JP2006225548A - Resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition which is excellent in toughness, produces a molded product having a small warpage, and has a processing temperature of ≥300°C, and to provide a molded product which is obtained by molding the thermoplastic resin composition. <P>SOLUTION: The thermoplastic resin composition contains a specific amount of a thermoplastic resin composition (A) having a glass transition temperature of ≥167°C or a melting point of ≥270°C, and a modified product (B) of specific phyllosilicate obtained by ion-exchanging a metal ion contained in a swelling phyllosilicate (B-1) with an aminium ion containing a benzil group. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a thermoplastic resin composition having excellent toughness, little warping of a molded product, and a molding processing temperature of 300 ° C. or higher.

 Among thermoplastic resins, a group that is particularly excellent in heat resistance, specifically, aromatic ring-containing polyamide, polyamideimide, polyphenylene sulfide, polyarylate, polysulfone, polyethernitrile, polyetherketone, polyimide, etc. are widely used in the metal replacement field. Applied.

  The product shape attachment is mainly performed by extrusion molding or injection molding, and these resins are characterized by a high molding processing temperature exceeding 300 ° C. According to Non-Patent Document 1, it is known that the extrusion temperature (Tpa) of an amorphous resin and the extrusion temperature (Tpc) of a crystalline resin are represented by the following formulas (1) and (2), respectively. ing.

Tpa (° C.) = 1.25 × (Tg (° C.) + 70) (1)
Tpc (° C.) = 0.75 × Tm (° C.) + 100 (2)
Here, Tg is a glass transition temperature and Tm is a melting point. From these equations, it can be seen that the extrusion temperature exceeds 300 ° C. when the glass transition temperature is about 167 ° C. or more for the amorphous resin and the melting point is about 270 ° C. or more for the crystalline resin. The above-mentioned thermoplastic resin group exactly applies to this condition. Further, in injection molding, generally, the molding temperature is set to be higher by 10 to 50 ° C. than extrusion molding. For this reason, restrictions naturally apply to the low molecular weight organic additives that can be added to these resins.

On the other hand, in recent years, these resins have been increasingly used in the field of electric and electronic parts, for example, as materials for slots and connectors. In this type of application, since the parts are joined together, the accuracy of the shape of the molded product and the energy (toughness) leading to breakage when stress is applied are emphasized.
However, when the thickness of the molded product is reduced as in recent years and the injection pressure required for filling is increased, the residual stress inside the obtained molded product is increased, and the “warp” generated in the molded product tends to become remarkable. Further, in the case of a reinforced material filled with inorganic fibers such as glass fibers, “warping” is more likely to occur due to the anisotropy of the shrinkage of the molded product accompanying the fiber orientation.
In such a case, as disclosed in Non-Patent Document 2, for example, mica, glass flakes, talc, sericite, kaolinite, boron nitride, graphite, metal flakes and the like are inorganic having a large aspect ratio. There is a technique that can reduce warpage by adding a filler. However, in this case, it is necessary to add as much as 30 to 60 parts by mass of these inorganic fillers, which causes problems such as damage to the toughness of the molded product and an increase in specific gravity.
Patent Document 1 discloses a technique in which a swellable layered silicate is treated with an azabicyclo ring compound such as quinuclidine, and then added to a thermoplastic resin to peel the layered silicate in the resin. Yes. According to this method, since the plate-like inorganic filler having a large aspect ratio can be dispersed at a finer level than usual, it is effective against warping with a small amount of addition, but the heat resistance of the azabicyclo ring compound used is Since it is not sufficient, there is a problem in that the applicable resin is limited. Specifically, there is a limit to so-called general-purpose engineering plastics having an extrusion temperature of around 250 ° C. such as polycaproamide (nylon 6) and polyoxymethylene (POM). Therefore, when the above technique is applied to a resin having an extrusion processing temperature exceeding 300 ° C. as mentioned in the present invention, the azabicyclo ring compound is not decomposed to achieve the original purpose, but discoloration and toughness are reduced. There was a problem that happened.
WO97 / 11998 Publication Hirota Hirota's “Extruder Manual Utilized in the Field” published by the Industrial Research Association, published on May 10, 1993, page 23 Asahi Kasei Amidus Co., Ltd., Plastics Editorial Department, “Plastic Data Book”, published by Industrial Research Council, published December 1, 1999, page 991

The present invention relates to a thermoplastic resin composition having excellent toughness and small warpage of a molded product, and a molding processing temperature of 300 ° C. or higher, more specifically, a glass transition temperature of the thermoplastic resin of 167 ° C. or higher or a melting point. It is providing the thermoplastic resin composition which is 270 degreeC or more.

