JPH041260A - Polyester resin composition - Google Patents

Abstract

PURPOSE:To obtain the title compsn. which can be molded into an article having excellent heat resistance, impact strength, and surface appearance even with a low-temp. mold by compounding a specific polyethylene terephthalate copolymer with a polybutylene terephthalate resin, a multi-phase structured thermoplastic resin, a fibrous reinforcement, and a crystallization accelerator. CONSTITUTION:The title compsn. is obtained by compounding 100 pts.wt. polyethylene terephthalate copolymer obtd. by the polycondensation of 65-97.8% polyethylene terephthalate oligomer obtd. by esterifying a dicarboxylic acid component mainly comprising terephthalic acid or a deriv. thereof with a diol component mainly comprising ethylene glycol, 1-20% alkylene glycol having an average mol.wt. of 500-20000, and 1.2-15% diethylene glycol with 5-450 pts.wt. polybutylene terephthalate, 1-300 pts.wt. multi-phase structured thermoplastic resin comprising 5-95% epoxidized olefin polymer and 95-5% vinyl polymer obtd. from a vinyl monomer and having a mean diameter of dispersed particles of 0.01-10mum, 5-800 pts.wt. fibrous reinforcement, and 0.1-200 pts.wt. crystallization accelerator.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is used for various heating appliances, electrical parts, automobile parts, etc., and has excellent mechanical properties, heat resistance, molded appearance, impact resistance, etc. The present invention relates to a fiber-reinforced polyester resin composition.

[Conventional technology]

The various properties of crystalline polymers such as polyethylene terephthalate resin (hereinafter abbreviated as PET) strongly depend on the degree of crystallinity, so if you want to obtain sufficient heat resistance, it is necessary to It was necessary to add a crystal nucleating agent such as a salt or an inorganic compound, and set the mold temperature to a high temperature of 130°C to 140°C. By post-processing, such as post-heating a molded product in a partially crystallized state to promote crystallization, or immersing the molded product in a liquid that promotes crystallization. A method was known to promote crystallization and increase heat resistance.

However, the use of high-temperature molds and post-processing have been problematic in terms of work stability and economy. Besides, 1
When molding was performed at a low mold temperature of 00° C. or lower, the crystallization of the resin did not proceed sufficiently, resulting in poor mold release properties. Therefore, in order to improve mold releasability, it is necessary to cool slowly, and cooling takes a long time.

It is known that various crystallization promoters are used as a method to improve this drawback and perform molding at a low mold temperature.

For example, Japanese Patent Publication No. 45-26225 discloses a method of adding an ionic copolymer consisting of an α-olefin and a salt of α, β-unsaturated carboxylic acid to PET. Further, a method of using polyalkylene glycol and an inorganic filler such as talc in combination is disclosed in Japanese Patent Publication No. 3027/1983.

In addition, JP-A 59/1989 also describes a combination system of ionic copolymers, polyalkylene glycol compounds, and inorganic fillers.
It is disclosed in Japanese Patent No.-22958.

Also known are methods for improving the crystallization rate by copolymerizing a soft segment with PET or using a crystallization promoter in combination. For example, JP-A-56-55451 discloses a method of adding an ionomer to a copolymer of polyalkylene glycol and PUT. Also,
A method of adding an ionomer and a polyolefin to a copolymer of polyalkylene glycol and PET?
It is disclosed in Japanese Patent No.-223850.

However, when injection molding is performed using such a composition in a mold with a temperature that can be controlled with an economical hot water circulation type temperature control device, for example, about 80°C, it is difficult to release the composition. Although the properties and mechanical strength were good, the appearance of the molded product was not necessarily satisfactory.

In addition, polybutylene terephthalate (FPB) is added to PET.
A method of blending (abbreviated as T)
It is disclosed in Japanese Patent No. 832. However, in this case, the amount of PET is smaller than the amount of PBT, for example, PET/PBT=10/70 to 20/80 (weight ratio).
Otherwise, a good surface appearance could not be developed at a mold temperature of 80°C.

Furthermore, since PETi resin has lower impact strength than PBT resin or nylon resin, problems arise, such as the connectors of PET electronic components often cracking when pins are press-fitted. From these viewpoints, there is a strong desire to improve the impact strength of PET resins.

