CN1930242A - Polyester resin composition - Google Patents

Abstract

The present invention provides a polyester resin composition comprising a polyester and a layered silicate modified with 60 to 100% organic phosphonium ions, wherein the layered silicate is contained in an amount of 0.01 to 20% by weight as inorganic ash and the amount of OH terminal groups is 0.1 to 45 equivalents per ton. The present invention also provides a method for producing the polyester resin composition and a molded article formed therefrom.

Description

polyester resin composition

technical field

The present invention relates to a polyester resin composition composed of polyester and a layered silicate modified with a specific organic phosphonium ion, a method for producing the composition, and a molded article composed of the composition. Specifically, it relates to a polyester resin composition comprising polyester and a layered silicate modified by a specific organic phosphonium ion, the amount of OH terminal groups in the composition is within a specific range, and the layered silicate is suitable The polyester resin composition is dispersed and excellent in heat resistance; and further relates to a polyester resin composition capable of providing a molded article with excellent surface smoothness, a method for producing the same, and a molded article composed of the polyester resin composition.

Background technique

Polyester can be used in various applications by making use of its mechanical properties, moldability, dimensional stability, weather resistance, light resistance, and chemical resistance. However, in recent years, resins have been required to have higher characteristics in accordance with the application with the advancement of technology. As one of techniques for satisfying the above-mentioned required properties, a composition in which a layered compound is dispersed in a thermoplastic resin at a nanoscale, that is, a so-called nanocomposite, has recently attracted attention. By forming a nanocomposite, it is possible to improve various properties such as high heat resistance, high elasticity, flame retardancy, and gas barrier performance (Nakajo Sumiko, "Nanocomposite no World", Industrial Research Society, 2000 ). In order to form a nanocomposite, layered compounds must be dispersed at the nanoscale, and various methods have been tried. Unlike the well-known example of polyamide, it is difficult to disperse a nanocomposite using polyester to the same extent as polyamide, and various proposals have been made to exert the effect of the nanocomposite. For example, it is disclosed that an exchangeable cation such as an ammonium salt is used for an organic modified body of a layered compound when producing a polyester composite material in which the layered compound is dispersed at a monolayer level (JP-A-2000-53847). In this way, in order to achieve good dispersibility in a system in which phyllosilicates are difficult to disperse, such as polyesters, phyllosilicates modified with organic modifying groups that can improve compatibility with mixed resins, Layered silicates with open interlayers.

In addition, its kneading method was also studied. For example, there is described a polyester resin composition in which a layered silicate with an interlayer distance of 15 to 35 Ȧ is melt-mixed into a polyester resin, and a layered structure of 5 to 20 layers is maintained while being uniformly dispersed (JP-A-2001 -261947 Bulletin). The conditions of these dispersion processes are high temperature, high shear, etc., and it is also necessary to suppress the deterioration of the physical properties of the polyester resin composition by using a phyllosilicate having resistance that does not deteriorate as much as possible during dispersion.

Contents of the invention

The object of the present invention is to provide a polyester resin composition, which is composed of polyester and layered silicate modified with 60-100% of specific organic phosphonium ions, wherein the polyester resin composition has excellent heat resistance , containing 0.01 to 20% by weight of the phyllosilicate as inorganic ashes, and 0.1 to 45 equivalents/ton of OH terminal groups; also provides its production method, and the formation of films, fibers, etc., which are composed of it and have excellent surface smoothness body.

Another object of the present invention is a method for producing the polyester resin composition, which comprises polymerizing polyester in the presence of a phyllosilicate modified with a specific organic phosphonium ion in an amount of 60 to 100%, followed by melt mixing.

The phyllosilicate of the polyester resin composition of the present invention is well dispersed, thereby improving physical properties such as heat resistance, high elastic modulus, and gas barrier properties, and further forming films and fibers with excellent surface smoothness. Taste.

Other objects and advantages of the present invention will be apparent from the following description.

Description of drawings

Fig. 1 is the electron micrograph of the polyester resin composition of embodiment 5.

2 is an electron micrograph of the polyester resin composition of Example 6.

3 is an electron micrograph of the polyester resin composition of Example 7.

4 is an electron micrograph of the polyester film of Example 10.

Detailed ways

The layered silicate used in the present invention is a layered silicate containing an octahedral sheet structure such as Al, Mg, Li, etc. sandwiched between two _SiO4 tetrahedral sheet structures, specifically saponite , hectorite, fluorohectorite, montmorillonite, beidellite, magnesium-rich montmorillonite and other montmorillonite clay minerals; Swelling synthetic mica such as mica, Li-type tetrasilicon fluorine mica; vermiculite, fluorine vermiculite, halloysite, swelling mica, etc. Can be natural or synthetic. Among them, montmorillonite-based clay minerals such as montmorillonite and hectorite, and phyllosilicates such as Li-type fluorotaenolite and Na-type tetrasilicofluoromica are preferable from the viewpoint of cation exchange capacity and the like.

The organic phosphonium ion is represented by the following formula (1).

(In the formula, R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrocarbon group having 1 to 30 carbon atoms or a hydrocarbon group containing a heteroatom.)

Examples of the hydrocarbon group having 1 to 30 carbon atoms include an alkyl group and an aryl group. The alkyl group is preferably a hydrocarbon group with 1 to 18 carbon atoms, such as methyl, ethyl, n-propyl, n-butyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl , n-hexadecyl, n-heptadecyl and n-octadecyl. Examples of the aryl group include phenyl, biphenyl, benzyl, tolyl and the like. R ₁ to R ₄ may have substituents such as methyl, ethyl, fluorine, chlorine, etc. that do not affect their thermal stability.

Specific examples of the aforementioned organic phosphonium ions include tetraethylphosphonium, triethylbenzylphosphonium, tetrabutylphosphonium, tetraoctylphosphonium, trimethyldecylphosphonium, trimethyldodecylphosphonium, trimethyldecylphosphonium Hexaalkylphosphonium, Trimethyloctadecylphosphonium, Tributylmethylphosphonium, Tributyldodecylphosphonium, Tributyloctadecylphosphonium, Trioctylethylphosphonium, Tributylhexadecane phosphonium, methyltriphenylphosphonium, ethyltriphenylphosphonium, diphenyldioctylphosphonium, triphenyloctadecylphosphonium, tetraphenylphosphonium, tributylallylphosphonium, etc.

Examples of the heteroatom-containing hydrocarbon group include hydroxy-substituted hydrocarbon groups, alkoxy-substituted hydrocarbon groups, and phenoxy-substituted hydrocarbon groups having 1 to 30 carbon atoms, preferably the following substituents and their isomers. (In the following formula, a and b are integers of 1 to 29, and the number of carbon atoms in the substituent is an integer of 30 or less.)

Hydroxyl Substituted Hydrocarbyl:

Alkoxy substituted hydrocarbyl

Phenoxy substituted hydrocarbyl

The above-mentioned organic phosphonium ions may be used alone or in combination.

The phyllosilicate of the present invention is ion-exchanged by 60 to 100% of the cation exchange capacity of the phyllosilicate using the organic phosphonium ions. The cation exchange capacity of layered silicates can be measured by conventionally known methods. As the ion exchange capacity of the phyllosilicate used in the present invention, it is preferable to have an exchange capacity of 0.2 to 3 meq/g in the above-mentioned phyllosilicate. When the cation exchange capacity is 0.2 milliequivalent/g or more, the introduction rate of organic phosphonium ions is increased, which is preferable in terms of dispersibility. On the other hand, when it is 3 milliequivalents/g or less, introduction of organic phosphonium ions becomes easy, and it is preferable from the point of view of producing the phyllosilicate of the present invention. The cation exchange capacity is more preferably 0.8 to 1.5 meq/g.

The above-mentioned cation exchange rate is calculated by the following formula (2).

Cation exchange rate (%)={W _f /(1-W _f }/M _org /M _si )×100 (2)

(W _f is the weight loss rate of layered silicate measured by differential thermobalance from 120°C to 800°C at a heating rate of 20°C/min, M _org is the molecular weight of the phosphonium ion, _Msi represents layered silicate Molecular weight per charge of the cationic part of the salt. The molecular weight per charge of the cationic part of the layered silicate is a value calculated from the reciprocal of the cation exchange capacity (unit: eq/g) of the layered silicate.)

By exchanging the cations of the layered silicate with organic phosphonium ions, the organic phosphonium ions enter the interlayer to widen the interlayer. The average value of this interlayer distance can be calculated from the peak position by X-ray diffraction. A preferable average interlayer distance is 1.5 nm or more. If it is less than 1.5 nm, dispersion in the polyester described below will become difficult.

As a method of exchanging cations of layered silicate with organic phosphonium ions, conventionally known methods can be used. Specifically, there is a method of first dispersing layered silicate as a raw material in a polar solvent such as water, ethanol, and methanol, and then adding organic phosphonium ions or a solution containing organic phosphonium ions thereto. As a preferable concentration for the modification reaction, the concentration of layered silicate is preferably 0.1 to 5% by weight, and reacts with dissolved organic phosphonium ions. When the concentration is less than 0.1% by weight, the amount of the entire solution is too large, which may not be preferable from the viewpoint of handling. When it exceeds 5% by weight, the viscosity of the phyllosilicate dispersion liquid becomes too high, so the cation exchange rate may decrease. The viscosity of the phyllosilicate is more preferably 0.5 to 4.5% by weight, more preferably 1 to 4% by weight. The temperature at the time of the reaction should be a temperature that has a sufficiently low viscosity when the layered silicate dispersion is stirred. For example, in the case of water, it is preferable to carry out the cation exchange reaction at about 20 to 100°C.

