JPH07268192A - Glass fiber-reinforced polyethylene terephthalate composition and injection molded product comprising the same - Google Patents

Abstract

PURPOSE:To provide the composition comprising a polyethylene terephthalate resin and a glass fiber-containing olefinic polymer in a specific ratio, excellent in impact resistance, mechanical properties, cost, etc., and capable of providing pallets, containers, etc. CONSTITUTION:The subject composition comprises (A) 97-70 pts.wt. of a polyethylene terephthalate resin especially preferably having an intrinsic viscosity of 0.35-0.75 and (B) 3-30 pts.wt. of an olefinic polymer containing 40-90% of glass fibers, has a crystallization temperature of 140-200 deg.C measured at a temperature-rising rate after melted and then quenched, and has a glass concentration (W) of 1-20wt.%. The glass fibers have preferably an average length L (mum) satisfying equations of formulas I and II.

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 composition excellent in impact resistance, mechanical properties and cost.

[0002]

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 polyethylene, polypropylene, etc., and are practically useful in general applications.

However, when such a pallet or container made of synthetic resin is used for a special purpose, problems may occur due to its material. That is, since the melting point is inherently low and the bending strength is weak, there are restrictions when used at a high temperature of around 80 ° C. or higher, or when used for transportation or storage of very heavy loads. As a method for solving such a problem, an attempt has been made to apply polyethylene terephthalate to a synthetic resin pallet as described in JP-A-5-193653.

The glass fiber reinforced polyethylene terephthalate is not limited to bending strength, heat resistance and chemical resistance as described in, for example, JP-B-44-457 and JP-A-51-37943. It is also an excellent material in terms of cost. However, the molded product of glass fiber reinforced polyethylene terephthalate has an insufficient effect of improving impact resistance as compared with the molded product of polyethylene or polypropylene. Therefore, the pallet obtained from glass fiber reinforced polyethylene terephthalate cannot completely solve the above-mentioned problems because the impact resistance is insufficient. Furthermore, when a molded product is used at a high temperature, the impact resistance is often inferior, so that it cannot be put to practical use.

[0005]

Various methods have heretofore been proposed in an attempt to improve the impact resistance of thermoplastic polyester such as polyethylene terephthalate. For example, a method of adding ethylene-propylene rubber, polyisobutene, polybutene, or the like to polyester (Japanese Patent Publication No. 46-5225), a degree of crystallinity of not more than 75% obtained by graft-polymerizing α, β-unsaturated carboxylic acid or its derivative onto polyester. Melt-mixing the modified ethylene polymer described in JP-B-57-54058 and JP-B-57-59.
No. 261), or a composition of a polyester and a specific random copolymer having a polar group such as an α, β-unsaturated carboxylic acid derivative or an unsaturated epoxide (Japanese Patent Publication No. 59-28223). Has been done.

However, in either method,
Although the impact resistance was improved, it was still insufficient.
Furthermore, a composition obtained by adding a copolymer of an α-olefin and a glycidyl ester of an α, β-unsaturated carboxylic acid and an ethylene copolymer to polyester (JP-A-58-1).
7148) or a composition obtained by adding an ethylene-α-olefin copolymer obtained by grafting an unsaturated carboxylic acid or its anhydride to a polyester and a polyepoxy compound (JP-A-60-28446). .

Even with such a method, although the impact resistance was improved, it was still insufficient, and the melt fluidity was lowered and the moldability was deteriorated. Further, the method of blending a special impact resistance improver such as the above method is often disadvantageous in terms of cost, and even if the impact resistance is improved, one of the most characteristic features of polyethylene terephthalate. The cost advantage, which is one of the problems, is lost.

Thus, there has been a strong demand for a glass fiber reinforced polyethylene terephthalate composition suitable for synthetic resin pallets, containers, etc., which has excellent impact resistance, can be used even at high temperatures, and has high strength. is there.

