JPS61207458A - Impact-resistant polyester resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled compsn. having excellent mold release characteristics and resistance to impact and heat, consisting of a polyester, a modified polyolefin, an ester plasticizer and a reinforcing fiber. CONSTITUTION:0.05-10pts. (by weight; the same applies hereinbelow) at least one member (A) selected from an inorg. nucleating agent having an average particle size of 50mu or below and org. compd. contg. a carboxyl group in the form of a metal salt or high-molecular compd. thereof, 3-30pts. modified polyolefin (B) obtd. by adding 0.001-10mol% of an alicyclic carboxylic aid contg. a cis double bond in its ring to a polyolefin, 1-20pts. copolymer (C) composed of 80-99% alpha-olefin, 1-20% glycidyl (meth)acrylate and 0-19% vinyl acetate, 0.3-10pts. ester plasticizer (D) and 0-150pts. reinforcing fiber (E) are blended with 100pts. polyester (F) composed of 40-97pts. polyethylene terephthalate and 3-60pts. ethylene terephthalate polyester obtd. by copolymerizing 2-25wt% polyalkylene glycol (derivative) having a MW of 500-20,000.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a polyester resin composition that has good moldability and provides molded articles with excellent impact strength and heat resistance. More specifically, we provide a product that has a high crystallization rate (exhibits excellent mold releasability even at a mold temperature of about 120°C or less during injection molding, and has excellent impact strength and high heat distortion temperature). The present invention relates to an impact-resistant polyester resin composition.

(Prior Art) Polyethylene terephthalate has excellent mechanical properties, electrical properties, heat resistance, chemical resistance, etc., and is used in many industrial products as fibers and films.

In this way, when used as fiber or film, 9
Normally, stretched products are used, but for example, when trying to use them as injection molded products for plastic purposes, they are not subjected to the stretching process described above.
It is known that various problems occur in molding and physical properties. In other words, because the crystallization rate at low temperatures is low,2 the crystallization rate is insufficient at mold temperatures of about 120°C or lower, which are normally used when injection molding other plastics, so the resulting molded product has There is a difference in crystallinity between the two parts, and as a result, the mechanical properties (9) dimensional stability and shape stability become non-uniform, making it extremely difficult to obtain a molded product that can withstand practical use.

As a conventional method to solve such problems.

Many methods have been proposed, such as using a high-temperature mold, adding a crystal nucleating agent or crystallization accelerator, and blending an ethylene terephthalate copolymer with excellent low-temperature crystallinity, all of which have proven to be quite effective. It recognized. Polyethylene terephthalate or compositions sufficiently crystallized in this way, especially those blended with fibrous reinforcing materials such as glass fiber, exhibit excellent mechanical properties and high heat distortion temperatures, and have established themselves as engineering plastics. It has arrived today. However, one drawback of polyethylene terephthalate compositions or reinforced polyethylene terephthalate compositions blended with glass fibers is that they have low impact resistance.
In other words, there is a problem of poor toughness, and there is currently a strong desire to improve this problem.

Various proposals have been made to solve the above problems, that is, to improve impact strength. For example, JP-A-51-144452, JP-A-52-3
No. 2045, JP 58-17148, JP 5B-17151, USP 4.284,5
40 and USP 4.461.871 propose that impact strength can be improved by blending a copolymer 1 having a glycidyl group, such as ethylene/vinyl acetate/glycidyl (meth)acrylate copolymer, with polyester. . However, when an olefin polymer copolymerized with glycidyl (meth)acrylate, that is, a polyolefin having an epoxy group, is blended with polyethylene terephthalate (hereinafter abbreviated as pH!T), the impact resistance strength is improved, but the There is a problem that the mold releasability is extremely poor and the surface gloss is poor when the low temperature mold 9 is used, for example, at a mold temperature of 120° C. or lower. An even bigger problem is that when producing pellets by blending polyolefin with epoxy groups into PET and heating and kneading it in an extruder, some gel-like substances are generated, and in some cases, a large amount of gel-like substances are generated. There is a problem that it is not possible to operate due to this.

Furthermore, in Japanese Patent Application No. 57-228823, the present applicant has added a modified polyolefin or modified olefin elastomer which is the (b) component of the present invention to a thermoplastic polyester, and a glycidyl (meth)acrylate copolymerized polyolefin which is the (c) component. It was proposed that when a specific amount of these two components is blended, the impact resistance strength can be significantly improved due to the combined effects of both of the nine components. In this composition.

