JPH066663B2 - Polyester resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a polyester resin composition.
More specifically, the present invention relates to a polyester resin composition having excellent mechanical properties such as impact resistance and hydrolysis resistance, which is suitable for use in electric / electronic parts, automobile parts and other industrial materials.

[Prior art]

A composition comprising a polyester resin, a butadiene-based graft copolymer and an epoxy compound, which is excellent in impact resistance, acid resistance and moldability (JP-A-50-23448), or a polyester resin, a butadiene-based graft copolymer and a carbodiimide. A composition comprising a compound having excellent mechanical properties, heat resistance and hydrolysis resistance (JP-A-59-6251) is known.

These compositions are greatly improved in mechanical properties such as impact resistance, but when blending a butadiene-based graft copolymer with a polyester resin, they tend to reduce hydrolysis resistance. The decrease in hydrolyzability cannot be suppressed to a satisfactory level even if a carbodiimide compound is added.

[Object of the Invention]

As a result of intensive studies to improve the hydrolysis resistance of a composition composed of a polyester resin and a butadiene-based graft copolymer, the present inventors have found that the polyester resin, the epoxy compound and the carbodiimide are added to the polyester resin together with the butadiene-based graft copolymer. The present invention has been completed by knowing that a polyester resin composition having excellent mechanical properties such as impact resistance and hydrolysis resistance can be obtained when a compound is compounded.

[Structure of Invention]

The gist of the present invention is a polyester resin composition comprising a thermoplastic polyester resin, a butadiene-based graft copolymer, a halogen-free epoxy compound and a carbodiimide compound, wherein the ratio of the thermoplastic polyester resin to the butadiene-based graft copolymer is , 99.5: 0.5-40: 60
The weight ratio is 0.01 to 5% by weight of the halogen-free epoxy compound and the amount of the carbodiimide compound relative to the total amount of the thermoplastic resin and the butadiene-based graft copolymer.
It exists in the polyester resin composition characterized by being 0.01 to 5 weight%.

The thermoplastic polyester used in the present invention is a polyalkylene terephthalate obtained by a polycondensation reaction of terephthalic acid or its dialkyl ester and an aliphatic glycol, or a copolymer mainly composed of polyalkylene terephthalate. , Polyethylene terephthalate, polybutylene terephthalate and the like.

Examples of the above-mentioned aliphatic glycols include ethylene glycol, propylene glycol, tetramethylene glycol, hexamethylene glycol, and the like. With these aliphatic glycols, other diols or polyhydric alcohols, for example, aliphatic glycols 3
0% by weight or less of cyclohexanediol, cyclohexanedimethanol, xylylene glycol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4
-Hydroxy-3,5-dibromophenyl) propane, 2,2
-Bis (4-hydroxyethoxyphenyl) propane,
2,2-bis (4-hydroxyethoxy-3,5-dibromophenyl) propane, glycerin, pentaerythritol and the like may be mixed and used.

In addition to terephthalic acid or a dialkyl ester thereof, other dibasic acid, polybasic acid or an alkyl ester thereof, for example, 30% by weight or less of terephthalic acid or its dialkyl ester, phthalic acid, isophthalic acid,
You may mix and use naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, adipic acid, sebacic acid, trimesic acid, trimellitic acid, those alkyl esters, etc.

The graft ratio of the polybutadiene-based graft copolymer is 15
It is necessary to be up to 200%, and 30 to 120% is particularly preferable. When the graft ratio is less than 15%, it is considered that the compatibility is insufficient, but the impact resistance is not sufficiently improved, and the appearance characteristics of the molded product are not good, while the graft ratio is more than 200%. In this case, it is considered that the rubber elasticity of the rubber component [(a) component] is lost, but the impact resistance is still insufficiently improved. Here, the graft ratio is a value obtained by the following equation.

However, the acetone insoluble content in the formula was determined by thoroughly immersing the graft copolymer in acetone and then strictly collecting the insoluble precipitate by centrifugation.

The butadiene-based graft copolymer used in the present invention is
It can be produced by any method of bulk polymerization, suspension polymerization, bulk suspension polymerization, solution polymerization or emulsion polymerization. In particular, when a copolymer having a high rubber content is produced, it is preferably produced by emulsion graft polymerization.