The modified phyllosilicate obtained above is preferably washed sufficiently after the reaction to remove unreacted organic phosphonium ions. Since the dispersion in polyester is at a high temperature of 250° C. or higher, if there is a component decomposed at this temperature, it will adversely affect the physical properties of the polyester resin composition afterward. The washing method is not particularly limited, and examples thereof include washing with good solvents for organic phosphonium ions such as organic solvents.

Furthermore, with respect to the presence or absence of phosphonium ions that do not participate in cation exchange in the layered silicate of the present invention, the presence or absence of counter ions of the organic phosphonium ions used in the raw materials can be measured by conventionally known methods such as fluorescent X-rays and atomic absorption analysis. No waiting to confirm.

From the perspective of dispersibility, it is advantageous to have a cation exchange rate of 60% or more, which can increase the rate of introduction of organic phosphonium ions to the layered silicate. From the viewpoint of thermal stability, it is advantageous that the cation exchange rate is 100% or less, and the counter ion of the organic phosphonium ion compound used as the raw material can be eliminated. The cation exchange rate is more preferably 65 to 99%, more preferably 70 to 99%.

The layered silicate of the present invention preferably has a temperature at which the weight decreases by 5% by weight as measured by a differential thermobalance at a temperature increase rate of 20°C/min in a nitrogen atmosphere of 310°C or higher. If the temperature at which the weight is reduced by 5% by weight is lower than 310° C., the decomposition during melt-mixing with polyester is large, causing re-agglomeration of layered silicate, or generation of decomposition gas, which may lower the properties of the resin. From the viewpoint of the above, the temperature at which the weight decreases by 5% by weight is preferably high temperature. For the layered silicate of the present invention, in order to obtain an onium salt capable of imparting good dispersibility, it is preferably 330° C. or higher, more preferably 340° C. above, and more preferably above 350°C. It is preferable that the specific surface area of the layered silicate used for manufacture of the resin composition of this invention is 2.5-200 m ^<2> /g. The specific surface area can be determined by the BET method using nitrogen. When the specific surface area is 2.5 m ² /g or more, the dispersion efficiency at the time of dispersion in the resin can be improved, and a polyester resin composition of a well-uniformly dispersed layered silicate and a polyester resin can be obtained. Conversely, when the specific surface area exceeds 200 m ² /g, since fine particles with a large specific surface area are formed, the bulk density becomes high, and handling as a powder becomes difficult, or removal of adsorbed moisture becomes difficult. The specific surface area is preferably 3 to 100 m ² /g, more preferably 4 to 80 m ² /g, and still more preferably 5 to 50 m ² /g.

The phyllosilicate having the above-mentioned large specific surface area is preferably produced by freeze-drying the phyllosilicate ion-exchanged with organic phosphonium in a solvent having a melting point of -20°C or more and less than 100°C.

The solvent used for freeze-drying preferably has a melting point of -20°C or higher. If the melting point is lower than -20°C, the freezing temperature of the solvent will be too low, and the freezing temperature will be lowered, and the removal efficiency of the solvent will be lowered. The solvents preferably used for freeze-drying include water, benzene, cyclohexane, cyclohexanone, benzyl alcohol, p-dioxane, cresol, p-xylene, acetic acid, cyclohexanol and the like. The dispersion liquid of the phyllosilicate used in the freeze-drying may be the dispersion used in the cation exchange reaction, or a solvent in which the phyllosilicate after the cation exchange reaction is well dispersed may be used. In particular, when using a solvent in which the phyllosilicate is well dispersed, the phyllosilicate can be directly freeze-dried while the silicate layer of the phyllosilicate is peeled off, so that the specific surface area can be greatly increased. Freeze-drying can be carried out by removing the solvent under reduced pressure after freezing the phyllosilicate dispersion, and it is usually performed at a phyllosilicate concentration of 1 to 70% by weight. When the layered silicate concentration is less than 1% by weight, it is preferable from the viewpoint of the dispersed state before drying, but the treatment after drying is complicated and the yield decreases. When the layered silicate concentration exceeds 70% by weight, the specific surface area of the product becomes small, making it difficult to disperse in the resin. From the above viewpoints, the layered silicate concentration before freeze-drying is preferably 5 to 60% by weight, more preferably 10 to 50% by weight, and still more preferably 12 to 40% by weight.

The polyester resin used in the present invention is formed by polycondensation of dicarboxylic acid and/or its derivative and diol, or contains hydroxycarboxylic acid, or is a copolymer thereof. The dicarboxylic acid component constituting the polyester includes terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 4 , 4'-biphenyl dicarboxylic acid, 2,2'-biphenyl dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-diphenylmethane dicarboxylic acid, 4,4'-diphenyl Aromatic dicarboxylic acids such as sulfone dicarboxylic acid, 4,4'-diphenylisopropylidene dicarboxylic acid, 5-sodium sulfoisophthalic acid; oxalic acid, succinic acid, adipic acid, sebacic acid, dodecane Aliphatic dicarboxylic acids such as alkyl dicarboxylic acid, octadecyl dicarboxylic acid, maleic acid, and fumaric acid; cyclic aliphatic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid; and the like.

Diols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2,2-dimethylpropanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanediol Methanol, 1,2-cyclohexanedimethanol, propylene glycol, butylene glycol, pentylene glycol, octamethylene glycol, diethylene glycol, dipropylene glycol and other aliphatic glycols; hydrogen Bisphenols such as quinone, resorcinol, bisphenol A and 2,2-bis(2'-hydroxyethoxyphenyl)propane.

Examples of the hydroxycarboxylic acid include p-hydroxybenzoic acid, p-(hydroxyethoxybenzoic acid, 6-hydroxy-2-naphthoic acid, 7-hydroxy-2-naphthoic acid, 4'-hydroxy-biphenyl-4-carboxylic acid, etc. Aromatic hydroxycarboxylic acids, etc.

Preferred polyesters are aromatic polyesters, specifically polyethylene terephthalate (PET), polytrimethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate Cyclohexanedimethanol, polyethylene 2,6-naphthalate, polybutylene naphthalate, polyethylene isophthalate-terephthalate copolymer, terephthalate Hydroxybenzoic acid-6-hydroxy-2-naphthoic acid copolymer, etc. Among them, the polyester is preferably at least one selected from polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate and polyethylene 2,6-naphthalate. A sort of.

In the present invention, the resin composition comprising polyester and layered silicate modified with organic phosphonium ions contains 0.01 to 20% by weight of the layered silicate as inorganic ashes. Inorganic ash is a value calculated from the residue when burned in air to 1000°C. The content of the inorganic ashes is 0.01% by weight or more, which is preferable in order to exhibit the effect of layered silicate addition. It is preferably 20% by weight or less in terms of performing melt molding of the obtained polyester resin composition. The content of the inorganic ashes is more preferably 0.1 to 12% by weight, more preferably 0.4 to 8% by weight.

The amount of OH end groups in the polyester resin composition of the present invention is 0.1 to 45 equivalents/ton. The amount of OH terminal groups was measured by 1H-NMR in a solution mixed with isopropylamine in hexafluoroisopropanol:deuterochloroform=1:3 at 50°C and 600 MHz. Assignment by NMR can be confirmed by known literature or the like. This amount of OH terminal groups is in a lower range than the amount of OH terminal groups of polyester obtained during normal polymerization. The details are not clear, but it has been shown that a part of the hydroxyl groups of the polyester interacts with the phyllosilicate to some extent, and is considered to contribute to the improvement of physical properties such as dispersibility and elastic modulus of the phyllosilicate. The terminal group concentration of the polyester should reflect the number average molecular weight of the polyester. In the resin composition of the present invention, even compared with the polyester with the same solution viscosity, the overall terminal group concentration (in the case of polyester, OH terminal group and COOH terminal group) is 90% or less of the layered silicate-free polyester. This is presumed to be the reduction of terminal OH groups due to the interaction of a part of the above-mentioned OH groups with the phyllosilicate. Therefore, the overall terminal group concentration (OH terminal group and COOH terminal group in the case of polyester) is preferably 85% or less, more preferably 80% or less, of that of the polyester containing no phyllosilicate.

Therefore, when the amount of OH terminal groups is less than 0.1 equivalent/ton, it corresponds to the situation where the interaction becomes too large and the melt viscosity is too large, or the polyester itself has excessive COOH terminal groups. Therefore, in the former case, it is difficult to Melt molding, or in the latter case, impairs chemical stability such as hydrolysis resistance of polyester itself, so it is not preferable. When it is 45 equivalents/ton or more, since the interaction between the phyllosilicate and the OH terminal group decreases, the effect of improving physical properties such as elastic modulus decreases, which is not preferable. From the above reasons, the amount of OH terminal groups is preferably 1 to 40 equivalents/ton, more preferably 1 to 35 equivalents/ton, and still more preferably 1 to 30 equivalents/ton.

The method for producing the resin composition of the present invention preferably includes (A) dissolving a dicarboxylic acid or its ester in the presence of an ion-exchanged phyllosilicate having an ion-exchange capacity ratio of 60 to 100% with an organic phosphonium ion. Derivatives and aliphatic diol/or hydroxycarboxylic acid are polymerized to obtain a polyester resin composition with 0.01 to 30 parts by weight of phyllosilicate relative to 100 parts by weight of polyester, and further,

(B) Manufactured through a melt-kneading step at a shear rate of 250/s or higher at a temperature equal to or higher than the melting point of the polyester resin composition.

