JPS63251421A - Impact-resistant polyester resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition which can give a molding excellent in moldability, impact strength and heat resistance, by mixing a specified polyester with a specified nucleator, a specified copolymer and a specified ester plasticizer. CONSTITUTION:A resin composition comprising 100pts.wt. polyester component comprising 40-97pts.wt. polyethylene terephthalate (PET) and 3-60pts.wt. copolymer PET having 2-25wt.% copolymerized dibasic acid of the formula or its derivative, 0.05-10pts.wt. inorganic nucleator, organic compound having a metal carboxylate group or polymeric compound (a) having a metal carboxylate group, 3-30pts.wt. copolymer (b) obtained by copolymerizing ethylene with an alpha,beta-unsaturated dicarboxylic acid anhydride in amount to give a comonomer ratio of 0.01-20mol.%, 1-30pts.wt. copolymer (c) comprising 80-99wt.% alpha-olefin and 1-20pts.wt. glycidyl (meth)acrylate and 0.3-10pts.wt. ester plasticizer (d).

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.

(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, 1
Normally, stretched products are used, but if the product is to be used for plastic purposes as an injection molded product, for example, it is not subjected to the above stretching process.
It is known that some problems occur in terms of molding and physical properties. In other words, because 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 is There is a difference in crystallinity between the surface and the inside, resulting in uneven mechanical properties, three-dimensional stability, and shape stability, and it is extremely difficult to obtain a molded product that can be put to practical use.

Conventional methods to solve these problems include using a high-temperature mold, adding a crystal nucleating agent or crystallization accelerator, and 1) blending an ethylene tereclate copolymer with excellent low-temperature crystallinity. Many such 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 fibers, exhibit excellent mechanical properties and high heat distortion temperatures, and have established themselves as engineering plastics. And it has come to this day.

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
40 and 115P4.46L871 propose that impact resistance 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. 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 PET), although the impact resistance strength is improved, it is difficult to separate from the mold during molding. There is a problem that the moldability becomes extremely poor and the surface gloss is poor when the low temperature mold 3 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.

(Problems to be Solved by the Present Invention) The purpose of the present invention is to solve the problems of the prior art as described above, and to provide a molded product with excellent operational stability, good molded product gloss and mold releasability, and quick impact strength. The object of the present invention is to obtain a polyethylene terephthalate resin composition.

(Means for solving the problems) As a result of intensive research to solve various problems such as those mentioned in item 1, we have found that all of these problems can be solved by adding specific other components to PIET. The present invention has been developed based on the discovery that this can be done.

That is, the present invention uses polyethylene terephthalate 40-9
Ethylene terephthalate polyester 3-60 copolymerized with 7 parts by weight and 5-25% by weight of a dibasic acid or its derivative represented by the following general formula N)
For 100 parts by weight of polyester consisting of parts by weight.

1100 C-C son-in-law C00I+ (1)R
1,++2: A group selected from hydrogen, an alkyl group, and a phenyl group, and R1 and R2 are the same or different groups.

n: an integer of 10 or more + (l) 0.05 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. ~10 parts by weight, (b) ethylene and one or more α
, the copolymerization ratio of α,β-unsaturated dicarboxylic acid anhydride in the ethylene copolymer obtained by copolymerizing β-unsaturated dicarboxylic acid anhydride and, if necessary, further α,β-unsaturated carboxylic acid ester. 3 to 30 parts by weight of 0.01 to 20 mol%.

(c) α-olefin 80-99% by weight, glycidyl methacrylate or glycidyl acrylate 1-20%
1 to 30 parts by weight of a copolymer consisting of 0 to 19 weight % of vinyl acetate, and (d) 0.3 to 1 part of an ester plasticizer.
The present invention relates to an impact-resistant polyester resin composition containing 0 parts by weight and (e) 0 to 150 parts by weight of a fibrous reinforcing material.

PUT used in the present invention is obtained by melt polymerization of terefucuric 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 PUT used with PUT.

