JP2001098145A - Thermoplastic polyester resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic polyester resin composition having not only mechanical characteristics and durability but also sufficiently excellent moldability. SOLUTION: This thermoplastic polyester resin composition is obtained by compounding 100 pts.wt. of a thermoplastic polyester resin (A) with 0.1-10 pts.wt. of a carboxylic acid reactive group-containing polymer (B-1) and/or a compound (B-2) containing plural oxazoline groups in the molecule and 0.01-5 pts.wt. of a carboxylic acid anhydride (C). Another thermoplastic polyester resin composition is obtained by melting and kneading 100 pts.wt. of the component A with 0.1-10 pts.wt. of the component (B-1) and/or the component (B-2) and 0.01-5 pts.wt. of the component C. This method for producings thermoplastic polyester resin molding product is a method for producing a molding product comprising the thermoplastic polyester resin as a material and is obtained by molding the thermoplastic polyester resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a thermoplastic polyester resin composition and a method of using the same. More particularly, it relates to a thermoplastic polyester resin composition having excellent moldability and a method for using the same.

[0002]

2. Description of the Related Art Thermoplastic polyester resins, in particular, polyalkylene terephthalates represented by polyethylene terephthalate (PET) and polybutylene terephthalate have many excellent properties, and therefore, are used for industrial fibers,
It is widely used as a material for films and other molded articles, but is required to have better mechanical properties, heat resistance, hydrolysis resistance, and moldability. In particular, for use in blow molding or extrusion molding, polyester resins generally have too low a melt viscosity and severe drawdown, and it is extremely difficult to obtain a molded product having a desired shape. In addition, when waste PET is recycled, melting is repeated during the collection operation.
The intrinsic viscosity (IV) was lowered, and it was no longer suitable for spin molding, and a fiber having sufficient strength and elongation could not be obtained. To improve these, increase the degree of polymerization,
It is effective to reduce the terminal carboxyl groups in the polyester, and as a method for modifying the polyester for such a purpose, a chain extender capable of extending the polymer chain by reacting with the terminal group of the polyester resin is used. There is a way. For example, a method using a bisoxazoline compound (JP-A-55-161823) or a method using a polyfunctional compound (JP-B-47-13860, JP-A-2-2768)
20, JP-A-5-506056) and the like.

[0003] However, these methods can impart some mechanical properties, heat resistance and hydrolysis resistance to the polyester resin, but do not provide sufficient performance in terms of moldability. For example, a method using the above-mentioned bisoxazoline compound (JP-A-55-16182)
In 3), the mechanical properties and durability cannot be said to be sufficient, and further, a melt viscosity and IV sufficient to be suitable for various molding methods cannot be provided. Further, a method using the above-mentioned polyfunctional compound (JP-B-47-13860, JP-A-2-276820,
According to JP-A-5-506056), when a polyfunctional epoxy compound, a polyfunctional isocyanate, or the like is used, sufficient melt viscosity and IV cannot be imparted, and when applied to extrusion molding, injection molding, and blow molding, the molecular weight is low. Is not enough, resin draws down, and when applied to foam molding, there is a drawback that uniform and fine foam cannot be obtained due to low resin viscosity. In this case, there is a disadvantage that yarn breakage occurs during spinning. It is also known that when the amount of these compounds is increased to increase the melt viscosity, the composition gels and the moldability is significantly deteriorated. Furthermore, these polyfunctional compounds volatilize during the molding process, causing mold contamination and impairing the appearance of molded articles.

[0004]

Accordingly, an object of the present invention is to provide a thermoplastic polyester resin composition having not only excellent mechanical properties and durability but also excellent moldability. It is.

[0005]

Means for Solving the Problems The present inventor has made intensive studies to solve the above-mentioned problems. As a result, a composition obtained by blending a thermoplastic polyester resin with a carboxylic acid anhydride and further a specific reactive group-containing polymer and / or a compound having a specific group in a molecule is an object of the present invention. Was found to be applicable to various molding methods. The present invention has been completed in this manner.

[0006] That is, the thermoplastic polyester resin composition according to the present invention is a thermoplastic polyester resin composition containing a thermoplastic polyester resin as an essential component, based on 100 parts by weight of the thermoplastic polyester resin (A).
0.1 to 10 parts by weight of a polymer having a carboxylic acid-reactive group (B-1) and / or a compound having a plurality of oxazoline groups in a molecule (B-2), and 0.01 to 5 parts by weight of It is characterized by being compounded with a carboxylic anhydride (C).

