JPH11323102A - Reinforced polyester resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a reinforced polyester resin composition having high mechanical properties, heat resistance and dimensional stability. SOLUTION: A reinforced polyester resin composition contains a thermoplastic polyester resin, a fibrous filler and a silane-clay composite, wherein the silane- clay composite is prepared by introducing a silane compound of the following general formula: Yn SiX4-n (wherein n is an integer of from 0 to 3; Y is a 1-25C hydrocarbon group or an organic functional group comprising a 1-25C hydrocarbon group and a substituent; X is a hydrolyzable and/or hydroxyl group; and each of the n Ys and 4-n Xs is identical to or different from each other) into a swellable silicate. Also, the average layer thickness of the silane-clay composite in the reinforced polyester resin composition is larger than 50 Å but not larger than 500 Å.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a polyester resin composition containing a thermoplastic polyester resin, a fibrous filler and a silane clay composite.

[0002]

2. Description of the Related Art In order to improve elastic modulus and deflection temperature under load of thermoplastic polyester resin such as polyethylene terephthalate, and to reduce warpage and improve dimensional stability,
Conventionally, various countermeasures have been proposed. As such a technique, for example, a technique of adding a non-fibrous inorganic substance to polyethylene terephthalate and glass fiber (JP-A-54-748)
No. 52), a technique of combining polybutylene terephthalate, GF and crushed mineral fibers (Japanese Patent Laid-Open No. 61-254655).
), A technique of combining polyethylene terephthalate, glass fiber and mica (Japanese Patent Application Laid-Open No. 62-59661), and a method of combining glass fiber with another inorganic filler.

[0003]

However, in the above prior art, when the addition amount of the glass fiber and the inorganic filler is increased in order to obtain the reinforcing effect and the dimensional stabilizing effect, the specific gravity increases and the surface appearance of the molded product deteriorates. , And a decrease in strength occurs. In addition, if the addition amount of either the glass fiber or the inorganic filler is insufficient, the reinforcing effect and the dimensional stability cannot be balanced.

Accordingly, an object of the present invention is to solve the above-mentioned conventional problems, and to increase the specific gravity by using a very fine inorganic filler and a smaller amount of a fibrous filler as compared with the conventional one. It is an object of the present invention to provide a reinforced polyester resin composition which is excellent in dimensional stability by reducing warpage of a molded product without causing deterioration of surface appearance, and is excellent in elastic modulus and deflection temperature under load. .

[0005]

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, it is a reinforced polyester resin composition containing a thermoplastic polyester resin, a fibrous filler, and a silane clay composite having an average layer thickness of more than 50 ° and not more than 500 °.

According to the present invention, a reinforced polyester resin composition according to claim 1 is a reinforced polyester resin composition containing a thermoplastic polyester resin, a fibrous filler, and a silane clay composite. There following general formula swellable silicate _{(1) Y n SiX 4-} n (1) ( where, n is an integer of 0 to 3, Y is 1 to carbon atoms
X is a hydrolyzable group and / or a hydroxyl group, which is an organic functional group composed of 25 hydrocarbon groups and a hydrocarbon group having 1 to 25 carbon atoms and a substituent. n Y and 4-n X may be the same or different. ), And the average thickness of the silane clay composite in the reinforced polyester resin composition is more than 50 ° and not more than 500 °.

[0007] The polyester resin composition according to claim 2 is the reinforced polyester resin composition according to claim 1,
The maximum layer thickness of the silane clay composite in the reinforced polyester resin composition is more than 100 ° and not more than 2000 °. The polyester resin composition according to claim 3 is the reinforced polyester resin composition according to claim 1 or 2,
The fibrous filler is 0.5 to 20 parts by weight based on 100 parts by weight of the thermoplastic polyester resin.

The polyester resin composition according to claim 4 is the reinforced polyester resin composition according to claim 1, 2 or 3, wherein the silane clay composite is 0.5 to 100 parts by weight of the thermoplastic polyester resin. 15 parts by weight.

[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.

The molecular weight of the above-mentioned thermoplastic polyester resin is selected in consideration of the molding fluidity in the molding step and the physical properties of the final product. is there. That is, the molecular weight of the thermoplastic polyester resin is determined by using a mixed solvent of phenol / tetrachloroethane (5/5 weight ratio).
Logarithmic viscosity measured at 5 ° C. is 0.3 to 2.0 (dl / g)
, Preferably 0.35 to 1.9 (dl / g), and more preferably 0.4 to 1.8 (dl / g).
When the logarithmic viscosity is less than 0.3 (dl / g), the mechanical properties of the molded product of the obtained polyester resin composition are low,
On the other hand, if it is larger than 2.0 (dl / g), there tends to be a problem in processability such as fluidity during molding.

The fibrous filler used in the present invention is not particularly limited, and generally used fibrous materials can be used. Specific examples of the fibrous filler include glass fiber, carbon fiber, aramid fiber, silicon carbide fiber, alumina fiber and boron fiber, silicon carbide whisker, silicon nitride whisker, magnesium oxide whisker, potassium titanate whisker and aluminoborate. Whiskers such as whiskers, wollastonite, zonotolite, PMF, gypsum fiber, dawsonite, MO
Needle-like crystals such as S, phosphate fibers and sepiolite.

