JPH08170021A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE: To obtain the subject composition, well balanced among impact resistance, strength, rigidity and heat resistance and useful for the field of automobiles, etc., by using a fibrous xonotlite having specific properties. CONSTITUTION: This resin composition comprises (A) a thermoplastic resin (preferably a polyamide resin, etc.), (B) a rubber (preferably an ethylene- propylene rubber, etc.) or a thermoplastic elastomer or a thermoplastic resin modified with the rubber and (C) a fibrous xonotlite, having >=21m<2> /g BET specific surface area according to nitrogen adsorption and the surface treated with a surfactant and/or a coupling agent and granulated into a granular shape. Furthermore, formula I [A] is the weight of the component (A) in the objective composition; [B] is the weight of the component (B); [C] is the weight of the component (C); wf is the weight percentage of the component (C) in the objective composition} is within the range of 5<=wf<=70 and formula II [wb is the weight percentage of the component (B) in the total weight of the components (A) and (B) in the objective composition] is within the range of 5<=wb<=40.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition reinforced with fibrous xonotlite. A molded article obtained by using the composition has impact resistance, strength, rigidity and heat resistance. It has a good balance with and can be used as a material in the fields of automobiles, electric / electronics, precision machinery, etc.

[0002]

2. Description of the Related Art Heretofore, as a method for improving the impact resistance of a thermoplastic resin, a method of blending a rubber, a thermoplastic elastomer, or a rubber-modified thermoplastic resin as a modifier has been widely known. However, this method is known to reduce strength, elastic modulus, and heat resistance. For example, a method of blending an ionomer with a polyamide resin (PA resin) (see Japanese Patent Application Laid-Open No. 62-68851) or a polypropylene resin (PP resin) with ethylene-propylene rubber (EP).
R) (see JP-A-61-292752, etc.), or a method in which a styrene-butadiene-styrene elastomer (SBS) is blended with a polyarylene sulfide resin (PPS resin) (JP-A-5-1952).
No. 6-118456, etc.) is known, but these methods have a drawback that the strength, elastic modulus, and heat resistance are lowered as described above.

In order to prevent a decrease in strength, elastic modulus and heat resistance of the thermoplastic resin due to the blending of the rubber, the thermoplastic elastomer or the rubber-modified thermoplastic resin with the thermoplastic resin as described above, an inorganic filler is added. A filling method (see JP-A-61-2745, JP-A-1-74266, JP-A-2-255761 and JP-A-4-504139) is also known. Then, as an example of this inorganic filler, a method using fibrous zonotolite (see Japanese Patent Application Laid-Open No. 5-104428) is also proposed.

However, the conventionally known xonotlite is liable to agglomerate, so that it has poor wettability with the thermoplastic resin and has low dispersibility in the thermoplastic resin, so that the expected effect can be obtained. could not. In order to improve this point, a method of treating the surface of xonotlite with a coupling agent (see Japanese Patent Application Laid-Open No. 5-32889, etc.) has been tried, but a sufficient effect has not been obtained.

[0005]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to solve the problems of the above-mentioned conventionally known thermoplastic resins, namely impact resistance and strength, elastic modulus and heat resistance. To provide a thermoplastic resin composition that is well balanced with.

[0006]

The inventors of the present invention have conducted extensive studies to solve the above problems in the prior art, and as a result, in the wettability with the thermoplastic resin which is the matrix resin and in the thermoplastic resin. Impact resistance and strength by blending fibrous zonotolite having specific properties with excellent dispersibility and rubber or thermoplastic elastomer or thermoplastic resin modified with rubber in a specific ratio The present invention has been completed by finding that a thermoplastic resin composition having a good balance of elastic modulus and heat resistance can be provided, and that the problems of the above-mentioned prior art can be overcome thereby.

That is, according to the first aspect of the invention, the thermoplastic resin (A), the rubber or the thermoplastic elastomer or the thermoplastic resin (B) modified with the rubber, and the BET specific surface area by nitrogen adsorption of 21 m ² / G or more,
The component (A), which is surface-treated with a surfactant and / or a coupling agent, and is composed of a fibrous zonotolite (C) granulated into granules, which is represented by the above formula (I), and the above The weight percentage (wf) of the component (C) in the total composition comprising the component (B) and the component (C) is 5% by weight or more and 70% by weight or less, and is represented by the formula (II). The thermoplastic resin, wherein the weight percentage (wb) of the component (B) in the sum of the weight of the component (A) and the weight of the component (B) is 5 wt% or more and 40 wt% or less. This can be achieved by providing a resin composition.

According to the second aspect of the present invention, the fibrous xonotlite (C) has 0.1 μm ≦ D <0.5 μm,
1 μm ≦ L <5 μm and 10 ≦ L / D <20 (where D and L are fibrous zonotolite (C), respectively)
The average fiber diameter and the average fiber length of are shown. ) At the same time, it is a fibrous zonotolite characterized by satisfying
This can be achieved by providing the thermoplastic resin composition according to the invention described in 1.

