JPH07330962A - Bead filler rubber composition - Google Patents

Abstract

PURPOSE:To obtain a bead filler rubber composition giving a vulcanizate excellent in modulus, flex cracking resistance, etc., by incorporating given amounts of natural rubber, polyisoprene, carbon black, etc., into a fiber-reinforced thermoplastic composition having a specific composition. CONSTITUTION:A fiber-reinforced thermoplastic resin (A) obtained by dispersing fine fibers of a thermoplastic polymer having amide groups in the main chain into a matrix comprising a polyolefin and a vulcanizable rubber to bond the fibers to the matrix is mixed with a natural rubber and/or polyisoprene (B), a diene rubber (C) other than the ingredient (B), and carbon black (D) to obtain the objective composition. The amount of the thermoplastic polymers is 2-20 pts.wt. per 100 pts.wt. all rubber, and the sum of the natural rubber or polyisoprene in the ingredient (A) and the ingredient (B) is 100-55wt.% based on all rubbers. The amount of the ingredient (D) is 50-70 pts.wt. per 100 pts.wt. all rubbers. This composition is regulated so as to give a vulcanizate having a modulus at 50% elongation of 30kg/cm<2> or higher.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION This invention relates to the Mooney viscosity (M
The present invention relates to a bead filler rubber composition having a small L), excellent workability, and good flex crack growth resistance of a vulcanized product.

[0002]

2. Description of the Related Art Recently, with the development of highways and the like, tires are required to have more severe high-speed durability. It is well known that the higher the speed of a tire, the more likely it is that a standing wave phenomenon will occur, leading to tire destruction. One of the effective methods of suppressing this standing wave phenomenon is to improve the rigidity of the bead portion. In addition, since increasing the elastic modulus of the bead portion is also effective in reducing rolling resistance,
A bead filler rubber having a high elastic modulus is preferable. On the other hand, once the standing wave phenomenon occurs, the bead portion is largely deformed. Therefore, from a safety point of view, it is necessary that the bead filler rubber has good crack growth resistance and does not directly lead to tire destruction. That is, the conditions required for the bead filler rubber to improve the high speed durability of the tire include high elastic modulus and good crack growth resistance.

Various methods have hitherto been attempted as a method for obtaining a rubber having a high elastic modulus. The method of blending a large amount of carbon black is such that the rubber is not well organized in the processing step, the electric power load is increased when kneading the Banbury mixer, and the blending ML becomes large, which causes difficulty in tire molding work. Therefore, it is not preferable. In the method of adding a large amount of sulfur, the plume of sulfur and the physical properties such as bending crack growth property due to an increase in crosslink density are remarkably lowered. Addition of a thermosetting resin is also a method of giving a highly elastic rubber. However, since a large amount of thermosetting resin has low compatibility with natural rubber and diene rubber, manufacturing conditions such as prolonging the kneading time are severely restricted in order to obtain a good dispersion state. In addition, since a kneaded dough containing a large amount of thermosetting resin is hard even when it is not vulcanized, it causes a large load and poor molding workability during kneading and extrusion. In the method of simply blending the short fibers, the creep is increased or the fatigue life is shortened because the short fibers and the rubber are not sufficiently bonded.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to obtain a bead filler rubber composition having a large vulcanizate elastic modulus, good flex crack growth resistance and small Mooney viscosity.

[0005]

The present invention is directed to a fiber reinforced thermoplastic composition, that is, (1) polyolefin ((1) component) (2) vulcanizable rubber ((2) component) (3) main Thermoplastic polymer having amide groups in the chain
(Component (3)), wherein component (1) and component (2) constitute a matrix, and (3) is contained in the matrix.
A composition in which the components are dispersed as fine fibers, and the component (3) is combined with the components (1) and (2), natural rubber, polyisoprene, or a mixture of both (B). ), A diene rubber (C) excluding natural rubber and polyisoprene, and carbon black (D), and satisfying the following conditions (i) to (iv): The present invention relates to a rubber composition. (I) The amount of the thermoplastic polymer (component (3)) is 2 to 20 parts by weight based on 100 parts by weight of the total rubber component, and (ii) the natural rubber in the component (A) in the rubber component. Alternatively, the total amount of polyisoprene and the component (B) is 100 to 5
5% by weight, (iii) the amount of carbon black (D) is 50 to 70 parts by weight based on 100 parts by weight of the total of the rubber components, and (iv) the vulcanized product has a 50% tensile modulus. M ₅₀ is 30 kg / cm ² or more.

