JP2002037989A - Heat resistant thermoplastic polyester-based resin composition and usage in molding of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic polyester-based resin molding not only whose shock resistance, which is a disadvantageous point of thermoplastic polyester resins, but also heat resistance and hot-water resistance have been improved, and to recycle a used material of the thermoplastic polyester-based resin molding. SOLUTION: The molding is formed from a thermoplastic polyester-based resin composition comprising a thermoplastic polyester resin (A), polymer particles (B) having multilayered structure with a hard layer on the outermost layer and a rubbery layer in the inner part, and an alkali metal salt (C) of an ethylenic copolymer having carboxyl groups.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic polyester resin composition having excellent heat resistance, hot water resistance and impact resistance.

[0002]

2. Description of the Related Art Thermoplastic polyester resin represented by polyethylene terephthalate has mechanical strength, heat resistance,
Due to its excellent properties such as electrical properties and moldability, it is widely accepted by consumers and is mass-produced industrially. This has been pointed out as a disadvantage.
Attempts have been made to add various impact modifiers in order to improve the disadvantages of such thermoplastic polyester resins. For example, a method of blending a multilayer structure polymer (Japanese Patent Publication No. 60-3101) Gazette). Also, a method for imparting transparency by blending a double-layered polymer particle having a specific inner core rubber layer and an outer shell resin layer composed of radically polymerizable monomer units (Japanese Patent Laid-Open No. 10-10 / 1998)
No. 1917) is also disclosed.

[0003] The thermoplastic polyester resin having improved impact resistance in this way can be applied to everyday miscellaneous goods such as shopping baskets, combs, fan patterns, and is used at relatively high temperatures. It is expected to be applied to containers such as electric parts such as electric motor covers, hot water drain receptacles and tableware bases. However, simply adding the above-mentioned impact resistance improver causes a problem that the heat-resistant temperature of the obtained molded article is low, or the molded article is deformed in warm water and the aesthetic appearance is impaired. At present, it is limited.

On the other hand, polyethylene terephthalate (PE)
T) thermoplastic polyester resin molded products represented by
Especially as the consumption of PET bottles continues to increase,
The treatment after use of the molded article has become a social problem. In view of such a current situation, it is extremely important that the plastic molded article should be recyclable as a property to be provided. However, conventional plastic molded articles are generally treated by being incinerated or buried in landfills, and it is difficult to say that they meet social needs as described above. When a used thermoplastic polyester resin molded article such as a PET bottle is treated and reused, impact resistance is significantly reduced due to a decrease in molecular weight and the like. After melt-spinning to fibers, wadding,
They are used only as textiles such as carpets, and as a result, the amount of reuse is much smaller than the amount of waste of the molded article. Therefore, if impact resistance can be imparted to the thermoplastic polyester resin, it can be an effective factor for reducing the amount of waste plastic waste.

Against this background, there has been disclosed, for example, a thermoplastic polyester resin composition obtained by melt-mixing a pulverized product of the resin molded article and polymer particles having a multilayer structure (JP-A-11-60922). No.). Since the composition improves the impact resistance, it can be said that the composition is an effective technique especially in the reuse of waste plastics, but the composition is still sufficient in heat resistance and hot water resistance. Absent. Therefore, the development of a thermoplastic polyester resin composition having all of impact resistance, heat resistance and hot water resistance not only promotes the expansion of its use but also extremely reduces the amount of waste plastic by recycling. It is significant.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is not only to improve the impact resistance, which is a drawback of the thermoplastic polyester resin, but also to improve the heat resistance and hot water resistance, and to improve the appearance. An object of the present invention is to provide a polyester resin molded article, and thereby contribute to effective use of a used thermoplastic polyester resin molded article.

[0007]

Means for Solving the Problems In order to solve the above problems, the present inventors have conducted intensive studies and as a result, have obtained a pulverized thermoplastic polyester resin or a molded product thereof, a hard layer as an outermost layer and a rubber layer. It was surprisingly found that the compounding of the multi-layered polymer particles and the specific ionomer contained therein resulted in a thermoplastic polyester resin molded article having not only excellent impact resistance but also excellent heat resistance and hot water resistance. The invention has been completed.

