JPS63245427A - Impact-resistant polyester resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition which is excellent in moldability and can give a molding excellent in impact and heat resistance, by mixing a polyester with two specified compounds, an ethylene copolymer, an ester plasticizer and a fibrous reinforcement. CONSTITUTION:A polyester (A) is obtained by mixing 40-97pts.wt. polyethylene terephthalate with 3-60pts.wt. ethylene terephthalate polyester containing 2-25wt.% polyalkylene glycol (derivative) of an MW of 500-20,000. 100pts.wt. component A is mixed with 0.05-10pts.wt. at least one member (B) selected from an inorganic nucleator of an average particle diameter <=50mu and an organic or polymeric compound having a metal carboxylate group, 3-30pts.wt. ethylene copolymer (C) comprising ethylene, an alpha,beta-ethylenically unsaturated dicarboxylic acid anhydride and, optionally, an alpha,beta-unsaturated carboxylic acid ester, 1-20pts.wt. copolymer (D) comprising 80-99wt.% alpha-olefin, 1-20wt.% glycidyl (meth)acrylate and 0-19wt.% vinyl acetate, 0.3-10pts.wt. ester plasticizer (E) and 0-150pts.wt. fibrous reinforcement (F).

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, it has a high crystallization rate, exhibits excellent mold releasability even at a mold temperature of about 120°C or less during injection molding, and provides a molded product with excellent impact strength and high heat distortion temperature. The present invention relates to a polyester resin composition.

(Conventional technology) Polyethylene terephthalate has excellent mechanical properties, electrical properties, heat resistance, chemical resistance, etc. It is used as fiber and film in many industrial products.

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 some problems occur in terms of molding and physical properties. In other words, since the crystallization rate at low temperatures is low, 1 the crystallization rate is insufficient at mold temperatures of about 120°C or lower, which are normally used when injection molding other plastics, and the resulting molded product has There is a difference in the degree of crystallinity inside the mold, which results in uneven mechanical properties, dimensional stability, and shape stability, making it extremely difficult to obtain a molded product that can withstand practical use.

Conventional methods to solve these problems include using a high-temperature mold, adding a crystal nucleating agent or crystallization accelerator, and blending an ethylene terephthalate copolymer with excellent low-temperature crystallinity. A number of methods have been proposed and are recognized to be quite effective. 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, a disadvantage of polyethylene terephthalate compositions or reinforced polyethylene terephthalate compositions blended with glass fiber, etc. is that they have low impact strength, that is, poor toughness, and there is currently a strong desire to improve this. be.

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
2045, JP 58-17148, JP 58-17151, USP 4,284,5
No. 40 and USP No. 4.461,871 propose that impact strength can be improved by blending a copolymer 1 having a glycidyl group, such as an ethylene/vinyl acetate/glycidyl (meth)acrylate copolymer, with polyester. ing. However, when olefin-based poly-7-5 copolymerized with glycidyl (meth)acrylate, that is, polyolefin having an epoxy group, is blended with polyethylene terephthalate (hereinafter abbreviated as PET),
Although the weight impact resistance is improved, the releasability from the mold during molding becomes extremely poor.
There is a problem that the surface gloss is poor below ℃. An even bigger problem is that when a polyolefin having an epoxy group is blended into r'lET and heated and kneaded in an extruder to make pellets, a gel-like substance is formed in some cases. There is a problem that operations cannot be carried out due to the generation of large numbers of bodies.

(The problem that the invention seeks to solve).

The purpose of the present invention is to solve the problems of the prior art as described above, and to obtain a polyethylene terephthalate resin composition that has excellent operational stability, good molded product gloss and mold release properties, and has excellent impact strength. .

(Means for solving the problems) As a result of intensive research to solve the various problems mentioned above, it has been found that all of these problems can be solved by adding specific other constituents to PUT. This is what we discovered and arrived at the present invention.

That is, the present invention uses polyethylene terephthalate 40-9
Based on 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) a la-free crystal nucleating agent with an average particle size of 50μ 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, each containing a small amount of 0.05 to 10 parts by weight, (b) ethylene and one or more α.

