JPH07216133A - Reinforced organic polymer composition - Google Patents

Abstract

PURPOSE:To obtain a composite material of an org. polymer material which has high strengths and stiffness, a good balance between heat resistance and impact resistance, and an excellent surface smoothness. CONSTITUTION:This polymer compsn. has a BET specific surface area by nitrogen adsorption of 21m<2>/g or higher, pref. 30m<2>/g or higher, and the surface treated with a surfactant and/or a coupling agent, and comprises a fibrous xonotlite in the form of granules and an org. polymer material.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an organic polymer composition reinforced with a fibrous inorganic filler. This molded product is lightweight, has high strength, high elastic modulus, high heat resistance, and has excellent surface smoothness.
It can be used as a material for electronics, civil engineering, precision machinery, etc.

[0002]

2. Description of the Related Art Conventionally, a fibrous inorganic substance is mixed with an organic polymer substance for the purpose of improving the rigidity, strength, heat resistance, molding shrinkage, dimensional stability, etc. of the organic polymer substance. It is widely practiced. One of them is fibrous zonotolite, which is well known as a reinforcing material for resins and rubbers (JP-A-48-19498, JP-A-50-52145, and JP-A-53-30).
499, JP-A-53-33245, etc.). However, the conventionally known fibrous xonotlite is poorly dispersed in the matrix because it is easily aggregated, and the wettability with the organic polymer substance serving as the matrix is not sufficient, and as a result, the resulting composite material is , I could not show the expected physical properties.

Further, in order to improve it, attempts have been made to treat the surface of the fibrous zonotolite with a coupling agent or the like (Japanese Patent Laid-Open Nos. 158647/50 and 158647/1993).
0-158648, JP-A-51-7055, JP-A-4-108855, etc.), but no satisfactory effect is obtained.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a fibrous zonotolite / organic polymer composite material which has significantly improved wettability with an organic polymer material and which has physical properties far superior to those of conventional materials. Is what you are trying to do.

[0005]

DISCLOSURE OF THE INVENTION The inventors of the present invention have made extensive studies as to solving the above-mentioned problems of the prior art, and as a result, by using a fibrous zonotolite having a specific property, that is, By using a fibrous zonotolite which has a specific surface area and which has been surface-treated and wholly granulated into granules,
They found that they could be overcome, and completed the present invention.

That is, according to the present invention, BE by nitrogen adsorption is used.
T specific surface area is 21 m ² / g or more, the surface of which is treated with a surfactant and / or a coupling agent, and is composed of fibrous zonotolite granulated and an organic polymer substance It is an object of the present invention to solve the above-mentioned problems by providing a reinforced organic polymer composition, that is, a fibrous xonotlite / organic polymer composite material.

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 21m²Fibrous Zonotry smaller than / g
In this case, the wettability with organic polymer substances is poor, and
Cannot achieve the target.

Further, in the present invention, the shape of the fiber 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. If D is less than 0.1 μm or L is 5 μm or more, the fibrous xonotlite may be broken during granulation or mixing / kneading with an organic polymer substance, and D is 0.5 μm or more. And L is less than 1 μm, the effect of improving the mechanical strength of the composite material by the fibrous zonotolite may not be sufficient. In addition, when L / D is less than 10, the resulting composite material may not be able to obtain sufficient mechanical strength, and when L / D is 20 or more, the bulk of the fibrous xonotlite may be obtained. The specific gravity may become too small, and it may be difficult to knead when producing a composite material.

The above-mentioned fibrous zonotolite of the present invention is
As described in detail below, it is produced by the production method described in Japanese Patent Application No. 5-190336, that is, a calcareous raw material and a siliceous raw material are blended at a specific ratio by a hydrothermal synthesis reaction.

Examples of calcareous raw materials include quick lime and slaked lime, and those with few impurities are preferable. Further, as the siliceous raw material, crushed products of silica stone, silica sand and quartz,
Silicic acid, silicic acid anhydride, 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. The proportion of water to be mixed is 5 to 40 times, preferably 8 times the total amount of calcareous raw material and siliceous raw material.
It is desirable to be 30 times.

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 the reaction time are important factors, and fibrous xonotlite having a specific surface area used in the present invention cannot be obtained outside the above range.