That is, the present invention relates to a thermoplastic polyester resin (A), a multilayer polymer particle (B) having a hard layer as an outermost layer and a rubber layer inside, and an ethylene copolymer having a carboxyl group. The present invention relates to a thermoplastic polyester resin composition containing an alkali metal salt (C). The present invention also provides a part of the thermoplastic polyester resin (A), a multilayer polymer particle (B) having a hard layer as the outermost layer and a rubber layer inside, and an ethylene copolymer having a carboxyl group. Is mixed under melting conditions to obtain a masterbatch (D), and the masterbatch and the remainder of the thermoplastic polyester resin (A) are mixed under melting conditions to form the thermoplastic polyester-based resin. It relates to a resin composition. Furthermore, the present invention relates to the thermoplastic polyester resin composition, wherein ΔH _H / ΔH _C is 0.25 or less. The present invention also relates to the thermoplastic polyester resin composition, wherein the thermoplastic polyester resin (A) is a polyethylene terephthalate resin. Further, the present invention relates to the thermoplastic polyester resin composition, wherein the thermoplastic polyester resin (A) is a pulverized product of a molded article made of a polyethylene terephthalate resin. Furthermore, the present invention relates to a molding material comprising the thermoplastic polyester resin composition. The present invention also relates to a molded article comprising the thermoplastic polyester resin composition.

[0009]

Embodiments of the present invention will be described below. The thermoplastic polyester resin (A) in the present invention is not necessarily limited.
It is a polyester mainly composed of one or more dicarboxylic acid units and one or more diol units. Examples of the dicarboxylic acid unit include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid,
1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracenedicarboxylic acid, 4,
Aromatic dicarboxylic acids such as 4'-diphenyl ether dicarboxylic acid and sodium 5-sulfoisophthalate; aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid and dodecandioic acid; 1,3-cyclohexanedicarboxylic acid; Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; and dicarboxylic acid units derived from ester-forming derivatives thereof (lower alkyl esters such as methyl ester and ethyl ester). Examples of the above-mentioned diol unit include those having 2 to 1 carbon atoms such as ethylene glycol, propylene glycol, neopentyl glycol, 2-methylpropanediol, 1,5-pentanediol, cyclohexanedimethanol, and cyclohexanediol.
0 aliphatic diol; molecular weight of 600 such as diethylene glycol, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, etc.
A diol unit derived from a polyalkylene glycol having 0 or less can be exemplified. The thermoplastic polyester resin (A) has a small proportion (for example, 1% based on the total structural units) in addition to the dicarboxylic acid units and the diol units.
(Mole% or less), for example, it may have one or more structural units derived from trifunctional or higher functional monomers such as glycerin, trimethylolpropane, pentaerythritol, trimellitic acid, and pyromellitic acid.

Therefore, the thermoplastic polyester resin (A) includes polyethylene terephthalate (PE)
T), a copolyester containing a small amount of a copolymer component with ethylene terephthalate as a main repeating unit, polycyclohexyl dimethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate and the like are included, and generally, PET and ethylene terephthalate are mainly used as a main repeating unit. Ethylene terephthalate-based polyesters such as copolyesters containing a small amount of a copolymer component as a unit are preferred. Representative examples of the PET-based resin may be a so-called homopolymer composed of only a terephthalic acid unit and an ethylene glycol unit, or a so-called copolymer having a copolymer component. The thermoplastic polyester-based resin (A) constituting the thermoplastic polyester-based resin composition of the present invention has a chemical structure of 2 types even if only one type is used.
There may be more than one species.

In the present invention, as a molded article which gives a pulverized product of a molded article made of a thermoplastic polyester resin, P
ET bottles are typical, but not limiting. The molded article may be used, but is not limited thereto.
Burrs generated in the manufacturing process of ET bottles and PET films,
Ears, defective products, etc. can also be targeted.

The molded article made of the thermoplastic polyester resin is pulverized or pulverized into a pulverized product. The means may be any of various known means, and is not particularly limited. In addition, since waste products made of thermoplastic polyester resin obtained by scrap, such as PET bottles and PET containers, are generally collected together with containers made of other materials, if necessary, use X-rays or the like. It is preferable to remove the container made of another material using. The separated and recovered thermoplastic polyester resin molded product is washed with alkaline water or the like as necessary, then crushed or crushed by a method such as wet crushing, and further, if necessary, metal, other resin or the like. By subjecting the impurities to post-treatment and / or drying,
A predetermined pulverized product can be obtained.

