JPH08170022A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE: To obtain the subject composition, well balanced among mechanical characteristics such as strength and rigidity and heat and impact resistances, having a low anisotropy 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, (B) any polymer of a rubber or a thermoplastic elastomer and a thermoplastic resin modified with the rubber and (C) a nonfibrous filler or a reinforcing fiber. The component (C) has >=21m<2> /g BET specific surface area according to nitrogen adsorption and the surface treated with a surfactant and/or a coupling agent and is granulated into a granular shape. Furthermore, formula I [A], [B], [C] and [D] are respective weights of the components (A), (B), (C) and (D); wf is the sum total of the weight percentages of the components (C) and (D)} is within the range of 5<=wf<=65 and formulas II and III [wb is the weight percentage of the component (B) in the total weight of the components (A) and (B); wc is the weight percentage of the components (C) in the total weight of the components (B) and (C)] are within the ranges of 5<=wb and wc<=70, respectively.

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, and a molded article obtained by using the composition has mechanical properties, heat resistance and impact resistance. It has an excellent balance and a small anisotropy, and can be used as a material in fields such as automobiles, electric / electronics, and precision machinery.

[0002]

2. Description of the Related Art As a method for improving the impact resistance of a thermoplastic resin, a method of blending a polymer such as rubber, a thermoplastic elastomer, or a rubber-modified thermoplastic resin as a modifier (Japanese Patent Application Laid-Open No. 2004-242242). 56-11845
6, JP-A-61-192752, and JP-A-6-192752.
No. 2-68851) is widely known, but it is known that strength, elastic modulus, and heat resistance are reduced by this method.

As a method for solving this problem, a known method has been known in which a reinforcing fiber, a fibrous filler, or a granular or plate-like non-fibrous filler is further compounded therein. However, a method of blending reinforcing fibers (Japanese Patent Laid-Open No. 62-
No. 12745, etc.) has an effect of improving mechanical properties such as strength and elastic modulus and heat resistance, but the resulting molded article has poor appearance and anisotropy. Also, a method of blending a granular or plate-like non-fibrous filler (Japanese Patent Laid-Open No. 25576/1990).
However, it is well known that the above-mentioned improvement effect is small, although the appearance failure and anisotropy are less likely to occur.

Therefore, as one of the methods for solving this problem, a method of combining the above-mentioned non-fibrous filler and fibrous filler (so-called hybrid of filler) (Japanese Patent Laid-Open No. 4-318064, etc.) Or a method of combining a fibrous filler with a reinforcing fiber such as glass fiber or carbon fiber (see Japanese Patent Laid-Open No. 4-288341). Then, as an example of the fibrous filler used for the above purpose, a method using fibrous zonotolite (Japanese Patent Application Laid-Open No. 61-69848, Japanese Patent Application Laid-Open No. 3-69848).
-45652).

However, the conventionally known xonotlite is prone to agglomeration and has poor wettability with thermoplastic resins and the above-mentioned modifiers, so that it has the drawback of low dispersibility in them. For this reason, the above-mentioned expected effects were not sufficiently exhibited even in the composition in which the above-mentioned fibrous zonotolite and the non-fibrous filler or the reinforcing fiber were combined.

[0006]

SUMMARY OF THE INVENTION The object of the present invention is to solve the problems of the above-mentioned conventionally known thermoplastic resins, that is, mechanical properties, heat resistance and impact resistance. It is to provide a thermoplastic resin composition having excellent balance and small anisotropy.

[0007]

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. A fibrous xonotrite having specific properties excellent in dispersibility, a non-fibrous filler or a reinforcing fiber, and a rubber or a thermoplastic elastomer or a thermoplastic resin modified with a rubber, in a specific ratio, the matrix resin By blending with a thermoplastic resin that is, strength, mechanical properties such as elastic modulus, excellent balance of heat resistance and impact resistance, it is possible to provide a thermoplastic resin composition having a small anisotropy, and As a result, they have found that the problems of the above-mentioned conventional techniques can be overcome, and have completed the present invention.