Considering the effects of improving the elastic modulus and the deflection temperature under load, and the availability, fibrous fillers include glass fibers, carbon fibers, potassium titanate whiskers, silicon nitride whiskers, and aramid. Fiber and alumina fiber, more preferably glass fiber and carbon fiber. The shape of the fibrous filler used in the present invention is not particularly limited, but if the fiber diameter is too small, its production is difficult, and if it is too large, the mechanical properties and the like of the obtained molded article tend to decrease,
If the aspect ratio is too small, the reinforcing effect is small, and if it is too large, the appearance of the molded article tends to be impaired or the dimensional stability tends to be reduced. Therefore, the shape of the reinforcing filler is, for example, 2 to 20 μm, preferably 3 to 18 μm, and more preferably 4 to 15 μm in the case of glass fiber and carbon fiber. Fiber diameter 2μ
If it is smaller than m, it is difficult to produce it, and if it is larger than 20 μm, the resulting molded article tends to have reduced surface properties and mechanical properties. Further, the aspect ratio (fiber length / fiber diameter ratio) in the molded body is preferably 2 to 70,
Preferably it is 3-60, More preferably, it is 5-50. If the aspect ratio is less than 2, the effect of improving the elastic modulus and the heat distortion temperature tends to be small, and if it is more than 70, the appearance of the molded article tends to be impaired and the dimensional stability tends to be reduced. The aspect ratio of the fibrous filler is a value obtained by dividing the fiber length of the fibrous filler in the reinforced polyester resin composition of the present invention by the fiber diameter. In the present specification, the term "fiber length" means a number average value of the lengths of individual fibrous fillers dispersed in the reinforced polyester resin composition of the present invention. The measurement of fiber length and fiber diameter is performed by selecting an arbitrary area including 100 or more fibrous fillers on a photographic image taken by a microscope or the like, converting the image into an image using an image processing device, and performing computer processing. It can be quantified by a method or a method of directly measuring from a photograph.

In the reinforced polyester resin composition of the present invention, the fibrous filler is 0.5 to 20 parts by weight, preferably 1.0 to 18 parts by weight, based on 100 parts by weight of the thermoplastic polyester resin. , More preferably 1.5 to
15 parts by weight. If the addition amount is less than 0.5 parts by weight, it is difficult to obtain a reinforcing effect such as an elastic modulus or a deflection temperature under load. If the addition amount is more than 20 parts by weight, warpage or specific gravity of a molded article increases, or surface properties are impaired. , Strength tends to decrease.

The silane clay composite used in the present invention refers to a swellable silicate represented by the following general formula (1): Y _n SiX _4-n (1) (where n is an integer of 0 to 3; Has 1 to 1 carbon atoms
X is a hydrolyzable group and / or a hydroxyl group, which is an organic functional group composed of 25 hydrocarbon groups and a hydrocarbon group having 1 to 25 carbon atoms and a substituent. n Y and 4-n X may be the same or different. ) Is introduced.

The above-mentioned swellable silicate is mainly composed of a tetrahedral sheet of silicon oxide and an octahedral sheet of metal hydroxide, and examples thereof include smectite clay and swellable mica. The smectite group clay is represented by the following general formula (2): X _0.2 to _0.6 Y ₂ to ₃ Z ₄ O ₁₀ (OH) ₂ .nH ₂ O (2) (where X is K, Na, １ ／ Ca, 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 (3): X _0.5 to _1.0 Y ₂ to ₃ (Z ₄ O ₁₀ ) (F, OH) ₂ (3) (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 (4) (Mg, Fe, Al) 2 ~ 3 (Si 4-x Al x) O 10 (OH) 2 · (M +, M 2+ 1/2) x · nH ₂ O (4) (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.
As the silane compound to be introduced into the swellable silicate, any compound generally used can be used, and preferably a compound represented by the following general formula (1) Y _n SiX _4-n (1) It is. Here, n is an integer of 0-3. Y is a hydrocarbon group having 1 to 25 carbon atoms, and 1
To 25 organic functional groups consisting of a hydrocarbon group and a substituent, provided that the substituent is an ester group, an ether group, an epoxy group, an amino group, a carboxyl group, a carbonyl group, an amide group, a mercapto group, a sulfonyl group, a sulfinyl. Group,
At least one selected from the group consisting of a nitro group, a nitroso group, a nitrile group, a halogen atom, and a hydroxyl group. X
Is a hydrolyzable group and / or a hydroxyl group, and the hydrolyzable group is selected from the group consisting of an alkoxy group, an alkenyloxy group, a ketoxime group, an acyloxy group, an amino group, an aminoxy group, an amide group, and a halogen atom. More than a species. Here, n Y and 4-n X may be the same or different.

As used herein, the term "hydrocarbon group" means a linear or branched (ie, having a side chain) saturated or unsaturated monovalent or polyvalent aliphatic hydrocarbon group, and an aromatic hydrocarbon group. An alicyclic hydrocarbon group means 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, the alkenyl group, alkynyl group, phenyl group, naphthyl group, and cycloalkyl group include alkenylene group, alkynylene group, phenylene group, naphthylene group, cycloalkylene group, and the like, respectively.

In the above general formula (1), Y has 1 carbon atom.
Examples of the case of a hydrocarbon group having a polymethylene chain such as decyltrimethoxysilane,
Those having a lower alkyl group such as methyltrimethoxysilane, those having an unsaturated hydrocarbon group such as 2-hexenyltrimethoxysilane, those having a side chain such as 2-ethylhexyltrimethoxysilane, phenyltriethoxy Those having a phenyl group such as silane, 3-β-
Examples include those having a naphthyl group such as naphthylpropyltrimethoxysilane, and those having a phenylene group such as p-vinylbenzyltrimethoxysilane. Y
When is a group having a vinyl group, examples thereof include vinyltrimethoxysilane, vinyltrichlorosilane, and vinyltriacetoxysilane. Examples of a case where Y is a group having an ester group include γ-methacryloxypropyltrimethoxysilane. Examples of the case where Y is a group having an ether group include γ-polyoxyethylenepropyltrimethoxysilane,
Ethoxyethyltrimethoxysilane is mentioned. Examples of a case where Y is a group having an epoxy group include γ-glycidoxypropyltrimethoxysilane.
Examples of the case where Y is a group having an amino group include γ-
Aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, and γ-
Anilinopropyltrimethoxysilane is mentioned. Y
Is a group having a carbonyl group, for example, γ
-Ureidopropyltriethoxysilane.
Examples of the case where Y is a group having a mercapto group include:
γ-mercaptopropyltrimethoxysilane. Examples of the case where Y is a group having a halogen include:
γ-chloropropyltriethoxysilane.
Examples of the case where Y is a group having a sulfonyl group include:
γ-phenylsulfonylpropyltrimethoxysilane. Examples of a case where Y is a group having a sulfinyl group include γ-phenylsulfinylpropyltrimethoxysilane. Examples of a case where Y is a group having a nitro group include γ-nitropropyltriethoxysilane. Examples of a case where Y is a group having a nitroso group include γ-nitrosopropyltriethoxysilane. Examples where Y is a group having a nitrile group include γ-cyanoethyltriethoxysilane and γ-cyanopropyltriethoxysilane. Examples of a case where Y is a group having a carboxyl group include γ- (4-carboxyphenyl) propyltrimethoxysilane.

