JPH08199038A - Polyporopylene composition - Google Patents

Abstract

PURPOSE: To obtain a polypropylene composition which can give a molding being excellent in a blance among properties and having a good appearance by mixing a specified ethylene/propylene block copolymer with a thermoplastic elastomer, fibrous xonotlite and a nonfibrous filler. CONSTITUTION: This composition comprises a crystalline ethylene/propylene block copolymer (A) [having an ethylene content of 0.5-10wt.%, MFI (at 230 deg.C) of 5-70g/10min and a content of boiling n-heptane insolubles of the PP component of 95wt.% or above], a thermoplastic olefin/styrene elastomer (B), fibrous xonotlite (C) and a nonfibrous filler (D), provided that the sum of the percentages by weight of components C and D is 5-65% based on the total composition, the percentage by weight of component B is 5-50% based on the sum of the weights of component A and B, and the percentage by weight of component C is 5-100% based on the sum of the weights of components C and D.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polypropylene composition reinforced with fibrous xonotlite,
A molded article obtained by using the composition has an excellent balance of mechanical properties, heat resistance and impact resistance, and further has a good appearance of the molded article, which is suitable for use in fields such as automobiles, electric / electronics and precision machinery. It can be used as a material.

[0002]

2. Description of the Related Art As a method for improving the impact resistance of polypropylene, a method of blending a rubber or a thermoplastic elastomer as a modifier (“Polymer Blend”, written by Kunio Goto, published by Nikkan Kogyo Shimbun (Showa 45) However, this method is known to reduce strength, elastic modulus, and heat resistance.

Therefore, as a method for solving this problem,
A known method is to further add a reinforcing fiber, a fibrous filler, or a granular or plate-like non-fibrous filler to these. However, a method of blending the reinforcing fibers (Japanese Patent Laid-Open No. H03-31187)
No. 227342, etc.) has an effect of improving strength, elastic modulus, and heat resistance, but has poor fluidity, resulting in poor appearance of the molded product. Further, it is well known that the method of blending a granular or plate-like non-fibrous filler (see Japanese Patent Application Laid-Open No. 57-55952, etc.) is less likely to cause defective appearance, but has a small improvement effect. .

On the other hand, wollastonite, gypsum fiber,
A fibrous filler such as potassium titanate or fibrous magnesium oxysulfate is added to give a molded article having a good appearance while improving the elastic modulus and heat resistance (JP-A-62-115048). reference). Furthermore, a method of combining the above-mentioned non-fibrous filler and fibrous filler (so-called hybrid of filler) (see Japanese Patent Laid-Open No. 4-275351, etc.) has been attempted. Then, as an example of the fibrous filler used for the above purpose, a method using calcium silicate fibers (including fibrous zonotolite) (Japanese Patent Laid-Open No. 61-6).
No. 9848, etc.) is disclosed.

However, the conventionally known fibrous xonotlite has a drawback that it is liable to agglomerate and has poor wettability with polypropylene and the above-mentioned modifiers, and therefore has low dispersibility in them. For this reason, the expected effects as described above were not sufficiently exhibited.

[0006]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to solve the problems of the above-mentioned known techniques, that is, to balance mechanical properties, heat resistance and impact resistance. An object is to provide a polypropylene composition which is excellent and has a good appearance of a molded product.

[0007]

The inventors of the present invention have conducted extensive studies to solve the above-mentioned problems in the prior art, and as a result, the wettability with polypropylene, which is a matrix resin, and a thermoplastic elastomer, and these matrix resins. In the fibrous zonotolite having a specific property excellent in dispersibility in the, and a non-fibrous filler, at a specific ratio, by blending with the polypropylene or thermoplastic elastomer which is the matrix resin, strength, elasticity It has an excellent balance of mechanical properties such as rate and heat resistance and impact resistance, and that it is possible to provide a polypropylene composition having a good appearance of a molded article, and it is found that it is possible to overcome the problems of the above-mentioned prior art, The present invention has been completed.

