastic resin composition having an improved balance of physical properties such as heat resistance, impact resistance, tensile strength, water absorption, and moldability. The purpose is to do.

[0007]

[Means for Solving the Problems] As a result of intensive investigations, the inventors of the present invention have found that a hydroxyl group-modified aromatic vinyl copolymer obtained by copolymerizing an α, β-unsaturated carboxylic acid ester compound having a hydroxyl group is copolymerized. The present invention has been completed by finding that the polymer and the saturated polyester have extremely good affinity.

That is, the present invention is a thermoplastic resin composition containing the following components (A) and (B): (A) saturated polyester (B) (a) aromatic vinyl compound unit 50 to 99. 9
%, (B) 0.1 to 20% by weight of an α, β-unsaturated carboxylic acid ester-based compound unit having a hydroxyl group, (c) 0 to 50% by weight of a vinyl cyanide-based compound unit, and (d) the above (a). ), (B) and (c), other hydroxyl-modified aromatic vinyl-based random copolymer containing 0 to 40% by weight of another copolymerizable vinyl-based compound unit.

Further, it is a thermoplastic resin composition containing the following components (A) and (B '). . (A) Saturated polyester (B ') 95-10% by weight of the hydroxyl group-modified aromatic vinyl random copolymer (B) and a hydroxyl group-modified aromatic vinyl random copolymer (B) are rubber-like grafted. A rubber-reinforced hydroxyl group-modified aromatic vinyl-based graft copolymer comprising 5 to 90% by weight of the polymer.

[0010]

The hydroxyl group-modified aromatic vinyl copolymer obtained by copolymerizing the α, β-unsaturated carboxylic acid ester compound having a hydroxyl group used in the present invention and the saturated polyester show good affinity to each other. This is because the carboxyl group or ester group of the saturated polyester reacts with each other to form a graft copolymer that serves as a compatibilizer for the aromatic vinyl copolymer and the saturated polyester.

The present invention will be described in detail below. <Saturated Polyester (A)> The saturated polyester (A) used in the present invention includes dicarboxylic acid or a lower alkyl ester thereof, an acid halide or an acid anhydride derivative,
It is a thermoplastic saturated polyester obtained by polycondensation with glycol or dihydric phenol.

Specific examples of the dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, sebacic acid, terephthalic acid, isophthalic acid, p-carboxyphenoxyacetic acid, 2,6-naphthalene dicarboxylic acid, 2,7- Examples thereof include naphthalene dicarboxylic acid.

Specific examples of glycols or dihydric phenols include linear alkylene glycols having 2 to 12 carbon atoms such as ethylene glycol, 1,3-propylene glycol, 1,4-butanediol and 1,6-hexanediol; Examples include dihydric phenols such as pyrocatechol, resorcinol, and hydroquinone; alicyclic glycols such as cyclohexanedimethanol; and alkyl-substituted derivatives of these compounds.

Suitable saturated polyesters (A) include
Examples thereof include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and poly (1,4-cyclohexanedimethylene terephthalate).
Liquid crystalline polyesters such as X7G manufactured by Eastman Kodak Co., Vectra manufactured by Hoechst Celanese Co., Ltd., and Econol manufactured by Sumitomo Chemical Co., Ltd. are also preferable. These may be used alone or in combination of two or more.

<Hydroxyl group-modified aromatic vinyl random copolymer (B)> The aromatic vinyl compound (a) is represented by the following formula (I).

[0016]

[Chemical 1]

(In the formula, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Ar represents an aromatic group having 6 to 18 carbon atoms and optionally having a substituent. Is preferably an alkyl group, a halogen atom, etc.)

Specific examples of the aromatic vinyl compound (a) include styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, t-butylstyrene and α-.
Methylvinyltoluene, dimethylstyrene, chlorostyrene, dichlorostyrene, bromstyrene, dibromostyrene, vinylnaphthalene and the like can be mentioned, with styrene and α-methylstyrene being preferred. These can be used alone or in combination of two or more.

