JPH1160922A - Thermoplastic polyester-based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition excellent in heat resistance, mechanical strength and impact resistance, and useful as a molding material or pallet by melt blending of a ground thermoplastic polyester resin molded product with specific multilayer-structured polymer particles. SOLUTION: This composition is obtained by melting 100 pts.wt. of a ground product (e.g. flaky ground product 1-50 mm in average size and 50-2,000 μm in average thickness) of a thermoplastic polyester resin molded product (e.g. PET bottles) followed by compounding the melt with 1-30 (pref. 2-30) pts.wt. of multilayer-structured polymer particles with a hard layer as the outermost layer (e.g. polymer layer >=25 deg.C in glass transition temperature) and a rubber layer inside (e.g. acrylic rubber polymer layer <=25 deg.C in glass transition temperature) (pref. 0.02-2 μm in size containing 20-95 wt.% of the rubber layer) and then conducting a melt blending at e.g. 240-300 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a thermoplastic polyester resin composition and its use.
More specifically, the present invention is obtained from a collected molded article made of a thermoplastic polyester resin, such as a bottle or cup made of polyethylene terephthalate used for a carbonated beverage bottle, a soy sauce container, a pudding container, and the like. The present invention relates to a thermoplastic resin composition containing a recycled polyester resin, a use of a molding material and a molded article made of the thermoplastic resin composition, and a method for producing a molded article containing the recycled polyester resin as a basic component. Since the thermoplastic resin composition of the present invention is excellent not only in mechanical strength and heat resistance but also in impact resistance, it is useful as a molding material for molded articles such as large pallets and containers.

[0002]

2. Description of the Related Art At present, polyethylene terephthalate (P)
ET) is a bottle made of thermoplastic polyester resin that matches the needs of consumers and is closely related to consumer life, and the production volume is enormous. Is in question. Generally, incineration and landfill disposal has been used as a method of treating used plastic molded products.However, these methods are not effective in reusing resources effectively. Recycling for reuse has become socially important.

[0003] As a method of recycling a thermoplastic polyester resin bottle that is no longer needed, there is a method of pulverizing and melt-spinning to a fiber, and using it as a fiber product such as cotton wadding or carpet. Since the amount is smaller than the enormous amount of discarded thermoplastic polyester resin bottles, expansion to other uses is desired.

[0004] On the other hand, in recent years, for applications such as product transportation and storage,
Pallets and containers made of synthetic resin, which are highly hygienic and easy to manufacture, are increasingly used. Many pallets and containers made of synthetic resin are injection-molded using polyolefins such as polyethylene and polypropylene as raw materials, and because of their high water resistance, they are mainly used as colarate, beer crate, and electronic component transport pallets. I have. However, in applications such as pallets and containers made of polyolefin, problems may occur due to the material. In other words, polyolefins have essentially low melting points and low flexural strength,
There is a problem when used in a container for bottles that are sterilized at a high temperature of about 80 ° C. or higher, or when used in a large pallet used for transporting or storing extremely heavy luggage.

[0005]

In view of the above situation, the present inventors utilize recycled polyester resin obtained from a collected thermoplastic polyester resin molded product such as a bottle as a molding material. However, since the recycled polyester resin has a remarkable decrease in impact resistance compared to a normal thermoplastic polyester resin that is not a recycled product,
It has been found that the use is limited. For example, recycled polyester resin has a higher melting point and higher flexural strength than polyolefin, but has a problem in using it as a molding material for containers and pallets due to low impact resistance. An object of the present invention is to provide a polymer material which utilizes a recycled polyester resin having excellent heat resistance and mechanical strength, and which has an improved impact resistance as a drawback. Another object of the present invention is to provide a molding material and a pallet in which the features are effectively exhibited. Another object of the present invention is to provide a method for producing a recycled polyester resin-based molded product that can exhibit this feature.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above problems, and as a result, by blending a specific component into a recycled polyester resin, its impact resistance has been improved. The present inventors have found that a thermoplastic polyester resin composition excellent in not only heat resistance and mechanical strength but also impact resistance can be obtained, and have reached the present invention.