In addition to the above, silane compounds in which Y is a group having a hydroxyl group can also be used. Such examples include
N, N-di (2-hydroxyethyl) amino-3-propyltriethoxysilane is exemplified. Hydroxyl groups can also be in the form of silanol groups (SiOH). Substitutes or derivatives of the above silane compounds may also be used. These silane compounds can be used alone or in combination of two or more.

The silane-clay composite is obtained by adding a silane-based compound after expanding the swellable silicate in a dispersion medium to increase the distance between the bottom surfaces. 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. As the polar solvent, for example,
Methanol, ethanol, alcohols such as isopropanol, ethylene glycol, propylene glycol,
Glycols such as 1,4-butanediol, acetone,
Ketones such as methyl ethyl ketone, diethyl ether,
Examples thereof include ethers such as tetrahydrofuran, amide compounds such as dimethylformamide, and other solvents such as dimethyl sulfoxide and 2-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 5 times or more, as compared with the distance between the bottom surfaces of the initial swellable silicate. There is no particular upper limit. However,
When the distance between the bottom surfaces is increased by about 10 times or more, it becomes difficult to measure the distance between the bottom surfaces. In this case, the swellable silicate is substantially present in a unit layer.

Here, in the present specification, the initial spacing between the bottom surfaces of the swellable silicate means a particulate swellable silicate in which the unit layers are stacked and aggregated before being added to the dispersion medium. It is intended to be the bottom spacing. The distance between the bottom surfaces can be confirmed by small angle X-ray diffraction (SAXS) or the like. That is, an X-ray diffraction peak angle value of a dispersion comprising a dispersion medium and a swellable silicate is measured by SAXS, and the peak angle value is determined by Bragg.
The bottom surface interval can be obtained by calculating by applying the formula to g.

In order to efficiently increase the distance between the bottom surfaces of the swellable silicate, stirring at several thousand rpm or more or a method of applying a physical external force as described below can be mentioned. 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 distance between the bottom surfaces of the swellable silicate is increased, in other words, the layers that have been in the aggregated state are cleaved and separated, and after the swellable silicates are independently present, the silane compound is added. Stir. In this way, a silane clay composite is obtained by introducing the silane compound to the surface of the cleaved swellable silicate layer. In the case of a method using a dispersion medium, the introduction of the silane-based compound can be performed by adding the silane-based compound to a dispersion containing the swellable silicate having an enlarged bottom surface space and the dispersion medium, followed by stirring. . When it is desired to introduce the silane compound more efficiently, the rotation speed of the stirring is set to 1000 rpm or more, preferably 1500 rpm.
m or more, more preferably 2000 rpm or more,
Alternatively, using a wet mill or the like, 500 (1 / s) or more,
Preferably at least 1000 (1 / s), more preferably 1
Apply a shear rate of 500 (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 500,000 (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.

In the case of a method using a physical external force, a silane compound is added to the swellable silicate while applying a physical external force thereto (for example, wet milling).
A silane compound may be introduced. Alternatively, by adding a swellable silicate having a bottom surface spacing expanded by a physical external force to a dispersion medium and adding a silane-based compound thereto in the same manner as in the method using the above-described dispersion medium, a silane-based compound is added. The compounds can also be introduced into swellable silicates.

The hydroxyl group present on the surface of the swellable silicate and the hydrolyzable group or hydroxyl group of the silane compound (formula 1)
By reacting with X), a silane compound can be introduced into the swellable silicate. The reaction between the swellable silicate and the silane compound can proceed sufficiently at room temperature, but the reaction system may be heated if necessary. The maximum temperature during heating can be arbitrarily set as long as it is lower than the decomposition temperature of the silane compound used and lower than the boiling point of the dispersion medium.

The silane compound introduced into the swellable silicate further reacts with a reactive group such as a hydroxyl group, a carboxyl group, an amino group, an epoxy group or a vinyl group (substituent of Y in the formula 1). ), It is also possible to further add a compound capable of reacting with such a reactive group and react this compound with this reactive group. Thus, the chain length of the functional group chain of the silane compound introduced into the swellable silicate and the polarity can be changed. In this case, as the compound to be added, the above-mentioned silane-based compound itself can be used, but the compound is not limited thereto, and any compound can be used according to the purpose. For example, an epoxy group-containing compound, an amino group Examples of the compound include a compound containing a carboxyl group, a compound containing an acid anhydride group, and a compound containing a hydroxyl group.

The amount of the silane compound to be used depends on the obtained silane clay composite and a dispersion medium such as a thermoplastic polyester resin or a glycol compound (in a dispersion adding step in a preferred method for producing the polyester resin composition of the present invention described later). To be used) and dispersibility can be sufficiently increased. If necessary, a plurality of silane compounds having different functional groups may be used in combination. Therefore, the amount of the silane compound to be added is not limited to a numerical value, 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 from 0.3 to 16 parts by weight.
0 parts by weight, more preferably 0.4 to 140 parts by weight, particularly preferably 0.5 to 120 parts by weight. When the amount of the silane compound is less than 0.1 part by weight, the effect of finely dispersing the obtained silane clay composite 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 spacing between the bottom surfaces of the silane clay composite obtained as described above can be enlarged as compared with the initial spacing between the bottom surfaces of the swellable silicate due to the presence of the introduced silane compound. For example, a swellable silicate dispersed in a dispersion medium and having an increased bottom surface interval, when the silane-based compound is not introduced, when the dispersion medium is removed, the layers return to a state in which the layers are aggregated again. For example, by introducing the silane compound after expanding the bottom surface interval, even after removing the dispersion medium, the obtained silane clay composite can exist in a state where the bottom surface interval is expanded without the layers being aggregated. . The distance between the bottom surfaces of the silane clay complex is at least 1.3 times, preferably at least 1.5 times, more preferably at least 1.7 times, particularly preferably at least 2 times, the initial distance of the swellable silicate. It is expanding.

