JP3336787B2 - Polyethylene terephthalate resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a polyethylene terephthalate resin composition having excellent thermal stability and improved crystallinity. The resin composition of the present invention is useful as a structural material in a wide range of fields such as mechanical parts, electric / electronic parts, automobile parts, heat-resistant food containers and the like.

[0002]

2. Description of the Related Art Polyethylene terephthalate resin is a material having excellent heat resistance and rigidity when crystallized, but has a drawback that crystallization from a molten state is slow.
Therefore, melt molding polyethylene terephthalate resin,
It is necessary to increase the crystallization rate, especially when trying to apply a method requiring a fast molding cycle such as injection molding.

Various nucleating agents have been studied in an attempt to increase the crystallization rate of polyethylene terephthalate resin. For example, talc, kaolin, clay and the like are already known as inorganic nucleating agents, and salts of aromatic acid derivatives such as sodium salts of p-phenolsulfonic acid and p-hydroxybenzoic acid as organic nucleating agents are already known. Conventionally, it is also known to use a plasticizer such as polyethylene glycol in combination.

However, even if talc, which is considered to be one of the most excellent inorganic nucleating agents, is used, its nucleating effect is not always sufficient, and an organic nucleating agent is used in combination for the purpose of promoting post-crystallization of the surface layer. Although it is necessary, the organic nucleating agent has a drawback that the molecular weight of the polyethylene terephthalate resin is reduced in a molten state, and there is a problem in thermal stability. JP-A-5-186
No. 672 discloses a technique using a metal thiocyanate exhibiting an excellent nucleating agent effect,
Since it contains an alkali component such as sodium ion, there still remains a problem in thermal stability.

[0005]

SUMMARY OF THE INVENTION In view of the present state of the art relating to such a crystal nucleating agent for polyethylene terephthalate resin, the present invention has a high solidification rate in injection molding and the like, has excellent retention heat stability, and has a wide range of structural materials. It is an object of the present invention to provide a polyethylene terephthalate resin composition useful as a resin.

[0006]

That is, according to the present invention, a layered silicate containing an organic onium ion between layers is added to a polyethylene terephthalate resin in an amount of 0.01 to ash.
The present invention provides a polyethylene terephthalate resin composition which is fast in crystallization and has excellent heat stability, containing 0.1 to 5% by weight of a modified polyolefin having at least one epoxy group in a molecule and 10 to 10% by weight. is there.

Hereinafter, the present invention will be described in detail. Polyethylene terephthalate resin is a polyester,
It is a polymer containing terephthalic acid as an acid component of the repeating unit and ethylene glycol as a diol component. In the polyethylene terephthalate resin used in the present invention, both the acid component and the diol component may contain a copolymerization component, but terephthalic acid as the acid component, ethylene glycol as the diol component, and 50% of the acid component and the diol component, respectively. It is desirably at least 70 mol%, preferably at least 70 mol%, more preferably at least 80 mol%, most preferably at least 90 mol%. If these amounts are less than 50 mol%, the characteristics of the polyethylene terephthalate resin, that is, excellent heat resistance and rigidity when crystallized, may be lost.

The copolymer component used in the polyethylene terephthalate resin includes, as an acid component, aromatic dicarboxylic acids such as isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid. Acids; aliphatic dicarboxylic acids such as adipic acid and sebacic acid; and ester-forming derivatives such as alkyl esters and acid halides thereof. Examples of the diol component include tetramethylene glycol,
Hexamethylene glycol, diethylene glycol, cyclohexanedimethanol, cyclohexanediol,
Examples thereof include low molecular diols such as 1,4-bisoxyethoxybenzene and bisphenol A; high molecular diols such as polyethylene glycol, polytetramethylene glycol and polyhexamethylene glycol; and ester-forming derivatives thereof.

These acid components and diol components may be used in combination of a plurality of types. Further, plural kinds of polyethylene terephthalate resins having different compositions may be used in combination. As the layered silicate used in the present invention, a 2: 1 type in which an octahedral sheet structure containing Al, Mg, Li or the like is sandwiched between two silicate tetrahedral sheet structures is preferable. The thickness of a certain layer is usually about 9.5 angstroms.