When using polybutylene lenticulate as a thermoplastic polyester, there are no major problems in molding, but when using PUT as a thermoplastic polyester,
It was found that there were some problems with molding. That is, apart from the case of molding a simple shaped product such as a test piece, the mold releasability is extremely poor in a molded product with a slightly complicated shape such as an actual product.

In addition, if the mold temperature is low 1 For example, if the mold temperature is lower than 120℃, not only will the appearance of the molded product be bad, but also the heat distortion temperature will increase even if it is reinforced with glass fiber etc. due to insufficient crystallization. It was also found that although the impact resistance at room temperature improved, the impact resistance at low temperatures of -10°C to -30°C did not improve as much as expected. .

(Problems to be Solved by the Invention) As a result of intensive research to solve the various problems mentioned above, we found that the (f) component, that is, a polyolefin copolymerized with glycidyl (meth)acrylate, and the (b) component, that is, a specific In the composition of Japanese Patent Application No. 57-228823 which combines a modified polyolefin or olefin elastomer, a part of PI'T is replaced with a specific polyalkylene glycol or its derivative, and an ester plasticizer (component) is further added. This suppresses gel formation when producing pellets by heating and kneading, improving operational stability.Furthermore, when ingredients (a) and (b), that is, an ester plasticizer, are added, the crystallization rate of PET increases. Even when molded in a low-temperature mold of 120°C or lower, a molded product with excellent surface gloss can be obtained, and the mold releasability is significantly improved. If the polyester resin composition is replaced with a copolymerized PET, the low-temperature crystallinity and the moldability in a low-temperature mold are further improved. The present invention was achieved by discovering that the impact strength can be further improved.

(Means for solving the problem) That is, the present invention provides polyethylene terephthalate 40-9
For 100 parts by weight of a polyester consisting of 7 parts by weight and 3 to 60 parts by weight of an ethylene terephthalate polyester copolymerized with 2 to 25 parts by weight of at least one of polyalkylene glycols or derivatives thereof having a molecular weight of about 500 to 20,000, (a) 0.05 to 10 parts by weight of at least one of an inorganic crystal nucleating agent with an average particle size of 50 μ or less, an organic compound having a metal salt of a carboxyl group, and a polymer compound having a metal salt of a carboxyl group; (1) A modified polyolefin obtained by adding 0.001 to 10 mol% of at least one compound selected from the group consisting of alicyclic carboxylic acids having a cis double bond in the ring or functional derivatives thereof to a polyolefin or olefin elastomer. or 3 to 30 parts by weight of modified olefin elastomer, (c) 80 to 99% by weight of α-olefin, glycidyl methacrylate or glycidyl acrylate 1
1 to 20 parts by weight of a copolymer consisting of ~20% by weight and 0 to 19% by weight of vinyl acetate, and 0.3 parts by weight of an ester plasticizer.
The present invention relates to an impact-resistant polyester resin composition containing ~10 parts by weight and (e) ~150 parts by weight of a fibrous reinforcing material.

(Function) The PET used in the present invention is obtained by melt polymerization of terephthalic acid or its ester derivative and ethylene glycol, or by solid phase polymerization thereof, and its molecular weight is not particularly limited.

Also, as a copolymerized PET used with PET.

A copolymer of polyalkylene glycol or a derivative thereof is effective, and if the molecular weight is less than about 500, the effect of improving impact strength in a low temperature region is small.

Conversely, when the molecular weight is greater than about 20.000, copolymerized P
This is not preferable because the production of ET itself becomes difficult. As for the copolymerization ratio, if it is less than 2% by weight, it is not desirable because the effect of improving the impact strength in the low temperature region and the effect of promoting crystallization will be reduced. On the other hand, if the copolymerization ratio exceeds 25% by weight, the heat resistance of the resin composition will decrease, which is not preferable. Therefore, the copolymerization ratio of polyalkylene glycol or its derivative is 2 to 25% by weight, preferably 10 to 20% by weight.

The ratio of PUT and copolymerized PET varies depending on the type of copolymerized PET, but generally speaking, if the amount of copolymerized PET is less than 3 parts by weight of the total polyester component, it will have the effect of improving impact resistance strength in the low temperature region. The effect of promoting crystallization is small, and if the amount exceeds 60ii parts, the thermal properties deteriorate, which is not preferable. Therefore, the amount of ethylene terephthalate polyester copolymerized with polyalkylene glycol or its derivatives in the total polyester is
The amount is 3 to 60 parts by weight, preferably 10 to 50 parts by weight.

