JPH08199016A - Reinforced polypropylene composition - Google Patents

Abstract

PURPOSE: To obtain a reinforced polypropylene composition which can give a molding having a good balance between heat resistance and impact resistance and good appearance by mixing xonotlite having specified properties with a specified modified thermoplastic elastomer and a filler in a specified mixing ratio. CONSTITUTION: A reinforced polypropylene composition comprising a crystalline polypropylene (A), a modified thermoplastic elastomer (B) selected from among thermoplastic olefin or styrene elastomers onto which an unsaturated carboxylic acid (derivative) is grafted, granulated fibrous xonotlite (C) having a BET specific surface area of 21m<2> /g or above (as measured by nitrogen adsorption) and surface-treated with a coupling agent and a nonfibrous filler (D), wherein Wf defined by formula I (wherein [A] to [D] are the weights of components A to D) satisfies the relationship: 5<=Wf<=65, Wb defined by formula II satisfies the relationship: 5<=Wb<=50, and Wc defined by formula III satisfies the relationship: 5<=Wc<=100. Component D is a filler which is granular or platy in shape.

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 product obtained by using the composition has an excellent balance of heat resistance and impact resistance, and the molded product has a good appearance, and can be used as a material in the fields of automobiles, electric / electronics, precision machinery, etc. .

[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 method of further adding a fibrous filler to these is known. That is, blending of fibrous fillers such as wollastonite, gypsum fiber, potassium titanate, and fibrous magnesium oxysulfate improves the elastic modulus and heat resistance (see JP-A-62-115048). Furthermore, a method of combining these fibrous fillers with a granular or plate-shaped non-fibrous filler (so-called hybrid of fillers) (see Japanese Patent Laid-Open No. 4-275351, etc.) has been attempted. However, all of the above methods have heat resistance (eg rigidity at high temperature).
And the impact resistance are not always well balanced, and there are drawbacks such that it is difficult to obtain a molded product having a good appearance such as generation of flow marks on the surface and deterioration of surface smoothness.

As a technique for solving such a problem,
A method of using a rubber or elastomer graft-modified with an unsaturated carboxylic acid and / or a derivative thereof is disclosed (see Japanese Patent Publication No. 63-35179, etc.).
However, there still remains a problem that it is difficult to obtain a molded product having a well-balanced heat resistance, impact resistance and appearance. Incidentally, among the above-mentioned fibrous fillers that can be used, fibrous zonotolite, which is one of calcium silicate fibers, can be mentioned as a generally known one (Japanese Patent Laid-Open No. Hei 4).
-183733 gazette etc.).

However, the conventionally known fibrous zonotolite is apt to cause agglomeration and has poor wettability with the above-mentioned modified rubber or elastomer, so that it has a drawback of low dispersibility in them. There is. For this reason, the expected effects as described above were not sufficiently exhibited.

[0006]

SUMMARY OF THE INVENTION The object of the present invention is to solve the problems of the above-mentioned known techniques, that is, the excellent balance between heat resistance and impact resistance, and It is intended to provide a polypropylene composition having a good appearance of a molded product.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve the above problems in the prior art, and as a result, the wettability with polypropylene which is a matrix resin and a modified thermoplastic elastomer and the matrix thereof. Crystallization of fibrous zonotolite, which has specific properties with excellent dispersibility in resin, and thermoplastic elastomer and non-fibrous filler graft-modified with unsaturated carboxylic acid and / or its derivatives, in a specific ratio It has been found that by blending with polypropylene, it is possible to provide a polypropylene composition having an excellent balance between heat resistance and impact resistance, and having a good appearance of molded articles, and by which it is possible to overcome the above-mentioned problems of the prior art. The present invention has been completed.

That is, the first aspect of the present invention is to provide a crystalline polypropylene (A) and an olefin-based thermoplastic elastomer or styrene-based thermoplastic elastomer modified with an unsaturated carboxylic acid and / or a derivative thereof. A selected modified thermoplastic elastomer (B),
A fibrous zonotolite (C) having a BET specific surface area of 21 m ² / g or more by nitrogen adsorption, surface-treated with a coupling agent, and granulated into granules, and a non-fibrous filler (D) Of the component (A), the component (B), the component (C) and the component (D) represented by the formula (I), and the weight of the component (C) in the total composition. The sum of the percentage and the weight percentage of the component (D) (Wf) is 5% by weight or more and 65% by weight or less, and the weight of the component (A) and the component (B) represented by the formula (II). The weight percentage (Wb) of the component (B) in the sum of weight is 5% by weight or more and 50% by weight or less,
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 reinforced 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, which is a fibrous zonotolite, which is a reinforced polypropylene composition according to the first invention. It can be achieved by providing things.