That is, the present invention firstly provides a pulverized product (1) of a molded article made of a thermoplastic polyester resin and a multilayer polymer particle (2) having a hard layer as an outermost layer and a rubber layer inside. It is a thermoplastic resin composition mixed under melting conditions. Secondly, the present invention is a molding material comprising the thermoplastic resin composition. Thirdly, the present invention is a pallet made of the thermoplastic resin composition. Fourth, the present invention relates to a method for producing a recycled polyester resin-based molded article by molding the above-mentioned pulverized product (1) into a predetermined shape after melting the pulverized product (1). A method for producing a recycled polyester resin-based molded article, comprising blending polymer particles (2).

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
In the present invention, a molded article made of a thermoplastic polyester resin used in the form of the pulverized product (1) is typically a PET bottle, but is not limited thereto. As the molded article, used articles can be used. However, the article is not limited thereto, and burrs, ears, defective articles, and the like generated in the production process of PET bottles and PET films can be also used. Here, as an example of the above thermoplastic polyester resin, if a bottle is used, P
The main component is ET (homopolyester having ethylene terephthalate as a repeating unit), but the invention is not limited thereto. Copolyester containing ethylene terephthalate as a main repeating unit and containing a small amount of a copolymer component, polycyclohexyl dimethylene terephthalate, polyethylene na Phthalate may be used.

The molded article made of the thermoplastic polyester resin is pulverized or pulverized to obtain a pulverized product (1). The means may be any of various known means, and is not particularly limited.

[0010] Incidentally, waste molded articles 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. It is preferable to remove the container made of another material by a method such as X-ray. 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 impurities to separation and / or post-treatment for drying, a predetermined pulverized product (1) can be obtained.

In the melt mixing for producing the thermoplastic resin composition of the present invention, the shape of the pulverized material (1) to be used is not necessarily limited, but a flake shape is generally used. The average particle size of the flake pulverized material is preferably 1 to 50 mm, more preferably 3 to 20 mm. Further, the average thickness is preferably from 50 to 2000 μm, more preferably from 100 to 700 μm. In addition, pelletized material after pulverization may be used for melt mixing.

The multilayer polymer particles (2) used in the present invention are characterized by having 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 (2) 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)
/ Hard layer (outermost layer) or rubber layer (center layer) / hard layer (intermediate layer) / hard layer (outermost layer). In the case of a four-layer structure, for example, rubber layer (center layer) / It has a hard layer (intermediate layer) / rubber layer (intermediate layer) / hard layer (outermost layer) configuration.

However, the multilayer polymer particles (2) used in the present invention have a mode in which the inner layer is partially wrapped by the outer layer, or a micro void (micro void,
(Including voids and cavities), such as having one or more microvoids in the inner layer or particle and having one or more passages connecting the space outside the particles. Embodiments and the like are also included. In addition, the term “particle” used in the present invention completely includes the concept generally used in polymer chemistry.

The multilayer polymer particles (2) in the present invention
Although the composition of the rubber layer is not particularly limited, examples of preferred polymers for constituting the rubber layer include polybutadiene, polyisoprene, butadiene-isoprene copolymer, polychloroprene, styrene-butadiene copolymer, and acrylonitrile-isoprene copolymer. Conjugated diene-based polymers such as polymers, styrene-isoprene copolymers, acrylate-butadiene copolymers, acrylate-isoprene copolymers; hydrogenated conjugated diene-based polymers; ethylene-propylene copolymers Olefin rubbers such as polymers; acrylic rubbers such as polyacrylates; polyorganosiloxanes; thermoplastic elastomers; ethylene ionomer copolymers;
These are used alone or in combination of two or more. 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 above-mentioned 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-based 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 other monofunctional polymerizable monomers is 2% of the entire polymerizable monomers forming the rubber layer.
It is desirably 0% by weight or less.

The rubber layer constituting a part of the multilayer polymer particles (2) 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 is preferably used. However, if the amount of the polyfunctional polymerizable monomer is too large, the performance as a rubber is reduced, and, in that case, the thermoplastic polyester resin composition obtained using the multilayer polymer particles in that case. Since the impact resistance is reduced, the amount of the polyfunctional polymerizable monomer used is preferably limited to 10% by weight or less based on 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 itself functions as a crosslinking point or a grafting point, it is not always necessary to use a polyfunctional polymerizable monomer in combination. .

