JP2001323145A - Polyester resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a polyester resin composition excellent in the balance of physical properties by improving heat stability in a molten state while maintaining low warpage, good external appearances and excellent mechanical characteristics. SOLUTION: The polyester resin composition comprises a thermoplastic polyester resin and a layered compound treated with a polyether compound having a cyclic hydrocarbyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyester resin composition containing a thermoplastic polyester resin and a layered compound treated with a polyether compound having a cyclic hydrocarbon group.

[0002]

2. Description of the Related Art Thermoplastic polyester resins such as polyethylene terephthalate are excellent in heat resistance, chemical resistance, weather resistance, mechanical properties, electrical properties, etc., and are used in many industrial applications as injection molding materials, fibers and films. Although they are used, higher mechanical properties and heat resistance are required. In general, attempts have been made to meet such demands by blending various inorganic particles.However, this impairs the surface appearance of the product and the orientation of the fibrous inorganic material during injection molding causes anisotropy. There was a problem that the nature occurs.

[0003] Such defects of the inorganic particles are generally considered to be caused by poor dispersion of the inorganic particles or an excessively large dispersed particle size, and a technique for finely dispersing the inorganic particles has been desired.

[0004] Among inorganic particles, layered compounds, especially layered silicates, include a polymer compound (intercalant polymer) such as polyvinylpyrrolidone as a technique for facilitating cleavage and fine dispersion of the layered silicate layer. (Japanese Unexamined Patent Publication No. Hei 9-118518) discloses a method of intercalating a compound into an interlayer compound between layered silicates. However, in the above invention, although an interlayer compound is disclosed, a technique of cleaving the interlayer compound and finely dispersing it in a thermoplastic polyester resin is not disclosed,
It was difficult to finely disperse the layered silicate in a thermoplastic polyester resin.

On the other hand, the present inventors have proposed that a layered silicate be cleaved and finely dispersed in a thermoplastic polyester resin by treating the layered silicate with a polyether compound to form a clay interlayer compound. It has been found that it is particularly effective to use a polyester resin composition containing a thermoplastic polyester resin and a clay intercalation compound (JP-A-10-259016, JP-A-10-31).
No. 0420). By this technique, the elastic modulus and heat resistance could be increased without lowering the surface appearance or causing warpage. However, the thermal stability in the molten state is not always sufficient, and in some cases, the strength tends to decrease when staying in the molten state.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems, to improve the thermal retention in the molten state while improving the elasticity and heat resistance with low warpage, and to improve the melt retention. It is an object of the present invention to provide a polyester resin composition which prevents a decrease in strength at the time and has an excellent balance of physical properties.

[0007]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, completed the present invention.

That is, the present invention relates to a polyester resin composition containing a thermoplastic polyester resin and a layered compound treated with a polyether compound having a cyclic hydrocarbon group.

In a preferred embodiment, the invention relates to the polyester resin composition as described above, wherein the cyclic hydrocarbon group is an aromatic hydrocarbon group.

In a further preferred embodiment, the polyether compound has the following general formula (1) in the main chain:

[0011]

Embedded image(Wherein -A- is -O-, -S-, -SO-, -SO
_Two-, -CO-, an alkylene group having 1 to 20 carbon atoms, or
An alkylidene group having 6 to 20 carbon atoms;¹, R ^Two, R^Three,
R^Four, R^Five, R⁶, R⁷, And R⁸Is a hydrogen atom,
A hydrogen atom or a monovalent hydrocarbon group having 1 to 5 carbon atoms
And they may be the same or different
good. Characterized in that it has a unit represented by)
Some embodiments relate to the polyester resin composition described in any of the above.

In a further preferred embodiment, the polyether compound is represented by the following general formula (2):

[0013]

Embedded image(Wherein -A- is -O-, -S-, -SO-, -SO
_Two-, -CO-, an alkylene group having 1 to 20 carbon atoms, or
An alkylidene group having 6 to 20 carbon atoms;¹, R ^Two, R^Three,
R^Four, R^Five, R⁶, R⁷, And R⁸Is a hydrogen atom,
A hydrogen atom or a monovalent hydrocarbon group having 1 to 5 carbon atoms
Yes, R⁹, R^TenIs a divalent carbon having 1 to 5 carbon atoms.
A hydrogen group,¹¹, R¹²Are hydrogen atoms and carbon numbers
1-20 monovalent hydrocarbon groups, each of which is
They may be the same or different. m and n are oki
Indicates the number of repeating units of a silalkylene unit, and 2 ≦ m + n
≤50. )
The present invention relates to the polyester resin composition described in any of the above.

In a further preferred embodiment, the layered compound treated with the polyether compound is obtained by mixing the layered compound and the polyether compound in water or a polar solvent containing water. The present invention relates to the polyester resin composition according to any one of the above.

In a further preferred embodiment, the ratio of the layered compound having an equivalent area circle diameter [D] of 3000 ° or less in the polyester resin composition is 20% or less.
% Of the polyester resin composition according to any one of the above.

