JPH08170015A - Polyamide resin composition - Google Patents

Abstract

PURPOSE: To obtain the subject composition produced by using fibrous xonotlite having a specific shape, offering a good balance in strength, rigidity, heat resistance, etc., having excellent dimensional stability and useful in the field of automobiles, etc. CONSTITUTION: This composition is composed of (A) a polyamide resin, (B) a polyolefin resin and (C) fibrous xonotlite. The component C has a BET specific surface area of >=21m<2> /g determined by nitrogen absorption and its surface is treated with a surfactant and/or a coupling agent. Further, the component C is formed in granulated shape, and wf shown by formula I ([A] is the weight of the component A in the objective composition; [B] is the weight of the component B; [C] is the weight of the component C) satisfies 5<=wf<=70 and wb shown by formula II satisfies 5<=wb<=50.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polyamide resin composition reinforced with fibrous xonotlite,
Molded articles obtained using this composition have a good balance of strength, rigidity, heat resistance, etc., and have excellent dimensional stability, and are used as materials in fields such as automobiles, electric / electronics, and precision machinery. it can.

[0002]

2. Description of the Related Art Improving the properties of polyamide resins (for example, preventing dimensional change due to moisture absorption)
As a method, a method of blending a polyolefin resin is widely known (JP-A-60-179455,
See JP-A-62-236857). But,
It is recognized that these methods reduce mechanical properties such as strength and elastic modulus and heat resistance. In order to prevent deterioration of mechanical properties such as strength and elastic modulus of the polyamide resin and heat resistance caused by blending the polyolefin resin with the polyamide resin as described above, a method of further filling them with an inorganic filler (JP-A-3- 146
553, JP-A-5-98153, etc.)
Is also known. Then, as an example of this inorganic filler, a method using fibrous zonotolite (Japanese Patent Laid-Open No. 4-10)
8855, etc.) has already been disclosed.

However, the conventionally known fibrous zonotolite is apt to aggregate, so that it is poorly wetted with the polyamide resin and has low dispersibility in the polyamide resin, and the expected effects as described above are obtained. Could not be mentioned enough.

In order to improve this point, a method of treating the surface of the fibrous xonotlite with a coupling agent (Japanese Patent Laid-Open No. 3-2980).
-115458, etc.) has also been tried,
No satisfactory effect has been obtained.

[0005]

SUMMARY OF THE INVENTION The object of the present invention is to solve the problems of the above-mentioned conventional polyamide resins, that is, to balance strength, rigidity, and heat resistance. And to provide a polyamide resin composition having excellent dimensional stability.

[0006]

DISCLOSURE OF THE INVENTION 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 a polyamide resin which is a matrix resin and the dispersion in a polyamide resin. Fibrous zonotolite having a specific property excellent in properties, and a polyolefin resin, at a specific ratio, by blending with the polyamide resin that is the matrix resin, strength, elastic modulus and heat resistance and the like are balanced, And by providing a polyamide resin composition having excellent dimensional stability,
It has been found that the present invention can be achieved.

That is, the first invention according to claim 1 is that the polyamide resin (A), the polyolefin resin (B), and the BET specific surface area due to nitrogen adsorption of 21 m ² /
g or more, surface-treated with a surfactant and / or a coupling agent, and composed of fibrous zonotolite (C) granulated into granules, represented by the above formula (I), The weight percentage (wf) of the component (C) in the total composition of the component (A), the component (B), and the component (C) is 5% by weight or more and 70% by weight or less, and The weight percentage (wb) of the component (B) in the sum of the weight of the component (A) and the weight of the component (B) represented by (II) is 5% by weight or more and 50% by weight or less. This can be achieved by providing a characteristic polyamide resin composition.

In a second aspect of the present invention, the fibrous zonotolite (C) has 0.1 μm ≦ D <0.5 μ.
m, 1 μm ≦ L <5 μm and 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. This can be achieved by providing the polyamide resin composition according to the first invention, which is a fibrous zonotolite.