In the polymerization of polyester, dicarboxylic acids, mainly aromatic dicarboxylic acids, or their ester derivatives, are reacted with aliphatic diols. Alternatively, hydroxycarboxylic acids are reacted. As the dicarboxylic acid, aliphatic diol, and hydroxycarboxylic acid to be used, the above-mentioned compounds can be mentioned. This is a reaction well known to those skilled in the art, which includes the following steps: an esterification reaction in which a dicarboxylic acid and a diol are heated under normal pressure or under pressure, or an ester of a dicarboxylic acid is formed into a derivative with a diol A step of performing a transesterification reaction by heating the reaction under normal pressure or increased pressure, and a step of subjecting a reaction product to a polycondensation reaction while removing a diol component under reduced pressure.

The organically modified phyllosilicate can be added at any stage of the above-mentioned polyester polycondensation step. It is particularly preferable to add the ester after the exchange reaction and at the beginning of the polycondensation reaction. By adding organically modified phyllosilicates during the polymerization process, the affinity of phyllosilicates to polyester is increased, resulting in the layer diffusion of phyllosilicates in polyester, through the next step (B ) can be evenly dispersed. Since the degree of polymerization can be sufficiently increased by the step (A), the decrease in the molecular weight of the polyester resin obtained by the step (B) can be moderated.

The phyllosilicate modified with organic phosphonium ions can be added in the form of powder or slurry. Adding as a powder is effective because the step of removing the solvent can be omitted. On the contrary, depending on the adding method, re-agglomeration of the organically modified phyllosilicate occurs, which causes deterioration of dispersibility. When adding in the form of a slurry, the air contained in the powder can be removed in advance, and it is easy to mix with the reactant after transesterification, which is preferable. It is particularly preferable to use a diol capable of constituting polyester to be produced as a solvent in the case of adding in a slurry state. When other solvents are used, there is a possibility of separating from the diol component or entering into a part of the polyester structure. The method for producing the slurry is not particularly limited, and for example, physical dispersion using a ball mill, a solvent-stirred mill, ultrasonic treatment with a homogenizer, or the like is preferably performed. The concentration of the phyllosilicate in the slurry is preferably 0.05 to 90% by weight. When it is 0.05% by weight or less, the amount of diol is too large, and subsequent removal is troublesome, so it is not preferable. When it is more than 90% by weight, it is difficult to manufacture a slurry suitable for addition. The concentration of the phyllosilicate in the slurry is more preferably 0.1 to 70% by weight, and still more preferably 1 to 50% by weight. In order to obtain a uniform slurry, the phyllosilicate preferably has a sufficient specific surface area when dispersed in a solvent. Specifically, the specific surface area in the three-point method using nitrogen gas is preferably 1 m ² /g or more, more preferably 2 m ² /g or more.

The following reactions can be carried out in the same manner as the usual polyester polymerization reaction.

In this way, in the layered silicate-containing polyester resin composition obtained in the polymerization step (A), it is preferable that the layered silicate whose interlayer distance d _A calculated from the diffraction peak of X-ray scattering is 2.0 nm or more is 50% or more, and the average layer number N _A of the phyllosilicate calculated from the ray scattering peak and the half peak width by the following Scherrer formula (3) is 7 or less.

D＝K·λ/βcosθ (3)

Here, D: crystal size, λ: measurement X-ray wavelength, β: half-peak width, θ: Bragg angle of diffraction line, K: Scherrer constant.

The interlayer distance of the layered silicate can be obtained by X-ray scattering using the scattering angle of the scattering peak due to the scattering between layers of the layered silicate. When the phyllosilicate was exfoliated into a single layer, no peak was detected in X-scattering. In this case, it means that the interlayer distance is infinite. If the interlayer distance is large, especially in step B, peeling of the phyllosilicate is likely to occur, and it is preferable from the viewpoint of dispersion. More preferably 2.5 nm or more.

The ratio of the layered silicate whose interlayer distance d _A satisfies 2.0 nm or more can be calculated from the peak area ratio in X-ray diffraction. That is, the ratio of the sum of the peak intensities of the peaks whose interlayer distance d _A satisfies 2.0 nm or more to the sum of the peak areas attributed to the interlayer diffraction of the layered silicate is preferably 50% or more. When it is 50% or less, the dispersibility of the phyllosilicate in the final composition will be insufficient, and the physical strength may decrease when forming a molded article, for example, so it is not preferable. More preferably, it is 55% or more, and it is still more preferable that it is 60% or more.

The diffraction peak was measured by X-ray diffraction, the crystal size was calculated from the above-mentioned Scherrer formula, and the average number of layers was calculated by dividing by the interlayer distance. The smaller the average number of layers, the more dispersed the phyllosilicate and improve the physical properties such as the elastic modulus of the obtained molded body, so it is preferable.

A phyllosilicate that is completely exfoliated into a single layer does not exhibit X-ray diffraction. At this time, the distance between layers is infinite, and the number of layers is 1. In the range of X-ray diffraction observation, no peaks due to interlayer diffraction are observed at all, phyllosilicates satisfying the interlayer distance d _A of 2.0 nm or more account for 50% or more, and the average number of layers N _A is 7 or less.

Next, through (B) the step of melting and kneading the polyester resin composition at a temperature above the melting point of the polyester at a shear rate of 250/s or more, the resin obtained in the step A) is fed at a rate of 250/s or more The desired polyester resin composition can preferably be obtained through melt kneading at a shear rate of .

The shear rate was obtained by the following formula (4).

γ=π×d×(N/60)/C (4)

γ: shear rate (/s), d: screw inner diameter (mm), N: screw rotation speed (rpm), C: distance between screw and drum (mm).

A conventionally known method can be used for the above-mentioned melt-kneading, for example, an extruder such as a single-screw extruder or a twin-screw extruder can be used. When the shear rate at this time is 250/s or less, the kneading ability is insufficient, and the dispersibility of the phyllosilicate in the target polyester resin composition is insufficient, which is not preferable. A more preferable shear rate is 280/s or higher, and still more preferably 300/s or higher.

The temperature at the time of melt kneading is preferably not less than the flow start temperature of the polyester (glass transition temperature for non-crystalline resins and melting point for crystalline resins) to 350°C, more preferably (flow start temperature + 5)°C or higher to 330°C Hereinafter, it is more preferably (flow initiation temperature+10)°C or higher to 320°C or lower. If the temperature is lower than the flow start temperature, it is not preferable because it becomes difficult to melt and form. If the temperature is too high than 350° C., the decomposition of the ion-exchanged phyllosilicate is severe, which is not preferable.

In this way, in the polyester resin composition obtained by the melt-kneading step of (B), it is preferable that 50% or more of layered silicates have an interlayer distance d _B calculated from an X-ray scattering diffraction peak of 2.0 nm or more. , and the average layer number N _B of the layered silicate calculated from the ray scattering peak and its half-peak width by the Scherrer formula is 5 or less.

The interlayer distance d _B of the layered silicate can be obtained by X-ray scattering using the diffraction angle of the scattering peak due to interlayer scattering of the layered silicate. When the phyllosilicate was exfoliated into a single layer, no peak was detected in X-scattering. In this case, it means that the interlayer distance is infinite. The larger the interlayer distance, the easier it is to cause exfoliation of the layered silicate, which is preferable from the viewpoint of dispersion. A more preferable interlayer distance is 2.5 nm or more.

The proportion of layered silicate having an interlayer distance d _B of 2.0 nm or more can be calculated from the peak area in X-ray diffraction. That is, it is preferable that the ratio of the sum of the peak areas of the peaks whose interlayer distance d _B satisfies 2.0 nm or more to the sum of the peak areas attributable to the interlayer diffraction of the layered silicate is 50% or more. When it is below 50%, if it is below 50%, it means that the phyllosilicate is not sufficiently modified by organic phosphonium ions. In this case, the intended gas barrier properties and sufficient improvement in physical properties cannot be obtained, which is not preferable. More preferably 80% or more, still more preferably 90% or more, still more preferably 95% or more.

The smaller the average number of layers, the more dispersed the phyllosilicate is, which is preferable from the viewpoint of improving physical properties such as elastic modulus of the molded article obtained, and the average number of layers _NB is preferably 5 or less.

Hereinafter, in the present invention, the polyester resin composition capable of further providing a molded article having excellent surface smoothness, and the layered silicate constituting it will be described.

The phyllosilicate in the present invention removes calcium element from the above-mentioned natural or synthetic phyllosilicate, and the calcium content measured by fluorescent X-ray is preferably 0.5% or less in terms of element ratio. In the naturally calculated montmorillonite, in addition to alkali metals such as sodium ions and potassium ions, alkaline earth metals such as calcium ions and magnesium ions are also contained between the layers. Calcium ion step. When the calcium ion content in the phyllosilicate exceeds 0.5% in terms of element ratio, coarse agglomerates of more than 50 layers of phyllosilicate are easily produced by-products, and are used in moldings that require surface smoothness. Problems arise when using. The calcium content is preferably as low as possible, and the calcium content is more preferably 0.3% or less, more preferably 0.1% or less in terms of element ratio.

