JPH08239562A - Polyethylene terephthalate resin composition - Google Patents

Abstract

PURPOSE: To obtain a composition produced by using reclaimed PET as a raw material and useful for the molding of a large-sized molded article such as pallet or container having excellent heat-resistance and strength. CONSTITUTION: This polyethylene terephthalate resin composition is composed of (A) 52-92wt.% of polyethylene terephthalate, (B) 5-45wt.% of a poly(ethylene-2,6-naphthalate) or a thermoplastic polyester produced by reacting terephthalic acid with a glycol component consisting of 50-95mol% of ethylene glycol and 50-5mol% of 1,4-cyclohexanedimethanol and (C) 3-30wt.% of a vinyl polymer containing glass-fiber, having a glass transition point of the polymer of 80-150 deg.C and produced by polymerizing 60-10wt.% of a vinyl monomer in the presence of 40-90wt.% of glass fiber.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glass fiber reinforced polyethylene terephthalate resin composition having excellent impact resistance, mechanical properties, heat resistance and the like.

The present invention is useful as a technique for reusing polyethylene terephthalate bottles and cups used for carbonated beverages, soy sauce containers, pudding containers, etc. to recycle them into large pallets and containers.

[0003]

2. Description of the Related Art In recent years, pallets and containers made of synthetic resin have been increasingly used for product transportation and storage. The reasons why synthetic resin products have come to be used often include their hygiene and easiness of production. Many synthetic resin pallets and containers are injection-molded from polyolefins such as polyethylene and polypropylene, and have excellent water resistance, and are mainly used as corrates, beer crates, and electronic component transfer pallets.

However, when such a polyolefin pallet, container or the like is used for a special purpose, problems may occur due to its material. That is, since polyolefin has a low melting point and a weak bending strength, it is used as a container for bottles that are sterilized under a high temperature of about 80 ° C or higher, or used for transportation and storage of extremely heavy loads. There is a problem with large pallets.

As a method for solving the problems of heat resistance and low waist strength, Japanese Patent Laid-Open No. 5-193653 discloses
It has been proposed to apply glass fiber reinforced / polyethylene terephthalate to pallet raw materials. Glass fiber reinforced polyethylene terephthalate is a material which is excellent not only in bending strength, heat resistance and chemical resistance, but also in cost.

However, the molded product of glass fiber reinforced polyethylene terephthalate is insufficient in the effect of improving impact resistance as compared with the polyolefin or polypropylene container or pallet of polyethylene or polypropylene, and therefore the glass fiber reinforced polyethylene terephthalate pallet has been put into practical use. Not not. On the other hand, although some PET (PET) bottles are collected and reused, most of them are incinerated or mixed in landfills, and new usage is expected. .

[0007]

DISCLOSURE OF THE INVENTION The present invention provides a large-sized molded product such as a pallet or container made of glass fiber reinforced polyethylene terephthalate, which has excellent impact resistance, can be used even under high temperature, and has high strength, and a side plate of a truck. An object of the present invention is to provide a polyethylene resin composition suitable for

[0008]

Means for Solving the Problems The present invention provides (A) polyethylene terephthalate 52 to 92% by weight (B) poly (ethylene 2,6-naphthalate) or terephthalic acid and ethylene glycol 50 to 95 mol% as a glycol component. And a thermoplastic polyester obtained by reacting 50 to 5 mol% of 1,4-cyclohexanedimethanol 5 to 45 wt% (C) In the presence of 40 to 90 wt% of glass fiber, a vinyl monomer 60 to A glass fiber-containing polymer obtained by polymerizing 10% by weight, wherein the glass transition point of the polymer is 80 to 150 ° C., a glass fiber-containing vinyl polymer 3 to 30% by weight (A), (B) And a polyethylene terephthalate-based resin composition containing components (C).

[0009]

The heat resistance is improved by blending (B) and the special glass fiber-containing vinyl polymer (C) with polyester such as polyethylene naphthalate, which has good compatibility with polyethylene terephthalate (A) and is excellent in heat resistance and rigidity. , The bending strength is improved. Moreover, since the surface of the glass fiber is coated with a polymer of vinyl monomer, the compatibility of the component (C) with the resins (A) and (B) is improved, and the molding has excellent impact resistance. You can get the goods.

(Detailed Description of the Invention) (A) Polyethylene terephthalate Polyethylene terephthalate (A) is a thermoplastic polyester obtained by using terephthalic acid or its ester and ethylene glycol as main starting materials. Unit is 60-10
It has 0%, preferably 80 to 100%.

When the ethylene terephthalate unit is not 100%, isophthalic acid, phthalic acid, 2,6 may be used as a carboxylic acid other than terephthalic acid for supplementing other units.
-Naphthalenedicarboxylic acid, adipic acid, sebacic acid,
An oxycarboxylic acid (eg, p-oxyethoxybenzoic acid, lactic acid, etc.) can be used. As the glycol component other than ethylene glycol, it is possible to use one kind or two or more kinds of diethylene glycol, propylene glycol, 1,4-butanediol and neopentyl glycol. In particular, supplementation with 5 to 20 mol% of 2,6-naphthalenedicarboxylic acid as the carboxylic acid component and 1 to 5 mol% of diethylene glycol as the glycol component is preferable from the viewpoint of moldability and heat resistance.