The present invention will be described in detail below. The present invention
The fibrous zonotolite (C) described in Section 1.
(Determination formula: Ca ₆Si₆O₁₇(OH)₂, Chemical formula: 6C
aO ・ 6SiO₂・ H₂O) means a needle-shaped crystalline substance. Book
In the invention, the value of the specific surface area is very important.
m²/ G or more, preferably 30 m²/ G or more (however,
Unless it is the value measured by the BET method by nitrogen adsorption)
I won't. This value is 30m²Fibrous Zono smaller than / g
For Trite, polyamide resin (A) and polyolefin
The wettability with the resin (B) may deteriorate, and in particular, 2
1m²For fibrous xonotlites smaller than / g, this wetting
Achievement of the object of the present invention because the deterioration of the reflexibility is remarkable
I can't.

Further, in the present invention, as the shape of the fiber,
Especially, the average fiber length (L) is 1 μm ≦ L <5 μm, the average fiber diameter (D) is 0.1 μm ≦ D <0.5 μm, and the aspect ratio (L / D) is 10 ≦ L / D <20. Those satisfying at the same time can be preferably used. When D is less than 0.1 μm or L is 5 μm or more, when the fibrous zonotolite (C) is formed into granules, the polyamide resin (A) is used.
And the fibrous zonotolite (C) may be broken during mixing and kneading with the polyolefin resin (B), while D having a value of 0.5 μm or more and L having a value of less than 1 μm give a polyamide resin composition. In some cases, the effect of improving the mechanical strength of the fibrous zonotolite (C) is not sufficient. Further, when L / D is less than 10, the obtained polyamide resin composition 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) may become too small, and it may be difficult to knead when producing the polyamide resin composition of the present invention.

The above-mentioned fibrous xonotlite (C) of the present invention is described in detail below in Japanese Patent Application No. 5-1903.
No. 36 specification, that is, a calcareous raw material and a siliceous raw material are mixed in a specific ratio to produce a hydrothermal synthesis reaction. Examples of calcareous raw materials include quick lime and slaked lime, and those with few impurities are preferable. As the siliceous raw material, silica stone, crushed silica sand and quartz, silicic acid, silicic acid anhydride, silica gel, diatomaceous earth and the like are preferable, and fine powders having few impurities and an average particle diameter of 10 μm or less are desirable. The mixing ratio of both of these (Ca / Si ratio) is preferably slightly smaller than the theoretical equivalent and is 0.8 to 0.99. The proportion of water to be mixed is 5 to 40 times, preferably 8 times the total amount of the calcareous raw material and the 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 above calcined 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 has a reinforcing effect on the composition comprising the polyamide resin (A) described later and the polyolefin resin (B) described later. In order to further improve, it is desirable that the surface is 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 that serves as a matrix, that is, the component (A) or the component (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, any of anionic, cationic, amphoteric and nonionic surfactants can be used. Anionic surfactants include alkyl ether sulfates, dodecylbenzene sulfonates, stearates, etc.Cationic surfactants include tetradecylamine acetate, alkyltrimethylammonium chlorides, and amphoteric surfactants. Examples of the agent include dimethylalkyllaurylpetine, and examples of the nonionic surfactant include polyoxyethylene octadecylamine and polyoxyethylene lauryl ether. Examples of the coupling agent include silane-based coupling agents, titanate-based coupling agents, aluminum-based coupling agents, chromium-based coupling agents, boron-based coupling agents and the like.

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

In the present invention, the fibrous zonotolite slurry obtained by the above-mentioned 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 surface treatment agent is added to the fibrous zonotolite slurry as it is or after adding an appropriate amount of water, and the mixture is stirred and stirred in an appropriate apparatus in a slurry state. Then, excess water is filtered and separated by a centrifugal dehydrator or a filter press to obtain cake-like fibrous zonotolite. Further, for this surface treatment, after drying the fibrous zonotolite slurry, it may be carried out using a surface treatment agent dissolved in a small amount of water or a solvent, but the operation becomes complicated, and the effect of the surface treatment agent is It is small and has no particular merit.

