JPH11323106A - Polyester resin composition and preparation thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester resin composition having good mechanical properties, heat resistance, dimensional stability and surface appearance and a preparation process of a polyester resin composition. SOLUTION: A polyester resin composition contains a thermoplastic polyester resin and an intercalation compound, wherein the intercalation compound is prepared by mixing a swellable silicate and an amino compound in a dispersion medium and wherein the amino compound is a 1-25C hydrocarbon compound which contains at least one amino group chosen from the group consisting of primary, secondary and tertiary amino groups and optionally has at least one substituent chosen from the group consisting of a hydroxyl group, a mercapto group, an ether group, a carbonyl group, a nitro group and a chlorine atom.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a polyester resin composition containing a thermoplastic polyester resin and an intercalation compound, and a method for producing the polyester resin composition.

[0002]

2. Description of the Related Art Ancol International is an intercalation compound comprising an intercalant monomer having various functional groups introduced between layers of a layered silicate.
And EP 078, which discloses an invention relating to a resin composition comprising the interlayer compound and a resin matrix capable of being melt-processed.
No. 0340. According to the above-mentioned technology of Ancol International, an interlayer compound comprising an intercalant monomer such as hexamethylenediamine and a layered silicate is disclosed, but no resin composition comprising the interlayer compound and a resin matrix is disclosed. It has not been.

[0003]

That is, at present, a resin composition comprising the above interlayer compound and a resin matrix has not yet been obtained. Therefore, the object of the present invention is to
Polyester resin composition with improved mechanical properties, deflection temperature under load and dimensional stability, and excellent appearance of molded products by dispersing the intercalation compound in the resin matrix as extremely fine plate-like particles having a thickness of nm order independently. It is an object to provide

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have reached the present invention. That is, a polyester resin composition in which an interlayer compound prepared by mixing an amino compound having an amino group as an essential functional group and a swellable silicate is finely dispersed in a thermoplastic polyester resin, and a method for producing the same. It is.

According to the present invention, a polyester resin composition according to claim 1 is a polyester resin composition containing a thermoplastic polyester resin and an interlayer compound, wherein the interlayer compound is a swellable silicate and an amino compound. Is mixed in a dispersion medium, wherein the amino compound has at least one amino group selected from the group consisting of primary, secondary and tertiary amino groups, a hydroxyl group, a mercapto group A hydrocarbon compound having 1 to 25 carbon atoms which may have one or more substituents selected from the group consisting of a group, an ether group, a carbonyl group, a nitro group and a chlorine atom.

According to a second aspect of the present invention, there is provided the polyester resin composition according to the first aspect, wherein the average thickness of the interlayer compound in the polyester resin composition is 500.
Å It is below. The polyester resin composition according to claim 3,
3. The polyester resin composition according to claim 1, wherein the maximum thickness of the interlayer compound in the polyester resin composition is 2000 ° or less.

The method for producing a polyester resin composition according to claim 4 is the method for producing a polyester resin composition according to claim 1, 2 or 3, wherein (A) a clay dispersion containing an intercalation compound and a dispersion medium. (B) a step of mixing at least one selected from a polyester polymerizable monomer, a polyester unit and a polyester low-polymer with the above-mentioned clay dispersion, and (C) a step of polymerizing the polyester. .

[0008] The method for producing a polyester resin composition according to claim 5 is the method for producing a polyester resin composition according to claim 4, wherein the bottom surface interval of the interlayer compound in the clay dispersion obtained in the step (A). Is at least four times the bottom spacing of the swellable silicate.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The thermoplastic polyester resin used in the present invention includes a dicarboxylic acid compound and / or an ester-forming derivative of dicarboxylic acid and a diol compound and / or an ester-forming derivative of a diol compound. And specific examples thereof include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexane-1,4-dimethyl terephthalate, neopentyl terephthalate, polyethylene isophthalate, and polyethylene naphthalene. Examples thereof include phthalate, polybutylene naphthalate, polyhexamethylene naphthalate, and the like, and copolymerized polyesters thereof. They may be used alone or in combination of two or more.

[0010] Among the above thermoplastic polyester resins, polyethylene terephthalate and polybutylene terephthalate can be preferably used. The molecular weight of the above-mentioned thermoplastic polyester resin is selected in consideration of the molding fluidity in the molding step and various physical properties of the final product. That is, the molecular weight of the thermoplastic polyester resin has a logarithmic viscosity of 0.3 to 2.0 (dl / g) measured at 25 ° C. using a phenol / tetrachloroethane (5/5 weight ratio) mixed solvent, Preferably 0.3
5 to 1.9 (dl / g), and more preferably 0.4 to 1.9 (dl / g).
1.8 (dl / g). When the logarithmic viscosity is 0.3 (dl /
When the amount is less than g), the mechanical properties of a molded article of the obtained polyester resin composition are low, and when it is more than 2.0 (dl / g), there is a tendency that problems occur in processability such as fluidity during molding. is there.

[0011] The intercalation compound used in the present invention is a compound having at least one swellable silicate and an amino group in a dispersion medium.
It is prepared by mixing with an amino compound having one. The swellable silicate is mainly composed of a tetrahedral sheet of silicon oxide and an octahedral sheet of metal hydroxide, and specific examples thereof include smectite clay and swellable mica.

The smectite-group clay is represented by the following general formula (1): X _0.2 to _0.6 Y ₂ to ₃ Z ₄ O ₁₀ (OH) ₂ .nH ₂ O (1) (where X is K, Na, 1 / 2Ca , And 1 / 2Mg
At least one member selected from the group consisting of
e, Mn, Ni, Zn, Li, Al, and at least one member selected from the group consisting of Cr, and Z is at least one member selected from the group consisting of Si and Al. Note that H ₂ O represents a water molecule bonded to an interlayer ion, and n significantly varies depending on the interlayer ion and the relative humidity.)
Natural or synthetic. 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. Can be

The swellable mica is represented by the following general formula (2): X _0.5 to _1.0 Y ₂ to ₃ (Z ₄ O ₁₀ ) (F, OH) ₂ (2) (where X is Li, Na, K , Rb, Ca, Ba, and Sr, at least one selected from the group consisting of
g, one or more selected from the group consisting of Fe, Ni, Mn, Al, and Li, and Z is Si, Ge, Al, F
at least one selected from the group consisting of e and B. )
And 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 following equivalents of vermiculite can also be used.