The shape of the pulverized product of the molded article made of the thermoplastic polyester resin to be used is not necessarily limited, but a flake shape is generally used. The average particle size of the flake-like pulverized product is preferably 1 to 50 mm,
-20 mm is more preferable. The average thickness is preferably 50 to 2000 μm, and 100 to 700 μm.
m is more preferred. Moreover, you may use what was pelletized after grinding | pulverization.

The multilayer polymer particles (B) used in the present invention are characterized in that they have a hard layer as the outermost layer and a rubber layer inside. The rubber layer referred to here is a polymer layer having a glass transition temperature (hereinafter, referred to as Tg) of 25 ° C. or lower, and the hard layer is a polymer layer having a Tg higher than 25 ° C.

The multilayer polymer particles (B) used in the present invention generally have a layer structure called a core / shell, that is, an inner layer / outer layer structure in which an inner layer is covered by an outer layer. It may be composed of two or three layers, or may be composed of four or more layers. In the case of a two-layer structure, it has a rubber layer (center layer) / hard layer (outermost layer) structure, and in the case of a three-layer structure, a hard layer (center layer) / rubber layer (intermediate layer) / hard layer (most layer). Outer layer), rubber layer (center layer) / rubber layer (middle layer) /
It has a hard layer (outermost layer) or a rubber layer (center layer) / hard layer (intermediate layer) / hard layer (outermost layer). In the case of a four-layer structure, for example, a rubber layer (center layer) / hard layer Layer (middle layer)
/ Rubber layer (intermediate layer) / hard layer (outermost layer).

The multi-layered polymer particles (B) used in the present invention have a mode in which the inner layer is partially enveloped by the outer layer, and include minute voids (micro voids, voids, cavities) in the inner layer or in the particles. ), One or more microvoids in the inner layer or in the particles, and the voids have one or more passages connecting to the space outside the particles. . In addition, the term “particle” used in the present invention completely includes the concept generally used in polymer chemistry.

The composition of the rubber layer of the multilayer polymer particles (B) is not particularly limited. Examples of preferred polymers for constituting the rubber layer include polybutadiene, polyisoprene, butadiene-isoprene copolymer, polychloroprene, and the like. Conjugated diene polymers such as styrene-butadiene copolymer, acrylonitrile-isoprene copolymer, styrene-isoprene copolymer, acrylate-butadiene copolymer, and acrylate-isoprene copolymer; Hydrogenated polymers; olefin rubbers such as ethylene-propylene copolymers; acrylic rubbers such as polyacrylates; polyorganosiloxanes; thermoplastic elastomers; ethylene ionomer copolymers; One or two
Used in more than species. Among them, an acrylic rubber, a conjugated diene polymer or a hydrogenated product of a conjugated diene polymer is preferable.

Examples of the acrylate used in the polymerization for forming the acrylic rubber include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate and the like. And acrylic acid alkyl esters. Among them, butyl acrylate or 2-ethylhexyl acrylate is preferred.

In the polymerization of a monomer system mainly composed of an acrylate ester and / or a conjugated diene compound for producing the above-mentioned acrylic rubber or the above-mentioned conjugated diene polymer, if necessary, In addition to the components, other monofunctional polymerizable monomers can be copolymerized. Other monomers that can be copolymerized include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, Methacrylates such as decyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, benzyl methacrylate, naphthyl methacrylate and isobornyl methacrylate; styrene, α
Aromatic vinyl compounds such as -methylstyrene; acrylonitrile; The amount of these monofunctional polymerizable monomers is desirably 20% by weight or less of the entire polymerizable monomers forming the rubber layer.

The rubber layer constituting a part of the multilayer polymer particles (B) used in the present invention preferably has a crosslinked molecular chain structure for exhibiting rubber elasticity. It is preferable that the molecular chains of the layer and the molecular chains in the layer adjacent thereto are grafted by a chemical bond. For that purpose, in the polymerization of the monomer system for forming the rubber layer, it may be desirable to use a small amount of a polyfunctional polymerizable monomer as a crosslinking agent or a grafting agent. The polyfunctional polymerizable monomer is a monomer having two or more carbon-carbon double bonds in the molecule, for example, unsaturated carboxylic acid such as acrylic acid, methacrylic acid, cinnamic acid and allyl. Esters with alcohols, unsaturated alcohols such as methallyl alcohol or glycols such as ethylene glycol and butanediol; phthalic acid, terephthalic acid,
Examples include esters of dicarboxylic acids such as isophthalic acid and maleic acid with the above-mentioned unsaturated alcohols. Specific examples include allyl acrylate, methallyl acrylate, allyl methacrylate, methacrylic methallyl, allyl cinnamate, and cinnamic acid. Examples include methallyl, diallyl maleate, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, divinylbenzene, ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, and hexanediol di (meth) acrylate.
The term "di (meth) acrylate" means a general term for "diacrylate" and "dimethacrylate". The polyfunctional polymerizable monomers may be used alone or in combination of two or more. Among them, allyl methacrylate and hexanediol diacrylate are preferably used.

