JP2000169689A - Polycarbonate resin composition and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a polycarbonate resin composition capable of suppressing an increase in specific gravity or the anisotropy and excellent in mechanical characteristics and deflection temperature under load without deteriorating the transparency or surface appearance. SOLUTION: This polycarbonate resin composition contains a polycarbonate resin and an intercalation compound which is prepared by mixing a swellable silicic salt with an amino compound in a dispersion medium. The amino compound is a 1-25C hydrocarbon compound which has at least one amino group of one or more kinds selected from the group consisting of primary, secondary and tertiary amino groups and may have one or more kinds of substituent groups selected from the group consisting of hydroxy group, mercapto group, ether group, carbonyl group, nitro group and chlorine atom.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a polycarbonate resin composition containing a polycarbonate resin and an interlayer compound, and a method for producing the resin composition.

[0002]

2. Description of the Related Art Polycarbonate resins are widely used in various fields such as precision machine parts, automobile parts, OA equipment parts, etc., utilizing their transparency, impact resistance, dimensional stability and heat resistance. Further, higher mechanical properties and heat resistance are required. For such purposes, various fillers, for example, glass fiber, carbon fiber, fibrous inorganic substances such as potassium titanate whiskers, glass flakes, glass beads, talc, mica, and the like are mixed with particulate inorganic substances such as kaolin. Have been. Although the mechanical properties and the like are certainly improved by the incorporation of the above-mentioned inorganic substances, in addition to transparency, which is a great feature of the polycarbonate resin, the surface appearance of the molded article is impaired, and there are problems such as an increase in specific gravity.
As another problem, there is a problem that anisotropy occurs due to the orientation of the fibrous inorganic material during injection molding.

It is generally considered that such defects in the compounding of the fibrous inorganic substance and the particulate inorganic substance are caused by poor dispersion of the inorganic substance and an excessively large size of the dispersed particles.

On the other hand, in Japanese Patent Application Laid-Open No. 9-175816 and European Patent No. 0780340, a low molecular weight compound (intercalant monomer) such as hexamethylenediamine is used for the purpose of facilitating cleavage of the layered silicate layer. A technique has been disclosed in which an interlayer compound is formed by intercalating between layers.

[0005]

As described above, the intercalation compound is disclosed, but the technique of cleaving the intercalation compound and finely dispersing the same in a polycarbonate resin is not disclosed. Was difficult to finely disperse.

Accordingly, the layered silicate layer is cleaved and dispersed in the form of a small thin plate in the polycarbonate resin, and the mechanical properties, deflection temperature under load, transparency, surface properties, dimensional stability and specific gravity are well balanced. At present, a technique for obtaining such a polycarbonate resin composition has not yet been provided, and an object of the present invention is to solve such a conventional problem.

[0007]

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, an amino compound having an amino group as an essential functional group and a swellable silicate are mixed to form an interlayer compound, and a polycarbonate resin composition obtained by dispersing the interlayer compound in a fine thin plate shape in a polycarbonate resin; and The manufacturing method.

According to the present invention, the polycarbonate resin composition according to claim 1 is a polycarbonate resin composition containing a polycarbonate resin and an interlayer compound,
The intercalation compound is prepared by mixing a swellable silicate and an amino compound in a dispersion medium, wherein the amino compound is at least one selected from the group consisting of primary, secondary and tertiary amino groups. It has at least one amino group and may have one or more substituents selected from the group consisting of a hydroxyl group, a mercapto group, an ether group, a carbonyl group, a nitro group and a chlorine atom. 25 hydrocarbon compounds.

According to a second aspect of the present invention, there is provided the polycarbonate resin composition according to the first aspect, wherein the average thickness of the interlayer compound is 500 ° or less.

A third aspect of the present invention is the polycarbonate resin composition according to the first or second aspect, wherein the maximum thickness of the interlayer compound is 2000 ° or less.

The polycarbonate resin composition according to claim 4 is the polycarbonate resin composition according to claim 1, 2 or 3, wherein the [N] value of the intercalation compound is 30 or more, wherein the [N] value is: 100 μm area of resin composition
² is defined as the number of particles per unit ratio of the intercalation compound.

The polycarbonate resin composition according to claim 5 is the polycarbonate resin composition according to claim 1, 2, 3 or 4, wherein the average aspect ratio of the interlayer compound (the ratio of layer length / layer thickness) is 10 to 10. 300.

The method for producing a polycarbonate resin composition according to claim 6 is the method for producing a polycarbonate resin composition according to claim 1, 2, 3, 4 or 5, wherein (A)
Step of preparing a clay dispersion containing an intercalation compound and a dispersion medium,
(B) a step of mixing a polymerizable prepolymer of a polycarbonate resin with the above clay dispersion, and (C) a step of polymerizing the polymerizable prepolymer.

According to a seventh aspect of the present invention, there is provided the method for producing a polycarbonate resin composition according to the sixth aspect, wherein the distance between the bottom surfaces of the intercalation compounds in the clay dispersion obtained in the step (A) is swellable silica. It is at least three times the distance between the bottom surfaces of the acid salts.