In the invention according to claim 3, the thermoplastic resin (A) is at least one polymer selected from the group consisting of polyamide resin, polyester resin, polyolefin resin, polyacetal resin and polyarylene sulfide resin. Alternatively, the thermoplastic resin composition according to the invention according to claim 1 or 2 which is a polymer mixture, and the invention according to claim 4 is characterized in that the component (B) is ethylene propylene rubber, ethylene propylene diene rubber, ionomer, styrene. A butadiene-styrene elastomer, a styrene-ethylene-butadiene-styrene elastomer, and at least one rubber selected from the group consisting of impact-resistant ABS resins, a thermoplastic elastomer, or a rubber-modified thermoplastic resin. 1 to 3 Or a thermoplastic resin composition according to the invention described in item 1 can be achieved by providing, respectively.

The present invention will be described in detail below. The present invention
The fibrous zonotolite described in 1.
Formula: Ca₆Si ₆O₁₇(OH)₂, Chemical formula: 6CaO
6 SiO₂・ H₂O) means a needle-shaped crystalline substance. In the present invention
The value of its specific surface area is very important.²/
g or more, preferably 30 m²/ G or more (However, nitrogen absorption
Be measured by the BET method by wearing
Yes. This value is 30m²Fibrous Zonotry smaller than / g
The thermoplastic resin (A), rubber or thermoplastic
Thermoplastic resin modified with elastomer or rubber
There is a tendency that the wettability with (B) deteriorates, and in particular, 21
m ²In the case of fibrous zonotolite smaller than / g, the tendency is
Therefore, the purpose of the present invention cannot be achieved.
Yes.

Further, in the present invention, the fiber shape is
Especially, the average fiber length (L) is 1 μm ≦ L <5 μm, the average fiber diameter (D) is 0.1 μm ≦ D <0.5 μm, and the aspect ratio (L / D) is 10 ≦ L / D <20. Those satisfying at the same time can be preferably used. When D is less than 0.1 μm or L is 5 μm or more, when fibrous zonotolite (C) is formed into granules and modified with thermoplastic resin (A), rubber or thermoplastic elastomer or rubber The fibrous zonotolite (C) may be broken during mixing and kneading with the thermoplastic resin (B) prepared, and when D is 0.5 μm or more and L is less than 1 μm, the thermoplastic resin obtained is The effect of improving the mechanical strength of the composition by the fibrous zonotolite (C) may not be sufficient. When L / D is less than 10, the resulting thermoplastic resin composition may not be able to obtain sufficient mechanical strength, and when L / D is 20 or more, it may be fibrous. The bulk specific gravity of zonotolite (C) may become too small, and it may be difficult to knead when producing the thermoplastic resin composition of the present invention.

The above-mentioned fibrous xonotlite (C) of the present invention is described in detail below in Japanese Patent Application No. 5-1903.
No. 36 specification, that is, a calcareous raw material and a siliceous raw material are mixed in a specific ratio to produce a hydrothermal synthesis reaction. Examples of calcareous raw materials include quick lime and slaked lime, and those with few impurities are preferable. As the siliceous raw material, pulverized silica stone, silica sand and quartz, silicic acid, anhydrous silicic acid, silica gel, diatomaceous earth, etc., which are finely powdered with few impurities and having an average particle size of 10 μm or less, are desirable. Mixing ratio of both (Ca / Si ratio)
Is preferably slightly smaller than the theoretical equivalent and is preferably 0.8 to 0.99. Further, the proportion of water to be mixed is 5 to 40 times, preferably 8 to 30 times the total amount of the calcareous raw material and the siliceous raw material.

The hydrothermal synthesis reaction is usually carried out at 180 to 240 ° C. for 1 to 8 hours while the aforesaid calcareous raw material, siliceous raw material and water are charged into the autoclave and stirred. The reaction temperature and reaction time are important factors, and fibrous xonotrite having the specific surface area used in the present invention as described above cannot be obtained outside the above range.

In the present invention, the fibrous zonotolite (C) obtained by the above-mentioned production method comprises the thermoplastic resin (A) described below and a thermoplastic resin (B) modified with rubber or a thermoplastic elastomer or rubber. In order to further enhance the reinforcing effect on the composition comprising (1), the surface is preferably further treated with a surfactant and / or a coupling agent (hereinafter referred to as a surface treatment agent). That is, the surface treatment agent is a thermoplastic resin (A) serving as a matrix of the fibrous zonotolite (C).
Or improving the affinity with rubber or a thermoplastic elastomer or a thermoplastic resin (B) modified with rubber,
It is used for the purpose of enhancing the reinforcing effect, that is, mechanical strength, and specifically, the following can be used. As the surfactant, any of anionic, cationic, amphoteric and nonionic surfactants can be used. Anionic surfactants include alkyl ether sulfates, dodecylbenzene sulfonates, stearates, etc.Cationic surfactants include tetradecylamine acetate, alkyltrimethylammonium chlorides, and amphoteric surfactants. Examples of the agent include dimethylalkyllaurylpetine, and examples of the nonionic surfactant include polyoxyethylene octadecylamine and polyoxyethylene lauryl ether. Examples of the coupling agent include silane-based coupling agents, titanate-based coupling agents, aluminum-based coupling agents, chromium-based coupling agents, boron-based coupling agents and the like.

The amount of these surface treatment agents added should be 0.1 to 10% by weight, preferably 0.5 to 8% by weight, based on the fibrous zonotolite (C) (dry matter basis).
If the addition amount is less than 0.1% by weight, the above-mentioned effect is not sufficient, and if the addition amount exceeds 10% by weight, the above-mentioned effect is hardly improved even if the addition amount is increased. In addition,
If the addition amount is in the range of 0.1 to 0.5% by weight, the above effects may not be sufficient, and if the addition amount is in the range of 8 to 10% by weight, the improvement of the above effects may not be expected.