The methods for removing calcium ions include: 1) Treating with water-soluble ammonium salt, completely exchanging the ion-exchanging cations contained in the interlayer, and then treating with organic phosphonium ions. 2) Treatment with a water-soluble ammonium salt to completely exchange the ion-exchangeable cations contained between the layers, followed by treatment with an alkali metal salt such as sodium chloride, potassium chloride, etc., to load the alkali metal between the layers. It is then treated with organic phosphonium ions. In this way, calcium existing between the layers of the phyllosilicate can be completely removed. Whether or not calcium ions are completely removed can be confirmed by fluorescent X-ray analysis.

The water-soluble ammonium salt is not particularly limited, and examples thereof include ammonium sulfate, ammonium nitrate, ammonium acetate, ammonium chloride, and ammonium bromide. From the viewpoint of common use, ammonium acetate and ammonium chloride are preferred. Ammonium acetate is more preferred. These water-soluble ammonium salts are preferably used alone, but may also be used in combination. Specifically, the phyllosilicate as a starting material is dispersed in ion-exchanged water. At this time, the concentration of the phyllosilicate is in the range of 0.1% by weight to 10% by weight. Preferably it is 1 weight% - 5 weight%, More preferably, it is the range of 1.5 weight% - 3 weight%. An aliphatic ammonium salt or a solution containing an aliphatic ammonium salt is added to the phyllosilicate dispersion solution. After that, it can be treated with organic phosphonium ions, or it can be treated with organic phosphonium ions by replacing the aliphatic ammonium ions with alkali metal ions with alkali metal salts such as sodium chloride and potassium chloride.

When treating with an alkali metal salt, disperse and suspend layered silicate containing aliphatic ammonium ions between layers in ion-exchanged water, and add 1.0 to 10 times the equivalent relative layered silicate ion exchange capacity range to add. Preferably it is 1.0 times - 5.0 times, More preferably, it is the range of 1.0 times - 2.0 times. After the addition, it was filtered and washed well with ion-exchanged water. At this time, as washing proceeds, it is dispersed in ion-exchanged water. In this state, organic phosphonium ions are added to support the organic phosphonium ions between the layers of the layered silicate. The organic phosphonium salt is added in an equivalent range of 1.0 to 10 times the ion exchange capacity of the layered silicate. It is preferably in the range of 1.0 to 5.0 times, and more preferably in the range of 1.0 to 2.0 times.

Furthermore, in order to provide a molded article with excellent surface smoothness, the content of quartz in the polyester resin composition of the present invention is preferably 0.009% by weight or less. In particular, natural montmorillonite may contain quartz which is a silicon oxide compound. Quartz cannot be modified by the method of exchanging organic ions, which is a common method for modifying layered silicates, and as a result, it cannot be sufficiently dispersed in the matrix, resulting in a decrease in formability, surface properties or defects, and a decrease in mechanical properties. It is preferable to remove as much quartz as possible from the phyllosilicate, but since the density of quartz is similar to that of phyllosilicate, it is difficult to remove, and it may be observed even in the final product.

)作成。从聚酯树脂组合物中的层状硅酸盐的含量以及X射线散射中石英的峰强度以及层状硅酸盐的峰强度算出。石英含量如果在0.009重量％以上时，得到成形体时，将成为表面性降低、缺陷的原因。更优选为0.008重量％以下。The quartz contained in the polyester resin composition can be quantified by comparing the intensity of the diffraction peak of X-ray scattering with the peak intensity of the layered silicate. The intensity of the analytical peak is proportional to the quartz composition. The detection peaks used can be derived from, for example, peaks of quartz components of known content (3.35 ) and the analytical peaks of phyllosilicates with known content (such as 4.48 in the case of montmorillonite

) made. Calculated from the content of layered silicate in the polyester resin composition and the peak intensity of quartz and the peak intensity of layered silicate in X-ray scattering. If the content of quartz is more than 0.009% by weight, it will cause a decrease in surface properties and defects when a molded article is obtained. More preferably, it is 0.008 weight% or less.

The method for removing quartz can be realized by dispersing a layered silicate mixed with quartz in a solvent, settling high-density quartz, and recovering the supernatant. If necessary, lower concentrations of quartz can be obtained by concentrating the supernatant, redispersing in water, and repeating the above operation. The solvent at this time is not particularly limited, as long as it can disperse the phyllosilicate well, for example, methanol, ethanol, ethylene glycol, N-methylpyrrolidone, formamide, N-methylformazol Amide, N-dimethylformamide, water, etc. The concentration of the phyllosilicate in the solvent at this time may be such that only the quartz is selectively precipitated without excessively increasing the viscosity of the solution. Specifically, it is 10 weight% or less, More preferably, it is 8 weight% or less. The phyllosilicate can be well dispersed due to overheating or the like during dispersion. Sedimentation and separation of quartz can use a common centrifuge, decanter, and the like.

The polyester resin composition of the present invention can be used in the production of moldings by conventionally known methods such as injection molding, and is preferably used in the production of films or sheets by melt film forming, or fibers by melt spinning. The melt molding temperature is preferably above the flow start temperature of the polyester resin (glass transition temperature for non-crystalline resins and melting point for crystalline resins) to 350°C, more preferably (flow start temperature+5)°C to 330°C or less, More preferably (flow start temperature+10)°C or higher to 320°C or lower. When the temperature is too lower than the flow start temperature, melt molding becomes difficult. The phyllosilicate of the present invention is characterized by excellent heat resistance, but even so, if the melt-forming temperature is excessively higher than 350° C., the ion-exchanged phyllosilicate may be violently decomposed.

When producing a highly elastic film, it is preferable to further stretch it. Examples of stretching methods include conventionally known methods, for example, stretching sequentially or simultaneously in uniaxial or biaxial directions. The stretching temperature is preferably not less than the glass transition point of the resin composition and not more than +90°C, more preferably not less than the glass transition point of the resin composition and not more than +70°C, more preferably the glass transition point Above to glass transition point +60°C or below. If the stretching temperature is too low or too high, it is difficult to produce a uniform film, which is not preferable. The draw ratio is, in terms of area ratio, preferably 2 times to 100 times, more preferably 4 times to 70 times, and still more preferably 6 times to 50 times.

When the polyester resin is crystalline, it is preferable to perform heat treatment after stretching and orientation of the film. The temperature of the heat treatment is preferably not less than the glass transition point of the polyester and not more than the melting point. More preferable temperature is determined according to the crystallization temperature of the obtained film, the physical properties of the obtained film, and the like.

Regarding the interlayer diffraction peak intensity of the layered silicate in X-ray diffraction in the cross-sectional direction of the polyester film, the orientation coefficient fc in the following formula (5) is preferably 0.8 or less,

$\mathrm{<span\; class="notranslate">\; fc</span>}<span\; class="notranslate">\; =</span>\frac{\mathrm{<span\; class="notranslate">\; 3</span>}<span\; class="notranslate">\; <</span>{\mathrm{<span\; class="notranslate">\; <figure-callout\; id="2"\; label="cos"\; filenames="A20058000714500351.png"\; state="\{\{state\}\}">cos</figure-callout></span>}}^{\mathrm{<span\; class="notranslate">\; 2</span>}}\mathrm{<span\; class="notranslate">\; \&phi;</span>}<span\; class="notranslate">\; ></span>\mathrm{<span\; class="notranslate">\; c</span>}<span\; class="notranslate">\; -</span>\mathrm{<span\; class="notranslate">\; 1</span>}}{\mathrm{<span\; class="notranslate">\; 2</span>}}<span\; class="notranslate">\; ,</span><span\; class="notranslate">\; <</span>{\mathrm{<span\; class="notranslate">\; <figure-callout\; id="2"\; label="cos"\; filenames="A20058000714500351.png"\; state="\{\{state\}\}">cos</figure-callout></span>}}^{\mathrm{<span\; class="notranslate">\; 2</span>}}\mathrm{<span\; class="notranslate">\; \&phi;</span>}<span\; class="notranslate">\; ></span>\mathrm{<span\; class="notranslate">\; c</span>}<span\; class="notranslate">\; =</span>\frac{{<span\; class="notranslate">\; \&Integral;</span>}_{\mathrm{<span\; class="notranslate">\; 0</span>}}^{\mathrm{<span\; class="notranslate">\; \&pi;</span>}<span\; class="notranslate">\; /</span>\mathrm{<span\; class="notranslate">\; 2</span>}}\mathrm{<span\; class="notranslate">\; IC</span>}<span\; class="notranslate">\; (</span>\mathrm{<span\; class="notranslate">\; \&phi;</span>}<span\; class="notranslate">\; )</span>{\mathrm{<span\; class="notranslate">\; <figure-callout\; id="2"\; label="cos"\; filenames="A20058000714500351.png"\; state="\{\{state\}\}">cos</figure-callout></span>}}^{\mathrm{<span\; class="notranslate">\; 2</span>}}\mathrm{<span\; class="notranslate">\; \&phi;</span>}\mathrm{<span\; class="notranslate">\; sin</span>}\mathrm{<span\; class="notranslate">\; \&phi;d\&phi;</span>}}{{<span\; class="notranslate">\; \&Integral;</span>}_{\mathrm{<span\; class="notranslate">\; 0</span>}}^{\mathrm{<span\; class="notranslate">\; \&pi;</span>}<span\; class="notranslate">\; /</span>\mathrm{<span\; class="notranslate">\; 2</span>}}\mathrm{<span\; class="notranslate">\; IC</span>}<span\; class="notranslate">\; (</span>\mathrm{<span\; class="notranslate">\; \&phi;</span>}<span\; class="notranslate">\; )</span>\mathrm{<span\; class="notranslate">\; sin</span>}\mathrm{<span\; class="notranslate">\; \&phi;d\&phi;</span>}}<span\; class="notranslate">\; .</span><span\; class="notranslate">\; .</span><span\; class="notranslate">\; .</span><span\; class="notranslate">\; (</span>\mathrm{<span\; class="notranslate">\; 5</span>}<span\; class="notranslate">\; )</span>$

(fc is the orientation coefficient, φ is the azimuth angle relative to the in-plane direction of the film, and Ic(φ) is the scattering intensity at the azimuth angle φ).

