JPH10158490A - Polyethylene terephthalate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition having excellent impact strength by mixing a polyethylene terephthalate type thermoplastic polyester produced by using a germanium catalyst with an epoxy compound having an internal epoxy group and an ester bond and a fibrous reinforcement surface-treated with an epoxysilane compound in a specified mixing ratio. SOLUTION: Dimethyl terephthalate is reacted with ethylene glycol in the presence of a magnesium acetate catalyst to form an oligomer, and this oligomer is polycondensed in the presence of a catalyst (e.g. GeO2 ) to produce a polyethylene terephthalate thermoplastic polyester. 100 pts.wt. this polyester is mixed with 0.05-30 pts.wt. compound having two internal epoxy groups and ester bonds (e.g. ethylene/glycidyl methacrylate copolymer) and 2-150 pts.wt. fibrous reinforcement treated with 0.1-5wt.% epoxysilane compound. The obtained mixture is optionally mixed with an antioxidant, a heat stabilizer, etc., and the entire mixture is melt-kneaded.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyethylene terephthalate-based resin composition having improved impact strength, retention heat stability and the like without lowering fluidity.

[0002]

2. Description of the Related Art Polyethylene terephthalate resin is
Because of its excellent mechanical properties and chemical properties, it has been widely used as fibers, films, molding materials and the like. As a catalyst used in the polymerization of polyethylene terephthalate resin, an antimony compound is generally used because it is most advantageous industrially, but other catalysts include germanium compounds, tin compounds, and titanium compounds. Compounds are known.

In general, thermoplastic polyesters such as polyethylene terephthalate resin alone cannot be said to have very good impact strength. For this reason, various additives for improving impact resistance have been used. For example,
JP-A-52-32145 discloses a method of adding a glycidyl group-containing olefin copolymer to a saturated polyester. However, if the glycidyl group-containing olefin copolymer is added to a general polyethylene terephthalate resin produced using an antimony compound as a catalyst, it cannot be used because of problems such as formation of a gelled product. On the other hand, Tokiko 6-70171
Japanese Patent Publication No. 2005-189686 discloses that by adding a glycidyl group-containing olefin copolymer to polyethylene terephthalate produced using a germanium compound as a catalyst, a comparison is made with polyethylene terephthalate produced using an antimony compound or the like as a catalyst. Thus, it is shown that a composition having an excellent appearance can be obtained.

[0004] On the other hand, polyethylene terephthalate-based thermoplastic polyesters are greatly enhanced in strength and heat resistance by being reinforced with fibrous reinforcing agents such as glass fibers and carbon fibers, and can be applied to injection molding applications. Becomes At this time, in order to improve the adhesion between the fibrous reinforcing agent and polyethylene terephthalate, the fibrous reinforcing agent is generally subjected to a surface treatment with a treating agent such as a silane coupling agent. When the fibrous reinforcing agent is not treated with the silane coupling agent, the adhesiveness between the fibrous reinforcing agent and the resin is poor, so that a sufficient reinforcing effect is not exhibited.

[0005]

However, Japanese Patent Publication No. Hei 6-70171 discloses a composition obtained by adding a glycidyl group-containing olefin copolymer to polyethylene terephthalate with a reinforcing filler. Is described as unfavorable because it deteriorates. The present inventors have also studied, when adding a glycidyl group-containing olefin copolymer or the like to polyethylene terephthalate produced using a germanium-based catalyst and reinforcing it with a fibrous reinforcing agent, the resin and fibrous reinforcing agent are used. When a fibrous reinforcing agent treated with a silane coupling agent is added to enhance the adhesion with the agent, the fluidity and the retention heat stability are significantly reduced,
It was confirmed that there was a problem that the appearance was not good.

[0006]

Means for Solving the Problems In order to solve the above problems, the present inventors have conducted various studies on a surface treatment agent for a fibrous reinforcing agent, and as a result, it has been found that the surface treatment agent for a fibrous reinforcing agent is treated with an epoxysilane-based compound. Only when the fibrous reinforcing filler is used, it is possible to obtain a polyethylene terephthalate-based resin composition which exhibits excellent impact strength and retention heat stability without lowering the fluidity, and has a good appearance of the molded product. And found the present invention.

That is, the present invention relates to (B) 100 parts by weight of a polyethylene terephthalate-based thermoplastic polyester mainly composed of ethylene terephthalate repeating units produced by using a germanium-based catalyst, and (B) at least two units per molecule. 0.05 to 30 parts by weight of at least one epoxy compound having an epoxy group and having an ester bond in the molecule, (C) a fibrous reinforcing filler 2-150 surface-treated with an epoxysilane-based compound. A gist of the present invention is a polyethylene terephthalate-based resin composition obtained by blending parts by weight.