(B) Polyethylene naphthalate, telef
Talic acid and ethylene glycol and 1,4-cyclohexyl
Polyester obtained by reacting with xanthimethanol
Le heat resistance, improve the rigidity component (B) polyethylene naphthalate is a thermoplastic polyester obtained and 2,6-naphthalene dicarboxylic acid, or its ester, with ethylene glycol as the main starting material, the repeating structural units of ethylene Naphthalate unit is 50-100
%, Preferably 70 to 95%.

This ethylene naphthalate unit is 100%
When the above condition is not satisfied, isophthalic acid, terephthalic acid, adipic acid, sebacic acid, oxycarboxylic acid and the like can be used as a carboxylic acid supplementing the above. or,
As the glycol component other than ethylene glycol, diethylene glycol, propylene glycol, 1,4-
Butanediol, 1,4-cyclohexanedimethanol and neopentyl glycol can be used.

Further, as an aromatic carboxylic acid, 50 to 10
0 mol% terephthalic acid and 50 as glycol component
~ 95 mol% ethylene glycol, 50 ~ 5 mol%
The thermoplastic polyester obtained by reacting with 1,4-cyclohexanedimethanol is also useful for improving heat resistance. In the production of this polyester or PET, in addition to the terephthalic acid, the above-mentioned carboxylic acid or oxycarboxylic acid is used as a glycol component in ethylene glycol,
A glycol other than 1,4-cyclohexanedimethanol, for example, diethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol may be used in combination as a raw material.

In particular, in the polyethylene terephthalate (A), the polyethylene naphthalate (B) or the polyester, when the glycol component contains diethylene glycol as a structural unit in an amount of 1 to 5 mol%, crystallization of these polyesters. Without damaging
In other words, moldability can be improved without impairing heat resistance and rigidity. The polyethylene terephthalate (PET) of the component (A) and the polyethylene naphthalate (PEN) or the copolyester of the component (B) can be used as bottles and films that are discarded by consumers.

(C) Glass Fiber-Containing Vinyl Polymer (C) The glass fiber-containing vinyl polymer as the component (C) is one or two or more vinyl monomers in an amount of 60 to 10% by weight in the presence of 40 to 90% by weight of glass fibers. % In the form of particles or fibers obtained by suspension polymerization in the presence of a polymerization initiator. And the glass transition point of vinyl polymer is 8
It is 0 to 150 ° C.

The average value of the glass fiber length is 1 to 20 m.
The range of m is preferable, the range of 1 to 5 mm is more preferable, and the range of 2 to 4 mm is particularly preferable. The vinyl monomer used as the raw material for the vinyl polymer is styrene (100 ° C.), α
-Methylstyrene (134 ° C), vinyltoluene (14
8 ° C.), vinyl aromatic compounds such as chlorostyrene, vinyl cyan compounds such as acrylonitrile (134 ° C.) and methacrylonitrile, and other α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid and maleic anhydride, methacryl Examples thereof include esters such as methyl acidate (105 ° C.) and butyl acrylate. These monomers may be used alone, but a combination of two or more kinds which are copolymerizable with each other is preferable. (The temperature in parentheses is the temperature of the glass transition point (Tg) of the homopolymer of the vinyl monomer, and when two or more vinyl monomers are used, the Tg of the polymer is the same as that of each vinyl monomer. It is calculated from the molar ratio (n ₁ , n ₂ , n ₃ ...) Used for the monomer and Tg ₁ (Tg ₁ , Tg ₂ , Tg ₃ ...) By the following formula.

[0018]

[Equation 1]

During the suspension polymerization, in order to further improve the impact resistance of the composition of the present invention, in addition to the vinyl monomer,
A rubbery polymer may be blended. Such rubbery polymers include diene rubber, ethylene-propylene rubber,
The ethylene-propylene-diene copolymer rubber, the acrylate rubber, and the mixture thereof may be present in an amount of 3 to 30% by weight.

Therefore, taking a vinyl polymer as an example, styrene / acrylonitrile copolymer, ABS, AES, styrene / maleic acid copolymer, styrene / methacrylate copolymer, styrene / α-methylstyrene / butyl acrylate copolymer There are polymers and the like. When the rubber is used, it is preferable to dissolve the rubbery polymer in the vinyl monomer in advance and then carry out suspension polymerization in the presence of glass fiber.

As the glass fiber, a commercially available glass fiber may be used as it is, but a vinyl-based product obtained by dipping the prepared glass fiber chopped strand in a monomer solution used for polymerization in advance and moistening it It is particularly preferable that each of the microfibers constituting the glass fiber contained in the polymer is completely covered with the polymer.

In the suspension polymerization, the ratio of the aqueous medium to the vinyl monomer is preferably 100 to 3000 parts by weight with respect to 100 parts by weight of the vinyl monomer. When the amount of the aqueous medium is less than 100 parts by weight, the entire product mixture becomes extremely highly viscous as the polymerization proceeds, it becomes difficult to stir the product mixture, and further heat transfer or temperature control becomes difficult, resulting in a uniform mixture. This is not preferable because problems such as the resin not being obtained occur. Conversely, the aqueous medium is 3
If it exceeds 000 parts by weight, the amount of the charged monomer is limited and the productivity is lowered, which is not preferable.