In producing the copolymer, the amount of the butadiene-based polymer (A) is 10 to 85% by weight, and it is particularly preferable to use 30 to 70% by weight. If the amount used is less than 10% by weight, the impact strength of the obtained resin composition is low, while if it is more than 85% by weight, the moldability of the obtained resin composition is lowered, which is not preferable. When the butadiene polymer (a) is a copolymer, it is a copolymer of a butadiene-based monomer and a vinyl-based monomer (for example, styrene), and the butadiene component is 50% by weight from the viewpoint of improving impact resistance. Must be at least%.

The vinyl-based monomer that is graft-copolymerized with the butadiene-based polymer (a) is at least one of a methacrylic acid ester, an aromatic monovinyl compound, and a vinyl cyanide compound. The usage ratio is arbitrary, and a small proportion may be replaced with another vinyl-based monomer before use. Further, the order of use in graft-copolymerizing the vinyl-based monomer is arbitrary, and two or more kinds may be used at the same time, or they may be used separately for graft-copolymerization. As the methacrylic acid ester, an alkyl ester having 1 to 4 carbon atoms is preferable, and a methyl ester is particularly preferable. Examples of aromatic monovinyl compounds include styrene and vinyltoluene α
-Methylstyrene, nuclear halogenated styrene, vinylnaphthalene, etc. are mentioned, and styrene is particularly preferable. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile α-halogenated acrylonitrile, and acrylonitrile is particularly preferable.

Specific examples include those marketed under the names ABS, MBS, SBR, NBR and the like.

The halogen-free epoxy compound, allyl glycidyl ether, bisepoxydicyclopentadienyl ether of ethylene glycol, epoxidized soybean oil, epoxidized linseed oil, butadiene diepoxide,
Octyl epoxytalates, aliphatic epoxy compounds such as epoxidized polybutadiene, bisphenol A diglycidyl ether, tetraphenylethylene epoxide, aromatic epoxy compounds such as diglycidyl ester of phthalic acid, 3,4-epoxycyclohexylmethyl-
3,4-epoxycyclohexanecarboxylate, 3,4-
Epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate,
2,3-Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 4- (3,4-epoxy-5-methylcyclohexyl) butyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylethylene oxide , Cyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4
-Epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, vinylcyclohexene oxide, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)
Examples thereof include alicyclic epoxy compounds such as cyclohexane-metadioxane.

The carbodiimide compound is produced, for example, by heating and decarboxylation from an isocyanate compound, and specific examples thereof include diphenylcarbodiimide, ditolylcarbodiimide, di (propylphenyl) carbodiimide, di (butylphenyl) carbodiimide, dinaphthylcarbodiimide. , Bis (dipropylphenyl) carbodiimide, polyphenylenecarbodiimide, polytolylenecarbodiimide, poly (propylphenylene) carbodiimide, poly (dipropylphenylene) carbodiimide, poly (diphenylmethane) carbodiimide, polynaphthylenecarbodiimide and the like. The amount is 0.01 to 5% by weight, preferably 0.02 to 2% by weight, based on the total amount of the thermoplastic polyester resin and the butadiene-based graft copolymer. If it is too small, the effect is small, and if it is too large, the mechanical properties are adversely affected.

The ratio of the thermoplastic polyester resin to the butadiene-based graft copolymer is 99.5: 0.5 to 40:60 by weight, preferably 99: 1 to 70:30, more preferably 97: 5.
~ 80: 20. If the amount of the butadiene-based graft copolymer is too small, a composition having excellent impact resistance cannot be obtained. On the other hand, if the amount is too large, mechanical properties such as tensile strength and bending strength will deteriorate.

The amount of the halogen-free epoxy compound is 0.01 to 5% by weight, preferably 0.02 to 2% by weight, based on the total amount of the thermoplastic polyester resin and the butadiene-based graft copolymer. If it is too small, the effect cannot be expected, and if it is too large, coloring will occur.

As a method for compounding the above composition, a method of dry blending, a method of melt-mixing the dry blended product using an extruder and extruding into pellets, a master containing a large amount of an ester of pentaerythritol and / or an epoxy compound. A well-known method such as a method of preparing pellets and mixing the pellets with a dilution pellet can be employed.