The vermiculite has three octahedral types and two
There is octahedral, the following general formula (3) (Mg, Fe, Al) 2 ~ 3 (Si 4-x Al x) O 10 (OH) 2 · (M +, M 2+ 1/2) x · nH ₂ O (3) (where M is an exchangeable cation of an alkali or alkaline earth metal such as Na and Mg, x = 0.6 to 0.9, n =
3.5-5).

The swellable silicates described above are used alone or in combination of two or more. The crystal structure of the swellable silicate is desirably high in purity, which is regularly stacked in the c-axis direction, but a so-called mixed layer mineral in which the crystal cycle is disordered and a plurality of types of crystal structures are mixed may be used.
Among the above swellable silicates, montmorillonite, bentonite, hectorite, saponite and N between the layers
Swellable mica containing a ions can be preferably used.

The amino compound used in the present invention is 1
Having at least one amino group selected from the group consisting of primary, secondary and tertiary amino groups, and selected from the group consisting of hydroxyl, ether, mercapto, carbonyl, nitro and chlorine. It is a hydrocarbon compound having 1 to 25 carbon atoms which may have one or more selected substituents.

As used herein, the term "hydrocarbon group" refers to a linear or branched (ie, having a side chain) saturated or unsaturated monovalent or polyvalent aliphatic hydrocarbon group, aromatic hydrocarbon group, or aliphatic hydrocarbon group. It means a cyclic hydrocarbon group, for example, an alkyl group, an alkenyl group, an alkynyl group, a phenyl group, a naphthyl group, a cycloalkyl group and the like. In the present specification, the term “alkyl group” is intended to include a polyvalent hydrocarbon group such as an “alkylene group” unless otherwise specified. Similarly, an alkenyl group, an alkynyl group,
The phenyl group, naphthyl group, and cycloalkyl group each include an alkenylene group, an alkynylene group, a phenylene group, a naphthylene group, a cycloalkylene group, and the like.

As specific examples of the above-mentioned amino compounds, examples in which an amino group and a hydrocarbon group having 1 to 25 carbon atoms are constituents include butylamine, N, N-dimethylbutylamine and 1,2-dimethylpropyl. Amines, dodecylamine, hexylamine, N-methylhexylamine,
3-pentylamine, dimethylaminoethylamine, 2
Octylamine, ethylaminoethylamine, diethylaminoethylamine, tetramethylethylenediamine, 1,2-diaminopropane, methylaminopropylamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminopropylamine, tetramethyl-1,3-diaminopropane , 1,2-diaminobutane, 1,4-diaminobutane, N- (3-aminopropyl) -1,3-propanediamine, pentamethyldiethylenetriamine, N, N'-bis (aminopropyl) -1,3- Propylenediamine, N, N'-bis (aminopropyl) -1,4-butylenediamine, diallylamine, isoamylamine, N-ethylisoamylamine, 2-hexenylamine, N, N-diisopropylaminoethylamine N, N- diisopropylethylamine, 2-ethylhexylamine, N- ethyl-1,
2-dimethylpropylamine, diisobutylamine, 2
-Ethylhexylamine, aniline, β-naphthylamine, o-phenylenediamine, p-phenylenediamine, toluene-2,4-diamine, N, N′-dimethyl-p-phenylenediamine, divinylpropylamine and the like. Examples of the amino compound having a hydroxyl group include 2- (hydroxymethylamino) ethanol, N-
Isomethyldiethanolamine, 2-aminopropanol, 3-aminopropanol, 3-dimethylaminopropanol, 4-aminobutanol, 4-methylaminobutanol, 2-hydroxyethylaminopropylamine, diethanolaminopropylamine, 1-amino-
3-phenoxy-2-propanol and the like. Examples of amino compounds having an ether group include bis (3
-Aminopropyl) ether, dimethylaminoethoxypropylamine, 1,2-bis (3-aminopropoxy) ethane, 1,3-bis (3-aminopropoxy)-
2,2-dimethylpropane, α, ω-bis (3-aminopropyl) polyethylene glycol ether, α, ω-
Bis (3-aminopropyl) diethylene glycol ether, 3-methoxypropylamine, 3-ethoxypropylamine, 3-propoxypropylamine, 3-isopropoxypropylamine, 3-butoxypropylamine, 3-isobutoxypropylamine, 2- Ethylhexyloxypropylamine, 3-decyloxypropylamine and the like. Examples of amino compounds having a mercapto group include 2-mercaptoethylamine, N- (2
-Mercaptoethyl) acetamide, 2-mercaptopyridine and the like. Examples of amino compounds having a carbonyl group include formanilide, acetanilide,
Examples include acetoacetanilide, dodecylamide, tetradecylamide, hexadecylamide and the like. Examples of the amino compound having a nitro group include 2-nitroaniline, 3-nitroaniline, 2,4-dinitroaniline,
2,4,6-trinitroaniline. Examples of the amino compound having a chlorine atom include 2-chloroaniline, 3-chloroaniline, and 2,5-dichloroaniline.

Among the above-mentioned amino compounds, dimethylaminoethylamine, ethylaminoethylamine, diethylaminoethylamine, tetramethylethylenediamine, 1,2-diaminopropane, methylaminopropylamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminopropyl Amines, tetramethyl-1,3-diaminopropane, 1,2-diaminobutane, 1,4-diaminobutane, N- (3-aminopropyl) -1,3-propanediamine, pentamethyldiethylenetriamine and N, N ' -Bis (aminopropyl) -1,3-propylenediamine, etc.
An amino compound having two or more amino groups in one molecule,
2- (hydroxymethylamino) ethanol, N-isomethyldiethanolamine, 2-aminopropanol,
Amino having a hydroxyl group such as 3-aminopropanol, 3-dimethylaminopropanol, 4-aminobutanol, 4-methylaminobutanol, 2-hydroxyethylaminopropylamine and 1-amino-3-phenoxy-2-propanol; Compound, bis (3-aminopropyl) ether, dimethylaminoethoxypropylamine, 1,2-bis (3-aminopropoxy) ethane, 1,3-bis (3-aminopropoxy) -2,2-
Amino compounds having an ether group such as dimethylpropane, α, ω-bis (3-aminopropyl) polyethylene glycol ether and α, ω-bis (3-aminopropyl) diethylene glycol ether can be preferably used.