Further, the fibrous zonotolite (C) used in the present invention is granulated for the purpose of easily mixing and kneading with the polyamide resin (A) and the polyolefin resin (B) described later. Granular fibrous zonotolite is
The cake-like fibrous zonotolite to which the surface treatment agent is attached is formed into granules having a diameter of 1 to 8 mm by a granulator, dried, and when a coupling agent is used as the surface treatment agent, It is obtained by performing heat treatment. In this case, the granulator is not particularly limited, and includes a rotary vertical granulator, a rotary drum granulator, a rotary sieving granulator, a screw extrusion granulator, a roll extrusion granulator. A known granulator can be used. When the diameter of the fibrous zonotolite granulated product obtained by granulation deviates from the above range, a single-screw extruder or a twin-screw extruder is used for mixing and kneading with the polyamide resin (A) or the polyolefin resin (B). It becomes difficult to mix and knead with a machine, etc., and it is necessary to sequentially fill and mix and knead with a roll or Banbury mixer, etc., and the fibers may be significantly broken and the mechanical strength may decrease. It is not preferable. 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. .

The polyamide resin (A) used in the present invention is
It is a known one, and a cycloaliphatic lactam (for example, ε-
Polyamides obtained by ring-opening polymerization of caprolactam, enantolactam, lauryllactam, etc., or diamines (hydrazine, ethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, decamethylenediamine, undecamethylenediamine, dodeca). Methylenediamine, 2,2,4-
Trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, m-xylylenediamine, P-xylylenediamine, 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, bis-p- Aminocyclohexylmethane, bis-p-aminocyclohexylpropane, isophoronediamine, etc. and dicarboxylic acid (eg, oxalic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanoic acid, 1,4-cyclohexanedicarboxylic acid) , 1,3-cyclohexanedicarboxylic acid, etc.), or polyamides obtained by polycondensation, or aromatic dicarboxylic acids (eg, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, etc.) in place of the dicarboxylic acid. Happo Group polyamides, polyamides obtained by condensation polymerization of amino acids (eg, ε-aminocaproic acid, 11-aminoundecanoic acid, α-amino acids, etc.), or copolymerized polyamides obtained by copolymerizing these And so on.

Specifically, polycaproamide (nylon 6), polytetramethylene adipamide (nylon 4)
6), polyhexamethylene adipamide (nylon 6
6), polyhexamethylene sebacamide (nylon 61
0), polyhexamethylene dodecanoamide (nylon 6
12), polyhexamethylene terephthalamide (nylon 6T), polyhexamethylene isophthalamide (nylon 6I), polyundecane amide (nylon 11),
Polydodecanamide (nylon 12) and the like, and as copolyamides, nylon 6/66, nylon 6/11, nylon 6/12, nylon 6/610, nylon 6/612, nylon 66/610, nylon 6
/ 66/610, nylon 6/66/12, nylon 6
/ 6T, nylon 6 / 6I, nylon 66 / 6T, nylon 66 / 6I, nylon 6/11 / 6T, nylon 6
/ 12 / 6T, nylon 66/11 / 6T, nylon 6
6/12 / 6T, nylon 11 / 6T / 6I, nylon 12 / 6T / 6I and the like. Further, a mixture of these and the like can be given as a specific example. Among these, nylon 6, nylon 66, nylon 12, nylon 6 /
66, nylon 6/66/12, nylon 66 / 6T and the like can be mentioned as particularly preferable examples. Further, the polyamide resin used in the present invention is not particularly limited in the type and concentration of the terminal group, or the molecular weight and the molecular weight distribution.