[Invention or problem to be solved]

The present inventors have solved the above-mentioned drawbacks, improved the mechanical strength, and achieved high heat distortion temperature and excellent moldability and surface appearance even when molded with a low-temperature mold. As a result of intensive studies to obtain a polyester resin composition with high strength and high crystallinity, we found that the average molecular weight was 500 to 20,000.
A specific amount of PBT resin, a multiphase thermoplastic resin, a crystallization accelerator, and a fibrous reinforcing material are blended into a PET copolymer obtained by copolymerizing a polyalkylene glycol component and a diethylene glycol component in a specific amount range. The present inventors have discovered that a polyester resin composition with excellent heat resistance, impact resistance, and surface appearance can be obtained even in low-temperature molds, and have completed the present invention.

(Means for Solving the Problems) That is, the present invention comprises (A) a dicarboxylic acid component (a-1) mainly composed of terephthalic acid and its derivatives and a diol component (a-2) mainly composed of ethylene glycol. Botethylene terephthalate oligomer (a) obtained by esterifying 65~
Polyethylene terephthalate-based copolymer obtained by polycondensing 97.8% by weight and 1 to 20% by weight of polyalkylene glycol (b) having an average molecular weight of 500 to 20,000 and 1.2 to 5% by weight of diethylene glycol (c). (B) PBT 5 N450 for 100 parts by weight of polymer
Part by weight (C) Epoxy group-containing olefin polymer 5 to 95
% by weight and 95 to 5% by weight of a vinyl polymer obtained from at least one vinyl monomer, and the average particle size of dispersed particles in the resin is 0.01 to 10μ. A polyester resin composition containing 1 to 300 parts by weight (D) 5 to 800 parts by weight of Mll-shaped reinforcing material and 0.1 to 200 parts by weight of (E) a crystallization accelerator.

Another aspect of the present invention is that (B) PBT is added to 100 parts by weight of the PET copolymer (A).
5 N450 parts by weight (C) 95 to 5% by weight of a vinyl polymer obtained from 5 to 95% by weight of an epoxy group-containing olefin polymer and at least one vinyl monomer
and the average particle diameter of the dispersed particles in the resin is 0.0]
~10p multiphase structure thermal 0T plastic resin 1~7
00 parts by weight (D) Fibrous reinforcement 5-20
00 parts by weight (E) Crystallization accelerator 0.1-3
50 parts by weight (F) Polymer type brominated flame retardant 2-60
This is a flame-retardant polyester resin composition containing 0 parts by weight and 1 to 300 parts by weight of (G) an antimony compound.

[Effect]

The PET copolymer (A) used in the resin composition of the present invention comprises a dicarboxylic acid component (a-1) mainly composed of terephthalic acid and its derivatives and a diol component (a-2) mainly composed of ethylene glycol. P obtained by esterifying
ET oligomer (a) and an average molecular weight of 500 to 20,
It is a copolymer of 000 polyalkylene glycol (b) and diethylene glycol (C).

The PET oligomer (a) used in the present invention preferably has a dicarboxylic acid component (at least 90 mol%) of which is terephthalic acid and its derivatives (e.g. dimethyl ester).
It is obtained by direct esterification or transesterification from a-1) and a diol component (a-2), preferably at least 90 mol% of which is ethylene glycol.

Examples of substances that can be used in combination with terephthalic acid or its derivatives in a proportion of 0 to 10 mol% in the dicarboxylic acid component (a-1) include phthalic acid, isophthalic acid, adipic acid, sebacic acid, naphthalene-1, 4 or -2 , 6-dicarboxylic acid, diphenyl ether-4,4-dicarboxylic acid, and derivatives thereof, such as dimethyl esters of these dicarboxylic acids.

In addition, examples of glycols that can be used in combination with ethylene glycol in a proportion of 0 to 10 mol % in the diol component (a-2) include propylene glycol, butylene glycol, neopentyl glycol, cyclohexane dimetatool, 2.2 -His(4-hydroxyphenyl)propane and the like.

In addition, oxyacids such as p-hydroxybenzoic acid, p-hydroxymethylbenzoic acid, and P-hydroxyethylbenzoic acid are also used in a range of 10 mol% or less (based on 1 mol condensate unit of dicarboxylic acid and diol). be able to.