The suspension stabilizer which can be used in the suspension polymerization may be one usually used when the above-mentioned monomers are polymerized by the suspension polymerization method, for example, polyvinyl alcohol, styrene-maleic acid copolymer. Examples thereof include water-soluble polymer compounds such as polymers, sodium polymethacrylate, and ethylhexyl acrylate-acrylic acid copolymer. These may be used alone or in combination of two or more.

Further, a surfactant may be used in combination with such a suspending agent. Furthermore, it is also possible to use an inorganic compound such as calcium triphosphate or calcium carbonate. As the polymerization initiator, a radical generating polymerization agent that is usually used is preferable, and the amount thereof is particularly preferably 0.005 to 3.0 parts by weight with respect to 100 parts by weight of the monomer.

For the suspension polymerization reaction, a vertical reactor, a horizontal reactor or the like used for ordinary suspension polymerization is used, and it is not particularly limited. In the glass fiber-containing vinyl polymer thus obtained, a large number of glass fibers are arrayed and aggregated in a certain direction, respectively, and the glass fibers are still bundled and the surface thereof is covered with the vinyl polymer. Is. The glass fiber-containing vinyl polymer preferably has an average particle size of 2.5 to 35 mesh pass on a Tyler standard sieve. Also, such vinyl polymer pellets,
It is particularly preferable that 10 to several hundred glass fiber chopped strands are bundled.

Composition The resin composition of the present invention contains (A) polyethylene terephthalate in an amount of 52 to 92% by weight, preferably 5%, in the resin composition.
5-87 wt%, (B) polyethylene naphthalate or PECT 5-45 wt%, preferably 8-20 wt%, (C) glass fiber-containing vinyl polymer 3-30 wt%, preferably 5-25 wt% It is a thing.

With such a composition ratio, the intrinsic viscosity of the composition can be 0.4 to 1.0 dl / g. When the intrinsic viscosity is less than 0.4 dl / g, the mechanical properties of the obtained molded product, particularly the impact resistance, are poor, which is not preferable. On the other hand, if the intrinsic viscosity exceeds 1.2 dl / g, the glass fibers will be significantly broken during molding.

Also, using a differential thermal scanner I & E DSC2O type manufactured by Seiko Denshi KK, about 10 mg of a part of a molded product obtained by injection molding the composition was heated to 300 ° C. and melted for 3 minutes. Then, after quenching with dry ice, 20 ℃ /
From the DSC curve obtained by measurement at a heating rate of 1 minute, the average temperature (Tav) of the temperatures of the glass transition point start point (a) and end point (b) is 85 to 150 ° C., preferably 85 to 12 ° C.
It is understood that the composition shows 0 ° C. and has a good balance between heat resistance and moldability.

If the average temperature (Tav) exceeds 150 ° C., problems during the molding process, such as poor plasticization and poor solidification, are unfavorable. This T
The highest peak temperature (Tcc) of the DSC curve during the temperature rise of the DSC curve during the av measurement is 170 to 200 ° C, preferably 180 to 200 ° C. If this Tcc, that is, the temperature-rising crystallization temperature is less than 170 ° C., crystallization easily proceeds when the molded product is left under high temperature for a long time, and the effect of improving impact resistance is impaired. On the other hand, when Tcc exceeds 200 ° C., melt moldability is poor, or mechanical properties such as bending strength are poor. By the way, the melting temperature Tm of the molded product obtained from the composition of the present invention after melting and quenching is 200 to 270 ° C.

Optional Ingredients A stabilizer may be incorporated into the composition of the present invention, if desired. Examples of such stabilizers include hindered phenol-based, thioether-based and amine-based antioxidants, benzophenone-based and hindered amine-based weathering agents, and the like, and hindered phenol-based stabilizers are particularly preferable. The compounding amount thereof is 0.001 to 10 parts by weight with respect to 100 parts by weight of the entire composition of the present invention,
The range of 0.01 to 3 parts by weight is more preferable.
By incorporating a stabilizer into the composition of the present invention, the excellent effect of improving impact resistance exhibited by the method of the present invention is maintained, which is preferable.

It is also a preferred form to incorporate a release agent into the composition of the present invention. Examples of such a release agent include paraffin wax, polyethylene wax, montanic acid ester wax, montanic acid metal salt,
Examples thereof include metal stearates, silicone oils and fluorine-containing polymers. The compounding amount thereof is 0.01 to 5 parts by weight, more preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the entire composition of the present invention. If the blending amount is less than 0.01 part by weight, the releasability during injection molding is inferior, which causes problems such as poor appearance of the molded product and reduced productivity, which is not preferable. On the other hand, if the compounding amount exceeds 5 parts by weight, it is not preferable because the release agent adheres to the molded product and / or the mechanical properties are impaired during injection molding.

As a preferable releasing agent for large-sized molded articles such as pallets and containers, natural wax and polyethylene wax are more preferable, and paraffin wax is particularly preferable, from the viewpoint of releasing property and cost. The melting point of the wax is measured in accordance with JIS K2235-5.3, and the melting point is preferably in the range of 40 to 200 ° C, more preferably 50 to 150 ° C, and further preferably 50 to 50 ° C. The range of 100 ° C. is particularly preferable.