Specific examples of the polyolefin resin (B) described in the present invention are polyethylene having various densities and molecular weights, linear low-density polyethylene, ethylene copolymers (ethylene / vinyl acetate copolymer, ethylene / propylene). Copolymer), polypropylene homopolymer, polypropylene copolymer (ethylene
Propylene block copolymer, etc.), polybutene-
1, poly-4-methylpentene-1, etc., and modified products thereof. As the modified product, maleic acid,
Unsaturation of fumaric acid, acrylic acid, itaconic acid, citraconic acid, methacrylic acid, crotonic acid, isocrotonic acid, tetrahydrophthalic acid, endo-bicyclo [2,2,1] -5-heptene-2,3-dicarboxylic acid, etc. Examples thereof include those modified with carboxylic acids and their anhydrides, esters, metal salts, amide compounds, imide compounds and other derivatives. Also, a mixture of these can be used. As the denaturing method, various known methods can be adopted,
For example, the above-mentioned unsaturated carboxylic acid or its derivative is added to polyolefin, and a reaction initiator (hydroperoxide,
Organic peroxides such as dialkyl peroxides and peroxyesters, specifically, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, cyclohexanone peroxide, t-butylperoxybenzoate, etc.) and melt kneading, or , A method in which a polyolefin is dissolved in a solvent and the above-mentioned unsaturated carboxylic acid or derivative thereof and the above reaction initiator are added and reacted. The amount of the unsaturated carboxylic acid or its derivative and the reaction initiator added is 100 parts by weight of the polyolefin.
The amount of unsaturated carboxylic acid or its derivative is 0.001 to 5 parts by weight and the amount of the reaction initiator is 0.001 to 5 parts by weight. In the present invention, among the above polyolefins and modified products thereof, modified products of polypropylene and modified products of polyethylene are often used.

Further, various auxiliary materials added for improving the properties and production of the composition comprising the above-mentioned polyamide resin (A) and polyolefin resin (B), that is, a heat stabilizer, a light stabilizer and a plasticizer. , Cross-linking agent, antioxidant, flame retardant, reinforcing agent, pigment, dye, lubricant, antistatic agent, release agent,
The combined use of a fragrance or the like and the fibrous zonotolite (C) used in the present invention does not cause any problem as long as the reinforcing effect of the fibrous zonotolite (C) of the present invention is not impaired.

By the way, in the present invention, the fiber in the polyamide resin composition represented by the formula (I), which comprises the polyamide resin (A), the polyolefin resin (B) and the fibrous zonotolite (C). The weight percentage (wf) of the zonotolite (C) is from 5% by weight to 70% by weight, preferably from 10% by weight to 50%.
It is necessary that the content is not more than 10% by weight, more preferably not less than 10% by weight and not more than 40% by weight. The weight percentage (wf)
Is less than 5% by weight, mechanical strength and rigidity of the obtained polyamide resin composition are not improved, which is not preferable. On the other hand, if it is more than 70% by weight, the melt flowability of the obtained polyamide resin composition is lowered, molding becomes difficult, and the appearance of the obtained molded product is deteriorated, which is not preferable. In order to surely prevent the occurrence of these unfavorable phenomena, the weight percentage (wf) of the fibrous zonotolite (C) should be in the above-mentioned preferable range, particularly in the more preferable range.

Next, in the present invention, the weight percentage (wb) of the polyolefin resin (B) in both components of the polyamide resin (A) and the polyolefin resin (B) represented by the formula (II). Is 5% by weight or more and 50% by weight or less, preferably 10% by weight or more and 40% by weight
Should be: If the weight percentage (wb) is less than 5% by weight, the effect of modifying them is small. If the weight percentage (wb) is more than 50% by weight, the original characteristics of the polyamide resin (A) as a matrix resin are impaired, which is not preferable. . The weight percentage (wb) is 5% by weight or more and 10
If it is less than 40% by weight or more than 40% by weight and not more than 50% by weight, the above-mentioned undesirable phenomenon may occur.

The polyamide resin composition of the present invention can be manufactured as follows. That is, the polyamide resin composition comprising the fibrous zonotolite (C), the polyamide resin (A) and the polyolefin resin (B) is manufactured by a known method. Generally, the predetermined amount of fibrous zonotolite (C) and polyamide resin (A)
The polyolefin resin (B) and the polyolefin resin (B) are melt-kneaded using a kneader to obtain the polyamide resin composition of the present invention.