Substitutes or derivatives of the above amino compounds can also be used. These amino compounds are used alone,
Alternatively, two or more kinds may be used in combination. The interlayer compound can be obtained by expanding the bottom surface interval of the swellable silicate in the dispersion medium, and then adding and mixing the above amino compound. The above-mentioned dispersion medium intends water, a polar solvent compatible with water in an arbitrary ratio, and a mixed solvent of water and the polar solvent. Examples of the polar solvent include alcohols such as methanol, ethanol and isopropanol; glycols such as ethylene glycol, propylene glycol and 1,4-butanediol; ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether and tetrahydrofuran. , Amide compounds such as dimethylformamide, and other solvents such as dimethyl sulfoxide and 2-
And pyrrolidone.

These polar solvents may be used alone.
It may be used in combination of more than one kind. Increasing the spacing between the bottom surfaces of the swellable silicate in the dispersion medium can be achieved by sufficiently stirring and dispersing the swellable silicate in the dispersion medium. The distance between the bottom surfaces after the enlargement is preferably 3 times or more, more preferably 4 times or more, and still more preferably 5 times or more, compared to the initial distance between the bottom surfaces of the swellable silicate. There is no particular upper limit. However, when the distance between the bottom surfaces is increased by about 10 times or more, the measurement of the distance between the bottom surfaces becomes difficult. In this case, the swellable silicate is substantially present in a unit layer. In the present specification, the initial bottom surface interval of the swellable silicate is a bottom surface interval of the particulate swellable silicate in which unit layers are stacked and aggregated before being added to the dispersion medium. Intended. The distance between the bottom surfaces can be confirmed by small angle X-ray diffraction (SAXS) or the like. That is, the X-ray diffraction peak angle value of the mixture comprising the dispersion medium and the swellable silicate is measured by SAXS, and the peak angle value is substituted into Bragg's formula to calculate the bottom surface interval.

In order to efficiently increase the distance between the bottom surfaces of the swellable silicate, stirring may be performed at a speed of several thousand rpm or more, or a method of applying a physical external force as described below. Physical external forces can be applied by using commonly performed wet milling of fillers. As a general wet-milling method of a filler, for example, a method using hard particles can be mentioned. In this method, the hard particles, the swellable silicate, and an optional solvent are mixed and stirred, and the swellable silicate is separated by physical collision between the hard particles and the swellable silicate. Hard particles generally used are filler grinding beads, for example, glass beads or zirconia beads. These grinding beads are selected in consideration of the hardness of the swellable silicate or the material of the stirrer, and are not limited to the above-mentioned glass or zirconia. The particle size is also not specifically limited by a numerical value because it is determined in consideration of the size of the swellable silicate and the like, but a particle having a diameter of 0.1 to 6.0 mm is preferable. . Although the solvent used here is not particularly limited, for example, the above-described dispersion medium is preferable.

As described above, the spacing between the bottom surfaces of the swellable silicate is increased in the dispersion medium. In other words, the unit layers that have been aggregated are cleaved and separated to be present independently.
Thereafter, the amino compound is added, and the mixture is sufficiently stirred and mixed to obtain an interlayer compound. The treatment of the swellable silicate with the amino compound is carried out by adding the amino compound to a mixture containing the swellable silicate having an enlarged bottom surface spacing and a dispersion medium and stirring the mixture. When it is desired to perform the stirring more efficiently, the rotation speed of the stirring is set to 1000 rpm or more, preferably 1500 rpm or more,
It is more preferably at least 2,000 rpm, or at least 500 (1 / s), preferably at least 1,000 (1 / s), more preferably 1500 using a wet mill or the like.
Apply a shear rate of (1 / s) or more. The upper limit of the number of revolutions is about 25,000 rpm, and the upper limit of the shear rate is about 50.
0000 (1 / s). It is not necessary to stir at a value larger than the upper limit since stirring does not tend to change the effect even if the stirring is performed at a value larger than the upper limit or shearing is applied. Although the treatment of the swellable silicate with the amino compound can be sufficiently performed at room temperature, the system may be heated if necessary. The maximum temperature at the time of heating can be arbitrarily set as long as it is lower than the decomposition temperature of the amino compound to be used and lower than the boiling point of the dispersion medium.

The amount of the amino compound to be used is such that the dispersibility of the obtained interlayer compound and the thermoplastic polyester resin or clay dispersion (used in the method for producing the polyester resin composition of the present invention described later) is sufficiently enhanced. Can be prepared. If necessary, a plurality of amino compounds having different structures can be used in combination. Accordingly, the amount of the amino compound to be added is not necessarily limited by numerical values, but is 0.1 to 200 parts by weight, preferably 0.2 to 180 parts by weight, based on 100 parts by weight of the swellable silicate. Parts by weight, more preferably 0.3 to 160 parts by weight, still more preferably 0.4 to 140 parts by weight, particularly preferably 0.5 to 120 parts by weight. When the amount of the amino compound is 0.
If the amount is less than 1 part by weight, the effect of finely dispersing the obtained interlayer compound tends to be insufficient. If the amount is more than 200 parts by weight, the effect does not change. Therefore, it is not necessary to add more than 200 parts by weight.

The distance between the bottom surfaces of the interlayer compound obtained as described above can be enlarged as compared with the initial distance between the bottom surfaces of the swellable silicate due to the presence of the introduced amino compound. For example, the swellable silicate dispersed in the dispersion medium and the bottom surface interval is enlarged, when the amino compound is not introduced, when the dispersion medium is removed, the layers return to a state where the layers are aggregated again. After the dispersion medium is removed by introducing the amino compound after increasing the bottom surface interval, the obtained interlayer compound can exist in a state where the bottom surface interval is increased without agglomeration of the layers. The distance between the bottom surfaces of the interlayer compounds is 1.1 times or more, preferably 1.2 times or more, more preferably 1.3 times or more, and particularly preferably 1.5 times, as compared with the initial distance between the bottom surfaces of the swellable silicate. It is expanding. The distance between the bottom surfaces can be confirmed by small angle X-ray diffraction (SAXS) or the like. In this method, the X-ray diffraction peak angle derived from the (001) plane of the dried and powdered intercalation compound is measured by SAXS,
By substituting into the formula of ragg and calculating, the bottom surface interval can be obtained. Similarly, the base spacing of the initial swellable silicate is measured, and by comparing the two, the expansion of the base spacing can be confirmed. By confirming that the distance between the bottom surfaces is thus increased, it can be confirmed that an interlayer compound has been generated.