However, if the amount of the polyfunctional polymerizable monomer is too large, the performance as a rubber is reduced, and the thermoplastic polyester resin obtained by using the multilayer structure polymer particles in that case is obtained. Since the impact resistance of the composition is reduced, the amount of the polyfunctional polymerizable monomer used is preferably limited to 10% by weight or less of the entire polymerizable monomer forming the rubber layer. When a monomer system containing a conjugated diene-based compound as a main component is used, since it functions as a crosslinking point or a grafting point, it is not always necessary to use a polyfunctional polymerizable monomer. .

In the present invention, the multilayer polymer particles (B)
Examples of the polymerizable monomer that can be used to form the hard layer include, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate , Cyclohexyl methacrylate, octyl methacrylate, decyl methacrylate,
Methacrylic acid esters such as dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, benzyl methacrylate, naphthyl methacrylate, and isobornyl methacrylate; aromatic vinyl compounds such as styrene and α-methylstyrene; and acrylonitrile. Among these polymerizable monomers, it is preferable to use methyl methacrylate or styrene alone or in the form of a combination of two or more radical polymerizable monomers containing one of them as a main component.

The content of the rubber layer in the multilayer polymer particles (B) is preferably in the range of 20 to 95% by weight, more preferably in the range of 50 to 90% by weight. If the amount of the polymer portion forming the rubber layer is too small, the flexibility is insufficient, and the effect of improving the impact resistance when a thermoplastic resin composition is formed tends to be low. On the other hand, if the amount of the hard polymer portion forming the outermost layer is too small, the handling property of the multilayer polymer particles (B) tends to decrease.

In the present invention, the particle diameter of the multilayer polymer particles (B) is not particularly limited.
μm, preferably 0.05 to 0.5
More preferably, it is within the range of μm. If the particle size is too small, the handling properties of the multilayer polymer particles tend to decrease, while if it is too large, the effect of improving the impact resistance of the thermoplastic polyester resin composition tends to decrease. In addition, the multilayer structured polymer particles (B) are contained in the obtained thermoplastic polyester resin molded product in an amount of from 0.03 to 1%.
It is preferable that the particles are dispersed at an average particle interval in the range of μm, since impact resistance becomes particularly good.

The polymerization method for producing the multi-layered polymer particles (B) used in the present invention is not particularly limited. For example, the spherical multi-layered polymer particles can be obtained by a conventional emulsion polymerization. Can be easily obtained. In the emulsion polymerization method, a chain transfer agent such as octyl mercaptan or lauryl mercaptan can be used as necessary according to a known method. After the emulsion polymerization, the multi-layered polymer particles can be separated and obtained from the polymer latex according to a known method, for example, by coagulation and drying.

The coagulation form of the multi-layer polymer particles (B) is not particularly limited. For example, the coagulation form may be in the form of pellets fused to each other at the outermost layer.
It may be in the form of a powder or a granule.

In the present invention, the amount of the multilayer polymer particles (B) is 2 to 50 based on 100 parts by weight of the total of the thermoplastic polyester resin (A) and the multilayer polymer particles (B).
It is preferable that the amount be in the range of 3 parts by weight, more preferably 3 to 40 parts by weight, from the viewpoint of improving impact resistance.