At this time, the melt-kneading temperature depends on the polyamide resin (A) and the polyolefin resin (B) used.
A resin having a high melting temperature (usually a polyamide resin) is selected as a reference. That is, it is preferably 10 to 60 ° C. higher than the melting point of the resin having a high melting temperature, and preferably 10 to 40 ° C. higher than the melting point of the resin.
When the melt-kneading temperature is lower than the melting point of the resin + 10 ° C., the melt viscosity of the resin becomes too high in the kneading machine, and a portion having a temperature lower than the melting point of the resin occurs, and the resin solidifies during production. , There is a possibility of causing a kneading failure. Further, if the melt-kneading temperature is higher than the melting point of the resin + 60 ° C., the resin is thermally decomposed or deteriorated, which causes coloring or deterioration of physical properties, which is not preferable. It is needless to say that the melt-kneading temperature should be within the above-mentioned preferable range in order to 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 polyamide resin composition of the present invention is generally obtained in the form of pellets. Among these, an extruder is preferable, and a twin-screw extruder is particularly preferable.

Further, the fibrous zonotolite (C),
Polyamide resin (A) and polyolefin resin (B)
The addition and mixing order of these components during the melt kneading can be arbitrarily selected. For example, the fibrous zonotolite (C) can be prepared by mixing the polyamide resin (A) and the polyolefin resin (B) before the melt kneading. After mixing with
It may be supplied to the hopper of the extruder, or only the polyamide resin (A) and the polyolefin resin (B) may be supplied to the hopper of the extruder and the fibrous zonotolite (C) may be supplied.
May be supplied from the middle of the extruder. Alternatively, only the polyamide resin (A) may be supplied to the hopper of the extruder, and the polyolefin resin (B) and the fibrous zonotolite (C) may be supplied simultaneously or separately from the middle of the extruder. In addition, when manufacturing the said polyamide resin composition, the said various auxiliary materials can also be added simultaneously as needed.

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

[0028]

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

(1) Bending property: Tensilon UTM-5T manufactured by Orientec Co., Ltd. was used for measurement. After molding the desired polyamide resin composition,
Conditioning was performed in a desiccator at 23 ° C. for 48 hours. Then, the bending strength and bending elastic modulus are measured by ASTM D7.
90, 23 ° C. and absolute dryness.

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

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

(4) Dimensional stability Using the desired polyamide resin composition, the dimension is 100
After injection molding of a flat plate having a size of 100 mm × width 100 mm × thickness 3 mm and performing the same condition adjustment as in the above (1), the MD direction (flow direction) of this flat plate was measured by Mitsutoyo Co., Ltd. It measured using the former measuring device BX303. And further, after immersing this plate in hot water at 90 ° C. for 5 hours,
The dimension was measured by the above method, and the dimensional change rate was obtained.

Reference Example 1 Quick lime (a product of Calseed Co., Ca,
O purity: 98%) 430 g, siliceous silica powder as a siliceous raw material (product of Japan General Corp., Blaine specific surface area: 7,000 cm ² / g, SiO ₂ purity: 97%) 4
70 g and 18 liters of tap water were put into an autoclave equipped with a stirrer made of SUS316 and having an internal volume of 30 liters. Then, while stirring at a rotation speed of 80 rpm, the temperature is raised to a holding temperature of 220 ° C. at a rate of 2 ° C./min, and a holding temperature of 22 ° C.
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, about 920 g of this fibrous xonotlite slurry (based on solid content), about 18 liters of tap water and a nonionic surfactant (polyoxyethylene octadecylamine, a product of NOF Corporation, trade name: Nymeen 204) were used. ) 46 g (5 relative to fibrous zonotolite solids)
(% By weight) was added and surface treatment was performed while dispersing with a homogenizer. After dewatering this slurry with a nutche to form a cake, it was molded into a diameter of 3 mm with a granulator,
The surface-treated granular fibrous zonotolite was obtained by drying at 0 ° C. This granular fibrous Xonotlite was measured for the average fiber length and average fiber diameter by the measurement and scanning electron micrograph of the BET specific surface area by nitrogen adsorption, respectively, 39m ² /
g, 3 μm and 0.2 μm (hence the aspect ratio:
15). The fibrous zonotolite thus obtained is hereinafter referred to as "fibrous zonotolite A".