Specific examples of polyalkylene glycol include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, and examples of derivatives of polyalkylene glycol include bisphenol A.
Ethylene oxide on the phenolic hydroxyl group of bisphenol compounds such as.

Examples include polyether compounds obtained by ring-opening addition of propylene oxide, butylene oxide, etc.

The inorganic compound used as component (a) of the present invention is as follows.

The effect as a crystal nucleating agent varies depending on the particle size, and the effect decreases when the average particle size exceeds about 50 μm, so inorganic compounds with an average particle size of 50 μm or less are generally useful.

Specific examples of inorganic compounds with an average particle size of 5 μm or less used in the present invention include carbon blank, silica, calcium carbonate, synthetic silicic acid and silicates, zinc white, hallosite clay, kaolin, basic carbonate, etc. Magnesium, mica.

Examples include talc, quartz powder, diatomaceous earth, dolomite powder, titanium oxide, zinc oxide, antimony oxide, barium sulfate, calcium sulfate, alumina, calcium silicate, etc., and one or more of these inorganic compounds are used. Although you can.

Among them, mica, kaolin, talc, and silica are useful in the present invention.

Further, as the organic compound having a metal salt of a carboxyl group used in the present invention, any compound having a metal salt of a carboxyl group can be used, but usually has about 7 to 7 carbon atoms. 30 higher fatty acids, metal salts of aromatic acids are used, such as heptanoic acid,
pelargonic acid.

Lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, cerotic acid, montanic acid.

Metal salts of higher fatty acids such as melisic acid, benzoic acid.

Terephthalic acid, terephthalic acid monomethyl ester.

Specific examples include metal salts of aromatic acids such as isophthalic acid and monomethyl ester of isophthalic acid.

Further, the polymer compound having a metal salt of a carboxyl group is not particularly limited as long as it has a metal salt of a carboxyl group at the terminal or side chain of the polymer, but for example, a carboxyl group obtained by oxidation of polyethylene is used. Containing polyethylene, carboxyl group-containing polypropylene obtained by oxidizing polypropylene, copolymers of olefins such as ethylene, propylene, butene-1, and (meth)acrylic acid, copolymers of olefins and maleic anhydride, styrene and ( Specific examples include metal salts such as copolymers of meth)acrylic acid and copolymers of styrene and maleic anhydride.2 Usually, copolymers of olefin and (meth)acrylic acid or styrene and (meth)acrylic acid are used. Polymeric metal salts are used. As the metal that forms a salt with a carboxyl group, alkaline earth metals, alkali metals, etc. are usually used, and alkali metals are excellent in their effectiveness as crystal nucleating agents, with sodium and potassium being particularly useful.

In the present invention, the polyolefin or olefin elastomer used as a starting material in producing the modified polyolefin or modified olefin elastomer which is the component (b) is 1. For example, olefins such as polyethylene, polypropylene, polybutene-1, polypentene-1, etc. homopolymers or ethylene-propylene copolymers, ethylene-butene-1 copolymers, propylene-butene-1 copolymers, and ethylene-vinyl acetate copolymers.

Different types of olefins such as propylene-vinyl acetate copolymer, ethylene-butadiene copolymer, ethylene-isoprene copolymer, ethylene-chloroprene copolymer, propylene-butadiene copolymer, ethylene-propylene-butadiene copolymer, etc. Alternatively, copolymers with diolefins can be mentioned, and the copolymers are random copolymers.

Any of block copolymers, graft copolymers, and alternating copolymers may be used.

and especially ethylene-propylene copolymers, ethylene-
Butene-1 copolymer, ethylene-vinyl acetate copolymer L
Preferred examples include ethylene-propylene-butadiene copolymer, ethylene-propylene-isoprene copolymer, and ethylene-propylene-chlorobrene copolymer. Two or more types of polyolefins or olefin elastomers can also be used as a mixture.

The alicyclic carboxylic acid having a cis-type double bond in the ring as used in the present invention includes 1, for example, cis-4-cyclohexene-
1,2-dicarboxylic acid, endo-bicyclo-(2,2,
1) -5-hebutene-2,3-dicarboxylic acid, methyl-endo-cis-bicyclo-[2゜2.1)-5-hebutene-2,3-dicarboxylic acid, endo-bicyclo-(2
,2,1)-1,2,3,4,7,7-hexachloro-
Examples include 2-heptene-5,6-dicarboxylic acid, and functional derivatives thereof include acid anhydrides, esters, acid amides, acid halides, and the like.