Specifically, montmorillonite, hectorite, fluorine hectorite, saponite, beidellite,
Smectite clay minerals such as stevensite; swelling synthetic mica such as Li-type fluorine teniolite, Na-type fluorine teniolite, Na-type tetrasilicon fluoromica, Li-type tetrasilicon fluoromica; vermiculite, fluorine vermiculite, halloysite, and the like; Or synthesized.

In the present invention, the cation exchange capacity (CEC) of these layered silicates is usually 30 meq / 10
Although it is 0 g or more, it is preferably 50 meq / 100 g or more, more preferably 70 meq / 100 g or more. There is no particular upper limit, but usually the largest that is economically available is 120 meq / 100
g. The cation exchange capacity is measured by measuring the amount of adsorbed methylene blue. If the cation exchange capacity is less than 30 meq / 100 g, the intercalation amount of organic onium ions may be insufficient.

Among these layered silicates, smectite-based clay minerals such as montmorillonite and hectorite, Li-type fluorine teniolite, Na-type fluorine teniolite, Na-type tetrasilicon mica and the like are preferable from the viewpoint of cation exchange capacity and availability. Swellable synthetic mica is preferably used, and particularly in view of the effect of a nucleating agent, Li-type fluorine teniolite (the following formula a), Na-type fluorine teniolite (the following formula b), Na-type tetrasilicon fluorine mica (the following formula c), and the like. Swellable fluorine mica,
And synthetic hectorite (the following formula d, wherein X represents a hydroxyl group or a fluorine atom) is most suitable. Note that equations a, b,
c and d indicate ideal compositions, and do not need to exactly match.

[0013]

## EQU1 ## LiMg ₂ Li (Si ₄ O ₁₀ ) F ₂ (a) NaMg ₂ Li (Si ₄ O ₁₀ ) F ₂ (b) NaMg _2.5 (Si ₄ O ₁₀ ) F ₂ (c) Na _0.33 Mg _2.67 Li _0.33 (Si ₄ O ₁₀ ) X ₂ (d)

In the polyethylene terephthalate resin composition, it is desirable that the layered silicate is uniformly dispersed. In the present invention, an organic onium ion is added between the layers of the layered silicate in order to enhance the dispersibility of the layered silicate. It is necessary to do so, and the operation is generally called lipophilic treatment. Here, the uniform dispersion means that the average particle size of the dispersed particles is 10 to 500 nm, preferably 10 to 300 n.
m, most preferably from 10 to 100 nm. The average particle diameter is, for example, an amount determined from an image obtained by observation with a transmission electron microscope. The average particle size is 500
If it exceeds nm, the surface smoothness of the molded article may be impaired, and if it is less than 10 nm, the nucleating agent effect may be insufficient. In the present invention, by inserting the onium ions, it is considered that an organic structure having a small intermolecular force can be introduced between the layers of the negatively charged silicate layer, thereby improving the shear cleavage. The insertion of the onium ion between the layers is carried out by an ion exchange reaction of the onium ion with a layered silicate containing a negative layer lattice and exchangeable cations. The ion exchange reaction is described, for example, in JP-B-61-5492 and JP-A-60-4245.
The reaction can be carried out according to a known method described in, for example, No. 1 and the like, and preferable reaction conditions and the like are, for example, as follows.

The organic onium ion has a structure represented by an ammonium ion, a phosphonium ion, a sulfonium ion, an onium ion derived from a heteroaromatic ring, or the like. Among these, from the viewpoints of availability and stability, ammonium ions, phosphonium ions, and onium ions derived from a heteroaromatic ring are preferred. Examples of the ammonium ion include primary ammoniums, secondary ammoniums, tertiary ammoniums, and quaternary ammoniums.