In the present invention, the polymer particles having a multilayer structure (2)
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 (2) is preferably in the range of 20 to 95% by weight, more preferably 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 in the case of using a thermoplastic resin composition is small. On the other hand, when the amount of the hard polymer portion forming the outermost layer is too small, the handleability of the multilayer polymer particles (2) is reduced.

In the present invention, the particle diameter of the multilayer polymer particles (2) is not particularly limited.
μm, preferably 0.05 to 0.5
More preferably, it is within the range of μm. If the particle diameter is too small, the handleability of the multilayer polymer particles is reduced, and if it is too large, the effect of improving the impact resistance of the thermoplastic resin composition is small.

The polymerization method for producing the multilayered polymer particles (2) used in the present invention is not particularly limited. For example, the spherical multilayered polymer particles can be prepared 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 form of the multilayer polymer particles (2) to be used in the melt mixing for producing the thermoplastic resin composition of the present invention is not particularly limited. It may be in the form of pellets fused at a portion, or in the form of powder or granules.

The amount of the multilayer polymer particles (2) used in the thermoplastic resin composition of the present invention is determined based on the impact resistance, heat resistance and mechanical strength of the pulverized product of the thermoplastic polyester resin. 1 for 100 parts by weight of (1)
It is preferable that the amount be in the range of 30 parts by weight. When high impact resistance is required, the content is preferably in the range of 2 to 30 parts by weight. However, if the amount of the multilayer polymer particles (2) used is too large, the resulting thermoplastic resin composition will have improved impact resistance or flexibility, but will have reduced elastic modulus and heat resistance. This is not preferred because the characteristics of the thermoplastic polyester resin may be impaired.

The thermoplastic resin composition of the present invention is a pulverized product (1) of a molded article comprising the above-mentioned thermoplastic polyester resin.
And the multilayer structure polymer particles (2) can be obtained by mixing under melting conditions together with other components, if desired. Pulverized product (1) and multi-layer polymer particles (2)
Is a method in which a predetermined amount of each is melt-mixed in one step together with other components, if desired, and a part of the pulverized product (1) and the multilayer polymer particles (2) are optionally mixed with other components. After obtaining a masterbatch by melt-mixing with the above, a method of melt-mixing the masterbatch and the remaining portion of the pulverized product (1) with other components, if desired, can be adopted. Among these, the latter two-stage method of melt-mixing is preferred because the dispersibility of the multilayer polymer particles (2) can be more easily improved and the effect of improving impact resistance can be more effectively exerted. The method for melt-mixing the pulverized product (1) and the multilayer structure polymer particles (2) is not particularly limited, and a known method usually used for melt-mixing resins may be applied. it can. As a melt-kneading device at that time, a heating roll machine, a heating kneader machine, a screw-type extruder (extruder) or the like can be used. For example, the pulverized product (1) and the multi-layered polymer particles (2) may be mixed with other additives, if desired, using a screw-type extruder or the like, for example, from 240 to
It can be melt-kneaded at a temperature of 300 ° C.

The thermoplastic resin composition of the present invention may contain a pigment, a flow regulator, an antiblocking agent, a stabilizer, benzoin, 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 sterically hindered phenols, hydroquinones, phosphates and the like can be used. Further, as the ultraviolet absorber, for example, various substituted resorcinol,
One or more of salicylate, benzotriazole, benzophenone and the like can be used. Also,
The thermoplastic resin composition of the present invention may be mixed with a small amount of a thermoplastic polyester resin that is not a recycled product. In addition, the use form of the above-mentioned optional additive at the time of melt mixing for producing the thermoplastic resin composition is not particularly limited, and the additive may be added as it is, May be added to a part of the thermoplastic resin composition at a high concentration to obtain a masterbatch, and the masterbatch of the additive may be blended with the remainder of the thermoplastic resin composition at any time such as during molding.

The impact resistance of the multilayer polymer particles (2) is particularly good when they are dispersed in the thermoplastic resin composition of the present invention with an average particle diameter in the range of 0.03 to 1 μm. It is preferable in that it becomes. In addition, some of the multilayer structure polymer particles in the resin composition may be agglomerated with each other.

The multilayer polymer particles (2) dispersed and distributed in the thermoplastic resin composition of the present invention may not be completely melted, but the composition as a whole has excellent melt fluidity. A molded article having a desired shape and dimensions can be obtained by any molding method such as injection molding, extrusion molding, compression molding, blow molding, calendar molding, and casting.

