JPH01263149A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition, consisting of a thermoplastic polyester using a specified glycol component, ABS resin and epoxy group-containing styrene based polymer and improved in impact resistance without impairing mechanical characteristics essential to the polyester. CONSTITUTION:A resin composition obtained by mixing (A) 50-95wt.% thermoplastic polyester, consisting of >=10mol%, preferably 25-85mol% cyclohexanedimethanol in a glycol component and ethylene glycol as other glycol components with (B) 5-50wt.% ABS resin consisting of a graft copolymer prepared by grafting an aromatic vinyl compound and vinyl cyanide and/or other polymerizable vinyl monomers onto a conjugated diene based rubber and a copolymer consisting of the aromatic vinyl compound and vinyl cyanide and/or other polymerizable monomers and (C) 1-20wt.% epoxy group-containing styrene based copolymer (e.g., styrene/glycidyl methacrylate copolymer).

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to an impact-resistant resin composition comprising a thermoplastic polyester, an ABS resin, and an epoxy group-containing styrene copolymer using a specific glycol component. be.

Thermoplastic polyesters, represented by polyethylene terephthalate and polybutylene terephthalate, have excellent mechanical strength, abrasion resistance, solvent resistance, heat resistance, etc., and are widely used in fields such as mechanical parts, automobile parts, and electrical/electronic parts. However, it has the disadvantage of low impact strength, which limits its application.

In order to improve this drawback, attempts have been made to improve Wj91 resistance by adding ABS resin to polyethylene terephthalate, polybutylene terephthalate, etc. (West German Patent Application No. 2035390, 2348377t'f). , Japanese Patent Publication No. 49-97081,
However, in these methods, when a small amount of ABS resin is added, the impact resistance improvement effect is insufficient, and when a large amount is added, the strength of the poly resin composition is However, there was a drawback that the strength was excessively lower than that of the thermal polyester used.

[Means for Solving the Problems] As a result of intensive tests Δ-j aimed at obtaining a resin composition with improved impact resistance without deteriorating mechanical properties, a thermoplastic polyester with a specific structure was developed.

It has been found that the objective of "no-emission" can be achieved by a composition comprising an ABS resin and an epoxy group-containing styrenic copolymer.

That is, thermoplastic polyester 50-9 in which 10 mol% or more of the a6 glycol component is cyclohexaline methanol.
This can be achieved by a resin composition prepared by mixing 1 to 20 parts by weight of C and an epoxy group-containing styrenic polymer to ioomJn part of a mixture consisting of 5 to 50 parts by weight of C and epoxy group-containing styrene polymer.

The thermoplastic polyester resin used in the present invention is composed of glycol or its ester-forming derivative and dicarboxylic acid or its ester-forming derivative as monomers.
It is a resin obtained by a normal condensation reaction, and the glycol component thereof is 10 mol% or more, more preferably 25 to 25% by mole.
85 mol% is cyclohexalinemethanol (cis and trans isomers of 1,4-cyclohexalinemethanol, 1,3-cyclohexalinemethanol, etc.).

They are characterized by the fact that they can be used alone or in combination. If the amount of cyclohexaline methanol used is outside the above range, the mechanical strength of the mixture with the ABS resin will decrease, making it impossible to achieve objective 1-1 of the present invention.

Glycol components other than cyclohexaline methanol include ethylene glycol, 2,2-propylene glycol, and 1,3-propanediol.

2.2-dimethyl-1,3-propanediol, trans- or cis-2,2,4,4-tetramethyl-1,
3-cyclobutanediol, 1,4-butanediol,
Neopentyl gelcol, ■, 5-bentanediol,
1.6-hexanediol, decamethylene glycol,
Cyclohexanediol, p-xylene diol, and the like can be used alone or in combination of two or more. Among these, ethylene glycol is the most preferred.

Examples of dicarboxylic acids include terephthalic acid, isophthalic acid,
2-chloroterephthalic acid, 2,5-dichloroterephthalic acid, 2-methylterephthalic acid, 4,4-stilbenedicarboxylic acid, 4,4-biphenyldicarboxylic acid, orthophthalic acid, 2,6-naphthalene dicarboxylic acid, ammonium bis, 0. Fragrance acid, bis(p-carboxyphenyl)methane,
anthracene dicarboxylic acid, 4,4-diphenyl ether dicarboxylic acid.