As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have modified specific layered silicates obtained by ion exchange of metal ions contained in swellable layered silicates with aminium ions containing benzyl groups. The present inventors have found that a specific thermoplastic resin composition containing can solve the above-mentioned problems, and have completed the present invention.

That is, the present invention is specified by the matters described in [1] to [9] below.
[1] A resin composition comprising a thermoplastic resin (A) and a modified layered silicate (B), wherein the modified layered silicate (B) is a swellable layered silicate (B-1). Providing a thermoplastic resin composition obtained by ion-exchange of a metal ion contained therein with an aminium ion (B-2) containing a benzyl group.
[2] The thermoplastic resin composition according to the above [1], wherein the thermoplastic resin (A) is a thermoplastic resin having a glass transition temperature of 167 ° C or higher or a melting point of 270 ° C or higher.
[3] The above [1], wherein the thermoplastic resin (A) is at least one selected from aromatic ring-containing polyamide, polyamideimide, polyphenylene sulfide, polyarylate, polysulfone, polyethernitrile, polyetherketone, and polyimide. A thermoplastic resin composition as described in 1. above.
[4] The thermoplastic resin composition according to the above [1] to [3], wherein the swellable layered silicate (B-1) is synthetic fluorinated mica and / or montmorillonite.
[5] The provision of the thermoplastic resin composition according to the above [1] to [4], wherein the aminium ion (B-2) containing a benzyl group is represented by the general formula (1).

(M represents an integer of 0 to 2, n = 1 to 3, and m + n = 3. R represents hydrogen, an alkyl group or an aryl group, and may be different from each other. Hydrogen may be substituted with an alkyl group or a halogen atom)
[6] The amount of the inorganic component in the modified layered silicate (B) contained in the thermoplastic composition is 100% by mass in total of the thermoplastic resin (A) and the modified layered silicate (B). Provision of the thermoplastic resin composition according to the above [1] to [5], which is 0.1 to 15% by mass relative to the mass.
[7] The ion content ratio of the aminium ion (B-2) containing a benzyl group in the modified layered silicate (B) obtained by the mathematical formula (3) is 0.5 to 1.5. The provision of the thermoplastic resin composition according to [1] to [6].

IR = CE / IE (3)
(In Formula (3), IR is the ion content ratio of the aminium ion (B-2) containing a benzyl group, and CE is the aminium ion containing a benzyl group per 100 g of the swellable layered silicate (B-1) (B -2) chemical equivalent (meq / 100 g), IE is the ion exchange capacity (meq / 100 g) of the swellable layered silicate (B-1))
[8] Carbon fiber, glass fiber, metal fiber, ceramic fiber, alumina fiber, boron fiber, silicon carbide fiber with respect to a total of 100 parts by mass of the thermoplastic resin (A) and the modified layered silicate (B) The provision of the thermoplastic resin composition according to the above [1] to [7], comprising 1 to 50 parts by mass of at least one selected inorganic fiber.
[9] It is to provide a molded article obtained by molding the thermoplastic resin composition according to any one of [1] to [8].

The thermoplastic resin composition of the present invention is capable of improving the appearance of a molded article of a thermoplastic resin having a molding processing temperature of 300 ° C. or higher, and having a low specific gravity and high toughness. It can be used in a wide range of applications such as various machine parts, automobile parts, electrical / electronic parts, and packaging materials.

[Thermoplastic resin (A)]
The thermoplastic resin (A) used in the present invention has a glass transition temperature of 167 ° C. or higher, preferably 170 to 250 ° C. or a melting point of 270 ° C. or higher, preferably 280 to 400 ° C. Resin may be used, and any known resin can be used. Specific examples include aromatic ring-containing polyamide, polyamideimide, polyphenylene sulfide, polyarylate, polysulfone, polyether nitrile, polyether ketone, polyimide, and the like. Among these, aromatic ring-containing polyamide and polysulfone are particularly preferable.