In the present invention, a method of foaming at the time of injection molding can also be adopted. In particular, in applications of large-sized molded products such as pallets and containers, foam molding is preferable from the viewpoints of weight reduction and prevention of shrinkage of the molded products. Specifically, the blowing agent is added in an amount of 0.01 to 5 with respect to 100 parts by weight of the polyethylene terephthalate composition.
When compounded in parts by weight and injection-molded, the expansion ratio is 1.05
It is possible to obtain a molded product that is 2 times, and more preferably 1.1 to 1.6 times. If the expansion ratio is less than 1.05, the effect of foam molding is too small, and if the expansion ratio exceeds 2, the mechanical properties of the molded product, especially the impact resistance and bending strength, become poor. Not preferable. The density (specific gravity) of the molded product is preferably 0.8 to 1.4 g / cc, and 0.8 to 1.4 g / cc.
The range of 1.3 g / cc is more preferable, and 0.9 to 1.2
A range of g / cc is particularly preferred. When the density of such a molded product is less than 0.8 g / cc, impact resistance, bending strength, etc. are particularly deteriorated, which is not preferable. On the other hand, if the density of the molded product exceeds 1.4 g / cc, the handling property will be deteriorated, which is not preferable.

Specific examples of the foaming agent include diisopropylhydrazodicarboxylate, 5-phenyltetrazole, hydrazodicarbonamide, barium azodicarboxylate, and trihydrazinotriazine. Is preferably 150 ° C. or higher, more preferably 200 ° C. or higher, particularly preferably 240 ° C. or higher.

In the composition of the present invention, in addition to the above-mentioned stabilizer, releasing agent and foaming agent, if necessary, coloring agents such as dyes and pigments, ultraviolet ray blocking agents such as titanium oxide and carbon black, and usually Reinforcing agents such as glass fiber, flicker, mica, carbon fiber and potassium titanate, fillers such as silica, clay, calcium carbonate, calcium sulfate, glass beads, inorganic and organic nucleating agents, plasticizers, adhesives , An adhesion aid, a flame retardant, a flame retardant aid and the like may be optionally mixed.

Further, in order to further improve the impact resistance of the composition of the present invention, it is also preferable to add a known impact resistance improver. Such impact modifier is not particularly limited, for example, a composition such as a copolymer and an ethylene copolymer of α-olefin and α, β-unsaturated carboxylic acid glycidyl ester, Examples thereof include a composition obtained by adding an ethylene / α-olefin copolymer grafted with an unsaturated carboxylic acid or an anhydride thereof and a polyepoxy compound, and a polyester-based elastic resin.

In the present invention, a polyester elastic resin is more preferable as the impact resistance improver since it has a large effect of improving impact resistance and a small decrease in heat resistance. Further, among them, the aromatic polyester / polyether elastic resin is particularly preferable because of its great effect of improving impact resistance and easy handling such as blending. In such an aromatic polyester / polyether elastic resin,
The molecular weight of the polyether moiety is preferably 1,000 to 3,000, more preferably 1,500 to 3,000. When the molecular weight is less than 1,000, the impact resistance improving effect is too small, while when the molecular weight exceeds 3,000, the handling is deteriorated and physical properties such as bending strength of the finally obtained composition. It is not preferable because it causes deterioration.

The amount of the unit of polytel is 30 to 9
0 mol% is preferable, and 50 to 80 mol% is more preferable. When the amount of the unit is less than 30 mol%, the effect of improving the impact resistance is too small, while the amount of the unit is 90%.
If it exceeds mol%, the handling will be deteriorated, and the physical properties such as bending strength of the finally obtained composition will be deteriorated.
Not preferred.

The method of blending the above-mentioned additives such as the stabilizer, the release agent, and the impact resistance improver is not particularly limited. For example, such additives may be added in advance in the polyethylene terephthalate resin composition. Alternatively, a master batch of the additive may be blended and blended at the time of molding. Also,
In the present invention, it may be directly dry blended with the molding material from the viewpoint that the effect of improving the cost is great.

Preparation of Composition In the composition of the present invention, the components (A), (B) and (C) may be mixed at the same time, but after the components (A) and (B) are melt-kneaded in advance. Then, it is preferable to melt-knead with the melted component (C).

[0041] Injection molding, extrusion molding as molding molding method, compression molding, pressure forming, co-empty molding or the like can be used. When the glass fiber-reinforced polyethylene terephthalate-based resin composition of the present invention is molded, since the surface of the glass fiber is covered with the vinyl-based polymer, the glass fiber is less likely to be broken and the molding machine is less damaged. Since the composition of the present invention has excellent heat resistance, rigidity and impact resistance, the product weight is 1 kg or more, preferably 5 k.
It is useful as a material for large molded articles such as panels, pallets, side plates of trucks, containers and the like having a weight of g or more, more preferably 10 kg or more.