Further, according to the present invention, the fine fibers of the thermoplastic polymer (component (3)) having an amide group in its main chain in the fiber reinforced thermoplastic composition (A) have a fine fiber content of 0.05 to 1. 0μ
A bead filler rubber composition having an average diameter of m.

In the present invention, the polyolefin ((1) component) in the fiber-reinforced thermoplastic composition (A) is 50 ° C.
The present invention relates to a bead filler rubber composition having a softening point or a melting point in the range of 80 to 250 ° C.

Further, in the present invention, the vulcanizable rubber (component (2)) in the fiber-reinforced thermoplastic composition (A) is 10 to 100 parts by weight of polyolefin (component (1)).
It relates to a bead filler rubber composition which is 400 parts by weight.

The bead filler rubber composition of the present invention comprises
The Mooney viscosity ML _{1 + 4} (100 ° C.) (hereinafter sometimes simply referred to as ML) is small, and the vulcanized product has a 50% modulus (hereinafter sometimes simply referred to as M ₅₀ ) of 30 kg /
cm ² or more, the number of times of bending by the bending crack growth resistance test is 1000 times or more, the workability is excellent, the elastic modulus of the vulcanized product is large, and the crack growth resistance is good.

In the present invention, a composition comprising (1) a polyolefin, (2) a vulcanizable rubber, and (3) a thermoplastic polymer having an amide group in the main chain,
The component (1) and the component (2) constitute a matrix, the component (3) is dispersed as fine fibers in the matrix, and the component (3) is the component (1) and the component (2). ) It is essential to blend a fiber-reinforced thermoplastic composition bonded to the component, and thereby a rubber composition having excellent processability can be obtained despite blending the fibers of the thermoplastic polymer. is there.

First, the fiber-reinforced thermoplastic composition of the present invention will be described. This fiber reinforced thermoplastic composition,
(1) Polyolefin, (2) Vulcanizable rubber, and (3) Thermoplastic polymer having an amide group in the main chain are main constituent components, and (1) component and (2) component form a matrix. Most of the component (3) is dispersed as fine fibers in the matrix. Then, the fine short fibers of the component (3) are bonded to the matrix.

The components (1), (2) and (3) of this fiber reinforced thermoplastic composition will be described below. The component (1) is a polyolefin, and is 80-
It has a melting point of 250 ° C. Further, those having a Vicat softening point of 50 ° C. or higher, particularly those having a Vicat softening point of 50 to 200 ° C. are also preferably used. Examples of such polyolefins include homopolymers and copolymers of olefins of C ₂ -C _8, and, olefin and styrene and chlorostyrene of C ₂ -C _8, such as α- methylstyrene and an aromatic vinyl compound copolymers, copolymers of olefin and vinyl acetate C ₂ -C _8, a copolymer of an olefin with acrylic acid or its esters of C ₂ -C _8, olefin and methacrylic acid C ₂ -C ₈ Alternatively, a copolymer with an ester thereof and a copolymer of a C _{2 to} C ₈ olefin and a vinylsilane compound are preferably used.

Specifically, for example, high density polyethylene, low density polyethylene, polypropylene, ethylene
Propylene block copolymer, ethylene / propylene random copolymer, linear low density polyethylene, poly-4-methylpentene-1, polybutene-1, polyhexene-
1, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ethylene / methyl acrylate copolymer,
Ethylene / ethyl acrylate copolymer, ethylene / propyl acrylate copolymer, ethylene / butyl acrylate copolymer, ethylene / 2-ethylhexyl acrylate copolymer, ethylene / hydroxyethyl acrylate copolymer, ethylene / Examples thereof include a vinyltrimethoxysilane copolymer, an ethylene / vinyltriethoxysilane copolymer, an ethylene / vinylsilane copolymer, an ethylene / styrene copolymer, and a propylene / styrene copolymer. or,
Halogenated polyolefins such as chlorinated polyethylene, brominated polyethylene and chlorosulfonated polyethylene are also preferably used. These polyolefins may be used alone or in combination of two or more.