Examples of the α, β-unsaturated carboxylic acid ester compound (b) having a hydroxyl group include (meth) acrylic acid ester, maleic acid monoester or diester, and fumaric acid monoester or diester. Examples of the (meth) acrylic acid ester include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate,
2,3-dihydroxypropyl methacrylate, 2,3
-Dihydroxypropyl acrylate, 2-hydroxymethyl-3-hydroxypropyl methacrylate, 2-
Hydroxymethyl-3-hydroxypropyl acrylate, 2,2-bis (hydroxymethyl) -3-hydroxypropyl methacrylate, 2,2-bis (hydroxymethyl) -3-hydroxypropyl acrylate, ethylene glycol having 4 to 40 carbon atoms or Examples thereof include methacrylic acid or acrylic acid ester of propylene glycol oligomer.

Examples of maleic acid monoesters or diesters and phthalic acid monoesters or diesters include bis (2-hydroxyethyl) malate and bis (2
-Hydroxyethyl) fumarate, bis (2-hydroxypropyl) malate, bis (2-hydroxypropyl) fumarate, bis (2,3-dihydroxypropyl) malate, bis (2,3-dihydroxypropyl)
Fumarate, bis (2-hydroxymethyl-3-hydroxypropyl) malate, bis (2-hydroxymethyl-3-hydroxypropyl) fumarate, bis (2,2
-Bishydroxymethyl-3-hydroxypropyl) maleate, bis (2,2-bishydroxymethyl-3-hydroxypropyl) fumarate, maleic acid or fumaric acid ester of an oligomer of ethylene glycol or propylene glycol having 4 to 40 carbon atoms, etc. Is mentioned. Incidentally, maleic acid or fumaric acid ester can be exemplified as a similar monomer when two carboxylic acids are not esters of a hydroxyalkyl group as described above but only one is an ester.

The above α, β-unsaturated carboxylic acid ester compounds having a hydroxyl group can be used alone or in combination of two or more kinds. Among these, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, methacrylic acid or acrylic acid ester of an oligomer of ethylene glycol or propylene glycol having 4 to 40 carbon atoms, etc. preferable.

The vinyl cyanide compound (c) is represented by the following formula (II).

[0023]

[Chemical 2]

(In the formula, R ¹ , R ² and R ³ each represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cyano group or a cyanoalkyl group)

Specific examples of the vinyl cyanide-based compound (c) include acrylonitrile, methacrylonitrile, fumaronitrile and the like, among which acrylonitrile is preferred. These may be used alone or in combination of two or more.

Other copolymerizable vinyl compounds (d) include aromatic vinyl compounds (a), hydroxyl group-containing α, β-unsaturated carboxylic acid ester compounds (b) and vinyl cyanide compounds ( Vinyl compounds other than c). Specific examples of other copolymerizable vinyl compounds (d) include (meth) acrylic acid esters such as methyl methacrylate and acrylic acid lower alkyl esters (wherein the alkyl group has 1 to 6 carbon atoms); maleimide, N Examples thereof include N-substituted maleimides such as -phenylmaleimide, N-methylmaleimide, N-cyclohexylmaleimide, and N-butylmaleimide, and these can be used alone or in combination of two or more.

Specific examples of these hydroxyl group-modified aromatic vinyl random copolymers (B) include, for example, 2-hydroxyethyl methacrylate-styrene copolymer and 2-hydroxyethyl methacrylate-styrene copolymer.
Hydroxyethyl methacrylate-styrene-acrylonitrile copolymer, 2-hydroxyethyl methacrylate-α-methylstyrene-acrylonitrile copolymer,
2-hydroxyethyl methacrylate-styrene-α-
Methylstyrene-acrylonitrile copolymer, 2-hydroxyethylmethacrylate-styrene-acrylonitrile-methylmethacrylate copolymer, 2-hydroxyethylmethacrylate-styrene-acrylonitrile-N
-Phenylmaleimide copolymer, 2-hydroxyethylmethacrylate-α-methylstyrene-acrylonitrile-methylmethacrylate copolymer, 2-hydroxyethylmethacrylate-α-methylstyrene-acrylonitrile-N-phenylmaleimide copolymer, 2- Hydroxyethyl methacrylate-styrene-acrylonitrile-methyl methacrylate-N-phenylmaleimide copolymer, 2-hydroxyethyl methacrylate-styrene methyl methacrylate copolymer, 2-hydroxyethyl methacrylate-α-methylstyrene copolymer, 2- Hydroxyethyl methacrylate-α-methylstyrene-N-
Examples thereof include a phenylmaleimide copolymer and a 2-hydroxyethylmethacrylate-styrene-α-methylstyrene-methylmethacrylate-N-phenylmaleimide copolymer.