[0009]

Means for Solving the Problems The inventors of the present invention have made earnest studies in view of the above problems, and as a result, if the molded product is obtained by injection molding a specific polyethylene terephthalate by a specific method, the above problems will be solved. The present invention has been solved and the present invention has been solved. That is, the gist of the present invention is
A composition comprising 97 to 70 parts by weight of a polyethylene terephthalate resin and 3 to 30 parts by weight of an olefin polymer containing 40 to 90% by weight of glass fiber, the composition being melted and rapidly cooled. The temperature rising crystallization temperature (Tcc) measured at a temperature rate of 20 ° C / min is 140 to 200 ° C, and the concentration (W) of the glass fiber in the entire composition is 1 to 2
A glass fiber reinforced polyethylene terephthalate composition characterized by being 5% by weight.

The present invention will be described in detail below. The polyethylene terephthalate resin in the present invention is a polyester obtained from an aromatic dicarboxylic acid or its ester and a glycol as main starting materials, and has 70 to 100%, preferably 90 to 100%, and more preferably a repeating structural unit. 90 to 99%, particularly preferably 95 to 98
% Refers to polyesters having ethylene terephthalate units. When the ethylene terephthalate unit is less than 70%, the resulting molded product is inferior in mechanical properties such as bending strength, which is not preferable.

As the aromatic dicarboxylic acid component, terephthalic acid is preferable, and in addition to this, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, oxycarboxylic acid (for example, p-oxyethoxybenzoic acid, etc.) ) Or the like can be used. On the other hand, ethylene glycol is preferable as the glycol component, and in addition to this, one or more of diethylene glycol, propylene glycol, 1,4-butanediol, 1,4-cyclohexanedimethanol, and neopentyl glycol can be used.

Particularly preferred is a glycol component containing diethylene glycol as a structural unit. The content thereof is preferably 1 to 5% by weight, more preferably 2 to 4% by weight, and particularly preferably 2 to 3.5, based on the whole polyethylene terephthalate.
It is in the range of% by weight. The method of incorporating a predetermined amount of diethylene glycol in the glycol component is advantageous in terms of cost without impairing mechanical properties and is preferably used in the present invention. When the amount of diethylene glycol is within the range of 1 to 5% by weight, Tcc, which is one of the constituent features of the invention described later, can be easily brought within the specified range.

In the present invention, it is also preferable to use recycled flakes of bottles for beverages, etc., which are made of polyethylene terephthalate resin as the polyethylene terephthalate resin. The intrinsic viscosity of the polyethylene terephthalate resin of the present invention is preferably 0.3 to 1.2, more preferably 0.35 to 0.8,
0.35-0.75 is especially preferable. If the intrinsic viscosity is less than 0.3, the mechanical properties of the resulting molded article, particularly impact resistance, are poor, which is not preferable. On the other hand, the intrinsic viscosity is 1.
When it exceeds 2, when the glass olefin-containing polymer described below is mixed with polyethylene terephthalate resin and injection molding is performed, the breakage of the glass fiber becomes remarkable. Therefore, the effect of "improvement of impact resistance", which is one of the main purposes of the present invention, becomes insufficient, which is not preferable.

The composition of the present invention contains 40 to 90% by weight of glass fiber in the polyethylene terephthalate resin.
It is prepared by blending the contained olefin polymer. Generally, a glass fiber reinforced polyethylene terephthalate molding material is obtained by blending polyethylene terephthalate resin with glass fibers and melt-kneading with an extruder, and usually a molded product is obtained by further melt-molding it. . However, such a molded product is insufficient in the effect of improving impact resistance.

On the other hand, according to the method of molding using the composition of the present invention, that is, the composition in which the olefin polymer containing 40 to 90% by weight of glass fiber in advance is mixed with the above-mentioned polyethylene terephthalate resin, Surprisingly, it is possible to obtain a molded product having extremely excellent properties such as impact resistance. The glass fiber-containing olefin polymer used in the present invention will be described below.

As the monomer constituting the olefin polymer, styrene, α-methylstyrene, vinyltoluene,
Vinyl aromatic compounds such as chlorostyrene, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile,
Other examples include α, β-unsaturated carboxylic acids such as acrylic acid and methacrylic acid. These monomers may be used alone, but a combination of two or more kinds which are copolymerizable with each other is more preferable.