Although the thermoplastic resin composition of the present invention can be used as various molding materials, it weighs 1 kg because of its excellent impact resistance, mechanical strength and heat resistance.
As described above, the present invention is particularly useful as a molding material for large molded articles such as panels, pallets, truck side plates, and containers, preferably 5 kg or more.

[0030]

EXAMPLES Next, examples of the present invention will be described, but the present invention is not limited thereto. The measurement of the physical properties and the evaluation of the molded product in the examples were performed using the following methods (1) to
Performed in (5).

(1) Particle size: The average value of the particle size of the multilayer polymer particles is measured by a dynamic light scattering method using a laser particle size analyzer (“PAR-III” manufactured by Otsuka Electronics Co., Ltd.). did.

(2) Glass transition temperature: DSC (“TA-4000” manufactured by Mettler) was used, and the temperature was raised at a rate of 10 ° C./m.
It was measured under the conditions of "in".

(3) Intrinsic viscosity: 1 g of a sample of recycled polyethylene terephthalate was dissolved in 100 ml of hexafluoroisopropanol solvent and measured at 30 ° C.

(4) Impact resistance test of plate (DuPont impact resistance test): JIS K5400 No. 6.13.
A falling ball impact test was performed according to the method described in section 3. The weight of the weight (falling ball) used here is 1kg and 2k
g. The numerical value of the evaluation result is the number of samples destroyed when the weight was evaluated under the condition of the predetermined drop height (the number of tests was 5).

(5) Evaluation of pallet characteristics: The pallets thus produced were evaluated by the following methods (a) to (d).

(A) Appearance: Visually evaluated according to the following criteria. X: The gloss of the surface of the pallet was extremely low, or there was uneven release, chipping due to cracks during molding, etc., and the appearance was poor, so it was judged that it was not practical. ：: There is no particular problem, and the appearance is good. Δ: Intermediate situation between the above-mentioned × and ○.

(B) Impact resistance: The pallet was heated at 23 ° C.
It was dropped horizontally from a height of 0.75 m, and the presence or absence of damage was visually determined. This operation was performed for ten pallets, and the evaluation was made according to the following evaluation criteria. ×: Damage was clearly observed in 5 or more pallets out of 10, and it was judged that the pallets were not practical. ：: Damage was not observed at all for all 10 pallets, which was extremely good. Δ: Intermediate situation between the above-mentioned × and ○.

(C) Flexural strength: 23 for pallets
At a temperature of 100 ° C., a load of 1000 kg and a compression speed of 12 mm /
The deflection amount was measured under the conditions of minutes and an interval of 900 mm.
This operation was performed on 10 pallets, and the evaluation was made according to the following evaluation criteria. ×: Deflection amount of more than 5 pallets out of 10 exceeds 15 mm, which is judged to be inappropriate for use as a high-strength pallet. ：: Deflection amount is 1 for all 10 pallets
It is less than 0 mm, which is extremely good. Δ: Intermediate situation between the above-mentioned × and ○.

(D) Heat resistance: The following accelerated test was performed to evaluate the possibility of long-term use in a high temperature environment of 40 to 60 ° C. After leaving the pallet at 70 ° C. for 168 hours, the pallet was dropped horizontally at a temperature of 23 ° C. from a height of 0.50 m and visually checked for damage. This operation was performed for ten pallets, and the evaluation was made according to the following evaluation criteria. ×: Damage was clearly observed in 5 or more pallets out of 10, and it was judged that the pallets were not practical for heat-resistant pallets. ：: No damage was observed in any of the ten pallets, and the pallets were extremely good as heat-resistant pallets. Δ: Intermediate situation between the above-mentioned × and ○.