In the present invention, as described above, the fibrous zonotolite slurry obtained by the hydrothermal synthesis reaction is extracted from the autoclave, and the fibrous zonotolite is surface-treated. The surface treatment method is not particularly limited,
For example, the surface treatment agent is added to the fibrous zonotolite slurry as it is or after adding an appropriate amount of water, and the mixture is stirred and stirred in an appropriate apparatus in a slurry state.
Then, excess water is filtered and separated by a centrifugal dehydrator or a filter press to obtain cake-like fibrous zonotolite. Further, for this surface treatment, after drying the fibrous zonotolite slurry, it may be carried out using a surface treatment agent dissolved in a small amount of water or a solvent, but the operation becomes complicated, and the effect of the surface treatment agent is It is small and has no particular merit.

Further, the fibrous zonotolite (C) used in the present invention is prepared by mixing and kneading a thermoplastic resin (A) described later with a rubber or a thermoplastic elastomer or a thermoplastic resin (B) modified with a rubber. Granules are formed for the purpose of easily carrying out. Granular fibrous zonotolite is
The cake-like fibrous zonotolite to which the surface treatment agent is attached is formed into granules having a diameter of 1 to 8 mm by a granulator, dried, and when a coupling agent is used as the surface treatment agent, It is obtained by performing heat treatment. In this case, the granulator is not particularly limited, and includes a rotary vertical granulator, a rotary drum granulator, a rotary sieving granulator, a screw extrusion granulator, a roll extrusion granulator. A known granulator can be used. When the diameter of the granular molded article of fibrous xonotlite obtained by granulation deviates from the above range, the thermoplastic resin (A), the rubber or the thermoplastic elastomer, or the thermoplastic resin modified with the rubber (B) is used. When mixing and kneading with, it becomes difficult to mix and knead with a single-screw extruder or a twin-screw extruder, and it is necessary to successively fill and mix and knead them with a roll or Banbury mixer. It is not preferable because it may be significantly broken to cause a decrease in mechanical strength. Further, the drying is a hot air circulation dryer,
Using a known dryer such as an infrared heating dryer, 100-
It is preferable to carry out the treatment at a temperature of 150 ° C. for 20 to 30 hours until the moisture content of the granular fibrous zonotolite becomes 1% by weight or less. Further, the heat treatment when a coupling agent is used is 100 to 150 ° C. and 20 to 30 ° C.
Preference is given to drying the water under heating for a period of time. The cake-like fibrous zonotolite may be dried and heat-treated as it is, and may be formed into granules by a method of crushing to a particle size of about 5 mm, but powder is likely to occur and the bulk is rather large and the handling is a little difficult. .

Next, the thermoplastic resin (A) described in the present invention
Specific examples of polyethylene having various densities and molecular weights, linear low-density polyethylene, ethylene copolymers (ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, etc.), polypropylene homopolymer, polypropylene copolymer (ethylene-propylene block). Copolymers), modified polypropylene,
Polyolefin resins such as polybutene-1 and poly-4-methylpentene-1, polyvinyl alcohol copolymer, polystyrene, high-impact polystyrene, acrylonitrile-butadiene-styrene (ABS) resin, polyvinyl chloride resin, acrylonitrile-styrene (AS ) Resin, maleic anhydride-styrene resin, polycaproamide (nylon 6), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66), polyhexamethylene sebacamide (nylon 61)
0), polyhexamethylene dodecanoamide (nylon 6
12), polyhexamethylene terephthalamide (nylon 6T), polyhexamethylene isophthalamide (nylon 6I), polyundecane amide (nylon 11),
Polydodecanamide (nylon 12), nylon 6/6
6, nylon 6/11, nylon 6/12, nylon 6
/ 610, Nylon 6/612, Nylon 66/61
0, nylon 6/66/610, nylon 6/66/1
2, nylon 6 / 6T, nylon 6 / 6I, nylon 6
6 / 6T, Nylon 66 / 6I, Nylon 6/11/6
T, Nylon 6/12 / 6T, Nylon 66/11/6
T, nylon 66/12 / 6T, nylon 11 / 6T /
Polyamide resins such as 6I and nylon 12 / 6T / 6I, polyester resins such as polybutylene terephthalate, polyethylene terephthalate and other aromatic polyesters, polycarbonates, polyacetal resins (including homopolymers and copolymers), polyphenylene ethers, modified polyphenylene ethers, Polyether ether ketone, polysulfone, polyether sulfone, polyarylene sulfide resin, polyetherimide, thermoplastic polyimide, thermoplastic polyamideimide, polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene- Ethylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, polychlorotriene Ruoroechiren, polyvinylidene fluoride, tetrafluoroethylene - hexafluoropropylene - perfluoroalkyl vinyl ether copolymer and the like, and mixtures thereof. Among these,
Polyamide resins, polyester resins, polyolefin resins, polyacetal resins and polyarylene sulfide resins, and mixtures thereof are particularly preferred specific examples.