In the polyester resin composition of the present invention, the compounding amount of the interlayer compound is typically 0.1 to 50 parts by weight based on 100 parts by weight of the thermoplastic polyester resin.
Preferably 0.2 to 45 parts by weight, more preferably 0.3 to 45 parts by weight.
The amount is adjusted to be 40 parts by weight, more preferably 0.4 to 35 parts by weight, particularly preferably 0.5 to 30 parts by weight. If the amount of the interlayer compound is less than 0.1 part by weight, the effect of improving mechanical properties, deflection temperature under load, and dimensional stability may be insufficient. Tends to be impaired.

The ash content of the polyester resin composition derived from the intercalation compound is typically 0.1 to 30% by weight, preferably 0.2 to 28% by weight, and more preferably 0.1 to 30% by weight.
3 to 25% by weight, more preferably 0.4 to 23% by weight,
It is particularly preferably prepared to be 0.5 to 20% by weight. If the ash content is less than 0.1% by weight, the effect of improving mechanical properties, deflection temperature under load, and dimensional stability may be insufficient, and if it exceeds 30% by weight, the appearance of the molded article and the fluidity during molding. Etc. tend to be impaired.

The structure of the intercalation compound dispersed in the polyester resin composition of the present invention is completely different from the aggregated structure in which a large number of unit layers are stacked, such as the swellable silicate before compounding. different. That is, compared to the aggregated structure in the initial swellable silicate, by polymerizing the thermoplastic polyester resin in the presence of the interlayer compound having an enlarged bottom surface interval, the interlayer compound becomes very fine in the polyester resin composition. Disperse into independent flakes. The dispersion state of the flaky interlayer compound is expressed by various parameters as described below.

When the average layer thickness is defined as a number average value of the layer thickness of the interlayer compound dispersed in a plate shape, the average layer thickness of the interlayer compound of the polyester resin composition of the present invention is 500 ° or less, preferably It is 450 ° or less, more preferably 400 ° or less, further preferably 350 ° or less, particularly preferably 300 ° or less. The lower limit is not particularly limited, but is about 10 °. When the average layer thickness is within the above range, the effect of improving the elastic modulus, the deflection temperature under load and the dimensional stability can be obtained more efficiently without impairing the appearance of the molded article obtained from the polyester resin composition of the present invention. .

When the maximum layer thickness is defined as the maximum value of the layer thickness of the interlayer compound dispersed in the polyester resin composition in the form of a plate, the maximum layer thickness of the interlayer compound in the polyester resin composition of the present invention is 2,000. Or less, preferably 1
It is 800 ° or less, more preferably 1500 ° or less, further preferably 1200 ° or less, and particularly preferably 1000 ° or less. When the maximum layer thickness is more than 2000 mm, the surface properties of a molded article obtained from the polyester resin composition of the present invention may be impaired, and furthermore, the effects of improving mechanical properties, deflection temperature under load and dimensional stability are sufficiently improved. It tends not to be obtained. The lower limit of the maximum layer thickness is not particularly limited, but is about 50 °.

The layer thickness is determined by heating and melting the polyester resin composition of the present invention and then hot pressing or stretching or casting, and a thin molded product obtained by injection molding a molten resin. Can be determined from an image captured using a microscope or the like. In other words, the film prepared by the above method on the XY plane
Alternatively, it is assumed that a thin flat injection-molded test piece having a thickness of about 0.5 to 2 mm is placed. A thin section is cut out from the above-mentioned film or flat plate in a plane parallel to the XZ plane or the YZ plane, and the thin section is transmitted through a transmission electron microscope (TEM).
It can be determined by observing at a high magnification of about 40,000 to 100,000 or more. Instead of the above film or plate,
The layer thickness can also be determined by uniaxially stretching the fibrous material, cutting a thin slice perpendicular to the stretching axis, and observing the same in a transmission electron microscope.

In the polyester resin composition of the present invention, the elasticity, strength, HDT and dimensional stability are improved without disturbing the appearance of the molded article by dispersing the interlayer compound in a state represented by the above parameters. can do. The dispersion state represented by the above parameters is obtained by the method for producing a polyester resin composition of the present invention using an amino compound having an amino group as an essential functional group.

The process for producing the polyester resin composition of the present invention comprises: (A) a step of preparing a clay dispersion containing an intercalation compound and a dispersion medium; (B) a polymerizable monomer of polyester, a polyester unit and a low-polymerized polyester. And the step of mixing (C) a polyester with the above-mentioned clay dispersion.

The dispersion medium used in the step (A) is the same as the dispersion medium used in the preparation of the intercalation compound, that is, water, a polar solvent compatible with water at an arbitrary ratio, or a mixture of water and the polar solvent. A mixed solvent is intended. The method for preparing the clay dispersion is not particularly limited. For example, a method using a system containing a dispersion medium and an intercalation compound as it is obtained when an intercalation compound is prepared (referred to as a direct method), or a method for preparing an intercalation compound A method of obtaining a newly added dispersion medium and an interlayer compound by replacing the used dispersion medium with another desired dispersion medium (referred to as a substitution method), or a method of removing the dispersion medium and preparing an interlayer compound. And a method of sufficiently mixing the dispersion medium. The direct method and the substitution method are preferred from the viewpoint of the dispersibility of the interlayer compound.

For efficient mixing, the rotation speed of the stirring should be 500 rpm or more, or 300 (1 / s).
Apply the above shear rate. The upper limit of the number of revolutions is 25000
rpm, and the upper limit of the shear rate is 500000 (1 /
s). There is a tendency that the effect does not change even if the stirring is performed at a value larger than the upper limit, so that it is not necessary to perform the stirring at a value larger than the upper limit.

In the intercalation compound contained in the clay dispersion obtained in the step (A), the initial layered / agglomerated structure, which the swellable silicate had, had almost completely disappeared. It expands to a so-called swollen state. The bottom surface interval can be used as an index indicating the swelling state. That is, the distance between the bottom surfaces of the interlayer compounds in the above clay dispersion is at least four times the initial distance between the bottom surfaces of the swellable silicate, and preferably 5 times.
It is at least 6 times, more preferably at least 6 times. If the distance between the bottom surfaces is less than four times, the interlayer compound tends not to be finely dispersed efficiently in the polyester resin composition of the present invention.