These can be used alone or in combination of two or more. As a method for producing the hydroxyl group-modified aromatic vinyl random copolymer (B), a radical polymerization method is usually used, and a bulk polymerization method, a solution polymerization method, a suspension polymerization method, an emulsion polymerization method, or a combination of these methods is used. , Japanese Patent Application Laid-Open No. 4-76042).

<Rubber Reinforced Hydroxyl Group Modified Aromatic Vinyl Graft Copolymer (B ')> The rubber reinforced silane modified aromatic vinyl type graft copolymer (B') used in the present invention is the above hydroxyl group modified aromatic vinyl type copolymer. Random copolymer (B) 95
10 to 10% by weight and a hydroxyl group-modified aromatic vinyl random copolymer (B) graft-bonded to a rubber-like polymer 5 to 90
It is a rubber-reinforced hydroxyl group-modified aromatic vinyl-based graft copolymer composed of wt%.

As the rubber-like polymer, JIS K 72
Flexural modulus measured according to No. 03 is 5,000 kg / cm ²
A rubber-like polymer having a glass transition temperature of −10 ° C. or less, and specifically, for example, polybutadiene rubber, polyisoprene rubber or hydrogenated products thereof, alkyl acrylate copolymer rubber, ethylene-propylene copolymer Examples thereof include polymer rubber, ethylene-propylene-diene copolymer rubber, ethylene-vinyl acetate copolymer and the like. These can be used alone or in combination of two or more. As the method of graft polymerization, a known emulsion polymerization method, solution polymerization method, bulk polymerization method, suspension polymerization method or a combination thereof may be used.

Specific examples of the rubber-reinforced hydroxyl group-modified aromatic vinyl-based graft copolymer (B ') include, for example, 2-hydroxyethyl methacrylate-styrene-butadiene copolymer and 2-hydroxyethyl methacrylate-styrene-isoprene copolymer. Polymer, 2-hydroxyethyl methacrylate-acrylonitrile-styrene-butadiene copolymer, 2-hydroxyethyl methacrylate-acrylonitrile-isoprene-styrene copolymer, or hydrogenated products thereof, 2-hydroxyethyl methacrylate-acrylonitrile-styrene- Examples thereof include alkyl acrylate rubber copolymers and 2-hydroxyethyl methacrylate-acrylonitrile-styrene-ethylene-propylene rubber copolymers. These may be used alone or in combination of two or more.

Further, some or all of these styrenes and / or acrylonitriles are α-methylstyrene, p-methylstyrene, pt-butylstyrene; acrylic acid or methacrylic acid or their methyl, ethyl, propyl, Esters such as n-butyl; maleimide-based monomers such as maleimide, N-methylmaleimide and N-phenylmaleimide; those substituted with a copolymerizable vinyl-based monomer such as acrylamide are also included. Preferred are a hydroxyl group-modified ABS resin, a hydroxyl group-modified AES resin, a hydroxyl group-modified MBS resin and the like.