[0008]

[Function] To improve the strength and heat resistance by adding a fibrous reinforcing agent such as glass fiber and carbon fiber to polyethylene terephthalate-based thermoplastic polyester, improve the adhesion between the fibrous reinforcing agent and polyethylene terephthalate. Therefore, when a fibrous reinforcing filler surface-treated with a commonly used aminosilane-based silane coupling agent is generally used as the fibrous reinforcing agent, the amino group of the silane coupling agent becomes (A ) The component (A) and the component (B) excessively react during the molding process because they act as a reaction catalyst between the polyethylene terephthalate-based thermoplastic polyester and the epoxy compound (B). As a result, a large amount of foreign substances such as gelled substances are generated in the resin,
It is considered that adverse effects such as a decrease in fluidity, a decrease in the retention heat stability and surface properties of the molded article, and a decrease in impact strength are caused. On the other hand, when a fibrous reinforcing filler (C) which has been surface-treated with an epoxysilane-based compound is used, the reaction between the component (A) and the component (B) becomes gentle, so that a gelled product such as Since the generation of foreign matter is suppressed and the component (A) and the component (B) are appropriately mixed, preferable physical properties can be obtained. Also, when a polyethylene terephthalate-based thermoplastic polyester produced using a catalyst other than a germanium-based catalyst such as an antimony catalyst is used, foreign substances such as a gelled substance are similarly generated. Physical properties such as The details of the reaction mechanism at this time are unknown.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The (A) polyethylene terephthalate-based thermoplastic polyester used in the present invention is polymerized using a germanium compound as a catalyst at the time of production. The germanium compound used as a catalyst during this production includes germanium oxides such as germanium dioxide, germanium tetraethoxide, germanium alkoxides such as germanium tetraisopropoxide, germanium hydroxide and alkali metal salts thereof, germanium glycolate, and chloride. germanium,
Germanium acetate and the like can be mentioned. Among these,
Preferably, germanium dioxide is used. The addition amount of the germanium compound is preferably 0.005 to 0.1% by weight based on polyethylene terephthalate,
-0.05% by weight is more preferred. The germanium-based catalyst may be added at any time before the start of the polymerization reaction.

The polyethylene terephthalate-based thermoplastic polyester used in the present invention is polyethylene terephthalate or at least 80% (ratio as a repeating unit, the same applies hereinafter), preferably 85.
% Or more, more preferably 90% or more of ethylene terephthalate repeating units. As the copolymerization component, a known acid component, alcohol and / or phenol component, or an ester-forming derivative thereof can be used. Examples of the acid component include an aromatic carboxylic acid having 8 to 22 carbon atoms and having a valency of 2 or more, an aliphatic carboxylic acid having 4 to 12 carbon atoms and having a valency of 2 or more, and an alicyclic ring having 8 to 15 carbon atoms and having a valence of 2 or more. Formula carboxylic acids, and ester-forming derivatives thereof, and the like. Specifically, besides terephthalic acid, for example, isophthalic acid, naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methaneanthracenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 1,2
-Bis (phenoxy) ethane-4,4'-dicarboxylic acid, 5-sodium sulfoisophthalic acid, adipic acid,
Sebacic acid, azelaic acid, dodecanedioic acid, maleic acid, trimesic acid, trimellitic acid, pyromellitic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and ester-forming derivatives thereof, and the like. Can be The alcohol and / or
Alternatively, as the phenol component, a C3 to C15 dihydric or higher aliphatic alcohol, a C6 to C20 divalent or higher alicyclic alcohol, a C6 to C40 divalent or higher aromatic alcohol or phenol And their ester-forming derivatives. Specifically, propanediol, butanediol, hexanediol, decanediol, neopentyl glycol, cyclohexanedimethanol, cyclohexanediol, 2,2′-bis (4
-Hydroxyphenyl) propane, 2,2′-bis (4
-Hydroxycyclohexyl) propane, hydroquinone, glycerin, pentaerythritol, and ester-forming derivatives thereof. Also, p-
Oxyacids such as oxybenzoic acid, p-hydroxyethoxybenzoic acid and their ester-forming derivatives, ε
-A cyclic ester such as caprolactone can also be used. Further, those obtained by partially copolymerizing polyalkylene glycol units such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol in a polymer chain can also be used.