A copolymer of a dibasic acid or its derivative having the structure of general formula N) is effective, and if n is about 9 or less, the effect of improving impact strength in a low temperature region is small. Regarding the copolymerization ratio of the general formula (H), if it is less than 5% 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 general formula (I) is 5 to 25% by weight.

The amount is desirably 10 to 20% by market weight. The ratio of PET and copolymerized PUT varies depending on the type of copolymerized PET, but in general, if the amount of copolymerized PET is less than 3 parts by weight based on the total polyester component, the impact resistance strength in the low temperature range will be improved. If the amount exceeds 60 parts by weight, the thermal properties will deteriorate, which is not preferable. Therefore, the amount of the ethylene tereclate polyester copolymerized with general formula (1) is 3 to 60 parts by weight, preferably 10 to 50 parts by weight, based on the total polyester.

In addition, as a specific example of the dibasic acid represented by the general formula (N), 1
For example, decane-1,IO-dicarboxylic acid.

Undecane-1,12-dicarboxylic acid, dodecane-I1
12-dicarboxylic acid, tetradecane-1,14-dicarboxylic acid, hexadecane-1,16-dicarboxylic acid, octadecane-1,18-dicarboxylic acid, 6-ethyl-hexadecane-1,16-dicarboxylic acid, 7,8-diphenyl -tetradecane-1,14-dicarboxylic acid, among others, octadecane-1,18-dicarboxylic acid, 6-nitylhexadecane-1°16-dicarboxylic acid, and tetradecane-1,14-dicarboxylic acid are useful. It is.

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 50 μm or less used in the present invention include carbon black, silica, calcium carbonate, synthetic silicic acid and silicates, zinc white, hallosite clay, chloride, base Magnesium carbonate, 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.

Furthermore, 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, myridic acid, palmitic acid, stearic acid, behenic acid, cerotic acid, montanic acid.

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

Terephthalic acid, terephculic 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 (meth)acrylic acid or styrene and (meth)acrylic acid are used. Polymeric metal salts are used. As metals that form salts with carboxyl groups, 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 α,β-unsaturated dicarboxylic acid ice-free product which is a copolymerization component of the acid anhydride-containing ethylene copolymer which is the component (b) is expressed by the following formula (where f?s, R+o are hydrogen, alkyl or a halogen group), examples of which include male/inic anhydride, methyl maleic anhydride, chloromaleic anhydride,
Examples include citraconic anhydride, butynyl anphosuccinic acid, and tetrahydrophthalic 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-ethyl methacrylate.
- Methacrylic esters such as hydroxyethyl, acrylic esters such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, etc., or mixtures thereof.

Styrene is a polymer that can be copolymerized with ethylene, α,β-unsaturated carboxylic acid esters, and α,ρ-unsaturated dicarboxylic acid anhydrides.

Styrenic compounds such as α-methylstyrene and vinyltoluene, α, β-unsaturated nitriles such as acrylonitrile and methacrylonitrile, and α, β-unsaturated carboxylic acids such as acrylic acid and methacrylic acid.

Examples include vinyl acetate and vinyl ether, 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 10 mol%.
It is mole%. As a method for producing such an acid anhydride-containing ethylene copolymer, a so-called known radical copolymerization method is used, and in addition, a radical generator is present in ethylene or an ethylene copolymer, and an unsaturated monomer having the above-mentioned groups is produced. Examples include a method in which one or more polymers are subjected to a radical graft reaction in the presence or absence of a solvent or dispersion medium. In particular, 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-olefin used as component (i) in the present invention
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, and when it is 1% by weight or less, the above-mentioned modified polyolefin Alternatively, when used in combination with a modified olefin elastomer, a sufficient effect is obtained for improving impact resistance, but if it is 20% by weight or more, side reactions such as gelation 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%, it is not preferred because the thermal stability of the resulting resin composition decreases. Various ester plasticizers can be used as the component (d), but among them, compounds represented by the following general formulas (TI), (IIT), and (TV) are particularly useful.