The introduction of the silane compound into the swellable silicate can be confirmed by various methods. As a method for confirmation, for example, the following method can be mentioned. First, the adsorbed silane compound is simply washed and removed by washing the silane clay complex with an organic solvent such as tetrahydrofuran or chloroform. The washed silane clay composite is powdered in a mortar or the like and then dried sufficiently.
Then, the silane clay composite was powdered into potassium bromide (K
A pressurized tablet is prepared by sufficiently mixing with a window material such as Br) at a predetermined ratio, and the absorption band derived from the silane compound is measured by a transmission method or the like using Fourier transform (FT) -IR. When more accurate measurement is desired, or when the amount of the introduced silane compound is small, it is possible to measure a sufficiently dried powdery silane clay complex by a diffuse reflection method (DRIFT) as it is. desirable.

It can be confirmed by various methods that the distance between the bottom surfaces of the silane clay composite is larger than that of the swellable silicate. As a method for confirmation, for example, the following method can be mentioned. That is, in the same manner as described above, the adsorbed silane compound is removed from the silane clay composite by washing with an organic solvent, dried, and then confirmed by small angle X-ray diffraction (SAXS) or the like. According to this method, the X-ray diffraction peak angle value derived from the (001) plane of the powdery silane clay composite is calculated as S
By measuring with AXS and applying to Bragg's formula to calculate, 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.

As described above, by confirming that the silane compound has been introduced and that the distance between the bottom surfaces has increased, it can be confirmed that a silane clay composite has been formed. As described above, according to the present invention, the affinity between the silane clay composite and the thermoplastic polyester resin or the glycol compound can be increased by introducing the silane-based compound and increasing the distance between the bottom surfaces. .

In the polyester resin composition of the present invention, the blending amount of the silane clay composite per 100 parts by weight of the thermoplastic polyester resin is typically 0.5 to 15 parts by weight, preferably 0.8 to 13 parts by weight. , More preferably 1.0 to 10 parts by weight. If the amount of the silane clay composite is less than 0.5 part by weight, the effect of improving mechanical properties, deflection temperature under load, and dimensional stability may be insufficient. Fluidity during molding tends to be impaired.

The ash content of the polyester resin composition derived from the silane clay composite is typically 0.5 to 12%.
%, Preferably 0.8 to 11% by weight, more preferably 1.0 to 9% by weight. If the ash content is less than 0.5% by weight, mechanical properties, deflection temperature under load,
In some cases, the effect of improving dimensional stability may be insufficient.
If the content is more than 10% by weight, the appearance of the molded article and the fluidity during molding tend to be impaired.

The structure of the silane clay composite dispersed in the polyester resin composition of the present invention has an agglomerated structure of a μm size in which a number of layers are laminated, such as the swellable silicate before compounding. Completely different. In other words, the layers are further cleaved by using a silane clay composite in which a silane compound having an affinity for the matrix is introduced and the bottom surface interval is increased as compared with the initial swellable silicate. As a result, the silane clay composite is dispersed in the polyester resin composition into very fine and independent flakes. Such a dispersed state of the flaky silane clay composite can be expressed by an average layer thickness and a maximum layer thickness described below.

First, when the average layer thickness is defined as the number average value of the layer thickness of the silane clay composite dispersed in a plate shape, the average layer thickness of the silane clay composite in the reinforced polyester resin composition of the present invention is defined. Is greater than 50 °, preferably 60 ° or more, and more preferably 70 ° or more.
The upper limit of the average layer thickness of the silane clay composite is 500 ° or less, preferably 450 ° or less, more preferably 400 ° or less. When the average layer thickness of the silane clay composite dispersed in the reinforced polyester resin composition is 100 ° or less, in addition to the effect of improving the dimensional stability of a molded article obtained from the reinforced polyester resin composition of the present invention, In some cases, the reinforcing effect such as the elastic modulus and the deflection temperature under load may not be sufficiently obtained. If the upper limit of the average layer thickness is more than 500 °, the surface property of the molded product is impaired, and the effect of improving the dimensional stability is not sufficient. May not be obtained.

If the maximum layer thickness is defined as the maximum value of the layer thickness of the silane clay composite dispersed in the form of a plate in the reinforced polyester resin composition, the silane clay composite in the reinforced polyester resin composition of the present invention is defined as The lower limit of the maximum layer thickness of
0 °, preferably 150 ° or more, more preferably 200 ° or more, still more preferably 300 ° or more.
Å or more, particularly preferably 400 ° or more. When the maximum layer thickness of the silane clay composite dispersed in the reinforced polyester resin composition is 100 ° or less, in addition to the effect of improving the dimensional stability of a molded product obtained from the reinforced polyester resin composition of the present invention, In some cases, a sufficient reinforcing effect such as an elastic modulus or a deflection temperature under load may not be obtained. The upper limit of the maximum layer thickness of the silane clay composite is 2000 °, preferably 1800 °, more preferably 1500 °, further preferably 1200 °, and particularly preferably 1000 °. If the upper limit of the maximum layer thickness is more than 2000 °, the surface properties of the molded article obtained from the reinforced polyester resin composition of the present invention will be impaired, and the effect of improving the dimensional stability tends to be insufficient.