In the formula (5), fc is an orientation coefficient due to scattering in a direction perpendicular to the layer of the layered silicate described above, and is calculated from <cos ² φ>. Furthermore, according to formula (5), in the X-ray diffraction when X-rays are irradiated from the direction perpendicular to the film cross section, for the azimuth angle φ relative to the direction perpendicular to the film surface, the scattering intensity Ic(φ ) and calculated.

When the orientation coefficient fc is less than 0.8, the in-plane orientation of the layered silicate film is insufficient, which is not preferable from the viewpoint of realizing a high elastic modulus film. The upper limit of the orientation coefficient fc is 1 from its definition. The orientation coefficient fc is more preferably 0.85 or more, still more preferably 0.88 or more, still more preferably 0.9 or more.

The method for producing fibers preferably includes a method in which the polymer is melted at the flow temperature of the polymer, discharged from a spinning nozzle, drawn, and produced into a fiber having a single fiber fineness of 3.3 to 33 dtex according to a conventional method. The drawing speed (spinning speed) at this time is melt spinning at a drawing speed (spinning speed) of 10 to 6000 m/min. The monofilament obtained is subjected to a suitable drawing operation. When the pulling speed is low, it is preferable to carry out stretching operation. The stretching ratio is about 2 to 20 times, preferably from the glass transition temperature of the polymer to the crystallization temperature of the polymer, more preferably from the glass transition temperature + 10°C to the crystallization temperature. It is carried out at a temperature of -10°C, more preferably at a glass transition temperature of +20°C or higher to a crystallization temperature of -20°C.

The polyester fiber obtained above is reinforced by the oriented phyllosilicate, and can be made into a polyester fiber with high modulus of elasticity and high strength.

When producing the fiber of the present invention, the shape of the nozzle used for spinning is not particularly limited, and any shape such as circular, irregular, solid, or hollow may be used.

The smaller the average number of layers of layered silicate in the molded body, the better the layered silicate is dispersed, which is preferable in terms of improving physical properties such as elastic modulus of the molded body obtained. In the molded article composed of the polyester resin composition of the present invention, the average number of layers N _C of the layered silicate calculated from the radiation scattering peak and its half width at half peak is preferably 5 or less.

Achieving complete delamination in polyester resins is difficult. In practice, physical properties such as elastic modulus can be fully realized with an average number of layers of about 2 to 3 or more.

From the polyester resin composition of the present invention, a layered silicate is well dispersed and a film or fiber having excellent surface smoothness can be obtained. In the case of a film, as the surface roughness range, a product having an average line thickness Ra of 30 nm or less can be obtained, and it can be used in various applications such as magnetic tapes and packaging films.

Example

The present invention will be described in detail below through examples. However, the present invention is not limited by the following examples.

(1) Layered silicate: Montmorillonite (Kunipia manufactured by Kunimine Industry Co., Ltd. (sodium exchange capacity: 109 meq/100 g) was used.

(2) Cation exchange rate: using a differential thermobalance TG8120 manufactured by Rigaku Co., Ltd., it was determined from the weight loss rate when heated to 800° C. at 20° C./min in an air atmosphere according to the following formula.

Cation exchange rate (%) = {Wf/(1-Wf)}/M _org /M _si )×100

(Wf is the weight loss rate of the layered silicate measured by a differential thermobalance from 120°C to 800°C at a heating rate of 20°C/min, M _org is the molecular weight of the phosphonium ion, and _Msi represents the layered silicate The molecular weight per charge of the cationic portion of the layered silicate. The molecular weight per charge of the cationic portion of the layered silicate is a value calculated from the reciprocal of the cation exchange capacity (unit: eq/g) of the layered silicate).

(3) Thermal decomposition temperature: the temperature at which the weight decreases by 5% by weight when measured at 20° C./min in nitrogen using a differential thermobalance TG8120 manufactured by Rigaku Corporation.

(4) Specific surface area: The specific surface area was measured by the three-point method using N ₂ gas in NOVA1200 manufactured by QUANTUM CHROME, and divided by the weight of the sample to obtain it.

(5) Weight ratio of the polyester resin in the resin composition to the inorganic ashes of the phyllosilicate: 20 g or more was added, and after drying at 180° C. for 5 hours, the weight after drying was measured. After that, the temperature was raised to 350°C at 10°C/min, and then to 620°C at 0.1°C/min. Furthermore, after raising the temperature to 1000 degreeC at 5 degreeC/min, it hold|maintained for 5 hours, and burned the organic component. The weight of the remaining components used in this way was calculated from the following formula.

Inorganic ash content = B/A × 100

Among them, A: the weight g of the polyester resin composition after drying, and B: the weight g after burning.

(6) Interlayer distance and average number of layers of phyllosilicate: Calculated from the diffraction peak position using powder X-ray diffractometer RAD-B manufactured by Rigaku Corporation. The average number of layers was calculated by dividing the crystal size calculated by the following formula by the interlayer distance. The Scherrer constant is 0.9.

D＝K·λ/βcosθ (3)

Here, D: crystal size, λ: measurement X-ray wavelength, β: half-peak width, θ: Bragg angle of diffraction line, K: Scherrer constant.

(7) Reduced viscosity (ηsp/C): The reduced viscosity was measured at a concentration of 1.2 g/dL and a temperature of 35° C. using a solution of phenol/tetrachloroethane (4:6 by weight).

(8) The amount of terminal hydroxyl groups: Hexafluoroisopropanol: deuterated chloroform = 1:3, measured under the conditions of 50°C and 600 MHz in a solution mixed with isopropylamine, from the methylene present at the β position of the OH terminal of 4.53ppm The integral value of 1H-NMR of the group was used to calculate the amount of terminal hydroxyl groups.

(9) Amount of terminal COOH group: Measured under the conditions of 50°C and 600 MHz in a solution mixed with isopropylamine in hexafluoroisopropanol: deuterated chloroform = 1:3, from 1H-NMR of the peak attributable to the polymer terminal The integral value is calculated.

(10) TEM/EDS measurement: TEM was analyzed with JEM-2010 accelerating voltage of 200kV by JEOL Ltd., and EDS was analyzed by NORAN from TRACOR NORTHERN Company with a probe diameter of 15nm.

(11) Quartz content: The layered silicate modified with organic phosphonium ions was measured using a powder X-ray diffractometer RAD-B manufactured by Rigaku Co., Ltd., and the peak intensity of the quartz peak and the layered silicate was measured. The ratio is calculated.

(12) Center surface average roughness Ra: Measured under conditions of a measurement magnification of 25 times and a measurement area of 188 μm×247 μm using a non-contact three-dimensional roughness meter (NT-2000) manufactured by Veeco. The measurement mode uses the PSI mode. Measure 2 points respectively, calculate the average value.

(13) Measurement of elastic modulus of film: A sample was cut into 5 mm×50 mm, and a traction test was performed at a tensile speed of 5 mm/min using a UCP-100 traction tester manufactured by E-Andy Co., Ltd.

(14) Fiber strength and modulus of elasticity of fibers: measured with UCT-1T manufactured by Orientec Co., Ltd.

[Reference Example 1] Synthesis of cation-exchanged layered silicate

After adding 1.5 kg of Kunipia F (interlayer distance 1.26 nm) to 40 L of ion-exchanged water, it was dispersed with a bead mill. Coarse particles were then removed with a 5 μm filter to obtain an aqueous dispersion containing 3% by weight of Kunipia F. 38 kg of the dispersion was heated and stirred at 80° C., and at the same time, a solution containing 1 kg of n-hexadecyltri-n-butylphosphonium bromide represented by the following formula and 3 L of ion-exchanged water was added,

The mixture was further stirred at 80° C. for 3 hours. The solid was filtered off from the mixture, washed three times with methanol and three times with water, and then freeze-dried to obtain a cation-exchanged layered silicate. The ion exchange rate is 85%. The phyllosilicate thus obtained had a specific surface area of 5.3 m ² /g. The average interlayer distance measured by X-ray scattering was 2.2 nm, and the average number of layers was 5.6. In addition, the 5% weight reduction temperature was 365°C.

Example 1

Use 0.120 parts by weight of manganese acetate as a transesterification catalyst, slowly raise the temperature from 180°C to 200°C, react 200 parts by weight of dimethyl 2,6-naphthalene dicarboxylate and 120 parts by weight of ethylene glycol, and then add 0.1 parts by weight of antimony oxide parts, and then slowly raised the temperature to 240°C for transesterification. After reaching 240° C., the transesterification catalyst was deactivated by adding trimethyl phosphate, and 31.1 parts by weight of the organically modified phyllosilicate produced in Reference Example 1 was added thereto.

Afterwards, the temperature was raised to 290° C., and the polycondensation reaction was carried out under a high vacuum below 1 mmHg to obtain a polyester resin composition with a reduced viscosity of 0.72 (dL/g).