4.4-Diphenoxyethanedicarboxylic acid, adipizic acid 2-sebacic acid, azelaic acid, dodecanniic acid.

1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, etc. can be used alone or in a mixture thereof. Among these compounds, terephthalic acid, isophthalic acid, and 4,4-stilbenedicarboxylic acid alone or a mixture thereof are particularly preferred.

The number average molecular weight of the thermoplastic polyester resin used in the present invention may be at least a.

A specific example of the thermal nf tffj polyester resin in which 10 mol% or more of the gelcol component is cyclohexaline methanol used in the present invention is KODARPET G6 sold by Eastman Chemical Company of the United States.
763, KODARPCTG 5445, KODARP
Examples include CTG10179 and KODARPCTA150.

The amount of such thermal itf plastic polyester used is 50 to 95%.
If it is less than 50% by weight and M1%, the strength inherent in thermoplastic polyester cannot be obtained, and if it is more than 95% by weight, the impact resistance improvement effect is insufficient, and the object of the invention cannot be achieved.

The ABS resin used in the present invention is a graft polymer (b-1) obtained by graft-polymerizing a conjugated diene rubber with an aromatic vinyl, vinyl cyanide, and/or a jit body in another polymerizable material, and an aromatic Vinyl and cyanide vinyl and/
Or a copolymer (b-2) consisting of other polymerizable monomers
Consists of.

Examples of the 8-functional die 2 rubber constituting the graft polymer (b-1) include polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, and the like. Note that the gel content of the conjugated diene rubber is not limited to 1.

Examples of the aromatic vinyl compound used in the graft copolymer (b-t) include styrene, α-methylstyrene, dimethylstyrene, vinyltoluene, and the like. As vinyl cyanide compounds, acrylonitrile,
Methacrylate trile and the like can be mentioned. Other polymerizable monomers include methyl acrylate, ethyl acrylate, butyl acrylate, and methyl methacrylate.

Ethyl methacrylate, butyl methacrylate.

Hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate and the like can be mentioned.

The conjugated diene rubber content in the graft polymer (b-1) is 20 to 70% by weight.

There is no particular restriction on the composition ratio of the graft polymer (b-1) and copolymer <b-2), but il? i attack.

Graft polymer (b-1
) 20 to 80% by weight, and copolymer (b-2) 80 to 20% by weight.

The amount of such ABS resin added is 5 to 50% by weight, and 5% by weight.
Below 5% by weight, the impact resistance improvement effect is insufficient.
If it exceeds 0% by weight, the inherent strength of the thermoplastic polyester decreases, making it impossible to achieve the object of the present invention.

The polystyrene-based copolymer containing an evocative group used in the present invention is styrene or methylstyrene.

Vinylxylene, chlorstyrene, dichlorostyrene,
It is a polymer produced by the reaction of a polymer whose main constituent is a styrene monomer such as bromustyrene, dibromustyrene, P-t-butylstyrene, ethylstyrene, or vinylnaphthalene with an unsaturated monomer having an epoxy group.

This polymer includes butadiene, butene, isoprene,
Acrylonitrile or the like may be copolymerized.

Examples of heptamines having an epoxy group include epoxy group-containing unsaturated compounds such as glycidyl acrylic acid, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, allyl glycidyl ether, and vinyl glycidyl ether. Preferred among these include glycidyl acrylate, glycidyl methacrylate, and allyl glycidyl ether.

Such an epoxy group-containing copolymer can be produced by bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization using known radical polymerization methods. Also, molten! Extruder for island grafting.

By using a melt mixer such as a Nigoo mixer or a Banbury mixer, the desired product can be easily obtained in a relatively short time. The number average molecular weight of this copolymer is 5.00
0-150,000, more preferably 20,000-8
The range is 0,000.

As specific examples of the epoxy group-containing styrenic copolymer used in the present invention, commercially available products include Blenmar P-15, Blenmar P-30 and Blenmar P-1 manufactured by NOF Corporation.
03A etc.