Examples of the polyalkylene glycol (b) used in the present invention include polyethylene glycol, polypropylene glycol, polytrimethylene glycol, polytetramethylene glycol, and random or block copolymers of polyethylene glycol and polytetramethylene glycol.

The weight average molecular weight of polyalkylene gelicol is 50
In the range of 0 to 20,000, preferably 1,000 to
is in the range of 6000. Weight average molecular weight is 50
If it is less than 0, the mold release properties will be poor when molded using a low-temperature mold, and the heat resistance of the resulting molded product will be reduced. On the other hand, when a resin having a molecular weight exceeding 20,000 is used, the retention stability of the resin composition during molding is poor.

The optimal copolymerization amount of polyalkylene glycol (b) is
Although it varies depending on its average molecular weight, in order to achieve the desired purpose, the amount of the content in the PET copolymer (A) is 1 to 20% by weight, preferably 2 to 15% by weight.

In a resin composition using a PET-based polymer with a copolymerization amount of polyalkylene glycol of less than 1% by weight, the effect of promoting crystallization is not noticeable, and in a PET-based copolymer with a copolymerization amount of polyalkylene glycol exceeding 20% by weight. In resin compositions using coalescence, retention stability during molding is reduced.

The PET copolymer (A) used in the present invention is a copolymer of diethylene glycol (C) (hereinafter abbreviated as DEC) in addition to the above polyalkylene glycol (b). The copolymerized amount of DEC is 1.2 to 15% by weight, preferably 1.5 to 10% by weight.

With a resin composition using a PET copolymer with a DEC copolymerization amount of less than 1.2% by weight, the appearance of the molded product in a low-temperature mold was insufficient, and the copolymerization amount exceeded 5% by weight. PET
In the case of a copolymer, the low F of its melting point becomes large, which is not preferable.

P B T (B) used in the present invention is a polymer obtained by polycondensation of terephthalic acid or a dialkyl ester of terephthalic acid and 1.4-butanediol. A part of terephthalic acid may be replaced with other dibasic acid or polybasic acid, and a part of 1,4-butanediol may be replaced with other diol or polyhydric alcohol. P B
The amount of T (B) is 5 to 450 parts by weight. If the amount is less than 5 parts by weight, the surface appearance at a mold temperature of 80° C. will be poor and the heat distortion temperature (HDT) will be low. On the other hand, 450
If the amount exceeds 1 part by weight, the HDT will decrease, which is not preferable.

The multiphase thermoplastic resin (C) used in the present invention is a vinyl polymer obtained from 5 to 95% by weight of an epoxy group-containing olefin polymer and at least one vinyl monomer.
% by weight, and is made by dispersing a different polymer in the form of particles with a particle size of 0.01 to 10 scales in a polymer matrix. The epoxy group-containing olefin polymer and vinyl polymer constituting this resin (C) may be either matrix or dispersed particles, as long as they can form dispersed particles with a particle size within the above range. good.

Examples of the epoxy group-containing olefin polymer constituting the multiphase thermoplastic resin (C) include modified products obtained by addition-reacting an olefin homopolymer or copolymer with an unsaturated glycidyl group-containing monomer. Ru.

Examples of olefin polymers for this purpose include homopolymers such as low density, medium density or high density polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, ethylene-propylene copolymer, ethylene-butene-1, etc.
1 copolymer, ethylene-hexene-1 copolymer, ethylene-4-methylpentene co-1 copolymer, ethylene-octene-1 copolymer, etc.
Copolymers with olefins; copolymers with other α-olefins containing propylene as a main component, such as propylene-ethylene block copolymers; ethylene-vinyl acetate copolymers;
Ethylene-acrylic acid copolymer; Ethylene-methacrylic acid copolymer; Copolymer of ethylene and ester of acrylic acid or methacrylic acid such as methyl, ethyl, propyl, isopropyl, butyl; Ethylene-maleic acid copolymer; Ethylene-propylene copolymer rubber; ethylene-propylene-diene copolymer rubber; liquid polybutadiene; ethylene-vinyl acetate-vinyl chloride copolymer and mixtures thereof, or mixtures of these with different synthetic resins or rubbers. Included in the present invention.