As the rubber or thermoplastic elastomer (B) used in the present invention, natural rubber, fluorine rubber, silicone rubber, acrylic rubber, styrene butadiene rubber, butadiene rubber, chloroprene rubber, nitrile rubber, ethylene propylene rubber (EPR). ), Ethylene propylene diene rubber (EPDM), isoprene rubber, butyl rubber, chlorosulfonated polyethylene and other unvulcanized or uncrosslinked rubbers, polystyrene-based (styrene-butadiene-styrene elastomer (SBS) and styrene-ethylene-butadiene-styrene). Elastomer (SE
BS) etc., polyurethane-based, olefin-based, polyester-based, polyamide-based, ethylene-vinyl acetate copolymer, 1,2-polybutadiene, ionomer, ethylene-acrylic acid ester copolymer, vinyl chloride-based thermoplastic elastomer, etc. And the like, and mixtures thereof. Among these, EPR, EPDM, SEB
Preferred examples include S, SBS, ionomers, and mixtures thereof.

The rubber-modified thermoplastic resin (B) used in the present invention includes impact-resistant acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-ethylene propylene-styrene resin, acrylonitrile-acrylic rubber-styrene. Resins, high-impact polystyrene resins, those produced by polymerization rather than mechanical mixing, and mixtures thereof,
Impact-resistant ABS resin is mentioned as a particularly suitable example.

In the present invention, the thermoplastic resin (A)
And a thermoplastic resin (B) modified with the above-mentioned rubber or thermoplastic elastomer or rubber, the polyamide resin is the component (A).
The PDM, ionomer, impact-resistant ABS resin, and a mixture thereof are used in combination with SEBS, SBS, impact-resistant ABS resin, and a mixture thereof when the polyester resin is the component (A). In the case of the component (A), EPR, EPDM, and a mixture thereof, SEBS in the case of the polyarylene sulfide resin being the component (A), and in the case of the polyacetal resin being the component (A). EPDM is preferably used as the component (B).

Further, various additives added to improve the characteristics and production of the composition comprising the above-mentioned thermoplastic resin (A) and rubber or a thermoplastic elastomer or a thermoplastic resin (B) modified with rubber. Material, ie
A heat stabilizer, a light stabilizer, a plasticizer, a cross-linking agent, an antioxidant, a flame retardant, a reinforcing agent, a pigment, a dye, a lubricant, an antistatic agent, a release agent, a perfume, and the fibrous zonotolite (C ) Together with the fibrous xonotlite (C) of the present invention
There is no problem as long as the reinforcing effect of is not hindered.

In the present invention, the thermoplastic resin (A) represented by the above formula (I), the rubber or the thermoplastic elastomer or the thermoplastic resin (B) modified with the rubber, and the fibrous zonotolite (C) are used. The weight percentage (wf) of the fibrous zonotolite (C) in the thermoplastic resin composition is 5% by weight or more and 70% by weight or less, preferably 10% by weight or more and 50% by weight or less, more preferably 10% by weight or more and 40% by weight. % Or less is required. When the weight percentage (wf) is less than 5% by weight, mechanical strength, rigidity, and
Heat resistance does not improve. On the other hand, if it is more than 70% by weight, the melt flowability of the obtained thermoplastic resin composition is lowered, molding becomes difficult, and the appearance of the obtained molded product is deteriorated, which is not preferable. In order to surely suppress the occurrence of these unfavorable phenomena, the weight percentage (wf) of the fibrous zonotolite (C) should be in the above-mentioned preferable range, particularly in the more preferable range.

Next, in both components of the thermoplastic resin (A) represented by the formula (II) and the rubber or the thermoplastic elastomer or the rubber-modified thermoplastic resin (B), rubber or heat is used. The weight percentage (wb) of the thermoplastic elastomer (B) modified with a plastic elastomer or rubber should be 5% by weight or more and 40% by weight or less, preferably 10% by weight or more and 30% by weight or less. When the weight percentage (wb) is less than 5% by weight, the impact resistance improving effect is small, and when it is more than 40% by weight, the original features of the thermoplastic resin (A) as the matrix resin are impaired, which is preferable. Absent. In addition, when the weight percentage (wb) of the rubber or the thermoplastic elastomer or the rubber-modified thermoplastic resin (B) is in the range of 5% by weight or more and less than 10% by weight or more than 30% by weight and 40% by weight or less, respectively, However, the above-mentioned undesirable phenomenon may occur.

By the way, the above-mentioned thermoplastic resin composition of the present invention can be manufactured as follows. That is, fibrous zonotolite (C) and thermoplastic resin (A)
A composition comprising a rubber, a thermoplastic elastomer, or a rubber-modified thermoplastic resin (B) is produced by a known method. Generally, the predetermined amount of the fibrous zonotolite (C), the thermoplastic resin (A) and the rubber or the thermoplastic elastomer or the thermoplastic resin (B) modified with the rubber are melt-kneaded by using a kneader. To obtain the thermoplastic resin composition of the present invention. At this time, the melt-kneading temperature is selected on the basis of a resin having a higher melting temperature among the thermoplastic resin (A) and the rubber-modified thermoplastic resin (B) to be used. If it is a crystalline resin, the temperature is 10 to 60 ° C. higher than the melting point of the resin, preferably 10 to 40 ° C. higher than the melting point of the resin, and if it is an amorphous resin, the glass transition of the resin. 110-1 from the point
60 ° C higher temperature, preferably 1 above the glass transition point of the resin
The temperature is preferably 10 to 140 ° C. higher. If the melt-kneading temperature is lower than the melting point of the crystalline resin + 10 ° C or the glass transition point of the amorphous resin + 110 ° C, the melt viscosity of the resin in the kneader becomes too high, and the melting point or the glass transition point of the resin or less There is a possibility that a kneading failure may occur due to the occurrence of a temperature-increased portion and solidification of the resin during production. Further, the melt-kneading temperature is the melting point of the crystalline resin + 60 ° C or the glass transition point of the amorphous resin +160.
When the temperature is higher than 0 ° C, the resin is thermally decomposed or deteriorated, which causes coloring or deterioration of physical properties, which is not preferable. It is needless to say that the melt-kneading temperature should be within the above-mentioned preferable range in order to reliably prevent the occurrence of these undesirable phenomena related to the melt-kneading temperature.