R3: Alkylene group R4, Rs: A group selected from an alkyl group, a benzyl group, and an aromatic substituted benzyl group.

R4 and R5 are the same or different groups It is.

m, n: integer (III) of 1 or more X: direct bond 1 alkylene group, -SO2-, -5-,
-0- or -C- Rs, R7: A group selected from an alkyl group, a benzyl group, a nyl group, or a derivative thereof, and R6 and Rf are the same or different groups.

Re, Rs: hydrogen, alkyl group, or halogen, and R8 and Rs are the same or different groups.

m, n: an integer of 1 or more R1111, R,: hydrogen, alkyl group, phenyl group.

Benzyl group or these derivatives A group selected from conductors, RIo.

R1, are the same or different groups; Ru.

R5λ: A group selected from a phenyl group, a benzyl group, or a derivative thereof.

R, ): A group consisting of hydrogen, an alkyl group or a group defined as -.

n: An integer of 4 or more.

In the ester plasticizer represented by the general formula (■), R3 represents an alkylene group, usually having 1 to 20 carbon atoms.
It is desirable to use a linear or branched alkyl group having a molecular symmetry of . R4.

Rs is methyl, ethyl, propyl, butyl.

Specific examples include pentyl, hexyl, heptyl, octyl, and benzyl. Regarding m and n, the larger m and n tend to be, the greater the effect as a crystallization accelerator, but conversely, the compatibility with PP and T decreases, and the heat resistance decreases. Usually m, n is 1~
Approximately 20. Preferably it is 1 to about 10.

In general formula (III), X is usually an alkylene group such as methylene, ethylene, propylene or -0
- is useful, and as R6 and Ih, an alkyl group having 5 or more carbon atoms, a benzyl group, and a phenyl group are usually effective, and m and n are preferably 1 to about 10.

In the general formula (TV), RIo, R,1 is hydrogen or an alkyl group, and RlZ I
A benzyl group is useful as RIB. 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, octadecane-1, Dibenzyl esters of 18-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, and titanate fibers; however, glass fibers are usually used. Ru. There are no particular restrictions on the diameter and length of the various fibers, but if the fiber length is too long, it may be difficult to uniformly mix and disperse the fibers with polyester or other compounding agents, i.e., component (A) or component (0). On the other hand, if the fiber length is too short, the effect as a reinforcing material will be insufficient.1 Usually, fibers 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
．． The thickness is preferably 1 to 7 mm, more preferably 0.3 to 4 mm. 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,
γ-methacryloxypropylmethoxysilane, β-(3
Silanes such as ゜4-epoxycyclohexyl)-ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-chloropropylmethoxysilane, γ-mercaptopropyltrimethoxysilane, etc. System treatment agent, methacrylate 1
- Those treated with a chromium-based treatment agent such as chromic 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 10 parts by weight or less. On the contrary, it is not preferable because it may induce a decrease in impact resistance strength. Therefore, the amount of component (a) is 0.
．． 05 to 10 parts by weight, preferably 0.5 to 5 parts by weight. (b) Component, namely α.

If the blending amount of the ethylene copolymer containing β-unsaturated dicarphonic anhydride is less than 3 parts by weight per 100 parts by weight of the polyester, the induction impact strength will be improved due to the combined effect with component ())). ''- is small, and 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 amount of ()\) component 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.

In other words, with regard to 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 blended in more than 30 parts by weight, the impact strength will not increase with the amount blended. This is not preferable because it shows a saturation value and promotes gelation during heating and kneading.

Therefore, the blending amount of component (iii) is 1 to 30 parts by weight, preferably 3 to 20 parts by weight, and most preferably 3 to 10 parts by weight. The mixing ratio of component (B) and component (C) is 10:1 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 amount of component (d), that is, the ester plasticizer, 0.3
If the amount is less than 110 parts by weight, the effect of promoting crystallization and the effect of improving mold releasability will be small, and if the amount is more than 110 parts by weight, heat resistance will decrease, which 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 fiber reinforcing material that is blended as necessary is 150 parts by weight or less.
00 parts by weight or less.