In the present specification, the thickness of a layer obtained by heating and melting the reinforced polyester resin composition of the present invention and then hot press molding or stretch molding, and a thin wall obtained by injection molding the molten resin. A molded article or the like can be determined from an image photographed 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. The above film or flat plate is cut out in a plane parallel to the XZ plane or the YZ plane, and the slice is determined by observing the thin section with a transmission electron microscope or the like at a high magnification of about 40,000 to 100,000 or more. Can be In place of the above-mentioned film or flat plate, a uniaxially stretched fibrous material is sliced perpendicularly to the stretching axis, and the layer thickness can be determined by transmission electron microscopy similarly. . The measurement was carried out by placing it on an elephant of a transmission electron microscope obtained by the above method,
Select any area containing more than one silane clay complex,
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 production of the reinforced polyester resin composition of the present invention containing the fibrous filler and the silane clay composite dispersed in a dispersion state as described above can be performed, for example, by preparing a thermoplastic polyester resin in the presence of the silane clay composite. It can be carried out by a method including a step of obtaining a polyester resin containing a silane clay composite by polymerization, and a step of melt-kneading the polyester resin containing the silane clay composite and a fibrous filler. Further, the reinforced polyester resin composition of the present invention comprises a step of melt-kneading the thermoplastic polyester resin and the fibrous filler, and depolymerizing the thermoplastic polyester resin containing the fibrous filler, and then the presence of the silane clay composite. It can also be produced by a method including a step of polymerizing a depolymerized thermoplastic polyester resin below.

The step of obtaining a polyester resin containing a silane clay composite by polymerizing a thermoplastic polyester resin in the presence of the silane clay composite can be performed, for example, as follows. First, a dispersion containing a polymerizable monomer of a silane clay composite and a thermoplastic polyester resin (hereinafter, referred to as a monomer dispersion) is prepared. A monomer dispersion is obtained by, for example, adding a silane clay composite to a polymerizable monomer of a polyester resin, for example, a glycol compound shown below, and stirring and mixing the mixture sufficiently, or preparation of a silane clay composite. Before removing the dispersion medium used sometimes, a polymerizable monomer of a desired polyester resin is added, and the mixture is stirred and mixed to obtain a mixture containing a silane clay composite, a dispersion medium, and a glycol compound. Thereafter, the dispersion medium is removed from the mixture. A method of obtaining a monomer dispersion by removal (referred to as a dispersion medium-monomer replacement method) or the like can be given. From the viewpoint of the dispersibility of the silane clay composite, the dispersion medium-monomer replacement method is preferred. In order to perform mixing efficiently, the rotation speed of stirring should be 500 rpm or more, or 3 rpm.
Apply a shear rate of 00 (1 / s) or more. The upper limit of the number of revolutions is 25000 rpm, and the upper limit of the shear rate is 50.
0000 (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.

Examples of the above glycol compounds include 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; Aromatic glycols such as 1,4-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, if the amount is small enough not to significantly lower the elastic modulus of the thermoplastic polyester resin, long chain diols (eg, polyethylene glycol, polytetramethylene glycol), and alkylene oxide addition polymers of bisphenols (eg, bisphenol At least one ethylene oxide addition polymer of A).

In the silane clay composite contained in the monomer dispersion obtained by the above-described method, the initial layered / agglomerated structure, which the swellable silicate had, has almost completely disappeared, and the distance between the layers has been reduced. Expands into 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 silane clay composite in the monomer dispersion is at least four times, preferably at least five times, and more preferably at least six times the initial distance between the bottom surfaces of the swellable silicate. When the distance between the bottom surfaces is less than four times, the silane clay composite tends not to be finely dispersed efficiently in the reinforced polyester resin composition of the present invention.

Next, the thermoplastic polyester resin can be polymerized using the monomer dispersion. In the polymerization, the monomer dispersion is used at an arbitrary time, and for example, there is a method in which the monomer dispersion is used from the start of the polymerization reaction. In this case, the monomer dispersion and the following aromatic dicarboxylic acid or an ester-forming derivative thereof are sufficiently mixed, and a glycol compound and an aromatic dicarboxylic acid or an ester-forming derivative thereof are transesterified in the presence of a silane clay complex. To form a polyester unit and then polymerize to polymerize. In addition to the above method, a method used during the polymerization of the thermoplastic polyester resin is also effective. In this method, a monomer dispersion is added to a previously prepared polyester unit and / or polyester low-polymer in a molten state,
Next, polymerization is performed. The method of adding the monomer dispersion is not particularly limited, and examples thereof include a method of continuously adding the monomer dispersion to a molten polyester unit and / or a low-polymer polyester. The rate of addition of the monomer dispersion is not particularly limited, but the monomer dispersion is added in an amount of 0.02 to 4.0 parts by weight / min, preferably 0.03 to 100 parts by weight of the polyester unit and / or low-polymerized polyester. To 3.8 parts by weight / minute, more preferably 0.05 to 5 parts by weight.
It is added continuously at 3.5 parts by weight / minute.

The aromatic dicarboxylic acids include, for example, terephthalic acid, isophthalic acid, orthophthalic acid,
2,5-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,4′-diphenyletherdicarboxylic acid, 4,4′-diphenylmethanedicarboxylic acid,
4,4′-diphenylsulfonedicarboxylic acid, 4,
4'-diphenylisopropylidene dicarboxylic acid and the like, and their substituted products and derivatives can also be used. Also,
Oxyacids such as p-oxybenzoic acid and p-hydroxyethoxybenzoic acid and their ester-forming derivatives may also be used. Two or more of these monomers may be used as a mixture. 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.

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. Further, 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 monomer dispersion containing a silane clay complex in a molten state. Has a molecular weight such that the melt viscosity is such that it can be sufficiently uniformly dispersed.

From the viewpoint of uniform dispersibility of the monomer 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). Less than 0.35 (dl / g), more preferably less than 0.35 (dl / g).
Less than 33 (dl / g), particularly preferably 0.30
(Dl / g).

When 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. As the glycol compound used in the depolymerization of the thermoplastic polyester resin, one or more of the same glycol compounds as those used in the step of preparing the monomer dispersion are used. in this case,
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 required 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 can be used. 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.