[Aromatic ring-containing polyamide]
The aromatic ring-containing polyamide contains terephthalic acid as an essential dicarboxylic acid component, and further contains an aromatic dicarboxylic acid other than terephthalic acid and / or an aliphatic dicarboxylic acid having 4 to 20 carbon atoms, and an aliphatic group. It consists of a repeating unit consisting of a diamine component consisting of diamine, and can be produced by a known method described in JP-A-7-53715. The dicarboxylic acid component is composed of 20 to 100 mol% of terephthalic acid and 0 to 80 mol% of an aromatic dicarboxylic acid other than terephthalic acid and / or an aliphatic dicarboxylic acid having 4 to 20 carbon atoms. Isophthalic acid is particularly preferred as the aromatic dicarboxylic acid component other than terephthalic acid, and adipic acid is particularly preferred as the aliphatic dicarboxylic acid component.

  Examples of the aliphatic diamine component include 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, , 11-diaminoundecane, 1,12-diaminododecane, etc., among which 1,6-diaminohexane is preferable. As specific examples of the aromatic ring-containing polyamide, for example, “Aalen (made by Mitsui Chemicals)”, “Amodel (made by Solvay Advance Polymers)”, “Zytel HTN (made by DuPont)” mainly composed of the repeating structure of the chemical formula (1) "Grivory HT (manufactured by MMS)" (both crystalline resin, melting point 300-330 ° C), "Genesta (manufactured by Kuraray)" mainly composed of the repeating structure of chemical formula (2) (crystalline resin, The melting point is 306 ° C.) and the like are available from the market.

[Polyamideimide]
Polyamideimide is a polymer obtained from an aromatic diamine and an aromatic tricarboxylic acid anhydride or a derivative thereof, and has both an amide bond and an imide bond in the skeleton. As the aromatic tricarboxylic acid anhydride, trimellitic acid anhydride is preferably used, and two or more aromatic diamine components may be used as a mixture. As a typical polyamide imide, a random copolymer having the chemical formula (3) is available under the trademark “Toron (manufactured by Amoco)” (amorphous resin, glass transition temperature is 280 ° C.).

[Polyphenylene sulfide]
The polyphenylene sulfide contains 60 mol% or more of the repeating unit represented by the chemical formula (4), and may contain an ether bond or a sulfone bond. The polyphenylene sulfide is roughly classified into a crosslinked type and a linear type. In the present invention, a linear type is preferable, and can be produced by a technique disclosed in JP-A-60-55029. Trademarks such as “FORTRON (manufactured by Kureha Chemical Industry Co., Ltd.)” (crystalline resin, melting point 285 ° C.) are readily available from the market.

[Polyarylate]
Polyarylate is obtained from a bisphenol component and an aromatic dicarboxylic acid component. Preferred bisphenols are bisphenol A, bisphenol AP and tetramethylbisphenol A, and aromatic dicarboxylic acid components are terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 4,4'-dicarboxydiphenyl, bis (p-carboxyphenyl) Examples include alkanes. Among these, terephthalic acid and isophthalic acid are most preferably used, and are mixed and used as necessary. For example, a compound mainly composed of the repeating structural unit represented by the chemical formula (5) is easily available from the market under the trademark “U-polymer (manufactured by Unitika)” (amorphous resin, glass transition temperature is 193 ° C.). is there.

[Polysulfone]
Polysulfone has a sulfone bond, an ether bond, and an arylene bond as essential components, and is a polymer produced by the method described in, for example, Japanese Patent Publication No. 40-10067. As a very typical example, for example, a polymer having a repeating unit represented by chemical formula (6) to chemical formula (8) can be mentioned, and these can be used alone or in admixture of two or more. For example, those having a repeating unit of the chemical formula (6) as a main component are those having trademarks such as “PES (manufactured by Mitsui Chemicals)” (amorphous resin, glass transition temperature of 225 ° C.). As the main unit, those having a trademark such as “Ultrason S (manufactured by BASF)” (amorphous resin, glass transition temperature is 190 ° C.) are based on the repeating unit of the chemical formula (8). "Radel (Amoco)" (non-crystalline resin, glass transition temperature is 220 ° C) and other brands are readily available from the market.

[Polyethernitrile]
Polyether nitrile is a polymer obtained by reacting a halide of an aromatic nitrile compound with resorcin using an amide solvent in the presence of sodium carbonate. As typical polyether nitrile, for example, “PEN (manufactured by Idemitsu Material Co., Ltd.)” (crystalline resin, melting point: 340 ° C.) mainly composed of the repeating unit of the chemical formula (9) is easily available from the market.