Further, in order to further improve the impact resistance of the composition of the present invention, a rubbery polymer may be blended in addition to the above monomers. Examples of such rubbery polymers include diene rubbers, ethylene-propylene rubbers, ethylene-propylene-diene monomer rubbers, acrylate rubbers, and mixtures thereof. Next, the content of the glass fiber contained in the olefin polymer is 40 to 90% by weight.
Must be within the range.

When the content is less than 40% by weight, the glass fiber reinforced polyethylene terephthalate composition obtained will contain a large amount of olefin polymer.
It is not preferable because mechanical properties such as bending strength of the polyethylene terephthalate composition are impaired. On the other hand, when the content exceeds 90% by weight, the effect of improving the impact resistance of the polyethylene terephthalate composition becomes insufficient, which is not preferable. A more preferable range of the content is
55 to 85% by weight, particularly preferably 70 to 85% by weight.

The average diameter of the glass fibers contained in the olefin polymer in the present invention is 5 to 20 μm.
Is preferable, and the range of 7 to 15 μm is more preferable. When the diameter is out of the above range, the effect of improving the impact resistance of the obtained glass fiber reinforced polyethylene terephthalate composition becomes small, which is not preferable. The average length of the glass fibers contained in the olefin polymer in the present invention is preferably in the range of 1 to 20 mm,
The range of 1 to 5 mm is more preferable, and the range of 2 to 4 mm is particularly preferable.

When the average value of the glass fiber length is less than 1 mm, the glass fiber shows only the property as a mere filler, so that the effect of improving the impact resistance of the finally obtained glass fiber-reinforced polyethylene terephthalate composition. Is small, which is not preferable. On the other hand, when it exceeds 20 mm, the polyethylene terephthalate composition finally obtained may be inferior in moldability and may cause problems such as poor appearance, which is not preferable.

The method for producing the glass fiber-containing olefin polymer used in the present invention is not particularly limited, but a preferable production method is to use glass fiber chopped strands as the starting material for the olefin polymer. Examples thereof include a method in which one or two or more types of bodies are allowed to coexist in a suspension polymerization system, and the monomers are subjected to suspension polymerization to produce them.

When the rubbery polymer is blended in order to further improve the impact resistance of the composition, the rubbery polymer is first dissolved in the monomer, and then the glass fiber is allowed to coexist. It is preferable to carry out suspension polymerization. The glass fiber may be a commercially available one as it is, but the prepared glass fiber chopped strand is preliminarily immersed in a monomer solution used for polymerization and wetted to obtain an olefin polymer. It is particularly preferable that each of the microfibers constituting the glass fiber contained is completely covered with the polymer.

The amount of the glass fiber present in the polymerization system during the polymerization is 5-80 with respect to 100 parts by weight of the monomer.
The proportion of 0 parts by weight is more preferable, and the proportion of 50 to 500 parts by weight is particularly preferable. Further, in the suspension polymerization, the ratio of the aqueous medium to the monomer is 100 parts by weight of the monomer,
A ratio of 100 to 3000 parts by weight is preferable. 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 3000
If the amount is more than parts by weight, the amount of the charged monomer is limited and the productivity is lowered, which is not preferable.

The suspension stabilizer that can be used in the suspension polymerization may be one that is usually used when the above-mentioned monomers are polymerized by the suspension polymerization method. For example, various saponified products of polyvinyl acetate ( Polyvinyl alcohol), styrene-maleic acid copolymer, polymethacrylic acid sodium, and a water-soluble polymer compound such as a copolymer of ethylhexyl acrylate and acrylic acid. These may be used alone or in combination of two or more kinds. You may use.

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 carbonate. As the polymerization initiator, a commonly used radical-generating polymerization agent is preferable, and the amount thereof is 0.005 to 100 parts by weight of the monomer.
A ratio of 3.0 parts by weight is particularly preferred. The suspension polymerization reaction is
A vertical reactor, a horizontal reactor, or the like used for ordinary suspension polymerization is used and is not particularly limited.

In the glass fiber-containing olefin polymer thus obtained, a large number of each glass fiber is arrayed and assembled in a certain direction, and further, the surface of the glass fiber remains olefin-based polymer while being bundled. It is a polymer which is covered with a united product and has an appearance similar to that of a pellet produced by an extruder, that is, a so-called collimated product, which is particularly preferably used as the glass fiber-containing olefin polymer used in the present invention.