That is, the first invention according to claim 1 has an ethylene content of 0.5 to 10% by weight and a melt flow index (measured at 230 ° C.) of 5 to 70 g / 10.
And the boiling n-heptane insoluble content of polypropylene component is 9
5% by weight or more of the crystalline ethylene / propylene block copolymer (A), a thermoplastic elastomer (B) selected from an olefinic thermoplastic elastomer or a styrene thermoplastic elastomer, and a BET specific surface area by nitrogen adsorption of 21 m ² / g or more, composed of a fibrous zonotolite (C) surface-treated with a surfactant and / or a coupling agent and granulated into granules, and a non-fibrous filler (D) And the weight percentage of the component (C) in the total composition of the component (A), the component (B), the component (C) and the component (D) represented by the formula (I). And the sum (Wf) of the weight percentages of the component (D) is 5% by weight or more and 65% by weight or less, and the weight of the component (A) and the weight of the component (B) represented by the formula (II). (B) the weight percentage of component (Wb) is not less 50 wt% 5 wt% or more or less in the sum,
Further, in the sum of the weight of the component (C) and the weight of the component (D) represented by the formula (III), the (C)
The weight percentage (Wc) of the component is 5% by weight or more and 100% by weight
It can be achieved by providing a polypropylene composition characterized by:

The second invention according to claim 2 is
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 respectively represent the average fiber diameter and the average fiber length of the fibrous zonotolite (C) at the same time.) The polypropylene composition according to the first invention, which is a fibrous xonotlite. Can be achieved by providing.

The third invention described in claim 3 is
The component (A) has a p-xylene soluble component amount of 3 to 2 at room temperature.
Crystallinity of 0% by weight, intrinsic viscosity of the p-xylene soluble component (measured in decalin solution at 135 ° C.) of 3 dl / g or more, and ethylene content of the p-xylene soluble component of 18 to 45% by weight. The polypropylene composition according to the first invention or the second invention, which is an ethylene / propylene block copolymer, has a fourth invention (4) according to the fourth invention.
The invention according to any one of the first to third aspects, wherein the component is at least one thermoplastic elastomer selected from the group consisting of ethylene / propylene rubber, ethylene / butylene rubber and styrene / ethylene / butylene / styrene rubber. The polypropylene composition according to the fifth aspect of the present invention is the polypropylene composition according to any one of the first to fourth aspects, wherein the non-fibrous filler (D) is talc. , Can be achieved by providing each.

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
Polypropylene (A) and thermoplastic elastomer
-Wetability with (B) tends to deteriorate, especially 2
1m²In the case of fibrous zonotolite smaller than / g, the inclination
Therefore, it is impossible to achieve the object of the present invention.
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, polypropylene (A), thermoplastic elastomer (B), or non-fibrous filler The fibrous xonotlite (C) may be broken during mixing and kneading with (D), and if D is 0.5 μm or more and L is less than 1 μm, the fibrous xonotlite of the obtained polypropylene composition is obtained. The effect of improving mechanical strength by (C) may not be sufficient. Also, L / D
When the ratio is less than 10, the resulting polypropylene composition may not be able to obtain sufficient mechanical strength, and when the L / D is 20 or more, the bulk specific gravity of the fibrous xonotlite (C) may be low. May become too small, making it difficult to knead when producing the polypropylene 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 polypropylene (A) described below, a thermoplastic elastomer (B), and
In order to further improve the reinforcing effect on the composition comprising the non-fibrous filler (D), 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 improves the affinity of the fibrous zonotolite (C) with the organic polymer substance serving as the matrix, that is, polypropylene (A) and the thermoplastic elastomer (B), and its reinforcing effect, that is, It is used for the purpose of further increasing the mechanical strength, and specifically, the following may be used. As the surfactant, anionic type,
Any of cationic, amphoteric and nonionic surfactants can be used. As the anionic surfactant, alkyl ether sulfate, dodecylbenzene sulfonate,
As cationic surfactants such as stearate,
Amphoteric surfactants such as tetradecylamine acetate and alkyltrimethylammonium chloride, and dimethylalkyllauryl petine, and nonionic surfactants such as polyoxyethylene octadecylamine and polyoxyethylene lauryl ether. Is mentioned. As the coupling agent, a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, a chromium coupling agent,
Examples thereof include boron coupling agents.