Further, another thermoplastic polyester resin composition according to the present invention comprises a thermoplastic polyester resin (A) 1
00 parts by weight of a polymer having a carboxylic acid-reactive group (B-
1) Melt kneading of 0.1 to 10 parts by weight of compound (B-2) having a plurality of oxazoline groups in a molecule and / or 0.01 to 5 parts by weight of carboxylic anhydride (C). .

A method for producing a thermoplastic polyester resin molded article according to the present invention is a method for producing a molded article using a thermoplastic polyester resin as a material. The method uses the thermoplastic polyester resin composition of the present invention. It is characterized by performing molding.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. (Composition) The thermoplastic polyester resin composition according to the present invention is a thermoplastic polyester resin composition containing a thermoplastic polyester resin as an essential component, and 0.1 parts by weight based on 100 parts by weight of the thermoplastic polyester resin (A). -10
Polymer (B-1) having parts by weight of carboxylic acid-reactive group
And / or a compound (B-2) having a plurality of oxazoline groups in a molecule, and 0.01 to 5 parts by weight of a carboxylic anhydride (C).

Further, another thermoplastic polyester resin composition according to the present invention comprises a thermoplastic polyester resin (A) 1
00 parts by weight of a polymer having a carboxylic acid-reactive group (B-
1) Melt kneading of 0.1 to 10 parts by weight of compound (B-2) having a plurality of oxazoline groups in a molecule and / or 0.01 to 5 parts by weight of carboxylic anhydride (C). .

Hereinafter, these resin compositions according to the present invention will be described first. Examples of the thermoplastic polyester resin (A) used in the present invention include acid components such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyl ether dicarboxylic acid, succinic acid, adipic acid, sebacic acid, cyclohexanedicarboxylic acid, and hydroxybenzoic acid. And a glycol component such as ethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, and cyclohexanedimethanol. In addition, the above 2
In addition to the functional components, tri- or more functional components such as trimellitic acid and pentaerythritol may be copolymerized. Also, p
-Oxyacids such as oxybenzoic acid and polyesters derived from their residues, polylactones such as polypiparolactone, aromatic ether dicarboxylic acids such as 1,2-bis (4,4-dicarboxymethylphenoxy) ethane And a copolyester obtained by combining dicarboxylic acids, oxyacids, glycols and the like described above. Further, there may be mentioned a block copolymerized polyester obtained by coupling two or more kinds of low molecular weight polyesters with a bifunctional chain extender.

Among these polyesters, polyethylene terephthalate and polybutylene terephthalate are preferred. It is also possible to use waste PET in the form of, for example, films, sheets, fibers, bottle moldings, etc. obtained from manufacturing operations and post-use disposal. The polymer (B-1) having a carboxylic acid-reactive group that can be used in the present invention refers to a polymer having a functional group capable of reacting with a carboxylic acid. Here, the functional group capable of reacting with the carboxylic acid includes, for example, an oxazoline group and an epoxy group, and is preferably an oxazoline group in order to sufficiently exert the effects of the present invention. The functional group contained in the polymer (B-1) may be one type or two or more types.

When the polymer (B-1) has an oxazoline group, the compound represented by the general formula (I)

[0014]

Embedded image

(Wherein R ¹ , R ² , R ³ and R ⁴ are each independently hydrogen, halogen, alkyl, aralkyl, phenyl or substituted phenyl, and R ⁵ is a noncyclic ring having an addition-polymerizable unsaturated bond. An organic group), and a side chain obtained by polymerizing an addition-polymerizable oxazoline compound (b-1) and, if necessary, at least one other monomer (b-2). It is a polymer having a plurality of oxazoline groups.

The addition polymerizable oxazoline compound (b-
Specific examples of 1) include, for example, 2-vinyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline, 4,4-dimethyl-2-vinyl-2-oxazoline, 4,4-dimethyl- 2-vinyl-5,5-dihydro-4H-1,3-oxazine, 4,4,6-trimethyl-2-vinyl-5,6-dihydro-4H-1,3-oxazine, 2-isopropenyl-2 -Oxazoline, 4,
Examples include vinyl oxazolines such as 4-dimethyl-2-isopropenyl-2-oxazoline, but are not particularly limited thereto. Among these monomers having an oxazoline group, 2-isopropenyl-2-oxazoline is preferred because it is easily available and has good reactivity.