And especially preferably endo-bicyclo-(2°2.1
)-5-hebutene-2,3-dicarboxylic acid or its acid anhydride. Note that the functional derivative does not necessarily need to be converted into a functional derivative before being added to the polyolefin or olefin elastomer.

For example, it can be converted during the modification process of polyolefin or olefin-based elastomer or as a thermoplastic polyester composition.

The modified polyolefin or modified olefin elastomer of the present invention is the above-mentioned polyolefin isolefin elastomer containing at least one kind selected from the group consisting of alicyclic carboxylic acids having a cis-type double bond in the ring or functional derivatives thereof. It means a modified polyolefin or modified olefin elastomer obtained by adding a compound, or a mixture thereof with an unmodified polyolefin or unmodified olefin elastomer. The modified polyolefin or modified olefin elastomer can be produced by various methods, but it is preferable to produce radicals by combining the above-mentioned polyolefin or olefin-based elastomer and the above-mentioned alicyclic carboxylic acid or functional derivative having a cis double bond in the ring. Agent 1 For example, an organic peroxide such as di-tert-butyl peroxide, dicumyl peroxide, or benzoyl peroxide is added and melted, or the polyolefin or olefin elastomer and the carboxylic acid or its functional derivative are mixed in water. The method is carried out by dispersing the mixture in water and heating it in the presence of the above-mentioned radical generator or water-soluble peroxide.

Here, the addition ratio of the carboxylic acid or its functional derivative to be added to the polyolefin or olefin elastomer varies depending on the type of polyolefin or olefin elastomer, their mixing ratio, and the type of the carboxylic acid or its functional derivative, but usually 9 The carboxylic acid or its functional derivative is added in an amount of 0.001 to 10 mol % to the polyolefin or olefin elastomer, preferably 0.01 mol %.
-5.0 mol%, more preferably 0.05-3.0 mol% is used.

The amount of the carboxylic acid or functional derivative added is 0.001
If it is less than 10% by mole, the synergistic effect on improving impact strength by using it in combination with component (c) will be sufficient, and if it is added in more than 10% by mole, the polyolefin will be Otherwise, side reactions such as lowering of the molecular weight of the olefin elastomer and gelation occur, which is undesirable.

In the present invention, the α-olefin-glycidyl (meth)acrylate copolymer or α-olefin used as the acid component (/→
- The content of glycidyl (meth)acrylate in the olefin-glycidyl (meth)acrylate-vinyl acetate copolymer is 1 to 20% by weight, preferably 1 to 10% by weight.
If the amount is 1% by weight or less, there is no sufficient effect in improving impact resistance when used in combination with the modified polyolefin or modified olefin elastomer (20% by weight).
In the above case 9, side reactions such as gelation occur during production of the resin composition of the present invention, which is not preferable. The α-olefin component in these copolymers is ethylene.

Propylene, butene-1, etc. The vinyl acetate component in the terpolymer can be contained in an amount of 0.1 to 19% by weight. If the vinyl acetate content exceeds 19% by weight, it is not preferred because the thermal stability of the resulting resin composition decreases. Although various ester plasticizers can be used as the component (2), compounds represented by the following general formulas (1)(n) and (I[[) are particularly useful.

R1: Alkylene group R, Rs: A group selected from an alkyl group, a benzyl group, and an aromatic substituted benzyl group.

R1 and Ih are the same or different groups It is.

(n) χ: Direct bond, alkylene group + -So! -+-5-
+S- or 10-R<+Rs: A group selected from an alkyl group, a benzyl group, a phenyl group, or a derivative thereof, and R41R8 are the same or different groups.

Rs, R? : Hydrogen, an alkyl group, or a halogen, and Rs and R are the same or different groups.

m+n: an integer of 1 or more Re l Rs: hydrogen, alkyl group, phenyl group.

Benzyl group or these derivatives A group selected from conductors, R8゜ Rs are the same or different groups Ru.

Rho: A group selected from a phenyl group, a benzyl group, or a derivative thereof.

R11: A group consisting of hydrogen, an alkyl group or a group defined by Rlo.

n: An integer of 4 or more.