Reference Example 1 (Multilayer polymer particles (A-1)
Production example of a) A polymerization vessel equipped with a stirring blade, a cooling pipe, and a dropping funnel,
Under a nitrogen atmosphere, 600 parts by weight of distilled water, 0.168 parts by weight of sodium lauryl sarcosinate as an emulsifier and 2.1 parts by weight of sodium stearate were added, and 70 ° C.
And uniformly dissolved. Next, at the same temperature, 150 parts by weight of butyl acrylate and 1.5 parts by weight of allyl methacrylate as a polyfunctional polymerizable monomer were added, and the mixture was stirred for 30 minutes, and then 0.15 parts by weight of potassium peroxodisulfate. Was added to initiate polymerization. Four hours later,
Gas chromatography confirmed that all of the monomers had been consumed. Thus, a copolymer latex was obtained. Next, after adding 0.3 parts by weight of potassium peroxodisulfate to the copolymer latex in the polymerization vessel, 50 parts by weight of methyl methacrylate was added dropwise from a dropping funnel over 2 hours. After the completion of the dropwise addition, the reaction was continued under stirring at 70 ° C. for another 30 minutes, and upon confirming that the monomer was consumed, the polymerization was terminated. The particle size of the latex thus obtained was 0.23 μm.

After the obtained latex was cooled to -20 ° C. for 24 hours to aggregate, the aggregate was taken out and washed three times with hot water at 80 ° C. Furthermore, it dried under reduced pressure at 50 degreeC for 2 days, and obtained the multilayer structure polymer particle (A-1). The obtained multilayer polymer particles (A-1) have an acrylic rubber (Tg = −54 ° C.) having butyl acrylate as a main component as an inner layer, and a polymethyl methacrylate (Tg = 105 ° C.) as a hard layer. It was a core / shell type two-layer particle having a particle diameter of 0.23 μm as an outer layer.

Reference Example 2 (Multilayer polymer particles (A-2)
Production Example) In an autoclave, 200 parts by weight of distilled water, 4.0 parts by weight of sodium oleate as an emulsifier, Rongalit (formaldehyde sodium sulfoxylate) 0.26
7 parts by weight, disodium ethylenediaminetetraacetate 0.1
3 parts by weight and 0.008 parts by weight of ferrous sulfate heptahydrate were charged and heated to 50 ° C. while stirring and replacing with nitrogen. After 30 minutes, 80 parts by weight of butadiene are added, and 3
Stirring was continued for 0 minutes while maintaining this temperature. Then, at the same temperature, 0.1 part by weight of cumene hydroperoxide was added to initiate polymerization. Four hours later, gas chromatography confirmed that all the monomers had been consumed. Thus, a polymer latex was obtained. Next, the obtained polymer latex, under a nitrogen atmosphere, stirring blades,
Transfer to a polymerization vessel equipped with a cooling pipe and a dropping funnel.
The temperature was raised to ° C. In addition, potassium peroxodisulfate 0.1.
After adding 1 part by weight, a mixture of 20 parts by weight of methyl methacrylate and 5 parts by weight of styrene was dropped from the dropping funnel over 2 hours. After the completion of the dropwise addition, the reaction was continued under stirring at 70 ° C. for another 30 minutes, and upon confirming that the monomer was consumed, the polymerization was terminated. The particle size of the latex thus obtained was 0.15 μm.

After the obtained latex was cooled to -20 ° C. for 24 hours to aggregate, the aggregate was taken out and washed three times with hot water at 80 ° C. Furthermore, it dried under reduced pressure at 50 degreeC for 2 days, and obtained the multilayer structure polymer particle (A-2). The obtained multilayer polymer particles (A-2) are made of a butadiene rubber (T
g = -102 ° C.) and a hard outermost layer (Tg = 105) having methyl methacrylate as a main component.
° C) having a particle size of 0.15 µm and a core / shell type two-layer structure.

Reference Example 3 (Multilayer polymer particles (A-3)
Production example of a) A polymerization vessel equipped with a stirring blade, a cooling pipe, and a dropping funnel,
Under a nitrogen atmosphere, 600 parts by weight of distilled water, 0.15 parts by weight of sodium lauryl sarcosinate as an emulsifier and 1.3 parts by weight of sodium stearate were added, and the mixture was heated to 70 ° C. and uniformly dissolved. Then, at the same temperature,
150 parts by weight of butyl acrylate, 0.5 parts by weight of hexanediol diacrylate as a cross-linking agent and 1.0 parts by weight of allyl cinnamate as a polyfunctional polymerizable monomer were added, and the mixture was stirred for 30 minutes. The polymerization was initiated by adding 0.15 parts by weight of potassium disulfate. Four hours later,
Gas chromatography confirmed that all of the monomers had been consumed. Thus, a copolymer latex was obtained. Subsequently, 0.3 parts by weight of potassium peroxodisulfate was added to the obtained copolymer latex, and then 40 parts by weight of methyl methacrylate and 10 parts of glycidyl methacrylate were added.
A part by weight of the mixture was dropped from the dropping funnel over 2 hours. After the completion of the dropwise addition, the reaction was continued under stirring at 70 ° C. for another 30 minutes, and upon confirming that the monomer was consumed, the polymerization was terminated. The particle size of the latex thus obtained was 0.22 μm.