As a further preferred embodiment, the present invention relates to the polyester resin composition according to any one of the above, wherein the average value of the equivalent area circle diameter [D] of the layered compound in the polyester resin composition is 5000 ° or less.

In a further preferred embodiment, the average thickness of the layered compound in the polyester resin composition is 500 °.
The present invention relates to the polyester resin composition according to any one of the above, wherein:

In a further preferred embodiment, the maximum thickness of the layered compound in the polyester resin composition is 2,000.
に 関 す る The present invention relates to the polyester resin composition according to any one of the above, which is characterized by the following.

In a further preferred embodiment, the layer compound in the polyester resin composition has an [N] value of 30 or more, where the [N] value is 100 μm in area of the resin composition.
The present invention relates to the polyester resin composition according to any one of the above, which is defined as the number of particles per unit ratio of the layered compound present in m ² .

As a further preferred embodiment, the present invention relates to the polyester resin composition according to any one of the above, wherein the average aspect ratio (layer length / layer thickness ratio) of the layered compound in the polyester resin composition is 10 to 300. .

In a further preferred embodiment, the present invention relates to the polyester resin composition according to any one of the above, wherein the layered compound is a layered silicate.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION The thermoplastic polyester resin used in the present invention includes an acid component containing a dicarboxylic acid compound and / or an ester-forming derivative of dicarboxylic acid as a main component, and a diol compound and / or an ester of a diol compound. Any known thermoplastic polyester resin obtained by a reaction with a diol component containing a forming derivative as a main component.

The term "main component" means that the proportion of each in the acid component or diol component is 80% or more, and more preferably 90% or more, and the upper limit is 100%.

Specific examples of the thermoplastic polyester resin include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, and polycyclohexane-1,4.
-Dimethyl terephthalate, neopentyl terephthalate, polyethylene isophthalate, polyethylene naphthalate, polybutylene naphthalate, polyhexamethylene naphthalate and the like. Further, a copolymerized polyester produced by using two or more kinds of acid components and / or diol components used for producing these resins may be mentioned.

The above-mentioned thermoplastic polyester resins can be used alone or in combination of two or more having different compositions or components and / or having different intrinsic viscosities.

Among the polyester resins, polyethylene terephthalate, polybutylene terephthalate, polycyclohexane-1,4-dimethyl terephthalate, and polyethylene naphthalate are preferred from the viewpoints of strength, elastic modulus, cost and the like.

The molecular weight of the thermoplastic polyester resin is such that the logarithmic viscosity measured at 25 ° C. using a phenol / tetrachloroethane (5/5 weight ratio) mixed solvent is 0.3 to 2.0.
0 (dl / g) is preferable, and more preferably 0.
3 to 1.8 (dl / g), more preferably 0.3 (dl / g).
To 1.5 (dl / g), particularly preferably 0.3 to
1.2 (dl / g). When the logarithmic viscosity is 0.3 (dl /
g), the mechanical properties and impact resistance of the obtained polyester resin composition are low, and 2.0 (dl /
If it is larger than g), the molding fluidity tends to decrease because the melt viscosity is high.

The layered compound used in the present invention includes silicate, phosphate such as zirconium phosphate, titanate such as potassium titanate, tungstate such as sodium tungstate, and uranium such as sodium uranate. Acid salts,
At least one selected from the group consisting of vanadates such as potassium vanadate, molybdates such as magnesium molybdate, niobates such as potassium niobate, and graphite. Layered silicates are preferably used from the viewpoints of availability, handling, and the like.

The above-mentioned layered silicate is mainly formed of a tetrahedral sheet of silicon oxide and an octahedral sheet of metal hydroxide, and examples thereof include smectite clay and swelling mica.

The aforementioned smectite clay following general formula _{^{(3): X 1 0.2 ~}} 0.6 Y 1 2 ~ 3 Z 1 4 O 10 (OH) 2 · nH 2 O (3) ( wherein, X ¹ is K , Na, 1 / 2Ca, and 1 / 2Mg
At least one element selected from the group consisting of, Y ¹ is Mg,
At least one selected from the group consisting of Fe, Mn, Ni, Zn, Li, Al, and Cr, wherein Z ¹ is Si and A
at least one member selected from the group consisting of In addition, H ₂ O
Represents a water molecule bound to an interlayer ion, and n varies remarkably depending on the interlayer ion and the relative humidity). Specific examples of the smectite group clay include, for example, montmorillonite, beidellite, nontronite, saponite, iron saponite, hectorite, sauconite, stevensite, bentonite, and the like, or their substituted products, derivatives, and mixtures thereof. . The distance between the bottom surfaces of the smectite group clay in the initial state of aggregation is about 1
0-17 °, and the average particle size of the smectite group clay in the agglomerated state is approximately 1000-1,000,000.