Further, it is particularly preferred that the average particle size of the pelletized polymer is 2.5 to 35 mesh on Tyler standard sieve. Also, such polymer pellets have 10
It is particularly preferable that a few to several hundred glass fiber chopped strands are bundled. When the shape and particle size of the polymer pellets are out of the above ranges, moldability and dispersibility of glass fibers in the finally obtained glass fiber-reinforced polyethylene terephthalate composition may be poor.

The glass fiber reinforced polyethylene terephthalate composition of the present invention is obtained by blending the above-mentioned polyethylene terephthalate resin with such glass fiber-containing olefin polymer pellets. The blending method is not particularly limited, but a dry blending method using various mixers is preferable. The composition of the present invention is an extremely excellent method in terms of cost, since the step of kneading the glass fiber and the resin to be blended with the glass fiber in the conventional method can be omitted.

When the glass fiber reinforced polyethylene terephthalate composition of the present invention is molded, since the surface of the glass fiber is coated with the olefin polymer, the glass fiber is less likely to break, and the molding machine Less damage.
The above composition of the present invention may further contain, as a third component, a polymer other than polyester, such as polycarbonate, polyolefin, polyamide, etc., within a range not exceeding the gist of the present invention, for example, 30% by weight or less of the whole. May be blended.

The glass fiber reinforced polyethylene terephthalate composition of the present invention thus obtained must further satisfy the following conditions. The temperature rise crystallization temperature Tcc after melting and quenching of the composition is 140
~ 200 ° C. Here, Tcc is the peak of the temperature rise crystallization temperature measured by melting the glass fiber reinforced polyethylene terephthalate composition in nitrogen for 3 minutes, quenching it with dry ice, and then raising the temperature at a constant rate. The value (° C) is shown. The heating rate is 20 ° C./min.

When the value of Tcc is less than 140 ° C., the composition is more likely to crystallize during molding or when the molded product is exposed to a high temperature of, for example, about 80 ° C. or more, resulting in impact resistance. The improvement effect is lost. On the other hand, when Tcc exceeds 200 ° C., the melt moldability becomes poor, or the mechanical properties such as bending strength become poor, which is not preferable. Incidentally, Tcc
Is preferably 150 ° C to 180 ° C, particularly preferably 155 ° C to 175 ° C.

As described above, in the present invention, the effect of improving the impact resistance of the obtained molded article is greatly influenced by the crystallization behavior of the glass fiber reinforced polyethylene terephthalate composition. It is possible to set the Tcc of the composition of the present invention within the above range by devising a combination and a blending amount of a nucleating agent, a plasticizer and the like. The concentration W of the glass fiber in the entire composition is 1 to 25% by weight.

When W is less than 1% by weight, the effect of improving the impact resistance by blending the glass fiber by the method of the present invention is insufficient, which is not preferable. On the other hand, when W exceeds 25% by weight, defects such as a decrease in impact resistance and a deterioration in the appearance of the molded product due to the incorporation of a large amount of glass fibers are not preferable. A more preferable range of W is 3 to 20% by weight, and a particularly preferable range is 5 to 13% by weight. Here, W is the concentration with respect to the weight of the entire composition including additives and the like.

In the glass fiber reinforced polyethylene terephthalate composition of the present invention, the average length L (μm) of the glass fiber in the composition preferably satisfies the following formulas (I) and (II).

[0035]

(3) 200 ≦ L ≦ 2000 (I) 500-10W ≦ L ≦ 1200-20W (II)

The L value is more preferably 400 to 100.
It is in the range of 0 μm, particularly preferably 500 to 100.
It is within the range of 0 μm. When the L value is less than 200 μm, the effect of improving impact resistance is insufficient, which is not preferable. On the other hand, when the L value is more than 2000 μm, the appearance of the obtained polyethylene terephthalate-based resin molded product is poor, which is preferable. Absent.