Furthermore, the composition of the present invention may contain various inorganic or organic compounds such as antioxidants, ultraviolet absorbers, colorants, fillers, etc., as 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 may 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 Polyethylene terephthalate (PET) with an intrinsic viscosity (measured in phenol/tetrachloroethane-6/4, concentration 0.5%, temperature 20°C) of 0.68, ethylene copolymerized with various dibasic acids Telecrate-based art combination (copolymerized PIET), crystal nucleating agent, plasticizer, modified polyolefin,
Glycidyl methacrylate copolymerized polyolefin (G
M copolymer) was mixed in a predetermined amount as shown in Table 1, and 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. Created a throat. While Examples 1 to 5 and Comparative Examples 1.2 exhibited good operational stability during pellet production, in Comparative Example 3, generation of gel-like substances was observed. Cylinder salt after vacuum drying the pellets
A 1/2 inch x 1/2 inch x 2.5 inch test piece was molded once at 60 °C and a mold temperature of 105 °C for 20 seconds and cooled to room temperature and 120 °C according to 8STM, D-638. The notched Izo impact strength at °C was measured, and the surface gloss was further evaluated. And the mold releasability is 10cm long x 7cm wide x 4cm deep at a mold temperature of 105℃.
Evaluation was made based on the minimum cooling time at which mold release was possible when a box-shaped molded product (wall thickness 1.5 mm) was molded. The shorter the minimum cooling time, the better the mold releasability. The results are summarized in Table 1.

Table 1 Reference example 1 Ethylene-maleic anhydride-acrylic acid copolymer (Sumika CDF"fJl!', Pontine AX 8040) Reference example 2 Ethylene-maleic anhydride-acrylic acid copolymer (Sumika C
Manufactured by Kanosha, Bondine IIX 8140) Reference example 3 Ethylene-maleic anhydride-acrylic acid copolymer (Sumika CDF71 [, Bondine TX 8030) Reference example 4 Ethylene-maleic anhydride-acrylic acid copolymer (Sumika CDF (Bondine 1,
TB: 15% by weight of tetradecane-1,14-dicarboxylic acid
Copolymerized PET C: 7% by weight of octadecane-1,18-dicarboxylic acid.
and 3% by weight copolymerization of 6-ethyl-hexadecane-1,16-dicarboxylic acid PINT C: Dibenzyl ester of azelaic acid d: Dibenzyl ester of adipic acid X: Ethylene (92% by weight)-glycidyl methacrylate (8% by weight ) Copolymer Y: Ethylene (91% by weight)-glycidyl methacrylate (7% by weight) copolymer-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 (4-layer 3 mm long chopped strand, product number Na429) so that it accounted for 30% by weight of the total composition, and a biaxial Pellets were prepared by kneading with an extruder (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), cylinder temperature 240-260 -260℃, mold temperature 105℃, cooling time 10 seconds to mold various test pieces,
Notched Izo impact strength (test piece thickness: 1/2 inch) and heat distortion temperature under a load of 18.56 Kg/- (test piece thickness: 1/8 inch) were measured according to ASTM.

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 2 (Effects of the invention) From the above, in the composition of Comparative Example 4 in which no nucleating agent, ester plasticizer, or copolymerized PUT is blended, low temperature mold (90°C)
However, the composition of the present invention has excellent impact strength, heat distortion temperature, and mold releasability. It can be seen that it has

Patent Applicant: Unitika Co., Ltd. Teshin Seifushoya+ (Voluntary) 1. Indication of the case Japanese Patent Application No. 62-84475 2, Name of the invention: Impact-resistant polyester 1, Shogawa Kei ■ Acid 3, Person making the amendment Connection with the case: Patent application 1i9ji Address: Higashihonmachi, Amaichi-shi, Hyogo prefecture 1-50 Name (4FlO) Unitika Co., Ltd. 4, Subject of amendment (1) [Claims and Detailed Description of the Invention] column 5 of the specification, Contents of amendment (1 Claims Correct as shown in the attached sheet.