After the obtained latex was cooled to -20 ° C. for 24 hours to coagulate, the coagulated product was taken out and washed three times with hot water at 80 ° C. Furthermore, it dried under reduced pressure at 50 degreeC for 2 days, and obtained the multilayer structure polymer particle (A-3). The obtained multilayer polymer particles (A-3) have an inner layer of an acrylic rubber (Tg = −54 ° C.) containing butyl acrylate as a main component and a hard outermost layer (T-3) containing methyl methacrylate as a main component.
g = 103 ° C.) with a core / shell type two-layer particle diameter of 0.22 μm.

Reference Example 4 (Multilayer polymer particles (A-4)
Production example of a) A polymerization vessel equipped with a stirring blade, a cooling pipe, and a dropping funnel,
Under a nitrogen atmosphere, 600 parts by weight of distilled water, 0.136 parts by weight of sodium lauryl sarcosinate as an emulsifier and 1.7 parts by weight of sodium stearate were added, and the mixture was heated at 70 ° C.
And uniformly dissolved. Then, at the same temperature, 100 parts by weight of butyl acrylate, 60 parts by weight of 2-ethylhexyl acrylate and 2.0 parts by weight of allyl methacrylate as a polyfunctional polymerizable monomer were added, and 30 parts by weight were added.
After stirring for 1 minute, 0.15 parts by weight of potassium peroxodisulfate was added to initiate polymerization. After 4 hours, gas chromatography confirmed that all the monomers had been consumed. Thus, a copolymer latex was obtained. Next, 0.3 parts by weight of potassium peroxodisulfate was added to the obtained copolymer latex, and methyl methacrylate 4 was added.
A mixture of 5 parts by weight, 5 parts by weight of methacrylic acid, and 0.1 part by weight of n-octylmercaptan as a chain transfer agent was dropped from the dropping funnel over 2 hours. After dropping, 7
The reaction was continued under stirring at 0 ° C. for another 30 minutes, and upon confirming that the monomer was consumed, the polymerization was terminated. The particle size of the latex thus obtained is 0.20 μm.
m.

After the obtained latex was cooled to -20 ° C. for 24 hours to aggregate, the aggregate was taken out and washed three times with hot water at 80 ° C. Furthermore, it dried under reduced pressure at 50 degreeC for 2 days, and obtained the multilayer structure polymer particle (A-4). The obtained multilayer polymer particles (A-4) have an inner layer of an acrylic rubber (Tg = −54 ° C.) containing butyl acrylate as a main component, and a hard outermost layer (T-4) containing methyl methacrylate as a main component.
g = 105 ° C.) containing a core having a particle diameter of 0.20 μm /
The particles had a shell-type two-layer structure.

Reference Example 5 (Production example of pulverized PET bottle (B)) From a group of used bottles mainly composed of PET bottles for beverages and the like used by general consumers for separation and collection, X
Lines were used to remove bottles of other materials. Next, the obtained PET bottle group was washed with a weak alkaline aqueous solution and water, and then subjected to wet pulverization. Further, by using the specific gravity difference to separate resin pieces and metal pieces other than polyethylene terephthalate, pulverized PET bottles (B)
I got 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 the polyethylene terephthalate recovered in the form of a pulverized product was 0.75 dl / g.