[0015]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The polycarbonate resin used in the present invention is not particularly limited, and includes any of aliphatic, alicyclic and aromatic polycarbonates. Among them, aromatic polycarbonates are preferred. Aromatic polycarbonates are produced by the reaction of one or more bisphenols, which may contain polyhydric phenols, with carbonates such as bisalkyl carbonates, bisaryl carbonates, phosgene and the like. As the bisphenols, specifically, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) propane, 2,2- Bis (4-hydroxyphenyl) propane or bisphenol A, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl)
-3-methylbutane, 2,2-bis (4-hydroxyphenyl) hexane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1 , 1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxy-
3-methylphenyl) methane, bis (4-hydroxy-3
-Methylphenyl) phenylmethane, 1,1-bis (4-
(Hydroxy-3-methylphenyl) ethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane,
2,2-bis (4-hydroxy-3-ethylphenyl) propane, 2,2-bis (4-hydroxy-3-isopropylphenyl) propane, 2,2-bis (4-hydroxy-3-sec-butylphenyl) ) Propane, bis (4-hydroxyphenyl) phenylmethane, 1,1-bis (4-
(Hydroxyphenyl) -1-phenylethane, 1,1-
Bis (4-hydroxyphenyl) -1-phenylpropane, bis (4-hydroxyphenyl) diphenylmethane,
Bis (4-hydroxyphenyl) dibenzylmethane, 4,
Examples include 4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxybenzophenone, phenolphthalein and the like. The most typical one is bisphenol A.

Although there is no limitation on the method for producing the polycarbonate resin used in the present invention, an organic solvent which dissolves the polymer produced from an alkali metal salt of a bisphenol and a carbonate derivative which is active in nucleophilic attack is used. An interfacial polymerization method in which a polycondensation reaction is carried out at the interface with alkaline water, a pyridine method in which bisphenols and a carbonate derivative active for nucleophilic attack are used as raw materials in a polycondensation reaction in an organic base such as pyridine, and bisphenols. A transesterification method in which a polycarbonate is formed by a transesterification reaction using a carbonate ester such as bisalkyl carbonate or bisaryl carbonate as a raw material is generally known. Here, examples of the carbonate derivative active in nucleophilic attack used in the interfacial polymerization method and the pyridine method include phosgene, carbodiimidazole and the like. Among them, the amount of phosgene is also generally used due to its availability. Specific examples of the carbonic acid ester used in the transesterification method include dimethyl carbonate, diethyl carbonate, and di-bisalkyl carbonate.
n-Propyl carbonate, diisopropyl carbonate, di-n-butyl carbonate and the like are diphenyl carbonate, bis (2,2) as bisaryl carbonate.
4-dichlorophenyl) carbonate, bis (2,4,6
-Trichlorophenyl) carbonate, bis (2-nitrophenyl) carbonate, bis (2-cyanophenyl) carbonate, bis (4-methylphenyl) carbonate,
Bis (3-methylphenyl) carbonate, dinaphthyl carbonate and the like can be mentioned. Of these, dimethyl carbonate, diethyl carbonate, and diphenyl carbonate are most preferably used in view of availability of raw materials and ease of reaction.

Although the molecular weight of the polycarbonate resin used in the present invention is not particularly limited, for example, the weight average molecular weight Mw measured at 40 ° C. by gel permeation chromatography (GPC) using a tetrahydrofuran (THF) solvent is a simple value. 15,000 to 80,000, preferably 30,0, in terms of molecular weight-dispersed polystyrene.
00 to 70,000. When the Mw is less than 15,000, the mechanical properties and impact resistance of a molded product of the obtained composition tend to be low, and when it is more than 80,000, there is a problem in processability such as fluidity during molding. Tends to occur.

The intercalation compound used in the present invention refers to a swellable silicate and at least one amino group in a dispersion medium.
It is prepared by mixing with an amino compound having one.

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 group clay and swellable mica. Can be When a smectite group clay and swellable mica are used as the swellable silicate, the dispersibility of the swellable silicate in the polycarbonate resin composition of the present invention, the availability of the swellable silicate and the improvement of the physical properties of the resin composition are improved. Preferred from the point.

The smectite-group clay is represented by the following general formula (1): X _0.2 to _0.6 Y ₂ to ₃ Z ₄ O ₁₀ (OH) ₂ .nH ₂ O (1) (where X is K, Na, 1 / 2Ca , And 1 / 2Mg
At least one member selected from the group consisting of
e, Mn, Ni, Zn, Li, Al, and at least one member selected from the group consisting of Cr, and Z is at least one member selected from the group consisting of Si and Al. Note that H ₂ O represents a water molecule bonded to an interlayer ion, and n varies remarkably depending on the interlayer ion and the relative humidity. Specific examples of the smectite group clay include, for example, montmorillonite,
Examples include beidellite, nontronite, saponite, iron saponite, hectorite, sauconite, stevensite, bentonite, and the like, and substituted substances, derivatives, and mixtures thereof. The distance between the bottom surfaces of the smectite group clay in the initial aggregation state is about 10 to 1
7 °, and the average particle size of the smectite group clay in the agglomerated state is approximately 1000-1,000,000 °.

The swellable mica is represented by the following general formula (2): X _0.5 to _1.0 Y ₂ to ₃ (Z ₄ O ₁₀ ) (F, OH) ₂ (2) (where X is Li, Na, K , Rb, Ca, Ba, and Sr, at least one selected from the group consisting of
g, one or more selected from the group consisting of Fe, Ni, Mn, Al, and Li, and Z is Si, Ge, Al, F
at least one selected from the group consisting of e and B. )
And natural or synthetic. These are substances having the property of swelling in water, a polar solvent compatible with water at an arbitrary ratio, and a mixed solvent of water and the polar solvent. For example, lithium-type teniolite, sodium-type teniolite, lithium-type Examples thereof include silicon mica, sodium tetrasilicic mica, and the like, and substituted substances, derivatives, and mixtures thereof. The distance between the bottom surfaces of the swellable mica in the initial aggregation state is approximately 10 to 17
Å, and the average particle size of the swellable mica in the aggregated state is about 10
It is 00 to 1,000,000 °.