Next, the step (B), that is, a step of mixing at least one selected from a polymerizable monomer of polyester, a polyester unit and a polyester low-polymer with the above-mentioned clay dispersion is performed. The method of mixing is not particularly limited. For example, a method of collectively mixing a polymerizable monomer and / or polyester unit and a clay dispersion of a polyester in a molten state or a solution, a method of mixing a polyester unit and / or a polyester having a low degree of polymerization in a molten state A method of continuously adding a clay dispersion to the body. In the case of continuous addition, the addition rate of the clay dispersion is not particularly limited, but the clay dispersion is added in an amount of 0.02 to 4.0 parts by weight per 100 parts by weight of the polyester unit and / or low-polymerized polyester. Minutes, preferably 0.0
3 to 3.8 parts by weight / minute, more preferably 0.05 to 3.5 parts by weight
Add continuously at parts by weight / min.

The polymerizable monomer of the above-mentioned polyester includes an acid component mainly composed of an aromatic dicarboxylic acid and / or an ester-forming derivative thereof, and a glycol compound mainly composed of a glycol compound and / or an ester-forming derivative thereof. Component. Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, orthophthalic acid, 2,5-naphthalenedicarboxylic acid,
4'-biphenyl dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-diphenylmethane dicarboxylic acid, 4,4'-diphenyl sulfone dicarboxylic acid, 4,4'-diphenyl isopropylidene dicarboxylic acid, and the like, Substitutes and derivatives of these may also be used. Also, oxyacids such as p-oxybenzoic acid and p-hydroxyethoxybenzoic acid and their ester-forming derivatives may be used. Two of these monomers
A mixture of more than one species may be used. If the amount is small enough not to impair the properties of the obtained polyester resin composition, one or more aliphatic dicarboxylic acids such as adipic acid, azelaic acid, dodecane diacid, sebacic acid and the like are mixed with these aromatic dicarboxylic acids. Can be used.

Further, as the above-mentioned glycol compound,
Aliphatic glycols such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol and the like, alicyclic glycols such as 1,4-cyclohexanedimethanol and the like, 1,
Aromatic glycols such as 4-phenylenedioxydimethanol and the like can be mentioned, and their substituted products and derivatives can also be used. Also, cyclic esters such as ε-caprolactone may be used. One or two or more of these are used in combination. Furthermore, long-chain diols (for example, polyethylene glycol, etc.) may be used in such a small amount that the elastic modulus of the thermoplastic polyester resin is not significantly reduced.
Polytetramethylene glycol) and at least one kind of an alkylene oxide addition polymer of bisphenols (for example, an ethylene oxide addition polymer of bisphenol A) can be mixed.

The above polyester unit means a condensate comprising one molecule of an aromatic dicarboxylic acid or an ester-forming derivative thereof and one molecule of a glycol compound or an ester-forming derivative thereof. The polyester low-polymer is a condensate composed of an aromatic dicarboxylic acid or an ester-forming derivative thereof and a glycol compound or an ester-forming derivative thereof, and a clay dispersion containing an interlayer compound in a molten state is sufficient. Having a molecular weight such that the melt viscosity is such that it can be uniformly dispersed in water.

From the viewpoint of uniform dispersibility of the clay dispersion, the logarithmic viscosity of the polyester unit and / or low-polymerized polyester is less than 0.4 (dl / g), preferably 0.38 (dl / g). And more preferably less than 0.1.
Less than 35 (dl / g), more preferably 0.33.
(Dl / g), particularly preferably 0.30 (d / g).
1 / g).

If the logarithmic viscosity is within the above range, the molten polyester unit and / or low-polymer polyester may contain an aromatic dicarboxylic acid or an ester-forming derivative thereof and a glycol compound or an ester-forming derivative thereof. One or more selected from the group consisting of sex derivatives may be newly added.

The method for obtaining the polyester unit and / or the polyester having a low degree of polymerization is not particularly limited. Examples thereof include a method of esterifying an aromatic dicarboxylic acid with a glycol compound and a method of transesterifying an alkyl ester of an aromatic dicarboxylic acid with a glycol compound. How to do
Usually, a method generally performed is used. Thus, an aromatic dicarboxylic acid or an ester-forming derivative thereof,
In addition to a method obtained by subjecting a glycol compound or an ester-forming derivative thereof to a condensation reaction, a method obtained by depolymerizing a part or all of a thermoplastic polyester resin with a glycol compound may also be used. That is, for example, a method of heating a mixture of a thermoplastic polyester resin as a raw material and a glycol compound and depolymerizing in a temperature range from about 150 ° C. to a temperature in the vicinity of the melting point of the thermoplastic polyester resin, or a thermoplastic polyester resin as a raw material A method in which a thermoplastic polyester resin is previously melted at a temperature equal to or higher than the melting point thereof, and a glycol compound is added thereto and depolymerized while stirring is used. When the resin component contained in the polyester resin composition of the present invention is to be a copolymerized polyester resin obtained by copolymerizing another glycol compound with a thermoplastic polyester resin as a raw material, the thermoplastic polyester resin is constituted. A glycol compound having a structure different from the glycol component to be used can be used for depolymerization of a thermoplastic polyester resin as a raw material.

The catalyst necessary for the reaction for obtaining the polyester unit and / or the polyester having a low degree of polymerization is a transesterification catalyst, and one or more of metal oxides, carbonates, acetates and alcoholates are used. Can be done. In the method obtained by depolymerization of the thermoplastic polyester resin, the catalyst required for the reaction is usually already contained in the thermoplastic polyester resin as a starting material, but if necessary, the above-mentioned transesterification catalyst may be newly added. It can be used by adding.

Finally, step (C), that is, a step of polymerizing the polyester, may be performed. The polymerization method is not particularly limited, and the polymerization can be performed by a generally performed polymerization method of a polyester resin. As such a method, for example, while stirring the melt of the polyester unit and / or polyester low-polymer, the excess glycol compound is removed out of the system, and then the system is melt-polycondensed by reducing the pressure of the system. Method, or at any time before the start of the melt polycondensation or after the start of the melt polycondensation to the end of the polymerization, the system is cooled, solidified and pulverized, pre-crystallized and dried.
A method of heating to below the melting point and lower than the melting point to carry out solid phase polymerization. When a polymerizable monomer of polyester is used, an acid component mainly composed of an aromatic dicarboxylic acid and / or an ester-forming derivative thereof and a glycol component mainly composed of a glycol compound and / or an ester-forming derivative thereof are used. After transesterification to produce a polyester unit, polymerization is carried out.

In the case where another glycol component is copolymerized with the resin component, a desired glycol compound is added and mixed at any time during the melt polycondensation reaction, and then the melt polycondensation reaction or solid phase polymerization is performed continuously. Is obtained by The catalyst necessary for the reaction is used by adding one or more of metal oxides, carbonates, acetates, and alcoholates as necessary.