The polyester resin composition of the present invention includes a glass fiber, a reinforcing agent such as carbon fiber, silica, alumina, silica alumina, silica magnesia, calcium carbonate, gypsum, a filler such as clay, a halogen-containing aromatic compound, A flame retardant such as a halogen-containing resin such as a halogen-containing acrylic resin or a polycarbonate resin, a flame-retardant aid such as antimony trioxide, and other well-known additives may be contained.

〔Example〕

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples unless it exceeds the gist.

In addition, "part" in an Example shows a "weight part."

The tensile strength and the tensile elongation are measured according to ASTM D638, and the Izod impact strength is measured according to ASTM D256.

Example 1 and Comparative Examples 1 to 3 Polybutylene terephthalate having an intrinsic viscosity of 1.10 dl / g,
Methyl methacrylate-butadiene-styrene copolymer (MBS) (trademark, Metablen C223, manufactured by Mitsubishi Rayon Co., Ltd.), glass fiber (Asahi Fiber Glass Co., Ltd.)
CSO3MA486), and bisphenol A-diglycidyl ether (trademark, manufactured by Adeka Argus Chemical Co., Ltd.)
A mixture of mark mark-17) and a mixture of bis (diisopropylphenyl) carbodiimide were prepared, melt-kneaded at 250 ° C. using a 40 mmφ extruder, and extruded into pellets.

The pellets were molded using a 3.9 ounce injection molding machine (manufactured by Japan Steel Works, Ltd., model N-100BIIV) and a test piece molding mold defined by ASTM, and the resin temperature was 258 ° C, the mold temperature was 80 ° C, and the injection time was 10 Injection molding was carried out with a cooling time of 20 seconds.

The obtained molded product was steam sterilized (Taniguchi Kagaku Co., Ltd., S
Hydrolysis test under pressure steam at 120 ° C. was performed using −90 N type), and the tensile strength and Izod impact strength of the molded product immediately after molding and the molded product after 90-hour test were measured.

The results are as shown in Table 1 below.

For comparison, the results when no epoxy compound was added are also shown.

Example 2 and Comparative Examples 4 to 6 The same operation as in Example 1 was carried out except that the glass fiber was not used, and the results shown in Table 2 below were obtained.

However, the hydrolysis test is 750 at 90 ℃ and 100% RH.
I went on time.

Examples 3 to 4 In place of bisphenol A-diglycidyl ether in Example 1, allyl glycidyl ether (trade name, Neoallyl G, manufactured by Osaka Soda Co., Ltd.) 0.5 part (Example 3),
Alternatively, 0.5 parts of 3,4-epoxycyclohexyl-3 ', 4'-epoxycyclohexanecarboxylate (trademark, ERL 4221 manufactured by Union Carbide) (Example 4) was used to obtain the results shown in Table 3 below.

[Effects of the Invention] The polyester resin composition of the present invention can be molded into various shapes such as three-dimensional molded articles, sheets, tubes, monofilaments by various molding methods such as injection molding, extrusion molding, compression molding and blow molding. And the hydrolysis resistance is improved, so that electric and electronic parts, automobile parts,
It has great value as a material for other industries.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takahiro Nagayama 1 2447 Fujita, Hachimansai-ku, Kitakyushu, Fukuoka Prefecture Mitsubishi Kasei Kogyo Co., Ltd. Kurosaki Plant (56) Reference JP-A-50-23448 (JP, A) JP-A-59-6251 (JP, A)

Claims (1)

[Claims] 1. A polyester resin composition comprising a thermoplastic polyester resin, a butadiene-based graft copolymer, a halogen-free epoxy compound and a carbodiimide compound, wherein the ratio of the thermoplastic polyester resin to the butadiene-based graft copolymer is 1. , 99.5: 0.5 to 40:60 by weight, and the amount of the halogen-free epoxy compound is 0.01 to 5% by weight and the amount of the carbodiimide compound is based on the total amount of the thermoplastic polyester resin and the butadiene-based graft copolymer. A polyester resin composition, which is 0.01 to 5% by weight.