<Composition Ratio of Constituent Components> The composition ratio of the components (A) and (B) in the thermoplastic resin composition of the present invention is from the viewpoint of harmonization of mechanical strength, heat resistance, solvent resistance and the like. 90 to 10% by weight of (A) and 10 to 90 of component (B)
% By weight, preferably 80 to 20% by weight of component (A) and 20 to 80% by weight of component (B), more preferably 70 to 30% by weight of component (A) and 30 to 70% of component (B).
It is in the range of% by weight. When the amount of the component (A) is less than 10% by weight, the effect of improving the solvent resistance is small as compared with the main resin of the component (B), for example, styrene-acrylonitrile copolymer resin, and when it exceeds 90% by weight, the saturated polyester Compared with (A), the effect of improving molding workability, water absorption resistance, etc. is small.

The content of the α, β-unsaturated carboxylic acid ester compound (b) unit having a hydroxyl group in the hydroxyl group-modified aromatic vinyl random copolymer (B) is 0.1 to 20% by weight, preferably It is in the range of 0.5 to 15% by weight, more preferably 0.5 to 10% by weight. Α having a hydroxyl group
When the content of the β-unsaturated carboxylic acid ester compound (b) unit is less than 0.1% by weight, the compatibility of the composition is lowered and the effect of improving mechanical strength and the like is small, and when it exceeds 20% by weight. Moldability may be difficult, which is not preferable.

The composition ratio of the component (A) and the component (B ') in the thermoplastic resin composition of the present invention is the component (A) from the viewpoint of harmonization of mechanical strength, heat resistance, solvent resistance and the like.
Is 90 to 10% by weight and the component (B ') is 10 to 90% by weight, preferably the component (A) is 80 to 20% by weight and the component (B') is 20 to 80% by weight, and more preferably the component (A). ) Is 70 to 30% by weight and the component (B ') is 30 to 7
It is in the range of 0% by weight. When the content of the component (A) is less than 10% by weight, the effect of improving the solvent resistance and the like is smaller than that of the main resin of the component (B '), such as ABS resin, and when it exceeds 90% by weight, the impact resistance and the like are improved. The effect is small.

<Additional component> The thermoplastic resin composition of the present invention may contain a component other than the components (A) and (B) or (B '). For example, an aromatic vinyl-based copolymer which does not include the α, β-unsaturated carboxylic acid ester compound (b) having a hydroxyl group as a part (up to 90% by weight) of the component (B) or (B ′) as a copolymerization component. It may be replaced by a polymer or a rubber-reinforced aromatic vinyl-based copolymer. In the resin composition, 0.5 to 3% by weight of an antioxidant, a weather resistance improver, a nucleating agent, a slip agent, etc .; 3 to 15% by weight of a plasticizer, a fluidity improver, a release agent, etc .; A catalyst such as tetrakis (2-ethylhexoxy) titanium or dibutyltin oxide can be used as an additional component. Furthermore, adding 5 to 40% by weight of an organic / inorganic filler and a reinforcing agent, particularly glass fiber, mica, talc, wollastonite, potassium titanate, calcium carbonate, silica, etc. to the resin composition provides rigidity and heat resistance. It is effective in improving the reliability, dimensional accuracy, and dimensional stability. For practical use, various colorants and their dispersants can be used in a proportion of 1 to 10% by weight.

Further, addition of a rubber component, particularly styrene-butadiene copolymer rubber, styrene-isoprene copolymer rubber or hydrogenated products thereof; ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber. , Polybutadiene rubber, acrylic rubber, silicone rubber, and their α, β-unsaturated carboxylic acid anhydride modified product, unsaturated glycidyl ester or unsaturated glycidyl ether modified product; a copolymer comprising an unsaturated epoxy compound and ethylene, or An unsaturated epoxy compound, a copolymer of ethylene and an ethylenically unsaturated compound, and the like are effective in improving the impact strength of the composition. The compounding amount of the rubber varies depending on the target physical property value, but in the case of improving the balance between the rigidity and the impact strength of the composition, it is 5 to 30% by weight in 100% by weight of the composition. Furthermore, polyphenylene ether, hydroxyalkylated polyphenylene ether, nylon 6, nylon 6,6, nylon 6,10,
Nylon 6,12, polycarbonate and the like may be contained in the resin composition in an amount of 1 to 70% by weight.