That is, the first invention according to claim 1 is at least one selected from the group consisting of a thermoplastic resin (A), rubber, a thermoplastic elastomer and a thermoplastic resin modified with rubber. And the BET specific surface area by nitrogen adsorption of 21 m ² / g or more,
It is composed of a fibrous zonotolite (C), which is surface-treated with a surfactant and / or a coupling agent, and is granulated into granules, and a non-fibrous filler or a reinforcing fiber (D). Weights of the component (C) and the component (D) in the total composition represented by the component (A), the component (B), the component (C) and the component (D). The sum of percentages (wf) is not less than 5% by weight and not more than 65% by weight, and the formula (I
The weight of the component (A) represented by I) and the weight of the component (B)
The weight percentage (wb) of the component (B) in the sum of the weights of the components is 5% by weight or more and 70% by weight or less, and further, the weight of the component (C) represented by the formula (III). The weight percentage (wc) of the component (C) in the total weight of the component (D) is 5% by weight or more and 70
It can be achieved by providing a thermoplastic resin composition characterized in that it is not more than wt%.

In a second aspect of the present invention, the fibrous zonotolite (C) has 0.1 μm ≦ D <0.5 μm, 1
μm ≦ L <5 μm and 10 ≦ L / D <20 (however,
D and L represent the average fiber diameter and the average fiber length of the fibrous zonotolite (C), respectively. ) Is simultaneously satisfied, it is possible to achieve by providing the thermoplastic resin composition according to the first invention, which is a fibrous zonotolite.

The third invention according to claim 3 is
The first or first thermoplastic resin (A) is at least one polymer or polymer mixture selected from the group consisting of polyolefin resin, polyamide resin, polyester resin, polyacetal resin, polyarylene sulfide resin and ABS resin. The thermoplastic resin composition according to the second aspect of the present invention is the fourth aspect of the fourth aspect, in which the component (B) is a group consisting of ethylene propylene rubber, an olefin elastomer, a styrene elastomer and an impact-resistant ABS resin. The first, which is at least one polymer or polymer mixture selected from
Alternatively, it can be achieved by providing the thermoplastic resin composition according to the second or third invention, 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), which is a matrix resin,
The wettability of the product tends to deteriorate, especially 21m²/ G
With smaller fibrous zonotolite, the tendency is remarkable
Therefore, the object of the present invention cannot be achieved.

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 the fibrous zonotolite is formed into granules, and the thermoplastic resin (A)
And kneading with at least one polymer (B) selected from the group consisting of rubber, a thermoplastic elastomer, and a thermoplastic resin modified with rubber, and a non-fibrous filler or reinforcing fiber (D). At times, the fibrous zonotolite (C) may be broken, and when D is 0.5 μm or more and L is less than 1 μm, the mechanical strength of the resulting thermoplastic resin composition due to the fibrous zonotolite is increased. The improvement effect may not be sufficient. Also, L / D is 10
If it is less than L, the resulting thermoplastic resin composition may not be able to obtain sufficient mechanical strength, and L /
When D is 20 or more, the bulk specific gravity of the fibrous zonotolite (C) becomes too small, and kneading may be difficult during the production of the thermoplastic resin composition of the present invention.