Specifically, as primary ammoniums,
Alkyl ammonium (dodecyl ammonium, hexadecyl ammonium, octadecyl ammonium, etc.),
ω-amino acid ammonium (6-aminohexanoic acid, 8
-Aminooctanoic acid, 10-aminodecanoic acid, 12-aminododecanoic acid, etc.). The secondary ammoniums include methyl dodecyl ammonium, butyl dodecyl ammonium, methyl octadecyl ammonium, and the tertiary ammoniums include dimethyl dodecyl ammonium, dimethyl hexadecyl ammonium, dimethyl octadecyl ammonium, diphenyl dodecyl ammonium, diphenyl octadecyl ammonium, and the like. Be mentioned

The quaternary ammoniums include tetraalkylammonium having only an alkyl group in the molecule;
And quaternary ammonium having a group other than an alkyl group. As tetraalkylammonium, specifically, ammonium having four identical alkyl groups (tetraethylammonium, tetrabutylammonium, tetraoctylammonium, etc.); ammonium having four different alkyl groups in the molecule, particularly having 1-4 carbon atoms Having a lower alkyl group and an alkyl group having 5 or more, preferably 8 or more carbon atoms, ie, an ammonium having three lower alkyl groups in a molecule, for example, trimethylammonium (trimethyloctyl ammonium, trimethyldecylammonium, trimethyldodecyl) Ammonium, trimethyltetradecylammonium, trimethylhexadecylammonium, trimethyloctadecylammonium, trimethyleicosanylammonium, trimethyloctadecenyla Moniumu, trimethyl octadecadienyl ammonium, etc.), triethylammonium (triethylammonium dodecyl ammonium, triethyl tetradecyl ammonium, triethyl hexadecyl ammonium, triethyl ammonium, etc.),
Tributylammonium (tributyldodecylammonium, tributyltetradecylammonium, tributylhexadecylammonium, tributyloctadecylammonium, etc.); ammonium having two lower alkyl groups in the molecule, such as dimethyldialkylammonium (dimethyldioctylammonium, dimethyldidecylammonium, dimethyl Ditetradecyl ammonium, dimethyl dihexadecyl ammonium, dimethyl dioctadecyl ammonium, dimethyl dioctadecenyl ammonium, dimethyl dioctadecadenyl ammonium, etc.), diethyl dialkyl ammonium (diethyl didodecyl ammonium, diethyl ditetradecyl ammonium, diethyl Dihexadecyl ammonium, diethyldioctadecyl Ammonium etc.), dibutyl dialkyl ammonium (dibutyl dodecyl ammonium,
Dibutylditetradecylammonium, dibutyldihexadecylammonium, dibutyldioctadecylammonium, etc.); ammonium having only one lower alkyl group in the molecule, such as trialkylmethylammonium (trioctylmethylammonium, tridodecylmethylammonium, tritetramethylammonium Decylmethylammonium, etc.), trialkylethylammonium (trioctylethylammonium, tridodecylethylammonium, etc.), and trialkylbutylammonium (trioctylbutylammonium, tridodecylbutylammonium, etc.).

Examples of the quaternary ammonium having a group other than the alkyl group include quaternary ammoniums having an aromatic ring (eg, methylbenzyldihexadecyl ammonium, dibenzyldihexadecyl ammonium, and trimethylbenzyl ammonium). A quaternary ammonium derived from an aromatic amine (such as trimethylphenyl ammonium) is exemplified.

Examples of the phosphonium ion include alkyl quaternary phosphoniums (tetrabutylphosphonium, tetraoctylphosphonium, trimethyldecylphosphonium, trimethyldodecylphosphonium, trimethylhexadecylphosphonium, trimethyloctadecylphosphonium, tributyldodecylphosphonium, tributylhexadecylphosphonium, tributylhexadecylphosphonium Quaternary phosphoniums such as octadecylphosphonium and the like and quaternary phosphoniums having a phenyl group (phenyltrimethylphosphonium, phenyltributylphosphonium, diphenyldioctylphosphonium, triphenyloctadecylphosphonium, tetraphenylphosphonium and the like). As onium ions, pyridinium and methyl Rijiniumu, dimethyl pyridinium, quinolinium, isoquinolinium, include onium such as nicotinic acid or nicotinamide.