Further, the swelling mica represented by the following general formula _{^{(4): X 2 0.5 ~}} 1.0 Y 2 2 ~ 3 (Z 2 4 O 10) (F, OH) 2 (4) ( wherein, X ² Is at least one member selected from the group consisting of Li, Na, K, Rb, Ca, Ba, and Sr, and Y ² is one member selected from the group consisting of Mg, Fe, Ni, Mn, Al, and Li. Z ² is Si, Ge, Al,
At least one selected from the group consisting of Fe and B. ), Natural or synthetic.
These are substances having the property of swelling in water, a polar solvent compatible with water at an arbitrary ratio, and a mixed solvent of water and the polar solvent. For example, lithium-type teniolite, sodium-type teniolite, lithium-type Examples thereof include silicon mica, sodium tetrasilicic mica, and the like, and substituted substances, derivatives, and mixtures thereof. The swellable mica has a bottom spacing of about 10 in the initial state of aggregation.
Å17 °, and the average particle size of the swellable mica in the aggregated state is about 1000-1,000,000 °.

Some of the above-mentioned swellable mica have a structure similar to that of vermiculite, and such a vermiculite equivalent can be used. The said vermiculite such equivalent has three octahedral type and dioctahedral the following general formula (5): (Mg, Fe , Al) 2 ~ 3 (Si 4-x Al x) O 10 (OH) 2 (M ⁺ , M ²⁺ _1/2 ) _x · nH ₂ O (5) (where M is an exchangeable cation of an alkali or alkaline earth metal such as Na and Mg, x = 0.6-0) .9, n =
3.5 to 5). In the initial state of aggregation of the vermiculite-equivalent product, the distance between the bottom surfaces is approximately 10 to 17 °, and the average particle size in the aggregated state is approximately 1000 to 5,000,000 °.

The crystal structure of the layered silicate is desirably high in purity, which is regularly stacked in the c-axis direction.
A so-called mixed layer mineral in which the crystal cycle is disturbed and a plurality of types of crystal structures are mixed can also be used.

The layered silicate may be used alone or in combination of two or more. Among them, montmorillonite, bentonite, hectorite, and swellable mica having sodium ions between layers are preferable from the viewpoint of the dispersibility in the obtained polyester resin composition and the effect of improving the physical properties of the polyester resin composition.

The polyether compound having a cyclic hydrocarbon group used in the present invention refers to a side chain and / or a main chain of a polyoxyalkylene compound such as polyoxyethylene or a polyoxyethylene-polyoxypropylene copolymer. Those having a cyclic hydrocarbon group therein are intended. The cyclic hydrocarbon group means an aromatic hydrocarbon group and / or an alicyclic hydrocarbon group, and includes, for example, a phenyl group, a naphthyl group, a cycloalkyl group and the like. In the present specification, a “phenyl group” is intended to include a polyvalent cyclic hydrocarbon group such as a “phenylene group” unless otherwise specified. Similarly, the naphthyl group and the cycloalkyl group include a naphthylene group and a cycloalkylene group, respectively.

The above-mentioned polyether compound may have a functional group other than a silicon-containing functional group capable of forming a Si—O—Si bond, such as an alkoxysilyl group or a silanol group. Any functional group can be used as long as it does not adversely affect the resin or the layered compound. Examples of the substituent include a saturated or unsaturated monovalent or polyvalent aliphatic hydrocarbon group, a group linked by an ester bond, an epoxy group, an amino group, a carboxyl group, and a group having a carbonyl group at a terminal. , Amide group, mercapto group,
Groups bonded by sulfonyl bond, groups bonded by sulfinyl bond, nitro group, nitroso group, nitrile group,
Examples include a halogen atom and a hydroxyl group. One of these may be substituted, or two or more may be substituted.

The composition ratio of the substituents in the polyether compound is not particularly limited, but it is desirable that the polyether compound be soluble in water or a polar solvent containing water. Specifically, for example, the solubility in 100 g of water at room temperature is 1 g or more, preferably 2 g or more, more preferably 5 g or more, and still more preferably 10 g.
And more preferably 20 g or more.

The above-mentioned polar solvent includes, for example, alcohols such as methanol, ethanol and isopropanol;
Ethylene glycol, propylene glycol, 1,4-
Glycols such as butanediol, ketones such as acetone and methyl ethyl ketone, ethers such as diethyl ether and tetrahydrofuran, amide compounds such as N, N-dimethylformamide and N, N-dimethylacetamide, and pyridine and dimethyl sulfoxide as other solvents And N-methylpyrrolidone. Also, carbonic acid diesters such as dimethyl carbonate and diethyl carbonate can be used. These polar solvents may be used alone or in combination of two or more.

Among the above cyclic hydrocarbon groups, aromatic hydrocarbon groups are preferred from the viewpoint of heat stability and dispersibility of the layered compound.

In the polyether compound used in the present invention, the following general formula (1) is contained in the main chain:

[0041]

Embedded image In the formula, -A- is -O-, -S-, -SO-, -SO
_2- , -CO-, an alkylene group having 1 to 20 carbon atoms, or an alkylidene group having 6 to 20 carbon atoms, and R ¹ , R ² , R ³ ,
R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ are all a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group having 1 to 5 carbon atoms. May be. Those having the unit represented by the formula (1) can be preferably used from the viewpoint of thermal stability and dispersibility of the layered compound.