The kneader may be, for example, an extruder such as a single screw extruder or a twin screw extruder, a twin screw continuous mixer,
Examples thereof include a Banbury mixer, a super mixer, a mixing roll, a kneader and a Brabender plastograph, and the composition is generally obtained in the form of pellets. Among these, an extruder is preferable, and a twin-screw extruder is particularly preferable.

Further, the fibrous zonotolite (C),
The addition and mixing order of these components at the time of melt-kneading the thermoplastic resin (A) and the rubber or the thermoplastic elastomer or the thermoplastic resin (B) modified with the rubber can be arbitrarily selected. The zonotolite (C) may be fed to the hopper of the extruder after being mixed with the thermoplastic resin (A) and the rubber or the thermoplastic elastomer or the rubber-modified thermoplastic resin (B) prior to melt-kneading. Further, only the thermoplastic resin (A) and the rubber or the thermoplastic resin (B) modified with the rubber or the thermoplastic elastomer is supplied to the hopper of the extruder, and the fibrous zonotolite (C) is supplied to the hopper of the extruder. You may supply from the middle. Alternatively, only the thermoplastic resin (A) is supplied to the hopper of the extruder, and the rubber or the thermoplastic elastomer or the thermoplastic resin (B) modified with the rubber and the fibrous zonotolite (C).
May be supplied simultaneously or separately from the middle of the extruder.
In addition, when manufacturing the said composition, the said various auxiliary materials can also be added simultaneously as needed.

The composition thus obtained is molded by various known molding methods such as injection molding, extrusion molding, compression molding and blow molding.

[0029]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples and Comparative Examples. In addition,
The methods for evaluating the physical properties of molded articles described in Examples and Comparative Examples were performed according to the following methods.

(1) Bending property: Tensilon UTM-5T manufactured by Orientec Co., Ltd. was used for measurement. After molding the desired thermoplastic resin composition, 2
Conditioning was carried out at 3 ° C. and a relative humidity of 50% (hereinafter abbreviated as “50% RH”) for 48 hours. Then, the bending strength and bending elastic modulus are measured at 23 ° C. and 50 ° C. according to ASTM D790.
% RH. In addition, in the case of a composition containing a polyamide resin as a main component, the composition is 4 ° C in a desiccator at 23 ° C.
Adjust the condition for 8 hours and measure the bending strength and flexural modulus.
According to ASTM D790, it was performed at 23 ° C. in an absolutely dry state.

(2) Izod impact strength Measured using an Izod impact tester manufactured by Toyo Seiki Co., Ltd. Then, according to ASTM D256, using a test piece that has been conditioned in the same manner as in (1) above, according to (1) above
The notched Izod impact strength was determined under the same temperature and humidity conditions as in Section.

(3) Deflection temperature under load Measured using a load deflection tester manufactured by Toyo Seiki Co., Ltd. Using a test piece that had been conditioned in the same manner as in (1) above, the value under a stress of 1.82 MPa was determined according to ASTM D648. In the case of a composition containing polypropylene resin as a main component, a value under a stress of 0.45 MPa was obtained.

Reference Example 1 Quick lime (a product of Calseed Co., Ca,
O purity: 98%) 430 g, siliceous silica powder as a siliceous raw material (product of Japan General Corp., Blaine specific surface area: 7,000 cm ² / g, SiO ₂ purity: 97%) 4
70 g and 18 liters of tap water were put into an autoclave equipped with a stirrer made of SUS316 and having an internal volume of 30 liters. Then, while stirring at a rotation speed of 80 rpm, the temperature is raised to a holding temperature of 220 ° C. at a rate of 2 ° C./min, and a holding temperature of 22 ° C.
After the mixture was kept at 0 ° C. for 5 hours to carry out the hydrothermal synthesis reaction, the mixture was allowed to cool for 10 hours or longer with stirring to obtain a fibrous zonotolite slurry. When X-ray diffraction of this slurry was measured, only xonotlite was identified.

Subsequently, about 920 g of this fibrous xonotlite slurry (based on solid content), about 18 liters of tap water and a nonionic surfactant (polyoxyethylene octadecylamine, a product of NOF Corporation, trade name: Nymeen 204) were used. ) 46 g (5 relative to fibrous zonotolite solids)
(% By weight) was added and surface treatment was performed while dispersing with a homogenizer. After dewatering this slurry with a nutche to form a cake, it was molded into a diameter of 3 mm with a granulator,
The surface-treated granular fibrous zonotolite was obtained by drying at 0 ° C. This granular fibrous Xonotlite was measured for the average fiber length and average fiber diameter by the measurement and scanning electron micrograph of the BET specific surface area by nitrogen adsorption, respectively, 39m ² /
g, 3 μm and 0.2 μm (hence the aspect ratio:
15). The fibrous zonotolite thus obtained is hereinafter referred to as "fibrous zonotolite A".