In the ethylene copolymer obtained by copolymerizing a β-unsaturated dicarboxylic acid anhydride and optionally an α, β-unsaturated carboxylic acid ester, α.

Copolymerization ratio of β-unsaturated dicarboxylic acid anhydride is 0.01~
Copolymer 1-20 consisting of 80-99% by weight of α-olefin, 1-20% by weight of glycidyl methacrylate or glycidyl acrylate, and 0-19% by weight of vinyl acetate The present invention relates to an impact-resistant polyester resin composition comprising (d) 0.3 to 10 parts by weight of an ester plasticizer, and (v) O to 150 parts by weight of a fibrous reinforcing material.

The POET 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. Further, other copolymerization components may be included as necessary.

Furthermore, as a copolymerized PIET used with PET, a copolymer of 1-polyalkylene gellicol or a derivative thereof is effective, and if the molecular weight is less than about 500, the effect of improving impact resistance strength in a low temperature region is small. On the other hand, if the molecular weight is thicker than about 20,000, the 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 I'lET and copolymerized r'1liT varies depending on the type of copolymerized PINT, but in general, if the amount of copolymerized PET is less than 3 parts by weight in the total polyester component, low temperature f! The effect of improving the impact strength in the region and the effect of promoting crystallization are small, and if the amount exceeds 60 parts, the thermal properties deteriorate, which is not preferable. Therefore, the amount of ethylene terephthalate polyester copolymerized with polyalkylene glycol or its derivatives is 3 to 60 parts by weight, preferably 10 to 5 parts by weight, based on the total polyester.
It is 0 parts by weight.

Specific examples of polyalkylene glycol include polyethylene glycol 1 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 50μ 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 2-terephthalic acid, and 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.1 Usually, copolymers of olefin and (ivy)acrylic acid or styrene and (meth)acrylic acid Polymeric metal salts are used. As a total compound that forms a salt with a carboxyl group, alkaline earth compounds, 2 alkali metals, etc. are usually used, but alkali metals have excellent effects as crystal nucleating agents, and among them, sodium and potassium are useful. be.

In the present invention, the α,β-unsaturated dicarboxylic acid anhydride which is a copolymerization component of the acid anhydride-containing ethylene copolymer which is the component (b) has the following formula (formula 11Rs, Rho is hydrogen, an alkyl group or a halogen group). Examples thereof include maleic anhydride, methylmaleic anhydride, chloromaleic anhydride, citraconic anhydride, butynylsuccinic anhydride, and terahydrophthalic anhydride.

α and β used as necessary as copolymerization components of the acid anhydride-containing ethylene copolymer used in the present invention
- Specific examples of unsaturated carboxylic acid esters include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and 2-methacrylate.
- Methacrylic esters such as hydroxyethyl, acrylic esters such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, etc., or mixtures thereof. Also ethylene, α, β-unsaturated carboxylic acid esters and α, β
- Monomers that can be copolymerized with unsaturated dicarboxylic anhydrides include styrene compounds such as styrene, α-methylstyrene, and vinyltoluene, α,β-unsaturated nitrites such as acrylonitrile, and methacrylonitrile, and acryl Examples include acids, α, β-unsaturated carboxylic acids such as methacrylic acid, vinyl acetate, vinyl ether, etc., and these can also be copolymerized if necessary.

The copolymerization ratio of α,β-unsaturated dicarboxylic acid anhydride in the acid anhydride-containing ethylene copolymer used in the present invention is 0.01 to 20 mol%, preferably 0.1 to 1O
It is mole%. As a method for producing such an acid anhydride-containing ethylene copolymer, a so-called known radical copolymerization method may be used.

Examples include a method in which a radical generator is present in ethylene or an ethylene-based copolymer, and one or more of the 11 unsaturated bodies having the above groups are subjected to a radical graft reaction in the presence or absence of a solvent or dispersion medium. Among these, when grafting is carried out in a molten state, by using a melt kneading machine such as an extruder, kneader, or Pampari mixer, the desired product can be obtained in a very short time with a simplified procedure.