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,
When the amount added is in the range of 0.1 to 0.5% by weight, the above-mentioned effects may not be sufficient, and when the amount added is in the range of 8 to 10% by weight, improvement of the above-mentioned 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 granulated for the purpose of easily mixing and kneading with the polypropylene (A) and the thermoplastic elastomer (B) 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, 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.
If the diameter of the fibrous zonotolite granulated product obtained by granulation deviates from the above range, the polypropylene (A), the thermoplastic elastomer (B) and the non-fibrous filler (D) are mixed and kneaded. At that time, it becomes difficult to mix and knead with a single-screw extruder or a twin-screw extruder, and it is necessary to sequentially fill and mix and knead them with a roll or a Banbury mixer, so that the fibrous zonotolite (C) is remarkable. It is not preferable because it may be broken to reduce the 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 present invention is characterized in that a crystalline ethylene / propylene block copolymer having specific properties is used as the polypropylene (A). That is, the ethylene content is 0.5 to 10% by weight, preferably 3
.About.8 wt%, the boiling n-heptane insoluble content of the polypropylene component is 95 wt% or more, preferably 97 wt% or more, and the melt flow index (230
5 to 70 g / 10 minutes, preferably 5 to 30)
It is a crystalline ethylene / propylene block copolymer of about g / 10 minutes. When the ethylene content is less than 0.5% by weight, impact resistance becomes insufficient, and when it exceeds 10% by weight, rigidity and heat resistance become insufficient, which is not preferable.
In addition, the boiling point n indicating the degree of crystallinity of the polypropylene component
-When the amount of the heptane-insoluble component is less than 95% by weight, the crystallinity is low and the physical properties are unsuitable. Further, when the melt flow index (measured at 230 ° C.) is less than 5 g / 10 minutes, the moldability is lowered and the appearance of the molded product is deteriorated, which is not preferable in practice. On the other hand, when the value is larger than 70 g / 10 minutes, the physical properties are poor and it cannot be practically used. In order to surely prevent the occurrence of the above-mentioned unfavorable phenomena, the ethylene content, the boiling n-heptane insoluble content of the polypropylene component and the melt flow index of the crystalline ethylene / propylene block copolymer are It is desirable that it is within the above-mentioned preferable range.

Further, in the present invention, when the crystalline ethylene / propylene block copolymer as the component (A) has a p-xylene-soluble component having a specific property at room temperature, its effect is obtained. Further improve.
However, the limitation of the properties relating to the p-xylene-soluble component at room temperature is not always essential for the practice of the present invention. In the present invention, the p-xylene-soluble component at room temperature has an amount of 3 to 20% by weight, an intrinsic viscosity (measured in decalin solution at 135 ° C.) of 3 dl / g or more, and
It is particularly suitable if its ethylene content is 18 to 45% by weight. The p-xylene soluble component at room temperature represents a low crystalline component in the crystalline ethylene / propylene block copolymer, and controls its impact resistance. Therefore, when the amount is less than 3% by weight, when the intrinsic viscosity (measured in decalin solution at 135 ° C.) is less than 3 dl / g, and when the ethylene content showing the chemical composition is less than 18% by weight, In either case, the development of impact resistance is unsatisfactory. However, on the contrary, when the amount is more than 20% by weight or when the ethylene content is more than 45% by weight, the rigidity and heat resistance are impaired.

In the present invention, as the component (B),
A thermoplastic elastomer selected from an olefin-based thermoplastic elastomer or a styrene-based thermoplastic elastomer is used. The olefin-based thermoplastic elastomers described here include ethylene / propylene rubber (EPR), ethylene / butylene rubber (EBR),
Ethylene / propylene / butylene rubber (EPBR),
Specific examples include ethylene / propylene / diene rubber (EPDM). Further, as the styrene-based thermoplastic elastomer, styrene / butadiene / styrene rubber (SBS), styrene / isoprene / styrene rubber (SIS), styrene / ethylene / butylene / styrene rubber (SEBS) which is a hydrogenated product of SBS, SI
S-hydrogenated products such as styrene, ethylene, propylene and styrene rubber (SEPS) are typical. In the present invention, as the component (B), at least one thermoplastic elastomer selected from the group consisting of the above olefinic thermoplastic elastomer and styrene thermoplastic elastomer is used. Of these, EPR, EBR, SEBS and mixtures thereof are particularly preferably used. And E
The PR has an ethylene content of 60 to 85% by weight and a melt flow index (measured at 230 ° C.) of 0.3 to 10 g / 10 minutes or Mooney viscosity (M
L1 _{+ 4} (100 ℃) of about 10-80, EBR
Has a butene-1 content of 10 to 25% by weight,
Moreover, the melt flow index (measured at 190 ° C.) is 0.5 to 10 g / 10 minutes or the Mooney viscosity (ML _{1 + 4}
(100 ° C)) about 5 to 20 and SEBS
Particularly preferred are those having a styrene content of 10 to 40% by weight and a melt flow index (measured at 200 ° C.) of about 0.2 to 10 g / 10 minutes.