Among these organic onium ions, from the viewpoint of the effectiveness of the hydrocarbon structure that contributes to the hydrophobicity between the silicate layers, one molecule has two or three methyl or ethyl groups in one molecule, and dodecyl, tetradecyl, Alkyl quaternary ammonium having one or two alkyl groups having 12 or more carbon atoms such as hexadecyl and octadecyl, and quaternary ammonium having three methyl, ethyl or butyl groups and one alkyl group having 12 or more carbon atoms in one molecule. An ion such as phosphonium is preferably used. Among them, quaternary ammonium having three methyl groups and one alkyl group having 16 or more carbon atoms in one molecule, and two methyl groups and two alkyl groups having 14 or more carbon atoms in one molecule.
An ion such as a quaternary ammonium having one, a quaternary phosphonium having an alkyl group having 14 or more carbon atoms is preferably used, and most preferably a trimethyloctadecyl ammonium ion, a dimethyldihexadecyl ammonium ion,
Dimethyl dioctadecyl ammonium ion, tributyl hexadecyl phosphonium ion, and tributyl octadecyl phosphonium ion are used. These organic onium ions can be used alone or as a mixture of a plurality of types.

The insertion of the organic onium ion between the layers of the layered silicate is carried out by ion exchange in a polar solvent, preferably a protic solvent such as water, methanol, ethanol, propanol or butanol, or a mixed solvent of two or more thereof. Depends on the reaction. Preferred solvents for producing the intercalation compound used in the present invention are water, methanol and ethanol, but water is most suitable unless the solubility of the organic onium salt is extremely low.

After the organic onium ion insertion reaction, the formed intercalation compound is subjected to batch washing in which a stirring and washing step in a solvent and a separation step such as centrifugal separation and filtration are repeated in order to remove extra ions remaining outside the interlayer. Purification is performed by an appropriate method such as washing or continuous washing in which a solvent is continuously flowed for washing. For example, when a quaternary ammonium halide is used as a raw material, the degree of purification can be confirmed by adding an aqueous solution of silver nitrate to the washing solution so that generation of white silver halide is not observed. If the purification is insufficient, the free compounds derived from the organic onium ions may cause a decrease in thermal stability during molding, smoke, mold contamination, odor and the like. The water content of the intercalated compound after purification is 10 wt% or less, preferably 5 wt% or less, more preferably 3 wt% or less, in order to reduce undesirable side reactions such as hydrolysis during mixing with the polyethylene terephthalate resin. Control. The water content is 10w
If it exceeds t%, the molecular weight of the polyethylene terephthalate resin is significantly reduced due to hydrolysis, and the toughness of the polyethylene terephthalate resin composition is greatly reduced.

The amount of the organic onium ion in the intercalation compound is 0.8 to the cation exchange capacity of the raw phyllosilicate.
There is no particular limitation as long as it is in the range of 2.0 to 2.0 equivalents, but it is about 0.9 to 1.3 equivalents under normal reaction conditions. When this amount is less than 0.8 equivalent, dispersibility is reduced, and when it is more than 2.0 equivalent, the free compound derived from the onium ion becomes remarkable, resulting in a decrease in thermal stability at the time of molding, smoking, mold contamination, odor and the like. May cause.

The content of the layered silicate containing organic onium ions between layers is 0.01 to 10% by weight, preferably 0.05 to 7% by weight, more preferably 0.05 to 7% by weight, based on the polyethylene terephthalate resin. 0.1 to 5% by weight. If this amount is less than 0.01% by weight, the nucleating agent effect will not be exhibited, and if it exceeds 10% by weight, the toughness will not be sufficient and the molding surface property will deteriorate, which is not preferable.

The amount of the layered silicate added to the polyethylene terephthalate resin composition may be in a range corresponding to the above-mentioned ash content, and is specifically about 0.01 to 20% by weight. The ash content can be determined from the weight fraction of the residue obtained by completely burning off the organic content of the polyethylene terephthalate resin in an electric furnace at 650 ° C. The polyethylene terephthalate resin composition of the present invention needs to contain a modified polyolefin having at least one epoxy group in a molecule. It is presumed that the modified polyolefin functions as a plasticizer that enhances the molecular chain mobility when the polyethylene terephthalate resin molecular chain folds and crystallizes.