α-olefin-glycidyl (meth)acrylate copolymer or α used as component (c) in the present invention
-Olefin-Glycidyl (meth)acrylate-Glycidyl (meth)acrylate in vinyl acetate copolymer
The content of 1- is 1 to 20% by weight, preferably 1 to 10% by weight, and when it is 1% by weight or less, it is sufficient to improve impact resistance when used in combination with the above-mentioned modified polyolefin or modified olefin elastomer. If the amount is 20% by weight or more, side reactions such as gelation may occur during the 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 preferable because the thermal stability of the resulting resin composition decreases. A variety of ester plasticizers can be used as the component (b), but among them, compounds represented by the following general formulas N) (IT) and (In) are particularly useful.

R1: Alkylene group h + R3: A group selected from an alkyl group, a Hensyl group, and an aromatic substituted benzyl group.

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

m, n: Integer greater than or equal to 1 (IT) X: Direct bond + 7 Lukylene 7f5 + -SO2-
+ -3-+ -0- or -C- +74, Rs: a group selected from an alkyl group, a benzyl group, a phenyl group or a derivative thereof, and R4 and R5 are the same or different groups.

Rs, R7: hydrogen, alkyl group, or halogen, and R6 and R are the same or different groups.

m, n: integers of 1 or more Ra, 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.

1? ,, : A group consisting of hydrogen, an alkyl group, or a group defined by Rho.

n: An integer of 4 or more.

In the ester plasticizer represented by the general formula (1), R1 represents an alkylene group, but usually has 1 to 20 carbon atoms.
It is desirable to use a linear or branched alkylene group having molecular symmetry. ! ? Specific examples of 2-1-3 include methyl, ethyl, propylpentyl, hexyl, heptyl, octyl, and benzyl. As for m and n, the effect as a crystallization accelerator increases as m and n become larger, but on the contrary, r
m and n are usually 1 to about 20, preferably 1 to about 1, since compatibility with 'lET and heat resistance are reduced.
It is 0.

In general formula (II), X is usually an alkylene group such as methylene, ethylene, propylene or -0-
is useful, and R4 and R5 are usually alkyl groups having 5 or more carbon atoms, benzyl groups. Phenyl group is effective・m and n are 1
~10 is desirable.

In the general formula (III), R8 and Rs are hydrogen and alkyl groups, and Rho + R
Benzyl group is useful as 1. If n is 3 or less, it will easily volatilize during heating and the effect as a crystallization promoter will be small, so n is 4 or more. For example, adipic acid, azelaic acid, decane-1,10-dicarboxylic acid. Dibenzyl ester of octadecane-1,18-dicarboxylic acid is useful.

Examples of the fibrous reinforcing material used in the present invention include glass fiber. Carbon fiber, aromatic polyamide fiber, silicon carbide fiber. Specific examples include titanate fibers. Glass fiber is usually used. Furthermore, there are no particular restrictions on the diameter and length of the various fibers. If the fiber length is too long, it will be difficult to mix and disperse uniformly with the polyester and other compounding agents, that is, component (a) or component (a), and conversely, if the fiber length is too short, the effect as a reinforcing material will be insufficient. Usually, fibers with a length of 0.1 to 10 mm are used. In particular, when the fibrous reinforcement is glass fiber, the fiber length is 0.
．． The thickness is preferably 1 to 7 mm, more preferably 0.3 to 4 mm. Also, fibrous reinforcement materials. If necessary, glass fibers treated with various compounds can be used to improve the interfacial adhesion with polyester and increase the reinforcing effect, but when using glass fibers as fibrous reinforcement, various surface treatment agents, such as vinyltriethoxysilane,
γ-methacryloxypropylmethoxysilane, β-(3
.