The carboxyl group-containing ethylene copolymer referred to in the present invention is a thermoplastic polymer having a small amount of carboxyl group in the side chain, terminal or main chain of a hydrophobic polymer main chain. As the alkali metal salt of the ethylene-based copolymer having a carboxyl group used in the present invention,
Any substance having a nucleating effect on the polyester resin and promoting crystallization as a crystal nucleating agent may be used, but typically, a sodium salt or potassium salt of an ethylene-based copolymer having a carboxyl group is used. is there. The mechanism for improving the heat resistance of the heat-resistant thermoplastic polyester-based resin composition of the present invention by the alkali metal salt of the ethylene-based copolymer having a carboxyl group is not necessarily clear. It is considered that the crystallization of A) is promoted, and the obtained molded article has significantly improved heat resistance and hot water resistance while maintaining impact resistance. As a result, the molded article is less likely to be deformed and has an excellent appearance.

The component (C) used in the present invention is not particularly limited as long as it has a nucleating action as described above. For example, olefins such as ethylene, propylene, butylene, styrene and α-methylstyrene and acrylic acid , Methacrylic acid, sodium or potassium salts of copolymers with unsaturated carboxylic acids such as maleic acid,
An alkali metal salt of an ethylene copolymer having a carboxyl group can be mentioned, and a sodium salt of a copolymer of ethylene and acrylic acid is particularly preferably used. The amount thereof, the thermoplastic polyester resin composition △ H _H
/ ΔH _C is an amount that is 0.25 or less. The thermoplastic polyethylene-based resin composition of the present invention has its ΔH _H / ΔH _C
Is 0.25 or less, the heat distortion temperature is high and the warm water resistance effect is large. In the present invention, ΔH _H / ΔH
_C is a value obtained by measuring the thermoplastic polyester composition with a differential scanning calorimeter (DSC-50) manufactured by Shimadzu Corporation.
Exotherm between 95 and 150 ° C. during heating at 0 ° C./min (／
H _H ) and 18 upon cooling from 290 ° C. at 10 ° C./min.
0-270 is a value determined by a separate heating (△ _{H C)} between ° C.. Crystallization is promoted with an increase in the amount of the alkali metal salt (C) of an ethylene-based copolymer having a carboxyl group. Excessive mixing not only reduces the effect of promoting crystallization, but also increases mechanical effect. It is not preferable because strength and heat resistance may decrease. Generally, the compounding amount of the component (C) is 0.05 to 8 parts by weight, preferably 0.1 to 5 parts by weight, more preferably 0 to 5 parts by weight based on 100 parts by weight of the thermoplastic polyester resin (A). 0.2 to 3 parts by weight. Further, the acid value of the ethylene-based copolymer containing a carboxyl group is preferably in the range of 30 to 200 mgKOH / g, and the content of the alkali metal ion is in the range of 0 to 50 mgKOH / g. It is preferable that the amount is within.

In the present invention, the component (C) is added to (1) a dry blend of the thermoplastic polyester resin (A) and the multi-layered polymer particles (B) and melt-kneaded, or (2) It is blended as a master batch (D) which is added to a part of the dry blend of the polymer particles (B) and the thermoplastic polyester resin (A) and melt-kneaded. The method of melt-mixing the dry blend is not particularly limited, and a known method generally used for melt-mixing resins can be applied. As a melt kneading device at that time, a heating roll machine,
A heating kneader, a screw type extruder (extruder) or the like can be used. For example, the pulverized product of the thermoplastic polyester resin (A), the multilayer polymer particles (B) and the component (C) are melted at a temperature of, for example, 240 to 300 ° C. using a screw extruder or the like. Can be kneaded.

In the present invention, the master batch (D) 10
The amount of the multilayer polymer particles (B) contained in 0 parts by weight is as follows:
Preferably 15 to 85 parts by weight, particularly preferably 20 to 8 parts by weight.
0 parts by weight, and the multi-layer polymer contained in the thermoplastic polyester resin composition obtained by mixing the master batch (D) and the remainder of the thermoplastic polyester resin (A) under melting conditions. The amount of the particles (B) is preferably in the range of 2 to 50 parts by weight, particularly preferably 3 to 40 parts by weight, from the viewpoint of improving impact resistance.

In the present invention, the thermoplastic polyester resin composition may contain a pigment, an antiblocking agent, a stabilizer, an antistatic agent, a plasticizer, and the like, if desired. Examples of the stabilizer include an antioxidant, a heat stabilizer, and an ultraviolet absorber. As the antioxidant or the heat stabilizer, for example, one or more of phenols, hydroquinones, phosphates and the like can be used. Further, as an ultraviolet absorber, for example,
One or more of various substituted resorcinols, salicylates, benzotriazoles, benzophenones and the like can be used. These additives are added at the time of molding, but can also be added using a known method such as a direct blending method or a master batch method.