In the ester plasticizer represented by the general formula (I>), R+ represents an alkylene group, usually having 1 to 20 carbon atoms.
It is desirable to use a branched alkyl group having a linear or molecular symmetry. R lazy.

R3 is methyl, ethyl, propyl, butyl.

Specific examples include pentyl, hexyl, heptyl, octyl, and benzyl. Regarding n, there is a tendency that the larger m and n are, the greater the effect as a crystallization accelerator, but conversely, the compatibility with PET decreases and the heat resistance decreases, so9 m and n are 1 to about 20. Preferably it is 1 to about 10.

In general formula (n), X is usually methylene,
Alkylene groups such as ethylene and propylene to 10- are useful, and as R4 and R11, alkyl groups having 5 or more carbon atoms, benzyl groups, and phenyl groups are usually effective, and m and n are 1
~10 is desirable.

In the general formula (II[), Re, Re is hydrogen or an alkyl group, and Rho, R,
, a benzyl group is useful. When n is 3 or less, it tends to volatilize during heating and has a small effect as a crystallization promoter, so n is 4 or more. For example, adipic acid, azelaic acid, decane-Illo-dicarboxylic acid, octadecane-1,18- Dibenzyl esters of dicarboxylic acids are useful.

Specific examples of the fibrous reinforcing material used in the present invention include glass fibers, carbon fibers, aromatic polyamide fibers, silicon carbide fibers, titanate fibers, etc.9 Usually, glass fibers are often used. Ru. There are no particular restrictions on the diameter and length of the various fibers, but if the fibers are too long, it may be difficult to mix and disperse them uniformly with the polyester and other compounding agents, i.e., component (a) or component (b). On the other hand, if the fiber length is too short, the effect as a reinforcing material will be insufficient.9 Usually, those with a fiber length of 0.1 to 10 mm are used, especially when the fibrous reinforcing material is glass fiber. In this case, the fiber length is 0
．． 1 to 7IIIll is preferable, and more preferably 0.3 to 4
mm is desirable. In addition, the fibrous reinforcing material can be treated with various compounds as necessary in order to improve the interfacial adhesion with polyester and increase the reinforcing effect. When used, two different surface treatment agents are used, such as vinyltriethoxysilane, T-methacryloxypropylmethoxysilane,
β-(3゜4-epoxycyclohexyl)-ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, T-aminopropyltriethoxysilane, γ
- Those treated with a silane treatment agent such as chloropropylmethoxysilane or γ-mercaptopropyltrimethoxysilane, or a chromium treatment agent such as methacrylate chromine chloride are used.

Regarding the blending amount of each component of the present invention, component (a).

In other words, the amount of the inorganic crystal nucleating agent and metal salt of carboxyl group is based on 100 parts by weight of polyester.
If it is less than 0.05 parts by weight, it will not be effective as a crystal nucleating agent, and conversely, if it is added in more than 10 parts by weight, the effect as a crystal nucleating agent will not be better than if it is less than 10 parts by weight. On the contrary, it is not preferable as it may induce a decrease in impact resistance strength.Therefore, the blending amount of component (a) is 0.
．． 05 to 10 parts by weight, preferably 0.5 to sii parts. If the amount of component (b), that is, modified polyolefin or modified olefin elastomer, is less than 3 parts by weight per 100 parts by weight of polyester, (/1
) The improvement in impact resistance strength due to the combined effect with components is small,
On the other hand, if more than 30 parts by weight is added, the thermal properties of the composition will deteriorate, which is not preferable. Therefore, the blending amount of component (c) is 3 to 30 parts by weight, preferably 5 to 25 parts by weight.

More preferably, it is 5 to 20 parts by weight. i) Ingredients.

That is, regarding the amount of glycidyl (meth)acrylate copolymerized polyolefin blended, if it is less than 1 part by weight, the effect of improving impact strength will be small, and if it is more than 30 parts by weight (even if it is blended, the impact strength will increase with the amount blended). Instead, it shows a saturation value and promotes gelation during heating and kneading, which is not preferable.

Therefore, the blending amount of component (ii) is 1 to 30 parts by weight, preferably 3 to 20 parts by weight, and more preferably 3 to 10 parts by weight. And the blending ratio of component (b) and component (c) is 1
0:1 to 1:10. Preferably 10:1 to 1:
2. Particularly preferably, a range of 5:1 to 1:1 is effective for improving the targeted impact strength. Regarding the blending amount of component 2), that is, the ester plasticizer, if it is less than 0.3 parts by weight, the effect of promoting crystallization and improving the mold release property will be small, and if it is blending more than 10 parts by weight, the heat resistance will decrease, so it is not preferable. . Therefore, the blending amount of component (iii) is 0.3 to 10 parts by weight.