Some of the above-mentioned swellable mica have a structure similar to that of vermiculite, and such a vermiculite equivalent can be used. The said vermiculite such equivalent has three octahedral type and dioctahedral the following general formula (3) (Mg, Fe, Al) 2 ~ 3 (Si 4-x Al x) O 10 (OH) 2 · (M ⁺ , M ²⁺ _1/2 ) _x · nH ₂ O (3) (where M is an exchangeable cation of an alkali or alkaline earth metal such as Na and Mg, x = 0.6 to 0.9) , N =
3.5 to 5). In the initial state of aggregation of the vermiculite-equivalent product, the distance between the bottom surfaces is approximately 10 to 17 °, and the average particle size in the aggregated state is approximately 1000 to 5,000,000 °.

The swellable silicate may be used alone.
It may be used in combination of more than one kind. Of these,
Montmorillonite, bentonite, hectorite, and swellable mica having sodium ions between layers are preferred from the viewpoint of dispersibility in the polycarbonate resin composition of the present invention, availability, and the effect of improving the physical properties of the resin composition.

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 is also used. Can be done.

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

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

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

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

Substitutes or derivatives of the above amino compounds may also be used. These amino compounds are used alone,
Alternatively, two or more kinds may be used in combination.

The intercalation compound can be obtained by increasing the distance between the bottom surfaces of the swellable silicate in a dispersion medium, and then adding and mixing the above amino compound.

The above-mentioned dispersion medium is intended to include water, a polar solvent compatible with water at an arbitrary ratio, and a mixed solvent of water and the polar solvent. Examples of the polar solvent include alcohols such as methanol, ethanol and isopropanol; glycols such as ethylene glycol, propylene glycol and 1,4-butanediol; ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether and tetrahydrofuran. , Amide compounds such as dimethylformamide, and other solvents such as dimethyl sulfoxide and
-Pyrrolidone and the like. These polar solvents may be used alone or in combination of two or more.

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

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

As described above, the spacing between the bottom surfaces of the swellable silicate is increased in the dispersion medium. In other words, the unit layers that have been aggregated are cleaved and separated to be present independently.
Thereafter, the amino compound is added, and the mixture is sufficiently stirred and mixed to obtain an interlayer compound.

The treatment of the swellable silicate with the amino compound is carried out by adding the amino compound to a mixture containing the swellable silicate having an enlarged bottom surface spacing and a dispersion medium and stirring the mixture. If it is desired to perform the processing more efficiently, the rotation speed of the stirring should be 1000 rpm or more,
Preferably 1500 rpm or more, more preferably 200 rpm
0 rpm or more, or 500 (1 / s) or more, preferably 1000 (1 / s) using a wet mill or the like.
As described above, more preferably, a shear rate of 1500 (1 / s) or more is applied. 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. Although the treatment of the swellable silicate with the amino compound can be sufficiently performed at room temperature, the system may be heated if necessary. The maximum temperature during heating is lower than the decomposition temperature of the amino compound used, and
If it is lower than the boiling point of the dispersion medium, it can be set arbitrarily.

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

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

In the polycarbonate resin composition of the present invention, the compounding amount of the interlayer compound is typically 0.1 to 50 parts by weight, preferably 0.2 to 45 parts by weight, more preferably 100 to 100 parts by weight of the polycarbonate resin. 0.3-4
It is prepared so as to be 0 parts by weight, more preferably 0.4 to 35 parts by weight, particularly preferably 0.5 to 30 parts by weight.
If the amount of the interlayer compound is less than 0.1 part by weight, the effect of improving mechanical properties, deflection temperature under load, and anisotropy may be insufficient. Tend to be impaired.

The ash content of the polycarbonate resin composition derived from the intercalation compound is typically 0.1 to 30% by weight, preferably 0.2 to 28% by weight, more preferably 0.3 to 25% by weight. %, More preferably 0.4 to 23% by weight, particularly preferably 0.5 to 20% by weight. If the ash content is less than 0.1% by weight, the effect of improving the mechanical properties, the deflection temperature under load, and the anisotropy may be insufficient, and if it exceeds 30% by weight, the appearance and transparency of the molded article are impaired. Tend to be

The structure of the intercalation compound dispersed in the polycarbonate resin composition of the present invention is different from that of a swellable silicate before compounding, which is a μm-sized aggregate structure in which a number of layers are laminated. Completely different. That is, by using an interlayer compound in which an amino compound having an affinity for the matrix resin is introduced and the interval between the bottom surfaces is enlarged as compared with the initial swellable silicate, the layers are cleaved and subdivided independently of each other. Become As a result, the interlayer compound is dispersed in the polycarbonate resin composition in a very fine and independent thin plate shape, and the number thereof is significantly increased as compared with the number of the swellable silicate as a raw material. Such a dispersion state of the thin plate-like interlayer compound can be expressed by an aspect ratio (ratio of layer length / layer thickness), number of dispersed particles, maximum layer thickness and average layer thickness described below.

First, when the average aspect ratio is defined as the number average value of the ratio of the layer length / layer thickness of the interlayer compound dispersed in the resin, the average aspect ratio of the interlayer compound in the polycarbonate resin composition of the present invention is defined. The ratio is 10-300,
Preferably it is 15-300. More preferably, 20 to
300. If the intercalation compound average aspect ratio is less than 10, the effect of improving the elastic modulus and the deflection temperature under load of the polycarbonate resin composition of the present invention may not be sufficiently obtained. Further, even if it is larger than 300, the effect does not change any more, so that it is not necessary to make the average aspect ratio larger than 300.