Among the above polyether compounds, the following general formula (2):

[0043]

Embedded image(Wherein -A- is -O-, -S-, -SO-, -SO
_Two-, -CO-, an alkylene group having 1 to 20 carbon atoms, or
An alkylidene group having 6 to 20 carbon atoms;¹, R ^Two, R^Three,
R^Four, R^Five, R⁶, R⁷, And R⁸Is a hydrogen atom,
A hydrogen atom or a monovalent hydrocarbon group having 1 to 5 carbon atoms
Yes, R⁹, R^TenIs a divalent carbon having 1 to 5 carbon atoms.
A hydrogen group,¹¹, R¹²Are hydrogen atoms and carbon numbers
1-20 monovalent hydrocarbon groups, each of which is
They may be the same or different. m and n are oki
Indicates the number of repeating units of a silalkylene unit, and 2 ≦ m + n
≤50. ) Represents thermal stability, layered compound
It is particularly preferably used in view of the dispersibility of the product and the availability.
Can be

The amount of the polyether compound used can be adjusted so that the affinity between the layer compound and the thermoplastic polyester resin and the dispersibility of the layer compound in the polyester resin composition are sufficiently enhanced. If necessary, plural kinds of polyether compounds having different functional groups can be used in combination. Therefore, the amount of the polyether compound used is not necessarily limited by numerical values, but the lower limit of the amount of the layered compound to 100 parts by weight of the layered compound is 0.1 part by weight,
Preferably 0.2 parts by weight, more preferably 0.3 parts by weight.
Parts by weight, more preferably 0.4 parts by weight, particularly preferably 0.5 parts by weight. The upper limit of the amount of the layered compound to 100 parts by weight of the layered compound is 200 parts by weight, preferably 180 parts by weight, more preferably 160 parts by weight, still more preferably 140 parts by weight, and particularly preferably. Is 120 parts by weight. If the lower limit of the amount of the polyether compound is less than 0.1 part by weight, the effect of finely dispersing the layered compound tends to be insufficient.
If the amount exceeds 200 parts by weight of the polyether compound, the effect does not change, so that it is not necessary to use more than 200 parts by weight.

In the present invention, the method for treating the layered compound with the polyether compound is not particularly limited, and may be, for example, the method described below.

First, the layered compound and the dispersion medium are stirred and mixed. The dispersion medium is intended to be water or a polar solvent containing water. More specifically, since it has already been described above, the description is omitted here.

The method of stirring the layered compound and the dispersion medium is not particularly limited. For example, the stirring is performed using a conventionally known wet stirrer. Examples of the wet stirrer include a high-speed stirrer in which a stirring blade rotates at a high speed and stirs, a wet mill for wet-milling a sample in a gap between a rotor and a stator at a high shear rate, and a mechanical method using a hard medium. Examples include wet-type pulverizers, wet-type collision pulverizers that collide a sample at a high speed with a jet nozzle, and the like, and wet-type ultrasonic pulverizer using ultrasonic waves. When it is desired to mix more efficiently, the rotation speed of the stirring is set to 1000 rpm or more, preferably 1500 rpm or more, more preferably 2000 rpm or more, or 500 (1 / s) or more, preferably 1000 (1 /
s) A shear rate of at least 1500 (1 / s) is applied. Upper limit of rotation speed is about 25000 rpm
And the upper limit of the shear rate is about 500000 (1 / s)
It is. It is not necessary to stir at a value greater than the upper limit because stirring tends to be performed at a value larger than the upper limit or does not change any more even when shearing is applied. The time required for mixing is 1 to 10 minutes or more. Next, after the polyether compound is added, stirring is further continued to mix well. Thereafter, it is dried and pulverized if necessary.

In the polyester resin composition of the present invention, the lower limit of the amount of the layered compound treated with the polyether compound having a cyclic hydrocarbon group per 100 parts by weight of the thermoplastic polyester resin is typically 0.1. Parts by weight, preferably 0.3 parts by weight, more preferably 0.5 parts by weight, still more preferably 1.0 parts by weight, particularly preferably 1.5 parts by weight. The upper limit of the amount is typically 150 parts by weight, preferably 100 parts by weight, more preferably 70 parts by weight, still more preferably 50 parts by weight, particularly preferably 30 parts by weight. It is prepared as follows. If the lower limit of the amount of the layered compound is less than 0.1 part by weight, the effect of improving mechanical properties and warpage may be insufficient, and the upper limit may be 15 parts by weight.
If the amount exceeds 0 parts by weight, the surface appearance of the molded article may be impaired.

The lower limit of the ash content of the polyester resin composition derived from the layered compound is typically 0.1% by weight, preferably 0.3% by weight, more preferably 0.5% by weight. % By weight, and more preferably 1.0% by weight.
It is particularly preferably prepared to be 1.5% by weight, and the upper limit of the ash content is typically 60% by weight, preferably 50% by weight, more preferably 40% by weight.
%, More preferably 30% by weight, particularly preferably 20% by weight. If the lower limit of the ash content is less than 0.1% by weight, the effect of improving mechanical properties and warpage may be insufficient, and if the upper limit is more than 60% by weight, the surface appearance of the molded article is impaired. There are cases.