In a third aspect of the present invention, the modified thermoplastic elastomer (B) is a group consisting of a modified ethylene / propylene rubber, a modified ethylene / butylene rubber and a modified styrene / ethylene / butylene / styrene rubber. The crystalline polypropylene (A) is unsaturated when the reinforced polypropylene composition according to the first or second invention is at least one elastomer selected from the above, and the crystalline polypropylene (A) is unsaturated. The reinforced polypropylene composition according to any one of the first to third inventions, which is a modified polypropylene graft-modified with a carboxylic acid and / or a derivative thereof, and the fifth invention according to claim 5. Any one of the first to fourth inventions, wherein the fibrous zonotolite (C) is surface-treated with a silane coupling agent. The reinforced polypropylene composition according to one can be achieved by providing, respectively.

The present invention will be described in detail below. The present invention
The fibrous zonotolite described in 1.
Formula: Ca₆Si ₆O₁₇(OH)₂, Chemical formula: 6CaO
6 SiO₂・ H₂O) means a needle-shaped crystalline substance. In the present invention
The value of its specific surface area is very important.²/
g or more, preferably 30 m²/ G or more (However, nitrogen absorption
Be measured by the BET method by wearing
Yes. This value is 30m²Fibrous Zonotry smaller than / g
For example, polypropylene (A) and unsaturated carboxylic acid
And / or its graft-modified thermoplastic
The tendency that the wettability with the elastomer (B) deteriorates was observed.
Especially, 21m²Fibrous zonotolite smaller than / g
Then, since the tendency is remarkable, the object of the present invention is achieved.
I can't.

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 xonotlite (C) is formed into a granule, and when grafted with polypropylene (A), unsaturated carboxylic acid and / or its derivative Modified thermoplastic elastomer (B),
The fibrous zonotolite (C) may be broken during mixing and kneading with the non-fibrous filler (D), and D is 0.5 μm.
If it is m or more or L is less than 1 μm, the obtained reinforced polypropylene composition is a fibrous zonotolite (C).
The effect of improving the mechanical strength due to may not be sufficient. Further, when L / D is less than 10, the reinforced polypropylene composition obtained may not be able to obtain sufficient mechanical strength, and when L / D is 20 or more, fibrous zonotolite. The bulk specific gravity of (C) becomes too small, and it may be difficult to knead when producing the reinforced 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 xonotlite (C) obtained by the above-mentioned production method is a thermoplastic elastomer (B) graft-modified with polypropylene (A), an unsaturated carboxylic acid and / or a derivative thereof described later. ) And the non-fibrous filler (D) to further enhance the reinforcing effect on the composition, it is desirable that the surface is further treated with a coupling agent. That is, the coupling agent is an organic polymer substance that serves as a matrix of the fibrous zonotolite (C), that is, polypropylene (A), or a thermoplastic elastomer graft-modified with an unsaturated carboxylic acid and / or a derivative thereof ( B) to improve the affinity and its reinforcing effect,
That is, it is used for the purpose of further increasing mechanical strength, and specifically, a silane coupling agent, a titanate coupling agent, an aluminum coupling agent or the like can be used. Of these, silane coupling agents are suitable. Examples of the silane coupling agent include vinyl silane, epoxy silane, methacryloxy silane, amino silane, chloropropyl silane, and mercapto silane, and amino silane is most suitable.

The amount of these coupling agents added is 0.1 to 5 relative to the fibrous zonotolite (C) (dry matter basis).
It should be wt%, preferably 0.5-3 wt%. If the addition amount is less than 0.1% by weight, the above-mentioned effect is not sufficient, and if the addition amount exceeds 5% 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-mentioned effect may not be sufficient, and if the addition amount is in the range of 3 to 5% by weight, the improvement of the above-mentioned effect 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 coupling agent is added to the fibrous xonotlite 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. Regarding this surface treatment, after drying the fibrous zonotolite slurry,
A coupling agent dissolved in a small amount of water or a solvent may be used, but the operation becomes complicated, and the effect of the above-mentioned coupling agent is small and there is no particular advantage.