The above-mentioned fibrous zonotolite (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 later, and the rubber, thermoplastic elastomer and rubber-modified heat which are also described later. At least one polymer (B) selected from the group consisting of plastic resins
In order to further enhance the reinforcing effect on a composition comprising a non-fibrous filler or a reinforcing fiber (D), which will be described later, the surface is further treated with a surfactant and / or a coupling agent (hereinafter referred to as a surface treatment agent). It is desirable to be processed by. That is, the surface treatment agent is composed of the organic polymer substance of the fibrous zonotolite (C) that serves as a matrix, that is, the thermoplastic resin (A), rubber, thermoplastic elastomer, and thermoplastic resin modified with rubber. The affinity with at least one or more polymers (B) selected from the group is improved, and its reinforcing effect, that is,
It is used for the purpose of further increasing mechanical strength,
Specifically, the following may 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 xonotlite (C) used in the present invention is selected from the group consisting of the thermoplastic resin (A) described later and the rubber, the thermoplastic elastomer and the rubber-modified thermoplastic resin also described later. Granules are granulated for the purpose of easily mixing and kneading at least one selected polymer (B) and a non-fibrous filler or reinforcing fiber (D), which will be described later. Granular fibrous zonotolite has a diameter of 1 to 8 mm obtained by granulating a cake-like fibrous zonotolite to which the above-mentioned surface treatment agent is attached by a granulator.
It is obtained by molding into granules, drying and further heat treatment when a coupling agent is used as the surface treatment agent. 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 fibrous zonotolite granular molded product obtained by granulation deviates from the above range, a group consisting of a thermoplastic resin (A), rubber, a thermoplastic elastomer and a rubber-modified thermoplastic resin When mixing and kneading with at least one or more polymers (B) selected from the above and the non-fibrous filler or reinforcing fiber (D), it becomes difficult to mix and knead with a single-screw extruder or a twin-screw extruder. It is not preferable because the filler must be successively filled with a roll, Banbury mixer, etc., and mixed and kneaded, and the filler can be remarkably broken and the mechanical strength deteriorates. 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, impact-resistant polystyrene, ABS resin, polyvinyl chloride resin, acrylonitrile-styrene resin, maleic anhydride-styrene resin, Polycaproamide (nylon 6), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66), polyhexamethylene sebacamide (nylon 6)
10), polyhexamethylene dodecanoamide (nylon 612), polyhexamethylene terephthalamide (nylon 6T), polyhexamethylene isophthalamide (nylon 6I), polyundecane amide (nylon 1)
1), polydodecanamide (nylon 12), nylon 6/66, nylon 6/11, nylon 6/12, nylon 6/610, nylon 6/612, nylon 66 /
610, nylon 6/66/610, nylon 6/66
/ 12, Nylon 6 / 6T, Nylon 6 / 6I, Nylon 66 / 6T, Nylon 66 / 6I, Nylon 6/11
/ 6T, nylon 6/12 / 6T, nylon 66/11
/ 6T, nylon 66/12 / 6T, nylon 11/6
Polyamide resins such as T / 6I and nylon 12 / 6T / 6I, polyester resins such as polybutylene terephthalate, polyethylene terephthalate and other aromatic polyesters, polycarbonate resins, polyacetal resins (including homopolymers and copolymers),
Polyphenylene ether, modified polyphenylene ether, 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, Fluororesin such as polychlorotrifluoroethylene, polyvinylidene fluoride and tetrafluoroethylene-hexafluoropropylene-perfluoroalkyl vinyl ether copolymer, and the like, and mixtures of two or more thereof. Among these, the polyolefin resin, polyamide resin, polyester resin, polyacetal resin, polyarylene sulfide resin,
ABS resins and the like, and mixtures of two or more thereof are mentioned as preferred specific examples. Polypropylene homopolymer, polypropylene copolymer (ethylene / propylene block copolymer), ABS resin, nylon 6, nylon 66, nylon 12, nylon 6/66. , Nylon 6/66/12, nylon 66 / 6T, polybutylene terephthalate, polyacetal resin, polyarylene sulfide resin, and the like, and mixtures of two or more thereof are particularly preferred specific examples.

As the rubber (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 (EPD
M), isoprene rubber, butyl rubber, unvulcanized or uncrosslinked rubber such as chlorosulfonated polyethylene, and mixtures of two or more thereof. On the other hand, as the thermoplastic elastomer (B) used in the present invention, polystyrene-based (styrene-butadiene-styrene elastomer (SBS) or styrene-ethylene-butadiene-styrene elastomer (SEBS)), polyurethane-based, olefin-based, polyester-based , Polyamide-based, ethylene-vinyl acetate copolymer, 1,2-polybutadiene, ionomer, ethylene-acrylic acid ester copolymer, thermoplastic elastomer such as vinyl chloride-based,
And mixtures of two or more thereof. Among these, EPR, EPDM, SEBS, SBS, ionomers, etc., and a mixture of two or more kinds thereof are mentioned as preferable examples.