Reference Example 2 The holding temperature of the hydrothermal synthesis reaction was 220 ° C. in Reference Example 1.
Granular fibrous zonotolite was produced in exactly the same manner as in Reference Example 1 except that the temperature was changed to 240 ° C.
Specific surface area: 24 m ² / g, average fiber length: 4 μm and average fiber diameter: 0.2 μm (hence aspect ratio: 20)
To obtain fibrous zonotolite. Hereinafter, this is referred to as "fibrous zonotolite B".

Reference Example 3 The holding temperature of the hydrothermal synthesis reaction was 220 ° C. in Reference Example 1.
A granular fibrous zonotolite was produced in exactly the same manner as in Reference Example 1, except that the temperature was changed to 260 ° C.
Specific surface area: 16 m ² / g, average fiber length: 10 μm and average fiber diameter: 0.2 μm (hence aspect ratio: 5
A fibrous xonotlite of 0) was obtained. Hereinafter, this is referred to as "fibrous zonotolite C".

Reference Example 4 A granular fibrous zonotolite was produced in the same manner as in Reference Example 1 except that a nonionic surfactant as a surface treatment agent was not added, and a BET specific surface area: 39.
m ² / g, average fiber length: 3 μm and average fiber diameter: 0.
A surface-untreated fibrous zonotolite of 2 μm (hence, aspect ratio: 15) was obtained. Hereinafter, this is referred to as "fibrous zonotolite D".

Reference Example 5 A dehydrated cake obtained by the same method as in Reference Example 1 was dried.
After drying, dry without granulating and further dry.
, BET specific surface area: 39m after crushing with impact mill ²/
g, average fiber length: 3 μm and average fiber diameter: 0.2 μm
(Therefore, aspect ratio: 15)
Got Notrite. This is referred to below as "fibrous zonotolite.
"E".

Reference Examples 6 and 7 In Reference Examples 6 and 7, γ-aminopropyltriethoxysilane and γ-glycidoxypropyltrimethoxysilane were used in place of the nonionic surfactant of Reference Example 1, respectively. Except for the above, after granulating the cake-like fibrous zonotolite in the same manner as in Reference Example 1, about 1
By drying at 00 ° C. and further heat treatment at 120 ° C. for 20 minutes, a surface-treated granular fibrous zonotolite was obtained. In both of Reference Examples 6 and 7, the obtained ones had a BET specific surface area of 39 m ² / g and an average fiber length of 3 μm.
And average fiber diameter: 0.2 μm (hence, aspect ratio: 15). Hereinafter, these are referred to as Reference Example 6
And 7 are referred to as "fibrous zonotolite F" and "fibrous zonotolite G", respectively.

Example 1 Using a co-rotating twin-screw extruder (PCM30 manufactured by Ikegai Tekko KK) having a cylinder diameter of φ30 mm, 2
87.5% by weight of nylon 6 (manufactured by Ube Industries, Ltd., trade name: UBE Nylon 1013B) and ionomer at 50 ° C. (however, the same applies to the temperature of the nozzle, hereinafter) using a V-type blender. (Mitsui DuPont Polychemical Co., Ltd., trade name: Himilan 1855) 12.5% by weight, and
Pellets composed of fibrous zonotolite A and 80% by weight and 20% by weight, respectively, melt-kneaded, 70% by weight of the nylon 6, 10% by weight of the ionomer and 20% by weight of the fibrous zonotolite A. Was produced. However, the first using the screw feeder
The fibrous zonotolite A is supplied from the vent port, and the second
Deaeration operation was performed from the vent port. Next, using an injection molding machine (N100 manufactured by Japan Steel Works, Ltd.), the above pellets are injected at a cylinder temperature (however, the temperature of the nozzle head portion, the same applies below) at 260 ° C and a mold temperature of 100 ° C. It shape | molded and produced the physical-property test piece. Table 1 shows the results of the physical property test.

Examples 2 and 3 The same operation as in Example 1 except that fibrous zonotolite B and F were used in place of fibrous zonotolite A in Example 1 in Examples 2 and 3, respectively. I went. The physical property test results of the materials obtained in Examples 2 and 3 are as shown in Table 1.

Comparative Examples 1-3 Comparative Examples 1, 2 and 3 were the same as Example 1 except that fibrous zonotolites C, D and E were used instead of the fibrous zonotolite A of Example 1, respectively. Exactly the same operation was performed. The physical property test results of the materials obtained in Comparative Examples 1 and 2 are shown in Table 1, respectively. Further, in the case of Comparative Example 3 using the fibrous zonotolite E, as shown in Table 1, a uniform kneaded product was not obtained,
Could not be molded.

Example 4 Polypropylene (ethylene / propylene block copolymer) made of nylon 6 (manufactured by Ube Industries, Ltd., trade name: UB)
E Polypro J709HK), the ionomer was replaced with ethylene propylene rubber (manufactured by Nippon Synthetic Rubber Co., Ltd.,
Product name: JSREP07P), the melt-kneading temperature was changed to 250 ° C to 240 ° C, the cylinder temperature of the injection molding machine was changed to 260 ° C to 240 ° C, and the gold of the injection molding machine was changed. The same operation as in Example 1 was performed except that the mold temperature was changed to 100 ° C. and the temperature was changed to 80 ° C. The physical property test results of the obtained material are as shown in Table 1.