Addition polymerizable oxazoline compound (b-1)
The use amount of is not particularly limited, but is preferably 0.5% by weight or more and less than 50% by weight in the oxazoline group-containing polymer. If the amount is less than 0.5% by weight, the effect of improving moldability and heat resistance is insufficient, and even if it is used in an amount of 50% by weight or more, the effect does not change and it is economically disadvantageous.

The other monomer (b-2) does not react with the oxazoline group, and is addition-polymerizable oxazoline (b-1).
There is no particular limitation as long as it is a monomer copolymerizable with (meth) acrylates such as methyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. Unsaturated nitriles such as (meth) acrylonitrile; (meth) acrylamide,
Unsaturated amides such as N-methylol (meth) acrylamide; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether;
Olefins; halogen-containing α, β-unsaturated monomers such as vinyl chloride, vinylidene chloride, and vinyl fluoride; and α, β-unsaturated aromatic monomers such as styrene and α-methylstyrene. One or a mixture of two or more can be used.

When the polymer (B-1) has an epoxy group, a monomer (b-3) having an epoxy group, and
A polymer having a plurality of epoxy groups as side chains, obtained by polymerizing at least one other monomer (b-2) as described above, if necessary. Specific examples of the monomer (b-3) having an epoxy group include, for example, glycidyl esters of unsaturated organic acids such as glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and glycidyl itaconate; allyl glycidyl ether And the like, but are not particularly limited. Among these, glycidyl acrylate and glycidyl methacrylate are preferred.

The polymer (B-1) may be, for example, an addition-polymerizable oxazoline compound (b-1) and / or an epoxy group-containing monomer (b-3), and if necessary, at least one other type. Can be produced by a conventionally known polymerization method, for example, a solution polymerization method, a suspension polymerization method, an emulsion polymerization method, a bulk polymerization method, or the like. The number average molecular weight of the polymer (B-1) having a carboxylic acid-reactive group used in the present invention is determined by GPC (gel permeation chromatography).
The range of 00 to 20000 is preferable, and 1500 to 100
A range of 00 is particularly preferred. If the number average molecular weight is less than 1,000, the resulting composition of the present invention has an insufficient molecular weight, so that the moldability tends to deteriorate, and the effect of improving heat resistance tends to decrease. Also, the moldability of the obtained composition of the present invention tends to be inferior.

The supply form of the polymer (B-1) is not particularly limited, but is preferably a solid or an organic solvent solution from the viewpoint of handling, and particularly preferably a solid. Compounds having a plurality of oxazoline groups in the molecule (B
-2) is, for example, 1,3-phenylenebis (2-oxazoline), 1,4-phenylenebis (2-oxazoline), 2,2-bis (2-oxazoline), 2,2-
Bis (4-methyl-2-oxazoline), 2,2-bis (4,4-dimethyl-2-oxazoline), 2,2-bis (4-ethyl-2-oxazoline), 2,2-bis (4 , 4-Diethyl-2-oxazoline), 2,2-bis (4-propyl-2-oxazoline), 2,2-bis (4-butyl-2-oxazoline), 2,2-bis (4
-Hexyl-2-oxazoline), 2,2-bis (4-
Phenyl-2-oxazoline), 2,2-bis (4-cyclohexyl-2-oxazoline), 2,2-bis (4
-Benzyl-2-oxazoline), 2,2-ethylenebis (2-oxazoline), 2,2-tetramethylenebis (2-oxazoline), 2,2-hexamethylenebis (2-oxazoline), 2,2- Octamethylenebis (2-oxazoline), 2,2-ethylenebis (4-ethyl-2-oxazoline), 2,2-tetraethylenebis (4-ethyl-2-oxazoline), 2,2-cyclohexylenebis ( Bisoxazoline compounds such as 4-ethyl-2-oxazoline).
1,3-phenylenebis (2-oxazoline) is exemplified.