In the present invention, the fibrous xonotlite obtained by the above-mentioned production method further has a surface and a surfactant and / or a coupling agent in order to further enhance the reinforcing effect on the organic polymer substance described later. (Hereinafter referred to as a surface treatment agent). That is, the surface-treating agent is used for the purpose of improving the affinity of the fibrous zonotolite with the organic polymer substance serving as the matrix and reinforcing the effect thereof, that is, the 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 is 0.1 to 10% by weight based on the fibrous zonotolite (dry matter basis).
It should preferably be 0.5 to 8% by weight. 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 the present invention, the fibrous zonotolite slurry obtained by the hydrothermal synthesis reaction is extracted from the autoclave and the surface treatment of the fibrous zonotolite is performed.
The surface treatment method is not particularly limited. For example, the fibrous xonotlite slurry is added as it is or after adding an appropriate amount of water, the surface treating agent is added, 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 used in the present invention is granulated for the purpose of easily mixing and kneading with an organic polymer substance described later. Granular fibrous zonotolite is obtained by molding cake-shaped fibrous zonotolite with the surface treatment agent attached thereto into a granule having a diameter of 1 to 8 mm by a granulator, drying and coupling as the surface treatment agent. When the agent is used, it can be obtained by further heat treatment. In this case, as the granulator,
It is not particularly limited, and it is possible to use a known granulator such as a rotary vertical granulator, a rotary drum granulator, a rotary surface granulator, a screw extrusion granulator, a roll extrusion granulator. it can. When the diameter of the granular molded article of fibrous zonotolite obtained by granulation deviates from the above range, when mixing and kneading with the organic polymer substance, mixing and kneading with a single-screw extruder or a twin-screw extruder is performed. Is difficult to be obtained, and it is necessary to carry out mixing and kneading sequentially by filling with a roll or a Banbury mixer etc., and the fibers may be remarkably broken to lower the mechanical strength, which is not preferable. The drying is performed at a temperature of 100 to 150 ° C. for 20 to 20 ° C. by using a known dryer such as a hot air circulation type dryer and an infrared heating type dryer.
The water content of granular fibrous zonotolite is 1 over 30 hours.
It is preferable to perform the treatment to the extent of not more than wt%. Furthermore, the heat treatment when a coupling agent is used is the same as the above 1
It is preferable to carry out drying of water under heating at 00 to 150 ° C. for 20 to 30 hours, followed by drying. 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 organic polymer substance described in the present invention is a well-known organic polymer substance containing a thermoplastic resin, a thermosetting resin and a rubber elastomer. The fibrous zonotolite used in the present invention is 6
Since it is a substance having a decomposition temperature of 80 to 700 ° C. (however, in air), an organic polymer substance having a high melting temperature can also be suitably used. As the thermoplastic resin, a polyolefin resin, a polystyrene resin,
Examples thereof include polyamide resin, polyester resin, polyether resin, polysulfone resin, polyphenylene sulfide resin, polyimide resin, and fluorine resin. Further, a thermoplastic resin obtained by mixing two or more kinds of these thermoplastic resins, a copolymer of monomer components of these thermoplastic resins, and a polymer alloy containing these thermoplastic resins as components are included.

Specific examples of the above thermoplastic resin include polyethylene having various densities and molecular weights, linear low density polyethylene, polypropylene homopolymer, polypropylene copolymer, modified polypropylene, polybutene-1, poly-4-methylpentene. -1, polyvinyl alcohol copolymer, polystyrene, impact resistant polystyrene, ABS resin, polyvinyl chloride resin, acrylonitrile-styrene resin, maleic anhydride-styrene resin, nylon 6, nylon 66, nylon 11, nylon 1
2. Nylon containing aromatic, nylon 612, nylon 46, polybutylene terephthalate, polyethylene terephthalate, polycarbonate, other aromatic polyester, polyacetal resin (including homopolymer and copolymer), modified polyphenylene oxide, polyether ether ketone, polysulfone , Polyethersulfone, polyphenylene sulfide, polyetherimide, thermoplastic polyimide, thermoplastic polyamideimide, polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene -Perfluoroalkyl vinyl ether copolymer,
Examples include polychlorotrifluoroethylene, polyvinylidene fluoride, and tetrafluoroethylene-hexafluoropropylene-perfluoroalkyl vinyl ether copolymer.