Precautions when using waste It is preferable to use scraps such as PET bottles and PET containers in order to inexpensively produce large molded articles. Since such waste PET and waste PEN are generally collected together with other containers, the bottles made of materials other than polyester are further removed by a method such as X-ray, if necessary. Then
Bottle washing using alkaline water or the like, wet pulverization, and if necessary, impurities such as metals and other resins are separated and / or dried. The shape of the recycled product has a preferable average diameter of 1
˜50 mm, more preferably 3 to 20 mm, with a preferred average thickness of 50 to 2000 μm, more preferably 100.
It is in the form of flakes of about 700 μm.

When the flaky molding material is dried, since its bulk density is very low, the capacity of the dryer is increased, and in order to compensate for the deterioration of heat conduction, the temperature is increased at a higher temperature for a longer time. Drying is required. As a method for solving such a problem, it is preferable to use an injection molding machine with a vent as the injection molding machine. The vented injection molding machine is an injection molding machine having at least one or more vent holes, and in order to remove water, at least one of the vent holes is preferably 100 Torr or less, more preferably Is maintained at a reduced pressure of 50 Torr or less, particularly preferably 30 Torr or less.

In order to mold recycled polyester in various shapes, bridging in the hopper of the molding machine and stable supply are difficult, bite failure of the material occurs, and further dispersion failure of the material occurs. Cheap. As a preferable method for solving this problem, there is a method of mounting a feeder on the injection molding machine, and particularly preferably a method of providing a material supply device such as a screw type feeder.

Here, the injection molding conditions are not particularly limited and known conditions are adopted, but for example, the melting temperature (resin temperature) is preferably in the range of 240 to 310 ° C. The actual temperature of the mold during injection molding is not particularly limited, but is preferably in the range of 0 to 70 ° C,
The range of 0 to 60 ° C is more preferable, and the range of 0 to 50 ° C is particularly preferable. Within such a range, the effect of improving impact resistance and releasability is great, and the productivity is good.

[0046]

EXAMPLES The present invention will be described in more detail below with reference to examples. The measuring methods and definitions of various physical properties and characteristics in the examples are as follows. In addition, "part" in Examples and Comparative Examples means "part by weight".

( 1) 1 g of a sample excluding ash in the limiting viscosity composition was mixed with 1 of phenol / tetrachloroethane = 50/50 (weight ratio).
It was dissolved in 00 ml and measured at 30 ° C. ( 2) Copolymerization component: diethylene glycol (DEG),
Cyclohexanedimethanol (CHDM) and 2,6-
Quantification of naphthalene dicarboxylic acid (NDCA) component Polyester collected from a molded product was hydrolyzed by a conventional method, quantified by gas chromatography, and / or quantified from ¹ H-NMR from the polyester collected from the molded product. This operation was repeated 10 times, and the average value was used as the quantitative value of the copolymerization component.

( 2) Wax and recycled polyethylene tere
Shape evaluation of phthalate 1000 pieces were arbitrarily taken out from wax and recycled polyethylene terephthalate, and the average diameter and average thickness were measured to evaluate the shape. ( 3) Average temperature of glass transition temperature (Tav) About 10 mg of a test piece was arbitrarily taken out from the molded product, melted in nitrogen at 300 ° C. for 3 minutes, and then rapidly cooled with dry ice. Such a quenching product is IEDSC2 manufactured by Seiko Denshi.
The temperature was raised from 30 ° C. to 30 ° C. at a heating rate of 20 ° C./min, the starting temperature of the glass transition point and the ending temperature of the melting peak were measured, and the intermediate temperature (Tav) between them was determined.

( 4) Temperature rising crystallization temperature (Tcc) and melting
Temperature (Tm) About 10 mg of a test piece was arbitrarily taken out from the molded product, melted in nitrogen at 300 ° C. for 3 minutes, and then rapidly cooled with dry ice. Such a quenched product is manufactured by Seiko Denshi IE DSC.
Tcc and Tm were calculated by measuring the peak temperature with a 20-type model at a temperature rising rate of 20 ° C./min. The melting point of the wax was measured according to JIS K 2235-5.3.

( 5) Average Length (L) of Glass Fiber A test piece of about 10 g was arbitrarily taken out from a molded product and fired at 600 ° C. for 3 hours. Then, for the obtained residue, the length of 100 glass fibers was measured by a photographic method, and the average value was obtained. This operation was repeated 10 times to determine the average length L value of the glass fiber. ( 6) Formability The formability was evaluated according to the following criteria. X: Releasability is poor at the time of molding, there is a problem in production, and it is judged that practical application is difficult. ◯: There are no particular problems and the moldability is good. Δ: An intermediate situation between the above X and O.

( 7) Characteristic evaluation of pallets 100 pallets were manufactured and the characteristics of the pallets were evaluated by the following method. (A) Appearance: The appearance was visually evaluated according to the following criteria. X: The gloss of the surface of the molded product is extremely low, or mold release unevenness,
It is judged that it cannot be put to practical use because it has a defective appearance due to cracks during molding and the like. ◯: There is no particular problem and the appearance is good. Δ: An intermediate situation between the above X and O.