The carboxylic anhydride (C) used in the present invention is most preferably, for example, aromatic tetracarboxylic dianhydride, particularly pyromellitic dianhydride. Other useful carboxylic anhydrides include, for example, 3,
3 ′, 4,4′-diphenyltetracarboxylic acid, (perylene-3,4,9,10) tetracarboxylic acid,
3 ′, 4,4′-benzophenonetetracarboxylic acid,
2,2-bis (3,4-dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) ether,
Bis (3,4-dicarboxyphenyl) sulfone, 1,
2,3,4-cyclobutanetetracarboxylic acid, and
Anhydrides such as 2,3,4,5-tetracarboxyhydrofuran, phthalic acid, and maleic acid are exemplified.

The carboxylic anhydride (C) may be a polymer, for example, a copolymer of styrene and maleic anhydride. One embodiment of the thermoplastic polyester resin composition of the present invention is a thermoplastic polyester resin (A)
0.1 to 10 parts by weight of the polymer (B-1) having a carboxylic acid-reactive group and / or the compound (B-2) having a plurality of oxazoline groups in a molecule, based on 100 parts by weight;
This is a form in which the carboxylic anhydride (C) is blended in a ratio of 0.01 to 5 parts by weight. This form is a resin (A),
The polymer (B-1) and / or the compound (B-2) and the acid anhydride (C) may be contained in the form of a mixture without reacting with each other. A partially reacted state, that is, a form in which a mixture and a reactant coexist may be contained, or a form in which each component is contained as a completely reacted reactant, Is also good.

The form of another thermoplastic polyester resin composition of the present invention is a thermoplastic polyester resin (A).
100 parts by weight of a polymer having a carboxylic acid-reactive group (B
-1) and / or 0.1 to 10 parts by weight of compound (B-2) having a plurality of oxazoline groups in the molecule, and
This is a form in which 0.01 to 5 parts by weight of a carboxylic anhydride (C) is melt-kneaded. In this embodiment, the resin (A), the polymer (B-1) and / or the compound (B-
2) and at least a part of the acid anhydride (C) reacts by melt-kneading, and the resin composition obtained through this specific reaction form not only has excellent mechanical properties and durability but also has a sufficient It has particularly good moldability. The melt-kneading of each component may be once pelletized using a single-screw or twin-screw extruder, and then provided for molding.
It may be subjected to molding immediately after melt kneading. The components may be melt-kneaded at once, or the components may be separately kneaded and then mixed, or the components may be added in two or more portions and melt-kneaded.

If the amount of the polymer (B-1) and / or the compound (B-2) is less than 0.1 part by weight, the effect of improving moldability and heat resistance is not exhibited, and the amount is more than 10 parts by weight. This causes problems such as deterioration of physical properties. Polymer (B
-1) and / or the compounding amount of the compound (B-2) is preferably 0.1 to 7 parts by weight, more preferably
0.2 to 5 parts by weight. When the amount of the carboxylic acid anhydride (C) is less than 0.01 part by weight, the effect of improving the moldability is not exhibited. When the amount is more than 5 parts by weight, the effect of improving the moldability cannot be obtained. Adversely affects the physical properties of the molded article. The amount of the carboxylic anhydride (C) is preferably 0.01 to 3 parts by weight, more preferably 0.05 to 3 parts by weight.
To 3 parts by weight, still more preferably 0.1 to 2 parts by weight.

At this time, the carboxylic acid-reactive group in the polymer (B-1) having a carboxylic acid-reactive group and / or the oxazoline group in the compound (B-2) / the carboxyl group in the polyester resin = 0. A range of 1 to 3 (molar ratio) is preferred. Further, in the present invention, the raw materials (A), (B-1) and / or (B-2), and (C) as long as the physical properties of the obtained polyester resin composition are not impaired.
At the time of compounding, at the time of molding, other additives, for example, polyethylene, polypropylene, polyolefins such as polybutylene, vinyl chloride resin, polyvinyl acetal, polyvinyl alcohol, polystyrene, AS resin, ABS resin, polyamide, polycarbonate, thermoplastic elastomers Other thermoplastics, pigments, dyes, reinforcing agents, etc.
Fillers such as calcium carbonate and talc, heat resistance improvers,
An antioxidant, a plasticizer, a weather resistance improver, a lubricant, a release agent, a crystal nucleating agent, a crystallization accelerator, a fluidity improver, an antistatic agent, a stabilizer, a flame retardant and the like may be added. The amount of addition is not particularly limited, but is preferably 0 to 50 parts by weight, more preferably 0 to 30 parts by weight, based on 100 parts by weight of the polyester resin (A).