The molecular weight of the resin whose molecular weight has been increased in the step (C) is phenol / tetrachloroethane (5/5
(Log ratio) The logarithmic viscosity measured at 25 ° C using a mixed solvent is 0.3 to 2.0 (dl / g), and preferably 0.1 to 2.0 (dl / g).
35 to 2.0 (dl / g), more preferably 0.3 (dl / g).
7 to 2.0 (dl / g), more preferably 0.40
１1.8 (dl / g). When the logarithmic viscosity is 0.3 (dl
/ G), mechanical properties are low, and 2.0 (dl)
/ G), the melt viscosity is high and the molding fluidity tends to decrease.

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. Also, mechanical properties, as long as the properties such as moldability are not impaired, any other resin, for example, unsaturated polyester resin, polyester carbonate resin,
A liquid crystal polyester resin, a polyolefin resin, a polyamide resin, a rubbery polymer reinforced styrene resin, a polyphenylene sulfide resin, a polyphenylene ether resin, a polyacetal resin, a polysulfone resin, and a polyarylate resin may be used alone or in combination of two or more.

Further, the polyester resin composition of the present invention may contain a pigment, a dye, a heat stabilizer, an antioxidant, an ultraviolet absorber, a light stabilizer, a lubricant, a plasticizer, a flame retardant,
And an additive such as an antistatic agent. The polyester resin composition of the present invention may be molded by injection molding or hot press molding, and can also be used for blow molding.

Further, the polyester resin composition of the present invention can be used for a biaxially stretched film which maintains transparency and has excellent mechanical properties. Since such molded products and films are excellent in appearance, mechanical properties and heat deformation resistance, for example, automobile parts, household electric appliance parts, precision machine parts,
It is suitably used for household goods, packaging and container materials, magnetic recording tape base materials, and other general industrial materials.

[0051]

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 shown below. Unless otherwise specified, the raw materials were not purified. (Thermoplastic polyester resin) ・ PET: polyethylene terephthalate resin manufactured by Kanebo Co., Ltd., trade name PBK2, logarithmic viscosity (η _inh ) = 0.63
(Dl / g) (hereinafter referred to as PET) PBT: polybutylene terephthalate resin manufactured by Kanebo Co., Ltd., trade name PBT120, logarithmic viscosity (η _inh ) = 0.8
2 (dl / g) (hereinafter referred to as PBT) As the (swellable silicate) montmorillonite, natural montmorillonite from Akita Prefecture (bottom spacing = 1.3 nm) was used.

The swellable mica used was synthesized as follows. Synthesis of swellable mica: 25.4 g of talc and 4.7 g of finely ground sodium silicofluoride were mixed and heat-treated at 800 ° C. to obtain 28.2 g of swellable mica (base spacing = 1.2 n)
m). (Amino compound) 1,2-bis- (3-aminopropoxy) ethane: manufactured by Koei Chemical Co., Ltd. (hereinafter referred to as BAPE) 2-Hydroxyethylamino-3-propylamine:
Made by Koei Chemical Co., Ltd. (hereinafter referred to as HEAPA) (dispersion medium) ・ Ethylene glycol: manufactured by Nippon Shokubai Co., Ltd., monoethylene glycol (hereinafter referred to as EG) ・ 1,4-butanediol: Tosoh Corporation Made, 1,4-
Butanediol (hereinafter referred to as 1,4-BD) (Polymerizable monomer of polyester) ・ Dimethyl terephthalate: manufactured by Wako Pure Chemical Industries, Ltd., special grade reagent (hereinafter referred to as DMT) (Polyester unit) ・ Bishydroxyethyl Terephthalate: NISSO B HET manufactured by Nisso Maruzen Chemical Co., Ltd.
(Referred to as ET) (Polyester low polymer)-PET obtained by depolymerizing PET with EG, or P
A product obtained by depolymerizing BT with 1,4-BD was used. Details will be described in Examples.

The evaluation methods in Examples and Comparative Examples are summarized below. (Transmission electron microscope (TEM)) Using a microtome,
A flaky sample having a thickness of 80 to 100 nm was cut out.
Using a transmission electron microscope (JEOL JEM-1200EX), the dispersion state of the intercalation compound was observed and photographed at an acceleration voltage of 80 kV and a magnification of 40,000 to 100,000. In the TEM photograph,
An arbitrary region in which 100 or more intercalation compounds are present (hereinafter referred to as a dispersion state measurement region) is selected, the maximum layer thickness is the maximum value among the thicknesses of the individual intercalation compounds, and the average layer thickness is an individual thickness. The number average value of the layer thickness of the interlayer compound was used.

The swellable silicate in the composition prepared in the comparative example was observed using an optical microscope. (Deflection temperature under load) Dry the polyester resin composition (1
(40 ° C, 5 hours). Using an injection molding machine (IS-75E, manufactured by Toshiba Machine Co., Ltd.) with a mold clamping pressure of 75 t, a resin temperature of 25
0-280 ° C, gauge pressure about 10MPa, injection speed about 50
Injection molding under the condition of%, dimensions about 10 × 100 × 6mm
Was prepared. The deflection temperature under load of the obtained test piece was measured according to ASTM D-648. (Flexural Modulus) The flexural modulus of a test piece prepared in the same manner as in the case of the deflection temperature under load was measured according to ASTM D-790. (Warp) Dry the polyester resin composition (140 ° C., 5
Time), using an injection molding machine (IS-75E, manufactured by Toshiba Machine Co., Ltd.) with a mold clamping pressure of 75 t, using a mold temperature of 120 ° C.
Injection molding is performed under the conditions of a resin temperature of 250 to 280 ° C., a gauge pressure of about 10 MPa, and an injection speed of about 50%.
A 120 × 1 mm flat test piece was prepared. The flat test piece was placed on a flat surface, one of the four corners of the test piece was pressed, and the value of the remaining three corners having the largest distance from the flat surface was measured using a caliper or the like. (Molding shrinkage ratio) Under the same conditions as above, a dimension of about 120 × 1
A 20 × 1 mm flat test piece is injection molded, and the M
The dimensions in the D and TD directions were measured, and the molding shrinkage was determined from the following equation. Molding shrinkage = {(actual size of mold) − (dimension of test piece after annealing)} × 100 / (actual size of mold) (%) (Linear expansion coefficient) Thickness produced under the same conditions as in the case of load deflection temperature A center portion of a JIS No. 1 dumbbell test piece having a thickness of about 3 mm was cut into about 7 mm × 7 mm, and the surface was polished with a paper file.