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 and the like, which are produced by polymerization rather than mechanical mixing, and mixtures of two or more thereof are included. Among these, impact resistant ABS resin is mentioned as a particularly preferable example. And in the present invention,
As the component (B), at least one polymer selected from the group consisting of the rubber, the thermoplastic elastomer and the rubber-modified thermoplastic resin described above can be used.

In the present invention, as a combination of the thermoplastic resin (A) and the rubber or the thermoplastic elastomer or the rubber-modified thermoplastic resin (B), a polyamide resin is the component (A). In some cases, EPDM, ionomers, high impact ABS resins, and mixtures thereof, and in the case where the polyester resin is the (A) component, SEBS, SBS, high impact ABS resins, and mixtures thereof, When the polyolefin resin is the component (A), EPR, EPDM, and a mixture thereof, when the polyarylene sulfide resin is the component (A), SEBS, and when the polyacetal resin is the component (A). EPDM if
Is preferably used as the component (B).

The non-fibrous filler (D) used in the present invention means a filler having a granular or plate-like shape. Specifically, wood flakes, iron, copper, silver, gold, aluminum and other flakes or powdered metals, carbon black, graphite, activated carbon, carbon materials such as hollow spheres, silica, alumina, silica-alumina, titanium oxide. , Oxides of iron oxide, zinc oxide, magnesia, calcia, silicates of talc, clay, mica, hydroxides of various metals, carbonates, sulfates, phosphates, borates, borosilicates, Aluminosilicate, titanate, basic sulfate, basic carbonate and other basic salts such as glass hollow spheres,
Examples thereof include glass materials such as glass flakes, ceramics such as silicon carbide, silicon nitride, aluminum nitride, mullite and cordierite, and wastes such as fly ash and micro silica. In the present invention, the above fillers may be used alone, or two or more kinds may be mixed and used.

Further, the reinforcing fiber (D) used in the present invention may be one which is usually used for the purpose of reinforcing the thermoplastic resin, and specifically, glass fiber, carbon fiber or aramid. Other organic polymer fibers such as polyetherketone, liquid crystal polyester and polyimide, silica fibers, alumina fibers, silica-alumina fibers, inorganic fibers such as silicon carbide and silicon nitride, stainless steel, aluminum, magnesium, iron, copper, titanium, brass ,
Examples include metal fibers such as gold and silver. The chopped strands are most suitable as their form, and their typical length is about 1 to 10 mm, preferably about 3 to 6 mm. The reinforcing fibers are not limited to the chopped strands, and rovings, woven fabrics, non-woven fabrics, mats and the like may be used. Further, these reinforcing fibers may be subjected to a known surface treatment such as surface coating treatment with a surface treatment agent such as the above-mentioned surfactant or coupling agent. Further, the above-mentioned reinforcing fibers are usually used alone, but it is also possible to use two or more kinds selected from them in combination.

In the present invention, as the component (D), at least one component selected from the above-mentioned non-fibrous filler or reinforcing fiber can be used.

Further, in the present invention, at least one polymer (B) selected from the group consisting of the above-mentioned thermoplastic resin (A), rubber, thermoplastic elastomer and thermoplastic resin modified with rubber, Various auxiliary materials added for improving the characteristics and production of the composition comprising the fibrous zonotolite (C) and the non-fibrous filler or the reinforcing fiber (D), that is, a heat stabilizer, a light stabilizer, a plasticizer ,
Use of 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 fragrance, etc. is not limited as long as the reinforcing effect of the fibrous zonotolite (C) of the present invention is not hindered. It doesn't matter.