The polyolefin is ethylene or α
-A polymer obtained by copolymerizing an olefin. Specific examples of α-olefins include propene, butene, pentene,
Examples include linear olefins such as hexene, heptene and octene, and olefins having a side chain such as 3-methylbutene, 3-methylpentene, 3-methylhexene, 4-methylpentene and 4-methylhexene. The copolymerization ratio of the olefin is not particularly limited. Further, the polymerization degree of the polyolefin is usually from 10 to 5,000 in total carbon number, preferably from 20 to 1000, more preferably from 20 to 500, more preferably from 20 to 200, most preferably from about 20 to 100 from the plasticizer effect. I do.

The method for introducing the epoxy group into the polyolefin and the bonding position thereof are not limited. For example, copolymerizable epoxy group-containing monomers such as vinyl glycidyl ether, allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate and glycidyl crotonate are used. The compound may be introduced by polymerization, or may be introduced into the terminal by using a compound having an epoxy group as a chain transfer agent, a terminator, or the like. The number of epoxy groups is usually about 1 to 5 to 100 carbon atoms of the polyolefin, preferably 10 to 10 carbon atoms.
About 1 to 50, more preferably 10 to 4 carbon atoms
About 1 for 0, most preferably 20 to 40 carbon atoms
About one.

The content of the modified polyolefin having one or more epoxy groups in the molecule is 0.1 to 5% by weight, preferably 0.1 to 5% by weight, based on the polyethylene terephthalate resin.
It is 4% by weight, more preferably 0.5 to 3% by weight. When the amount is less than 0.1% by weight, the nucleating agent effect is insufficient, and when it exceeds 5% by weight, bleeding out occurs and sufficient heat resistance cannot be obtained.

The polyethylene terephthalate resin composition of the present invention may contain a nucleating agent, a charging material, a reinforcing material,
An additive such as a plasticizer can be used in combination. For example, as a nucleating agent, filler or reinforcing material, talc, clay, carion,
Inorganic particles such as mica, silica, boron nitride and silicon nitride, carbon compounds such as carbon black and graphite,
Metal oxides such as alumina, titania, zirconia, and titanium dioxide; sulfates such as calcium sulfate and barium sulfate;
Phosphates such as calcium phosphate and barium phosphate; and carbonates such as calcium carbonate, barium carbonate and magnesium carbonate. Besides these, organic acid metal salts such as sodium salt of p-phenolsulfonic acid and sodium salt of p-hydroxybenzoic acid as crystal nucleating agents, and glass fiber, carbon fiber, glass flake, glass beads, titanium Acid fibers, aluminum borate fibers and the like can be mentioned.

These fillers and reinforcing materials can be treated with a functionalized silane coupling agent such as epoxy silane or amino silane to improve the compatibility with the polyethylene terephthalate resin. As the plasticizer, long chain fatty acid salts such as calcium stearate and barium stearate, montanic acid derivatives, metal glycolates and the like can be used.

The polyethylene terephthalate resin composition of the present invention may contain another thermoplastic resin if necessary. As such a thermoplastic resin, polybutylene terephthalate, polybutylene naphthalate, polyethylene naphthalate, polycyclohexylene terephthalate, aromatic polyester resin such as polyester composed of cyclohexane dimethanol and terephthalic acid, aromatic polycarbonate resin, polyamide resin, phenoxy resin , Epoxy resin, polyphenylene ether resin, polyarylene sulfide resin, polystyrene resin, acrylic resin, thermoplastic polyurethane resin, polyamide elastomer, polyester elastomer, polyether elastomer, acrylic rubber, core-shell acrylic rubber,
Examples include styrene-based thermoplastic elastomers, polyethylene glycol, polytetramethylene glycol, and the like.

The method for producing the resin composition of the present invention is not particularly limited, but usually, melt mixing is used. Specifically, twin-screw extruder, single-screw extruder, Brabender, roll,
A kneader such as a Henschel mixer, a Banbury mixer, or a kneader, and a mixer are used. At this time, heat stabilizers, ultraviolet absorbers, antioxidants, antistatic agents, flame retardants, pigments,
A lubricant or the like may be mixed.