SSC-5200 manufactured by Seiko Electronics Co., Ltd.
And TMA-120C. The measurement conditions were as follows: a sample was held at 20 ° C. for 5 minutes under a nitrogen atmosphere, and then the temperature was raised from 20 ° C. to 150 ° C. at a rate of 5 ° C./min. Calculated. (Center Line Roughness) Using the above-mentioned dumbbell-shaped test piece, the center line roughness was measured using a surface roughness meter "surfcom 1500A" manufactured by Tokyo Seimitsu Co., Ltd. (Logarithmic viscosity) After drying the obtained polyester resin composition (140 ° C., 4 hours), about 100 mg was precisely weighed and phenol / 1,1,2,2-tetrachloroethane (1/1, weight ratio). ) Add 20 ml of mixed solvent and add to 120 ° C
And dissolved. The solution viscosity was measured using a Ubbelohde viscometer and an automatic viscosity measurement device (manufactured by Lauda, Viscotimer) at a measurement temperature of 25 ° C., and the logarithmic viscosity (η in
h). η _inh = {ln (t / t ₀ )} / C (where, t is the value of the solution, t ₀ is the value of only the mixed solvent, C is the concentration (g / dl)) (ash content) intercalation compound The ash content of the polyester resin composition derived from was measured according to JIS K7052. (Production Examples 1 to 4) Ion-exchanged water was used as a dispersion medium.
The swellable silicate was added to the ion-exchanged water, and the mixture was stirred at 5000 rpm for 5 minutes using a wet mill (Nippon Seiki Co., Ltd.). Next, an amino compound was added, and further 5000r
pm for 3 hours. Table 1 shows the types and amounts of raw materials used.

(Example 1) Step (A) The mixture containing water and the intercalation compound obtained in Production Example 1 was used as a clay dispersion (indicated by H-Mo-water in Table 2). It was difficult to confirm the small-angle X-ray diffraction peak angle of the interlayer compound in the clay dispersion. Step (B) While heating 3600 g of the clay dispersion H-Mo-water to 80 to 90 ° C., 3300 g of BHET was added and dissolved, followed by thorough mixing. Step (C) The mixture obtained in Step (B) was dehydrated (including a trace amount of water) at about 120 to 140 ° C for about 3 hours. Then
Hindered phenol-based stabilizer (AO6 manufactured by Asahi Denka Co., Ltd.)
0, hereinafter referred to as AO60) 7.5 g, and antimony trioxide (Sb2O3, hereinafter referred to as Sb2O3) 0.45 g, which is a polymerization catalyst, were charged, the polymerization temperature was 280 ° C., and the pressure reduction degree was 0.4.
Melt polycondensation was performed at 5 to 5.0 torr to obtain and evaluate a polyester resin composition containing an interlayer compound.

Example 2 Step (A) A mixture containing the intercalation compound obtained in Production Example 1 and water, and 60 parts by weight of EG with respect to 100 parts by weight of the mixture were sufficiently mixed by a wet mill. (5000 rpm, 5 minutes or more). After mixing, the mixture is stirred for 3 hours or more while heating to a temperature of about 100 to 130 ° C., and further stirred for 1 hour to reduce the water contained in the system by reducing the pressure, and a clay dispersion containing an intercalation compound and EG (Indicated by H-Mo-EG in Table 2). It was difficult to confirm the small-angle X-ray diffraction peak angle of the intercalation compound in the above clay dispersion. Step (B): 2250 g of the clay dispersion H-Mo-EG was heated to 80 to 90C.
While heating, was added 2500 g of DMT and mixed well. Step (C) 7.5 g of AO60 was added to the mixture obtained in Step (B).
0.60 g of titanium tetrabutoxide (Ti (OBu) 4) was added as a transesterification catalyst, and a reaction temperature of about 16
The mixture was stirred at 0 to 190 ° C. for about 4 hours to transesterify DMT and EG.

Thereafter, 0.45 g of Sb2O3 was added, and melt polycondensation was carried out at a polymerization temperature of 280 ° C. and a degree of vacuum of 0.5 to 5.0 torr to obtain a polyester resin composition containing an intercalation compound, which was evaluated. (Example 3) Step (A) In the same manner as in Example 2, a clay dispersion containing the intercalation compound and EG (indicated by H-Mo-EG in Table 2) was prepared. Step (B) Under a dry nitrogen stream, 2500 g of PET, 650 g of E
G, 7.5 g of AO60 was stirred at 180 to 240 ° C. for about 1 hour and 30 minutes, and PET was depolymerized while flowing out excess EG to obtain a low polyester polymer. The logarithmic viscosity of the polyester low-polymer is 0.11.
(Dl / g). While keeping the polyester low-polymerization degree at 230 to 250 ° C. and stirring at 100 to 180 rpm, 2250 g of a clay dispersion H under a dry nitrogen stream.
-Mo-EG was added continuously and mixed well. The addition rate of the dispersion is about 2000 g / h. Step (C) While heating the mixture obtained in Step (B) to 280 ° C. and removing 70% by weight or more of the used EG out of the system, the system was decompressed (0.5 to 5.0 torr). ) To perform melt polycondensation. The obtained polyester resin composition was evaluated.

Example 4 Step (A) The mixture containing the intercalation compound and water obtained in Production Example 2 was used as a clay dispersion (in Table 2, indicated by H-Mo-water).
It was difficult to confirm the small-angle X-ray diffraction peak angle of the interlayer compound in the clay dispersion. -Steps (B) and (C) A polyester resin composition was obtained and evaluated in the same manner as in Example 1 except that 7,200 g of the clay dispersion H-Mo-water was used.