4-epoxycyclohexyl)-ethyltrimethoxysilane, T-glycidoxypropyltrimethoxysilane,
Silane treatment agents such as T-aminopropyltriethoxysilane, γ-chloropropylmethoxysilane, and T-mercaptopropyltrimethoxysilane. Those treated with a chromium-based treatment agent such as methacrylate chromic chloride are used.

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

That is, the amount of the inorganic crystal nucleating agent and metal salt of carboxyl group is 0.000 parts by weight per 100 parts by weight of polyester.
If it is less than 0.5 parts by weight, it will not be effective as a crystal nucleating agent,
On the other hand, even if more than 10 parts by weight is added, the effect as a crystal nucleating agent will not be better than if it is less than 10 parts by weight, and on the contrary, it may induce a decrease in impact strength, which is not preferable.

Therefore, the blending amount of component (a) is 0.05 to 10
Parts by weight, preferably 0.5 to 5 parts by weight. If the amount of the ethylene copolymer containing component (B), that is, α,β-unsaturated dicarboxylic acid anhydride, is less than 3 parts by weight per 100 parts by weight of polyester, the impact resistance due to the combined effect with component (X) The improvement in strength is small, and conversely, if more than 30 parts by weight is added, the thermal properties of the composition deteriorate, which is not preferable. Therefore, the amount of component (c) is 3 to 3
0 parts by weight, preferably 5 to 25 parts by weight, more preferably 5 to 20 parts by weight.

Regarding the blending amount of component (c), that is, the glycidyl (meth)acrylate copolymerized polyolefin, if it is less than 1 part by weight, the effect of improving impact strength will be small, and even if it is blended in an amount of more than 30 parts by weight, the impact strength will not improve. It does not increase with increasing amount, but shows a saturated value (7), which on the contrary promotes gelation during heating and kneading, which is not preferable.

Therefore, the blending amount of component (1) is 1 to 30 parts by weight, preferably 3 to 20 parts by weight, more preferably 3 to 1 part by weight.
0fff1 part. The mixing ratio of component (b) and component (b) is 10:1 to 1:10. Preferably 10:1
or l:2. Particularly preferably, the 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 the fibrous reinforcing material blended as necessary is 150 parts by weight or less (100 parts by weight or less) because if it exceeds 150 parts by weight, it is difficult to uniformly disperse and mix it in the resin. It is added in less than parts by weight.

Furthermore, the composition of the present invention may contain various inorganic or organic compounds such as an antioxidant, an ultraviolet absorber, a coloring agent, and a filler, as necessary, within a range that does not significantly reduce the impact strength. The method for producing the composition of the present invention is not particularly limited, and can be produced in various 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."

Examples 1-5. Comparative Examples 1 to 3 Intrinsic viscosity (measured in phenol/tetrachloroethane-6F4, concentration 0.5%, temperature 20°C) 0.6B P
l'ET, ethylene terephthalate copolymer copolymerized with various polyalkylene glycols (copolymerized PIET)
).

Crystal nucleating agent, plasticizer, ethylene copolymer, glycidyl methacrylate copolymerized polyolefin (GM copolymer)
were mixed in the prescribed amounts as shown in Table 1.

This mixture was kneaded and extruded using a co-rotating twin-screw extruder at a cylinder temperature of 260° C. and a screw rotation speed of 20 rpm to produce pellets. While Examples 1 to 5 and Comparative Example 1゜2 exhibited good operational stability during the production of pere-nod, gel-like material was observed in Example 3 of Comparative Example 1.

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.

Notched Izod t-f at room temperature and -20°C according to ASTM D-638! The impact strength was measured and the surface gloss was evaluated. And the mold releasability is 10cm long x 7cm wide x 4cm deep (wall thickness 1.5cm) at a mold temperature of 105℃.
The evaluation was based on the minimum cooling time at which mold release was possible when a box-shaped molded product of mm) was molded. The shorter the minimum cooling time, the better the mold releasability. The results are summarized in Table 1.