Next, the component (2) will be described.
The component (2) is a vulcanizable rubber, and examples thereof include natural rubber, polyisoprene, polybutadiene, styrene-butadiene rubber, butyl rubber, chlorinated butyl rubber, brominated butyl rubber, and acrylonitrile-butadiene rubber. Of these, natural rubber is preferable. Further, those obtained by subjecting these rubbers to epoxy modification, silane modification, or maleation are also used.

Next, the component (3) will be described.
The component (3) is a thermoplastic polymer having an amide group in the main chain and modified with a silane coupling agent.

Examples of the thermoplastic polymer having an amide group in the main chain include thermoplastic polyamide and urea resin. Of these, the melting point is preferably 135 ° C.
To 350 ° C., and particularly preferable is a thermoplastic polyamide having a melting point of 150 ° C. to 300 ° C.

As the thermoplastic polyamide, nylon 6, nylon 66, nylon 6-nylon 66 copolymer, nylon 610, nylon 612, nylon 46,
Nylon 11, Nylon 12, Nylon MXD6, Polycondensate of xylylenediamine and adipic acid, Polycondensate of xylylenediamine and pimelic acid, Polycondensate of xylylenediamine and speric acid, Xylylenediamine and azelaine Polycondensate with acid, Polycondensate with xylylenediamine and sebacic acid, Polycondensate with tetramethylenediamine and terephthalic acid, Polycondensate with hexamethylenediamine and terephthalic acid, Polycondensation with octamethylenediamine and terephthalic acid Body, polycondensate of trimethylhexamethylenediamine and terephthalic acid, polycondensate of decamethylenediamine and terephthalic acid, polycondensate of undecamethylenediamine and terephthalic acid, polycondensate of dodecamethylenediamine and terephthalic acid, tetramethylene Hexane, a polycondensate of diamine and isophthalic acid Polycondensate of methylenediamine and isophthalic acid, Polycondensate of octamethylenediamine and isophthalic acid, Polycondensate of trimethylhexamethylenediamine and isophthalic acid, Polycondensate of decamethylenediamine and isophthalic acid, Undecamethylenediamine and isophthalic acid Examples thereof include polycondensates of acids and polycondensates of dodecamethylenediamine and isophthalic acid.

Among these thermoplastic polyamides, the most preferable one is a thermoplastic polyamide having a melting point of 160 to 265 ° C., specifically, nylon 6, nylon 66, nylon 6-nylon 66 copolymer, nylon 6
10, nylon 612, nylon 46, nylon 11,
And nylon 12 and the like.

In the thermoplastic composition used in the present invention, the component (1) and the component (2) form a matrix. This matrix may have a structure in which the component (2) is dispersed in the component (1) in an island shape, and conversely, a structure in which the component (1) is dispersed in the component (2) in an island shape. May be taken. The component (1) and the component (2) are preferably bonded to each other at the interface.

Most of the component (3) is dispersed in the matrix as fine fibers. Specifically, 70% by weight, preferably 80% by weight, and particularly preferably 90% by weight or more are dispersed as fine fibers.
The average fiber diameter of the fibers of the component (3) is preferably 1 μm or less, and a particularly preferable range is 0.05 to 0.8 μm.
The range is m. Aspect ratio (fiber length / fiber diameter) is 1
It is preferably 0 or more. And the component (3) is
The matrix composed of the components (1) and (2) is bonded to the interface. This can be confirmed, for example, as follows. First, the fiber-reinforced thermoplastic composition is refluxed in a solvent that dissolves only the components (1) and (2), such as xylene, to remove the components (1) and (2). When the remaining fiber of the component (3) was dissolved in a solvent and the NMR was measured, the components (1) and (2)
The peaks derived from the components can be observed. This is considered to indicate that the component (1) and the component (2) are bound to the surface of the fiber in some form.