(B) Impact resistance: Molded articles at 23 ° C.
It was dropped horizontally from a height of 0.75 m and the presence or absence of damage was visually observed. This work was performed on 100 products and judged according to the following evaluation criteria. ×: Out of 100 pieces, 5 or more pieces were clearly found to be broken, and it was judged that they could not be put to practical use. ◯: Out of 100 pieces, there is no damage and it is extremely good. △: Intermediate situation between × and ○ above

(C) Bending strength; molded article at 23 ° C., load of 1000 kg, compression rate of 12 mm / min, interval of 900 m
The amount of deflection was measured at m, this operation was repeated for 100 molded articles, the average value of the amount of deflection was determined, and the evaluation was made according to the following evaluation criteria. ×: Deflection of 5 or more products out of 100 products is 1
It exceeds 5 mm and cannot be used as a high strength pallet. ◯: Deflection amount of 100 products is less than 10 mm,
Very good. △: Intermediate situation between × and ○ above

(D) Heat resistance: The following accelerated test was carried out in order to evaluate the possibility of long-term use in a high temperature environment of 40 to 60 ° C. After leaving the molded product at 70 ° C for 168 hours,
At 23 ° C., it was dropped horizontally from a height of 0.50 m and the presence or absence of damage was visually observed. This work was performed on 100 products and judged according to the following evaluation criteria. ×: Out of 100 pieces, 5 or more pieces were clearly damaged, and it was judged that the heat-resistant pallet could not be put to practical use. ◯: Out of 100 pieces, there is no breakage and it is extremely good as a heat resistant pallet. △: Intermediate situation between × and ○ above

( 8) Characteristic Evaluation of Containers 100 containers were manufactured, and the characteristics of molded articles were evaluated by the following methods. (A) Appearance: The appearance was visually evaluated according to the following criteria. X: The gloss of the surface of the molded product is extremely low, or mold release unevenness,
It is judged that it cannot be put to practical use because it has a defective appearance due to cracks during molding and the like. ◯: There is no particular problem and the appearance is good. △: Intermediate situation between × and ○ above

(B) Impact resistance: The container was dropped horizontally from a height of 0.75 m at 23 ° C. and visually inspected for damage. Do this for 100 products,
It was judged according to the following evaluation criteria. ×: Out of 100 pieces, 5 or more pieces were clearly found to be broken, and it was judged that they could not be put to practical use. ◯: Out of 100 pieces, there is no damage and it is extremely good. △: Intermediate situation between × and ○ above

(C) Bending strength; contents 20 in container
Kg was added, and the amount of deflection of the bottom surface was measured at 50 ° C. This operation was repeated for 100 molded articles, the average value of the amount of deflection was obtained, and the evaluation was made according to the following evaluation criteria. ×: Deflection of 5 or more products out of 100 products is 1
It exceeds 0 mm and cannot be used as a high strength container. ◯: Deflection amount of 100 products is less than 5 mm, which is extremely good. Δ: An intermediate situation between the above X and O.

(D) Heat resistance: The following accelerated test was carried out in order to evaluate the possibility of long-term use in a high temperature environment of 40 to 60 ° C. After leaving the container at 70 ° C. for 168 hours, it was dropped horizontally at 23 ° C. from a height of 0.50 m to visually check for damage. This work was performed on 100 products and judged according to the following evaluation criteria. X: Out of 100 pieces, 5 or more pieces were clearly found to be broken, and it was judged that the container could not be put to practical use as a heat resistant container. ◯: Out of 100 pieces, there is no breakage and it is extremely good as a heat resistant container. Δ: An intermediate situation between the above X and O.

[Recycled Polyethylene Terephthalate (A)
Production Example] Separately collected used PET bottles for beverages used by general consumers were used to remove bottles of other materials using X-rays. Next, the bottle was washed with a weakly alkaline aqueous solution and water, and then wet pulverized. Further, by utilizing the difference in specific gravity, resins and metals other than polyethylene terephthalate were separated to obtain flaky regenerated polyethylene terephthalate (A). The shape of the regenerated product was 5.0 mm in average diameter and 300 μm in average thickness.

[Production of glass fiber-containing vinyl polymer (B)
Example Using a vertical autoclave with a capacity of 3 liters equipped with a reflux condenser, thermometer, anchor type stirrer and baffle, glass fiber (chopped strand: diameter 10 μm, length 3 m)
m) 210 g, styrene 100 g, acrylonitrile 3
7 g and benzoyl peroxide (1.4 g) were charged, the pressure in the autoclave was reduced and nitrogen gas was introduced to perform nitrogen substitution, and the glass fiber was left for 10 minutes while being immersed in the monomer mixture.

Next, an aqueous solution containing 1750 ml of deionized water and 2.0 g of a suspending agent (ethylhexyl acrylate-acrylic acid copolymer) was charged into the autoclave, and the internal temperature was raised to 80 ° C. with stirring. Then, the suspension polymerization reaction was continued at this temperature for 5 hours. Then, unreacted monomer was removed by stripping. Incidentally, a styrene-acrylonitrile copolymer (Tg1
The conversion rate to 10 ° C) was 92%.

The slurry after completion of the polymerization was separated into water and copolymer particles, and the copolymer particles were washed with water and dried. The product obtained is a styrene-containing glass fiber in pellet form.
About 250 g of acrylonitrile copolymer (B) and about 90 g of the copolymer powder substantially free of glass fiber.
g. The pellet-shaped glass fiber-containing styrene-acrylonitrile copolymer (B) thus obtained has a shape of
The diameter was about 10 μm, the length was about 3 mm, and the glass fiber content was 80.0% by weight.