<Composition Preparation Method and Molding Method> The method for obtaining the thermoplastic resin composition of the present invention is not particularly limited, such as a melting method, a solution method, a suspension method, etc., but in practice, melt kneading is performed. Is preferred. As the melt-kneading method, a kneading method generally used for thermoplastic resins can be applied. For example, if necessary, the powdery or granular components are uniformly mixed with the additives described in the section of additional components by a Henschel mixer, a ribbon blender, a V-type blender, etc., and then uniaxially or polyaxially. It can be kneaded with a kneading extruder, roll, Banbury mixer, or the like.

The temperature of the melt-kneading of each component is 100
To 400 ° C., preferably 120 to 300 ° C. Further, the kneading order and method of each component are not particularly limited, and for example, the components (A) and (B)
Alternatively, a method in which (B ′) and an additional component are kneaded at once, a method in which the component (A) and a part or all of the component (B) or (B ′) are pre-kneaded, and then the remaining components are kneaded, Further, any method such as kneading under reduced pressure may be used. Further, an organic solvent such as chlorobenzene, trichlorobenzene, xylene or the like can be added during the melt kneading.

[0040]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. In the following, parts and percentages are based on weight.

Reference Example 1: Synthesis of 2-hydroxyethylmethacrylate-modified styrene-acrylonitrile copolymer-1 (hereinafter referred to as "HEMA-AS-1") Styrene was placed in a round-bottomed flask having an inner volume of 500 ml, which was sufficiently replaced with nitrogen gas. 64.0 g, acrylonitrile 30.0
g, 2-hydroxyethyl methacrylate 6.0 g,
0.62 g of 2,2'-azobis (isobutyronitrile) and 50 ml of xylene were added, and the mixture was stirred under a nitrogen stream to obtain 2,2
After confirming that the ′ -azobis (isobutyronitrile) was completely dissolved, the temperature was raised to 60 ° C. and polymerization was performed for 5 hours. After the polymerization, the temperature was lowered to room temperature, 200 ml of chloroform was added to completely dissolve the polymer, and then poured into 2 liters of methanol to precipitate the polymer. After filtering and drying, 90.5 g of a polymer was obtained. Infrared spectroscopy and ¹ H-N
By MR, the polymer composition was 65.4 styrene units.
% By weight, acrylonitrile unit 28.5% by weight, 2-hydroxyethyl methacrylate unit 6.1% by weight, and gel permeation chromatography (GP
C) By measurement, polystyrene-equivalent number average molecular weight (M
n): 40,500 and weight average molecular weight (Mw): 11
It was 1,300.

Reference Example 2: Synthesis of 2-hydroxyethyl methacrylate-modified styrene-acrylonitrile copolymer-2 (hereinafter referred to as "HEMA-AS-2") 67.0 g of styrene and 3.0 g of 2-hydroxyethyl methacrylate were used. Except for this, the same procedure as in Reference Example 1 was carried out to obtain 78.5 g of a polymer. By the same analysis as in Reference Example 1, the composition of the polymer was 70.7 styrene units.
% By weight, 26.4% by weight of acrylonitrile units and 2-
The hydroxyethyl methacrylate unit was 2.9% by weight, Mn: 86,200 and Mw: 195,000.