Unsaturated glycidyl group-containing monomers include lycidyl acrylate; glycidyl methacrylate; monocricidyl itaconate; butenetricarboxylic acid monocricidyl ester; butenetricarboxylic acid diglycidyl ester; butenetricarboxylic acid triglycidyl ester; Glycidyl esters or vinyl glycidyl ether such as α-chloroallyl, maleic acid, crotonic acid, fumaric acid; allyl glycidyl ether; glycidyloxyethyl vinyl ether; glycidyl ethers such as styrene-p-cricidyl ether; p-cricidyl styrene, etc. Among these, particularly preferred is lycidyl methacrylate: acrylic glycidyl ether.

Specific examples of the epoxy group-containing olefin copolymer include ethylene/glycidyl methacrylate copolymer: ethylene/vinyl acetate/glycidyl methacrylate copolymer;
Examples include ethylene/ethyl acrylate/glycidyl methacrylate copolymer: ethylene/carbon oxide/glycidyl methacrylate copolymer; ethylene/vinyl acetate/glycidyl acrylate copolymer. Among them, ethylene/glycidyl methacrylate copolymer is preferred.

These epoxy group-containing olefin copolymers can be used as a mixture.

The vinyl polymer constituting the multiphase thermoplastic resin (C) includes, for example, styrene, nuclear-substituted styrene (methylstyrene, dimethylstyrene, ethylstyrene, isopropylstyrene, chlorostyrene, etc.), α-substituted styrene (
Various vinyl aromatic monomers such as α-methylstyrene, α-ethylstyrene, etc.; acrylic acid or methacrylic acid methyl, ethyl, propyl, -isopropyl or butyl ester, etc. 7 (meth)acrylic acid alkyl ester monomer: (meth)
Acrylonitrile monomer; Vinyl ester monomers such as vinyl acetate and vinyl propionate; (meth)acrylamide immediate polymer; Maleic anhydride or maleic acid monoester or diester: one of various vinyl monomers Or it is a (co)polymer obtained by polymerizing two or more types. Among these, vinyl aromatic monomers, (meth)acrylic acid ester monomers, (meth)acrylonitrile monomers and vinyl ester monomers are preferably used. especially,
A vinyl (co)polymer containing 50% by weight or more of a vinyl aromatic monomer or a (meth)acrylic acid ester monomer,
It is preferable because it has good dispersibility in aromatic polyester resin.

The particle size of the spherical polymer dispersed in the matrix of the multiphase thermoplastic resin (C) is preferably 0.01 to 1O
μm, preferably 0.1 to 5 μm. This particle size is 0
．． If it is less than 0.01 μm or more than 1.0 μm, the dispersibility when blended with an aromatic polyester resin tends to be poor, and for example, the appearance may deteriorate or the effect of improving impact resistance may be insufficient.

Multiphase structure thermoplastic 'rJj: The number average degree of polymerization of the vinyl polymer in the resin (C) is desirably in the range of 5 to +0000, preferably 10 to 5000. Number average degree of polymerization 5
If it is less than that, it is possible to improve the impact resistance of the resin composition of the present invention, but the heat resistance tends to decrease. Furthermore, when the number average degree of polymerization exceeds 10,000, the melt viscosity tends to be high, the moldability is low, and the surface gloss tends to be low.

In the multiphase thermoplastic resin (C), the epoxy group-containing olefin copolymer accounts for 5 to 95% by weight, preferably 20 to 90% by weight, and the vinyl polymer accounts for 95 to 5% by weight, preferably 80 to IO weight %. If the content of the epoxy group-containing olefin copolymer is less than 5% by weight, the effect of improving impact resistance is insufficient. On the other hand, if the amount of the epoxy group-containing olefin copolymer exceeds 95% by weight, the effect of improving impact resistance may not be sufficiently obtained, or the heat resistance may deteriorate.

Regarding the blending amount of the multiphase structure thermoplastic resin (C), PE
T copolymer (8) 1 to 300 parts by weight per 100 parts by weight. In addition, when blending a polymeric brominated flame retardant (F) and an antimony compound (G), 1 to 70
It is 0 parts by weight. If the amount of component (C) is too small, the impact resistance will not be improved sufficiently, and if it is too large, the heat resistance and surface appearance will be poor.

Examples of the fibrous reinforcing material (D) include glass fibers, inorganic fibers other than glass fibers, carbon fibers, and heat-resistant organic fibers, and more specifically, glass fibers with a fiber diameter of 1 to 20 μm and a fiber length of 10 mm or less. Chopped strands of fibers or carbon fibers, milled glass fibers, pitch-based carbon fibers, aromatic polyamide fibers, aromatic polyimide fibers, aromatic polyamide-imide fibers, and combinations thereof may be mentioned. Among the stiff straws, chopped strands of glass fiber are particularly preferred.