(2) The formula (D) in No. 9 of the specification is corrected as follows and the following sentence is inserted.

r HOOC-(CH2h C0OH(r ) (However, (part or all of the hydrogen atoms of cH2h may be substituted with an alkyl group or a phenyl group.)
(3) 'R from the bottom line of page 9 to the second line of page JO of the specification
1, R2: hydrogen, alkyl cage phenyl group------
-----1---------- group. ” to be deleted.

(4) Immediately divide 1 zinc white -1 in the 6th line of the 13th shoulder of the specification by 1.

(5) "2 (■)" in the 15th paragraph of the specification is corrected to "Formula (V)".

(6) "Citraconic anhydride, butynyl succinic anhydride, and TeI-lahydrophthalic anhydride 1" from the second line to the bottom line from the bottom of No. 15 of the specification are deleted.

(7) Formula (U) on page 18 of the specification is corrected as follows.

(8) rm and nJ on page 19, line 3 of the specification are rm,
Correct it as mI J.

(9) Formula (m) in No. 19C of the specification is corrected as follows.

(I) 00) "Alkylene group" and r in line 7 of line 19 of the specification
-3Q2-J is inserted with a ``ni-alkylidene group''.

rR on page 19, lines 10 to 17 of song description
R9: alkyl group, benzyl group, phenyl group to 1-
-------------------mIn: an integer of 1 or more" is replaced by "R15, R7: hydrogen, alkyl group, phenyl group or a derivative thereof, R6゜R7 is the same or different group .

Rn, Rq: represents a substituent consisting of an alkyl group or a halogen.

m, m': Integer 1 and n type of IIL.

02) Between line 17 of specification 19W and formula (TV)'
p, Q: an integer from O to 4" is inserted.

The formula (TV) on page 19 of the specification is corrected as follows,
Insert the following sentence.

r ((B, L, -f C1 (part or all of the hydrogen atoms in 2h may be substituted with an alkyl group, phenyl group or benzyl group)" 04 Specification, page 20, No. 1 "R10, R11: hydrogen, alkyl group, phenyl group, benzyl group to one---
−−−−−−−−−−−−−・−−−−・・−−−−−
--n: An integer of 4 or more. ” is [RIo: a group selected from phenyl group, benzyl 7L4 and derivatives thereof.

R7: A group consisting of hydrogen, an alkyl group or a group defined by RIG.

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

Q5) rm on line 17 and line 18 directly below No. 15 of the specification,
Correct n J to rm, m “”.

rm, n J in the first line of page 21 of the aω specification, rm,
Correct it as "m"".

0'71 Specification, page 21, lines 4 to 5, ``alkylene group'' is corrected to ``alkylidene group such as alkylene group, isopropylidene group, etc.''.

(1B) rm, n J on page 21, line 7 of the specification is rl
Tl, correct it as m'J.

09) On page 21 of the specification, line 8 to line 10, "In the general formula (TV) - - - - - - - - - - -
--------1--benzyl group is useful. " in the general formula (IV), R6 is a group selected from a phenyl group, a benzyl group, or a derivative thereof;
As 1, hydrogen, an argyl group or a group defined by Ran is useful. ” he corrected.

QII) "n" on page 21, line 10 and line 12 of the specification
] is corrected to r.

Claims (1) Ethylene terephthalate polyester 3 obtained by combining 40 to 97 parts by weight of polyethylene terephthalate and 2 to 25 weight percent of at least one dibasic acid or its derivative represented by the following general formula (1). ~60 parts by weight of polyester.

n: an integer of 10 or more (a) 0.05 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. ~10 parts by weight, (b) ethylene and one or more α
, β-unsaturated dicarboxylic acid anhydride and optionally further α,β-unsaturated carboxylic acid ester. 3 to 30 parts by weight of those having a ratio of 0.01 to 20 mol%, (c) 80 to 80 parts by weight of α-olefin
99% by weight, 1-20% by weight of glycidyl methacrylate or glycidyl acrylate and 0-20% of vinyl acetate
An impact-resistant polyester containing 1 to 30 parts by weight of a copolymer containing 19% by weight, (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. Resin composition.