The amount of the epoxy group-containing styrene copolymer added is 1
-20% by weight, and if it is less than 1% by weight, the effect of improving impact resistance is sufficient, and if it is more than 20% by weight, molding processability decreases, which is not preferable.

Various reinforcing materials and fillers can be added to the resin composition of the present invention within a range that does not impair its moldability and physical properties.1 Specific examples of reinforcing materials and fillers include glass fiber, asbestos fiber, carbon v1m , silica LA fiber, silica/alumina fiber, alumina fiber, zirconia fiber, boron nitride M fiber, silicon nitride FI&M, boron fiber, stainless steel, aluminum, titanium.

Metals such as copper, brass, and magnesium mm.

and polyamide, fluororesin, and polyester.

Organic fibers such as acrylic resin, copper, iron, nickel, zinc, soot, lead, stainless steel, and aluminum.

Examples include metal powders such as gold and copper, fumed silica, aluminum silicate, glass beads, carbon black, quartz powder, talc, titanium oxide, iron oxide, calcium carbonate, and diatomite. tHaM￥.

The material has an average fiber diameter of 5 to 50 μm and a fiber length of 50 μm.
2m to 30mm can be used. These reinforcing materials and fillers may also be surface-treated with known silane coupling agents or titanate-based force/mumbling agents.

These reinforcing materials and fillers can be used alone or in combination of two or more. These reinforcing materials and fillers are used in an amount of 5 to 5 parts by weight based on 00 parts by weight of the resin Ml acid compound of the present invention.
By mixing 100 parts by weight, mechanical strength,
Significantly improves heat resistance.

The resin composition of the present invention contains antioxidants such as hindered phenols, hydroquinone, thioethers, phosphites, substituted products thereof, and copper compounds such as copper iodide, to the extent that the object of the present invention is not impaired. agents, heat stabilizers, and resorcinol.

UV absorbers such as salicylate, penztriazole, benzophenone, stearic acid and its salts, mold release agents such as stearyl alcohol, halogen-based, melamine or cyanuric acid-based flame retardants.

Flame retardant aid, F-decylbenzenesulfone sodium b,
It is also possible to add one or more additives such as antistatic agents, crystallization accelerators, dyes, and pigments to antistatic agents such as polyalkylene glycols.

Also small amounts of polyethylene and polypropylene.

Ethylene Φ vinyl acetate copolymer, ethylene Φ propylene copolymer, polystyrene, polyester elastomer,
Polyacetal, polycarbonate 1.

Heat-resistant plastic resins such as polysulfone and polyphenylene ether, phenolic resins, and melamine resins.

Thermosetting resins such as silicone resins and epoxy resins can also be added.

The method for producing the resin composition of the present invention can be carried out using ordinary melt-kneading processing equipment such as an extruder, a Henley mixer, or a kneader. Can be processed into molded products.

The present invention will be explained below with reference to Examples and Comparative Examples.

[Example] Bending strength retention rate described in Examples and Comparative Examples.

The 0+FI intensity was measured by the following method.

1) Bending strength retention rate This is a numerical value expressed by the following formula.

Bending strength retention rate (%) = The bending strength is 'A' according to ASTM D-638.
It was determined. ~2) Izot impact strength Measured according to ASTM D-256. l111
A test piece with a 1/8 inch notch was used for the determination.

(Unit: Kg-Cm/Cm) The epoxy-containing styrenic copolymer used in the examples was produced by the following method.

Production example: Styrene/glycidyl methacrylate copolymer (
Manufacturing method of Q), hereinafter referred to as SMG After sufficiently replacing the inside of a glass reaction vessel with a stirrer with nitrogen gas, 1600 g of styrene, 4 glycidyl methacrylate,
00g, azobisisobutyronitrile Log and 1500g of toluene were charged.

This reaction vessel was set in an oil bath at 80° C., and the reaction was allowed to proceed for 1 hour while stirring under a nitrogen gas atmosphere, and then the temperature of the oil bath was raised to 100° C., and the reaction was allowed to proceed for another 1 hour. After cooling the obtained reaction solution to room temperature.