If the relationship between the W value and the L value is out of the range represented by the formula (II), the impact resistance and / or appearance of the obtained polyethylene terephthalate resin molded article will be deteriorated, which is not preferable. . The relationship between the W value and the L value is
More preferably, the following formula should be satisfied.

[0038]

[Formula 4] 500-10W ≦ L ≦ 1000-20W

As described above, the glass fiber-reinforced polyethylene terephthalate-based composition of the present invention can be obtained by blending the glass fiber in the polyethylene terephthalate-based resin by a specific method. By injection-molding using, it is possible to obtain an injection-molded article having remarkably excellent impact resistance.

Here, the injection molding conditions are not particularly limited and well known conditions are adopted. For example, the melting temperature (resin temperature) is preferably 260 to 310 ° C., and the injection rate is 1000 to 5000 cc / sec. Conditions of some extent can be preferably adopted. The actual temperature of the mold during injection molding is not particularly limited, but is preferably in the range of 0 to 70 ° C, more preferably in the range of 0 to 60 ° C, particularly preferably in the range of 0 to 50 ° C. Within such a range, the effect of improving impact resistance is great and the productivity is good.

In this case, the glass fiber is often broken by melt-kneading at the time of injection molding, but the relational expressions represented by the above formulas (I) and (II) regarding the average length L (μm) of the glass fiber are It is preferable that the composition be filled with the composition after molding. Therefore, the molding conditions are preferably adjusted so that the average length L (μm) of the glass fiber in the obtained molded product satisfies the above formulas (I) and (II).

In the present invention, among the injection-molded products, the effect is remarkably exhibited especially in large-sized injection-molded products such as pallets and containers. Here, the large-sized molded product is, for example, 1 kg or more, and further 10 kg in weight.
The above molded products are shown. In such a molded article, since the weight of the molding material is very large and the cost aspect of the molding material is more important, and the impact resistance at a higher level is required, the impact resistance of the present invention is improved. A glass fiber-reinforced polyethylene terephthalate composition, which is excellent and advantageous in terms of cost, is preferably used as a large-sized molded article such as a pallet and a container.

The shape and structure of the pallet and the container are not particularly limited because they vary depending on their use and required strength. For example, in a pallet, a structure in which upper and lower deck boards and leg members that connect the deck boards to each other are integrally formed by injection molding, the deck board and the leg members, etc. are formed separately, and are combined by an adhesive. Those assembled by means of adhesion, welding by high frequency or ultrasonic waves, etc. are optional.

If desired, a predetermined stabilizer may be added to the composition of the present invention. Such stabilizers include known hindered phenol-based antioxidants, thioether-based and amine-based antioxidants, benzophenone-based antioxidants,
Examples thereof include hindered amine-based weathering agents and the like, and hindered phenol-based stabilizers are particularly preferable. The amount of the compound is 100 parts by weight of the entire composition of the present invention,
0.001-10 parts by weight, more preferably 0.01-3
A range of parts by weight is preferred. If the compounding amount is out of the range, it is not preferable because the effect as a stabilizer is too small or the mechanical properties are impaired. 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.

Furthermore, it is also effective to incorporate a release agent into the composition of the present invention. Examples of the releasing agent include paraffin wax, polyethylene wax, montanic acid ester wax, montanic acid metal salt, stearic acid metal salt, silicone oil, and fluorine-containing polymer. As the compounding amount, the composition of the present invention as a whole 1
The amount is 0.01 to 5 parts by weight, more preferably 0.1 to 2 parts by weight with respect to 00 parts by weight. 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 release agent for large products such as pallets and containers, paraffin wax and polyethylene wax are more preferable, and paraffin wax is particularly preferable, from the viewpoints of releasing property and cost. Also,
The melting point of the releasing agent is 5 from the viewpoint of its releasing property and handleability.
The range of 0 to 200 ° C is preferable, the range of 50 to 150 ° C is more preferable, and the range of 50 to 100 ° C is particularly preferable.