Reference example 4 Ethylene-maleic anhydride-acrylic acid copolymer Kusumika C 1 Bondain L x Old 10) Reference example 5 Ethylene-maleic anhydride-acrylic acid copolymer Kusumika Cl1F, Bondaia I'X 13000):
Polytetramethylene glycol 20 with a molecular weight of approximately 2000
Weight% copolymerized P[4T 11; polyethylene glycol 10 with a molecular weight of about 1000
Weight% copolymerized PET C: Typical copolymerized PET with 15% by weight of polytetramethylene glycol having a molecular weight of about 4000 C: Dibenzyl ester of azelaic acid d: Dibenzyl ester of adipic acid X: Ethylene (92% by weight)-glycidyl methacrylate (8 wt%) Copolymer Y: Ethylene (91 wt%)-glycidyl methacrylate (7 wt%)-vinyl acetate (2 wt%) copolymer Surlyn 1555: Ethylene-acrylic acid copolymer sodium salt (DuPont!! Example 6 Comparative Example 4 In addition to the composition shown in Example 1, glass fiber (Asahi Fiberglass ■, 3 Tocho Chopped Stran 1 package product number ll
1h429) was mixed in a proportion of 30% by weight in the total composition and kneaded in a twin-screw extruder to create a pellet (Example 6). Similarly, as a comparison, glass having the composition shown in Comparative Example 1 was prepared. Comparative Example 4) To prepare a pellet containing 30% by weight of fiber, various test pieces were molded at a cylinder temperature of 240-260-260°C, a mold temperature of 105°C, and a cooling time of 10 seconds.
Notched Izot impact strength (specimen thickness: 1/2 inch) and 18.56 Kg/c+a according to ASTH
The heat distortion temperature under load (specimen thickness 2178 inches) was measured.Furthermore, the mold temperature 9 was measured according to the method described above.
The mold releasability was evaluated based on the minimum cooling time during box molding at 0°C.

(Effect of the invention) In a composition that does not contain a nucleating agent, an ester plasticizer, or a copolymerized PIET, the crystallization rate in a low-temperature mold (90°C) is low, resulting in insufficient crystallization, resulting in an increase in the temperature of the Qi-shaped hot water. It can be seen that the composition of the present invention has excellent impact strength, heat distortion temperature, and mold releasability, whereas the composition of the present invention has excellent impact strength, heat distortion temperature, and mold releasability.

Patent Applicant: Unitika Co., Ltd. Tejo Seiho Seisho (self-proposal) February 18, 1988 1.11 Ushi no Meriroku Patent Application No. 1980-80455 2, Title of Invention 1lii Capturing Polyester Resin Composition Item 3: Relationship with the person making the amendment Patent applicant address 1-50 Higashihonmachi, Amagasaki City, Hyogo Prefecture Name (4)
50) Unitika Co., Ltd. 541 Address 4-68 Kitakyu Obe-cho, Higashi-ku, Osaka Name
Unitika Co., Ltd. Horosai 4, Subject of amendment (]) Column 5 of "Claims" and "Detailed Description of the Invention" of the specification, Contents of amendment (DIN U Claims are corrected as shown in the attached sheet.

(2) "Zinc white" in the second line from the bottom of page 12 of the specification.
! Eliminate ilj.

(3) “Citraconic anhydride” in lines 9 to 8 from the bottom of page 15 of the specification.

Butynyl succinic anhydride, tetrahydrophthalic anhydride”
i! ll+divide.

(4) Formula (n) on page 18 of the specification is corrected as follows.

(II) (5) "Alkylene group" and "
An "alkylidene group" is inserted between -8O□-j.

(6) Specification page 19, lines 8 to 10 'R6,R
7: Hydrogen, alkyl group ----111-- group. Correct J to 'R6, R7: represents 9M consisting of alkyl a4 or halogen.'

(7) Insert 'p, q: an integer from o to 4' between line 11 and 2 (III) on page 19 of the specification.

(8) The formula (TI[) on page 19 of the specification is corrected as shown below, and the following sentence is further inserted.