Further, the fibrous zonotolite (C) used in the present invention is a mixture of polypropylene (A) described below and a thermoplastic elastomer (B) graft-modified with an unsaturated carboxylic acid and / or a derivative thereof. Granulated into granules for the purpose of facilitating kneading. Granular fibrous zonotolite has a diameter of 1 to 8 obtained by granulating a cake-like fibrous zonotolite to which the coupling agent is attached by a granulator.
It can be obtained by molding into a granule of mm, and drying and heat treatment. In this case, the granulator is not particularly limited, and includes a rotary vertical granulator, a rotary drum granulator, a rotary sieving granulator, a screw extrusion granulator, a roll extrusion granulator. A known granulator can be used.
When the diameter of the fibrous zonotolite granular molded product obtained by granulation deviates from the above range, the thermoplastic elastomer (B) graft-modified with polypropylene (A), an unsaturated carboxylic acid and / or a derivative thereof is used. When mixing and kneading with the non-fibrous filler (D), it becomes difficult to mix and knead with a single-screw extruder or a twin-screw extruder, and the mixture is sequentially filled with a roll or Banbury mixer to mix and knead. It must be carried out, and the fibrous zonotolite (C) may be significantly destroyed, resulting in a decrease in mechanical strength, which is not preferable. In addition, the drying is performed by using a known dryer such as a hot air circulation dryer and an infrared heating dryer at a temperature of 100 to 150 ° C. for 20 to 30 hours, and the moisture content of the granular fibrous zonotolite is 1% by weight. It is preferable to carry out to the extent that Further, it is preferable that the heat treatment is performed after the moisture is dried under heating at 100 to 150 ° C. for 20 to 30 hours. 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. .

In the present invention, crystalline polypropylene (A)
As the propylene homopolymer, a propylene copolymer can be used. Among them, the crystalline ethylene / propylene block copolymer is most preferable. That is, as the most suitable crystalline polypropylene (A), the ethylene content is 0.5 to 10% by weight, preferably 3 to 8% by weight, and the boiling n-heptane insoluble content of the polypropylene component is 95% by weight or more. , Preferably 97% by weight or more, and having a melt flow index (measured at 230 ° C.) of 5 to 70 g / 10 minutes, preferably about 5 to 30 g / 10 minutes.
It is a propylene block copolymer. When the crystalline ethylene / propylene block copolymer is used, if the ethylene content is less than 0.5% by weight, the impact resistance is insufficient, and if it is more than 10% by weight, the rigidity and heat resistance are insufficient. Is not preferable. Further, when the amount of the boiling n-heptane insoluble component showing the degree of crystallinity of the polypropylene component is less than 95% by weight, the crystallinity is low and the physical properties are unsuitable, which is not preferable. Further, if the melt flow index (measured at 230 ° C.) is less than 5 g / 10 minutes, the moldability is lowered, which is not preferable in practical use. 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, which is not preferable. In order to reliably prevent the occurrence of the above-mentioned unfavorable phenomenon, the crystalline ethylene / propylene block copolymer has an ethylene content, a boiling n-heptane insoluble content of a polypropylene component, and a melt flow rate. The index is
It should be in the preferred range mentioned above.

By the way, in the present invention, as the crystalline polypropylene (A), the one in which a modified polypropylene graft-modified with an unsaturated carboxylic acid and / or its derivative is blended in place of the above-mentioned unmodified polypropylene is used. Then, the effect of the present invention is further enhanced, which is preferable. As the modified polypropylene graft-modified with such an unsaturated carboxylic acid and / or a derivative thereof, a known polypropylene can be used, and a production method thereof is already known (for example, Japanese Patent Publication No. 51-102).
65, etc.).

Examples of unsaturated carboxylic acids and their derivatives include acrylic acid, maleic anhydride, itaconic anhydride, glycidyl methacrylate, 2-hydroxyethyl methacrylate, γ-methacryloxypropyltrimethoxysilane and acrylamide. Of these, maleic anhydride and itaconic anhydride are the most representative. The amount used is 0.1 to 5 parts by weight with respect to 100 parts by weight of the crystalline polypropylene. When the amount used is less than 0.1 part by weight based on 100 parts by weight of the polypropylene, the modifying effect is not sufficient, and when it exceeds 5 parts by weight, unreacted monomer increases as the grafting efficiency decreases. Therefore, either case is not preferable.