The molding material comprising the thermoplastic polyester resin composition of the present invention is formed into a strand at a temperature of, for example, 240 to 300 ° C. by using a general screw type extruder or the like. It can be manufactured by extruding and cutting. The production of the molding material may be carried out simultaneously with the melt-kneading of the components (A) to (C).

In the present invention, in order to produce a molded article comprising the thermoplastic polyester resin composition, injection molding, extrusion molding, compression molding, blow molding, calender molding, cast molding, etc., which are generally used for molding a resin, are used. Any of the molding methods described above can be used. For example, a molded article having a desired shape and dimensions can be obtained at a temperature of 240 to 300 ° C.

[0035]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples. In Examples and Comparative Examples, various physical properties were evaluated or measured as follows. (1) Evaluation of heat resistance (measurement of deflection temperature under load (HDT)) The evaluation of heat resistance was performed on a test piece prepared according to ASTM D648 under a load of 1.8 MPa. (2) Measurement of Impact Strength (Izod) of Molded Product The impact strength of a molded product was measured by using a notching cutter (R = 2.5 cut blown) on a test piece prepared according to ASTM D256.
The measurement was performed at room temperature (23 ° C.). _{(3) △ H H / △} H Measurement of △ _{H H} / △ _{H C} of _C is a differential scanning calorimeter (manufactured by Shimadzu Corporation: DSC-50) used, _{N 2} atmosphere, 10
Calorific value between 95 and 150 ° C when the temperature is raised at ° C / min (△
H _H ) and 180 upon cooling at 290 ° C. at 10 ° C./min.
It was determined by another calorific value (比 H _C ) ratio between ２270 ° C. (4) Evaluation of hot water resistance The hot water resistance of a molded product was determined by immersing a test piece prepared according to ASTM D638 vertically in hot water at 75 ° C.
The subsequent change in shape was visually observed and evaluated according to the following criteria. :: The molded product is not deformed and retains its shape before immersion. Δ: The molded product was slightly bent, and did not maintain the shape before immersion. ×: The molded article was significantly deformed and did not maintain the shape before immersion.

The polyethylene terephthalate-based resin (A), the pulverized product of the polyethylene terephthalate-based resin, and the multilayer polymer particles (B) used in the following Examples and Comparative Examples are described in Examples 1 to 3. 3, and their physical properties were measured as in the following (5) to (7). (5) Measurement of intrinsic viscosity of polyethylene terephthalate The intrinsic viscosity of a pulverized product of a PET resin and a PET resin is determined by dissolving a polymer in o-chlorophenol, and measuring the viscosity at 25 ° C. It was measured using "Iwamoto Seisakusho's" automatic capillary viscometer "). (6) Measurement of Particle Diameter of Multilayer Structure Polymer The particle diameter of the multilayer structure polymer particles (B) in the latex was measured by a light scattering photometer (manufactured by Otsuka Electronics Co., Ltd .: DLS).
-600). (7) Glass transition temperature of multilayer structure polymer particles The glass transition temperature of the multilayer structure polymer particles (B) is DSC
(Shimadzu Corporation: DSC-50) was used, and the measurement was performed under a N ₂ atmosphere under the condition of a heating rate of 10 ° C./min.

Reference Example 1 (Production Example of PET Resin (A)) In a stainless steel preparation tank, 20.8 parts by weight of terephthalic acid, 8.0 parts by weight of ethylene glycol, 0.0027 parts by weight of germanium dioxide, and 0.1 part of phosphorous acid were added. 0023 parts by weight were charged to prepare a monomer mixture solution (I). Heaters, rectification towers,
The monomer mixed solution was supplied to a reaction layer equipped with a thermometer and a stirrer under a nitrogen atmosphere of 0.25 MPa at a supply rate of 0.43% by weight / minute such that the reaction tank liquid temperature was 250 ° C. After completion of the preparation, the liquid temperature of the reaction tank was further increased to 250 hours for 4 hours.
C. to produce a low polymer. Thereafter, the low polymer was transferred to a polymerization tank equipped with a heater, a vacuum pump, a condenser, a thermometer, and a stirrer, and 1.3 KPa, 280 ° C.
The polymerization was carried out for 3 hours under the conditions described above, and the obtained molten polymer was extruded into strands, cooled with water, and cut with a cutter to obtain pellets. The pellet was dried and crystallized at 200 ° C. for 5 hours, and then dried at 200 ° C. for 24 hours.
Polymerization was promoted for a period of time to obtain polyethylene terephthalate. The intrinsic viscosity of the obtained pellet is 0.1.
It was 75 dl / g.