When the [N] value is defined as the number of dispersed particles per unit weight ratio of the swellable silicate in the area of 100 μm ² of the polycarbonate resin composition,
The [N] value of the interlayer compound in the polycarbonate resin composition of the present invention is 30 or more, preferably 45 or more, more preferably 60 or more. There is no particular upper limit, but when the [N] value exceeds about 1000, the effect does not change any more. The [N] value can be obtained, for example, as follows. That is, about 5% of the polycarbonate resin composition is used.
On an image obtained by cutting out an ultrathin section having a thickness of 0 μm to 100 μm and photographing the section with a TEM or the like, the number of particles of the intercalation compound present in an arbitrary area having an area of 100 μm ² is determined by the weight of the swellable silicate used. It can be determined by dividing by a ratio.
Alternatively, on a TEM image, an arbitrary region (area is measured) in which 100 or more particles are present is selected, and the number of particles present in the region is divided by the weight ratio of the swellable silicate used. The value converted to the area of 100 μm ² may be used as the [N] value. Therefore, the [N] value can be quantified by using a TEM photograph or the like of the polycarbonate resin composition.

When the average layer thickness is defined as the number average value of the layer thickness of the interlayer compound dispersed in a thin plate shape, the upper limit of the average layer thickness of the interlayer compound in the polycarbonate resin composition of the present invention is 500 ° C. Or less, preferably 450 °
Or less, more preferably 400 ° or less. If the average layer thickness is larger than 500 °, the effects of improving the mechanical properties, deflection temperature under load and anisotropy of the polycarbonate resin composition of the present invention may not be sufficiently obtained. The lower limit of the average layer thickness is not particularly limited, but is about 10 °.

When the maximum layer thickness is defined as the maximum value of the layer thickness of the interlayer compound dispersed in the form of a thin plate in the polycarbonate resin composition of the present invention, the upper limit of the maximum layer thickness of the interlayer compound is 2,000 mm. Or less, preferably 180
0 ° or less, more preferably 1500 ° or less. If the maximum layer thickness is more than 2000 °, the balance of mechanical properties, deflection temperature under load, anisotropy, transparency and surface properties of the polycarbonate resin composition of the present invention may be impaired. The lower limit of the maximum thickness of the interlayer compound is not particularly limited, but is about 50 °.

The thickness and length of the layer are determined by heating and melting the polycarbonate resin composition of the present invention and then hot press molding or stretch molding, and a thin molded product obtained by injection molding the molten resin. Can be determined from an image captured using a microscope or the like.

That is, the thickness of the film prepared by the above method on the XY plane is about 0.5 to 0.5.
It is assumed that a thin flat injection-molded test piece of about 2 mm is placed. Approximately 50 μm to 100 μm of the above film or test piece in a plane parallel to the XZ plane or the YZ plane
The thickness can be determined by cutting out an ultrathin section and observing the section with a transmission electron microscope or the like at a high magnification of about 4 to 100,000 or more. The measurement is performed by placing an arbitrary region containing 100 or more intercalation compounds on an elephant of a transmission electron microscope obtained by the above method, forming an image with an image processing device or the like, and performing computer processing. Can be quantified. Alternatively, it can also be obtained by measuring using a ruler or the like.

The method for producing the polycarbonate resin composition of the present invention is not particularly limited. For example, (A) a step of preparing a clay dispersion containing an interlayer compound and a dispersion medium; (B) a polymerizable prepolymer of the polycarbonate resin; A method including a step of mixing a polymer and the above clay dispersion and a step of (C) polymerizing a polymerizable prepolymer are preferred.

The dispersion medium used in the above step (A) means water, a polar solvent compatible with water, or a mixed solvent of water and the polar solvent.

The method for preparing the clay dispersion is not particularly limited.
For example, a method in which a system containing a dispersion medium and an intercalation compound obtained when an intercalation compound is prepared is used as it is as a clay dispersion (referred to as a direct method: in this case, the preparation of the intercalation compound is performed in the step (A)). ), Or obtained by preparing an intercalation compound, by adding and mixing another desired dispersion medium to a system containing a dispersion medium and an intercalation compound, followed by substitution.
A method in which a system comprising a newly added desired dispersion medium and an intercalation compound is used as a clay dispersion (referred to as a substitution method), or an intercalation compound obtained by drying and removing a dispersion medium and a desired dispersion medium are sufficiently mixed. (Referred to as a mixing method). From the viewpoint of the dispersibility of the interlayer compound, the direct method and the substitution method are preferred, but of course, the mixing method can also be employed.

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

In the intercalation compound contained in the clay dispersion obtained in the step (A), the initial lamination / agglomeration structure as the swellable silicate had was almost completely eliminated and the interlaminar compound was fragmented into a thin plate shape. Or the distance between the layers is increased, resulting in a so-called swollen state. The bottom surface interval can be used as an index indicating the swelling state. The distance between the bottom surfaces of the intercalation compounds in the clay dispersion is
In order for the intercalation compound to be finely divided into a thin plate shape, it is preferably at least three times, more preferably at least four times, even more preferably at least five times the initial distance between the bottom surfaces of the swellable silicate.

Next, a step (B), that is, a step of mixing the above clay dispersion and a polymerizable prepolymer of a polycarbonate resin is performed. Here, the above-mentioned polymerizable prepolymer means at least one selected from a polymerizable monomer and a low polymer. The polymerizable monomer of the polycarbonate resin refers to bisphenols and carbonates, but specific examples have already been shown, and thus description thereof is omitted here. Further, the low-polymer of the polycarbonate resin is a condensate obtained by the reaction of the polymerizable monomer,
In addition, it means one having a molecular weight such that the clay dispersion containing the intercalation compound in the molten state has a melt viscosity of such an extent that the clay dispersion can be sufficiently uniformly dispersed.