Reference Example 3: Synthesis of 2-hydroxyethyl methacrylate modified ABS (hereinafter referred to as "HEMA-ABS") A polybutadiene latex (manufactured by Nippon Zeon Co., Ltd. Name: Nipol LX 111A) 38.5ml, distilled water 231.5
ml, sodium dodecylbenzenesulfonate 1.0 g,
Sodium formaldehyde sulfoxylate 0.2g
, 2.5 mg of ferrous sulfate and 1.0 mg of disodium ethylenediaminetetraacetate were added and stirred at room temperature for 15 minutes,
The temperature was raised to 60 ° C. Then add styrene 5 to this solution.
A mixed solution of 5.0 g, acrylonitrile 20.0 g, 2-hydroxyethyl methacrylate 5.0 g and cumene hydroperoxide 0.3 g was added dropwise over 5 hours, and the mixture was further polymerized for 1 hour, then cooled to room temperature and stirred. 5.0 g of anhydrous calcium chloride was added below to precipitate a polymer. After the polymer was separated by filtration, the polymer was washed with pure water five times and filtered, and then dried. The polymer obtained was 89.3 g. By the same analysis as in Reference Example 1, the polymer composition was found to be 56.5% by weight of styrene units and 1 of acrylonitrile units.
The content was 6.2% by weight, 2-hydroxyethylmethacrylate unit was 5.2% by weight, and butadiene unit was 22.1% by weight, and Mn was 80,300 and Mw was 295,000.

Reference Example 4: Synthesis of 2-hydroxyethyl methacrylate modified polystyrene (hereinafter referred to as "HEMA-P
S ") In a round-bottomed flask having an internal capacity of 500 ml, which was sufficiently replaced with nitrogen gas, 95.0 g of styrene, 5.0 g of 2-hydroxyethyl methacrylate, 0.6 g of dibenzoyl peroxide.
Then, 50 ml of xylene was added, and the mixture was stirred under a nitrogen stream, and after confirming that dibenzoyl peroxide was completely dissolved, the temperature was raised to 100 ° C. and polymerization was carried out for 5 hours. After the polymerization, the temperature was lowered to room temperature, 200 ml of methyl ethyl ketone was added to completely dissolve the polymer, and then poured into 2 liters of methanol to precipitate the polymer. After filtering and drying, 70.0 g of a polymer was obtained. By the same analysis as in Reference Example 1, the composition of the polymer was 94.8% by weight of styrene unit and 5.2% by weight of 2-hydroxyethyl methacrylate unit, and Mn: 39, 100, Mw: 97, 200. .

Reference Example 5 (Comparison): Synthesis of styrene-acrylonitrile copolymer (hereinafter referred to as "SAN-1") 75.0 g of styrene and 25. 0 g
, 2,2'-azobis (isobutyronitrile) 0.6g
Was added, and the mixture was stirred under a nitrogen stream to confirm that 2,2'-azobis (isobutyronitrile) was completely dissolved, and then the temperature was raised to 60 ° C and polymerization was performed for 5 hours. After the polymerization, the same treatment as in Reference Example 1 was carried out to obtain 75.1 g of a polymer. By the same analysis as in Reference Example 1, the composition of the polymer was found to be 75.8% by weight of styrene units and 24.24 of acrylonitrile units.
2% by weight, Mn: 31,400, Mw: 96,000
Met.

Reference Example 6 (Comparison): Synthesis of styrene-acrylonitrile copolymer (hereinafter referred to as "SAN-2") The procedure of Reference Example 5 was repeated except that 50 ml of xylene was added, and 51.0 g of polymer was added. Got By the same analysis as in Reference Example 1, the composition of the polymer was 75.3% by weight of styrene unit and 24.8% by weight of acrylonitrile unit.
It was Mn: 96,400 and Mw: 168,900.

Examples 1 to 7 and Comparative Examples 1 to 5 Modified HEMA-AS-1 and HEMA-synthesized in Reference Examples
AS-2, SAN-1, SAN-2 and HEMA-PS
And saturated polyester (polybutylene terephthalate 124 manufactured by Kanebo Co., Ltd., hereinafter referred to as “PBT124”, polyethylene terephthalate RT56 manufactured by Nippon Unipet Co., Ltd.
0CN, hereinafter referred to as "PET RT560CN") and polystyrene (Mitsubishi Kasei Co., Ltd., Dialex HF7).
7, hereinafter referred to as "PS HF77") and each component was used in accordance with the compounding ratio shown in Table 1 by using a Labo Plastomill kneader (manufactured by Toyo Seiki Seisakusho Ltd.) at 250 ° C.
After kneading for 5 minutes at m 2, it was pulverized to obtain a granular resin composition. The characteristics of the composition obtained are determined by the injection molding machine [custom
Scientific (Custom Scientific), CS
183MMX Nimimax], and a test piece for physical property evaluation was injection molded at a temperature of 280 ° C., and evaluated by the following methods, and the results are shown in Table 1. During the kneading and molding, the saturated polyester and the composition were kept at 80 ° C. for 5 minutes until immediately before that.
Vacuum dried for an hour.