The method for polymerizing the polyester unit containing a silane clay complex and / or the low-polymerized polyester obtained by the above method is not particularly limited, and the polymerization method of a thermoplastic polyester resin generally performed generally is generally used. Can be done by 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. After cooling, solidifying and pulverizing the system at any time before the start of the melt polycondensation or after the start of the melt polycondensation or after the end of the polymerization, pre-crystallization and drying,
A method of heating to 0 ° C. to the melting point or lower to carry out solid-phase polymerization is exemplified. When another glycol component is copolymerized with the resin component, it is obtained by adding and mixing a desired glycol compound at any time of the melt polycondensation reaction, and then performing the melt polycondensation reaction or solid phase polymerization continuously. . The catalyst necessary for the reaction is used by adding one or more of metal oxides, carbonates, acetates, and alcoholates as necessary. As the glycol compound constituting the above-mentioned polyester unit or low-polymer polyester, one or more of the same glycol compounds as those used in the dispersion preparation step are used.

The resin having a high molecular weight obtained by polymerization has a logarithmic viscosity of 0.3 to 2.0 (dl / dl) measured at 25 ° C. using a phenol / tetrachloroethane (5/5 weight ratio) mixed solvent. g), preferably 0.3
5 to 2.0 (dl / g), more preferably 0.37
~ 2.0 (dl / g), more preferably 0.40 ~
1.8 (dl / g). When the logarithmic viscosity is 0.3 (dl /
g), mechanical properties are low, and 2.0 (dl /
If the value is larger than g), the molding fluidity tends to decrease because the melt viscosity is high.

The step of melt-kneading the polyester resin containing the silane clay composite and the fibrous filler is not particularly limited, and can be carried out by using a commonly used kneader. Examples of such a kneader include a kneader capable of giving a high shearing force to the system, such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, and a roll. In particular, a meshing twin-screw extruder having a kneading disk portion is preferable.

Another method for producing the reinforced polyester resin composition of the present invention is a step of melt-kneading the thermoplastic polyester resin and the fibrous filler, and depolymerizing the thermoplastic polyester resin containing the fibrous filler. Then, in the method including the step of polymerizing the depolymerized thermoplastic polyester resin in the presence of the silane clay composite, the step of melt-kneading the thermoplastic polyester resin and the fibrous filler is performed by the above-described silane clay composite. Since the process can be performed in the same manner as in the step of melt-kneading the thermoplastic polyester resin containing the body and the fibrous filler, the description is omitted. The following step of depolymerizing the thermoplastic polyester resin containing the fibrous filler and then polymerizing the depolymerized thermoplastic polyester resin in the presence of the silane clay composite includes the above-mentioned molten polyester unit and / or Alternatively, the method is the same as the method of adding a monomer dispersion to a polyester low-polymer and polymerizing the same, and thus the description is omitted.

The polyester resin composition of the present invention may contain, 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 pigments and dyes, heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, lubricants, plasticizers, flame retardants,
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.

[0058]

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. (Swellable silicate) As montmorillonite, natural montmorillonite from Akita Prefecture (bottom spacing = 13 °) 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 heated at 800 ° C. to obtain 28.2 g of swellable mica (base spacing = 12).
Å). (Silane-based compound) γ- (2-aminoethyl) aminopropyltrimethoxysilane: manufactured by Nippon Unicar Co., Ltd., A-1120 (hereinafter A
.Gamma .- (polyoxyethylene) propyltrimethoxysilane: manufactured by Nippon Unicar Co., Ltd., A-1230 (hereinafter A)
(Glycol compound) ・ Ethylene glycol: manufactured by Nippon Shokubai Co., Ltd., monoethylene glycol (hereinafter referred to as EG) ・ 1,4-butanediol: manufactured by Tosoh Corporation, 1,4-butanediol (hereinafter, referred to as EG) (Polyester resin) PET: polyethylene terephthalate manufactured by Kanebo Co., Ltd., trade name PBK2, logarithmic viscosity (ηinh) = 0.63 (d)
1 / g) (hereinafter referred to as PET) PBT: polybutylene terephthalate manufactured by Kanebo Co., Ltd., trade name PBT120, ηinh = 0.82 (dl / g) (hereinafter referred to as PBT) (fibrous filler) Glass fiber: Glass fiber manufactured by Nippon Electric Glass Co., Ltd., trade name T-195H (hereinafter referred to as GF) Carbon fiber: carbon fiber manufactured by Osaka Gas Co., Ltd., trade name Donacarbo S-243 (hereinafter CF) The evaluation methods in Examples and Comparative Examples are collectively shown below. (FT-IR) 1.0 g of the silane clay complex was added to 50 ml of tetrahydrofuran (THF), and the mixture was stirred for 24 hours to wash and remove the adsorbed silane compound, followed by centrifugation to separate the supernatant. This washing operation was repeated three times. After washing, about 1 mg of the sufficiently dried silane clay complex and about 200 mg of KBr powder were sufficiently mixed using a mortar, and a KBr disk for measurement was prepared using a tabletop press. Next, an infrared spectrometer (Shimadzu Corporation)
, 8100M). The detector used was an MCT detector cooled with liquid nitrogen, and the resolution was 4c.
m-1 and the number of scans was 100 times. (Optical Microscope (OM)) A sample is melted at 260 ° C. using a hot stage THM600 manufactured by LINKAM, and the aspect ratio of the fibrous filler is measured with an optical microscope BH-2 manufactured by Olympus Optical Co., Ltd. in a molten state. did.
An arbitrary region where 100 or more fibrous fillers were present in the OM photograph was selected, and the value obtained by dividing the number average value of the fiber length of each fibrous filler by the fiber diameter was defined as the aspect ratio. (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 silane clay composite 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 area where 100 or more silane clay composites exist is selected, the maximum layer thickness is the maximum value among the individual silane clay composite layer thicknesses, and the average layer thickness is the individual silane clay composite. The number average value of the layer thickness of the composite was taken. (Measurement of bottom spacing by small angle X-ray diffraction (SAXS))
Using an X-ray generator (RU-200B, manufactured by Rigaku Corporation), target CuKα ray, Ni filter, voltage 4
0 kV, current 200 mA, scanning angle 2θ = 0.2 to 16.0
°, the step angle = 0.02 ° under the measurement conditions, the bottom spacing was measured.