The method for obtaining the above-mentioned low polymer is not particularly limited, and any of an interfacial polymerization method, a pyridine method, and a transesterification method can be employed. Among them, a low polymer obtained by a transesterification method is preferable. Further, the low polymer can also be obtained by depolymerizing a polycarbonate resin.

The method of mixing the clay dispersion and the polymerizable prepolymer is not particularly limited. For example, a method in which the polymerizable prepolymer and the clay dispersion in a molten state or a solution are mixed at once, A method of continuously adding a clay dispersion to the prepolymer is exemplified. In the case of continuous addition, the rate of addition of the clay dispersion is not particularly limited, but the clay dispersion is added in an amount of 0.02 to 4.0 parts by weight / min, preferably 0.03 to 100 parts by weight of the polymerizable prepolymer. ~ 3.
8 parts by weight / minute, more preferably 0.05 to 3.5 parts by weight /
Add continuously in minutes.

Then, step (C), that is, a step of polymerizing the polymerizable prepolymer, can be performed. The polymerization method is not particularly limited, and can be carried out by a generally-used polymerization method of a polycarbonate resin. From the viewpoint of operability and the like, a transesterification method is preferably employed. In the transesterification method, a bisphenol compound is added to a mixture containing a carbonic acid diester compound, and the system is stirred for about 280 to 3 while sufficiently stirring.
The mixture is heated to about 00 ° C., and transesterified in a molten state. Examples of the catalyst required for the transesterification method include simple metals / oxides of alkali metals or alkaline earth metals, hydroxides, amide compounds, alcoholates, phenolates, Sb2O3, ZnO, PbO, organic titanium compounds,
One or more kinds of quaternary ammonium salts may be added for use.

In the molecular weight of the polycarbonate resin obtained in the step (C), the weight average molecular weight Mw measured at 40 ° C. by gel permeation chromatography (GPC) using a tetrahydrofuran (THF) solvent is represented by the following formula: 15,000-80,0
00, preferably 30,000-70,000.

The polycarbonate resin composition of the present invention can also be produced by the following method.

First, a good solvent for a polycarbonate resin such as methylene chloride, chloroform, tetrahydrofuran (THF) and the like, and an interlayer compound prepared in advance are sufficiently mixed. The number of agitation during mixing and the like are the same as those described above, and the bottom spacing of the interlayer compound after mixing is preferably at least three times, more preferably at least four times, the initial bottom spacing of the swellable silicate. More preferably twice or more. Next, a polycarbonate resin composition is obtained by adding and dissolving the polycarbonate resin, sufficiently mixing and removing the solvent.

The reason why the polycarbonate resin composition of the present invention is excellent in mechanical properties and deflection temperature under load, has small anisotropy and does not impair the surface appearance and transparency is that a large number of intercalation compounds are contained in the resin. Into thin, plate-like particles,
This is because the average layer thickness, the maximum layer thickness, the number of dispersed particles, and the average aspect ratio of the interlayer compound, which are indicators of the dispersion state, are in the ranges described above.

The dispersion state of the intercalation compound can be controlled by one or more steps selected from the step of preparing the intercalation compound and the steps (A) and (B) in the above-mentioned method for producing a polycarbonate resin composition.

That is, for example, in the step of preparing the intercalation compound (ie, the direct method in step (A)), if the stirring force and the shearing force in dispersing the swellable silicate are constant, When the kind of the dispersion medium and plural kinds of dispersion medium are used, the state of swelling / cleavage of the swellable silicate changes according to the mixing ratio and the order of mixing. For example, when montmorillonite is used as the swellable silicate, if the dispersion medium is water alone, the montmorillonite swells and cleaves to a state close to the unit layer.In this state, the polarities such as hydroxyl group, mercapto group, and nitro group When an amino compound having a group having a high molecular weight is used, a dispersion in which an interlayer compound having a substantially unit layer thickness is dispersed is prepared. Meanwhile, ethanol,
Tetrahydrofuran (THF), methyl ethyl ketone (MEK), pyridine, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMA
c) When a mixed solvent of water and a polar solvent such as N-methylpyrrolidone (NMP) is used as a dispersion medium, or when montmorillonite is dispersed in the polar solvent and then water is added, about several sheets to about It is cleaved and subdivided into a state in which about one hundred and several tens of unit layers are stacked. If an amino compound is used in that state, a dispersion in which an interlayer compound having a thickness of about several to about several hundreds is dispersed is prepared. The dispersion state of the intercalation compound can be controlled by performing steps (A), (B) and (C) in the method for producing a polycarbonate resin composition so as to maintain those states.

In the substitution method (method of replacing the dispersion medium used for preparing the interlayer compound with another desired dispersion medium) in the step (A), the type of the dispersion medium to be newly added and the case where a plurality of types of dispersion medium are used are used. The dispersion state of the intercalation compound in the clay dispersion varies depending on the mixing ratio and the order of mixing. For example, when a polar solvent having a low affinity for the functional group of an amino compound is added to a dispersion of an aqueous matrix containing an interlayer compound in a unit layer state and replaced with water, about several sheets of the interlayer compound in a unit layer state are obtained.約 about tens of sheets can be aggregated and laminated. The dispersion state of the interlayer compound can be controlled by performing steps (B) and (C) in the method for producing a polycarbonate resin composition so as to maintain those states. Further, in the step (B), the dispersion state of the intercalation compound changes depending on the type and molecular weight of the polymerizable prepolymer mixed with the clay dispersion. The dispersion state of the intercalation compound can be controlled by performing step (C) in the method for producing a polycarbonate resin composition so as to maintain those states.