[Polyetherketone]
Polyether ketone is a polymer having a repeating unit in which aryl is bonded with ether and ketone. As a commercially available product, “PEEK-HT (manufactured by Victrex MC)” mainly composed of a repeating unit represented by the chemical formula (10) (crystalline resin, melting point: 374 ° C.), represented by the chemical formula (11) "PEEK (manufactured by Victrex MC)" (crystalline resin, melting point: 343 ° C), etc., mainly composed of repeating units are readily available from the market.

[Polyimide]
Polyimide is a polymer obtained by imidizing a polyamic acid obtained by a reaction between a biscarboxylic anhydride and an aromatic diamine, with an imide bond as an essential chemical structure, thermally or chemically. These are roughly classified into a non-thermoplastic type and a thermoplastic type. In the present invention, a thermoplastic type is preferably used. As the thermoplastic polyimide, “Aurum (manufactured by Mitsui Chemicals)” (crystalline resin, melting point is 388 ° C.) mainly composed of the repeating unit of the chemical formula (12) or repeating structural unit of the chemical formula (13) is mainly used. Trademarks such as “Ultem (manufactured by General Electric Co., Ltd.)” (amorphous resin, glass transition temperature is 217 ° C.) can be mentioned, and any of them is suitably used in the present invention.

In the present invention, one or more of the thermoplastic resin groups listed above can be selected and used.
[Swellable layered silicate (B-1)]
The swellable layered silicate (B-1) is obtained by further laminating a 2: 1 type plate-like crystal layer formed by overlapping a silicate tetrahedral sheet on top and bottom of an octahedral sheet containing elements such as aluminum and magnesium. And having an alkali metal and / or alkaline earth metal ion such as sodium, lithium and calcium between the crystal layers. These are characterized in that when they are put into water, water molecules enter between the crystal layers due to the strong hydration power of the metal ions, causing swelling. Further, in this state, it has a function of easily exchanging ions between other cations and metal ions between crystal layers. Specific examples include montmorillonite called the smectite group, balladenite, saponite, hectorite, soconite, stevensite, and artificially synthesized fluorine teniolite, and synthetic fluoric mica. Montmorillonite and synthetic fluoric mica are particularly preferred.

  Synthetic fluorine mica is heated by melting oxides, fluorides, carbonates, etc. to 1400 ° C or higher, as described in “With clay” (published by Shin Koga, 1997, published by Sankyo Publishing). It can be synthesized. Moreover, it is compoundable also by using talc as a starting material, mixing with alkali silicofluoride, and heat-processing in a 700-900 degreeC temperature range. Such synthetic fluorine mica is easily available from the market, for example, “Somasifu (manufactured by Corp Chemical Co., Ltd.)”, “DMA-80E (manufactured by Topy Industries, Ltd.)”. These clay minerals and synthetic fluorine mica can be used alone or in combination of two or more.

[Aminium ion containing benzyl group (B-2)]
The aminium ion (B-2) containing a benzyl group used for ion exchange of the metal ion contained in the swellable layered silicate (B-1) is composed of an amine containing a benzyl group and hydrohalic acid, sulfuric acid, nitric acid, etc. It is given by dissolving the salt formed with the mineral acid in water. Among them, the structure represented by the general formula (1) is preferable,

(M represents an integer of 0 to 2, n = 1 to 3, and m + n = 3. R represents hydrogen, an alkyl group or an aryl group, and may be different from each other. Hydrogen may be substituted with an alkyl group or a halogen atom)
For example, benzylaminium ion, dibenzylaminium ion, tribenzylaminium ion, dimethylbenzylaminium ion, diethylbenzylaminium ion, N, N-dibenzylanilinium ion, and the like can be mentioned. Aminium ion, dibenzylaminium ion and tribenzylaminium ion are preferably used, and dibenzylaminium ion is most preferably used from the balance of benzyl group content and water solubility. These aminium ions containing a benzyl group can be used alone or in combination of two or more.