Example 5 The same operation as in Example 4 was carried out except that fibrous zonotolite G was used instead of fibrous zonotolite A in Example 4. The physical property test results of the obtained material are as shown in Table 1.

Example 6 By changing the amounts of polypropylene and ethylene propylene rubber used in Example 4, the weight percentage of polypropylene and the weight percentage of ethylene propylene rubber in the resulting pellets were changed from 70% by weight to 10% by weight to 60% by weight, respectively. Except that it was changed to 20% by weight and
The completely same operation as in Example 4 was performed. The physical property test results of the obtained material are as shown in Table 1.

Example 7 By changing the amounts of polypropylene, ethylene propylene rubber and fibrous zonotolite A used in Example 4, the weight percentage of polypropylene, ethylene propylene rubber and fibrous zonotolite A in the obtained pellets was changed to 70%.
50% by weight, 50% by weight and 20% by weight respectively
The same operation as in Example 4 was carried out except that the amounts were changed to 15% by weight, 15% by weight and 35% by weight. The physical property test results of the obtained material are as shown in Table 1.

Comparative Example 4 By changing the amounts of polypropylene and ethylene propylene rubber used in Example 4, the weight percentage of polypropylene and the weight percentage of ethylene propylene rubber in the obtained pellets were changed from 70% by weight to 10% by weight to 77% by weight, respectively. % And 3% by weight, but the same operation as in Example 4 was performed. The physical property test results of the obtained material are as shown in Table 1.

Comparative Example 5 By changing the amounts of polypropylene and ethylene propylene rubber used in Example 4, the weight percentage of polypropylene and the weight percentage of ethylene propylene rubber in the obtained pellets were changed from 70% by weight to 10% by weight to 36% by weight, respectively. % And 44% by weight, but the same operation as in Example 4 was performed. The physical property test results of the obtained material are as shown in Table 1.

Example 8 To an emulsion containing 5 kg of polybutadiene rubber, 1.3 kg of acrylonitrile and 3.8 kg of styrene were added, 20 g of benzoyl peroxide was added, and the mixture was heated to 60 ° C.
Polymerization was carried out for 5 hours with stirring. Then, the polymerization liquid was coagulated with a small amount of sulfuric acid, filtered, washed and dried to obtain an impact-resistant ABS resin. The rubber content of the obtained impact resistant ABS resin is 50.
% By weight, and the average particle diameter of the rubber was 0.3 μm. Therefore, the ABS described above is used instead of the ionomer in Example 1.
Resin was used, and the amounts of nylon 6 and ABS resin were changed, and the weight percentages of nylon 6 and ABS resin in the resulting pellets were changed from 70% by weight and 10% by weight to 60% by weight and 20% by weight, respectively. %
280 by changing the melt-kneading temperature to 250 ° C
C. and Example 1 except that the cylinder temperature of the injection molding machine was changed to 260.degree. C. to 290.degree.
The same operation was performed. Table 1 shows the physical property test results of the obtained materials.

Example 9 SEBS (manufactured by Asahi Kasei Corp., trade name: Tuftec H10)
41) 2.6 parts by weight of glycidyl methacrylate and 0.1 part of t-butylperoxybenzoate per 100 parts by weight.
2 parts by weight were added, and kneading was performed in a nitrogen atmosphere at 260 ° C. for 10 minutes using a Brabender type melt kneader. The obtained kneaded product was pulverized and then washed with acetone to obtain modified SEBS. The modified SEBS has an epoxy group concentration of 7.1 according to the titration method (JIS K7236).
It was × 10 mol / g. Next, nylon 6 to PPS
Resin (manufactured by Ube Industries, Ltd., trade name: UBE PPSNR
-04), the ionomer was replaced with the above modified SEB.
The amount of PPS resin and modified SEBS used was 70% by weight and 10% by weight of the modified SEBS in the resulting pellets.
Change from wt% to 60 wt% and 20 wt% respectively, and change the melt-kneading temperature to 250 ° C.
It was set to 00 ° C, and the cylinder temperature of the injection molding machine was set to 26
The same operation as in Example 1 was performed except that the temperature was changed to 0 ° C. to 300 ° C., and the mold temperature of the injection molding machine was changed to 100 ° C. to 130 ° C. The physical property test results of the obtained material are as shown in Table 1.