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

Reference Example 3 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 C".

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

Reference Example 5 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 E".

Reference Examples 6 and 7 In Reference Examples 6 and 7, respectively,
Γ-Aminopropyltrieth instead of on-type surfactant
Xysilane and γ-glycidoxypropyltrimethoxy
Except for using silane, the same procedure as in Reference Example 1
After granulating the cake-like fibrous zonotolite,
Dry at 00 ℃ and heat treatment at 120 ℃ for 20 minutes.
Surface treated granular fibrous zonotoly
Got The obtained product was used for both Reference Examples 6 and 7.
BET specific surface area is 39m ²/ G, average fiber length
3 μm and an average fiber diameter of 0.2 μm (hence the asperity
The ratio was 15). Hereinafter, these are referred to as Reference Example 6 and
Regarding "7" and "7", "Fibrous zonotolite F" and
And "fibrous zonotolite G".

Example 1 Polypropylene resin (trade name: UB, manufactured by Ube Industries, Ltd.)
E Polypro B101H, abbreviated as "PP resin" hereinafter) 1
0.2 parts by weight of maleic anhydride and t-
Add 0.2 parts by weight of butyl peroxybenzoate and add 3
Kneaded at 230 ° C using a 0 mm single screw extruder to obtain modified PP
A resin was obtained. Next, using a co-rotating twin-screw extruder (cylinder diameter: φ30 mm, manufactured by Ikegai Iron Works Co., Ltd., model: PCM30) at 240 ° C. (however, the temperature of the nozzle part is the same below), Nylon 6 resin (manufactured by Ube Industries, Ltd., trade name: UBE Nylon 101) that was mixed in advance using a V-type blender
3B) A mixture of 87.5% by weight and the above-mentioned modified PP resin 12.5% by weight, and the fibrous zonotolite A obtained in Reference Example 1 in a proportion of 80 parts by weight of the mixture and 20 parts by weight of the fibrous zonotolite A. Were melt-kneaded to prepare pellets composed of 70% by weight of the nylon 6 resin, 10% by weight of the modified PP resin and 20% by weight of the fibrous zonotolite A. 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. Next, injection molding machine (manufactured by Japan Steel Works Ltd., model: N)
100) is used to injection-mold the pellets at a cylinder temperature (however, the temperature of the nozzle head portion, the same applies below) at 240 ° C. and a mold temperature of 75 ° C.,
Physical property test pieces and flat plates were prepared. Table 1 shows the results of the physical property tests of the obtained material.

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

Comparative Examples 1 to 3 In Comparative Examples 1, 2 and 3, the fibrous zonotolite A was used.
The same operation as in Example 1 was carried out except that the fibrous zonotolites C, D and E obtained in Reference Examples 3, 4 and 5 were used instead of, respectively. The physical property test results of the materials obtained in Comparative Examples 1 and 2 are shown in Table 1, respectively. Further, in the case of Comparative Example 3 using the fibrous zonotolite E, as shown in Table 1, a uniform kneaded product was not obtained and molding could not be performed.

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

Example 4 Nylon 66 resin (manufactured by Ube Industries, Ltd., trade name: UBE Nylon 2020B) was used instead of Nylon 6 resin, and the melting and kneading temperature was changed to 240 ° C. and 290 ° C.
The same as Example 1 except that the cylinder temperature of the injection molding machine was changed to 240 ° C. to 290 ° C., and the mold temperature of the injection molding machine was changed from 75 ° C. to 100 ° C. The operation was performed. Table 1 shows the physical property test results of the obtained materials.