Examples of the thermosetting resin include unsaturated polyester resin, epoxy resin, phenol resin, urea resin, diallyl phthalate resin, melamine resin, thermosetting polyimide resin, thermosetting polyamideimide resin, polyurethane resin, silicone resin. One or more selected from thermosetting resins such as

As the rubber / elastomer, natural rubber, fluorine rubber, silicone rubber, acrylic rubber, styrene-butadiene rubber, butadiene rubber, chloroprene rubber, nitrile rubber, ethylene propylene rubber, isoprene rubber, butyl rubber, chlorosulfonated polyethylene. Such as rubber and polystyrene, polyurethane, olefin, polyester, polyamide, ethylene-vinyl acetate copolymer, 1,2-polybutadiene, ionomer, ethylene-acrylic acid ester copolymer, vinyl chloride Examples thereof include plastic elastomers.

It goes without saying that a combination of the above three is also possible. For example, a rubber / elastomer may be added to a thermoplastic resin or a thermosetting resin for the purpose of improving impact resistance, or a blend of a thermoplastic resin / thermosetting resin may be performed.

Further, various auxiliary materials added to improve the characteristics and production of the organic polymer substance, that is, heat stabilizers, light stabilizers, plasticizers, cross-linking agents, antioxidants, flame retardants, strengthening agents. Agents, pigments, dyes, lubricants, antistatic agents, release agents,
Fragrances and other fillers such as whiskers such as wood flour, pulp as an organic substance and iron, copper, silver, gold, aluminum as an inorganic substance, flakes, fibers or powder metal, carbon black, graphite, carbon fiber, activated carbon , Including carbon materials such as hollow spheres, silica, alumina, titanium oxide, iron oxide, zinc oxide, magnesia, calcia, potassium titanate, various ferrites and basic magnesium sulfate, basic magnesium carbonate and other complex oxides Silicates such as oxides, talc, clay, mica, asbestos, rock wool and zinc silicate, hydroxides of various metals, carbonates, sulfates, phosphates, borates, borosilicates, aluminosilicates, Titanate, basic sulfate,
Glass materials such as glass fiber, glass hollow spheres, glass flakes, etc., such as basic carbonates and other basic salts,
When the fibrous zonotolite of the present invention is used in combination with ceramics such as silicon carbide, silicon nitride, aluminum nitride, mullite, cordierite, waste such as fly ash and microsilica, etc., the reinforcing effect of the fibrous zonotolite of the present invention is also obtained. Unless hindered, there is no problem.

In the present invention, the content of the fibrous zonotolite in the composition of the fibrous zonotolite and the thermoplastic resin or the rubber elastomer is 5 to 75% by weight, preferably 10 to 50% by weight. If the content is less than 5% by weight, the mechanical strength and rigidity of the molded product will not be improved. Further, if the content exceeds 75% by weight, kneading and molding become difficult, which is not preferable. on the other hand,
The content of the fibrous zonotolite in the composition of the fibrous zonotolite and the thermosetting resin is 5 to 96% by weight, preferably 10 to 70% by weight. If the content is less than 5% by weight, the mechanical strength and rigidity of the molded product will not be improved. On the other hand, if the content exceeds 96% by weight, it becomes difficult to mix, knead, and mold, and the strength of the molded product decreases, which is not preferable.