The non-fibrous filler (D) used in the present invention means a filler having a granular or plate-like shape. For example, wood powder, iron, copper, silver, gold, flakes such as aluminum, powdered metal, carbon black,
Carbon materials such as graphite, activated carbon, hollow spheres, oxides such as silica, alumina, silica-alumina, titanium oxide, iron oxide, zinc oxide, magnesia, calcia, silicates such as talc, clay and mica, water of various metals Oxides, carbonates, sulfates, phosphates, borates, borosilicates, aluminosilicates, titanates, basic sulphates, basic carbonates 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 non-fibrous filler (D) may be used alone, or two or more kinds may be mixed and used. Among these, talc, calcium carbonate, mica and the like are most representative.

Further, the above-mentioned polypropylene (A), thermoplastic elastomer (B), fibrous zonotolite (C)
And various auxiliary materials added for improving the properties and production of the polypropylene composition comprising the non-fibrous filler (D), that is, a heat stabilizer, a light stabilizer, a plasticizer, a crosslinking agent,
Antioxidant, flame retardant, pigment, dye, lubricant, antistatic agent,
Use of a release agent, a fragrance, or the like is also possible as long as the effects of the fibrous zonotolite (C) and the thermoplastic elastomer (B) of the present invention are not impaired.

By the way, in the present invention, the polypropylene (A), the thermoplastic elastomer (B), and the fibrous zonotolite (C) represented by the formula (I) are used.
The sum (Wf) of the weight percentages of the fibrous zonotolite (C) and the non-fibrous filler (D) in the polypropylene composition consisting of the non-fibrous filler (D) is 5% by weight or more and 65% by weight or less. , Preferably 10% by weight or more and 50
It needs to be less than or equal to wt%. If the sum of the weight percentages (Wf) is less than 5% by weight, mechanical strength, heat resistance, molding shrinkage and the like of the obtained polypropylene composition are not improved, which is not preferable. On the other hand, if it is more than 65% by weight, the melt flowability of the obtained polypropylene composition is lowered, molding becomes difficult, and the appearance of the obtained molded product is deteriorated, which is not preferable. When the sum of the above weight percentages (Wf) is 5% by weight or more and less than 10% by weight,
If the amount is more than 50% by weight and less than 65% by weight, the above-mentioned unfavorable phenomenon may occur.

Next, in the present invention, the above formula (II)
In the both components of the polypropylene (A) and the thermoplastic elastomer (B), the weight percentage (Wb) of the thermoplastic elastomer (B) is 5% by weight or more and 50% by weight or less, preferably 10% by weight or more 3
It is also necessary to be 0% by weight or less. This value (Wb)
Is less than 5% by weight, the impact resistance improving effect is small, and if it is more than 50% by weight, the original characteristics of the polypropylene (A) are impaired. When this value (Wb) is 5% by weight or more and less than 10% by weight, the impact resistance improving effect tends to be poor, and in the range of 30% by weight or more and less than 50% by weight, the polypropylene ( The original features of A) may be impaired.

Further, in the present invention, the fibrous zonotolite (C) in both components of the fibrous zonotolite (C) and the non-fibrous filler (D) represented by the formula (III) is contained. The weight percentage (Wc) is 5% by weight or more and 100% by weight or less, preferably 10% by weight or more and 100%.
It should be below wt%. Therefore, in the present invention, the non-fibrous filler (D) does not necessarily have to be included. When the weight percentage (Wc) is less than 5% by weight, the modifying effect of the fibrous zonotolite (C) becomes small, which is not preferable. When the weight percentage (Wc) is in the range of 5% by weight or more and less than 10% by weight, the above-mentioned undesirable phenomenon may occur.