Physical property evaluation methods: (1) Impact strength: A test piece having a length of 31.5 mm, a width of 6.2 mm and a thickness of 3.2 mm was injection-molded, and an Izod impact tester (made by Custom Scientific Co., Ltd.) was used. Minimax c
S-138TI type), notched Izod impact strength at 23 ° C. and notch tip R of 0.25 mm,
The Izod impact strength with a notch having a depth of 1.2 mm was measured. (2) Tensile strength: parallel part length 7 mm, parallel part diameter 1.5 mm
Of the tensile test piece was injection-molded, and the tensile strength at break and the elongation at break were measured by using a tensile tester (CS-183TE manufactured by Custom Scientific Co., Ltd.) under the conditions of 23 ° C. and a tensile speed of 1 cm / min. It was measured. (3) Elastic Modulus: A test piece having a length of 47 mm, a width of 5 mm, and a thickness of 2 mm was injection-molded, and a storage rigidity (at a frequency of 1 Hz was measured using a solid viscoelasticity measuring device (RSAII manufactured by Rheometrics Far East) ( Measure the temperature dependence of E ') and
And the value of the elastic modulus (E ') at 80 ° C were determined.

[0049]

[Table 1]

HEMA-AS-1 and HEMA-AB synthesized in Examples 8 to 11 and Comparative Examples 6 to 9
S and SAN-1 and polybutylene terephthalate (PBT124), styrene-acrylonitrile-butadiene copolymer (manufactured by Mitsubishi Kasei Co., ABS resin, toflex 410, butadiene content 15% by weight, hereinafter "ABS"
TFX-410 "and a product of Nippon JE Plastics Co., Ltd., Blendix 336, butadiene content 70% by weight, hereinafter referred to as" Blendix-336 ") according to the compounding ratio shown in Table 2. Kneading and molding were carried out in the same manner as in Examples 1 to 7, and the physical properties were evaluated. The results are shown in Table 2.

[0051]

[Table 2]

[0052]

From the evaluation results of the above Examples and Comparative Examples, the thermoplastic resin composition of the present invention has excellent compatibility with both saturated polyester and hydroxyl group-modified aromatic vinyl-based copolymer resin, rigidity and mechanical properties. Since it has a good balance of dynamic strength, it can be an industrially useful material.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Hiroshi Nakano 1 Toho-cho, Yokkaichi-shi, Mie Mitsubishi Petrochemical Co., Ltd. Yokkaichi Research Institute

Claims (2)

[Claims] 1. A thermoplastic resin composition containing the following components (A) and (B). (A) Saturated polyester (B) (a) Aromatic vinyl compound unit 50 to 99.9
%, (B) 0.1 to 20% by weight of an α, β-unsaturated carboxylic acid ester-based compound unit having a hydroxyl group, (c) 0 to 50% by weight of a vinyl cyanide-based compound unit, and (d) the above (a). ), (B) and (c) and other copolymerizable vinyl compound unit 0 to 40% by weight containing a hydroxyl group-modified aromatic vinyl random copolymer 2. A thermoplastic resin composition containing the following components (A) and (B ′). (A) Saturated polyester (B ') 95 to 10% by weight of the hydroxyl group-modified aromatic vinyl random copolymer (B) of claim 1 and the hydroxyl group-modified aromatic vinyl random copolymer (B) are graft-bonded. Rubber-reinforced hydroxyl group-modified aromatic vinyl-based graft copolymer comprising 5 to 90% by weight of rubber-like polymer