Organic peroxides are most commonly used as initiators for the graft modification reaction. A typical example is t
-Butyl peroxybenzoate, 2,5-dimethyl-
2,5-di (benzoylperoxy) hexane, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-
Butyl peroxy) hexane, t-butyl peroxy acetate, methyl ethyl ketone peroxide and the like. The addition amount is 0.05 to 1 part by weight with respect to 100 parts by weight of the crystalline polypropylene. If the addition amount is less than 0.05 parts by weight with respect to 100 parts by weight of the crystalline polypropylene, the graft efficiency cannot be expected sufficiently, which is not preferable. On the other hand, if the amount exceeds 1 part by weight, the crystalline polypropylene is significantly deteriorated or colored, which is not preferable.

The modified polypropylene of the present invention is obtained by mixing the crystalline polypropylene, the unsaturated carboxylic acid and / or its derivative and the reaction initiator in the above-mentioned predetermined ratios and using an extruder or a Banbury mixer. Then, a method of melt-kneading at a temperature of 180 to 250 ° C. for about 1 to 20 minutes, or after heating and dissolving the crystalline polypropylene in toluene or xylene in a reaction vessel,
It can be produced by a method of adding the above unsaturated carboxylic acid and / or its derivative and a reaction initiator and reacting with stirring. In particular, the former method is suitable as an industrial process. The modified polypropylene thus obtained has a monomer graft ratio of 0.05 to 5
Weight%, melt flow index (measured at 230 ° C)
Is about 1 to 100 g / 10 minutes. In the present invention, the modified polypropylene may be used alone, but may be used as a mixture with unmodified polypropylene.

Next, the present invention provides a modified thermoplastic elastomer selected from an olefinic thermoplastic elastomer or a styrene-based thermoplastic elastomer, which is graft-modified with an unsaturated carboxylic acid and / or a derivative thereof as the component (B). Is used. Specific examples of the olefin-based thermoplastic elastomer described here include ethylene / propylene rubber (EPR), ethylene / butylene rubber (EBR), ethylene / propylene / butylene rubber (EPBR), and ethylene / propylene / diene rubber (EPDM). Can be mentioned. 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, SIS Styrene, ethylene, propylene, and styrene rubber (SEPS), which are hydrogenated products, are typical ones.

In the present invention, as the component (B), at least one thermoplastic elastomer selected from the group consisting of the above-mentioned olefinic thermoplastic elastomer and styrene-based thermoplastic elastomer is used, and among them, EPR is particularly preferable. , EBR, SEBS and mixtures thereof are preferably used. And as for EPR,
The ethylene content is 60 to 85% by weight and the melt flow index (measured at 230 ° C) is 0.3 to 1
0 g / 10 minutes or Mooney viscosity (ML _{1 + 4} (100
C)) is about 10 to 80, and EBR has a butene-1 content of 10 to 25% by weight and a melt flow index (measured at 190 ° C.) of 0.5 to 10.
g / 10 minutes or Mooney viscosity (ML _{1 + 4} (100
C)) is about 5 to 20, and SEBS has a styrene content of 10 to 40% by weight and a melt flow index (measured at 200 ° C) of 0.2 to 10%.
Those having about g / 10 minutes can be particularly preferably used.

As the modified thermoplastic elastomer graft-modified with an unsaturated carboxylic acid and / or a derivative thereof, and a method for producing the same, known ones can be applied (see, for example, Japanese Patent Publication No. 63-35179). . That is, regarding the unsaturated carboxylic acid and / or its derivative or reaction initiator used for graft modification, and the method for producing the modified thermoplastic elastomer,
This is the same as the case of the modified polypropylene (A) described above. The modified thermoplastic elastomer obtained as described above has a monomer graft ratio of 0.05 to 5% by weight and a melt flow index (measured at 230 ° C.) of 0.0.
It is 5 to 20 g / 10 minutes. Graft ratio is 0.0
If it is less than 5% by weight, the modifying effect cannot be expected, and if it is more than 5% by weight, crosslinking proceeds, which is not preferable in any case. The melt flow index is 0.05g / 1
When it is less than 0 minutes, the moldability is deteriorated due to the decrease in fluidity, and when it is more than 20 g / 10 minutes, the physical properties are deteriorated, which is not preferable.