The proportions of the component (1), the component (2), and the component (3) are preferably as follows. The component (2) is preferably in the range of 10 to 400 parts by weight, particularly preferably in the range of 20 to 250 parts by weight, and most preferably in the range of 50 to 200 parts by weight, relative to 100 parts by weight of the component (1).
The ratio of the component (2) is 30 with respect to 100 parts by weight of the component (1).
If it is more than 0 parts by weight, only a fiber-reinforced thermoplastic composition which is difficult to pelletize can be obtained, which is not preferable. The ratio of the component (3) is 10 to 40 with respect to 100 parts by weight of the component (1).
It is preferably in the range of 0 parts by weight, particularly 5 to 300
A range of parts by weight is preferred and a range of 10 to 300 parts by weight is most preferred. The ratio of (3) component is (1) component 100
When it exceeds 400 parts by weight, fine fibers of the component (3) are not formed in the fiber-reinforced thermoplastic composition, so that a fiber-reinforced elastic body is produced using such a fiber-reinforced thermoplastic composition. This is because a fiber-reinforced elastic body having high strength cannot be obtained.

The fiber reinforced thermoplastic composition can be produced by the following steps. The fiber-reinforced thermoplastic composition of the present invention comprises the following steps, namely, step 1: a step of preparing a matrix comprising the components (1) and (2), step 2: the component (3) is reacted with a binder. Step, Step 3: A step of melting and kneading the matrix and the component (3) reacted with the binder, Step 4: The obtained kneaded product is extruded at a temperature equal to or higher than the melting point of the component (3), and then It can be produced by a step of stretching and / or rolling at a temperature lower than the melting point of the component (3).

First, the step of preparing a matrix comprising the component (1) and the component (2) will be described. To prepare a matrix composed of the components (1) and (2),
For example, the component (1) may be first melt-kneaded together with the binder to react, and this may be melted and kneaded with the component (2).
Further, the component (1) and the component (2) are melted together with a binder,
You may knead. The melting and kneading can be performed by an apparatus that is usually used for kneading resins and rubber. As such an apparatus, a Banbury type mixer, a kneader, a kneader extruder, an open roll, a uniaxial kneader,
A biaxial kneader or the like can be used.

The amount of the binder is preferably in the range of 0.1 to 2.0 parts by weight, particularly preferably 0.2 to 1.0 part by weight, based on 100 parts by weight of the component (1). When the amount of the binder is less than 0.1 part by weight, a composition having high strength cannot be obtained, and when it is more than 2.0 parts by weight, a composition having an excellent modulus cannot be obtained.

As the binder, a silane coupling agent,
Titanate coupling agent, novolac type alkylphenol formaldehyde initial condensation product, resol type alkylphenol formaldehyde initial condensation product, novolac type phenolformaldehyde initial condensation product, resole type phenolformaldehyde initial condensation product, unsaturated carboxylic acid and its derivatives, organic peroxides, etc. Any of the commonly used polymer coupling agents can be used. Among these binders, the silane coupling agent is preferable because it hardly gels the component (1) or the component (2) and can form a strong bond at the interface between these components. Examples of the silane coupling agent include vinylalkoxysilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltris (β-methoxyethoxy) silane, vinyltriacetylsilane, γ-methacryloxypropyltrimethoxysilane, γ- [N- (Β-
Methacryloxyethyl) -N, N-dimethylammonium (chloride)] propylmethoxysilane, styryldiaminosilane, etc., having a group and / or a polar group that easily desorbs a hydrogen atom from other groups such as vinyl group and alkyloxy group. Silane coupling agents are preferably used.

When using a silane coupling agent as a binder, an organic peroxide can be used together. As the organic peroxide, one having a one-minute half-life temperature in the range of the same temperature as the melting point of the component (1) or the melting point of the component (2), whichever is higher, or about 30 ° C. higher than this temperature. It is preferably used. Specifically, the one-minute half-life temperature is 110
Those having a temperature of about 200 ° C. are preferably used. Examples of the organic peroxide include 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane and 1,1-
Di-t-butylperoxycyclohexane, 2,2-di-t-butylperoxybutane, 4,4-di-t-butylperoxyvaleric acid n-butyl ester, 2,2-
Bis (4,4-di-t-butylperoxycyclohexane) propane, 2,2,4-trimethylpentyl peroxyneodecanoate, α-cumyl peroxyneodecanoate, t-butyl peroxyneohexanoate, peroxypivalin T-butyl acid, t-butyl peroxyacetate, t-butyl peroxylaurylate, t-peroxybenzoic acid
-Butyl, t-butyl peroxyisophthalate and the like can be mentioned.