The blending amount of the fibrous reinforcing material (D) is the same as that of the PET copolymer (A).
) 5 to 800 parts by weight per 100 parts by weight. In addition, when blending a polymeric brominated flame retardant (F) and an antimony compound (G), PET copolymer (A)
The amount is 5 to 2000 parts by weight per 100 parts by weight. If this (D) component is too small, the reinforcing effect will be insufficient,
If the amount is too large, flow processability will deteriorate.

As the crystallization accelerator (E), metal salts of Group 1a or Group Ua of the periodic table of organic carboxylic acids that are effective as crystal nucleating agents for polyester resins, benzoic acid esters, or esters of benzoic acid twisted conductors; Examples include fatty acid esters, metal salts of ionic copolymers, and inorganic powders effective as crystallization promoters. Specifically, sodium laurate, potassium laurate, sodium myristate,
Potassium myristate, calcium myristate, sodium stearate, potassium stearate, calcium stearate, sodium octacosanoate, calcium octacosanoate, sodium benzoate, potassium benzoate, calcium benzoate, lithium terephthalate, sodium terephthalate, potassium terephthalate , ethylene glycol monohenzoate, ethylene glycol dibenzoate, propylene glycol dibenzoate,
Propylene glycol dibenzoate, neobentyl glycol monohensoate, diethylene glycol dibenzoate, triethylene glycol dibenzoate,
It is possible to use ethylene glycol brobylene glycol cyhensoate, ethylene-sodium acrylate copolymer, ethylene-sodium methacrylate copolymer, talc, titanium oxide, zinc oxide, etc., and combinations thereof.

Compounds that further improve the crystallization rate when used in combination with these crystallization promoters (E), such as polyoxyethylene derivatives, epoxy compounds, and solhitan derivatives, can also be added.

The amount of crystallization accelerator (E) added is determined by the amount of crystallization accelerator (E) added.
) 0.1 to 200 parts by weight per 100 parts by weight. In addition, when blending a polymeric brominated flame retardant (F) and an antimony compound (G), a PET copolymer (
A) 350 parts by weight per 100 parts by weight. If the amount of component (E) is too small, the polyester resin will deteriorate significantly and molding will become difficult, which is undesirable. If it is too large, the degree of crystallinity will be low and the heat resistance of the molded product will be poor.

The resin composition of the present invention comprising components (A) to (F) described in 1 above can be injection molded using a low temperature mold of about 80°C, and has good surface appearance and impact resistance. , is a composition that can provide a molded article with excellent heat resistance, but if additional flame retardance is required, (F) and
Examples of polymeric brominated flame retardants (F) that may be blended with component (G) include pentabromopencyl polyacrylate, pentabromohensyl polymethacrylate, polytetrabromoxylylene hismethacrylate, brominated polycarbonate, poly(2 ,4,6
-tribromo)styrene, poly(2,4,5-tribromo)styrene, brominated crosslinked polystyrene, and the like. Brominated flame retardants that are not polymeric are not preferred because they bleed out.

The blending amount of the polymeric brominated flame retardant (F) is suitably 2 to 600 parts by weight per 100 parts by weight of the PET copolymer (A). If the amount of the resin composition is less than 2 parts by weight, little flame retardant effect can be expected.

In addition, in a resin composition containing more than 600 parts by weight,
The mechanical strength of the resulting molded product decreases.

The antimony compound (G) is a polymeric brominated flame retardant (
F) acts as a flame retardant aid, and specific examples include antimony trioxide, antimony pentoxide, and antimonic acid sorter.

The antimony compound (G) is suitably added in an amount of 1 to 300 parts by weight per 100 parts by weight of the PET copolymer (A). If the amount of the resin composition is less than 1 part by weight, the effect of the flame retardant aid will hardly be exhibited. Also, the blending amount is 30
If the amount of the resin composition exceeds 0 parts by weight, the mechanical strength of the resulting molded product will decrease.

Note that various additives such as light or heat stabilizers, dyes, or pigments may be added to the polyester resin composition of the present invention.