By the way, in the present invention, the thermoplastic resin (A) represented by the formula (I), the rubber,
Heat comprising at least one polymer (B) selected from the group consisting of thermoplastic elastomer and thermoplastic resin modified with rubber, fibrous zonotolite (C) and non-fibrous filler or reinforcing fiber (D) Sum of weight percentages (wf) of fibrous zonotolite (C) and non-fibrous filler or reinforcing fiber (D) in the plastic resin composition
Is required to be 5% by weight or more and 65% by weight or less, preferably 10% by weight or more and 50% by weight or less. When the sum of the weight percentages (wf) is less than 5% by weight, the mechanical strength, heat resistance and molding shrinkage of the resulting thermoplastic resin composition are not improved. On the other hand, if it is more than 65% 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 reliably suppress the occurrence of these undesirable phenomena, the above-mentioned fibrous zonotolite (C) and non-fibrous filler or reinforcing fiber (D) are used.
The sum of the weight percentages (wf) should be in the preferred range mentioned above.

Then, at least one polymer selected from the group consisting of the thermoplastic resin (A) represented by the formula (II), rubber, a thermoplastic elastomer and a rubber-modified thermoplastic resin. Weight percentage (wb) of at least one polymer (B) selected from the group consisting of rubber, thermoplastic elastomer, and rubber-modified thermoplastic resin in both components with (B).
Should be not less than 5% and not more than 70% by weight, preferably not less than 10% and not more than 65% by weight. If the weight percentage (wb) is less than 5% by weight, the impact resistance improving effect is small, and if it is more than 70% by weight, the original characteristics of the thermoplastic resin (A) as the matrix resin are impaired, which is preferable. Absent. The weight percentage (wb) of at least one polymer (B) selected from the group consisting of rubber, a thermoplastic elastomer and a rubber-modified thermoplastic resin is 5% by weight or more and less than 10% by weight and 65% by weight or less.
In the range of more than 70% by weight and less than 70% by weight, the above-mentioned undesirable phenomenon may occur.

Furthermore, the weight percentage of the fibrous zonotolite (C) in both components of the fibrous zonotolite (C) and the non-fibrous filler or the reinforcing fiber (D) represented by the above formula (III) ( wc) is 5% by weight or more 7
It is also necessary to be 0% by weight or less, preferably 10% by weight or more and 65% by weight or less. The weight percentage (wc) is 5
If it is less than wt%, the modifying effect by the fibrous zonotolite (C) is small, and if it is more than 70 wt%, the original features of the non-fibrous filler or the reinforcing fiber (D) are impaired, which is not preferable. The weight percentage (wc) is 5
When the content is not less than 10% by weight and more than 65% and not more than 70% by weight, the above-mentioned unfavorable phenomenon may occur.

Next, the thermoplastic resin composition of the present invention can be manufactured as follows. That is, at least one polymer (B) selected from the group consisting of a thermoplastic resin (A), rubber, a thermoplastic elastomer and a rubber-modified thermoplastic resin, a fibrous zonotolite (C) and a non-fibrous The composition comprising the filler or the reinforcing fiber (D) is manufactured by a known method.
Generally, the predetermined amount of the thermoplastic resin (A)
And at least one polymer (B) selected from the group consisting of rubber, thermoplastic elastomer and rubber-modified thermoplastic resin, and fibrous zonotolite (C)
And the non-fibrous filler or the reinforcing fiber (D) 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 the thermoplastic resin (A) and the rubber-modified thermoplastic resin (B) used, which have a higher melting temperature. 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. It is preferable that the temperature is 110 to 160 ° C. higher than the point, preferably 110 to 140 ° C. higher than the glass transition point of the resin. Melt-kneading temperature is melting point of crystalline resin + 10 ° C or glass transition point of amorphous resin + 110 ° C
If it is lower than the above, the melt viscosity of the resin becomes too high in the kneading machine, and a portion having a temperature below the melting point or glass transition point of the resin is generated, and the resin is solidified during the production, causing a kneading failure. there is a possibility. Further, if the melt-kneading temperature is higher than the melting point of the crystalline resin + 60 ° C. or the glass transition point of the amorphous resin + 160 ° C., the resin is thermally decomposed and deteriorated, which causes coloring and 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 thermoplastic resin (A), rubber,
Melt kneading of at least one polymer (B), fibrous zonotolite (C) and non-fibrous filler or reinforcing fiber (D) selected from the group consisting of thermoplastic elastomer and thermoplastic resin modified with rubber At this time, the addition and mixing order of these components can be arbitrarily selected. For example, the fibrous zonotolite (C) can be used as a thermoplastic resin (A), a rubber, a thermoplastic elastomer and a rubber prior to the melt-kneading. May be supplied to the hopper of the extruder after being mixed with at least one or more polymers (B) selected from the group consisting of thermoplastic resins modified with and non-fibrous fillers or reinforcing fibers (D), Further, the hopper of the extruder is selected from the group consisting of thermoplastic resin (A), rubber, thermoplastic elastomer and rubber-modified thermoplastic resin. Without even one or more polymers (B)
Alternatively, only the non-fibrous filler or the reinforcing fiber (D) may be supplied, and the fibrous zonotolite (C) may be supplied from the middle of the extruder. Alternatively, the hopper of the extruder is
Only at least one polymer (B) selected from the group consisting of thermoplastic resin (A), rubber, thermoplastic elastomer and rubber-modified thermoplastic resin is supplied,
The fibrous zonotolite (C) and the non-fibrous filler or the reinforcing fiber (D) may be fed simultaneously or separately from the middle of the extruder. In addition, when manufacturing the said thermoplastic resin composition, the said various auxiliary materials can also be added simultaneously as needed.