When the above additives and the like contain a polyolefin, specific examples include polyethylene, polypropylene, polybutylene and their copolymers, and mixtures thereof. It is a copolymer thereof, or a mixture thereof, and more preferably, polypropylene. The preferred molecular weight of the polyolefin is 500
0 to 1,000,000, more preferably 100
It is in the range of 00-100,000. The addition amount of the polyolefin is in the range of 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, and still more preferably 0.2 to 2 parts by weight, per 100 parts by weight of the polyester resin. Is within.

Incorporation of a reinforcing fiber as a reinforcing agent is a technique often used depending on the application, and examples thereof include glass fiber, aramid fiber and carbon fiber. Among them, glass fiber is particularly preferable, and glass fiber is more preferable. Is chopped glass fiber. The amount of the reinforcing fiber added is not particularly limited, but is preferably 5 to 50% by weight in the case of glass fiber with respect to the polyester resin.
0-45% is more preferred. In the case of aramid fiber or carbon fiber, the content is preferably 2 to 50% by weight,
5% by weight is more preferred. The length of the fiber is not particularly limited as long as it is a commonly used length, but is preferably 0.1 to 5
mm, more preferably 0.2 to 4 mm.

A polyester resin (A), a polymer (B-1) having a carboxylic acid-reactive group and / or a compound (B-2) having a plurality of oxazoline groups in a molecule, a carboxylic anhydride (C), The method of blending other additives and the like as necessary is not particularly limited. The thermoplastic polyester resin composition of the present invention comprises a polyester resin (A) and a polymer (B-1) having a carboxylic acid-reactive group.
And / or a compound (B-2) having a plurality of oxazoline groups in the molecule and a carboxylic anhydride (C), so that excellent moldability can be obtained as compared with a conventional thermoplastic polyester resin composition. have. This is because of the terminal carboxyl group and terminal hydroxyl group of the polyester resin (A), the carboxylic acid-reactive group in the polymer (B-1), the oxazoline group in the compound (B-2), and the carboxylic anhydride (C It is presumed that the acid anhydride group of (1) undergoes some reaction or interaction, resulting in a polymer having a molecular structure that can contribute to excellent moldability, for example, having long-chain branching. . On the other hand, when an epoxy compound such as bisphenol F-type glycidyl ether or the like is used, gelation often occurs unless the molding conditions are precisely controlled. (Use) The thermoplastic polyester resin composition of the present invention
As described above, since it is excellent in moldability, it is a very preferable embodiment to produce a molded article using a thermoplastic polyester resin as a material by using various molding methods. That is, the method for producing a thermoplastic polyester resin molded article of the present invention is a method for producing a molded article using a thermoplastic polyester resin as a material, and performing molding using the thermoplastic polyester resin composition of the present invention. It is characterized by.

The molding is preferably at least one selected from extrusion molding, injection molding, blow molding, foam molding, and spin molding. Since the thermoplastic polyester resin composition of the present invention is sufficiently excellent in moldability as compared with conventional products, in particular, extrusion molding, good moldability without drawdown of the resin during blow molding. In addition, in the case of foam molding, a uniform and fine foam is obtained, and a molded article having excellent mechanical properties and appearance is obtained by these molding methods. In spin molding,
Thread breakage is less likely to occur.

The molding machine used in these moldings is not particularly limited, and examples thereof include a usual injection molding machine, a so-called injection compression molding machine, a twin screw extruder, a single screw extruder, a vented twin screw extruder, A vented single screw extruder or the like is preferably used. In the case of extrusion molding, it can be molded by a usual method using a commonly used extruder. That is, the composition of the present invention is melted by an extruder, and is continuously extruded from a die having a desired shape to be formed into a sheet or a film.

In the case of injection molding, molding can be carried out by a usual method using a commonly used injection molding machine. That is, the composition of the present invention is melted in an extruder, the melted composition is injected from a cylinder into a mold, and a molded article having a desired shape can be obtained. In the case of blow molding, a blow molding machine generally used for blow molding of a thermoplastic resin may be used, and may be performed by an ordinary method. That is, the thermoplastic polyester resin composition of the present invention is plasticized by an extruder or the like, and is extruded or injected by an annular die to form an annular molten or softened intermediate parison, which is inserted into a mold. A gas is blown into the inside, inflated, cooled and solidified, and formed as a hollow body. The gas blown into the inside may be air, nitrogen or any other gas, but air is usually used from the viewpoint of economy, and the blowing pressure is 3 to 10 k.
g / cm ² is preferred. Furthermore, it can be molded by a special blow molding machine such as a three-dimensional blow molding machine. Further, the composition of the present invention may be composed of one or more layers, and may be combined with a layer of another material to form a multilayer blow molded product.