Reference Example 2 (Example of manufacturing pulverized product of molded article made of PET resin) PE for beverages and the like used and sorted and recovered by general consumers
From the used bottle group mainly composed of T bottles, other bottles were removed using X-rays. Next, after washing the obtained PET bottle group with a weak alkaline aqueous solution and water,
It was attached to a wet grinder. Further, by utilizing the difference in specific gravity, a resin piece other than polyethylene terephthalate and a metal piece were separated to obtain a pulverized PET bottle. The shape of the pulverized product was a flake having an average diameter of 5.0 mm and an average thickness of 300 μm. The intrinsic viscosity of polyethylene terephthalate recovered in the form of a crushed product is 0.68 dl /
g.

Reference Example 3 (Production Example of Multilayer Polymer Particle (B)) 147 parts by weight of ion-exchanged water was charged into a polymerization tank made of glass lining equipped with a condenser, a thermometer, and a stirrer, and alkyldiphenyl ether disulfonic acid was added. Sodium 0.
015 parts by weight and 0.005 parts by weight of sodium carbonate were dissolved and heated to 80 ° C. while stirring. Separately, 88.74 parts by weight of butyl acrylate and 0.3 part of 1,6-hexanediol diacrylate were placed in a stainless steel container.
6 parts by weight and 0.90 parts by weight of allyl methacrylate were added to prepare a monomer mixture (I). After 5% by weight of the monomer mixture (I) was added to the reaction vessel at a time, 0.09 part by weight of potassium persulfate was added as a polymerization initiator to initiate polymerization. Simultaneously with this operation, 0.43 parts by weight of sodium dioctyl sulfosuccinate was dissolved in the remaining 95% by weight of the monomer mixture (I), and the emulsifier-dissolved monomer mixture (I) was dissolved.
I) was prepared. Thirty minutes after the addition of potassium persulfate, the emulsifier-dissolved monomer mixture (II) was continuously supplied at a supply rate of 1.1% by weight / minute to carry out polymerization. When the supply of the emulsifier-dissolved monomer mixture (II) is completed, the mixture is stirred at 80 ° C.
For 60 minutes, and after adding 0.01 parts by weight of potassium persulfate, dissolution of an emulsifier comprising 9.50 parts by weight of methyl methacrylate, 0.50 parts by weight of methyl acrylate, and 0.05 parts by weight of sodium dioctylsulfosuccinate The monomer mixture (III) was continuously supplied at a supply rate of 5% by weight / minute to carry out polymerization. After the supply of the emulsifier-dissolved monomer mixture (III) was completed, the mixture was maintained at 80 ° C. for 60 minutes with stirring to complete the polymerization. The particle size of the latex thus obtained was 0.35 μm. The obtained latex was cooled at −30 ° C. for 12 hours to coagulate, then the coagulated product was taken out, washed with warm water of 40 ° C., dehydrated with a centrifugal dehydrator, and dried under reduced pressure and vibration at 50 ° C. for 12 hours. Thus, multilayer polymer particles (B) were obtained. The obtained multilayer polymer particles have an inner layer of an acrylic rubber (Tg = −54 ° C.) containing butyl acrylate as a main component and a polymethyl methacrylate (Tg = 105 ° C.) as a hard outermost layer. The particles had a core / shell type two-layer structure of 0.35 μm.

Examples 1 to 4 PET resin (A) produced according to Reference Example 1 and dried at 140 ° C. for 4 hours, multilayer polymer particles (B) produced according to Reference Example 3, and component (A) Sodium salt (C) of a copolymer of ethylene and acrylic acid (Ionomer, trade name: ALYN285) manufactured by Allied Signal Co., Ltd. was charged into a tumbler in an amount shown in Table 1 and mixed with 100 parts by weight. In each case, B and C were added by a direct kneading method. Each mixture was mixed with a twin screw extruder (L / D = 25, manufactured by Toyo Seiki Co., Ltd.).
After melt-kneading using a 2D25SW type (20 mmφ), the mixture was extruded into strands and cut to produce pellets of a thermoplastic polyester resin composition. After the obtained pellets were dried at 140 ° C. for 4 hours, the cylinder temperature was 280 ° C. and the resin temperature was 2 in an ASTM family mold using an N-70A type injection molding machine manufactured by Japan Steel Works, Ltd.
90-300 ° C, mold temperature 20 ° C, cycle time 35-
Injection molding was performed under the condition of 45 seconds. Examples 1 to 4 were obtained by changing the amounts of the components (B) and (C).
Were obtained.