[Modified product of layered silicate (B)]
The modified layered silicate (B) used in the present invention is obtained by ion exchange of metal ions contained in the swellable layered silicate (B-1) with an aminium ion (B-2) having a benzyl group. It is presumed that it has a sandwich type structure in which an aminium ion containing a benzyl group is inserted between the plate-like crystal layers of the layered silicate.
The amount of the aminium ion (B-2) containing a benzyl group in the modified layered silicate (B) used in the present invention is based on the formula (3), and the swellable layered silicate (B-1). ), The ion content ratio (IR) of the aminium ion (B-2) containing a benzyl group is 0.5 to 1.5, preferably 0.7 to 1.2, and It is preferably 9 to 1.1.

IR = CE / IE (3)
(In Formula (3), IR is the ion content ratio of the benzyl group-containing aminium ion (B-2), and CE is the benzyl group-containing aminium ion (B-2) per 100 g of the swellable layered silicate (B-1). The chemical equivalent (meq / 100 g), IE is the cation exchange capacity (meq / 100 g) of the swellable layered silicate (B-1).)
The ion exchange capacity of the swellable layered silicate (B-1) is a value measured by the method described in, for example, “Clay Handbook” (Japan Clay Society, 1967, published by Gihodo Publishing Co., Ltd.). The amount of aminium ion (B-2) containing a benzyl group, expressed in cation exchange capacity (equivalent) per 100 g of silicate (B) and contained in the modified layered silicate (B), Using differential heat / thermobalance measurement (DTA-TG) (temperature increase rate of 10 ° C./min), it is determined as the mass of the organic component measured as the mass loss of the modified layered silicate (B), After dividing the mass of the organic component by the formula amount of the aminium ion containing the benzyl group, the value obtained by multiplying the valence of the ion is the chemical equivalent of the aminium ion (B-2) containing the benzyl group. .
If the ion content ratio (IR) of the aminium ion (B-2) containing a benzyl group is 0.5 or more, sufficient hydrophobicity can be obtained and the affinity with the resin is high, and preferably 1.5 or less. For example, an aminium ion containing an excessive benzyl group is preferable because it causes a plasticizer action in the thermoplastic resin composition and does not impair physical properties.
The modified layered silicate (B) used in the present invention is subjected to an ion exchange reaction by contacting the swellable layered silicate (B-1) with an aminium ion (B-2) containing a benzyl group. Obtainable. More specifically, after sufficiently swelling the swellable layered silicate (B-1) with water, 0.5 to 1.5 times the cation exchange capacity of the swellable layered silicate (B-1). An aqueous solution of an aminium ion (B-2) containing a benzyl group having a chemical equivalent of 0.7 to 1.2, more preferably 0.9 to 1.1 times is preferably used as a swellable layered silicate (B-1 ) And stirring, the metal ions between the crystal layers contained in the swellable layered silicate (B-1) are replaced with aminium ions (B-2) containing a benzyl group to make them hydrophobic (ie, lipophilic). The modified layered silicate (B) of the present invention can be obtained by recovering, rinsing and drying the product.

[Thermoplastic resin composition of the present invention]
The thermoplastic resin composition of the present invention is a resin composition comprising a thermoplastic resin (A) and a modified layered silicate (B), wherein the modified layered silicate (B) is a swellable layered silicate. The thermoplastic resin composition is characterized in that the metal ion contained in (B-1) is ion-exchanged with an aminium ion (B-2) containing a benzyl group.

In the thermoplastic resin composition of the present invention, the inorganic component in the modified layered silicate (B) is 100% by mass of the total of the thermoplastic resin (A) and the modified layered silicate (B). 0.1 to 15% by mass, preferably 2 to 10% by mass. If the amount of the inorganic component is 0.1% by mass or more, the warp improving effect of the molded product can be sufficiently obtained, and if it is 15% by mass or less, the toughness of the molded product is not impaired.
The mass of the inorganic component in the modified layered silicate (B) is determined as a mass reduction amount of the modified layered silicate (B) measured using differential heat / thermobalance measurement (DTA-TG). It is calculated | required as what subtracted the mass of the organic component obtained, ie, the mass of the aminium ion containing a benzyl group, from the mass of the modified layered silicate (B) before DTA-TG measurement.
For example, if the mass reduction amount of the modified layered silicate (B) by DTA-TG measurement is 20% by mass of the weight of the modified layered silicate (B), the modified layered silicate (B) The value of 0.8 times the mass of is the mass of the inorganic component in the modified layered silicate (B), and the thermoplastic resin composition of the present invention is an inorganic material in the modified layered silicate (B). It is preferable to blend the thermoplastic resin (A) and the modified layered silicate (B) so as to contain the components in the above-mentioned range.