Example 1 (Example of preparation of thermoplastic resin composition,
Production Example of Plate) 50 parts by weight of the above-mentioned pulverized product (B), 50 parts by weight of multilayer polymer particles (A-1), a hindered phenol-based antioxidant (trade name “Irganox 10” manufactured by Ciba Geigy)
10 ") 0.5 part by weight and 1.1 parts by weight of a paraffin wax (manufactured by Nippon Seiwa Co., Ltd .; melting point 69 ° C.) are mixed and melt-mixed at a temperature of 280 ° C. using a twin screw extruder. The master batch (C-
1) was obtained. Resin temperature 280 using small injection molding machine
The above-mentioned pulverized material (B) and the above-mentioned master batch (C-1) were melt-mixed at a weight ratio of 80:20 and injection-molded at a temperature of 30 ° C. and a mold temperature of 30 ° C. Thus, a plate (size: 10 cm × 10 cm; thickness: 1 mm) made of a thermoplastic resin composition composed of recycled polyethylene terephthalate and multilayer structure polymer particles was prepared. Using the prepared plate, an impact resistance test was performed by a falling ball impact test method. Table 1 below shows the obtained evaluation results.
Shown in

Example 2 (Example of preparation of thermoplastic resin composition,
Production Example of Plate) A pellet-shaped masterbatch was prepared in the same manner as in Example 1, except that the multilayer polymer particles (A-2) having the same weight were used instead of the multilayer polymer particles (A-1). (C-
2) was obtained. Resin temperature 280 using small injection molding machine
The above-mentioned pulverized material (B) and the above-mentioned masterbatch (C-2) were melt-mixed at a weight ratio of 90:10 and injection-molded at a temperature of 30 ° C and a mold temperature of 30 ° C. Thus, a plate (size: 10 cm × 10 cm; thickness: 1 mm) made of a thermoplastic resin composition composed of recycled polyethylene terephthalate and multilayer structure polymer particles was prepared. Using the prepared plate, an impact resistance test was performed by a falling ball impact test method. Table 1 below shows the obtained evaluation results.
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Example 3 (Example of preparation of thermoplastic resin composition,
Production Example of Plate) 40 parts by weight of the above-mentioned pulverized product (B), 60 parts by weight of multilayer polymer particles (A-3), a hindered phenolic antioxidant (trade name “Irganox 10”, manufactured by Ciba Geigy)
10 ") 0.5 part by weight and 1.1 parts by weight of a paraffin wax (manufactured by Nippon Seiwa Co., Ltd .; melting point 69 ° C.) are mixed and melt-mixed at a temperature of 280 ° C. using a twin screw extruder. The master batch (C-
3) was obtained. Resin temperature 280 using small injection molding machine
The above-mentioned pulverized material (B) and the above-mentioned master batch (C-3) were melt-mixed at a weight ratio of 95: 5 and injection-molded at a temperature of 30 ° C. and a mold temperature of 30 ° C. Thus, a plate (size: 10 cm × 10 cm; thickness: 1 mm) made of a thermoplastic resin composition composed of recycled polyethylene terephthalate and multilayer structure polymer particles was prepared. Using the prepared plate, an impact resistance test was performed by a falling ball impact test method. Table 1 below shows the obtained evaluation results.
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Example 4 (Example of preparation of thermoplastic resin composition,
Production Example of Plate) 90 parts by weight of the above-mentioned pulverized product (B), 10 parts by weight of multilayer polymer particles (A-4), a hindered phenolic antioxidant (trade name “Irganox 10” manufactured by Ciba-Geigy)
10 ") 0.1 part by weight and 0.1 part by weight of a paraffin-based wax (manufactured by Nippon Seiro Co., Ltd .; melting point 69 ° C.) are mixed and melt-mixed at a temperature of 280 ° C. using a twin screw extruder. Thereby, a pellet-shaped thermoplastic resin composition was obtained. This thermoplastic resin composition was injection molded using a small injection molding machine under the conditions of a resin temperature of 280 ° C. and a mold temperature of 30 ° C. Thus, a plate (size: 10 cm × 10 cm; thickness: 1 mm) made of a thermoplastic resin composition composed of recycled polyethylene terephthalate and multilayer structure polymer particles was prepared. Using the prepared plate, an impact resistance test was performed by a falling ball impact test method. The obtained evaluation results are shown in Table 1 below.