Further, in the present invention, a method of foaming at the time of injection molding can 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, when 0.01 to 2 parts by weight of a foaming agent is mixed with 100 parts by weight of polyethylene terephthalate and injection molding is performed by the method of the present invention, the expansion ratio is 1.05 to 2 times, more preferably , 1.1 to 1.6 times the molded product is obtained. If the expansion ratio is less than 1.05, the effect of foam molding is too small, and if it exceeds 2, the mechanical properties of the molded product, particularly impact resistance and bending strength, are deteriorated, which is not preferable. The density (specific gravity) of the molded product is preferably 0.8 to 1.4 g / cc, and 0.8 to 1.3
The range of g / cc is more preferable, and the range of 0.9 to 1.2 g / cc is particularly preferable. If 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, the density of the molded product is 1.4g / cc
If it exceeds, it is not preferable because the handling property becomes poor.

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 Reinforcing agents such as ordinary 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 Agents, adhesion aids, flame retardants, flame retardant aids 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. The impact resistance improver is not particularly limited, but for example, a composition such as a copolymer of an α-olefin and a glycidyl ester of an α, β-unsaturated carboxylic acid and an ethylene copolymer, or Examples thereof include a composition in which an ethylene / α-olefin copolymer grafted with a saturated carboxylic acid or an anhydride thereof and a polyepoxy compound are added.

Particularly in the present invention, an acrylic ester elastomer is preferably used from the viewpoint of the effect of improving impact resistance and cost. The amount thereof to be added is preferably 1 to 20 parts by weight, more preferably 1 to 5 parts by weight, and particularly preferably 1 to 4 parts by weight, based on 100 parts by weight of the entire composition of the present invention. The method of blending the above-mentioned additives is not particularly limited. For example, such an additive may be blended in advance in a polyethylene terephthalate resin, or a masterbatch of the additive may be blended and blended at the time of molding. Good.

[0052]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. 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) Intrinsic viscosity 1 g of polymer is phenol / tetrachloroethane = 50
Dissolved in 100 ml of a mixed solvent of 50/50 (weight ratio),
It was measured at 30 ° C. (2) Temperature rising crystallization temperature (Tcc) 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. The quenched product is a DSC-made by Perkin Elmer.
In the 1B type, the temperature is raised at a temperature rising rate of 20 ° C./min,
The peak temperature was measured to determine Tcc.

(3) Average Length of Glass Fiber (L) About 10 g of a test piece was arbitrarily taken out from the 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. (4) Moldability The moldability was evaluated according to the following criteria. X: There is a problem in the plasticization or solidification rate during molding, or the mold releasability is poor, and there is a problem in production, and it is judged that practical application is difficult. Δ: Although there is some improvement effect on plasticization, solidification rate, releasability, etc., it is insufficient and not practically usable. ◯: No particular problem and good moldability.

(5) Evaluation of characteristics The characteristics of the molded products were evaluated by the following methods. Regarding the evaluation of impact resistance and bending strength,
After heat treatment at 00 ° C. for 1 hour, the characteristic evaluation was performed.

(A) Appearance The appearance of the molded product was evaluated visually by the following criteria. X: The surface of the molded product has extremely low gloss, unevenness of release, cracks due to cracking during molding, etc., and the appearance as a product is poor, so it is judged to be unusable for practical use. Δ: There is a slight improvement effect on the surface gloss of the molded product, mold release unevenness, cracking at the time of molding, etc., but it is insufficient and not practically usable. ◯: There is no particular problem and the appearance is good.

(B) Impact resistance The molded product was dropped horizontally from a height of 1.0 m at room temperature to visually check for damage, and this operation was repeated 30 times.
It was judged according to the following evaluation criteria. X: Out of 30 times, the damage was clearly seen 5 times or more, and it was judged that it could not be put to practical use. (Triangle | delta): Although it is less than 5 times in 30 times, a clear breakage is seen and it remains uneasy in practical use. ◯: Very good with no damage during 30 times.