The amount of organic peroxide used is (1) component 10
The range of 0.01 to 1.0 parts by weight is preferable with respect to 0 parts by weight.

However, when the components (1) and (2) are melted and kneaded together with a silane coupling agent to modify the silane, the component (2) includes natural rubber and polyisoprene.
Alternatively, when the styrene / isoprene / styrene block copolymer is used, the organic peroxide may not be used.
Rubber having an isoprene structure, such as natural rubber, polyisoprene, and styrene / isoprene / styrene block copolymers, is a type that has a -COO / group at the end of the main chain due to the main chain breaking due to a mechanochemical reaction during kneading. This is because it is considered that the above-mentioned peroxide is generated, and that this acts almost in the same manner as the above-mentioned organic peroxide.

Next, the step of kneading the component (3) with the above matrix will be described. The component (3) may be melt-kneaded with the binder in advance and reacted, and then melt-kneaded with the matrix, or may be melt-kneaded with the matrix in the presence of the binder. Melt kneading can be carried out with an apparatus usually used for kneading resins and rubbers, for example, Banbury type mixer, kneader, kneader extruder, open roll, uniaxial kneader, and biaxial kneader. The same as in the case of preparation.

In the case of the binder for the component (3),
When the total amount of the component (3) and the binder is 100% by weight, the range of 0.1 to 5.5% by weight is preferable, and the range of 0.2 to
A range of 5.5% by weight is particularly preferable, 0.2 to 3% by weight
Is most preferable.

As the binder, a silane coupling agent,
Titanate coupling agent, novolac type alkylphenol formaldehyde initial condensation product, resol type alkylphenol formaldehyde initial condensation product, novolac type phenolformaldehyde initial condensation product, resole type phenolformaldehyde initial condensation product, unsaturated carboxylic acid and its derivatives, organic peroxides, etc. Any of the commonly used polymer coupling agents can be used. Among these binders, the silane coupling agent is the most preferable in that it hardly gels the component (3) and can form a strong bond at the interface with the matrix. Examples of the silane coupling agent include those having a group capable of forming a bond with the nitrogen atom of the —NHCO— bond of the component (3), such as an alkyloxy group, by a dehydration reaction or a dealcoholization reaction. Examples of the silane coupling agent include vinylalkoxysilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltris (β-methoxyethoxy) silane, vinyltriacetylsilane, γ-methacryloxypropyltrimethoxysilane. , Γ- [N- (β-methacryloxyethyl) -N, N-dimethylammonium (chloride)]
Propylmethoxysilane, N-β (aminoethyl) γ-
Examples include aminopropyltrimethoxysilane, styryldiaminosilane, and γ-ureidopropyltriethoxysilane.

In this step, the matrix and (3)
The temperature for melting and kneading the components must be at least the melting point of the component (3). Even if melting and kneading are performed at a temperature lower than the melting point of the component (3), the kneaded product does not have a structure in which the fine particles of the component (3) are dispersed in the matrix, and thus the kneaded product is spun. The reason for this is that the component (3) cannot be made into fine fibers even when stretched. The kneading temperature is
It is preferable that the temperature is equal to or higher than the melting point or Vicat softening point of the component (1) polyolefin.

The kneaded product obtained in the above step is extruded from a spinneret, an inflation die or a T die, and then stretched or rolled.

In this step, the fine particles of the component (3) in the kneaded material are transformed into fibers by spinning or extrusion.
This fiber is subjected to a drawing treatment by subsequent drawing or rolling to become a stronger fiber. Therefore, spinning and extrusion must be carried out at a temperature above the melting point of component (3),
Stretching and rolling must be carried out at a temperature lower than the melting point of component (3).