The obtained composition had a terminal OH concentration of 30 equivalents/ton, a COOH concentration of 62 equivalents/ton, and an inorganic ash content of 10% by weight. The interlayer distance d _A measured by X-ray scattering was 2.7 nm, and the average layer number N _A was 6.3. In X-ray scattering, no peaks attributed to phyllosilicate having an interlayer distance of 2 nm or less were observed. Peaks attributed to other insufficiently reacted phyllosilicates were not observed.

Example 2

Using 0.01 parts by weight of manganese acetate as a transesterification catalyst, the temperature was slowly raised from 180°C to 200°C to react 25 parts by weight of dimethyl 2,6-naphthalene dicarboxylate and 15 parts by weight of ethylene glycol, and then add 0.01 parts by weight of oxidation antimony, and then slowly raise the temperature to 240°C for transesterification. After reaching 240° C., the transesterification catalyst was deactivated by adding trimethyl phosphate, and 3.8 parts by weight of an organically modified phyllosilicate and 22.4 parts by weight of ethylene glycol (hereinafter referred to as EG) The slurry that constitutes. Afterwards, the temperature was raised to 290° C., and the polycondensation reaction was carried out under a high vacuum below 1 mmHg to obtain a polyester resin composition with a reduced viscosity of 0.91 (dL/g).

The obtained composition had a terminal OH concentration of 7.6 equivalents/ton, a COOH concentration of 11.2 equivalents/ton, and an inorganic ash content of 10% by weight. The average interlayer distance d _A measured by X-ray scattering was 2.7 nm, and the average layer number N _A was 5.5.

Example 3

Use 0.02 parts by weight of manganese acetate as a transesterification catalyst, slowly raise the temperature from 180°C to 200°C, react 30 parts by weight of dimethyl 2,6-naphthalene dicarboxylate and 18 parts by weight of ethylene glycol, and then add 0.02 parts by weight of antimony oxide parts, and then slowly raised the temperature to 240°C for transesterification. After reaching 240° C., the transesterification catalyst was deactivated by adding trimethyl phosphate, and the slurry composed of 0.85 parts by weight of organically modified layer silicate and 5.6 parts by weight of ethylene glycol prepared in Reference Example 1 was added thereto. .

Afterwards, the temperature was raised to 290° C., and the polycondensation reaction was carried out under a high vacuum below 1 mmHg to obtain a polyester resin composition with a reduced viscosity of 1.24 (dL/g).

The obtained composition had a terminal OH concentration of 3.9 equivalents/ton, a COOH concentration of 7.3 equivalents/ton, and an inorganic ash content of 2% by weight. The average interlayer distance d _A measured by X-ray scattering was 2.7 nm, and the average layer number N _A was 5.0.

Example 4

Use 0.009 parts by weight of manganese acetate as a transesterification catalyst, slowly increase the temperature from 180°C to 200°C, react 30 parts by weight of dimethyl 2,6-naphthalene dicarboxylate and 14.5 parts by weight of ethylene glycol, and then add 0.0072 parts by weight of oxidation antimony, and then slowly raise the temperature to 240°C for transesterification. After reaching 240° C., the transesterification catalyst was deactivated by adding 0.0277 parts by weight of trimethyl phosphate, to which was added 0.850 parts by weight of organically modified phyllosilicate and 5.6 parts by weight of ethylene glycol manufactured in Reference Example 1. of slurry.

Afterwards, the temperature was raised to 290° C., and the polycondensation reaction was carried out under a high vacuum below 1 mmHg to obtain a polyester resin composition with a reduced viscosity of 0.89 (dL/g).

The obtained composition had a terminal OH concentration of 17.7 equivalents/ton, a COOH concentration of 27.4 equivalents/ton, and an inorganic ash content of 2% by weight. The interlayer distance d _A measured by X-ray scattering was 2.7 nm, and the average number of layers N _A was 5.0.

Example 5

Using the same direction twin-screw extruder (ZSK25), the pellet of the polyethylene (2,6-naphthalene dicarboxylate) of 600 parts by weight reduced viscosity 0.78 (dL/g) and embodiment 1 obtain 150 parts by weight of the polyester resin composition are kneaded under the conditions of extrusion temperature 280°C, screw rotation speed 280rpm, extrusion speed 10kg/hour, shear velocity 1800/second, to obtain a reduced viscosity of 0.68 (dL/g) Polyester resin composition. The obtained composition had a terminal OH group content of 15.3 equivalents/ton, a COOH concentration of 36.3 equivalents/ton, and an inorganic ash content of 2% by weight. The interlayer distance d _B measured by X-ray scattering was 2.8 nm, and the average number of layers N _B was 4.4. Peaks attributed to other insufficiently reacted phyllosilicates were not observed. The polyester resin composition was observed with a transmission electron microscope (FIG. 1). As shown, the phyllosilicates are highly dispersed.

Example 6

Using only the polyester resin composition obtained in Example 4, except that no polyethylene naphthalate was added, a polyester resin composition was obtained in the same manner as in Example 5 using a co-direction twin-screw extruder (ZSK25). things. The obtained composition had a terminal OH group content of 9.8 equivalents/ton, a COOH concentration of 34.5 equivalents/ton, a reduced viscosity of 0.71 (dL/g), and an inorganic ash content of 2% by weight. The interlayer distance d _B measured by X-ray scattering was 2.7 nm, and the average number of layers N _B was 3.5. The polyester resin composition was observed with a transmission electron microscope (FIG. 2). As shown, the phyllosilicate dispersion is very high. In addition, the phyllosilicate was further exfoliated.

Example 7

In addition to using 300 parts by weight of pellets of polyethylene (2,6-naphthalene dicarboxylate) with a reduced viscosity of 0.78 (dL/g) and 100 parts by weight of the polyester resin composition obtained in Example 4, with In Example 5, a polyester resin composition was obtained similarly using a co-direction twin-screw extruder (ZSK25). The obtained composition had a terminal OH group content of 31.4 equivalents/ton, a COOH concentration of 37.7 equivalents/ton, a reduced viscosity of 0.72 (dL/g), and an inorganic ash content of 0.5% by weight. The interlayer distance d _B measured by X-ray scattering was 2.7 nm, and the average number of layers N _B was 3.2. The polyester resin composition was observed with a transmission electron microscope (FIG. 3). As shown, the phyllosilicate dispersion is very high. In addition, the phyllosilicate was further exfoliated.

Embodiment 8～10

The polyester resin composition obtained in Examples 5-7 was dried at 180°C for 5 hours, melted at 300°C, and extruded on a rotating cooling drum with a surface temperature of 80°C through a 1.3mm slot die to obtain Stretch film. The unstretched film obtained above was stretched 4 times in the film-forming direction and the direction perpendicular thereto at a temperature of 150° C. to obtain a biaxially stretched film with a thickness of 15 μm. Further, the obtained biaxially stretched film was heat-set at 205° C. for a predetermined length for 1 minute to obtain a polyethylene naphthalate/layer silicate composition film. Table 1 shows the physical properties of the obtained film. The electron micrograph of the film obtained in Example 10 is shown in FIG. 4 .

Comparative example 1

The polyethylene 2,6-naphthalene dicarboxylate resin (terminal OH amount is 52.8 equivalent/ton, COOH concentration is 28.8 equivalent/ton, reduced viscosity 0.80dL/g) with the polyethylene 2,6-naphthalene dicarboxylate resin not containing layered silicate The same method as in Example 6 was melted and discharged. The obtained polyester had a terminal OH content of 53.9 equivalents/ton, a COOH concentration of 35.2 equivalents/ton, and a reduced viscosity of 0.72 dL/g.

Comparative example 2

A stretched film was obtained under the same conditions as in Example 8 except that the polyethylene naphthalate resin obtained in Comparative Example 1 was used instead of the polyester resin composition obtained in Example 5. The results are shown in Table 1.

Table 1

Inorganic ash (weight%) Surface roughness (nm) Elastic Modulus Average number of layers Nc MD direction (MPa) TD direction (MPa) Example 8 2 22.1 7168 7703 2.8 Example 9 2 19.8 7242 8365 2.9 Example 10 0.5 19.4 6788 6179 2.7 Comparative example 2 0 17 6032 5304 -

[Reference example 2]

Add 85 parts by weight of potassium phthalimide, 1008 parts by weight of 1,10-dibromodecane, and 430 parts by weight of dimethylformamide (fully dehydrated) into the flask, stir, and heat at 100°C for 20 hours . After heating, the volatile components were completely removed, and the residue was extracted with xylene. Volatile components were distilled from the extracted solution, and the residue was allowed to stand at room temperature to obtain crystals of phthalimide decamethylene imidazolium bromide.

[Reference example 3]

Add 20 parts by weight of trioctylphosphine and 20 parts by weight of the phthalimide decamethylene imidazolium bromide obtained in Reference Example 2 to the flask, stir, and react with stirring at about 100°C for 8 to 10 hours. The following N-phthalimide decamethylene-trioctylphosphonium bromide was obtained.

100 parts by weight of Knipia F, 3000 parts by weight of water, and 500 parts by weight of methanol were added to the flask, and heated and stirred at 80°C. A solution of 120 parts by weight of N-phthalimidedecamethylene-trioctylphosphonium bromide dissolved in 300 parts by weight of methanol was added thereto, followed by stirring at 80° C. for 3 hours. A solid was obtained by filtration of the mixture, washed three times with methanol and three times with water to give the cation-exchanged phyllosilicate. The cation exchange rate is 65%, the thermal decomposition temperature is 374°C, and the interlayer distance is 247nm.