The method for producing the above polyethylene terephthalate-based thermoplastic polyester is not particularly limited except that the catalyst used in the production is a gemnium-based catalyst.
Various known production methods can be used. For example,
First, terephthalic acid and ethylene glycol are used without a catalyst or with a catalyst (a tin compound or a titanium compound is used).
Low-polymerization by direct esterification in the presence of glycerol, or by transesterification of dimethyl terephthalate and ethylene glycol in the presence of a catalyst (compounds of magnesium, zinc, cobalt, calcium, manganese, etc.) The polymer having a low degree of polymerization is synthesized at a high temperature and under a high vacuum, and a polymerization catalyst comprising a germanium compound is added thereto, and condensation polymerization is performed by melt polycondensation or solid phase polycondensation. A method for producing a polyethylene terephthalate-based thermoplastic polyester by exchanging and removing ethylene glycol can be mentioned.

In the above case, when a polymer having a low degree of polymerization is subjected to condensation polymerization, a polyethylene terephthalate-based heat-polymerized polymer using a catalyst other than a germanium compound, for example, an antimony-based catalyst that is commonly used. The use of a plastic polyester is not preferred because the fluidity is significantly reduced and the retention heat stability of the molded article is also deteriorated.

When producing a polyethylene terephthalate-based thermoplastic polyester, a phosphoric acid compound such as phosphoric acid, phosphorous acid,
Hypophosphorous acid, monomethyl phosphate, dimethyl phosphate, trimethyl phosphate, methyl diethyl phosphate, triethyl phosphate, triisopropyl phosphate, tributyl phosphate, triphenyl phosphate, tribenzyl phosphate, tricyclohexyl phosphate, Compounds such as trimethyl phosphate, methyl diethyl phosphite, triethyl phosphite, triisopropyl phosphite, tributyl phosphite, and triphenyl phosphite may be added after the esterification reaction or transesterification reaction.

Further, in order to increase the crystallinity of the obtained polyethylene terephthalate-based thermoplastic polyester, various well-known organic or inorganic crystallization nucleating agents may be used alone or in combination of two or more at the time of polymerization or the like. May be added.

The polyethylene terephthalate-based thermoplastic polyester produced as described above is usually 0.3
Logarithmic viscosity of 5-1.20 (phenol / 1,1,2,2
-Tetrachloroethane = 50/50 (weight ratio), 0.5
% (Weight ratio, the same applies hereinafter), 25 ° C. (the same applies hereinafter, unit d1 / g), but from the viewpoint of the balance between the crystallization speed and the mechanical strength, the logarithmic viscosity is 0.40-0. .
95 is preferable, and 0.50 to 0.90 is more preferable.

Next, the epoxy compound (B) having at least two epoxy groups in the molecule and having an ester bond in the molecule used in the present invention improves the impact resistance and the like of the resin composition. Used to As the epoxy compound, a resin can be used.

As the epoxy compound (B), a glycidyl ester of a divalent or higher carboxylic acid, a glycidyl ether of a compound having both an ester bond and at least two OH groups in a molecule and the like are used. Specific examples of these include diglycidyl isophthalate, diglycidyl terephthalate, diglycidyl trimellitate, triglycidyl trimellitate, diglycidyl adipate, and the like.

As the resin as the epoxy compound (B), a compound having both a vinyl group and an epoxy group in a molecule, such as glycidyl acrylate and glycidyl methacrylate, and various other compounds having a vinyl group are known. It is possible to polymerize resins of various compositions by copolymerizing with the above various polymerization methods. Specific examples of these resins include ethylene-glycidyl methacrylate copolymer, ethylene-glycidyl methacrylate-
Vinyl acetate copolymer, ethylene-methyl acrylate
Glycidyl methacrylate copolymer, ethylene-ethyl acrylate-glycidyl methacrylate copolymer, ethylene-propylene-glycidyl methacrylate copolymer, propylene-glycidyl methacrylate copolymer,
Styrene-glycidyl methacrylate copolymer, α-methylstyrene-glycidyl methacrylate copolymer, styrene-acrylonitrile-glycidyl methacrylate copolymer, α-methylstyrene-acrylonitrile-glycidyl methacrylate copolymer, styrene-N-phenylmaleimide-glycidyl methacrylate Copolymer, methyl methacrylate-glycidyl methacrylate copolymer, styrene-methyl methacrylate-glycidyl methacrylate copolymer, butadiene-glycidyl methacrylate copolymer, butadiene-styrene-glycidyl methacrylate copolymer, butadiene-methyl methacrylate-glycidyl methacrylate copolymer Polymer, butyl acrylate-methyl methacrylate-glycidyl methacrylate copolymer, And various other combinations. These epoxy resins are all applicable to the composition of the present invention.