Example 5 A polyester resin composition was obtained and evaluated in the same manner as in Example 1 except that a mixture containing the intercalation compound obtained in Production Example 3 and water was used. (Example 6) Step (A) A mixture containing the intercalation compound obtained in Production Example 1 and water, and 60 parts by weight of 1,4-
A clay dispersion (referred to as H-Mo-BD) was obtained in the same manner as in Example 1 except that BD was used. Step (B) Under a stream of dry nitrogen, 2500 g of PBT, 650 g of 1,
4-BD, 7.5 g of AO60 was charged, and the reaction temperature was 20
The PBT was depolymerized by stirring at 0 to 240 ° C. for about 1 hour and 30 minutes to obtain a low-polymerized polyester. Thereafter, excess 1,4-BD was discharged at 240 to 270 ° C. After depolymerization, the logarithmic viscosity of the obtained polyester low-polymer was 0.16 (dl / g). The above polyester low-polymer is maintained at 230 to 240 ° C.,
While stirring at 80 rpm, 2250 g of clay dispersion H
-Mo-EG was added continuously. The addition rate of the dispersion is about 2000 g / h. Step (C) While the mixture obtained in Step (B) was heated to 270 ° C. and 70% by weight or more of 1,4-BD used was removed, the system was depressurized (0.5 to 0.5. 0 torr) to perform melt polycondensation. The obtained polyester resin composition was evaluated.

(Example 7) A polyester resin composition was obtained and evaluated in the same manner as in Example 1 except that a mixture containing water and the intercalation compound obtained in Production Example 4 was used. (Comparative Example 1) 125 g of montmorillonite and 3500 g
Of the ion-exchanged water in a wet mill (Nippon Seiki Co., Ltd.)
The mixture was prepared by stirring at 000 rpm for 5 minutes. It was difficult to confirm the small-angle X-ray diffraction peak angle of montmorillonite in the mixture.

In the same manner as in Example 1, the above mixture and BHET were sufficiently mixed, dehydrated, and then subjected to melt polycondensation to obtain a montmorillonite-containing resin composition, which was evaluated. (Comparative Example 2) 125 g of montmorillonite and 2160 g
Of EG at 5000r with wet mill (Nippon Seiki Co., Ltd.)
The mixture was prepared by stirring at pm 5 min.
The bottom spacing of montmorillonite in the mixture is 18 °
Met.

In the same manner as in Example 2, the above mixture was mixed with DMT, then DMT and EG were transesterified, and then melt polycondensation was performed to obtain a resin composition containing montmorillonite. did. Comparative Example 3 In the same manner as in Comparative Example 2, a mixture containing montmorillonite and EG was prepared.

Separately, a low-polymer polyester obtained by the same method as in Example 3 (logarithmic viscosity = 0.11 (dl / g))
The above mixture was continuously added thereto, mixed well, and then subjected to melt polycondensation to obtain a montmorillonite-containing resin composition, which was evaluated. Comparative Example 4 A resin composition was obtained and evaluated in the same manner as in Comparative Example 1, except that swellable mica was used instead of montmorillonite.

Comparative Example 5 A mixture was prepared by stirring 125 g of montmorillonite and 2160 g of 1,4-BD in a wet mill (manufactured by Nippon Seiki Co., Ltd.) at 5000 rpm for 5 minutes. The bottom spacing of the montmorillonite in the mixture was 17 °. Separately, a low-polymer polyester (logarithmic viscosity =) obtained in the same manner as in Example 6
0.16 (dl / g)), and the mixture was continuously added and thoroughly mixed, followed by melt polycondensation to obtain a montmorillonite-containing resin composition, which was evaluated.

Comparative Example 6 In the same manner as in Production Example 1, montmorillonite and HEAPA were mixed in ion-exchanged water. Thereafter, dehydration and drying were performed to obtain a powdery interlayer compound.
The distance between the bottom surfaces of the interlayer compounds was 16 °. Separately,
Powder 1 of the above-mentioned intercalation compound was obtained under a dry nitrogen stream while stirring at 100 to 180 rpm while keeping the low-polymerized polyester obtained in the same manner as in Example 3 at 230 to 250 ° C.
A composition was obtained by adding 40 g and then performing melt polycondensation, and evaluated.

(Comparative Example 7) 125 g of montmorillonite was added to 3500 g of ion-exchanged water, and the mixture was stirred at 5000 rpm for 5 minutes using a wet mill (manufactured by Nippon Seiki Co., Ltd.). Next, 19 g of n-butyraldehyde manufactured by Wako Pure Chemical Industries, Ltd.
Was added, and the mixture was further stirred at 5000 rpm for 3 hours to obtain a mixture. Then, in the same manner as in Example 1,
After sufficiently mixing the above mixture and BHET, the mixture was dehydrated, and then subjected to melt polycondensation to obtain and evaluate a resin composition containing montmorillonite.

[0068]

According to the present invention, very fine flakes are produced by mixing an swellable silicate with an amino compound having an amino group as an essential functional group in a thermoplastic polyester resin. By dispersing in a shape, the bending characteristics, deflection temperature under load, and dimensional stability (reduction of warpage, reduction of linear expansion coefficient and anisotropy of molding shrinkage) are improved, and a resin molded product having a good surface appearance can be obtained. The resulting polyester resin composition is obtained. The polyester resin composition comprises: (A) a step of preparing a clay dispersion containing an intercalation compound and a dispersion medium; (B) at least one selected from a polymerizable monomer of a polyester, a polyester unit and a polyester low-polymer. And (C) a step of polymerizing a polyester.

[0069]

[Table 1]

[0070]

[Table 2]

[0071]

[Table 3]

Claims (5)

[Claims] 1. A polyester resin composition comprising a thermoplastic polyester resin and an intercalation compound, wherein the intercalation compound is prepared by mixing a swellable silicate and an amino compound in a dispersion medium. The compound has at least one amino group selected from the group consisting of primary, secondary and tertiary amino groups, and is selected from a hydroxyl group, a mercapto group, an ether group, a carbonyl group, a nitro group and a chlorine atom. A polyester resin composition which is a hydrocarbon compound having 1 to 25 carbon atoms which may have one or more substituents selected from the group consisting of: 2. The polyester resin composition according to claim 1, wherein the average layer thickness of the interlayer compound in the polyester resin composition is 500 ° or less. 3. The method according to claim 1, wherein the maximum thickness of the intercalation compound in the polyester resin composition is 2000 ° or less.
The polyester resin composition according to the above. 4. A step of preparing (A) a clay dispersion containing an intercalation compound and a dispersion medium; (B) one or more selected from a polymerizable monomer of polyester, a polyester unit and a low-polymerized polyester, and the clay described above. Mixing with the dispersion, and (C) polymerizing the polyester.
A method for producing the polyester resin composition according to claim 1. 5. The method according to claim 1, wherein the distance between the bottom surfaces of the intercalation compounds in the clay dispersion obtained in the step (A) is 4 times the distance between the bottom surfaces of the swellable silicate.
The method for producing a polyester resin composition according to claim 4, wherein the ratio is at least twice.