[0051]

[Table 1]

Example 10 5 kg of 2,6-dimethylphenol, 54 g of cupric bromide and 63 g of di-n-butylamine-1 were added to 10 liters of toluene, 9 liters of n-butanol and 2.5 liters of methanol. It was dissolved in a mixed solvent and polymerized while stirring at 30 ° C. for 3.5 hours while blowing oxygen, and the precipitated polymer was filtered, a hydrochloric acid / methanol mixture was added to decatalyze, washed with methanol and dried. A polyphenylene ether (PPE) resin was obtained. Its intrinsic viscosity (30 ° C, 0.5 w / v% chloroform solution)
Was 0.4. This polyphenylene ether resin 1
0.5 parts by weight of maleic anhydride was further added to 00 parts by weight, and the mixture was modified at 280 ° C. using a 30 mm single screw extruder to obtain a modified PPE resin. Next, the PPS resin is made of nylon 66 (manufactured by Ube Industries, Ltd., trade name: UBE nylon 2
020B) and the modified PPE resin described above (66% by weight of nylon 66, 50% by weight of modified PPE resin and 10% by weight of modified PPE resin as the weight percentage in the resulting pellets), and the melt-kneading temperature was changed to 300 ° C. to obtain 260. 270 ℃ by changing the cylinder temperature of the injection molding machine to 300 ℃.
And the mold temperature of the injection molding machine was 130 ° C.
The procedure of Example 9 was repeated except that the temperature was changed to 110 ° C. The physical property test results of the obtained material are as shown in Table 2.

[0053]

[Table 2]

Example 11 An ionomer was mixed with ethylene propylene diene rubber (EPD).
M) (manufactured by Japan Synthetic Rubber Co., Ltd., trade name: JSR EP5)
7P) and nylon 6 and EPD
Examples except that the amount of M used was varied such that the weight percentages of nylon 6 and EPDM in the resulting pellets were 70 wt% and 10 wt% to 60 wt% and 20 wt%, respectively. The completely same operation as 1 was performed. The physical property test results of the obtained material are as shown in Table 3.

Example 12 Polypropylene (ethylene / propylene block copolymer) made of nylon 6 (manufactured by Ube Industries, Ltd., trade name: UB)
E Polypro J709HK), Example 11 except that the melt-kneading temperature was changed to 250 ° C. to 240 ° C., and the mold temperature of the injection molding machine was changed to 100 ° C. to 80 ° C. The same operation was performed. The physical property test results of the obtained material are as shown in Table 3.

Example 13 Nylon 6 was replaced with polyacetal resin (manufactured by Polyplastics Co., Ltd., trade name: DURACON M90-01, hereinafter abbreviated as “POM”), and the melt-kneading temperature was 25.
Other than changing the temperature to 0 ° C to 200 ° C, changing the cylinder temperature of the injection molding machine to 260 ° C to 210 ° C, and changing the mold temperature of the injection molding machine to 100 ° C to 95 ° C. The same operation as in Example 11 was performed. The physical property test results of the obtained material are as shown in Table 3.

Example 14 Nylon 6 was changed to polybutylene terephthalate (PBT)
(Ube Industries, Ltd., trade name: UBE PBT 100
0), the ionomer was replaced with the ABS resin obtained by the same operation as in Example 8, and the amounts of PBT and ABS resin used were changed to PBT in the obtained pellet.
And ABS resin weight percentages from 70 wt% and 10 wt% to 60 wt% and 20 wt%, respectively.
The melting and kneading temperature was changed to 250%
Changed to 240 ° C by changing to ℃, changed the cylinder temperature of the injection molding machine to 260 ° C and changed to 270 ° C, and changed the mold temperature of the injection molding machine to 100 ° C and changed to 110 ° C.
Except for the above, the same operation as in Example 1 was performed. The physical property test results of the obtained material are as shown in Table 3.

[0058]

[Table 3]

[0059]

As is apparent from the above Examples and Comparative Examples, the present invention uses a fibrous zonotolite having specific properties to balance impact resistance with strength, rigidity and heat resistance. It is possible to provide a good thermoplastic resin composition. Therefore, the thermoplastic resin composition obtained by the present invention can be used as a material in the fields of automobiles, electric / electronics, precision machines and the like.

Claims (4)

[Claims] 1. A resin composition comprising a thermoplastic resin (A), a rubber or a thermoplastic elastomer or a rubber-modified thermoplastic resin (B), and a fibrous zonotolite (C), The component (C) has a BET specific surface area of 21 m ² / g or more due to (1) nitrogen adsorption,
(2) is surface-treated with a surfactant and / or a coupling agent, and (3) is granulated into granules, and has the formula (I) The weight percentage (wf) of the component (C) in the total composition consisting of the component (A), the component (B), and the component (C) represented by
Furthermore, the mathematical expression (II) The weight percentage (w) of the component (B) in the sum of the weight of the component (A) and the weight of the component (B) represented by
b) is in the range of 5 ≦ wb ≦ 40, which is a thermoplastic resin composition. 2. The fibrous zonotolite (C) comprises (1)
0.1 μm ≦ D <0.5 μm, (2) 1 μm ≦ L <5 μ
m and (3) 10 ≦ L / D <20 (wherein D and L respectively represent the average fiber diameter and the average fiber length of the fibrous zonotolite (C)) are simultaneously satisfied. The thermoplastic resin composition according to. 3. The thermoplastic resin (A) is a polyamide resin,
The thermoplastic resin composition according to claim 1 or 2, which is at least one polymer or polymer mixture selected from the group consisting of polyester resins, polyolefin resins, polyacetal resins, and polyarylene sulfide resins. . 4. The component (B) is ethylene propylene rubber,
Modified with at least one rubber or thermoplastic elastomer or rubber selected from the group consisting of ethylene propylene diene rubber, ionomer, styrene-butadiene-styrene elastomer, styrene-ethylene-butadiene-styrene elastomer and impact resistant ABS resin. The thermoplastic resin composition according to any one of claims 1 to 3, which is a thermoplastic resin.