By the way, the composition of the fibrous xonotlite of the present invention and the organic polymer substance can be produced as follows. That is, the composition of fibrous zonotolite and thermoplastic resin is produced by a known method.
For example, the predetermined amount of the fibrous zonotolite and the thermoplastic resin are melt-kneaded using an extruder to form pellets of the composition. At this time, in the case of a crystalline thermoplastic resin, the melt-kneading 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 the amorphous In the case of a thermoplastic resin, the temperature is 110 to 160 ° C. higher than the glass transition point of the resin, preferably 110 to 140 ° C. higher than the glass transition point of the resin. Melt kneading temperature + melting point of crystalline resin
When the temperature is lower than 10 ° C or the glass transition point of the amorphous resin + 110 ° C, the melt viscosity of the thermoplastic resin becomes too high in the extruder, and a portion having a temperature below the melting point or glass transition point of the thermoplastic resin is generated. If it occurs, the thermoplastic resin may be solidified during manufacturing, which may cause ejection failure. In addition, the melt-kneading temperature is the melting point of the crystalline resin +
If the temperature is higher than 60 ° C. or the glass transition point of the amorphous resin + 160 ° C., thermal decomposition or thermal deterioration of the thermoplastic resin occurs, resulting in coloring or deterioration of physical properties, which is not preferable. Examples of the extruder include a screw type extruder such as a single screw extruder and a twin screw extruder, an elastic extruder, a hydrodynamic extruder, a ram type continuous extruder, and a gear type extruder. However, among these, a screw type extruder is preferable, and a twin screw extruder is particularly preferable. Furthermore, the addition and mixing order of these components at the time of melt-kneading the fibrous zonotolite and the thermoplastic resin can be arbitrarily selected. After that, it may be supplied to the hopper of the extruder, or only the thermoplastic resin may be supplied to the hopper of the extruder and the fibrous zonotolite may be supplied 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. Furthermore, it is also possible to use a so-called reactive molding, in which a polymer precursor such as a monomer or an oligomer and fibrous zonotolite are mixed and then polymerized and molded. Examples are reaction injection molding (RIM) and reaction extrusion molding. Representative examples of the monomer to which reactive processing can be applied in the production of the composition of the fibrous xonotlite and the thermoplastic resin of the present invention include lactams and methyl methacrylate.

Next, the composition of the fibrous zonotolite and the thermosetting resin is added with the above-mentioned auxiliary materials in addition to the curing agent, the curing catalyst and the curing accelerator, if necessary, and a mixer, a kneader, a roll, etc. Well mixed or kneaded, then compression molding, transfer molding, injection molding, RIM,
It is manufactured by molding by a method such as casting. In the present invention, the curing agent, the curing catalyst and the curing accelerator used for producing the composition of the fibrous zonotolite and the thermosetting resin are different depending on the type of the thermosetting resin and are not limited, but, for example, In the case of an unsaturated polyester resin, it is cured by a curing catalyst such as an organic peroxide or a combination thereof with a curing accelerator such as a cobalt-based or tertiary amine, and in the case of an epoxy resin, an aliphatic amine, Using a curing agent such as aromatic amine, organic acid anhydride, polyamide, phenol, BF ₃ · monomethylamine complex compound, in the case of a resol type phenol resin, it is cured only by pressurizing and heating. In such a case, a known method such as using a hexamethylenetetramine curing agent can be used. Optimal curing agent may be used a curing catalyst and a curing aid in accordance with the kind.

The composition comprising the rubber / elastomer and the fibrous zonotolite may be added with a crosslinking agent and a crosslinking aid, if necessary, in addition to the above-mentioned auxiliary materials, and then used in a Banbury mixer, a roll, a twin-screw kneading extruder or the like. After kneading,
It is produced by molding with a calender, an extruder or the like, and further by crosslinking using a press or the like. In the case of a thermoplastic elastomer that does not require a special crosslinking step, direct injection molding can be performed. In addition,
Preferred examples of the crosslinking agent include sulfur, sulfur-containing organic compounds (so-called vulcanizing agents), and non-sulfur crosslinking agents such as peroxides, metal oxides, polyfunctional amines, quinonedioximes, and azo compounds. be able to. Also,
The cross-linking aid is used particularly in the case of peroxide cross-linking, and polyfunctional monomers such as triallyl cyanurate, triallyl isocyanurate, divinylbenzene, and trimethylolpropane trimethacrylate are preferred.

[0026]

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. The methods for evaluating the physical properties of molded articles described in Examples and Comparative Examples were performed according to the following methods.

(1) Tensile Properties and Bending Properties It was measured using Tensilon UTM-5T manufactured by Orientec Co., Ltd. After molding a desired composition of fibrous xonotlite and organic polymer, condition the mixture at 23 ° C. and 50% relative humidity (hereinafter abbreviated as “50% RH”, but only in nylon in a desiccator) for 48 hours. did. And
The tensile properties such as tensile strength and tensile elastic modulus and the bending properties such as bending strength and bending elastic modulus are measured by AS.
23 according to TM D638 and ASTM D790
℃, 50% RH (However, in the case of nylon, it is absolutely dry)
I went to.