The structure of the layered compound dispersed in the polyester resin composition of the present invention is completely different from the μm-sized aggregated structure in which a number of layers are laminated, as the layered compound before use has. That is, by being treated with the polyether compound, the layers are cleaved and subdivided independently of each other. As a result, the layered compound is dispersed in the polyester resin composition in a very fine and independent lamellar form, and the number thereof is significantly increased as compared with the layered compound before use. The dispersion state of such a lamellar layered compound is determined by the equivalent area circle diameter [D] and the aspect ratio (layer length /
(Layer thickness ratio), the number of dispersed particles, the maximum layer thickness, and the average layer thickness.

First, the equivalent area circle diameter [D] is calculated as the diameter of a circle having an area equal to the area on the microscope image of each layered compound dispersed in various shapes in an image obtained by a microscope or the like. Is defined as In that case, among the layered compounds dispersed in the polyester resin composition, the ratio of the number of layered compounds having an equivalent area circle diameter [D] of 3000 ° or less is 20% or more, preferably 35% or more, and It is preferably at least 50%, particularly preferably 65%.
% Or more. If the ratio of the equivalent area circle diameter [D] of 3000 ° or less is less than 20%, the effect of improving the mechanical properties and warpage of the polyester resin composition tends to be insufficient. The average value of the equivalent area diameter [D] of the layered compound in the polyester resin composition of the present invention is 5000 °.
Or less, preferably 4500 ° or less, more preferably 4000 ° or less, and particularly preferably 35 ° or less.
00 ° or less. Average value of equivalent area circle diameter [D] is 5
If it is more than 000 °, the effect of improving the mechanical properties and warpage of the polyester resin composition may not be sufficient, and the surface appearance of the molded product may be impaired. Although there is no particular lower limit, the effect hardly changes when the angle is less than about 100 °.

The equivalent area circle diameter [D] is measured by selecting an arbitrary region containing 100 or more layers of a layered compound on an image taken using a microscope or the like, and using an image processing device or the like. And can be quantified by computer processing.

When the average aspect ratio is defined as the number average of the ratio of the layer length / layer thickness of the layered compound dispersed in the resin, the average aspect ratio of the layered compound in the polyester resin composition of the present invention is as follows. 10 to 300, preferably 15 to 300. More preferably, it is 20 to 300. If the average aspect ratio of the layered compound is less than 10, the effect of improving the mechanical properties of the polyester resin composition of the present invention may not be sufficiently obtained. Also, 30
If the value is larger than 0, the effect does not change any more, so it is not necessary to make the average aspect ratio larger than 300.

When the [N] value is defined as the number of dispersed particles per unit weight ratio of the layered compound in the area of 100 μm ² of the polyester resin composition, the [N] value of the layered compound in the polyester resin composition of the present invention is determined. N] value is 30 or more, preferably 45 or more, and more preferably 60 or more. There is no upper limit,
When the value of [N] exceeds about 1000, the effect does not change any more. If the [N] value is less than 30, the effect of improving the mechanical properties and warpage of the polyester resin composition may not be sufficient. The [N] value can be obtained, for example, as follows. That is, the polyester resin composition is about 50 μm
１００100 μm-thick ultrathin section, and the section
Can be determined by dividing the number of particles of the layered compound existing in an arbitrary region having an area of 100 μm ² by the weight ratio of the layered compound used. Or,
On the TEM image, an arbitrary region (area is measured) in which 100 or more particles are present is selected, and the number of particles present in the region is divided by the weight ratio of the layered compound used to obtain an area of 10 or more.
A value converted to 0 μm ² may be used as the [N] value. Therefore, the [N] value can be quantified by using a TEM photograph or the like of the polyester resin composition.

When the average layer thickness is defined as the number average value of the layer thickness of the layered compound dispersed in a thin plate, the upper limit of the average layer thickness of the layered compound in the polyester resin composition of the present invention is 500 °. Or less, preferably 450 ° or less, more preferably 400 ° or less. If the average layer thickness is larger than 500 °, the effect of improving the mechanical properties of the polyester resin composition of the present invention may not be sufficiently obtained. The lower limit of the average layer thickness is not particularly limited, but is preferably larger than 50 °, more preferably 60 ° or more, and further preferably 70 ° or more.

When the maximum layer thickness is defined as the maximum value of the layer thickness of the layered compound dispersed in the form of a thin plate in the polyester resin composition of the present invention, the upper limit of the maximum layer thickness of the layered compound is 2000 ° C. Or less, preferably 1800 °
Or less, more preferably 1500 ° or less. If the maximum layer thickness is more than 2000 °, the balance between the mechanical properties and the surface appearance of the polyester resin composition of the present invention may be impaired. The lower limit of the maximum layer thickness of the layered compound is not particularly limited, but is preferably larger than 100 °, more preferably 150 ° or more, and further preferably 20 ° or more.
0 ° or more.