[0033]

Hereinafter, the present invention will be described with reference to specific examples.
The present invention is not limited by these examples unless it departs from the gist thereof. The evaluation results of the following examples are summarized in Table 2. [Evaluation items] (1) Crystallinity 2 m by J28SA injection molding machine manufactured by Japan Steel Works, Ltd.
An m-thick flat plate (5 cm square) was molded under the conditions of a barrel temperature of 290 ° C., a mold temperature of 80 ° C., injection / cooling = 10/10 seconds, and an injection speed of maximum. Next, a small piece was cut out from the center of the flat plate with a cutter, and the DSC2000 manufactured by DuPont was used.
The temperature is raised and lowered at a rate of 16 ° C./min between 25 ° C. and 300 ° C. (held at 300 ° C. for 5 minutes), and the post-crystallization temperature Tcc (° C.) and the post-crystallization heat ΔHcc (J /
g), the heat of fusion of the specimen △ Hm (J / g), the crystallization temperature Tc (° C.) at the time of cooling, and the heat of crystallization △ Hc (J / g). (%) Was calculated to estimate the crystallinity of the flat plate.

[0034]

Dc = (△ Hm- △ Hcc) / △ Hc (e)

The equation e shows that the actual cooling rate in the mold is DS
Since the cooling rate in the C measurement is much higher than 16 ° C./min, the ultimate crystallinity of the portion that can be substantially crystallized by the temperature-reducing crystallization in the DSC measurement is defined as 100%. The crystallinity in actual molding is larger as ΔHcc is smaller and Dc is larger, and the crystallization ability of the sample is Tcc.
Is higher, Tc is higher, and ΔHc is higher.

(2) Molecular weight A sample was prepared using phenol / sym-tetrachloroethane (50
/ 50 wt%) in a mixed solution at a concentration of 1 g / dl, the solution viscosity was measured at 30 ° C, and the intrinsic viscosity [η] (dl /
g). (3) Thermal stability Shimadzu Corporation's Flow Tester CFT500C
The change in intrinsic viscosity [η] (dl / g) when the above-mentioned plate sample was packed in a cylinder at 280 ° C. and kept for 7 minutes was measured. (4) Layered silicate used Table 1 shows the name, mineral name, type, cation exchange capacity measured by methylene blue adsorption method, and manufacturer of the layered silicate used.

[0037]

[Table 1]

(5) Lipophilic treatment of layered silicate (Example 2)
And 3) About 100 g of the layered silicate was precisely weighed, and this was stirred and dispersed in 10 liters of water at room temperature, and a hydrochloride of ammonium ion equivalent to 1.2 times the ion exchange capacity was added thereto and stirred for 6 hours. The purified sedimentable solid was separated by filtration, washed with stirring in 30 liters of deionized water, and then filtered again. This washing and filtration operations were performed at least three times, and it was confirmed that chloride ions were not detected in the silver nitrate test of the washing solution. The obtained solid was air-dried for 3 to 7 days and then crushed in a mortar, and further dried in a mortar at 50 ° C. for 3 to 10 hours. Drying conditions vary depending on the type of ammonium ion of the guest, but the residual water content evaluated by ensuring pulverizability with a maximum particle size of about 100 microns and a decrease in thermogravity when kept at 120 ° C. for 1 hour under a nitrogen stream. Is 2 to 3 wt% as an index.

Example 1 Polyethylene terephthalate ([η] =) produced using antimony trioxide as a polymerization catalyst
0.64 (dl / g)) 97 parts by weight, lipophilic synthetic smectite (1.1 equivalents of dimethyl distearyl ammonium inserted between synthetic hectorite layers) [SAN manufactured by Corp Chemical Co.] 1.3 parts by weight Part and an α-olefin polymer having an epoxy group at one end (C30) [AOE-Z manufactured by Adeka Argus Co., Ltd.]
2 parts by weight are blended by dray, and TEM manufactured by Toshiba Machine Co., Ltd.
The mixture was melt-kneaded by a 35B twin screw extruder. The kneading conditions were a barrel temperature setting of 280 ° C., a screw having one kneading disk, and a rotation speed of 150 rpm. The obtained molten strand was water-cooled and pelletized. After vacuum drying the composition pellets, they were used for the above evaluation.