The thermoplastic resin composition of the present invention thus obtained is molded by various known molding methods such as injection molding, extrusion molding, compression molding and blow molding.

[0035]

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 thermoplastic resin composition containing polypropylene resin as a main component, stress 0.45M
The value under Pa was determined.

(4) Anisotropy Using the desired thermoplastic resin composition, the dimension is 100 m in length.
A flat plate of m × width 100 mm × thickness 3 mm was injection-molded and the same condition adjustment as in the above item (1) was performed. The MD (flow direction) and TD (right angle) dimensions of this flat plate were measured using a three-dimensional measuring instrument BX303 manufactured by Mitutoyo Co., Ltd., and the shrinkage rate with respect to the die dimension was determined for each direction. Further, TD / MD, which represents the anisotropy of molding shrinkage, was obtained.

(5) Appearance of molded product The appearance of the flat plate molded in the item (4) was visually observed. In addition, the meaning of the display of the evaluation result of the appearance observation in Table 1 is as follows. Good: The appearance was smooth and excellent. Poor; fibers were protruding from the surface of the molded product, and the appearance was poor due to lack of smoothness.

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) ) 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 A co-rotating twin screw extruder (PCM30 manufactured by Ikegai Tekko Co., Ltd.) having a cylinder diameter of 30 mm was used.
At 50 ° C (however, the same applies to the temperature of the nozzle section below), nylon 6 resin (manufactured by Ube Industries, Ltd., product name: UBE nylon 1013B) and ionomer (manufactured by Mitsui DuPont Polychemical Co., Ltd.) Name: Himilan 1855), fibrous zonotolite A, and glass fiber (chopped strand) (manufactured by Nitto Boseki Co., Ltd., trade name: CS-3PE 956, fiber diameter: 13 μm, fiber length: 3 mm). , The nylon 6 resin is 7
0% by weight, 10% by weight of the ionomer, 13% by weight of the fibrous zonotolite A and 7% by weight of the glass fiber.
Pellets consisting of wt% were prepared. However, using two screw feeders, the fibrous zonotolite A and the glass fiber were respectively supplied from the first vent port of the extruder, and deaeration operation was performed from the second vent port. Next, an injection molding machine (N10 manufactured by Japan Steel Works, Ltd.)
No. 0) was used to injection-mold the above pellets 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. to prepare physical property test pieces and flat plates. Table 1 shows the results of the physical property tests of the obtained material.

Example 2 The same operation as in Example 1 was carried out except that the fibrous zonotolite B obtained in Reference Example 2 was used instead of the fibrous zonotolite A. Table 1 shows the results of the physical property tests of the obtained material.

Comparative Examples 1 to 3 In Comparative Examples 1, 2 and 3, the fibrous zonotolite A was used.
The same operation as in Example 1 was carried out except that the fibrous zonotolites C, D and E obtained in Reference Examples 3, 4 and 5 were used instead of, respectively. 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 and molding could not be performed.