Reference example 4

109 parts by weight of Knipia F and 3000 parts by weight of water were added to a separable flask, and heated and stirred at 80°C. A solution obtained by dissolving 141 parts by weight of ammonium acetate in 300 parts by weight of ion-exchanged water was prepared in a separate container, and added to the layered silicate dispersion. After stirring for 2 hours thereafter, the precipitate was filtered.

A solution in which 77 parts by weight of ammonium acetate was dissolved in 2000 parts by weight of ion-exchanged water was prepared in a separate container. The above filtrate was added to this solution, and after stirring for 1 hour, it filtered. Thereafter, this operation was performed once more, followed by washing three times with 1500 parts by weight of ion-exchanged water. Furthermore, 200 parts by weight of sodium chloride was dissolved in 2000 parts by weight of ion-exchanged water (that is, the solution concentration was 1.7 M), and the filtrate was put into the solution, and stirred at 80° C. for about 1 hour. Afterwards, the supernatant was removed with a centrifuge. This operation was performed 2 more times. A solution obtained by dissolving 83 parts by weight of n-hexadecyltri-n-butylphosphonium bromide in 300 parts by weight of water was added thereto, followed by stirring at 80° C. for 3 hours. A solid was obtained by filtration of the mixture, washed three times with methanol and three times with water, and freeze-dried to obtain a cation-exchanged layered silicate. The ion exchange rate was 84%. The phyllosilicate obtained above was freeze-dried from an aqueous dispersion having a solid content of 20% by weight to obtain a cation-exchanged phyllosilicate having a specific surface area of 6.5 m ² /g. Further, by fluorescent X-ray measurement, it was confirmed that calcium was removed, and the element ratio of calcium was less than 0.1%.

Example 11

Next, the pellets of poly(2,6-ethylene naphthalate) (reduced viscosity 0.78dL/g) and the phyllosilicate obtained in Reference Example 4 were used in the same direction by a twin-screw extruder (Werner Company ZSK-25) was kneaded under the conditions of an extrusion temperature of 280° C., a discharge rate of 10 Kg/hour, and a screw rotation speed of 280 rpm to obtain a polyester resin composition. The obtained composition had a terminal OH group content of 30 equivalents/ton, a COOH concentration of 48 equivalents/ton, and an inorganic ash content of 2% by weight. The physical properties of the obtained polyester resin composition are shown in Table 2 below. Observation of the resin composition with a transmission electron microscope revealed that the phyllosilicate was well dispersed without coarse aggregation. Calcium was not detected when TEM/EDS was performed.

Example 12

The modifying agent of the phyllosilicate in Example 11 was changed to the phosphonium salt obtained in Reference Example 3, and the organic-modified phyllosilicate was produced in the same manner to produce a polyester resin composition. The physical properties of the obtained polyester resin composition are shown in Table 2 below.

Reference example 5

The filtrate was put into an aqueous sodium chloride solution, and a cation-exchanged phyllosilicate was obtained in the same manner as in Reference Example 4, except that the supernatant was removed without stirring. The ion exchange rate was 82%. The specific surface area of the layered silicate obtained above was 7.0 m ² /g. The element ratio of calcium is less than 0.1% as determined by fluorescent X-ray.

Example 13

Poly(2,6-ethylene naphthalate) (reduced viscosity 0.78dL/g) and the phyllosilicate obtained in Reference Example 5 are used in the same direction twin-screw extruder (Werner company ZSK-25 ) kneading under conditions of extrusion temperature 280° C., discharge rate 10 Kg/hour, and screw rotation speed 280 rpm to obtain a polyester resin composition. The obtained composition had a terminal OH group content of 28 equivalents/ton, a COOH concentration of 53 equivalents/ton, and an inorganic ash content of 2% by weight. The physical properties of the obtained polyester resin composition are shown in Table 2 below.

Table 2 Example 11 Example 12 Example 13 layered silicate layered silicate Kunipia F Kunipia F Kunipia F Aliphatic ammonium treatment have have have Alkali metal salt treatment have have - Modifier n-Hexadecyl tri-n-butyl phosphonium bromide N-phthalimide decamethylene-trioctylphosphonium bromide n-Hexadecyl tri-n-butyl phosphonium bromide Interlayer distance (nm) 2.74 2.41 2.76 Cation exchange rate (%) 84 68 82 Specific surface area (m ² /g) 6.5 10 7 Calcium ratio (%) <0.1 <0.1 <0.1 polyester resin composition polyester PEN PEN PEN Inorganic ash (weight%) 2 2 2 Melting point (°C) 268 268 270

Terminal OH group concentration (equivalent/ton) 30 35 28 Terminal COOH group concentration (equivalent/ton) 48 50 53

Example 14

The wire-shaped chips obtained in Example 11 were dried at 170° C. for 5 hours, supplied to the feed hopper of the extruder, melted at a melting temperature of 300° C., and extruded through a 1.3 mm slot die until the surface temperature was 80° C. On the drum, an unstretched film is obtained. The unstretched film obtained above was simultaneously biaxially stretched at a temperature of 150° C. to MD×TD=4.0×4.0 times to obtain a biaxially stretched film with a thickness of 15 μm. Furthermore, the obtained biaxially stretched film was heat-set at 205 degreeC for 1 minute, and the poly(ethylene-2,6-naphthalate)/layered silicate composition film was obtained. Table 3 shows the physical properties of the obtained film.

table 3 Example 14 resin Resin of Example 11 Stretch ratio (MD×TD) 4×4 Young's modulus (Gpa, MD direction) 8.2 Center plane surface roughness (nm) 25 Orientation coefficient (Fc) 0.86

Reference example 6

After adding 1.5 kg of Kunipia F (interlayer distance 1.26 nm, H(QUARTZ)/H(CLAY)=0.081) to 40 L of ion-exchanged water, it was dispersed at 80°C to obtain a dispersion. After this was removed with a centrifugal disperser to remove the precipitate, the supernatant was collected. A part of the sample was dried, and the concentration of the phyllosilicate in the dispersion was 2.5% by weight.

The obtained dispersion liquid was heated and stirred at 80° C., and at the same time, 1.5 times the molar equivalent of n-hexadecyltri-n-butylphosphonium bromide and 3 weight times of the organic phosphonium salt contained in the dispersion liquid were added. A solution composed of ion-exchanged water was stirred at 80° C. for 3 hours. A solid was obtained by filtration of the mixture, washed three times with methanol and three times with water, and freeze-dried to obtain a cation-exchanged layered silicate. Table 4 shows the physical properties of the layered silicates modified with various organic phosphonium ions. After proper modification with organic phosphonium ions, an organically modified layered silicate with quartz removed is obtained.

Reference example 7

After the dispersion liquid produced by the same method as in Reference Example 6 was allowed to stand at 23° C. for one week, the supernatant was collected. A part of the sample was dried, and the concentration of the phyllosilicate in the dispersion was 2.8% by weight. The same cation-exchanged layered silicate as in Reference Example 6 was obtained. The physical properties of the phyllosilicates modified by various organic phosphonium ions are shown in Table 4.

Reference example 8

The dispersion liquid produced by the same method as in Reference Example 6 was dispersed with a bead mill. After the precipitate was removed by decantation, coarse particles were removed with a 5 μm filter to obtain an aqueous dispersion. The concentration is 3.2% by weight. The same cation-exchanged layered silicate as in Reference Example 6 was obtained. The physical properties of the phyllosilicates modified with various organic phosphonium ions are shown in Table 4.

Table 4 Quartz content in phyllosilicate (weight %) Modification rate (%) Interlayer distance (nm) layers Reference example 6 0.10 91.3 2.3 4.7 Reference example 7 0.12 76.4 2.2 6.6 Reference example 8 0.41 83.8 2.4 4.0

Examples 15-17

After drying poly(2,6-ethylene naphthalate) (reduced viscosity: 0.78 dL/g) at 180°C for 6 hours, it was supplied to an extruder and melted at 280°C. ~9 The obtained phyllosilicate modified with organic phosphonium ions was supplied to a feeder, and melt-kneaded to obtain a polyester resin composition containing 2% by weight of inorganic ashes. Table 5 shows the physical properties of the polyester resin composition obtained above.

table 5

Example 15 Example 16 Example 17 phyllosilicate Reference example 6 Reference example 7 Reference example 8 Reduced viscosity (dL/g) 0.6 0.67 0.65 Quartz weight % 0.002 0.002 0.008 Terminal OH group concentration (equivalent/ton) 35 28 30 Terminal COOH group concentration (equivalent/ton) 53 62 42

Examples 18-20

The polyester resin composition obtained in Examples 15-17 was dried at 180° C. for 5 hours, melted at 300° C., and extruded through a 1.3 mm slot die onto a rotating cooling drum with a surface temperature of 80° C. to obtain Unstretched film. The unstretched film obtained above was stretched 4 times in the film-forming direction and the direction perpendicular thereto at a temperature of 150° C. to obtain a biaxially stretched film with a thickness of 15 μm. Further, the obtained biaxially stretched film was heat-set at 205° C. for a predetermined length for 1 minute to obtain a polyethylene naphthalate/layer silicate composition film. Table 6 shows the physical properties of the obtained film.