  In the present invention, an appropriate amount of inorganic fibers can be used in combination according to the purpose. Specific examples include glass fibers, carbon fibers, metal fibers, ceramic fibers, alumina fibers, boron fibers, silicon carbide fibers, and the like, and these inorganic fibers are a modification of the thermoplastic resin (A) and the layered silicate. 1 to 50 parts by weight, preferably 5 to 40 parts by weight, more preferably 10 to 30 parts by weight, based on 100 parts by weight of the total amount of the product (B). Can be selected and used.

  Further, other inorganic fillers and other thermoplastic resins can be used in combination as long as the object of the present invention is not impaired. As the inorganic filler, for example, potassium titanate whisker, aluminum borate whisker, carbon whisker, calcium carbonate whisker, wollastonite, zinc oxide whisker, titanium oxide whisker, glass flake, talc, sericite, kaolinite, boron nitride, graphite , Metal flakes, carbon black, magnesium carbonate, calcium carbonate, glass beads, silica, barium sulfate, metal powder, silica stone powder, molybdenum disulfide, antimony trioxide, aluminum hydroxide, magnesium hydroxide, asbestos, calcium metasilicate, silica Examples include algal clay, alumina, shirasu balun, hydrotalcite, zeolite, carbon nanotube, and various metal oxides. Other thermoplastic resins include polyolefins, polystyrenes, polyacrylates, vinyl resins (polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyvinyl alcohol, etc.), polycarbonates, aliphatic polyesters, aromatic polyesters, Examples thereof include aliphatic polyamide, polyphenylene ether, polyacetal, and liquid crystal polymer.

  Furthermore, non-thermoplastic resins such as fluororesins and silicone resins, colorants, mold release agents, various stabilizers, plasticizers, flame retardants, oils, and the like can be added within a range that does not impair the effects of the present invention. One or more of these can be selected and used.

  The thermoplastic resin composition of the present invention is a thermoplastic resin (A), a modified layered silicate (B), and if necessary, the above inorganic fibers and other components are mixed using a Henschel mixer, a tumbler blender, etc. After that, it can be produced using an extruder. That is, the thermoplastic resin composition of the present invention can be obtained by cleaving and exfoliating and dispersing the modified layered silicate (B) by melt kneading using an extruder. In this case, a multi-screw extruder is preferable to a single-screw extruder, and the ratio of the screw length to the screw diameter (L / D) is preferably 25 to 50, more preferably 30 to 45. When L / D is 25 or more, sufficient kneading can be obtained, and when L / D is 50 or less, it is preferable that the resin does not deteriorate during melt-kneading.

There are many unclear reasons why the aminium ion (B-2) containing a benzyl group used in the present invention is effective for a thermoplastic resin having a high processing temperature. In order to show high compatibility with family resins, it does not cause deterioration of physical properties due to gas burning such as fragments of fat attribute, but also promotes local interface wetting to cleave the layered silicate complex. It can be considered that it contributes.
The thermoplastic resin composition of the present invention is put to practical use mainly by extrusion molding or injection molding, but can also be by a known molding method such as compression molding.

[Molded body]
There is no restriction | limiting in the molded article obtained by shape | molding the resin composition of this invention, and it can apply widely. For example, power tool parts, machine parts such as gears and cams, automobile interior and exterior parts, automobile engine room internal parts, automobile electrical parts, IC packaging trays, IC manufacturing trays, IC sockets, wafer carriers, plasma rings, Focus ring, hard disk carrier, liquid crystal display carrier, crystal oscillator manufacturing tray, connector, slot, socket, relay box, copier separation claw, copier thermal insulation bearing, thrust washer, transmission ring, piston ring, oil seal ring It can be suitably used for bearing retainers, pump gears, conveyor chains, slide bushes for stretch machines, and the like.

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In the examples, each physical property value was measured by the following method.

[Glass transition temperature (Tg)]
It measured using the differential scanning calorimeter (DSC). The temperature was raised from room temperature at a rate of 10 ° C. per minute, and the temperature at which the change in specific heat started was taken as the glass transition temperature.