(2) Izod impact strength or Charpy impact strength It was measured using an Izod or Charpy impact tester manufactured by Toyo Seiki Co., Ltd. Then, using a test piece subjected to the same condition adjustment as in (1) above, according to ASTM D256, the notched Izod or Charpy impact strength was determined under the same temperature and humidity conditions as in (1) above.

(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 1.81 MPa was determined according to ASTM D648.

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 Co., Ltd., Blaine specific surface area 7,000 cm ² / g, SiO ₂ purity 97%) 470
g, and 18 liters of tap water were put into an autoclave with an internal volume of 30 liter and made of SUS316 equipped with a stirrer. Then, while stirring at a rotation speed of 80 rpm, the holding temperature 22
The temperature was raised to 0 ° C. at a rate of 2 ° C./minute, the temperature was maintained at 220 ° C. for 5 hours to carry out the hydrothermal synthesis reaction, and the mixture was allowed to cool for 10 hours or longer with stirring to give a fibrous zonotolite slurry. Obtained. 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 Nimine 2) were used.
04) 46 g (5% by weight with respect to the fibrous zonotolite solid content) was added, and surface treatment was performed while dispersing with a homogenizer. After dewatering this slurry with a nutche to form a cake, it is molded into a diameter of 3 mm with a granulator,
The surface-treated granular fibrous zonotolite was obtained by drying at ℃. The BET specific surface area of the granular fibrous zonotolite was measured by nitrogen adsorption, and the average fiber length and the average fiber diameter were measured by a scanning electron micrograph. The results were 39 m ² / g, respectively.
3 μm and 0.2 μm (hence aspect ratio 15). The fibrous zonotolite obtained there,
It is referred to as "fibrous zonotolite A".

Reference Example 2 The holding temperature of the hydrothermal synthesis reaction was 220 ° C. in Reference Example 1.
Except that the temperature was changed to 240 ° C., the granular fibrous zonotolite was produced in the same manner as in Reference Example 1, and BET was used.
A fibrous zonotolite having a specific surface area of 24 m ² / g, an average fiber length of 4 μm and an average fiber diameter of 0.2 μm (hence, an aspect ratio of 20) was obtained. 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.
Except that the temperature was changed to 260 ° C., and granular fibrous zonotolite was produced in the same manner as in Reference Example 1, and BET
A fibrous zonotolite having a specific surface area of 16 m ² / g, an average fiber length of 10 μm and an average fiber diameter of 0.2 μm (hence, an aspect ratio of 50) 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 of 39 m.
² / g, average fiber length 3 μm and average fiber diameter 0.2 μm
A surface-untreated fibrous zonotolite having an aspect ratio of 15 was thus 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, then dried without molding by a granulator, and further crushed by an impact mill to have a BET specific surface area of 39 m ² / g, an average fiber length of 3 μm and an average fiber diameter of 0.2 μm (thus an aspect ratio of 15) were obtained as ungranular fibrous zonotolite. Hereinafter, this is referred to as "fibrous zonotolite E".

Reference Examples 6 and 7 In Reference Examples 6 and 7, γ-aminopropyltriethoxysilane and γ-glycidoxypropyltrimethoxysilane were used instead 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. The obtained product has a BET specific surface area of 39 m ^2.
/ G, average fiber length 3 μm and average fiber diameter 0.2 μ
m (hence aspect ratio 15). Hereinafter, these are referred to as “fibrous zonotolite F” and “fibrous zonotolite G” for Reference Examples 6 and 7, 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.
Nylon 6 (manufactured by Ube Industries, Ltd., trade name U) at 0 ° C (however, the same applies to the temperature of the nozzle)
80 parts by weight of BE nylon 1013B) and 20 parts by weight of fibrous zonotolite A were melt-kneaded to prepare pellets. However, using a screw feeder, the fibrous zonotolite A was supplied from the first vent port and the deaeration operation was performed from the second vent port. Next, using an injection molding machine (NESTAL C250 manufactured by Sumitomo Heavy Industries, Ltd.), the pellets were prepared at a cylinder temperature (however, the temperature of the nozzle head portion, the same applies below) at 275 ° C. and a mold temperature of 80 ° C. Was injection-molded to prepare a physical property test piece. As a result of a physical property test, the tensile strength of this material was 115 MPa. Table 1 also shows other physical properties.