Preferably it is 1 to 7 parts by weight. Furthermore, in the present invention, the amount of fiber reinforcing material to be blended as necessary is 150 parts by weight or less9 because if it exceeds 150 parts by weight, it is difficult to uniformly disperse and mix it in the resin.
00 parts by weight or less.

Furthermore, various inorganic or organic compounds such as antioxidants, ultraviolet absorbers 1 colorants, fillers, etc. may be added to the composition of the present invention, if necessary, within a range that does not significantly reduce the impact strength. be able to. The method for producing the composition of the present invention is not particularly limited, and can be produced in two different forms:
For example, it can be molded into various molded products, sheets, fibrous materials, tubular materials, and the like.

(Example) Next, the present invention will be specifically described with reference to Examples and Comparative Examples.

Note that "parts" shown in Examples and Comparative Examples indicate "parts by weight."

Reference example 1 Melt index 2.0g / 10 minutes / 190°C,
1000 parts by weight of ethylene-propylene copolymer (hereinafter abbreviated as EPR) with an ethylene content of 72.0% by weight,
Endo-bicyclo-(2,2,1)-5-hebutene-
2,3-dicarboxylic anhydride (hereinafter referred to as dicarboxylic anhydride-H)
It is abbreviated as. ) and 1 part by weight of di-tert-butyl peroxide were mixed at room temperature using a Henschel mixer. This mixture was fed to a single screw extruder and
Cylindrical pellets of modified polyolefin having a diameter of 2+111111 and a length of 3 mm were prepared by extrusion at .degree.

Reference Examples 2 to 5 Ethylene-butene-1 copolymer (hereinafter abbreviated as E/B copolymer), polypropylene (hereinafter abbreviated as PP), polyethylene (hereinafter abbreviated as PP), having a melt index shown in Table 1 as polyolefin (abbreviated as PE) or ethylene-vinyl acetate copolymer (hereinafter abbreviated as EVA). ) was added to endo-bicyclo(2,2,1
) Reference Example 1 using -5-heptene-2,3 dicarboxylic anhydride (hereinafter abbreviated as dicarboxylic anhydride-H)
Modified polyolefin pellets to which alicyclic dicarboxylic anhydride was added in the proportions shown in Table 1 were obtained in the same manner as in Table 1.

Table 1 Examples 1-5. Comparative Examples 1 to 3 PE with intrinsic viscosity (measured in phenol/tetrachloroethane-6/4, concentration 0.5%, temperature 20°C) 0.68
T, ethylene terephthalate copolymer copolymerized with various polyalkylene glycols (copolymerized PIIIT).

Crystal nucleating agent, plasticizer, modified polyolefin, glycidyl methacrylate copolymerized polyolefin (GM copolymer)
were mixed in the prescribed amounts as shown in Table 2.

This mixture was extruded using a co-rotating twin-screw extruder under conditions of a cylinder temperature of 260° C. and a screw rotation speed of 20 rpm to produce pellets. After drying the pellets under reduced pressure, the cylinder temperature was 260°C.

1/2 inch x 1 with mold temperature 105℃ and cooling time 20 seconds
/2 inch x 2.5 inch test piece was molded.

Room temperature and -20°C according to ASTM, D-638
The notched Izo impact strength was measured, and the surface gloss was further evaluated. And the mold releasability is 10cm long x 7cm wide x 4cm deep (wall thickness 1.5m) at a mold temperature of 105℃.
Evaluation was made based on the minimum cooling time at which mold release was possible when the box-shaped molded product (m) was molded. The shorter the minimum cooling time, the better the mold releasability. The results are summarized in Table 2.

C: dibenzyl ester of azelaic acid d: dibenzyl ester of adipic acid )-Vinyl acetate (2% by weight) copolymer Surlyn 1555: Ethylene-acrylic acid copolymer sodium salt (manufactured by DuPont) Example 6. Comparative Example 4 The composition shown in Example 1 was further blended with glass fiber (Asahi Fiberglass ■, 3 mm long chopped strand, product number Na429) so that the total amount was 30% by weight, and the mixture was subjected to twin-screw extrusion. Pellets were prepared by kneading in a machine (Example 6). Similarly, for comparison, pellets containing 30% by weight of glass fibers having the composition shown in Comparative Example 1 were prepared. Comparative Example 4) The cylinder temperature was 240-260-260°C, the mold temperature was 105°C, and the cooling time was 10 seconds. The test piece was molded and tested for notched Izot impact strength (
specimen thickness = 1/2 inch) and 18.56 Kg/cd
The heat distortion temperature under load (specimen thickness 2178 inches) was measured.