(C) Bending strength (pallet) The molded product was heated at 23 ° C. under a load of 1000 kg and a compression speed of 12
The amount of deflection was measured at mm / min and the interval of 900 mm, this operation was repeated for 30 molded articles, the average value of the amount of deflection was determined, and the evaluation was made according to the following evaluation criteria. X: Deflection exceeds 15 mm and cannot be used as a high-strength pallet. B: The amount of deflection is 10 to 15 mm, which is slightly inferior as a high-strength pallet. ◯: The amount of deflection is less than 10 mm, which is extremely good. (C ') Bending strength (container)

20 kg of the content is evenly distributed in the molded product, and 5
The amount of deflection of the bottom surface was measured at 0 ° C. This operation is repeated for 30 molded products, and the average value of the amount of deflection is calculated.
It was judged according to the following evaluation criteria. X: Deflection exceeds 10 mm and cannot be used as a high strength container. B: The amount of deflection is 5 to 10 mm, which is slightly inferior as a high-strength container. ◯: The amount of deflection is less than 5 mm, which is extremely good.

(6) Expansion ratio Using a foamed molded product and a molded product (non-foamed molded product) produced in the same manner except that no foaming agent was added, the expansion ratio was determined by the following formula.

[0060]

[Equation 5]

Example 1 Production of Glass Fiber-Containing Olefin Polymer (A) Using a vertical autoclave with a capacity of 3 l equipped with a reflux condenser, a thermometer, an anchor type stirrer and a baffle, glass fibers (chopped Strand: diameter 10 μm, length 3 mm) 21
0 g, 100 g of styrene, 37 g of acrylonitrile, 1.4 g of benzoyl peroxide were charged, the inside of the autoclave was depressurized and nitrogen gas was introduced to replace the nitrogen, and the glass fiber was immersed in the above monomer mixture.
It was left for 0 minutes.

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

The slurry after the polymerization was separated into water and a polymer, and the polymer was washed with water and dried. The obtained product was about 250 g of the glass fiber-containing olefin polymer (A) in a pellet form, and about 90 g of the polymer powder substantially containing no glass fiber. The pellet-shaped glass fiber-containing olefin polymer (A) obtained here had a diameter of about 10 μm and a length of about 3 mm, and the glass fiber content was 80.4% by weight.

[Production of Polyethylene Terephthalate Composition (B)] The intrinsic viscosity is 0.64, and 2.5% by weight of diethylene glycol ( ¹ HN
1 part by weight of a hindered phenolic antioxidant (product name Irganox 1010), 100 parts by weight of a polyethylene terephthalate resin (value analyzed by MR), and paraffin wax (product name 155 ° F wax, melting point: (About 75 ° C.) 2.5 parts by weight, and an acrylic ester-based elastomer, Paraloid EXL231
15 parts by weight of 1 (manufactured by Kureha Chemical Co., Ltd.) were mixed and pelletized using a twin-screw extruder. The obtained pellet is used as a polyethylene terephthalate composition (B).

[Production of glass fiber reinforced polyethylene terephthalate composition (foam molded article)] 80 parts by weight of polyethylene terephthalate resin having an intrinsic viscosity of 0.64 and containing 2.5% of diethylene glycol as a glycol component. After drying 20 parts by weight of a polyethylene terephthalate-based resin composition (B), which is a masterbatch containing various additives, by a conventional method (20 hours at 130 ° C.), the glass fiber-containing olefin-based resin composition described above is added thereto. 14.3 parts by weight of the polymer (A) and 1 part by weight of the foaming agent diisopropylhydrazodicarboxylate were added and dry blended with a mixer, and then injection molding was performed under molding conditions of a resin temperature of 300 ° C. and a mold temperature of 32 ° C. And 1100 x 110
A pallet size of 0x140 cm was produced.

The received pallet was 35 kg. The evaluation results are shown in Table 1. The expansion ratio of the pallet was 1.4 and the density was 1 g / cc, and a pallet with extremely excellent performance was obtained. Comparative Example 1 66.1 parts by weight of the glass fiber-containing olefin polymer (A) of Example 1 was added to 100 parts by weight of a homopolyethylene terephthalate resin having an intrinsic viscosity of 0.65, and after drying, Pallets were manufactured under the same molding conditions as in Example 1. Table 1 shows the evaluation results of the obtained pallets.