The polycarbonate resin composition of the present invention may contain, if necessary, polybutadiene, butadiene-styrene copolymer, acrylic rubber, ionomer, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, and 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 a thermoplastic elastomer such as an olefin-based elastomer can be added. These may be modified with an acid compound such as maleic anhydride or an epoxy compound such as glycidyl methacrylate. In addition, other arbitrary resins, for example, a polyester resin, a polyester carbonate resin, a liquid crystal polyester resin, a polyolefin resin, a styrene-based resin, and a rubber-based polymer-reinforced styrene-based resin as long as the properties such as mechanical properties and moldability are not impaired Resin, polyamide resin, polyphenylene sulfide resin, polyphenylene ether resin, polyacetal resin, polysulfone resin, polyimide, polyetherimide resin, thermoplastic resin such as polyarylate resin, unsaturated polyester resin, epoxy resin, phenol novolak resin, etc. May be used alone or in combination of two or more.

Further, the polycarbonate resin composition of the present invention may contain a pigment, a dye, a heat stabilizer, an antioxidant, an ultraviolet absorber, a light stabilizer, a lubricant, a plasticizer, a flame retardant, Additives such as inhibitors can be added. The polycarbonate resin composition of the present invention may be molded by injection molding, extrusion molding, hot press molding, or can be used for blow molding.

Further, the polycarbonate resin composition of the present invention can be used for a 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 daily necessities, packaging / container materials, electromagnetic base materials, and other general industrial materials.

In the polycarbonate resin composition of the present invention, the intercalation compound is very fine and thin plate-like and is uniformly dispersed, so that the transparency and surface appearance are not impaired and the specific gravity is significantly increased. In addition, the elastic modulus and the deflection temperature under load can be improved, and the anisotropy can be suppressed.

[0067]

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

The main raw materials used in Examples and Comparative Examples are summarized below. Unless otherwise specified, the raw materials were not purified. (Raw materials) ・ Polycarbonate resin: Teflon A2200 (hereinafter, PC resin) manufactured by Idemitsu Petrochemical Co., Ltd. ・ Dimethyl carbonate: Dimethyl carbonate (hereinafter, DMC) manufactured by Wako Pure Chemical Industries, Ltd. was used. -Diethyl carbonate: Diethyl carbonate (hereinafter DEC) manufactured by Wako Pure Chemical Industries, Ltd. was used. Bisphenol A: Bisphenol A (hereinafter BPA) manufactured by Mitsui Chemicals, Inc. was used. Montmorillonite: Natural montmorillonite from Yamagata Prefecture (bottom spacing = 13 °) was used. Swellable mica: A mixture obtained by mixing 25.4 g of talc and 4.7 g of finely pulverized sodium silicofluoride and heat-treating the mixture at 800 ° C. (bottom interval = 12 °) was used. -Glass fiber: T-195H, manufactured by NEC Corporation
(Hereinafter referred to as GF) 1,2-bis- (3-aminopropoxy) ethane: An amino compound manufactured by Koei Chemical Co., Ltd. (hereinafter referred to as BAPE) was used. -2-hydroxyethylamino-3-propylamine:
An amino compound manufactured by Koei Chemical Co., Ltd. (hereinafter referred to as HEAPA) was used. The evaluation methods in Examples and Comparative Examples are summarized below. (Measurement of Dispersion State) The interlayer compound was measured as follows using TEM.

An ultrathin section having a thickness of 50 to 100 μm was used. Transmission electron microscope (JEOL JEM-1200E
Using X), the dispersion state of the interlayer compound was observed and photographed at an acceleration voltage of 80 kV and a magnification of 40,000 to 1,000,000 times. In the TEM photograph, a region where 100 or more dispersed particles are present is selected, and the number of particles ([N] value), the layer thickness and the layer length are measured manually using a ruler with a scale or, if necessary, interpolated. The measurement was performed by processing using an image analyzer PIASIII manufactured by Quest. The average aspect ratio was a number average value of the ratio between the layer length and the layer thickness of each interlayer compound. [N] value was measured as follows. First, on the TEM image, the number of particles of the interlayer compound present in the selected region is determined. Separately from this, the ash content of the resin composition derived from the interlayer compound is measured. The number of particles was divided by the ash content, and the area was 100 μm.
The value converted to m ² was used as the [N] value.

The average layer thickness was the number average of the layer thicknesses of the individual interlayer compounds, and the maximum layer thickness was the maximum value among the layer thicknesses of the individual interlayer compounds.

In the case where the dispersed particles are large and observation with a TEM is inappropriate, the [N] value is determined using an optical microscope (optical microscope BH-2 manufactured by Olympus Optical Co., Ltd.) in the same manner as described above. I asked. However, if necessary, the sample was melted at 270 to 290 ° C. using a hot stage THM600 manufactured by LINKAM, and the state of the dispersed particles was measured in the molten state.

The aspect ratio of the dispersed particles not dispersed in a plate shape was a value of major axis / minor axis. Here, the long diameter is intended to be the long side of the rectangle assuming a rectangle having the smallest area among rectangles circumscribing the target particle in a microscope image or the like. Further, the minor axis is intended to mean the short side of the minimum rectangle. (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.