In the present invention, the modified thermoplastic elastomer or the mixture thereof may be used alone, or may be used as a mixture with the unmodified thermoplastic elastomer as described above. However, in this case, it is desirable that the monomer graft amount is 0.05 parts by weight or more based on 100 parts by weight of the total amount of the modified thermoplastic elastomer and the unmodified thermoplastic elastomer. When the monomer graft amount deviates from this range, the above-mentioned modification effect cannot be expected.

The non-fibrous filler (D) used in the present invention is 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 crystalline polypropylene (A), a thermoplastic elastomer graft-modified with an unsaturated carboxylic acid and / or a derivative thereof, that is, a modified thermoplastic elastomer (B), a fibrous zonotolite (C) and a non-woven fabric. Various auxiliary materials added for improving the properties and production of the reinforced polypropylene composition comprising the fibrous filler (D), that is, heat stabilizer, light stabilizer, plasticizer, crosslinking agent, antioxidant, difficult Flame retardant, pigment, dye, lubricant,
Use of an antistatic agent, a release agent, a fragrance, etc. may be used as long as the effects of the fibrous zonotolite (C) and the modified thermoplastic elastomer (B) of the present invention are not impaired.

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

Next, in the present invention, the modified thermoplastic elastomer (B) in both components of the crystalline polypropylene (A) and the modified thermoplastic elastomer (B) represented by the formula (II) is used. Weight percentage (W
b) is 5% by weight or more and 50% by weight or less, preferably 10% by weight
It should be above 30% by weight. If the weight percentage (Wb) is less than 5% by weight, the impact resistance improving effect is small, and if it exceeds 50% by weight, the original characteristics of the crystalline polypropylene (A) are impaired. Is also not preferable. The weight percentage (W
When b) is in the range of 5% by weight or more and less than 10% by weight, the effect of improving the impact resistance tends to decrease, and in the range of more than 30% by weight and 50% by weight or less, the crystalline polypropylene (A) There is a tendency for the original features of the to 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 mathematical formula (III) is used. Weight percentage (Wc) is 5% by weight or more 100
It is also necessary that the content is not more than 10% by weight, preferably not less than 10% by weight and not more than 100% by weight. Therefore, in the present invention, the non-fibrous filler (D) does not necessarily have to be included. If the weight percentage (Wc) is less than 5% by weight, the effect of modification by the fibrous zonotolite (C) is small, which is not preferable. When this value (Wc) is 5% by weight or more and less than 10% by weight, the above-mentioned undesirable phenomenon may occur.

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

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., the melt viscosity of the crystalline polypropylene (A) or the modified thermoplastic elastomer (B), that is, the resin becomes too high in the kneader, and the temperature is not higher than the melting point of the resin. May occur, and the resin may be solidified during production, resulting in poor kneading. The melt-kneading temperature is 250 ° C.
When it is higher than the above range, 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 these undesirable phenomena related to the melt-kneading temperature.

Examples of the kneading machine include extruders such as a single-screw extruder and 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 reinforced 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, regarding the addition and mixing order of these components during the melt-kneading of the crystalline polypropylene (A), the modified thermoplastic elastomer (B), the fibrous zonotolite (C) and the non-fibrous filler (D). Can be arbitrarily selected. For example, fibrous zonotolite (C) is mixed with crystalline polypropylene (A), modified thermoplastic elastomer (B) and non-fibrous filler (D) prior to melt-kneading. After that, it may be supplied to the hopper of the extruder, or only the crystalline polypropylene (A), the modified thermoplastic elastomer (B) and the non-fibrous filler (D) may be supplied to the hopper of the extruder. The fibrous zonotolite (C) may be supplied from the middle of the extruder. Alternatively, only the crystalline polypropylene (A) and the modified thermoplastic elastomer (B) are supplied to the hopper of the extruder, and the fibrous zonotolite (C) and the non-fibrous filler (D) are fed from the middle of the extruder. They may be supplied simultaneously or separately. In addition, when manufacturing the said reinforced polypropylene composition, the said various auxiliary materials can also be added simultaneously as needed.

The reinforced 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.

[0038]

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 modified polypropylene, modified thermoplastic elastomer, and physical properties of molded articles described in Examples and Comparative Examples were evaluated according to the following methods.

(1) Quantification of maleic anhydride graft ratio of modified polypropylene and modified thermoplastic elastomer A sample (modified polypropylene or modified thermoplastic elastomer) was dissolved in p-xylene, reprecipitated in acetone, filtered and dried, It is again dissolved in p-xylene. Then, KOH was added in the heated and dissolved state, and titration was performed with HCl using thymol blue as an indicator.