Comparative Example 2 0.3 part by weight of a disodium salt of benzoic acid, 1.0 part by weight of talc having an average particle diameter of 3 μm, relative to 100 parts by weight of a homopolyethylene terephthalate resin having an intrinsic viscosity of 0.90, 1. Polyethylene glycol having a molecular weight of 2500 and having one methyl group at the end 2.
0 parts by weight and 0.05 parts by weight of polyethylene wax (melting point 125 ° C.) as a release agent were mixed, and a polyethylene terephthalate composition (C) was obtained in the form of pellets using a twin-screw extruder. 23.6 parts by weight of the obtained pellets (C) and the glass fiber-containing olefin polymer (A) of Example 1 were blended and dried by a conventional method, and then, under the same molding conditions as in Example 1, Produced pallets. Table 2 shows the evaluation results of the obtained pallets.

Comparative Example 3 100 parts by weight of homopolyethylene terephthalate resin having an intrinsic viscosity of 0.65, 17.6 parts of glass fiber chopped strands having an average diameter of 10 μm and an average length of about 3 mm, and a release agent. As a mixture, 0.05 part by weight of polyethylene wax (melting point 125 ° C.) was mixed, and a pellet-shaped polyethylene terephthalate composition (D) was obtained using a twin-screw extruder. After drying the obtained pellet (D) by a conventional method, a pallet was manufactured under the same molding conditions as in Example 1. Table 2 shows the evaluation results of the obtained pallets.

Example 2 In Example 1, injection molding was performed using the same material as in Example 1 except that the mold was changed to produce a container having a size of 50 × 80 × 29 cm. The weight of the obtained container was 15 kg.
The evaluation results are shown in Table 3. The expansion ratio of the container was 1.4 and the density was 1.0 g / cc, and a container with extremely excellent performance was obtained.

<Comparative Example 4> In Comparative Example 1, injection molding was performed using the same material as in Comparative Example 1 except that the mold was changed to produce a container having a size of 50 × 80 × 29 cm. Table 3 shows the evaluation results of the obtained containers. <Comparative Example 5> In Comparative Example 2, injection molding was performed using the same material as Comparative Example 2 except that the mold was changed, and 50 × 80.
A container having a size of 29 cm was manufactured. Table 4 shows the evaluation results of the obtained containers. <Comparative Example 6> In Comparative Example 2, injection molding was performed using the same material as in Comparative Example 3 except that the mold was changed to 50 × 80.
A container having a size of 29 cm was manufactured. Table 4 shows the evaluation results of the obtained containers.

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[Table 1]

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[Table 2]

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[Table 3]

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[Table 4]

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The glass fiber reinforced polyethylene terephthalate composition of the present invention has not only excellent physical properties such as impact resistance but also excellent cost. In particular, it is suitable as a large product such as a pallet or a container, and its industrial value is extremely high.

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Claims (7)

[Claims] 1. A polyethylene terephthalate resin 97-
A composition comprising 3 to 30 parts by weight of an olefin polymer containing 40 to 90% by weight of glass fiber with respect to 70 parts by weight, the composition being melt-quenched and then heated at a rate of 20 ° C.
Temperature rising crystallization temperature (Tcc) measured at 140 / min is 140-
A glass fiber reinforced polyethylene terephthalate-based composition, characterized in that the glass fiber concentration (W) in the entire composition is 200 ° C. and 1 to 25% by weight. 2. The glass fiber reinforced polyethylene terephthalate composition according to claim 1, wherein the average length L (μm) of the glass fiber in the composition satisfies the following formulas (I) and (II). object. ## EQU1 ## 200 ≦ L ≦ 2000 (I) 500-10W ≦ L ≦ 1200-20W (II) 3. An injection-molded article obtained by injection-molding the glass fiber-reinforced polyethylene terephthalate composition according to claim 1. 4. The average length L of glass fibers in a molded product.
The injection-molded article according to claim 3, wherein (μm) satisfies the following formulas (I) and (II). (2) 200 ≦ L ≦ 2000 (I) 500-10W ≦ L ≦ 1200-20W (II) 5. The large-sized molded product according to claim 3, wherein the injection-molded product is a large-sized injection-molded product having a weight of 1 kg or more. 6. The large-sized molded product according to claim 5, wherein the large-sized injection-molded product is a pallet. 7. The large molded product according to claim 5, wherein the large molded product is a container.