Example 3 Example 1 was repeated except that the fibrous zonotolite F obtained in Reference Example 6 was used in place of the fibrous zonotolite A.
The same operation was performed. Table 1 shows the results of the physical property tests of the obtained material.

Comparative Example 4 By changing the amounts of the fibrous zonotolite A and the glass fiber used in Example 1, the weight percentage of the fibrous zonotolite A and the glass fiber in the obtained pellet was 13% by weight.
And 7% to 0% and 20% respectively
The same operation as in Example 1 was performed except that the procedure was changed to. The physical property test results of the obtained material are as shown in Table 1.

[0053]

[Table 1]

Example 4 Polypropylene resin (ethylene / propylene block copolymer) in place of nylon 6 resin (Ube Industries, Ltd.)
Manufactured by UBE Polypro J709HK), ethylene propylene rubber (manufactured by Japan Synthetic Rubber Co., Ltd., trade name: JSR EP07) in place of the ionomer.
P), talc (manufactured by Hayashi Kasei Co., Ltd., trade name: talcan powder PK-C, average particle size: 11 μm) was used in place of the glass fiber, and the melt-kneading temperature was 2
Other than changing to 50 ° C to 230 ° C, changing the cylinder temperature of the injection molding machine to 260 ° C to 230 ° C, and changing the mold temperature of the injection molding machine from 100 ° C to 80 ° C. The same operation as in Example 1 was performed.
The physical property test results of the obtained material are as shown in Table 2.

Example 5 Example 4 was repeated except that the fibrous zonotolite G obtained in Reference Example 7 was used in place of the fibrous zonotolite A.
The same operation was performed. Table 2 shows the results of the physical property test of the obtained material.

Example 6 The polypropylene resin, the fibrous zonotolite A and the talc in Example 4 were used in various amounts, and the weight percentages of the polypropylene resin, the fibrous zonotolite A and the talc in the obtained pellets were 70% by weight and 7% by weight, respectively. % And 1
3 wt% to 45 wt%, 25 wt% and 2 respectively
Except for changing to 0% by weight, the same operation as in Example 4 was performed. The physical property test results of the obtained material are as shown in Table 2.

Comparative Example 5 By changing the amounts of fibrous zonotolite A and talc used in Example 4, the weight percentages of fibrous zonotolite A and talc in the resulting pellets were 7% by weight and 13% by weight.
The same operation as in Example 4 was performed except that the weight% was changed to 0% and 20% by weight, respectively. The physical property test results of the obtained material are as shown in Table 2.

Comparative Example 6 By changing the amounts of fibrous zonotolite A and talc used in Example 4, the weight percentages of fibrous zonotolite A and talc in the resulting pellets were 7% by weight and 13% by weight.
Except for changing from 20% by weight to 0% by weight and 0% by weight respectively, the same operation as in Example 4 was performed. The physical property test results of the obtained material are as shown in Table 2.

Example 7 By changing the amounts of polypropylene resin and ethylene propylene rubber used in Example 4, the weight percentages of polypropylene resin and ethylene propylene rubber in the resulting pellets were changed from 70% by weight to 10% by weight to 6%, respectively.
Except for changing to 0% by weight and 20% by weight, the same operation as in Example 4 was performed. The physical property test results of the obtained material are as shown in Table 2.

Comparative Example 7 By changing the amounts of polypropylene resin and ethylene propylene rubber used in Example 4, the weight percentages of polypropylene resin and ethylene propylene rubber in the obtained pellets were changed from 70% by weight to 10% by weight to 7% by weight, respectively.
Example 4 except for changing to 7 wt% and 3 wt%
The same operation was performed. The physical property test results of the obtained material are as shown in Table 2.

Comparative Example 8 By changing the amounts of polypropylene resin and ethylene propylene rubber used in Example 4, the weight percentages of polypropylene resin and ethylene propylene rubber in the obtained pellets were changed from 70% by weight to 10% by weight to 3%, respectively.
The same operation as in Example 4 was performed except that the amounts were changed to 6% by weight and 44% by weight. The physical property test results of the obtained material are as shown in Table 2.