The layer thickness and the layer length are determined by heating and melting the polyester resin composition of the present invention and then hot press molding or stretch molding, and a thin molded product obtained by injection molding the molten resin. Can be determined from an image captured using a microscope or the like. That is, it is assumed that a thin plate-shaped injection-molded test piece of a film prepared by the above method or a thin plate having a thickness of about 0.5 to 2 mm is placed on the XY plane. An ultra-thin section of about 50 μm to 100 μm in thickness is cut out from the above film or test piece in a plane parallel to the XZ plane or the YZ plane, and the section is cut out for about 4 to 10
It can be determined by observing at a high magnification of 10,000 times or more. The measurement was placed on the elephant of the transmission electron microscope obtained by the above method,
Select any region containing 100 or more layered compounds,
It can be quantified by forming an image with an image processing device or the like and performing computer processing. Alternatively, it can also be obtained by measuring using a ruler or the like.

The method for producing the polyester resin composition of the present invention is not particularly limited. For example, a thermoplastic polyester resin and a layered compound treated with a polyether compound are mixed using various general kneaders. Examples of the method include melt kneading. Examples of the kneader include a single-screw extruder, a twin-screw extruder, a roll, a Banbury mixer, a kneader, and the like, and a kneader having a high shearing efficiency is particularly preferable. The layered compound treated with the thermoplastic polyester resin and the polyether compound may be melt-kneaded by being fed into the above kneading machine at a time, or the layered compound may be added to the thermoplastic polyester resin previously melted. You may melt-knead.

In the polyester resin composition of the present invention, if necessary, polybutadiene, butadiene-styrene copolymer, acrylic rubber, ionomer, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, natural rubber , Chlorinated butyl rubber, homopolymer of α-olefin, copolymer of two or more α-olefins (including any copolymer such as random, block and graft, and a mixture thereof); Alternatively, an impact modifier such as an olefin-based elastomer can be added. These may be modified with an acid compound such as maleic anhydride or an epoxy compound such as glycidyl methacrylate. In addition, other arbitrary thermoplastic resins or thermosetting resins, for example, unsaturated polyester resins, polyester carbonate resins, liquid crystal polyester resins, polyolefin resins, polyamide resins, rubber materials, as long as the properties such as mechanical properties are not impaired. Polymer-reinforced styrene resins, polyphenylene sulfide resins, polyphenylene ether resins, polyacetal resins, polysulfone resins, polyarylate resins, and the like can be used alone or in combination of two or more.

Further, according to the purpose, additives such as pigments and dyes, heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, lubricants, plasticizers, flame retardants, and antistatic agents may be added. Can be.

The polyester resin composition obtained in the present invention may be molded by injection molding or hot press molding, and can also be used for blow molding. The resulting molded article is excellent in appearance, mechanical properties, heat distortion resistance, and the like, and is therefore suitably used for, for example, automobile parts, household electric parts, household daily necessities, packaging materials, and other general industrial materials.

[0062]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention.

The main raw materials used in Examples and Comparative Examples are summarized below. Unless otherwise specified, the raw materials were not purified. (Raw materials)-Thermoplastic polyester resin: Polyethylene terephthalate resin (Velpet EFG85A, Kanebo Co., Ltd., logarithmic viscosity (η _inh ) = 0.85 (dl / g), hereinafter referred to as PET), polybutylene terephthalate resin (KOLON) KP210 (hereinafter referred to as PBT).・ Layered compound: Montmorillonite (Kunimine Industry Co., Ltd.)
Kunipia F, hereinafter referred to as Kunipia F) and swellable mica (Somasif ME100 of Corp Chemical Co., Ltd., hereinafter referred to as ME100). Polyether compounds: Polyethylene glycol containing bisphenol A units in the main chain (bisol 18EN and bisol 10EN from Toho Chemical Co., Ltd.) and polyethylene glycol (PEG400 and PEG1000 from Sanyo Chemical Co., Ltd.) were used. (Measurement of dispersion state) Ultrathin sections having a thickness of 50 to 100 µm were used. Transmission electron microscope (JEOL JEM-1200
Using EX), the dispersion state of the layered compound was observed and photographed at an acceleration voltage of 80 kV and a magnification of 40,000 to 1,000,000 times. In the TEM photograph, an arbitrary region where 100 or more dispersed particles are present is selected, and the layer thickness, the layer length, the number of particles ([N] value), the equivalent area circle diameter [D], and a ruler with a scale are used. It was measured by manual measurement or by processing using an image analyzer PIASIII manufactured by Interquest.