(2) Melt flow index: Measured at 230 ° C. according to ASTM D1238.

(3) Bending property The bending property was measured by using Tensilon UTM-5T manufactured by Orientec Co., Ltd. After molding the desired reinforced polypropylene composition, it was conditioned for 48 hours at 23 ° C. and 50% relative humidity (hereinafter abbreviated as “50% RH”). Then, the bending strength and the bending elastic modulus are measured according to ASTM D790.
It was carried out at 50 ° C and 50% RH.

(4) Izod impact strength Measured using an Izod impact tester manufactured by Toyo Seiki Co., Ltd. Then, according to ASTM D256, using the test piece that has been conditioned in the same manner as in the above (3), the above (3)
The notched Izod impact strength was determined under the same temperature and humidity conditions as in Section.

(5) 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 was conditioned in the same manner as in (3) above.

(6) 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 the 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.
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 silane coupling agent (γ-aminopropyltriethoxysilane, a product of Shin-Etsu Chemical Co., Ltd., trade name: KBE)
903) 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,
By drying at 0 ° C. and further heat treatment at 120 ° C. for 20 minutes, a surface-treated granular fibrous zonotolite was obtained. With respect to this granular fibrous zonotolite, the BET specific surface area 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, 3 μm and 0.2 μm, respectively. (Thus, the aspect ratio was 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.
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 B".

Reference Example 3 A granular fibrous zonotolite was produced in exactly the same manner as in Reference Example 1 except that the silane coupling agent as the surface treatment agent was not added, and the BET specific surface area: 3
9 m ² / g, average fiber length: 3 μm and average fiber diameter:
A surface-untreated fibrous zonotolite of 0.2 μm (hence, aspect ratio: 15) was obtained. Hereinafter, this is referred to as "fibrous zonotolite C".

Reference Example 4 The 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".

Example 1 Ethylene propylene rubber (manufactured by Nippon Synthetic Rubber Co., Ltd.,
Product name: JSR EP07P) 100 parts by weight at 100 ° C
Of p-xylene, 1.3 parts by weight of maleic anhydride and 0.4 parts by weight of dicumyl peroxide were added with stirring, and the mixture was reacted for 4 hours to give a maleic anhydride graft ratio of 1 part by weight. %, And a modified ethylene-propylene rubber having a melt flow index of 1 g / 10 min was obtained. Then, using a co-rotating twin screw extruder (model: PCM30, manufactured by Ikegai Iron Works Co., Ltd.) with a cylinder diameter of φ30 mm at 230 ° C. (however, the temperature of the nozzle part is the same below), crystallinity is obtained. Ethylene / propylene block copolymer (Ube Industries, Ltd.)
(Trade name: UBE Polypro J709HK), the modified ethylene / propylene rubber and the fibrous zonotolite A obtained in Reference Example 1 are melt-kneaded, and the crystalline ethylene / propylene block copolymer is 70% by weight, and the modified Pellets composed of 10% by weight of ethylene / propylene rubber and 20% by weight of the fibrous zonotolite A were prepared. However, the fibrous zonotolite A was supplied from the first vent port using a screw feeder, and deaeration operation was performed from the second vent port. Next, using an injection molding machine (manufactured by Japan Steel Works Ltd., model: N100),
Cylinder temperature (however, the temperature of the nozzle head,
The same applies hereinafter) 230 [deg.] C. and a mold temperature of 80 [deg.] C. 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 fibrous zonotolite A, 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 components other than the crystalline ethylene / propylene block copolymer and the modified ethylene / propylene rubber in the resulting pellets from fibrous zonotolite A: 20% by weight to fibrous. Zonotolite A: 7% by weight and the above talc: 13
The same operation as in Example 1 was carried out except that the weight% was changed. Table 1 shows the physical property test results of the obtained materials.

Comparative Examples 1 to 3 Instead of the fibrous zonotolite A, the fibrous zonotolite B obtained in Reference Example 2 (in the case of Comparative Example 1) and the fibrous zonotolite C obtained in Reference Example 3 (comparison) were used. Example 2) and fibrous zonotolite D obtained with reference diameter 4
The same operation as in Example 1 was performed except that (in the case of Comparative Example 3) was used. Table 1 shows the physical property test results of the obtained materials.