Table 6 Example 18 Example 19 Example 20 resin composition Example 15 Example 16 Example 17 Surface roughness (nm) 34.3 24.1 22.1 Number of layers (Nc) 3.5 3.8 3.3 Orientation coefficient (Fc) 0.87 0.86 0.88 Elastic modulus (kg/mm ² ) 7200 7900 7400

Example 21

Add 250 parts by weight of 2,6-bis(hydroxyethyl) naphthalene dicarboxylate, phyllosilicate obtained in 21 parts by weight of reference example 3, 0.04 parts by weight of antimony trioxide in the flask, and stir under normal pressure The temperature was raised from 230°C to 290°C over 2 hours. Then at 290°C for 1 hour, the pressure was reduced from atmospheric pressure to 66.66Pa, and the above state was kept for polymerization for 1 hour to obtain a composition of poly(2,6-ethylene naphthalate) and layered silicate (poly( 2,6-naphthalene dicarboxylate) and the weight ratio of inorganic components is 100:7). The composition had a melting point of 265°C and a reduced viscosity of 0.54 dL/g. The terminal OH concentration of the obtained composition was 22 equivalent/ton, and the COOH group concentration was 35 equivalent/ton. The interlayer distance d _A measured by X-ray scattering was 2.6 nm, and the average number of layers N _A was 6.2. In X-ray scattering, no peaks attributed to phyllosilicate having an interlayer distance of 2 nm or less were observed. Peaks attributed to other insufficiently reacted phyllosilicates were not observed.

Using a twin-screw extruder, 860 parts by weight of the composition obtained by the above operation and 2240 parts by weight of poly(2,6-ethylene naphthalate) (reduced viscosity 0.78dL/g) were melted at a melting temperature of 300°C Melt kneading. The interlayer distance d _B measured by X-ray scattering was 2.6 nm, and the average number of layers N _B was 5.2.

The obtained composition was formed into a precursor at a speed of 33 m/min at a melting temperature of 300° C. using a spinning device having a spinning nozzle diameter of 0.3 mm, and stretched 7.9 times at 150° C. The fineness of the obtained fiber was 6.6 dtex, the fiber strength was 6.0 cN/dtex, and the Young's modulus was 31 GPa. The interlayer distance d _C measured by X-ray scattering was 2.7 nm, and the average number of layers N _C was 4.4. Table 7 shows the physical properties of the obtained fibers.

Example 22

Except that the drawing temperature of the fiber was 160°C, the same operation as in Example 21 was carried out, and the fineness of the obtained fiber was 6.6 dtex, the fiber strength was 5.296 cN/dtex, and the Young's modulus was 29 GPa. Physical properties of the obtained fiber As shown in Table 7.

Example 23

Except using the layered silicate obtained in Reference Example 4 instead of the layered silicate obtained in Reference Example 3, the same operation as in Example 21 was carried out, and the fineness of the obtained fiber was 6.4 dtex, and the fiber strength was 5.4 cN/dtex , Young's modulus is 31GPa. The physical properties of the obtained fibers are shown in Table 7.

Example 23

Except that the layered silicate obtained in Reference Example 6 was used instead of the layered silicate obtained in Reference Example 3, the same operation as in Example 21 was carried out, and the fineness of the obtained fiber was 6.7 dtex, and the fiber strength was 5.3 cN/dtex , Young's modulus is 28GPa. The physical properties of the obtained fibers are shown in Table 7.

Comparative example 3

In addition to using poly(2,6-naphthalene dicarboxylate) without layered silicate (terminal OH concentration is 52.8 equivalents/ton, COOH group weight is 28.8 equivalents/ton, reduced viscosity is 0.78dL/g ), except that the draw ratio was 8.8 times, the same operation as in Example 21 was carried out to obtain poly(2,6-ethylene naphthalate) fibers. The fineness of the obtained fiber is 5.39dtex, the fiber strength is 5.825cN/dtex, and the Young's modulus is 28GPa. The physical properties of the obtained fiber are shown in Table 7.

Comparative example 4

In addition to using poly(2,6-ethylene naphthalate) (terminal OH concentration of 52.8 equivalents/ton, COOH group amount of 28.8 equivalents/ton, reduced viscosity of 0.78 dL/g), the draw ratio is 8.8 times Except that, the same operation as in Example 22 was carried out to obtain poly(ethylene 2,6-naphthalate) fibers. The fineness of the obtained fiber is 5.28dtex, the fiber strength is 5.913cN/dtex, and the Young's modulus is 27GPa. The physical properties of the obtained fiber are shown in Table 7.

Table 7 Example 21 Example 22 Example 23 Example 24 Comparative example 3 Comparative example 4 layered silicate Reference example 3 Reference example 3 Reference example 4 Reference example 6 none none Terminal OH group concentration (equivalent/ton) twenty two twenty two 30 35 52.8 52.8 Terminal COOH group concentration (equivalent/ton) 35 36 48 53 28.8 28.8 Layer distance d _A 2.6 2.6 2.4 2.4 - - Average number of layers N _A 6.2 6.1 6 4.8 - - Layer distance d _B 2.6 2.5 2.5 2.4 - - Average number of layers N _B 5.2 5.3 5.6 4.2 - - Layer distance d _c 2.7 2.7 2.4 2.5 - - Average number of layers N _C 4.4 4.5 4.1 3.8 - - Denier (dtex) 6.6 6.6 6.4 6.7 5.39 5.28 Fiber Strength (cN/dtex) 6 5.296 5.4 5.3 5.825 5.913 Young's modulus (GPa) 31 29 31 28 28 27

Claims (13)

1. polyester and resin composition, it is made of the layered silicate through organic  ion modification 60～100% shown in polyester and the following formula (1), wherein, containing the terminal base unit weight of this layered silicate 0.01～20 weight %, OH as inorganic ash content is 0.1～45 equivalent/ton

In the formula, R ₁, R ₂, R ₃And R ₄The alkyl of independent separately expression carbonatoms 1～30 or contain heteroatomic alkyl, or R arbitrarily ₁, R ₂, R ₃And R ₄Also can form ring.

2. the described polyester and resin composition of claim 1, wherein, polyester is to be selected from polyethylene terephthalate, Poly(Trimethylene Terephthalate), polybutylene terephthalate and poly--2, at least a in the 6-(ethylene naphthalate).

3. the described polyester and resin composition of claim 1, it is characterized in that, for the layered silicate through organic  ion modification, under nitrogen atmosphere, the temperature the when weight of being measured by the differential thermobalance under 20 ℃/minute the heat-up rate reduces by 5 weight % is more than 310 ℃.

4. the described polyester and resin composition of claim 1, wherein, the interfloor distance d that calculates by the diffraction peak of X ray scattering _BAt the layered silicate more than the 2.0nm is more than 50%, and from the ray scattering peak and the average number of plies N of the peak width at half height layered silicate of calculating by the Scherrer formula _BBe below 5.

5. the described polyester and resin composition of claim 1 is characterized by, and the calcium contents of the layered silicate of measuring by fluorescent X-ray is counted below 0.5% with elemental ratio.

6. the described polyester and resin composition of claim 1 is characterized by, and quartz content is below the 0.009 weight %.

7. the molding that is constituted by the described polyester and resin composition of claim 1.

8. the described molding of claim 7, it is a film.

9. the described molding of claim 8, in the X-ray diffraction from the cross-wise direction of film, about the interlayer diffraction peak intensity of layered silicate, the orientation coefficient fc in the following formula (5) is below 0.8,

$\mathrm{fc}=\frac{3<{\cos }^2\mathrm{\&phi;}>c-1}{2},<{\cos }^2\mathrm{\&phi;}>c=\frac{{\&Integral;}_0^{\mathrm{\&pi;}/2}\mathrm{Ic}\left(\mathrm{\&phi;}\right){\cos }^2\mathrm{\&phi;}\sin \mathrm{\&phi;d\&phi;}}{{\&Integral;}_0^{\mathrm{\&pi;}/2}\mathrm{Ic}\left(\mathrm{\&phi;}\right)\sin \mathrm{\&phi;d\&phi;}}\left(5\right)$

In the formula (I), fc is an orientation coefficient, and φ is the position angle with respect to direction in the face of film, and Ic (φ) is the scattering strength of position angle φ.

10. the described molding of claim 7, it is a fiber.

11. the described molding of claim 7 is from the ray scattering peak and the average number of plies N of the peak width at half height layered silicate of calculating by the Scherrer formula _CBe below 5.

12. the manufacture method of the described polyester and resin composition of claim 1 is characterized in that,

(A) carried out through organic  ion after the ion-exchange capacity contrast is 60～100% ion-exchange layered silicate in the presence of, make dicarboxylic acid or its ester derivative and aliphatic diol/or hydroxycarboxylic acid generation polymerization, obtain thus with respect to 100 weight part polyester, layered silicate is the polyester and resin composition of 0.01～30 weight part, then

(B) under the temperature more than the fusing point of polyester and resin composition, make with the step of the process of the velocity of shear more than 250/s melting mixing.

13. the manufacture method of the described polyester and resin composition of claim 12, in the polyester and resin composition of the layered silicate that the polymerization procedure that contains by (A) obtains, the interfloor distance d that calculates by the diffraction peak of X ray scattering _AAt the layered silicate more than the 2.0nm is more than 50%, and from the ray scattering peak and the average number of plies N of the peak width at half height layered silicate of calculating by the Scherrer formula _ABe below 7.

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