The equivalent area circle diameter [D] was measured by processing using an image analyzer PIASIII manufactured by Interquest. [N] value was measured as follows. First, on the TEM image, the number of particles of the layered compound present in the selected region is determined. Separately from this, the ash content of the resin composition derived from the layered compound is measured. The value obtained by dividing the number of particles by the ash content and converting the area to 100 μm ² was [N].
Value. The average layer thickness was the number average value of the layer thicknesses of the individual layered compounds, and the maximum layer thickness was the maximum value among the layer thicknesses of the individual layered compounds. If the dispersed particles are large and observation with a TEM is inappropriate, use an optical microscope (optical microscope BH-2 manufactured by Olympus Optical Co., Ltd.) in the same manner as described above to obtain [N].
The value was determined. However, if necessary, sample
250 using KAM hot stage THM600
It was melted at ２270 ° C., and the state of the dispersed particles was measured in the molten state. The average aspect ratio was a number average value of the ratio of the layer length to the layer thickness of each layered compound. The aspect ratio of the dispersed particles that do not disperse in a plate shape was a value of major axis / minor axis. Here, the long diameter is intended to be the long side of the rectangle assuming a rectangle having the smallest area among rectangles circumscribing the target particle in a microscope image or the like. Also, the minor axis is
The short side of the minimum rectangle is intended. (Bending characteristics) The polyester resin composition of the present invention was dried (140 ° C, 5 hours). Using an injection molding machine with a mold clamping pressure of 75 t, at a resin temperature of 250 to 270 ° C., a size of about 10 × 1
A test piece of 00 × 6 mm was injection molded. ASTM D-
According to 790, the bending strength and the flexural modulus of the obtained test piece were measured. (Melting heat stability) 250 ~ in the cylinder of the injection molding machine
After staying at 270 ° C. for 5 minutes, a test piece was obtained under the same conditions as the above bending characteristics, and the bending characteristics were evaluated. (Warp) Dry the polyester resin composition of the present invention (14
(0 ° C, 5 hours), mold temperature 120 ° C, resin temperature 2
Under the condition of 50-280 ° C, dimensions are about 120 × 120 × 1m
m plate-shaped test pieces were injection molded. Place the above-mentioned plate-shaped test piece on a flat surface, hold down one of the four corners of the test piece,
Of the remaining three corners, the value with the largest distance from the plane was measured using calipers or the like. Each of the four corners was pressed, and the average value of the obtained warpage values was obtained. (Surface Gloss) The surface gloss of a flat test piece molded under the same conditions as the warpage was measured. The measurement was performed at a reflection angle of 60 ° using a mini gloss master manufactured by ERICHSEN. Standard board 50%
Relative value to (Ash content) According to JIS K7052, the ash content of the polyester resin composition derived from the layered compound was measured. Production Example 1 Deionized water and a layered compound were mixed. The processing was then continued by adding the polyether compound and continuing mixing for 15-30 minutes. Thereafter, layered compounds (clays A-1 to A-8 and clays B-1 to B-3) which were pulverized and treated with a polyether compound were obtained. Table 1 shows the weight ratio of the raw materials used in the production examples.

[0065]

[Table 1] Production Example 2 76 parts by weight of propylene glycol and 0.0 part by weight of dimethyl terephthalate (DMT) were added to a reactor.
03 parts by weight of a hindered phenol-based stabilizer (Adeka Stab AO60, hereinafter referred to as AO60) and 0.00025 parts by weight of Ti (OBu) ₄ are added, and the mixture is stirred at a reaction temperature of about 150 to 200 ° C. DMT and propylene glycol were transesterified. afterwards,
0.00025 parts by weight of Sb ₂ O ₃ was added and the reaction temperature was 2
70-280 ° C. under reduced pressure (0.8-5.0 torr (0.
107-0.665 MPa)) to carry out melt polycondensation to obtain a polypropylene terephthalate (PPT) resin. Examples 1 to 9 Biaxial extrusion of 0.2 parts by weight of AO60 with respect to 100 parts by weight of PET and the layered compounds (A-1 to A-8) obtained in Preparation Example 1 and the weight ratio of PET shown in Table 2 Machine (Nippon Steel Corporation)
And TEX44) to obtain and evaluate a polyester resin composition. Table 2 shows the results.

[0066]

[Table 2] Comparative Examples 1 to 6 PET having a weight ratio shown in Table 3, layered compounds (B-1 to B-3) obtained in Production Example 1, ME100, Kunipia F, glass fibers (T-195H of NEC Corporation) ) And AO
60 was melt-kneaded in the same manner as in Example 1 and evaluated. Table 3 shows the results.

[0067]

[Table 3] As shown in Table 3, when ME100 and Kunipia F were not treated with the polyether compound, the bending properties were not improved, and good flat test pieces were not obtained. Polyether compounds having no cyclic hydrocarbon group (PEG400, PEG100
In the case of the treatment in 0), the bending properties after molding were improved, but the melting stability was remarkably reduced and the thermal stability was low. Glass fibers suffered from warpage and gloss. Therefore, Comparative Examples 1 to 6 could not be obtained with excellent balance. Examples 10 and 11 PBT having a weight ratio shown in Table 4, the layered compounds (A-2 and A-4) obtained in Production Example 1, and AO60 were melt-kneaded in the same manner as in Example 1 to obtain a polyester resin composition. ,evaluated. Table 4 shows the results. Comparative Examples 7 and 8 PBT having a weight ratio shown in Table 4, the layered compound (B-1) obtained in Production Example 1, ME100 and AO60 were melt-kneaded in the same manner as in Example 1 and evaluated. Table 4 shows the results.