In the case of foam molding, for example, the composition of the present invention and the thickener are mixed and melted in an extruder, and the molten mixture is mixed with a foaming agent under high pressure to obtain a mixture. The mixture can be extruded into a low-pressure region such as the atmosphere to perform molding. As an extruder that can be used in foam molding, for example, an extruder such as a single-screw extruder, a multi-screw extruder, or a tandem extruder can be used. The mixture is extruded from the base into a low pressure region.

As the foaming agent, a physical foaming agent having a property of being vaporized or expanded by heating can be used. Examples of the foaming agent include, for example, an inert gas such as carbon dioxide gas and nitrogen gas; methane, ethane, normal butane, isobutane, normal pentane, isopentane, neopentane, normal hexane, 2-methylpentane, and 3-methylpentane. Saturated aliphatic hydrocarbons such as 2,2-dimethylbutane and 2,3-dimethylbutane; saturated alicyclic hydrocarbons such as methylcyclopropane, cyclopentane, ethylcyclobutane and 1,1,2-trimethylcyclopropane; Aromatic hydrocarbons such as benzene; halogenated hydrocarbons such as trichloromonofluoromethane, dichlorofluoromethane, monochlorodifluoromethane, trichlorotrifluoroethane and dichlorotetrafluoroethane; ethers such as dimethyl ether and 2-ethoxyethanol; Emissions, methyl ethyl ketone, such as ketones such as acetylacetone and the like,
These can be used alone or in combination of two or more.

The amount of the foaming agent used is 0.5 parts by weight or more, preferably 1 part by weight or more, based on 100 parts by weight of the molten mixture so that the obtained molded article has a desired expansion ratio. In order to prevent the dimensional stability of the molded article from being reduced during extrusion molding, the molten mixture 10
10 parts by weight or less is preferable with respect to 0 parts by weight, and 7.5 parts by weight.
It is more preferred to be parts by weight.

In foam molding, it is preferable to add a foam nucleating agent in order to make air bubbles fine. Foaming nucleating agents are generated by heating inorganic substances such as talc, silica, kaolin, clay, calcium carbonate, and aluminum sulfate, fatty acid metal salts such as barium stearate and calcium stearate, and inorganic gases such as carbon dioxide and nitrogen. Azodicarbonamide, azobisisobutyldinitrile, azodicarbamic acid amide, benzenesulfonyl hydrazide, etc., which are organic compounds that are used. The foam nucleating agent is preferably added in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the resin composition of the present invention. In the case of foam molding, a known reaction accelerator can be used to improve moldability. Examples thereof include Group I, II, and III metal compounds such as sodium carbonate, and organic metal compounds such as aluminum stearate. The addition amount is 0.01 parts by weight based on 100 parts by weight of the resin composition of the present invention.
-5 parts by weight is a preferred range.

When a polyester fiber is obtained by spin molding, ordinary spin molding conditions can be employed, but the spinning speed is 1000 to 6000 m / min, preferably 1 to 6000 m / min.
500-5000 m / min, more preferably 1500-500 m / min
4000 m / min. Further, even if the melt-spun yarn is taken up as it is, it is once taken up by the first hot roll, stretched between the second hot rolls, and wound up after heat setting (so-called direct spinning), but once on the spinning wire. After cooling to a temperature below the glass transition temperature of the polymer, the polymer may be passed through a non-contact hot tube, heated and stretched, and then wound up.

[0038]

EXAMPLES The present invention will be described in detail below, but the present invention is not limited to these examples. (Molecular weight) The number average molecular weight of the polymer was measured by gel permeation chromatography (GPC). (Intrinsic viscosity (IV)) It measured at 25 degreeC using the mixed solvent of 6: 4 (weight ratio) of phenol and tetrachloroethane.