When manufacturing a molded article from the resin composition of the present invention,
As in the past, a predetermined amount of the components can be put into a kneading machine such as an extruder, and after being melted and kneaded to form a pellet, a molded product can be obtained by subjecting it to injection molding or pressure molding. . At this time, another feature is that it can be molded at a mold temperature of 80°C or less.

〔Example〕

Hereinafter, the present invention will be explained in more detail using examples.

Examples 1 to 7 The average molecular weight of PET oligomers synthesized by direct esterification method! ! 4,000 Bois ethylene glycol (
(hereinafter abbreviated as PEG) 5% by weight and DEG 1
．． PET copolymer (A-1) was obtained by copolymerizing 3%
I got it. DEC is 0.9% by weight in PUT oligomer
Since D is produced as a by-product, D in the copolymer (A-1)
The content of EC was 2.2% by weight.

To this copolymer (A-1), chopped strand crow fiber (D) of 3 mm length, PBT (B), multiphase structure thermoplastic resin (C) and crystallization accelerator (E) were added as shown in Table 1. The mixture was mixed in a V-type blender for 5 minutes to make it homogeneous. Divide the resulting mixture into diameter 4
The resin composition was put into a 0+nm vented melt extruder and extruded at a cylinder temperature of 260 to 280°C to obtain a pellet of the resin composition of the present invention.

The crystallization rate of the obtained resin composition was measured using a differential calorimeter (DSC), and 3 ounces (85 g)
Using a screw injection molding machine with a diameter of 32 mm, the cylinder temperature was 270°C, the mold temperature was 80°C, and the molding cycle was 30.
ASTMI dumbbell specimens were formed from the pellets in seconds and subjected to a tensile test according to ASTM D 538.

Further, the isot impact strength was evaluated according to ASTM D 256, the heat distortion temperature (HDT) was evaluated according to ASTM D 648, and the surface appearance of the molded product was evaluated using an ASTM No. 1 dumbbell specimen molded at a mold temperature of 80°C.

The evaluation results of these physical properties are shown in Table 1.

Examples 8 to 9 10% by weight of polytetramethylene glycol (hereinafter abbreviated as PTMG) with an average molecular weight of 1,000 and DE were added to a PET oligomer synthesized by a direct esterification method.
PET copolymer copolymerized with 2.0% by weight of G (A
-2) was prepared. The content of DEC in the copolymer (8-2) was 2.9% by weight. This copolymer (A-2
) was used in the same manner as in Examples 1 to 7 to obtain resin compositions of the present invention. The evaluation results of various physical properties are shown in Table 1.

Comparative Examples 1 to 4 PET homopolymer (A-3) is used as a heath polymer instead of PET copolymer (A), or
Resin compositions were produced in the same manner as in the above Examples, except that the amount of B T (B) or the multiphase thermoplastic resin (C) added was outside the range of the present invention, and various physical properties were evaluated. The results are shown in Table 1.

The abbreviations in the table have the following meanings.

＾4100: (Product name) Motyper A4100, manufactured by Nippon Yuka ■ (Composition) EGMA-g-PS (weight ratio) EGM 8/He S = 70/30 (fractional particle size) 0.3 scales EGMA = ethylene methacrylic Glycidyl acid (E/G
MA-85/15) (weight ratio EGMA/AS" = 70730 (fractional particle size) 0.3 scales EGMA = ethylene glycidyl methacrylate (E/G
MA=85/+5) AS=Acrylonitrile/styrene copolymer *Acrylonitrile content is 30% by weightg=Kraft PS=Polystyrene E-1: Polyoxyethylene monononylphenyl ether A4200: (Product name) Modiva A 4200 (Structure) ) EGMA-g-PMMA (weight ratio) EGMA/PMMA = 70/30 (fractional particle size) 0.2μ EGM8 = hethylene lysidyl methacrylate (E/G
MA=85/+5): Polyoxyethylene dinonylphenyl ether PMM^=methyl methacrylate E-3: Ethylene/methacrylic acid (weight ratio 85/15
) Copolymer with 60% of methacrylic acid neutralized with sodium A4400: (Product name) Modiper-A 4400 (Composition) EGMA-g-AS As expected (viewing (mold temperature 80°C)) ○, good ×°As is clear from Table 1, in which the glass fibers on the coating surface stand out, the resin compositions of Examples 1 to 9 had sufficient tensile properties, superior to HDT, and also had very good isot strength. , and a molded product with good appearance (surface gloss) can be obtained even at a mold temperature of 80°C.