Example 2 In Example 1, swellable synthetic mica (fluorinated teniolite structure) was used in place of lipophilic synthetic smectite [ME-10 manufactured by Corp Chemical Co., Ltd.].
0], the same experiment was carried out using the same lipophilic treatment, that is, one obtained by inserting 1.05 equivalent of dimethyldistearyl ammonium. [Example 3] In Example 1, 1.05 equivalent of trimethyldecyl ammonium was inserted into untreated synthetic smectite (hectorite structure) [SWN manufactured by Corp Chemical Co., Ltd.] instead of lipophilic synthetic smectite SAN. A similar experiment was carried out using the obtained one.

[Comparative Example 1] The same melt-kneading operation and evaluation as in Example 1 were performed using only the polyethylene terephthalate of Example 1, and the solidification was slow in the mold at the time of forming a flat plate and the crystallization speed was low. It was low. [Comparative Example 2] In Example 1, lipophilic synthetic smectite S
When the same experiment was performed without adding AN, the solidification in the mold at the time of forming a flat plate was slow and the crystallization speed was low.

[Comparative Example 3] In Example 2, swellable synthetic mica ME-100 was not subjected to lipophilic treatment, and ME-100 was not used.
The same experiment was carried out using 1 part by weight of. [Comparative Example 4] The same experiment was performed as in Example 1, except that the modified α-olefin polymer AOE-Z was replaced with polyethylene glycol (number average molecular weight 6,000) end-blocked by a phenyl group. During the molding of the flat plate, the solidification in the mold was clearly slow and the crystallization rate was low, so no evaluation was performed.

[Comparative Example 5] A similar experiment was conducted in Example 1 without adding the modified α-olefin polymer AOE-Z. As a result, the solidification in the mold at the time of forming a flat plate was clearly slow. Evaluation was not performed because the crystallization rate was low. [Comparative Example 6] In Example 1, 90 parts by weight of polyethylene terephthalate was used, and the modified α-olefin polymer AOE-Z was used.
Was adjusted to 10 parts by weight, and the same experiment as in Example 1 was carried out. Bleed-out was observed on the surface of the flat plate, and thus no evaluation was performed.

Comparative Example 7 (Comparison with polyethylene terephthalate resin composition of general grade for injection molding) 97% by weight of polyethylene terephthalate of Example 1, 0.7% by weight of talc, p-hydroxybenzoic acid · 2Na Was dry-blended with 0.3% by weight of polyethylene glycol and 2% by weight of polyethylene glycol end-blocked with a phenyl group in Comparative Example 4, and the same melt kneading and evaluation as in Example 1 were performed. As shown in Table 2, the polyethylene terephthalate resin composition of the present invention is compared with a general injection molding grade composition.
Particularly excellent in thermal stability.

[0045]

[Table 2]

[0046]

Since the polyethylene terephthalate resin composition of the present invention has excellent crystallinity and thermal stability, it has a high solidification rate in injection molding and the like, has excellent retention heat stability, and is useful as a structural material in a wide range of fields. is there.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 67/00-67/02

Claims (6)

(57) [Claims] 1. A polyethylene terephthalate resin comprising 0.01 to 10% by weight of a layered silicate containing an organic onium ion between layers as an ash content, and 0.1% of a modified polyolefin having one or more epoxy groups in a molecule. 1-5
A polyethylene terephthalate resin composition which is contained by weight%. 2. The polyethylene terephthalate resin composition according to claim 1, wherein the layered silicate is hectorite. 3. The polyethylene terephthalate resin composition according to claim 1, wherein the layered silicate is a swellable fluoromica. 4. The polyethylene terephthalate resin composition according to claim 1, wherein the organic onium ion is a quaternary ammonium ion having an alkyl group having 12 or more carbon atoms. 5. The polyethylene terephthalate resin composition according to claim 4, wherein the quaternary ammonium ion is a tetraalkyl ammonium having a lower alkyl group and an alkyl group having 12 or more carbon atoms in the molecule. 6. The modified polyolefin having one epoxy group for 5 to 100 carbon atoms of the polyolefin.
6. The polyethylene terephthalate resin composition according to claim 1, which is an olefin polymer.