Further, a method of introducing an epoxy group into a resin having an ester bond by reacting a resin having both an ester bond and a plurality of double bonds with a peroxide or the like; It is also possible to produce a resin having an ester bond and at least two epoxy groups by a method of glycidyl etherification of a resin having both OH groups. Specific examples of the resin having both an ester bond and a plurality of double bonds include a butadiene-methyl methacrylate copolymer and a butadiene-styrene-methyl methacrylate copolymer. In addition, the ester bond and a plurality of OH
Specific examples of the resin having both groups include a polyester in which both ends of a polymer are OH groups.

Among the above-mentioned compounds and resins, an olefin copolymer containing at least two chrysidyl groups is preferable because the obtained resin has an excellent effect of improving the impact resistance.

If the number of epoxy groups contained in the molecule of the epoxy compound (B) is less than 2, it is not preferable because the obtained resin has almost no effect of improving the impact resistance. Also, if the epoxy compound has no ester bond in the molecule,
It is not preferable because the compatibility with the polyethylene terephthalate-based thermoplastic resin decreases and the effect of improving the impact resistance decreases.

The amount of the epoxy compound (B) used is as follows:
(A) 0.05 to 30 parts by weight, preferably 0.1 to 25 parts by weight, more preferably 0.1 to 30 parts by weight, based on 100 parts by weight of polyethylene terephthalate-based thermoplastic polyester.
5 to 20 parts by weight. (B) The epoxy compound is 0.1%.
When the amount is less than 05 parts by weight, the effect of improving the impact strength of the obtained molded article is small, and when it exceeds 30 parts by weight, the fluidity of the obtained resin composition is undesirably reduced.

The fibrous reinforcing filler treated with the epoxysilane compound (C) used in the present invention includes:
Glass fibers having a diameter of 1 to 20 μm and a length of about 0.05 to 50 mm are preferred. From the viewpoint of workability, it is preferable to use chopped strand glass fibers treated with a sizing agent.

Further, it is necessary to use an epoxysilane-based compound as the surface treatment agent used for enhancing the adhesion between (A) the polyethylene terephthalate-based thermoplastic polyester and (C) the fibrous reinforcing agent. As the epoxysilane-based compound, for example, compounds such as γ-glycidoxypropyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane are used. As a surface treatment agent for the fibrous reinforcing agent, when an aminosilane compound such as γ-aminopropyltriethoxysilane, which is generally used for polyester, is used, the fluidity of the obtained resin composition is significantly reduced, and molding is performed. This is not preferable because the heat retention stability of the body tends to decrease.

The number of parts to be added when the fibrous reinforcing agent is treated with the above-mentioned epoxysilane compound is not limited as long as the physical properties of the obtained resin composition are not reduced, but is preferably 100 parts by weight of the fibrous reinforcing agent. The amount is 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight. Even if it is added in an amount exceeding 10 parts by weight, the effect is hardly obtained, although it is economically disadvantageous, and if it is less than 0.01 part by weight, the effect of increasing the adhesion between the fibrous reinforcing agent and the resin is not sufficiently exhibited. Tend not to be.

(C) The amount of the fibrous reinforcing agent used is (A) polyethylene terephthalate thermoplastic polyester 10
2 to 150 parts by weight, preferably 5 to 0 parts by weight
It is 120 parts by weight, more preferably 10 to 100 parts by weight. If the amount of the fibrous reinforcing agent (C) exceeds 150 parts by weight, the molding processability is poor, and furthermore, the heat generation during the molding process becomes severe, and the decomposition and deterioration of the resin are promoted. When the amount of the fibrous reinforcing agent (C) used is 2 parts by weight or less, the effect of improving the mechanical strength cannot be obtained satisfactorily.

The resin composition of the present invention may further contain any other thermoplastic or thermosetting resin, for example, a saturated resin other than polyethylene terephthalate, as long as the properties of the resin composition intended for the present invention are not impaired. Or unsaturated polyester resin, liquid crystal polyester resin, polyester ester elastomer resin, polyester ether elastomer resin, polyolefin resin, polyamide resin, polycarbonate resin, rubber polymer reinforced styrene resin, polyphenylene sulfide resin ,
A polyphenylene ether resin, a polyacetal resin, a polysulfone resin, a polyarylate resin, or the like may be added alone or in combination of two or more.