[Of recycled polyethylene naphthalate (C)]
Production Example] [Recycled polyethylene terephthalate (A)]
Production Example], a used PEN [poly (ethylene 2,6-naphthalate)] bottle made of polyethylene naphthalate (PEN) was separately collected instead of the PET bottle. Then, a flaky regenerated polyethylene naphthalate (C) was obtained in the same manner as in the production method (A). The shape of the recycled product was 5 mm in average diameter and 290 μm in average thickness.

[ Masterbatch of Release Agent and Stabilizer (D)
Production Example] 53.8 parts by weight of the regenerated polyethylene terephthalate (A), 44.1 parts by weight of the regenerated polyethylene naphthalate (C), a hindered phenolic antioxidant (trade name, manufactured by Ciba Geigy; Irganox 10)
10 parts by weight of 0.6) and paraffin wax (manufactured by Nippon Seiro Co., Ltd .: melting point: 69 ° C.) are mixed by 1.5 parts by weight,
The mixture was mixed using a twin-screw extruder to obtain a masterbatch (D) made of 2,6-naphthalenedicarboxylic acid (NDCA) copolymerized polyethylene terephthalate.

Example 1 [Manufacture of large-sized injection-molded article and pallet] 57.5 parts by weight of the regenerated polyethylene terephthalate (A) and 12.5 parts by weight of the glass fiber-containing styrene-acrylonitrile copolymer (B). Parts, 30 parts by weight of a masterbatch (D) of a release agent and a stabilizer are undried, dry-blended with a mixer installed on an injection molding machine with a vent, and a screw-type material supply device is used. The blended molding material (composition: Table 1) was fed into the molding machine.

Next, the resin temperature is 275 ° C. and the mold temperature is 30.
Injection molding was performed under the molding conditions of ℃, and the two fittings were separately molded using the same molding material, using 9 fitting legs (0.2 kg / 1 piece).
A pallet having a size of m, a height of 38 cm and a weight of 15 kg was manufactured. Table 1 shows the evaluation results of the obtained pallets. A heat resistant pallet with extremely excellent performance was obtained.

Example 2 [Production of Masterbatch (E) of Release Agent and Stabilizer] 62.2 parts by weight of the regenerated polyethylene terephthalate (A), 100 mol of terephthalic acid and 7 parts of ethylene glycol.
0 mol and cyclohexanedimethanol (CHDM) 30
36.2 parts by weight of copolymerized polyethylene terephthalate (PETG) obtained by copolymerizing moles, 0.5 part by weight of a hindered phenolic antioxidant (trade name Irganox 1010), and a paraffin wax (Nippon Seiwa Co., Ltd.) 1.1 parts by weight of Co., Ltd. (melting point: 69 ° C.) were mixed and mixed using a twin-screw extruder to obtain a cyclohexanedimethanol (CHDM) copolymerized polyethylene terephthalate masterbatch (E).

[Manufacturing Example of Large Injection Molded Product, Pallet] 47.5 parts by weight of the above-mentioned recycled polyethylene terephthalate (A), 12.5 parts by weight of the above-mentioned glass fiber-containing styrene-acrylonitrile copolymer (B), mold release 40 parts by weight of the masterbatch (E) of a stabilizer and a stabilizer are undried, dry-blended with a mixer installed on an injection molding machine with a vent, and then mixed into a molding machine using a screw-type material supply device. The blended molding material was supplied.

Next, injection molding was carried out under the molding conditions of a resin temperature of 280 ° C. and a mold temperature of substantially 30 ° C., and nine fitting leg members (0.2 kg / 1 piece) separately molded with the same molding material were used. 110 cm in length and 100 in width for two molded products
cm, height 38 cm, weight 15 kg pallets were produced. Table 1 shows the evaluation results of the obtained pallets. A heat resistant pallet with extremely excellent performance was obtained.

Comparative Example 1 [Production of Masterbatch (F) of Release Agent and Stabilizer] 96.5 parts by weight of homopolyethylene terephthalate (PET) having an intrinsic viscosity of 0.65 dl / g and hindered phenol. Type antioxidant (Product name Irganox 1010)
Was mixed with 1.0 part by weight and 2.5 parts by weight of paraffin wax (manufactured by Nippon Seiro Co., Ltd .: melting point 69 ° C.) and mixed using a twin-screw extruder. The obtained polyethylene terephthalate masterbatch is referred to as (F).

[Manufacturing Example of Large-sized Injection Molded Products and Pallets] As a molding material, 70.0 parts by weight of homopolyethylene terephthalate having an intrinsic viscosity of 0.65 dl / g, and the above-mentioned glass fiber-containing styrene-acrylonitrile copolymer ( B) 12.5 parts by weight, Example 1 except that 17.5 parts by weight of the masterbatch (F) of the release agent and stabilizer described above are used.
A pallet was manufactured in the same manner as in. Table 1 shows the evaluation results of the obtained pallets.

Comparative Example 2 Intrinsic viscosity is 0.65 dl / g
Example 1 except that 62.5 parts by weight of homopolyethylene terephthalate, which is a mixture of styrene-acrylonitrile copolymer (B) and 37.5 parts by weight of glass fiber-containing styrene-acrylonitrile copolymer, was used as the molding material and the resin temperature was 290 ° C. A pallet was manufactured under the same molding conditions as in. Table 1 shows the evaluation results of the obtained pallets.