The polypropylene composition of the present invention can be manufactured as follows. That is, the polypropylene composition of the present invention comprising polypropylene (A), thermoplastic elastomer (B), fibrous zonotolite (C) and non-fibrous filler (D) is produced by a known method. Generally, the predetermined amount of the polypropylene (A), the thermoplastic elastomer (B), the fibrous zonotolite (C) and the non-fibrous filler (D) are melt-kneaded by using a kneader to obtain the present invention. Of the polypropylene composition.

At this time, the melt-kneading temperature is 170 to 250.
C., preferably 190 to 230.degree. When the melt-kneading temperature is lower than 170 ° C., in the kneader, the polypropylene (A) and the thermoplastic elastomer (B), that is, the melt viscosity of the resin becomes too high, and the temperature of the portion below the melting point of the resin becomes high. Occurs,
Kneading failure may occur due to resin solidification during production. On the other hand, if the melt-kneading temperature is higher than 250 ° C., thermal decomposition or thermal deterioration of the resin occurs, 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 surely prevent the occurrence of the above-mentioned undesirable phenomenon 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. The polypropylene 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 addition and mixing order of these components during melt-kneading of the polypropylene (A), the thermoplastic elastomer (B), the fibrous zonotolite (C) and the non-fibrous filler (D) are optional. For example, the fibrous zonotolite (C) may be mixed with the polypropylene (A), the thermoplastic elastomer (B) and the non-fibrous filler (D) prior to the melt-kneading, and then added to the extruder. The polypropylene may be supplied to the hopper, and only the polypropylene (A), the thermoplastic elastomer (B) and the non-fibrous filler (D) may be supplied to the hopper of the extruder, and the fibrous xonotlite (C) may be supplied to the hopper of the extruder. It may be supplied from the middle of the extruder. Alternatively, only polypropylene (A) and thermoplastic elastomer (B) are supplied to the hopper of the extruder, and fibrous zonotolite (C) and non-fibrous filler (D) are fed simultaneously or separately from the middle of the extruder. May be supplied to. In addition, when manufacturing the said polypropylene composition, the said various auxiliary materials can also be added simultaneously as needed.

The polypropylene 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.

[0032]

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 method for evaluating the physical properties of the crystalline ethylene / propylene block copolymer and the molded product described in Examples and Comparative Examples was carried out according to the following methods.

[0033] (1) using the ethylene content pressed film of the crystalline ethylene-propylene block copolymer was determined from absorbance ratio of infrared absorption spectrum of 974 cm ^-1 and 720 cm ^-1.

(2) Melt Flow Index of Crystalline Ethylene / Propylene Block Copolymer Measured at 230 ° C. according to ASTM D1238.

(3) Boiling n-heptane insoluble content of polypropylene component of crystalline ethylene-propylene block copolymer Extraction was carried out for 6 hours with boiling n-heptane using a Soxhlet extractor, and insoluble content was measured. I asked.

(4) Bending property: Tensilon UTM-5T manufactured by Orientec Co., Ltd. was used for measurement. After molding the desired polypropylene composition,
23 ° C, relative humidity 50% (hereinafter abbreviated as "50% RH")
I conditioned for 48 hours. Then, the flexural strength and flexural modulus were measured at 23 ° C. according to ASTM D790, 5
Performed at 0% RH.

(5) 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 (4) above, according to (4) above.
The notched Izod impact strength was determined under the same temperature and humidity conditions as in Section.

(6) Deflection temperature under load Measured using a load deflection tester manufactured by Toyo Seiki Co., Ltd. The value under stress 0.45 MPa was determined according to ASTM D648 using a test piece that had been conditioned in the same manner as in (4) above.

(7) Appearance of molded product A flat plate having a length of 100 mm, a width of 100 mm and a thickness of 3 mm was molded, and its appearance 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: The surface of the molded product was not smooth and the appearance was poor.

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.
A hydrothermal synthesis reaction was carried out by holding at 0 ° C for 5 hours. afterwards,
The mixture was allowed to cool for 10 hours or more with stirring to obtain a fibrous zonotolite slurry. When X-ray diffraction of this slurry was measured, only xonotlite was identified.