(However, some or all of the hydrogen atoms in +co and -h may be substituted with a phenyl group or a benzyl group.) (9) Line 6 from the bottom of No. 19 of the specification ~Page 20, line 4 “Re, Rq
:Hydrogen, alkino-hydrogen, phenyl group----・--・-・
-----------------n: An integer of 4 or more. "rR," is a group selected from a phenyl group, a benzyl group, or a derivative thereof.

R1: A group consisting of hydrogen, an alkyl group or a group defined by R8.

r: An integer of 4 or more. ” he corrected.

Ql) "Alkylene group or J" in page 20, line 18 to line 19 of the specification is corrected to "an alkylene group or an alkylidene group such as an alkylene group or an isopropylidene group."

02) “General formula (
In III) -1・−・−・・−・−−−1・
--- Benzyl group is useful. ” to “general formula (I
TS), R is preferably a group selected from a phenyl group, a benzyl group or a derivative thereof, and R1 is preferably hydrogen, an alkyl group or a group defined by R. ” he corrected.

Replace “n” with “r” on page 21, line 4 and line 6 of the specification.
I am corrected.

Claims (1) 40 to 97 parts by weight of polyethylene terephthalate and at least one of polyalkylene glycols or derivatives thereof having a molecular weight of about 500 to 20,000.
Polyester 100 consisting of 3 to 60 parts by weight of ethylene terephthalate polyester copolymerized with ~25% by weight
Based on parts by weight, (a) an inorganic crystal nucleating agent with an average particle size of 50 μm or less, an organic compound having 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) ethylene, one or more α,β-unsaturated dicarboxylic acid anhydrides, and optionally α.

In the ethylene copolymer obtained by copolymerizing β-unsaturated carboxylic acid ester, the copolymerization ratio of α, β-unsaturated dicarboxylic acid anhydride is 0.01 to 20 mol%. parts by weight, (c) 1 to 20 parts by weight of a copolymer consisting of 80 to 99% by weight of α-olefin, 1 to 20% by weight of glycidyl methacrylate or glycidyl acrylate, and 0 to 19% by weight of vinyl acetate, (d) ester plasticizer agent 0.3 to 10 parts by weight.

(E) An impact-resistant polyester resin TA compound containing 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 attached to the phenolic hydroxyl group of a bisphenol compound such as bisphenol A with ethylene oxide, propylene oxide, or butylene oxide. 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 formulas (I) and (U).

The polyester resin composition according to claim 1, which is at least one ester compound of (II[).

R3: Alkylene group R,, R,: A group selected from an alkyl group, a benzyl group, and an aromatic substituted benzyl group, and R2° and R3 are the same or different groups.

m・n: An integer of 1 or more (U) X: Direct bond, alkylene group,
5o2-. -s-, -o- or -C-R4,R5: a group selected from an alkyl group, a benzyl group, a phenyl group, or a derivative thereof.

R,, R1, are the same or different groups.

m+n: Large integer greater than or equal to 1 CIl□b's 71, Part or all 6 of Estopu Ushi 1 Nifco Seizeri (U5p Dachi Otsu 2 Next 522) "L: Phenyl A group selected from a benzyl group, a benzyl group, and a derivative thereof.

``1: A group consisting of hydrogen, an alkyl group, or a group defined in □.

-L: 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) A compound having a metal salt of a carboxyl group.

The polyester resin composition according to claim 1, which is a compound having about 7 to 3 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: When it is a copolymer of meth)acrylic acid
The polyester resin composition described in .

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) ethylene and one or more α,β-unsaturated dicarboxylic acid anhydrides, and optionally further α, In the ethylene copolymer obtained by copolymerizing β-unsaturated carboxylic acid ester, α, β
- Copolymerization ratio of unsaturated dicarboxylic acid anhydride is 0.01 to 2
3 to 30 parts by weight of 0 mol%, (c) copolymers 1 to 1 containing 80 to 99% by weight of α-olefin, 1 to 20% by weight of glycidyl methacrylate or glycidyl acrylate, and 0 to 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 R4 and R5 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 .