[0062]

[Table 2]

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 obtained polymerization liquid is coagulated with a small amount of sulfuric acid, filtered, washed, and dried to obtain impact resistance AB.
S resin was obtained. The rubber content of the obtained impact resistant ABS resin was 50% by weight, and the average particle diameter of the rubber was 0.3 μm. Therefore, the impact-resistant ABS resin was used in place of the ionomer in Example 1, and glass beads (manufactured by Toshiba Ballotini Co., Ltd., trade name: GB210A, average particle size: 17 μm) were used in place of the glass fibers. The same operation as in Example 1 was performed except that the melt-kneading temperature was changed from 250 ° C. to 280 ° C., and the cylinder temperature of the injection molding machine was changed from 260 ° C. to 290 ° C. The physical property test results of the obtained material are as shown in Table 3.

Example 9 2.6 parts by weight of glycidyl methacrylate and t-butylperoxy were added to 100 parts by weight of styrene-ethylene-butadiene-styrene elastomer (SEBS) (manufactured by Asahi Kasei Corporation, trade name: Tuftec H1041). 0.2 parts by weight of benzoate was 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 a modified SEBS thermoplastic elastomer. A modified method of the modified SEBS thermoplastic elastomer (JIS
Epoxy group concentration according to K7236) is 7.1 x 10 m
It was ol / g. Next, a polyarylene sulfide resin (manufactured by Ube Industries, Ltd., trade name: UBE PPS NR-04) was used in place of the nylon 6 resin, and the modified SEBS thermoplastic elastomer was used in place of the ionomer. Mica in place of glass fiber (manufactured by Kuraray Co., Ltd., trade name: Szolite Mica 200)
-KI, average particle size: 90 μm), the melt-kneading temperature was changed from 250 ° C to 300 ° C, the cylinder temperature of the injection molding machine was changed to 260 ° C to 300 ° C, and the injection molding was performed. The same operation as in Example 1 was performed except that the mold temperature of the machine was changed to 100 ° C. to 130 ° C. The physical property test results of the obtained material are as shown in Table 3.

[0065]

[Table 3]

[0066]

As is apparent from the above Examples and Comparative Examples, the present invention comprises a group consisting of fibrous zonotolite having a specific property, rubber, a thermoplastic elastomer and a rubber-modified thermoplastic resin. By using at least one selected polymer and a non-fibrous filler or reinforcing fiber, mechanical properties such as strength and rigidity, heat resistance, and impact resistance are excellently balanced, and A thermoplastic resin composition having small anisotropy can be provided. 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 thermoplastic resin (A), at least one polymer (B) selected from the group consisting of rubber, a thermoplastic elastomer and a rubber-modified thermoplastic resin, and a fibrous xonotlite (C). And a non-fibrous filler or a reinforcing fiber (D), wherein the component (C) is (1) BE by nitrogen adsorption.
T specific surface area is 21 m ² / g or more, (2) is surface-treated with a surfactant and / or a coupling agent, and (3) is granulated into granules, and the formula (I) Number 1] Of the weight percentage of the component (C) and the component (D) in the total composition represented by the component (A), the component (B), the component (C) and the component (D). The sum (wf) is in the range of 5 ≦ wf ≦ 65, and the formula (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 ≦ 70, and also the formula (III) The weight percentage (w) of the component (C) in the sum of the weight of the component (C) and the weight of the component (D) represented by
The thermoplastic resin composition is characterized in that c) is in the range of 5 ≦ wc ≦ 70. 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 polyolefin resin, a polyamide resin, a polyester resin, a polyacetal resin, a polyarylene sulfide resin or AB.
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 S resins. 4. The component (B) is at least one polymer or polymer mixture selected from the group consisting of ethylene propylene rubber, olefin elastomers, styrene elastomers and impact resistant ABS resins. The thermoplastic resin composition according to any one of claims 1 to 3.