(2) The dibasic acid represented by general formula (1) is octadecane-1118-dicarboxylic acid, 6-ethyl-hexadecane-1,16-dicarboxylic acid or tetradecane-Li2
- dicarboxylic acid, the polyester resin composition according to claim 1.

(3) The ester plasticizer has the following general formula (n), (I
I[).

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

R4, R5: A group selected from an alkyl group, a benzyl group, and an aromatic substituted benzyl group, and R4° and R5 are the same or different groups.

m, an integer greater than or equal to 1 (II[) X: Direct bond, alkylene group, Eruto U? 7 units.

-SO□-, -S-, -O- or -C-m, an integer greater than or equal to 221 : A group selected from a phenyl group, a benzyl group, or a derivative thereof.

-λ is a group consisting of hydrogen, an alkyl group or a group defined by RIo.

It is an integer from 2 to 24 or more.

(4) The polyester resin according to claim 1, wherein one or more inorganic substances selected from the group of talc, mica, kaolin, and silica are used as the inorganic compound having an average particle size of 50 μm or less. Composition.

(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 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 .

Claims (7)

[Claims] (1) 3 to 60 parts by weight of an ethylene terephthalate polyester obtained by copolymerizing 40 to 97 parts by weight of polyethylene terephthalate and 2 to 25% by weight of at least one dibasic acid or its derivative represented by the following general formula (I); For 100 parts by weight of polyester consisting of: ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) R_1, R_2: Groups selected from hydrogen, alkyl groups, and phenyl groups, and R_1 and R_2 are the same or different groups. n: an integer of 10 or more (a) 0.05 at least one of the following: 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. ~10 parts by weight, (b) ethylene and one or more α
In the ethylene copolymer obtained by copolymerizing β-unsaturated dicarboxylic acid anhydride and, if necessary, α,β-unsaturated carboxylic acid ester, the copolymerization ratio of α,β-unsaturated dicarboxylic acid anhydride (c) α-olefin 80-9
9% by weight, 1-20% by weight of glycidyl methacrylate or glycidyl acrylate and 0-1% of vinyl acetate.
An impact-resistant polyester containing 1 to 30 parts by weight of a copolymer containing 9% by weight, (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. Resin composition. (2) The dibasic acid represented by the general formula (I) is octadecane-1,18-dicarboxylic acid, 6-ethyl-hexadecane-1,16-dicarboxylic acid or tetradecane-1,
The polyester resin composition according to claim 1, which is a 14-dicarboxylic acid. (3) The ester plasticizer has the following general formula (II) or (III)
The polyester resin composition according to claim 1, which is at least one ester compound of (IV). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) R_3: Alkylene group R_4, R_5: Groups selected from alkyl groups, benzyl groups, and aromatic substituted benzyl groups, and R_4 and R_5 are the same or different groups. m, n: Integer greater than or equal to 1 ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (III) X: Direct bond, alkylene group, -SO_2-, -S-,
-O- or ▲ Numerical formula, chemical formula, table, etc. ▼ R_6, R_7: A group selected from an alkyl group, a benzyl group, a phenyl group, or a derivative thereof. R_6 and R_7 are the same or different groups. R_8, R_9: hydrogen, alkyl group, or halogen, and R_8 and R_9 are the same or different groups. m, n: Integers of 1 or more ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (IV) R_1_0, R_1_1: A group selected from hydrogen, an alkyl group, a phenyl group, a benzyl group, or a derivative thereof, where R_1_0 and R are They are the same or different groups. R_1_2: A group selected from a phenyl group, a benzyl group, or a derivative thereof. R_1_3: 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 .