[Melting point (Tm)]
The temperature was measured in the same manner as the glass transition temperature, and the temperature at the top of the endothermic peak accompanying melting was taken as the melting point.

[Amount of organic component contained in modified layered silicate (B)]
The layered silicate obtained by measuring the temperature of the modified layered silicate (B) from room temperature to 800 ° C at a rate of temperature increase of 10 ° C / min using differential heat / thermobalance measurement (DTA-TG) The mass reduction amount of the modified product (B) was determined as the amount of the organic component in the modified silicate layer (B).

[warp]
On the horizontal plate, place the convex side of the 200 × 140 × 3 mm flat plate obtained by injection molding in contact with the flat surface of the horizontal plate, and place one end of the flat plate in the longitudinal direction with a weight on the horizontal plate. The maximum distance (height) at which one end of the flat plate that was not fixed was lifted from the plane of the horizontal plate was measured with a height meter.

[Toughness]
An area enclosed by a stress-strain curve when a 40 × 5 × 1 mm test piece obtained by injection molding is subjected to a bending test at a span distance of 26 mm in accordance with ASTM D-790 and the test piece breaks. Was integrated to find the energy required for destruction.

[Production Example 1]
Swellable layered silicate (B-1) (synthetic fluorine mica, manufactured by Co-op Chemical Co., Ltd., trade name “Somasif ME-100”, cation exchange capacity = 120 meq / 100 g) is 5 mass% in distilled water. Then, the mixture was heated to 80 ° C. to obtain a swellable layered silicate sol. A dibenzylaminium ion aqueous solution prepared from 2N hydrochloric acid and dibenzylamine (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) as an aminium ion (B-2) containing a benzyl group was added to the swellable layered silicate. After adding and stirring so that it might become equivalent with respect to an ion exchange capacity | capacitance, after performing ion exchange reaction at 80 degreeC for 4 hours, the reaction liquid was centrifuged and the content was collect | recovered. Subsequently, it was washed and dried to obtain a modified layered silicate (B). The ion content ratio of the dibenzylaminium ion was determined according to the formula (3) to be 0.99, and it was found that almost all of the charged dibenzylaminium ion was consumed. Table 1 shows the evaluation results of each physical property value of the modified layered silicate (B) obtained in Production Example 1.

[Production Example 2]
A modified layered silicate (B) was obtained in the same manner as in Production Example 1 except that dibenzylamine was changed to benzylamine (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.). The ion content ratio of benzylaminium ions was 1.00, and all of the charged benzylaminium ions were consumed. Table 1 shows the evaluation results of each physical property value of the modified layered silicate (B) obtained in Production Example 2.

[Production Example 3]
A modified layered silicate (B) was obtained in the same manner as in Production Example 1 except that the salt used for ion exchange was quinuclidine hydrochloride (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.). The ion content ratio of the quinuclidine cation was 0.97, and almost all of the charged quinuclidine cation was consumed. Table 1 shows the evaluation results of the physical properties of the modified layered silicate (B) obtained in Production Example 3.

[Examples 1 to 4]
As the thermoplastic resin (A), an aromatic ring-containing polyamide having a repeating structural unit of the chemical formula (2) (Aren C2000, manufactured by Mitsui Chemicals, melting point 310 ° C.) and the layered silicate obtained in Production Example 1 and Production Example 2 The modified product (B) was blended in the proportions shown in Table 2 and then thoroughly mixed with a tumbler mixer. The screw diameter was 37 mm, L / D = 32 twin screw extruder at 340 ° C., screw rotation speed 200 rpm. It melt-mixed and extruded and obtained the pellet-shaped thermoplastic resin composition. Next, the pellets were molded into test pieces with an injection molding machine set at 350 ° C., and the physical properties were evaluated. The results are shown in Table 2.

[Examples 5 to 6]
As the thermoplastic resin composition (A), a polysulfone (PES E2010, manufactured by Mitsui Chemicals, glass transition temperature 225 ° C.) having a repeating structural unit of the chemical formula (7), and the layered form obtained in Production Example 1 and Production Example 2 After blending the modified silicate (B) in the proportions shown in Table 2, the physical properties were evaluated in the same manner as in Example 1 except that the melt extrusion temperature was 370 ° C and the injection molding temperature was 380 ° C. The results are shown in Table 2. [Example 7 to Example 8]
The physical properties were evaluated in the same manner as in Example 2 and Example 4 except that glass fiber chopped strands (manufactured by Nippon Sheet Glass Co., Ltd., RES03-TP78) were used in the proportions shown in Table 2. The results are shown in Table 2.