On the other hand, from the resin compositions of Comparative Examples 1 to 3, only molded products with poor impact strength were obtained, and from the resin composition of Comparative Example 4, only molded products with reduced surface appearance and IDT were obtained.

Examples 10 to 18 Same as Examples 1 to 9 except that in Examples 1 to 9, a crystallization promoter (E) and a polymeric brominated flame retardant (F) were further blended in the proportions shown in Table 2. A pellet was prepared using the same method as above, and the same evaluation was conducted, and the flame retardancy was also evaluated (L941/16''). The evaluation results of these physical properties are shown in Table 2.

Comparative Examples 5 to 9 Comparative Examples 1 to 4 except that a crystallization promoter (E) and a polymeric brominated flame retardant (F) were further blended in the proportions shown in Table 2. Similarly, a pellet outside the scope of the present invention was produced and evaluated. The evaluation results of these physical properties are shown in Table 2.

The abbreviations in the table have the following meanings.

F-1 = Brominated polystyrene (product name) Pyrocheck 68PB, Nissan Fellow ■
F-2 = Brominated polystyrene (product name) EBR370FK, F manufactured by Matsunaga Chemical Industry ■
-3 = Pentabromobenzyl polyacrylate (manufactured by Dead Sea Co., Ltd.) As is clear from Table 2, the resin compositions of Examples 10 to 18 had the same excellent properties as Examples 1 to 9, and A flammable molded article was obtained.

On the other hand, the resin compositions of Comparative Examples 5 to 7 gave only inferior results in impact strength, and the resin composition of Comparative Example 8 only gave results with lower surface appearance and HDT.

〔Effect of the invention〕

The polyester resin composition of the present invention can be injection molded using a low-temperature mold of about 80°C, and can yield molded products with excellent surface appearance, impact resistance, and heat resistance.
If desired, it is possible to obtain a molded article with further flame retardancy.

Patent applicant: Mitsubishi Rayon Co., Ltd.

Claims (2)

[Claims] (1) (A) Polyethylene terephthalate oligomer (a) obtained by esterifying a dicarboxylic acid component (a-1) mainly composed of terephthalic acid and its derivatives and a diol component (a-2) mainly composed of ethylene glycol
65-97.8% by weight, average molecular weight 500-20,0
00 polyalkylene glycol (b) 1-20% by weight
and diethylene glycol (c) 1.2-15% by weight
(B) 5 to 450 parts by weight of polybutylene terephthalate resin (C) 5 to 95 parts by weight of olefin polymer containing epoxy group, based on 100 parts by weight of polyethylene terephthalate copolymer obtained by polycondensation of
and 95 to 5% by weight of a vinyl polymer obtained from at least one kind of vinyl monomer, and the average particle diameter of the dispersed particles in the resin is 0.01 to 10 μm. A polyester resin composition containing 300 parts by weight (D) of 5 to 800 parts by weight of a fibrous reinforcing material and (E) 0.1 to 200 parts by weight of a crystallization accelerator. (2) (A) Polyethylene terephthalate oligomer (a) obtained by esterifying a dicarboxylic acid component (a-1) mainly composed of terephthalic acid and its derivatives and a diol component (a-2) mainly composed of ethylene glycol
65-97.8% by weight, average molecular weight 500-20,0
00 polyalkylene glycol (b) 1-20% by weight
and diethylene glycol (c) 1.2-15% by weight
(B) 5 to 450 parts by weight of polybutylene terephthalate resin (C) 5 to 95 parts by weight of olefin polymer containing epoxy group, based on 100 parts by weight of polyethylene terephthalate copolymer obtained by polycondensation of
and 95 to 5% by weight of a vinyl polymer obtained from at least one kind of vinyl monomer, and the average particle diameter of the dispersed particles in the resin is 0.01 to 10 μm. 700 parts by weight (D) 5 to 2000 parts by weight of fibrous reinforcement (E) 0.1 to 350 parts by weight of crystallization promoter (F) 2 to 600 parts by weight of polymeric brominated flame retardant and (G) Antimony A flame-retardant polyester resin composition containing 1 to 300 parts by weight of a polyester compound.