Further, the mold releasability was evaluated based on the minimum cooling time during box molding at a mold temperature of 90° C. according to the method described above.

Table 3 (Effects of the invention) Nucleating agent, ester plasticizer, copolymerized PI! In a composition that does not contain T, the crystallization rate in a low-temperature mold (90°C) is low, resulting in insufficient crystallization, resulting in no increase in heat distortion temperature and poor mold release properties. It can be seen that the composition has excellent impact strength and heat distortion temperature of 1% itt type property.

Claims (7)

[Claims] (1) 40 to 97 parts by weight of polyethylene terephthalate and 2 to 2 parts of at least one of polyalkylene glycols or derivatives thereof having a molecular weight of about 500 to 20,000;
For 100 parts by weight of a polyester consisting of 3 to 60 parts by weight of 5% by weight copolymerized ethylene terephthalate polyester, (a) an organic compound having an inorganic crystal nucleating agent with an average particle size of 50μ or less and a metal salt of a carboxyl group; , 0.05 to 10 parts by weight of at least one polymeric compound having a metal salt of a carboxyl group, (b) an alicyclic carboxylic acid having a cis-type double bond in the ring in a polyolefin or olefin elastomer; At least one compound selected from the group consisting of functional derivatives thereof.
3 to 30 parts by weight of modified polyolefin or modified olefin elastomer added with 001 to 10 mol%, (c)
α-olefin 80-99% by weight, glycidyl methacrylate or glycidyl acrylate 1-20% by weight
and copolymer 1-1 consisting of 0-19% by weight of vinyl acetate
(d) 0.3 to 10 parts by weight of an ester plasticizer, and (e) 0 to 150 parts by weight of a fibrous reinforcing material. (2) The polyalkylene glycol is a glycol selected from polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, and the polyalkylene glycol derivative is a glycol selected from ethylene oxide, propylene oxide, and butylene oxide to the phenolic hydroxyl group of a bisphenol compound such as bisphenol A. 2. The polyester resin composition according to claim 1, wherein the polyester resin composition is a glycol selected from polyether compounds obtained by adding at least one type of glycol. (3) The ester plasticizer has the following general formula (I) or (II)
The polyester resin composition according to claim 1, which is an ester compound of at least one of (III). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) R_1: Alkylene group R_2, R_3: Groups selected from alkyl groups, benzyl groups, and aromatic substituted benzyl groups, and R_2 and R_3 are the same or different groups. m, n: Integer greater than or equal to 1 ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (II) X: Direct bond, alkylene group, -SO_2-, -S-,
-O- or ▲ Numerical formula, chemical formula, table, etc. ▼ R_4, R_5: A group selected from an alkyl group, a benzyl group, a phenyl group, or a derivative thereof, and R_4 and R_5 are the same or different groups. R_6, R_7: hydrogen, alkyl group, or halogen, and R_6 and R_7 are the same or different groups. m, n: Integers of 1 or more ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (III) R_8, R_9: Groups selected from hydrogen, alkyl groups, phenyl groups, benzyl groups, or derivatives thereof, and R_8 and R_9 are They are the same or different groups. R_1_0: A group selected from a phenyl group, a benzyl group, or a derivative thereof. R_1_1: A group consisting of hydrogen, an alkyl group, or a group defined by R_1_0. n: An integer of 4 or more. (4) The polyester resin composition according to claim 1, wherein at least one inorganic substance selected from the group of talc, mica, kaolin, and silica is used as the inorganic compound having an average particle size of 50 μm or less. . (5) The polyester resin composition according to claim 1, wherein the metal salt of the carboxyl group is a sodium salt or potassium salt of the carboxyl group. (6) The polyester resin composition according to claim 1, wherein the compound having a metal salt of a carboxyl group is a compound having about 7 to 30 carbon atoms. (7) The polymer compound having a carboxyl group is a copolymer of olefin and (meth)acrylic acid or a copolymer of styrene and (
Claim 1, which is a copolymer of meth)acrylic acid
The polyester resin composition described in .