Example 5 Multilayer-structured polymer particles (B) 5 produced in Reference Example 3
A sodium salt of a copolymer of ethylene and acrylic acid (C) is added to 0 parts by weight and 50 parts by weight of a PET resin (A) produced according to Reference Example 1 and dried at 140 ° C. for 4 hours.
(Allied Signal Ionomer Product Name: AC
(LYN285) 2.5 parts by weight were charged into a tumbler and mixed. The dried mixture is melt-kneaded using a twin screw extruder (L / D = 252D25SW type, 20 mmφ) manufactured by Toyo Seiki Co., Ltd., extruded into strands and cut to produce pellets of master batch (D). did. 20.5 parts by weight of the master batch (D) and 90 parts by weight of the pulverized PET resin were put into a tumbler, mixed, and dried at 140 ° C. for 4 hours. A test piece was prepared from the obtained mixture by injection molding in the same manner as in Examples 1 to 4.

Example 6 Injection molding was performed in the same manner as in Example 1 except that a pulverized product (recycled PET flake) of a molded article made of the resin was used as the PET resin and the amount shown in Table 1 was added. Each test piece was prepared.

Comparative Example 1 Each test piece was prepared by injection molding in the same manner as in Example 1 except that the component (C) was not added. Comparative Example 2 Example 1 except that the multilayer structure particles (B) were not added.
Each test piece was produced by injection molding in the same manner as described above. Comparative Example 3 Each test was performed by injection molding in the same manner as in Example 1 except that a calcium salt of an ethylene-based copolymer having a carboxyl group (Ionomer trade name: ALYN201 manufactured by Allied Signal Co., Ltd.) was used as the component (C). A piece was prepared. Comparative Example 4 Each test piece was produced by injection molding in the same manner as in Example 1 except that talc was used as the component (C). .

The results are as shown in Table 1. That is, it has been revealed that the thermoplastic polyester resin composition according to the present invention is excellent not only in impact resistance but also in heat resistance and hot water resistance.

[0045]

[Table 1]

[0046]

According to the thermoplastic polyester resin composition of the present invention, not only a thermoplastic polyester resin molded article excellent in not only impact resistance but also heat resistance and hot water resistance is obtained, but also Since the plastic polyester resin molded article can be recycled, resources can be effectively reused.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C08L 51/04 C08L 51/04 (72) Inventor Takashi Yamashita 41 Miyukigaoka, Tsukuba-shi, Ibaraki Kuraray F-term (Ref.)

Claims (7)

[Claims] 1. A thermoplastic polyester resin (A), a multilayer polymer particle (B) having a hard layer as an outermost layer and a rubber layer inside, and an alkali metal salt of an ethylene copolymer having a carboxyl group ( A thermoplastic polyester resin composition containing (C). 2. A part of a thermoplastic polyester resin (A), a multilayered polymer particle (B) having a hard layer as an outermost layer and a rubber layer inside, and an alkali of an ethylene copolymer having a carboxyl group. Metal salt (C)
Is mixed under melting conditions to obtain a masterbatch (D), and the masterbatch and the remainder of the component (A) are mixed under melting conditions. . Wherein △ _{H H} / △ _{H C} is 0.25 or less,
The thermoplastic polyester resin composition according to claim 1 or 2. 4. The thermoplastic polyester resin composition according to claim 1, wherein the thermoplastic polyester resin (A) is a polyethylene terephthalate resin. 5. The thermoplastic polyester resin composition according to claim 1, wherein the thermoplastic polyester resin (A) is a pulverized product of a molded article made of a polyethylene terephthalate resin. 6. A molding material comprising the thermoplastic polyester resin composition according to claim 1. 7. A molded article comprising the thermoplastic polyester resin composition according to claim 1.