Comparative Example 1 (Production example of plate from recycled polyethylene terephthalate) 100 parts by weight of the above-mentioned pulverized product (B), a hindered phenolic antioxidant (trade name "Irganox 1010", manufactured by Ciba Geigy). 5 parts by weight and 1.1 parts by weight of paraffin-based wax (manufactured by Nippon Seiro Co., Ltd .; melting point: 69 ° C.) are mixed and melt-mixed at a temperature of 280 ° C. using a twin screw extruder to obtain pellets. A master batch (C-4) was obtained. Resin temperature 2 using a small injection molding machine
Under the conditions of 80 ° C. and a mold temperature of 30 ° C., the pulverized product (B) and the master batch (C-4) were mixed with 80:
The mixture was melt-mixed at a weight ratio of 20 and injection molded. Thus, a plate made of recycled polyethylene terephthalate (size: 10 cm × 10 cm; thickness: 1 m)
m) was prepared. Using the prepared plate, an impact resistance test was performed by a falling ball impact test method. The evaluation results obtained are shown in Table 1 below.

[0054]

[Table 1]

From Table 1 above, it can be seen that Examples 1 to 5 according to the present invention were used.
The thermoplastic resin composition obtained in 4 has a significantly improved impact resistance as compared with the recycled polyester resin of Comparative Example 1 which is different from the present invention in that it does not contain multilayer polymer particles. I understand.

Example 5 (Example of preparation of thermoplastic resin composition,
Production Example of Large Pallet) 80 parts by weight of the above-mentioned pulverized material (B) and 20 parts by weight of the same master batch (C-1) obtained in Example 1 were used.
Dry blending was performed by a mixer provided on an injection molding machine equipped with a vent, and the mixture was supplied to the molding machine using a screw type material supply device. Next, a plate member and a leg member were prepared by melt-mixing and injection molding under the conditions of a resin temperature of 280 ° C. and a mold temperature of 30 ° C.,
Using these, a pallet weighing 15 kg was assembled.
Table 2 below shows the evaluation results of the obtained pallets.

Comparative Example 2 (Production Example of Large Pallet from Recycled Polyethylene Terephthalate) 80 parts by weight of the above crushed product (B) and 20 parts by weight of the same master batch (C-4) obtained in Comparative Example 1 ,
Dry blending was performed by a mixer provided on an injection molding machine equipped with a vent, and the mixture was supplied to the molding machine using a screw type material supply device. Next, a plate member and a leg member were prepared by melt-mixing and injection molding under the conditions of a resin temperature of 280 ° C. and a mold temperature of 30 ° C.,
Using these, a pallet weighing 15 kg was assembled.
Table 2 below shows the evaluation results of the obtained pallets.

[0058]

[Table 2]

From Table 2 above, the pallet comprising the thermoplastic resin composition obtained in Example 5 according to the present invention was obtained in Comparative Example 2 which was different from the present invention in that it did not contain the multilayer polymer particles. It can be seen that the impact resistance is improved as compared with the pallet made of recycled polyester resin.
In addition, it can be seen that the pallet of Example 5 according to the present invention is excellent in appearance, bending strength and heat resistance.

[0060]

According to the present invention, although the recycled polyester resin obtained from the recovered molded product such as a used PET bottle is used as a basic component, the impact resistance is excellent, so that the original excellent heat resistance is obtained. And coupled with mechanical strength,
A thermoplastic resin composition suitable as a molding material is provided. Since the thermoplastic resin composition can also be used as a material for large molded articles such as pallets, according to the present invention, it is possible to expand the range of use of the recycled polyester resin, and it is possible to effectively utilize resources and prevent environmental pollution. Become.

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Claims (5)

[Claims] 1. A pulverized product (1) of a molded article made of a thermoplastic polyester resin and a multilayered polymer particle (2) having a hard layer as an outermost layer and having a rubber layer inside.
A thermoplastic resin composition obtained by mixing under a melting condition. 2. A masterbatch is obtained by melt-mixing a part of the pulverized product (1) and the multilayer polymer particles (2), and then melt-mixing the masterbatch and the rest of the pulverized product (1). The thermoplastic resin composition according to claim 1. 3. A molding material comprising the thermoplastic resin composition according to claim 1. 4. A pallet comprising the thermoplastic resin composition according to claim 1. 5. A molten polyester (1) made of a thermoplastic polyester resin is melted and then molded into a predetermined shape to produce a recycled polyester resin-based molded product. Characterized in that a multilayered polymer particle (2) having a rubber layer inside and a rubber layer inside is blended.