Comparative Example 4 The same as Example 1 except that unmodified ethylene-propylene rubber (manufactured by Japan Synthetic Rubber Co., Ltd., trade name: JSR EP07P) was used in place of the modified ethylene-propylene rubber. The operation was performed. Table 1 shows the physical property test results of the obtained materials.

Example 3 Crystalline ethylene / propylene block copolymer (manufactured by Ube Industries, Ltd., trade name: UBE Polypro J701H) 1
00 parts by weight, 0.5 parts by weight of itaconic anhydride and 0.2 parts by weight of t-butylperoxybenzoate were mixed in a V-type blender, and then melt-kneaded at 200 ° C. for 2 minutes using a uniaxial extruder, Graft ratio of itaconic anhydride is 0.4
5% by weight and the melt flow index (2
A modified ethylene / propylene block copolymer having a (measured at 30 ° C.) of 25 g / 10 min was obtained. Therefore, instead of the crystalline ethylene / propylene block copolymer of Example 1,
The same operation as in Example 1 was carried out except that the above modified ethylene / propylene block copolymer was used. The physical property test results of the obtained material are as shown in Table 1.

[0055]

[Table 1]

Example 4 Instead of the modified ethylene / propylene rubber, modified styrene / ethylene / butylene / styrene rubber (manufactured by Shell Chemical Co., trade name: Kraton FG1901X, maleic anhydride graft ratio: 2% by weight) was used. Except for the above, the same operation as in Example 1 was performed. Table 2 shows the physical property test results of the obtained materials.

Examples 5 and 6 and Comparative Examples 5 to 7 Pellets obtained by changing the amounts of the four components of crystalline ethylene / propylene block copolymer, modified ethylene / propylene rubber, fibrous zonotolite A and talc. The same operation as in Example 2 was performed except that the weight percentages of these 4 components were changed to the values shown in Table 2. In Examples 5 and 6 and Comparative Examples 5 to 7,
The physical property test results of the obtained materials are shown in Table 2.

Example 7 Instead of the modified ethylene / propylene rubber, 70% by weight of the modified ethylene / propylene rubber and unmodified ethylene / propylene rubber (manufactured by Nippon Synthetic Rubber Co., Ltd., trade name:
JSR EP07P) was used in a mixture with 30% by weight, and therefore crystalline ethylene.
The weight percentage of the components other than the propylene block copolymer and the fibrous zonotolite A was changed from 10% by weight of unmodified ethylene / propylene rubber to 7% by weight of modified ethylene / propylene rubber and 3% by weight of unmodified ethylene / propylene rubber. Except for changing it, the same operation as in Example 1 was performed. The physical property test results of the obtained materials are shown in Table 2.
Shown in

[0059]

[Table 2]

[0060]

As is clear from the above examples and comparative examples, the present invention is based on the use of crystalline polypropylene, modified thermoplastic elastomer and fibrous zonotolite having specific properties, or these components. In addition to the above, by using a non-fibrous filler, a reinforced polypropylene composition having an excellent balance between heat resistance and impact resistance and a good appearance of a molded article is provided. Therefore, the reinforced 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 modified thermoplastic elastomer selected from (A) crystalline polypropylene, (B) an olefin-based thermoplastic elastomer graft-modified with an unsaturated carboxylic acid and / or a derivative thereof, or a styrene-based thermoplastic elastomer, C) (1) BET specific surface area due to nitrogen adsorption is 21 m ²
/ G or more, (2) a surface treatment with a coupling agent, and (3) a granulated granular fibrous zonotolite, and (D) a non-fibrous filler reinforced polypropylene composition And the following equation (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 (D). The sum of percentages (Wf) is in the range of 5 ≦ Wf ≦ 65, and the following formula (II) 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 reinforced 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 respectively represent the average fiber diameter and the average fiber length of the fibrous zonotolite (C)) are simultaneously satisfied. A reinforced polypropylene composition as described in 1. 3. The modified thermoplastic elastomer (B) is at least one elastomer selected from the group consisting of modified ethylene / propylene rubber, modified ethylene / butylene rubber and modified styrene / ethylene / butylene / styrene rubber. The reinforced polypropylene composition according to claim 1 or 2. 4. The reinforced polypropylene composition according to claim 1, wherein the crystalline polypropylene (A) is a modified polypropylene graft-modified with an unsaturated carboxylic acid and / or a derivative thereof. 5. The reinforced polypropylene composition according to claim 1, wherein the coupling agent is a silane coupling agent.