(Evaluation of Moldability) Foam Moldability: ○ The expansion ratio is 20 times or more. Δ The expansion ratio is more than 10 times and less than 20 times. × The expansion ratio is 10 times or less. Blow moldability: 成形 A molded product having a uniform thickness can be obtained without drawdown. △ Breakage during blowing may occur. × Drawdown or tearing during blowing occurs. Injection moldability: Good surface appearance. × There is a slight undulation. Spin formability: Good without breaking yarn. × Thread breakage occurs frequently.

Reference Example 1 A flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer and a dropping funnel was charged with 665 parts of toluene, and heated to 90 ° C. while gently flowing nitrogen gas. There, 512 parts of styrene, 2
A mixture consisting of 128 parts of isopropenyl-2-oxazoline and 25 parts of perbutyl O (manufactured by NOF Corporation) was added dropwise over 2 hours. Further, the mixture was stirred at 90 ° C. for 6 hours to complete the reaction, and then cooled to room temperature to obtain a resin solution. Next, the obtained resin solution was transferred to a rotary evaporator, and toluene was distilled off at a predetermined temperature and pressure, and then the residue was pulverized to obtain an oxazoline group-containing polymer (B-1a). The presence of the oxazoline group in the polymer (B-1a) was confirmed by IR spectrum
It was confirmed by characteristic absorption at 655 cm ^-1 .

The resulting oxazoline group-containing polymer (B-
When the number average molecular weight of 1a) was measured by GPC, 6
000. Reference Example 2 An epoxy group-containing polymer (B-1b) was carried out in the same manner as in Reference Example 1, except that the 2-isopropenyl-2-oxazoline was changed to glycidyl methacrylate.
I got The presence of an epoxy group in the polymer (B-1b) was confirmed by IR spectrum having characteristic absorption at 910 cm ^-1 .

The obtained epoxy group-containing polymer (B-1)
When the number average molecular weight of b) was measured by GPC, it was found to be 60
00. [Examples 1 to 4, Comparative Examples 1 to 5] Thermoplastic polyester resin PET-1 (manufactured by Kanebo, trade name: Pervet PBK-
1), oxazoline group-containing polymer (B-1a), epoxy group-containing polymer (B-1b), 1,3-phenylenebisoxazoline (hereinafter sometimes abbreviated as Ox compound),
At least one compound selected from bisphenol F-type glycidyl ether (hereinafter may be abbreviated as Ep compound) and pyromellitic dianhydride (hereinafter may be abbreviated as PMDA) may be mixed in a proportion shown in Table 1 ( (Parts by weight) into a twin-screw extruder, melt-kneaded, cooled, and prepared with a Starland cutter to prepare resin composition pellets. Table 1 shows the results of measuring the IV of the pellets obtained by melt-kneading.

In Examples 1 to 4 and Comparative Examples 1 to 4, using the obtained resin composition pellets, a blow molding machine (S-45ND, manufactured by Placo Co., Ltd.) was used to form a die (die diameter: 50 mm, die interval). 3mm) temperature 270 ° C, mold temperature 80 ° C, blowing pressure 5kg / cm ² , average thickness 2.5
A cylindrical hollow container having a diameter of 500 mm and a capacity of 500 cc was molded, and the blow moldability was evaluated. Table 1 shows the evaluation results.

Further, Examples 3 and 4 and Comparative Examples 1 to 4
In the above, the obtained resin composition pellets are injected into an injection molding machine (SG25-HIPRO MI, manufactured by Sumitomo Heavy Industries, Ltd.).
1), nozzle temperature 280 ° C, barrel temperature 280
The composition was molded at 70 ° C. and a filling pressure of 70%, and injection moldability was evaluated. Table 1 shows the evaluation results. The bisphenol F-type glycidyl ether used in Comparative Example 5 had a molecular weight of 1000.
And is produced without going through a so-called polymerization reaction in the production process, and does not fall under the polymer (B-1) according to the present invention.