In order to improve the performance of the resin composition of the present invention, an antioxidant such as a phenolic antioxidant and a thioether antioxidant, and a heat stabilizer such as a phosphorus stabilizer are used alone. Alternatively, it is preferable to use two or more kinds in combination. In addition, if necessary, usually well-known inorganic or organic crystallization nucleating agents, stabilizers, lubricants, mold release agents, plasticizers, flame retardants, flame retardants, UV absorbers, light stabilizers, pigments , Dye, antistatic agent, conductivity imparting agent, dispersant,
Additives such as a compatibilizer, an antibacterial agent, and an epoxy group reaction catalyst can be used alone or in combination of two or more.

The method for producing the polyethylene terephthalate resin composition of the present invention is not particularly limited. For example, the above components (A) to (C), other additives, resins and the like are dried and then melt-kneaded by a melt-kneading machine such as a single-screw or twin-screw extruder. be able to.

The method of molding the polyethylene terephthalate resin composition of the present invention is not particularly limited, and molding methods generally used for thermoplastic resins, namely, injection molding, hollow molding, extrusion molding, sheet molding, and the like. Forming methods such as forming, roll forming, press forming, laminating forming, film forming by melt casting, and spinning can be applied.

[0031]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto. Prior to the description of the examples, a method for evaluating the obtained resin composition is described. In the following, "parts" means parts by weight and "%" means% by weight unless otherwise specified.

[Evaluation Method] (I) Impact Strength and Fluidity (I-1) Preparation of Test Piece: The obtained resin composition was dried at 140 ° C. for 4 hours using a hot air dryer, and then subjected to a 50 t injection molding machine. Using a cylinder temperature of 270 ° C and a mold temperature of 120 ° C
, And a test piece was obtained and subjected to physical property measurement. (I-2) Impact strength: (unit: J / m) 6.4 mm thick bar (width 12.7 mm, length 127 m)
m) The test pieces were evaluated in a notched IZOD impact test according to ASTM D-256. (I-3) Fluidity: (unit: 10 ^-2 cc / sec) According to JIS K-7210, the method B flow was measured at a set temperature of 280 ° C for a preheating time of 15 minutes. (II) Thermal stability and appearance of molded product: 100 mm x 5
Using a 75t injection molding machine, a flat plate of 0 mm x 3 mm
20 shots were molded at a cylinder temperature of 280 ° C., a mold temperature of 120 ° C. and a molding cycle of 3 minutes, and the surface properties of the molded product were visually evaluated for the last 5 shots according to the following criteria. ：: Good surface properties and moldability. Δ: There is unevenness on the surface. X: The surface has significant unevenness.

Example 1 (A-1) A 1.8-fold molar amount of ethylene glycol was added to dimethyl terephthalate, and the mixture was stirred. 06 parts and 0.02 parts of germanium dioxide as a polymerization reaction catalyst were added. After the temperature was raised to 250 ° C., transesterification was performed at normal pressure to obtain a low polymer, which was further reduced to 0.03 Torr and 280 ° C. over 1 hour,
By polymerizing for 2 hours, a polyethylene terephthalate-based thermoplastic polyester having an logarithmic viscosity of 0.75 was obtained. (B-1) Bond First E as an epoxy compound
(Registered trademark, manufactured by Sumitomo Chemical Co., Ltd., copolymer of ethylene and glycidyl methacrylate; glycidyl methacrylate ratio = 12%) was used. 100 parts of (A-1) and 5 parts of (B-1) are mixed,
Further, 0.3 parts of ADK STAB AO-60 (manufactured by Asahi Denka Co., Ltd.) as a hindered phenolic antioxidant, and ADK STAB AO-412S as a thioether-based stabilizer.
After adding 0.2 parts (made by Asahi Denka Co., Ltd.) and stirring with a super mixer, the barrel temperature was set to 260 ° C. with a vented twin-screw extruder (TEX44 manufactured by Nippon Steel Works, Ltd.) I put it in from the hopper. Further, from the side feeder of the extruder, (C-1) a glass fiber having a fiber length of 3 mm and a fiber diameter of 11 μm surface-treated with 0.5 part of γ-glycidoxypropyltrimethoxysilane as a fibrous reinforcing agent. 45 parts, and melt extruded,
A resin composition was obtained.