[Comparative Examples 1 to 2]
The physical properties were evaluated in the same manner as in Example 1 except that the content of the inorganic component contained in the modified layered silicate (B) in the thermoplastic resin composition was outside the scope of the present invention. The results are shown in Table 3.

[Comparative Example 3]
The physical properties were evaluated in the same manner as in Example 1 except that the swellable layered silicate (B-1) was not ion-exchanged with dibenzylaminium ions. The results are shown in Table 3.

[Comparative Example 4]
The physical properties were the same as in Example 1 except that glass fiber chopped strands (manufactured by Nippon Sheet Glass Co., Ltd., RES03-TP78) were used in the ratio shown in Table 3 instead of the modified layered silicate (B). Evaluated. The results are shown in Table 3.

[Comparative Example 5]
The same procedure as in Example 1 was performed except that non-swellable natural mica (manufactured by Repco Co., Ltd., M-400) was used in the ratio shown in Table 3 instead of the modified layered silicate (B). Physical properties were evaluated. The results are shown in Table 3.

[Comparative Example 6]
The physical properties were evaluated in the same manner as in Comparative Example 5 except that the amount of natural mica in Comparative Example 5 was increased to 20% by mass where the warpage of the molded product was reduced. The results are shown in Table 3.

[Comparative Example 7]
The physical properties were evaluated in the same manner as in Example 1 except that the modified layered silicate (B) obtained in Production Example 3 was used. The results are shown in Table 3.

[Comparative Examples 8 to 9]
The physical properties were evaluated in the same manner as in Examples 1 and 5 except that the modified layered silicate was not used. The results are shown in Table 3.

Claims (9)

A resin composition comprising a thermoplastic resin (A) and a modified layered silicate (B), wherein the modified layered silicate (B) is a metal ion contained in the swellable layered silicate (B-1) Is a thermoplastic resin composition that is ion-exchanged with an aminium ion (B-2) containing a benzyl group. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin (A) is a thermoplastic resin having a glass transition temperature of 167 ° C or higher or a melting point of 270 ° C or higher. 2. The heat according to claim 1, wherein the thermoplastic resin (A) is at least one selected from aromatic ring-containing polyamide, polyamideimide, polyphenylene sulfide, polyarylate, polysulfone, polyethernitrile, polyetherketone, and polyimide. Plastic resin composition. The thermoplastic resin composition according to claim 1, wherein the swellable layered silicate (B-1) is synthetic fluorinated mica and / or montmorillonite. The thermoplastic resin composition according to claim 1, wherein the aminium ion (B-2) containing a benzyl group is represented by the general formula (1).

(M represents an integer of 0 to 2, n = 1 to 3, and m + n = 3. R represents hydrogen, an alkyl group or an aryl group, and may be different from each other. Hydrogen may be substituted with an alkyl group or a halogen atom) The amount of the inorganic component in the modified layered silicate (B) contained in the thermoplastic composition is 0 with respect to 100% by mass in total of the thermoplastic resin (A) and the modified layered silicate (B). The thermoplastic resin composition of Claims 1-5 which is 0.1-15 mass%. The ion content ratio (IR) of the aminium ion (B-2) containing a benzyl group in the modified layered silicate (B) obtained by the mathematical formula (3) is 0.5 to 1.5. The thermoplastic resin composition according to claim 1.
IR = CE / IE (3)
(In Formula (3), IR is the ion content ratio of the aminium ion (B-2) containing a benzyl group, and CE is the aminium ion containing a benzyl group per 100 g of the swellable layered silicate (B-1) (B -2) chemical equivalent (meq / 100 g), IE is the ion exchange capacity (meq / 100 g) of the swellable layered silicate (B-1)) At least selected from carbon fiber, glass fiber, metal fiber, ceramic fiber, alumina fiber, boron fiber, and silicon carbide fiber with respect to a total of 100 parts by mass of the thermoplastic resin (A) and the modified layered silicate (B). The thermoplastic resin composition according to claim 1, comprising 1 to 50 parts by mass of one or more inorganic fibers. The molded object obtained by shape | molding the thermoplastic resin composition in any one of Claims 1-8.