[0045]

[Table 1]

Examples 5-8, Comparative Examples 6-10 Thermoplastic polyester resin PET-1 (manufactured by Kanebo, trade name: Pervet PBK-1), oxazoline group-containing polymer (B-
1a), an epoxy group-containing polymer (B-1b), 1,3-
In phenylene bisoxazoline (hereinafter sometimes abbreviated as Ox compound), bisphenol F glycidyl ether (hereinafter sometimes abbreviated as Ep compound), and pyromellitic dianhydride (hereinafter sometimes abbreviated as PMDA) And talc as a foaming nucleating agent are mixed in a tumbler at a blending ratio (parts by weight) shown in Table 2, and then put into an extruder hopper and melt-mixed, and 4 parts by weight of a foaming agent (Isopentane) was injected into the molten mixture from the middle of the extruder, extruded and foamed into a rod shape from a nozzle mold into the atmosphere, and cooled to form a foam. The set temperature of each part of the extruder is as follows: supply section: 268 to 280 ° C, compression section: 2
The temperature was adjusted within a range of 85 to 290 ° C, a melting portion: 274 to 283 ° C, a head portion: 280 to 290 ° C, and a mold: 265 to 270 ° C. The foam moldability of the obtained molded body was evaluated. Table 2 shows the evaluation results.

The bisphenol F type glycidyl ether used in Comparative Example 10 has a molecular weight of less than 1000, is produced without undergoing a so-called polymerization reaction in the production process, and is added to the polymer (B-1) according to the present invention. Is not applicable.

[0048]

[Table 2]

[Examples 9 to 12, Comparative Examples 11 to 15] Thermoplastic polyester resin PET-2 (PET pellets recovered from PET film shavings), oxazoline group-containing polymer (B-1a), epoxy group-containing polymer Coalescing (B-1
b) 1,3-phenylenebisoxazoline (hereinafter referred to as O
x compound), bisphenol F type epoxy resin (hereinafter sometimes abbreviated as Ep compound), and pyromellitic dianhydride (hereinafter sometimes abbreviated as PMDA). Was fed into a vented twin-screw extruder at the compounding ratio (parts by weight) shown in Table 3, and was melted at a barrel temperature of 280 ° C. Using the melt after the melt extrusion, melt spinning was performed by a conventional method, and the film was wound at a nozzle temperature of 280 ° C. and a winding speed of 5000 m / min. Further, the melt before spinning was taken out and the IV was measured. The results are shown in Table 3, and the evaluation results of spinnability are also shown in Table 3.

The bisphenol F type glycidyl ether used in Comparative Example 15 has a molecular weight of less than 1000, is produced without undergoing a so-called polymerization reaction in the production process, and is added to the polymer (B-1) according to the present invention. Is not applicable.

[0051]

[Table 3]

[0052]

According to the present invention, it is possible to provide a thermoplastic polyester resin composition having not only excellent mechanical properties and durability but also sufficiently excellent moldability. In particular, the thermoplastic polyester resin composition of the present invention has a high molecular weight and IV, and can also impart strength such as toughness. Specifically, the resin exhibits good moldability without drawdown of the resin during extrusion molding or blow molding, and a uniform fine foam can be obtained during foam molding. Further, since the resin is provided with toughness and toughness, the molded article is less likely to be broken during blow molding. In spin molding, the problem of yarn breakage is less likely to occur.

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Claims (6)

[Claims] 1. A thermoplastic polyester resin composition containing a thermoplastic polyester resin as an essential component, in an amount of 0.1 to 0.1 parts by weight of the thermoplastic polyester resin (A).
Polymer having a carboxylic acid-reactive group of 10 to 10 parts by weight (B
-1) and / or a compound (B-2) having a plurality of oxazoline groups in a molecule, and 0.01 to 5 parts by weight of a carboxylic anhydride (C), Thermoplastic polyester resin composition. 2. 100 parts by weight of a thermoplastic polyester resin (A), a polymer (B-1) having a carboxylic acid-reactive group and / or a compound (B-2) having a plurality of oxazoline groups in a molecule. A thermoplastic polyester resin composition obtained by melt-kneading 1 to 10 parts by weight and 0.01 to 5 parts by weight of a carboxylic anhydride (C). 3. The thermoplastic polyester resin composition according to claim 1, wherein the carboxylic acid-reactive group in the polymer (B-1) is an oxazoline group and / or an epoxy group. 4. The polymer (B-1) has a number average molecular weight of 1
The thermoplastic polyester resin composition according to any one of claims 1 to 3, which is in a range of 000 to 20,000. 5. A method for producing a molded article using a thermoplastic polyester resin as a material, wherein molding is performed using the thermoplastic polyester resin composition according to any one of claims 1 to 4. A method for producing a thermoplastic polyester resin molded article. 6. The method for producing a thermoplastic polyester resin molded article according to claim 5, wherein said molding is at least one selected from extrusion molding, injection molding, blow molding, foam molding, and spinning molding.