Example 5 Example 4 was repeated except that the fibrous zonotolite G obtained in Reference Example 7 was used in place of the fibrous zonotolite A.
The same operation was performed. Table 1 shows the physical property test results of the obtained materials.

Example 6 The weight percentages of nylon 6 resin and modified PP resin in the resulting pellets were changed from 70% by weight and 10% by weight, respectively, by changing the amounts of nylon 6 resin and modified PP resin used in Example 1. The same operation as in Example 1 was performed except that the amounts were changed to 60% by weight and 20% by weight. Table 1 shows the physical property test results of the obtained materials.

Example 7 The weight percentages of nylon 6 resin, modified PP resin and fibrous zonotolite A in the obtained pellets were changed by changing the amounts of nylon 6 resin, modified PP resin and fibrous zonotolite A used in Example 1. , 70% by weight, 10% by weight
And 20 to 50% by weight, 15% by weight, respectively
And the same operation as in Example 1 except that the content was changed to 35% by weight. Table 1 shows the physical property test results of the obtained materials.

Comparative Example 4 By changing the amounts of the nylon 6 resin and the modified PP resin used in Example 1, the weight percentages of the nylon 6 resin and the modified PP resin in the obtained pellets were 70% by weight and 10% by weight, respectively. The same operation as in Example 1 was performed except that the amounts were changed to 77% by weight and 3% by weight.
Table 1 shows the physical property test results of the obtained materials.

Comparative Example 5 By changing the amounts of the nylon 6 resin and the modified PP resin used in Example 1, the weight percentages of the nylon 6 resin and the modified PP resin in the pellets obtained were 70% by weight and 10% by weight, respectively. Except for changing to 36% by weight and 44% by weight, the same operation as in Example 1 was performed. Table 1 shows the physical property test results of the obtained materials.

Example 8 With respect to 100 parts by weight of a high-density polyethylene resin (trade name: J-6311, manufactured by Tonen Petrochemical Co., Ltd.), 0.2 part by weight of maleic anhydride and 0.2 part of t-butylperoxybenzoate. 25 parts by weight using a 30 mm single screw extruder.
The mixture was kneaded at 0 ° C to obtain a modified polyethylene resin. Therefore,
The above modified polyethylene resin was used in place of the modified PP resin of Example 1, the melt-kneading temperature was changed to 240 ° C to 280 ° C, and the cylinder temperature of the injection molding machine was changed to 240 ° C to 290 ° C. And the same operation as in Example 1 except that the mold temperature of the injection molding machine was changed from 75 ° C to 100 ° C. Table 1 shows the physical property test results of the obtained materials.

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[Table 1]

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As is clear from the above Examples and Comparative Examples, the present invention makes it possible to balance strength, rigidity, heat resistance, etc. by using fibrous zonotolite having specific properties. A polyamide resin composition having excellent dimensional stability can be provided. Therefore, the polyamide resin composition obtained by the present invention can be used as a material in the fields of automobiles, electric / electronics, precision machinery and the like.

Claims (2)

[Claims] 1. A polyamide resin (A), a polyolefin resin (B) and a fibrous zonotolite (C), wherein the component (C) has a BET specific surface area of 21 m ² / g or more due to (1) nitrogen adsorption. And (2) is surface-treated with a surfactant and / or a coupling agent, and
(3) Granulated into granules, and the numerical formula (I) The weight percentage (wf) of the component (C) in the total composition consisting of the component (A), the component (B), and the component (C) represented by
Furthermore, the mathematical expression (II) The weight percentage (w) of the component (B) in the sum of the weight of the component (A) and the weight of the component (B) represented by
b) is in the range of 5 ≦ wb ≦ 50, wherein the polyamide resin composition is characterized. 2. The fibrous zonotolite (C) comprises (1)
0.1 μm ≦ D <0.5 μm, (2) 1 μm ≦ L <5 μ
m and (3) 10 ≦ L / D <20 (wherein D and L respectively represent the average fiber diameter and the average fiber length of the fibrous zonotolite (C)) are simultaneously satisfied. The polyamide resin composition described in 1.