The distance between the bottom surfaces is represented by a small angle X-ray diffraction peak angle value of B
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 polycarbonate resin composition was dried (120 ° 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 300 ° C., a gauge pressure of about 10 MPa, and an injection speed of about 50%, and a dimension of about 10 × 100. × 6 mm test pieces were prepared. The deflection temperature under load of the obtained test piece,
Measured according to ASTM D-648. (Bending characteristics) The bending strength and the bending elastic modulus of the test piece prepared in the same manner as in the case of the deflection temperature under load were determined by ASTM D-
790. (Anisotropic) MD of dumbbell-shaped JIS No. 1 specimen of about 3 mm produced under the same conditions as the deflection temperature under load.
The anisotropy was evaluated based on the ratio of the coefficient of linear expansion in the TD direction and the TD direction. The closer the ratio is to 1, the smaller the anisotropy and the more isotropic. The coefficient of linear expansion was measured as follows.

The center of the above dumbbell-shaped test piece was
It was cut into mm × 7 mm. Using SSC-5200 and TMA-120C manufactured by Seiko Electronics Co., Ltd., 20
After holding at 5 ° C. for 5 minutes, the temperature was raised in the range of 20 ° C. to 150 ° C. at a rate of 5 ° C./min. The linear expansion coefficient in the range of 30 to 120 ° C was calculated. (Warp) Dry the polycarbonate resin composition (120
(5 ° C., 5 hours), and then using an injection molding machine (IS-75E, manufactured by Toshiba Machine Co., Ltd.) with a mold clamping pressure of 75 t, and a mold temperature of 80
C., resin temperature 300.degree. C., gauge pressure about 10 MPa, injection speed about 50%, and injection molding, dimensions about 120.times.12
A 0 × 1 mm flat test piece was prepared. The flat test piece was placed on a flat surface, and the degree of warpage was checked. (Transparency) Transparency was evaluated by the haze (haze value) of a JIS No. 1 dumbbell-shaped test piece having a thickness of about 3 mm and manufactured under the same conditions as the deflection temperature under load.

The haze was measured according to JIS K7103 using a turbidimeter NDH- # 80 manufactured by Nippon Denshoku Industries Co., Ltd. (Surface Appearance) The surface appearance was evaluated by the center line average roughness of a JIS No. 1 dumbbell-shaped test piece having a thickness of about 3 mm and manufactured under the same conditions as in the case of the deflection temperature under load.

The center line surface roughness was measured using a surface roughness meter (Surfcom 1500A, manufactured by Tokyo Seimitsu Co., Ltd.). (Ash content) The ash content of the polycarbonate resin composition derived from the interlayer compound was measured according to JIS K7052.

(Example 1) Step (A) 125 g of montmorillonite was added to 7000 g of ion-exchanged water, and the resulting mixture was mixed with a wet mill manufactured by Nippon Seiki Co., Ltd. for 500 minutes.
The mixture was stirred at 0 rpm for 5 minutes and mixed. Thereafter, 18 g of HEAPA was added, and the mixture was further stirred under the conditions shown in Table 1 to prepare an interlayer compound. (Confirmation of the intercalation compound is based on SAXS
The measurement was carried out by measuring the bottom distance. The results are shown in Table 1. Examples 2 to 5 are similar). Then 1000g
DEC is added and mixed well, and then heated to remove water. That is, the intercalation compound and D are removed by a substitution method.
Clay dispersion containing EC (referred to as HE-Mo1 / DEC)
Was prepared. The distance between the bottom surfaces of the intercalation compounds in the clay dispersion is
> 100 °. Step (B) 2240 g of bisphenol A and 2000 g of DMC,
20 g of dibutyltin oxide was charged into the autoclave, and reacted by bubbling with dry nitrogen gas at a temperature of 160 ° C., a pressure of 7 kg / cm 2, to prepare bismethyl carbonate of bisphenol A (referred to as polymerizable prepolymer a). Keep at 230-240 ° C, 180rpm
m, the clay dispersion HE-Mo1 / DEC prepared in step (A) was sequentially added and mixed with vigorous stirring. The rate of addition of the clay dispersion is about 1300 g / hour. Step (C) Next, a polycarbonate resin composition containing an intercalation compound was obtained by melt polycondensation at a reaction temperature of 230 ° C. to 240 ° C. and 1 torr or less, and evaluated. The ash content and properties are shown in Table 2 together with the following examples.

(Example 2) In step (A), HEA
With the amount of PA being 12 g, the clay dispersion (H
E-Mo2 / DEC; the bottom surface spacing of the intercalation compound in the clay dispersion was> 100 °), except that it was prepared in the same manner as in Example 1 to obtain a polycarbonate resin composition containing the intercalation compound. evaluated.

(Example 3) In step (A), HEA
Example 3 Except that 26 g of BAPE was used in place of PA and a clay dispersion (BA-Mo / DEC; the bottom surface interval of the intercalation compound in the clay dispersion was> 100 °) was prepared by a substitution method. In the same manner as in Example 1, except that the addition rate of the clay dispersion was about 1000 g / hour, a polycarbonate resin composition containing an interlayer compound was obtained and evaluated.

(Example 4) In step (A), swelling mica was used in place of montmorillonite, and the amount of HEAPA was 30 g, and the clay dispersion (HE-Mi /
DEC: The distance between the bottom surfaces of the intercalation compounds in the clay dispersion is 65
Was Å. ) Was prepared in the same manner as in Example 1 (however, the addition rate of the clay dispersion was about 800 g / hour), and a polycarbonate resin composition containing an interlayer compound was obtained and evaluated.