Methyl alcohol was added dropwise under strong stirring to precipitate the reaction product, and the separated 0 reaction product was thoroughly washed with methyl alcohol and dried to obtain a styrene/glycidyl methacrylate copolymer (SMG).

The number average molecular weight of this SMG is 30.000, and the SM
The amount of glycidyl methacrylate in G was 19.9% by weight.

Example 1 KODARPET G6763 (manufactured by Eastman Co., Ltd. Nigellicol component is about 35 mol% of cyclohexaline methanol)
and thermal J+ consisting of about 65 mol% ethylene glycol
fq polyester), ABS polymer (manufactured by Ube Cycon Co., Ltd.: Cycolac T), and SM produced in the production example
G was tri-blended at the composition ratio shown in Pyrotechnics, and melt-kneaded using a twin-screw extruder at a cylinder temperature of 260°C to obtain pellets of the resin composition. The obtained pellets were injection molded at a cylinder temperature of 260°C to prepare test pieces for measuring various physical properties. Table 1 shows the results of various physical property measurements.

Comparative Example 1 The same method as Example 1 was carried out except that the epoxy group-containing styrene copolymer was not used. The results are shown in Table 1.

Comparative Example 2 The same method as in Example 1 except that polybutylene terephthalate (manufactured by Mitsubishi Rayon Co., Ltd.: Tuffela N-1200) was used instead of KODARPET G6763 in Example 1, and the epoxy group-containing styrenic copolymer was not used. It was carried out in The results are shown in Table 1.

Examples 2 to 4 KODARPET G6763 (manufactured by Eastman Co., Ltd., a thermoplastic polyester whose nigericol component consists of about 35 mol% of cyclohexaline methanol and about 65 mol% of ethylene glycol), ABSi combination (manufactured by Ube Cycon Co., Ltd.: Cycolac T), and Epoxy group-containing styrene copolymer (manufactured by 11 Hon Yushi Co., Ltd.: Bremmer〇P-510S
A) was triblended at the composition ratio shown in Table 1, and melt-kneaded using a twin-screw extruder at a cylinder temperature of 260°C.
Pellets of the resin composition were obtained. The obtained pellets were injection molded at a cylinder temperature of 260°C and various physical properties were determined. Jllll Sadagawa test constant voltage test piece. Table 1 shows the results of various physical property measurements.

Example 5 KO instead of KODARPET G6763 in Example 1
Example 1 except that DARPCTG10179 (a thermoplastic polyester manufactured by Eastman Co., Ltd. whose nigericol component consists of about 80 mol% of cyclohexaline methanol and about 20 mol% of ethylene glycol) and that Blenmar CP-510SA was used instead of SMG. It was carried out in a similar manner. The results are shown in Table 1.

Example 6 KO instead of KODARPET G6763 in Example 1
DARPCTG5445 (a thermoplastic polyester manufactured by Eastman Co., Ltd. whose nigericol component consists of about 65 mol% of cyclohexaline methanol and about 35 mol% of ethylene glycol) was used, and Blemmer C was used instead of SMG.
It was carried out in the same manner as in Example 1 except that P-510SA was used. The results are shown in Table 1.

(Hereinafter, blank space) [Effects of the invention] The present invention has the advantage that 10 moles of ABS polymer and glycol component
? By blending 1 to 20 parts by weight of an epoxy-containing styrenic polymer to 100 parts by weight of a mixture consisting of a thermoplastic polyester in which the above component is cyclohexaline methanol, the inherent mechanical strength of the thermoplastic polyester is reduced. It is possible to obtain a resin Mll animal with excellent impact properties without any problems.

Patent applicant: Ube Industries Co., Ltd.

Claims (1)

[Scope of Claims] a. Thermoplastic polyester 50-95 in which 10 mol% or more of the glycol component is cyclohexaline methanol
A resin composition prepared by mixing 1 to 20 parts by weight of a styrenic polymer containing an epoxy group to 100 parts by weight of a mixture consisting of 5 to 50 parts by weight of an ABS resin and 5 to 50 parts by weight of an ABS resin.