Comparative Example 3 Intrinsic viscosity is 0.90 dl / g
To 100 parts by weight of homopolyethylene terephthalate, 0.3 parts by weight of benzoic acid disodium salt, 1.0 part by weight of talc having an average particle size of 3 μm, and a molecular weight of 2,500 having one methyl group at the end. 2.0 parts by weight of polyethylene glycol, 0.20 parts by weight of hindered phenolic antioxidant (Irganox 1010) and polyethylene wax (melting point 110 ° C) 0.5 as a release agent
0 parts by weight were mixed, extruded into a strant form at 280 ° C. using a twin-screw extruder, and cut to obtain a polyethylene terephthalate composition (G) in a pellet form. 81.2 parts by weight of the obtained pellet (G) and 18.8 parts by weight of the glass fiber-containing styrene-acrylonitrile copolymer (B) were used as a molding material, and the resin temperature was 290 ° C.
A pallet was manufactured in the same manner as in Example 1 except that Table 1 shows the evaluation results of the obtained pallets.

Comparative Example 4 Intrinsic viscosity is 0.65 dl / g
84.5 parts by weight of homopolyethylene terephthalate, 15 parts by weight of glass fiber chopped strands having an average diameter of 10 μm and an average length of about 3 mm, a hindered phenolic antioxidant (trade name Irganox 1010) 0. 20 parts by weight and 0.50 parts by weight of polyethylene wax (melting point 125 ° C.) as a release agent are mixed,
Using a twin-screw extruder, it was extruded at 280 ° C. into a strant form and cut to obtain a pellet-shaped polyethylene terephthalate composition (H). Example 1 except that the obtained pellet (H) was used as a molding material and the resin temperature was 290 ° C.
A pallet was manufactured in the same manner as in. Table 1 shows the evaluation results of the obtained pallets.

Example 3 Example 1 is different from Example 1 except that the pallet mold is changed to a container molding mold.
Injection molding with the same material as the above, length 50 cm, width 80
A container having a size of cm and a height of 29 cm was manufactured.
The weight of the obtained container was 22 Kg. Table 2 shows the evaluation results. A heat-resistant container with extremely excellent performance was obtained.

<Embodiment 4> Injection molding was performed using the same material as in Embodiment 2 except that the mold was changed to a container forming mold, and the length was 50 cm, the width was 80 cm, and the height was 29 cm. The size of the container was manufactured. The weight of the obtained container was 22 Kg. The evaluation results are shown in Table 2.
Shown in A heat-resistant container with extremely excellent performance was obtained.

<Comparative Example 5> In Comparative Example 1, injection molding was performed using the same material as Comparative Example 1 except that the mold was changed to a container molding mold, and the length was 50 cm, the width was 80 cm, and the height was 29 cm. The size of the container was manufactured. Table 2 shows the evaluation results of the obtained containers. <Comparative Example 6> In Comparative Example 2, injection molding was performed using the same material as Comparative Example 2 except that the mold was changed to a container molding mold, and the size was 50 cm in length, 80 cm in width, and 29 cm in height. Manufactured container. Table 2 shows the evaluation results of the obtained containers.

<Comparative Example 7> In Comparative Example 3, injection molding was performed using the same material as Comparative Example 3 except that the mold was changed to a container molding mold, and the length was 50 cm, the width was 80 cm, and the height was 29 cm. The size of the container was manufactured. Table 2 shows the evaluation results of the obtained containers. <Comparative Example 8> In Comparative Example 4, injection molding was performed using the same material as Comparative Example 3 except that the mold was changed to a container molding mold, and the size was 50 cm in length, 80 cm in width, and 29 cm in height. Manufactured container. Table 2 shows the evaluation results of the obtained containers.

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[Table 1]

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[Table 2]

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Industrial Applicability The glass fiber reinforced polyethylene terephthalate resin composition of the present invention provides a large-sized molded article having excellent rigidity, impact resistance and heat resistance, particularly a pallet, a container and the like. Furthermore, the present invention is extremely valuable because it can be applied to the effective utilization of used bottle waste made of polyethylene terephthalate and can provide a solution to environmental problems.

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Claims (2)

[Claims] 1. (A) Polyethylene terephthalate 52 to 92% by weight (B) Poly (ethylene 2,6-naphthalate) or terephthalic acid and ethylene glycol 50 to 95 mol% as a glycol component, and 1,4-cyclohexene. Thermoplastic polyester obtained by reacting with 50 to 5 mol% of sandimethanol 5 to 45% by weight (C) Obtained by polymerizing 60 to 10% by weight of vinyl monomer in the presence of 40 to 90% by weight of glass fiber Glass fiber-containing polymer to be used, wherein the glass transition point of the polymer is 80 to 150 ° C. Glass fiber-containing vinyl polymer 3 to 30% by weight Containing the components (A), (B) and (C) A polyethylene terephthalate resin composition. 2. A resin composition in which the polymer constituting the glass fiber-containing polymer is a styrene / acrylonitrile copolymer.