Example 2 The tensile strength of the material obtained by the same method as in Example 1 was 112 MPa except that the fibrous zonotolite B was used in place of the fibrous zonotolite A in Example 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. As a result, fibrous zonotolite C
The tensile strengths of the materials obtained with and D were 84 MPa and 81 MPa, respectively. Further, when fibrous zonotolite E was used, a uniform kneaded product could not be obtained and molding could not be performed.

Examples 3 to 5 In Examples 3, 4 and 5, the blending ratio (weight ratio) of nylon 6 and fibrous zonotolite A was 8 of Example 1.
0/20 to 90/10, 70/30 and 6 respectively
Except for changing to 0/40, the same operation as in Example 1 was performed. The physical property test results of the obtained material are as shown in Table 1.

Example 6 The same operation as in Example 1 was carried out except that fibrous zonotolite F was used in place of fibrous zonotolite A in Example 1. Table 1 shows the physical property test results of the obtained materials.

Example 7 Nylon 66 (manufactured by Ube Industries, Ltd., in place of Nylon 6;
The product name UBE nylon 2020B) was used, the kneading temperature was changed to 250 ° C. to 280 ° C., and the injection molding machine cylinder temperature was changed to 275 ° C. to 285 ° 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 1.

Example 8 The same operation as in Example 7 was carried out except that fibrous zonotolite G was used instead of fibrous zonotolite A in Example 7. Table 1 shows the physical property test results of the obtained materials.

Example 9 Polybutylene terephthalate (manufactured by Ube Industries, Ltd., trade name UBE PBT 1000F) was used in place of nylon 6, the kneading temperature was changed to 250 ° C. and 270 ° C., and the mold was used. The same operation as in Example 1 was performed except that the temperature was changed to 80 ° C. and the temperature was changed to 70 ° C. The physical property test results of the obtained material are as shown in Table 1.

Example 10 A modified polyphenylene oxide (manufactured by Engineering Plastics Co., Ltd., trade name Noryl 731J) was used in place of nylon 6, the kneading temperature was changed to 250 ° C. and 280 ° C., and injection was performed. Molding machine cylinder temperature is 2
The same operation as in Example 1 was performed except that the temperature was changed to 75 ° C. to 280 ° C., and the mold temperature was changed to 80 ° C. to 90 ° C. The physical property test results of the obtained material are as shown in Table 1.

Example 11 Polyacetal copolymer (manufactured by Mitsubishi Gas Chemical Co., Inc., trade name Iupital F20-13) was used in place of nylon 6, the kneading temperature was changed to 250 ° C. and 210 ° C., and injection was performed. Except for changing the cylinder temperature of the molding machine to 210 ° C. instead of 275 ° C., the same operation as in Example 1 was performed. The physical property test results of the obtained material are shown in Table 1.
It was as shown in.

Example 12 A crystalline ethylene / propylene block copolymer (manufactured by Ube Industries, Ltd., trade name UBE Polypro J703H) was used in place of nylon 6, and the kneading temperature was changed from 250 ° C. to 210 ° C. Example 1 except that the injection molding machine cylinder temperature was changed to 275 ° C. to 220 ° C. and the mold temperature was changed to 80 ° C. to 60 ° C.
The same operation was performed. The physical property test results of the obtained material are as shown in Table 1.

[0048]

[Table 1]

Example 13 Using two rolls having a diameter of 10 inches, phenol novolac resin: 42.5 parts by weight, curing agent (hexamethylenetetramine): 6.5 parts by weight, curing aid [Ca (O
H) ₂ ]: 4 parts by weight, fibrous zonotolite A: 40 parts by weight, plasticizer (furfural / water): 3 parts by weight (furfural: 1 part by weight, water: 2 parts by weight) and mold release agent (zinc stearate) ): 1.2 parts by weight were kneaded at 150 ° C. to obtain a phenol resin composition. Then, using a thermosetting injection molding machine (IR-80AM manufactured by Toshiba Machine Co., Ltd.), the composition was molded at a cylinder temperature of 95 ° C. and a mold temperature of 175 ° C. to prepare a physical property test piece. As a result of a physical property test, this material was found to have a bending strength of 148 MPa, a Charpy impact strength of 4.0 KPa · m and a deflection temperature under load of 167.
° C.