As for the distance between the bottom surfaces, the small-angle X-ray diffraction peak angle
It was calculated by substituting into the formula of ragg. However, when it is difficult to confirm the small-angle X-ray peak angle value, it is confirmed that the layer has been sufficiently cleaved and the crystallinity has substantially disappeared, or the peak angle value is approximately 0.8 ° or less. Was considered difficult, and the evaluation result of the bottom surface spacing was set to> 100 °. (Deflection temperature under load) The reinforced polyester resin composition of the present invention was dried (140 ° C, 5 hours). Using an injection molding machine (IS-75E, manufactured by Toshiba Machine Co., Ltd.) with a mold clamping pressure of 75 t,
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 test piece of 00 × 6 mm was prepared. The deflection temperature under load of the obtained test piece was measured according to ASTM D-648. (Bending Characteristics) The bending elastic 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. (Warpage) After drying (140 ° C., 5 hours) the reinforced polyester resin composition of the present invention, the mold temperature was set to 120 using an injection molding machine (IS-75E, manufactured by Toshiba Machine Co., Ltd.) with a mold clamping pressure of 75 t. ° C, resin temperature 250-280 ° C, gauge pressure about 1
Injection molding was performed under the conditions of 0 MPa and an injection speed of about 50% to produce a flat test piece having a size of about 120 × 120 × 1 mm. The above-mentioned 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 gap gauge, calipers or the like. . Each of the four corners was pressed, and the average value of the obtained warpage values was obtained. (Linear Expansion Coefficient) A center portion of a JIS No. 1 dumbbell test piece having a thickness of about 3 mm and manufactured under the same conditions as the deflection temperature under load was cut to 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. (Specific gravity) Using the above dumbbell-shaped test piece, specific gravity was measured using an electronic hydrometer ED-120T manufactured by Mirage Trading Co., Ltd. (Logarithmic viscosity) After the obtained reinforced polyester resin composition was dried (140 ° C, 4 hours), about 100 mg was precisely weighed and phenol / 1,1,2,2-tetrachloroethane (1/1, weight Ratio) Add 120 ml of mixed solvent and add to 120 ° C
And dissolved. Using an Ubbelohde viscometer, the solution viscosity was measured using an automatic viscosity measurement device (manufactured by Lauda Co., Viscotimer) at a measurement temperature of 25 ° C for the PET system and 20 ° C for the PBT system, The logarithmic viscosity (η _inh ) was determined from the following equation. η _inh = {ln (t / t ₀ )} / C (where, t is the value of the solution, t ₀ is the value of the mixed solvent only, C is the concentration (g / dl)) (ash content) fibrous The ash content of the reinforced polyester resin composition derived from the filler and the silane clay composite is determined according to JIS.
It was measured according to K7052.

(Production Examples 1 to 4) Preparation of Monomer Dispersion 125 g of swellable silicate was added to 3500 g of ion-exchanged water, and the mixture was wetted using a wet mill made by Nippon Seiki Co.
The mixture was dispersed by stirring at 5 rpm for 5 minutes. Thereafter, using a simple pipette, the following silane-based compound was dropped, and the mixture was further stirred to prepare a silane clay composite. As the silane compound, A1120 (γ- (2-aminoethyl) aminopropyltrimethoxysilane) was used as it was,
1230 (γ-polyoxyethylenepropyltrimethoxysilane) used was hydrolyzed with water adjusted to pH 3.0 with hydrochloric acid.

The silane clay composite was confirmed by separating the solid content from the dispersion, drying and pulverizing, measuring the distance between the bottom surfaces by SAXS, and washing with THF to obtain FT-IR.
By measuring the absorption band of the functional group derived from the silane-based compound. The results are shown in Table 1. Then
To a system containing a silane clay complex and water, 1800 g of a glycol compound is added and mixed well, and a temperature of about 100 to 13 is added.
By stirring at 0 ° C. for about 4 hours to remove water, a monomer dispersion containing a silane clay complex and a glycol compound (abbreviated in Table 1) was prepared. The distance between the bottom surfaces of the silane clay composite in the monomer dispersion was measured, and the results are shown in Table 1.

Example 1 2500 g of PET, 650 g of EG, and 7.5 g of a hindered phenol-based stabilizer (Adeka Stab AO60 manufactured by Asahi Denka Co., Ltd., hereinafter referred to as AO60) were placed in a polymerization machine equipped with a distillation tube. At a reaction temperature of 180 to 240 ° C. for about 1 hour 30 under a dry nitrogen stream.
After stirring for minutes, PET was depolymerized while excess EG was allowed to flow. After depolymerization, the logarithmic viscosity of the obtained polyester low-polymer was 0.11 (dl / g). Keeping the polyester low polymer at 230-250 ° C.
Under a dry nitrogen stream while stirring at 0 to 180 rpm, 1
800 g of the monomer dispersion A-Mo-EG were continuously added. The rate of addition of the monomer dispersion is about 2000 g / hour. After the monomer dispersion was added, 70% by weight or more of the used EG was removed from the system while the temperature of the system was raised to 280 ° C., and then the system was decompressed (0.5 to 5.0 torr) to carry out melt polycondensation. As a result, a silane clay composite-containing PET resin was obtained.