(Example 5) Step (A) In the same manner as in Example 1, the HE-Mo1 / D
EC was prepared. Step (B) Bisphenol A (2240 g) which is a reactive monomer of a polycarbonate resin, and the clay dispersion HE-Mo1
/ DEC and 20 g of dibutyltin oxide are charged into an autoclave, mixed by bubbling with a temperature of 160 ° C., a pressure of 7 kg / cm 2 and dry nitrogen gas, and reacted to prepare a bisethyl carbonate of bisphenol A containing an intercalation compound. did. Step (C) Then, the reaction temperature is 230 ° C. to 240 ° C., and the degree of reduced pressure is 1 ton.
The polycarbonate resin composition containing the intercalation compound was obtained by melt polycondensation of not more than r.

Comparative Example 1 A polycarbonate resin was obtained and evaluated in the same manner as in Example 1 without using a clay dispersion. The results are shown in Table 3 together with the following comparative examples.

Comparative Example 2 Clay Dispersion HE-Mo1 / D
A polycarbonate resin composition was obtained and evaluated in the same manner as in Example 1 except that 125 g of montmorillonite was used instead of EC.

(Comparative Example 3) 18 g of HEAPA was directly sprayed on 125 g of montmorillonite using a spray.
The montmorillonite was amino treated by mixing for 1 hour. Amino-treated montmorillonite bottom spacing is 13
Was Å.

A polycarbonate resin composition was obtained and evaluated in the same manner as in Example 1 except that the above-mentioned amino-treated montmorillonite was used instead of the clay dispersion HE-Mo1 / DEC.

Comparative Example 4 125 g of montmorillonite and 1000 g of DEC were wet milled at 5000 rpm and 5 rpm.
The mixture was stirred and mixed for minutes to obtain a mixed solution. Clay dispersion HE-M
A polycarbonate resin composition was obtained and evaluated in the same manner as in Example 1 except that the above mixture was used instead of o1 / DEC. (Comparative Example 5) A wet mill (Nippon Seiki Co., Ltd.) was prepared by adding 125 g of montmorillonite to 7000 g of ion-exchanged water.
Was stirred at 5000 rpm for 5 minutes. Next, 30 g of n-butyraldehyde manufactured by Wako Pure Chemical Industries, Ltd. was added, and the mixture was further stirred at 5000 rpm for 3 hours to obtain a mixture. Next, a polycarbonate resin composition was obtained by performing melt polycondensation in the same manner as in Example 1,
evaluated.

Comparative Example 6 2500 g of PC resin and 250 g of GF were mixed with a twin screw extruder (LA manufactured by Nippon Steel Corporation, LA).
BOTEX30, set temperature 270-290 ° C, rotation speed 1
(00 rpm) to obtain and evaluate a resin composition.

[0088]

As described above in detail, in the polycarbonate resin, the unit layers of the swellable silicate are separated and cleaved to form a very large number of aggregated particles of the swellable silicate. Subdivision into small lamellar layers, ie, to reduce the average layer thickness to 500 ° or less, or to reduce the maximum layer thickness to 2000 ° or less as necessary, or to reduce the average aspect ratio (layer length / layer thickness) Is 10 to 300
By making the number of particles per unit ratio of the intercalation compound present in an area of 100 μm ² 30 or more,
The effect of improving mechanical properties, deflection temperature under load, and suppressing anisotropy can be efficiently obtained without adversely affecting transparency and surface appearance. In order to subdivide the swellable silicate into a thin plate as described above in the polycarbonate resin, it is essential to introduce an amino compound into the swellable silicate to form an interlayer compound. The polycarbonate resin composition of the present invention can be produced, for example, by the production method of the present invention, that is, (A) a step of preparing a clay dispersion containing an interlayer compound and a dispersion medium, (B) a polymerizable prepolymer of a polycarbonate resin and It is obtained by a production method including a step of mixing with a clay dispersion and a step of (C) polymerizing a polymerizable prepolymer.

[0089]

[Table 1]

[0090]

[Table 2]

[0091]

[Table 3]

Claims (7)

[Claims] 1. A polycarbonate resin composition containing a polycarbonate resin and an intercalation compound, wherein the intercalation compound is prepared by mixing a swellable silicate and an amino compound in a dispersion medium, wherein the amino compound is A group comprising at least one amino group selected from the group consisting of primary, secondary and tertiary amino groups, and comprising a hydroxyl group, a mercapto group, an ether group, a carbonyl group, a nitro group and a chlorine atom A polycarbonate resin composition which is a hydrocarbon compound having 1 to 25 carbon atoms which may have one or more substituents selected. 2. The polycarbonate resin composition according to claim 1, wherein the average thickness of the interlayer compound in the polycarbonate resin composition is 500 ° or less. 3. The polycarbonate resin composition according to claim 1, wherein the maximum thickness of the interlayer compound in the polycarbonate resin composition is 2000 ° or less. 4. The [N] value of the intercalation compound in the polycarbonate resin composition is 30 or more, wherein the [N] value is
4. The polycarbonate resin composition according to claim 1, wherein the number of particles per unit ratio of an intercalation compound is defined in an area of 100 μm ^{2 of the} resin composition. 5. 5. The average aspect ratio (ratio of layer length / layer thickness) of an interlayer compound in a polycarbonate resin composition is 10 to 10.
The polycarbonate resin composition according to claim 1, wherein the composition is 300. 6. A) a step of preparing a clay dispersion containing an intercalation compound and a dispersion medium, and (B) a step of mixing a polymerizable prepolymer of a polycarbonate resin with the clay dispersion.
(C) a step of polymerizing a polymerizable prepolymer,
A method for producing the polycarbonate resin composition according to claim 1, 2, 3, 4, or 5. 7. The bottom surface interval of the intercalation compound in the clay dispersion obtained in the step (A) is 3 times the bottom surface interval of the swellable silicate.
The method for producing a polycarbonate resin composition according to claim 6, wherein the ratio is at least twice.