Subsequently, 920 g of this fibrous xonotlite slurry (based on solid content) was added with 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 changed to 220 ° C. and 260 ° C.
Granular fibrous zonotolite was produced in exactly the same manner as in Reference Example 1, except that the BET specific surface area: 1
6 m ² / g, average fiber length: 10 μm and average fiber diameter:
A fibrous zonotolite having a size of 0.2 μm (and thus an aspect ratio of 50) was obtained. Hereinafter, this is referred to as "fibrous zonotolite B".

Reference Example 3 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 C".

Reference Example 4 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 obtain a BET specific surface area: 39m ² /
g, average fiber length: 3 μm and average fiber diameter: 0.2 μm
Thus, an ungranular fibrous zonotolite having an aspect ratio of 15 was obtained. Hereinafter, this is referred to as "fibrous zonotolite D".

Reference Example 5 Instead of the nonionic surfactant of Reference Example 1, γ-aminopropyltriethoxysilane (Shin-Etsu Chemical Co., Ltd.)
Manufactured, trade name: KBE903) except that the cake-like fibrous zonotolite is granulated in exactly the same manner as in Reference Example 1, dried at about 100 ° C., and further heat-treated at 120 ° C. for 20 minutes. Thus, a surface-treated granular fibrous zonotolite was obtained. The obtained one is BET
Specific surface area: 39 m ² / g, average fiber length: 3 μm and average fiber diameter: 0.2 μm (hence aspect ratio: 15)
Met. Hereinafter, this is referred to as "fibrous zonotolite E".

Example 1 Using a co-rotating twin-screw extruder (model: PCM30, manufactured by Ikegai Tekko Co., Ltd.) having a cylinder diameter of φ30 mm, the temperature was 230 ° C. (however, the same applies to the temperature of the nozzle section below). In, a crystalline ethylene / propylene block copolymer (ethylene content: 6.8% by weight, boiling n-heptane insoluble component of polypropylene component: 97.1% by weight, melt flow index: 9 g / 10 min) Propylene rubber (manufactured by Japan Synthetic Rubber Co., Ltd., trade name: JSR EP07P) and the fibrous zonotolite A obtained in Reference Example 1 were melt-kneaded, and the crystalline ethylene / propylene block copolymer was 70% by weight. A pellet made of 10% by weight of the ethylene / propylene rubber and 20% by weight of the fibrous zonotolite A. did. However, using a screw feeder, fibrous zonotolite A was supplied from the first vent port of the extruder, and deaeration operation was performed from the second vent port. Then, using an injection molding machine (manufactured by Japan Steel Works Ltd., model: N100), the cylinder temperature (however, the temperature of the nozzle head, the same applies below) 230 ° C and the mold temperature 80 ° C.
In, the above pellets were injection-molded 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 Instead of the fibrous zonotolite A, the fibrous zonotolite A: 35% by weight and talc (manufactured by Hayashi Kasei Co., Ltd., trade name: talcan powder PKC, average particle size: 11 μm): 65
% Of the mixture, and therefore the weight percentage of the components other than the crystalline ethylene / propylene block copolymer and ethylene / propylene rubber in the resulting pellets was changed from 20% by weight of fibrous zonotolite A to fibrous xonotlite. The same operation as in Example 1 was performed except that A: 7% by weight and talc: 13% by weight were changed. Table 1 shows the results of the physical property tests of the obtained material.

Example 3 and Comparative Examples 1 to 3 Instead of the fibrous zonotolite A, the fibrous zonotolite E obtained in Reference Example 5 (in the case of Example 3) and the fibrous form obtained in Reference Example 2, respectively. Zonotolite B (in the case of Comparative Example 1), fibrous zonotolite C obtained in Reference Example 3 (in the case of Comparative Example 2) and fibrous zonotolite D obtained in Reference Example 4 (in the case of Comparative Example 3) were used. Except for the above, the same operation as in Example 2 was performed. Table 1 shows the results of the physical property tests of the obtained materials.