For the melt kneading, a 30 mm twin screw extruder (LABOTEX 30 manufactured by Nippon Steel Corporation) was used. The silane clay composite-containing PET resin 2,500 g
g of GF, set temperature 260-280 ° C, rotation speed 1
A reinforced polyester resin composition was obtained by melt-kneading at 00 rpm and evaluated. (Example 2) Instead of the monomer dispersion A-Mo-EG,
A reinforced polyester resin composition was obtained and evaluated in the same manner as in Example 1 except that the monomer dispersion E-Mo-EG was used. (Example 3) Instead of the monomer dispersion A-Mo-EG,
A reinforced polyester resin composition was obtained and evaluated in the same manner as in Example 1, except that 2700 g of the monomer dispersion A-Mi-EG was used. (Example 4) A reinforced polyester resin composition was obtained in the same manner as in Example 1 except that CF was used instead of GF.
evaluated. (Example 5) 2500 g in a polymerization machine equipped with a distillation tube
PBT, 650 g 1,4-BD, 7.5 g AO6
0, and the reaction temperature is 200 to 240 under a dry nitrogen stream.
C. for about 1 hour and 30 minutes to depolymerize PBT.
Excess 1,4-BD was eluted at ２270 ° C. After depolymerization, the logarithmic viscosity of the obtained polyester low-polymerization degree is 0.1.
16 (dl / g). While maintaining the polyester low-polymerization degree at 230 to 240 ° C. and stirring at 100 to 180 rpm, 1800 g of the monomer dispersion A-Mo-B is stirred.
D was added continuously. The addition rate of the dispersion is about 200
0 g / h. Next, while removing 70% by weight or more of the 1,4-BD used while raising the temperature of the system to 270 ° C., the system is subjected to melt polycondensation by reducing the pressure (0.5 to 5.0 torr). Thus, a PBT resin containing a silane clay composite was obtained.

For the melt kneading, a 30 mm twin screw extruder (LABOTEX30, manufactured by Nippon Steel Corporation) was used. For 2,500 g of the PBT resin containing the silane clay composite, 290
g of GF, set temperature 240-260 ° C, rotation speed 1
A reinforced polyester resin composition was obtained by melt-kneading at 00 rpm and evaluated. Comparative Example 1 2500 g of PET, 290 g of GF and 125 g of montmorillonite were dry-blended and melt-kneaded in the same manner as in Example 1 by using an extruder to obtain a resin composition, which was evaluated.

Comparative Example 2 A resin composition was obtained and evaluated in the same manner as in Comparative Example 1 except that 190 g of swellable mica was used instead of montmorillonite. Comparative Example 3 A resin composition was obtained and evaluated in the same manner as in Comparative Example 1 except that CF was used instead of GF. (Comparative Example 4) A resin composition was obtained and evaluated in the same manner as in Comparative Example 1 except that PBT was used instead of PET. (Example 6) The amount of the monomer dispersion A-Mo-EG was 900
g and the amount of GF was 80 g, and a reinforced polyester resin composition was obtained and evaluated in the same manner as in Example 1. (Example 7) The amount of the monomer dispersion A-Mo-EG was 432
A reinforced polyester resin composition was obtained and evaluated in the same manner as in Example 1 except that the amount was 0 g and the amount of GF was 450 g. (Comparative Example 5) The amount of the monomer dispersion A-Mo-EG was 70 g.
And a resin composition was obtained and evaluated in the same manner as in Example 1 except that the amount of GF was changed to 80 g.

Comparative Example 6 Monomer Dispersion A-Mo-EG
The resin composition was obtained and evaluated in the same manner as in Example 1 except that the amount of GF was 4320 g and the amount of GF was 1125 g.

[0069]

As described in detail above, a system containing a thermoplastic polyester resin and a fibrous filler has an average layer thickness of 50 °.
If fine plate-like particles having a size of 500 ° or less are dispersed, the effect of reinforcing the polyester resin and the effect of dimensional stability can be efficiently obtained. If plate-like particles having the above-mentioned layer thickness are contained, a sufficient reinforcing effect can be obtained even with a small amount of fibrous filler compared to the prior art, so that a rise in specific gravity is small and warpage of a molded product is suppressed. And does not adversely affect the appearance of the molded article. In order to finely disperse the layered silicate in the form of a plate having an average layer thickness of more than 50 ° and not more than 500 °, it is essential to form a silane clay composite by treating with a silane compound.

[0070]

Thus, according to the present invention, there is provided a reinforced polyester resin composition comprising a thermoplastic polyester resin, a fibrous filler, and a fine plate-like silane clay composite having an average layer thickness of more than 50 ° and 500 ° or less. It is possible to provide a resin molded product having improved bending characteristics, deflection temperature under load, and dimensional stability (reduction in warpage, reduction in anisotropy in linear expansion coefficient and heat shrinkage) and excellent surface appearance.

[0071]

[Table 1]

[0072]

[Table 2]

[0073]

[Table 3]

Claims (4)

[Claims] 1. A reinforced polyester resin composition containing a thermoplastic polyester resin, a fibrous filler and a silane clay composite, wherein the silane clay composite has a swellable silicate represented by the following general formula (1): Y _n SiX _4-n (1) (where n is an integer of 0 to 3 and Y is 1 to 3 carbon atoms)
X is a hydrolyzable group and / or a hydroxyl group, which is an organic functional group composed of 25 hydrocarbon groups and a hydrocarbon group having 1 to 25 carbon atoms and a substituent. n Y and 4-n X may be the same or different. A reinforced polyester resin composition prepared by introducing a silane compound represented by the formula (1), wherein the average layer thickness of the silane clay composite in the reinforced polyester resin composition is more than 50 ° and not more than 500 °. 2. The method according to claim 1, wherein the maximum thickness of the silane clay composite in the reinforced polyester resin composition is greater than 100.degree.
The reinforced polyester resin composition according to claim 1, which is 0 ° or less. 3. The fibrous filler is 0.5 to 20 parts by weight based on 100 parts by weight of the thermoplastic polyester resin.
The reinforced polyester resin composition according to claim 1. 4. The reinforced polyester resin composition according to claim 1, wherein the silane clay composite is 0.5 to 15 parts by weight based on 100 parts by weight of the thermoplastic polyester resin.