Example 14 Nylon 12 type elastomer (manufactured by Ube Industries, Ltd., trade name UBE Polyamide Elastomer P) in place of Nylon 6
AE1200) was used, the kneading temperature was changed to 250 ° C. to 190 ° C., and the injection molding machine cylinder temperature was changed to 275 ° C. to 210 ° C.
A physical property test piece was prepared in exactly the same manner as in Example 1. As a result of a physical property test, this material showed a bending strength of 10 MPa and a bending elastic modulus of 320 MPa.

Example 15 RIM nylon 6 raw material (trade name: UB, manufactured by Ube Industries, Ltd.)
E Nylon RIM General type UX-A) 75 parts by weight of 25 parts by weight of fibrous zonotolite F is mixed, and RIM for high temperature is used.
RIM molding was performed using a molding machine. The molding conditions were a raw material tank temperature of 130 ° C. and a mold temperature of 170 ° C.
As for the physical properties of the obtained molded product, the bending strength was 130 MPa and the bending elastic modulus was 5.9 G as a result of the physical property test by the above-described test method.
Pa, Izod impact strength was 40 N · m / m, and deflection temperature under load was 180 ° C.

Example 16 Using a Henschel mixer, a vinyl chloride resin (manufactured by Mitsui Toatsu Chemical Co., Inc., trade name: VINICRON 3000P) 100
1 part by weight, plasticizer (dioctyl phthalate) 2 parts by weight, stabilizer (di-n-butyltin dimaleate) 3.5 parts by weight and lubricant (calcium stearate and butyl stearate, both polymerization ratio: 1/1). The parts were mixed.
Next, 80 parts by weight of the above mixture and 20 parts by weight of fibrous zonotolite A were melt-kneaded at 170 ° C. using an 8-inch diameter mixing roll. The kneaded material thus obtained was pressed at 170 ° C. to prepare a sheet. As a result of the physical property test by the above-mentioned test method, the tensile modulus of elasticity of this sheet is 2.5 GPa.
Met.

Example 17 In Example 1, ABS resin (trade name: SICOLAC T, manufactured by Ube Saikon Co., Ltd.) was used in place of nylon 6, and melt kneading was performed at 230 ° C. instead of 250 ° C. Pellets were produced in the same manner as in Example 1 except for the above. Next, the pellets were prepared in the same manner as in Example 1 except that the cylinder temperature of the injection molding machine was changed to 250 ° C. to 230 ° C., and the mold temperature was changed to 80 ° C. to 60 ° C. Injection molded. The obtained molded product is
As a result of the physical property test, the tensile strength was 500 MPa, the bending strength was 800 MPa, the bending elastic modulus was 5.7 GPa, and the deflection temperature under load was 96 ° C.

[0054]

INDUSTRIAL APPLICABILITY The present invention uses a fibrous xonotlite having a specific property, so that it has higher strength, higher rigidity, and higher heat resistance than a conventional fibrous inorganic substance / organic polymer substance composite material. It enables to provide an organic polymer composite material having a well-balanced impact resistance. Therefore, the reinforced organic polymer composition of the present invention can be used as a material for automobiles, electric / electronics, civil engineering, precision machinery and the like.

Claims (2)

[Claims] 1. A BET specific surface area due to nitrogen adsorption of 2
1 m ² / g or more, (2) its surface is treated with a surfactant and / or a coupling agent, and
(3) A reinforced organic polymer composition comprising a fibrous zonotolite granulated and an organic polymer substance. 2. The fibrous zonotolite is (1) 0.1
μm ≦ D <0.5 μm, (2) 1 μm ≦ L <5 μm and (3) 10 ≦ L / D <20 (however, D and L
Indicates the average fiber diameter and the average fiber length of the fibrous zonotolite, respectively. ) Are simultaneously satisfied, the reinforced organic polymer composition according to claim 1.