Examples 2 to 5 In addition to the above, (A-2) By a polymerization method substantially similar to that of (A-1),
A polyethylene terephthalate thermoplastic polyester having an logarithmic viscosity of 0.60 was polymerized. (B-2) Bond first 7 as an epoxy compound
B (registered trademark, Sumitomo Chemical Industries, Ltd., ethylene-glycidyl methacrylate-vinyl acetate copolymer; glycidyl methacrylate ratio = 12%, vinyl acetate ratio = 5%)
Was used. (B-3) Modiper A-44 as an epoxy compound
00 (registered trademark, manufactured by NOF CORPORATION, a graft copolymer comprising 70% of an ethylene-glycidyl methacrylate copolymer and 30% of an acrylonitrile-styrene copolymer). A resin composition was obtained in the same manner as in Example 1 except that the components were mixed at the ratios shown in Table 1.

[0035]

[Table 1]

Comparative Examples 1 to 8 In addition to the above, (AX) polyethylene terephthalate resin
Velvet PBK-2 (manufactured by Kanebo Co., Ltd., logarithmic viscosity: 0.
60; those polymerized using antimony trioxide, which is an antimony-based catalyst). As the (BX) epoxy compound, YD-126 (registered trademark of Toto Kasei Co., Ltd., bisphenol A type epoxy resin) was used. (CX) as a fibrous reinforcing filler, surface-treated with 0.5 part of γ-aminopropyltriethoxysilane,
Glass fiber with a fiber length of 3 mm and a fiber diameter of 11 mm. A resin composition was obtained in the same manner as in Example 1 except that the components were mixed at the ratios shown in Table 2.

[0037]

[Table 2]

As is clear from the results in Tables 1 and 2, in Comparative Example 1, (A) a polyethylene terephthalate resin polymerized using an antimony catalyst was used as the polyethylene terephthalate thermoplastic polyester. Compared to the corresponding examples, the fluidity is significantly reduced, and the retention heat stability and appearance tend to be inferior. Also,
In Comparative Examples 2-3, (C) As a fibrous reinforcing agent, a surface treatment with a silane coupling agent (γ-aminopropyltriethoxysilane) other than the present invention was used, so that the fluidity was large. And the heat retention stability and appearance are inferior. Further, in Comparative Example 4,
Since both (A) and (C) used those outside the scope of the present invention, the fluidity was significantly reduced, and molding was impossible. In Comparative Example 5, since the epoxy compound (B) was not added, the impact resistance was not improved. In Comparative Example 6, (C) the fibrous reinforcing agent was not used, so that the impact resistance was reduced, and the mechanical strength such as tensile strength and the heat resistance were also significantly reduced (according to ASTM D-648. When the HDT with a load of 1.85 MPa was measured with a 4 mm-thick bar, the value was 140 ° C. lower than that of the example.) In Comparative Example 7, since an epoxy compound (B) outside the scope of the present invention was used, the impact strength was poor. Furthermore, in Comparative Example 8, since the amount of the epoxy compound (B) was outside the range of the present invention, molding was difficult.

[0039]

According to the present invention, it is possible to easily produce a polyethylene terephthalate resin composition excellent in impact strength, retention heat stability and the like without lowering fluidity.
In addition, the present composition also has a good appearance of a molded article. These are very useful industrially.

Claims (4)

[Claims] (A) 100 parts by weight of a polyethylene terephthalate-based thermoplastic polyester mainly composed of ethylene terephthalate repeating units produced by using a germanium-based catalyst, and (B) at least two epoxy groups in a molecule. And at least one epoxy compound having an ester bond in the molecule, 0.05 to 30 parts by weight, (C) a fibrous reinforcing filler surface-treated with an epoxysilane-based compound, 2 to 150 parts by weight, And a polyethylene terephthalate resin composition. 2. The (B) epoxy compound having at least two epoxy groups in the molecule and having an ester bond in the molecule is an olefin copolymer containing at least two glycidyl groups. Item 7. A polyethylene terephthalate resin composition according to item 1. 3. The method according to claim 1, wherein the epoxysilane compound is γ-glycidoxypropyltrimethoxysilane,
The polyethylene terephthalate resin composition according to claim 1, which is (3,4-epoxycyclohexyl) ethyltrimethoxysilane. 4. An amount of 0.0 per 100 parts by weight of the fibrous reinforcing agent.
The polyethylene terephthalate-based resin composition according to claim 1 or 3, wherein the surface treatment is performed by adding 1 to 10 parts by weight of the epoxysilane-based compound.