Comparative Examples 4 and 5 Instead of the crystalline ethylene / propylene block copolymer, a crystalline ethylene / propylene block copolymer (ethylene content: 7.0% by weight, polypropylene component insoluble in boiling n-heptane) was used. Min: 97.7 wt%, melt flow index: 3 g / 10 min) (in the case of Comparative Example 4) and crystalline ethylene / propylene block copolymer (ethylene content: 6.8 wt%, boiling of polypropylene component n- Heptane insoluble matter: 92.2% by weight, melt flow index: 9 g / 10 minutes) (in the case of Comparative Example 5)
The same operation as in Example 2 was performed except that was used. Table 1 shows the results of the physical property tests of the obtained materials in Comparative Examples 4 and 5.

[0050]

[Table 1]

Examples 4 and 5 Instead of ethylene / propylene rubber, ethylene / butylene rubber (manufactured by Mitsui Petrochemical Co., Ltd., trade name: Toughmer A-1085) (in the case of Example 4) and styrene Ethylene / butylene / styrene rubber (manufactured by Shell Chemical Co., Ltd., trade name: Kraton G165)
7) The same operation as in Example 2 was performed except that (in the case of Example 5) was used. Table 2 shows the results of the physical property tests of the materials obtained in Examples 4 and 5.

Examples 6 and 7 and Comparative Examples 6 to 8 The crystalline ethylene / propylene block copolymer, ethylene / propylene rubber, fibrous zonotolite A and talc were used in different amounts, but the resulting pellets were changed. The same operation as in Example 2 was carried out except that the weight percentages of these four components were changed to the values shown in Table 2. Table 2 shows the results of the physical property tests of the materials obtained in Examples 6 and 7 and Comparative Examples 6 to 8.

[0053]

[Table 2]

[0054]

As is clear from the above Examples and Comparative Examples, the present invention has a polypropylene having a specific property, that is, a crystalline ethylene / propylene block copolymer, and a specific property. By using a thermoplastic elastomer in addition to fibrous zonotolite, or by using a non-fibrous filler in addition to these components, mechanical properties such as strength and rigidity, heat resistance and impact resistance A polypropylene composition having an excellent balance of properties and a good appearance of a molded article. Therefore, the polypropylene composition obtained by the present invention can be used as a material in the fields of automobiles, electric / electronics, precision machinery and the like.

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Claims (5)

[Claims] 1. (A) The ethylene content is 0.5 to 10% by weight, and the melt flow index (measured at 230 ° C.) is 5.
˜70 g / 10 minutes, and a crystalline ethylene / propylene block copolymer having a boiling n-heptane insoluble content of the polypropylene component of 95% by weight or more, (B) an olefin-based thermoplastic elastomer or a styrene-based thermoplastic elastomer. Thermoplastic elastomer, (C) (1) BET specific surface area due to nitrogen adsorption of 21 m ²
/ G or more, (2) surface-treated with a surfactant and / or a coupling agent, and (3) granulated into granules, and (D) a non-fibrous filler. A polypropylene composition comprising the following formula (I): Of the component (A), the component (B), the component (C), and the component (D) in the total composition, and the weight percentage of the component (C) and the component (D). The sum of weight percentages (Wf) is in the range of 5 ≦ Wf ≦ 65,
The following formula (II) [Equation 2] And 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).
b) is in the range of 5 ≦ Wb ≦ 50, and the following mathematical 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
A polypropylene composition, wherein c) is in the range of 5 ≦ Wc ≦ 100. 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 represent the average fiber diameter and the average fiber length of the fibrous zonotolite (C), respectively) at the same time. 1. The polypropylene composition according to 1. 3. The component (A) has a p-xylene-soluble component amount of 3 to 20% by weight at room temperature, and the intrinsic viscosity of the p-xylene-soluble component (measured in decalin solution at 135 ° C.) is 3 dl /
The polypropylene composition according to claim 1 or 2, which is a crystalline ethylene / propylene block copolymer having an ethylene content of 18 to 45% by weight in the p-xylene-soluble component. 4. The component (B) is at least one thermoplastic elastomer selected from the group consisting of ethylene / propylene rubber, ethylene / butylene rubber and styrene / ethylene / butylene / styrene rubber. The polypropylene composition according to any one of 1. 5. The polypropylene composition according to claim 1, wherein the non-fibrous filler (D) is talc.