[0068]

[Table 4] As shown in Table 4, when ME100 was not treated with the polyether compound, the bending properties were not improved, and no good flat test piece was obtained. When treated with a polyether compound having no cyclic hydrocarbon group (PEG1000), the bending properties after molding were improved, but were significantly reduced when retained in the melt, and the thermal stability was low. Therefore, Comparative Examples 7 and 8 did not have excellent balance. Examples 12 and 13 PPT obtained in Production Example 2 having the weight ratios shown in Table 5, the layered compounds (A-2 and A-4) obtained in Production Example 1, and AO60
Was melt-kneaded in the same manner as in Example 1 to obtain and evaluate a polyester resin composition. Table 5 shows the results. Comparative Examples 9 and 10 PPT obtained in Production Example 2 having the weight ratio shown in Table 5, layered compound (B-1) obtained in Production Example 1, ME100 and AO60.
Was melt-kneaded in the same manner as in Example 1 and evaluated. Table 5 shows the results
Shown in

[0069]

[Table 5] As shown in Table 5, when ME100 was not treated with the polyether compound, the bending characteristics were not improved, and no good flat test piece was obtained. When treated with a polyether compound having no cyclic hydrocarbon group (PEG1000), the bending properties after molding were improved, but were significantly reduced when retained in the melt, and the thermal stability was low. Therefore, Comparative Examples 9 and 10
Then, the thing which was excellent in balance was not obtained.

[0070]

As described in detail above, by uniformly and finely dispersing a layered compound treated with a polyether compound having a cyclic hydrocarbon group in a thermoplastic polyester resin, low warpage, good surface appearance and good surface appearance can be obtained. Provided is a polyester resin composition having improved mechanical properties, good thermal stability in a molten state, good strength after melt retention, and an excellent balance of physical properties.

Claims (12)

[Claims] 1. A polyester resin composition containing a thermoplastic polyester resin and a layered compound treated with a polyether compound having a cyclic hydrocarbon group. 2. The polyester resin composition according to claim 1, wherein the cyclic hydrocarbon group is an aromatic hydrocarbon group. 3. A polyether compound having one of the following
General formula (1):(Wherein -A- is -O-, -S-, -SO-, -SO
_Two-, -CO-, an alkylene group having 1 to 20 carbon atoms, or
An alkylidene group having 6 to 20 carbon atoms;¹, R ^Two, R^Three,
R^Four, R^Five, R⁶, R⁷, And R⁸Is a hydrogen atom,
A hydrogen atom or a monovalent hydrocarbon group having 1 to 5 carbon atoms
And they may be the same or different
good. Claim), characterized by having a unit represented by)
3. The polyester resin composition according to 1 or 2. 4. A polyether compound represented by the following general formula:
(2):(Wherein -A- is -O-, -S-, -SO-, -SO
_Two-, -CO-, an alkylene group having 1 to 20 carbon atoms, or
An alkylidene group having 6 to 20 carbon atoms;¹, R ^Two, R^Three,
R^Four, R^Five, R⁶, R⁷, And R⁸Is a hydrogen atom,
A hydrogen atom or a monovalent hydrocarbon group having 1 to 5 carbon atoms
Yes, R⁹, R^TenIs a divalent carbon having 1 to 5 carbon atoms.
A hydrogen group,¹¹, R¹²Are hydrogen atoms and carbon numbers
1-20 monovalent hydrocarbon groups, each of which is
They may be the same or different. m and n are oki
Indicates the number of repeating units of a silalkylene unit, and 2 ≦ m + n
≤50. ).
4. The polyester resin composition according to 1, 2, or 3. 5. The layered compound treated with the polyether compound is obtained by mixing the layered compound and the polyether compound in water or a polar solvent containing water. The polyester resin composition according to 1, 2, 3 or 4. 6. The polyester resin composition according to claim 1, wherein the ratio of the layer compound having an equivalent area circle diameter [D] of 3000 ° or less is 20% or more.
Or the polyester resin composition according to 5. 7. The polyester resin composition according to claim 1, wherein the average value of the equivalent area circle diameter [D] of the layered compound in the polyester resin composition is 5000 ° or less. . 8. The polyester resin composition according to claim 1, wherein the average layer thickness of the layered compound in the polyester resin composition is 500 ° or less. . 9. The polyester resin according to claim 1, wherein the maximum layer thickness of the layer compound in the polyester resin composition is 2000 ° or less. Composition. 10. The [N] value of the layered compound in the polyester resin composition is 30 or more, wherein the [N] value per unit ratio of the layered compound present in an area of 100 μm ² of the resin composition. The polyester resin composition according to claim 1, 2, 3, 4, 5, 6, 7, 8, or 9, wherein the number of particles is defined as the number of particles. 11. The layer compound in the polyester resin composition has an average aspect ratio (ratio of layer length / layer thickness) of 10 to 3.
1, 2, 3, 4, 5, 6, 7, 8,
The polyester resin composition according to 9 or 10. 12. The polyester resin composition according to claim 1, wherein the layered compound is a layered silicate.