The spinning or extrusion and the subsequent stretching or rolling may be carried out, for example, by extruding the kneaded product from the spinneret, spinning it into a string or thread, and winding it on a bobbin while drafting it. Can be implemented. Here, "drafting" means that the winding speed is higher than the spinning speed. The winding speed / spinning speed ratio (draft ratio) is 1.5 to
The range of 100 is preferable, and the range of 2 to 50 is particularly preferable. The most preferable draft ratio range is 3 to 30.

This step can also be carried out by continuously rolling the spun kneaded product with a rolling roll or the like. Further, the kneaded product can be extruded from an inflation die or a T die and wound on a roll or the like while being drafted. Further, instead of winding a draft while winding it on a roll, it may be rolled by a rolling roll or the like.

The stretched or rolled fiber-reinforced thermoplastic composition (A) is preferably pelletized. The fiber-reinforced thermoplastic composition is made into pellets, such as natural rubber, polyisoprene or a mixture of both (B), diene rubber (C) excluding natural rubber and polyisoprene, and carbon black (D), This is because they can be kneaded uniformly. Next, the bead filler rubber composition of the present invention,
The fiber-reinforced thermoplastic composition (A), natural rubber, polyisoprene or a mixture of both (B), a diene rubber (C) excluding natural rubber and polyisoprene, and carbon black (D) are blended. It is a thing.

Examples of the diene rubber (C) include polybutadiene, styrene-butadiene copolymer rubber, isoprene-isobutylene copolymer and the like. As the carbon black (D), those having a particle size of 90 mμ or less and a dibutyl phthalate (DBP) oil absorption amount of 70 ml / 100 g or more are preferably used. As carbon black, for example, HAF, FF, FEF, GPF, SAF, I
Various carbon blacks such as SAF and SRF are used.

In each of the above components, (i) the amount of the thermoplastic polymer (component (3)) is 2 to 20 parts by weight based on 100 parts by weight of the total of the rubber components, and (ii) in the rubber component,
The total amount of the natural rubber or polyisoprene in the component (A) and the component (B) is 100 to 55% by weight, and (iii)
The amount of carbon black (D) is 50 to 70 parts by weight based on 100 parts by weight of the total of the rubber component, and the vulcanized product of (iv) composition has a 50% tensile modulus M ₅₀ of 30 kg / cm ² . Blend so as to satisfy each condition of and.

If the amount of the thermoplastic polymer is less than the above lower limit, a rubber composition having a small ML and a large elastic modulus and a large number of bendings cannot be obtained. If the amount of the thermoplastic polymer is more than the above upper limit, The ML of the composition becomes large and processing becomes difficult. If the blending ratio of natural rubber or polyisoprene is outside the above range, the number of flexing of the vulcanized product tends to be small. If the amount of carbon black is less than the lower limit, the elastic modulus of the vulcanized product will be small, and if the amount of carbon black is more than the upper limit, the ML of the rubber composition will be large.
Further, if the M _{50 of the} vulcanized product is outside the above range, it is not suitable as a bead filler rubber composition.

The bead filler rubber composition of the present invention comprises
It can be obtained by mixing the above components using a kneader such as a Banbury mixer, a kneader, an open roll, and a twin-screw kneader. The kneading temperature needs to be lower than the melting point of the thermoplastic polymer that constitutes the fine short fibers in the fiber-reinforced thermoplastic composition. Kneading at a temperature higher than the melting point of this thermoplastic polymer is not preferable because the fine short fibers in the fiber-reinforced thermoplastic composition are melted and transformed into spherical particles or the like.

Further, the fiber-reinforced thermoplastic composition is preferably pelletized. When the pellet-shaped fiber-reinforced thermoplastic composition is used, the fiber-reinforced thermoplastic composition (A) can be uniformly kneaded with the components (B), (C) and (D), and fine fibers are uniformly dispersed. This is because the bead filler rubber composition can be easily obtained.

Additives such as a vulcanizing agent are added to the bead filler rubber composition of the present invention. As the vulcanizing agent, known vulcanizing agents such as sulfur, organic peroxides, and sulfur-containing compounds can be used. The method of compounding the vulcanizing agent with the rubber composition is not particularly limited, and a compounding method known per se can be adopted. With the vulcanizing agent,
Thermosetting resin, white carbon, activated calcium carbonate, ultrafine magnesium silicate, high styrene resin, coumarone indene resin, phenol resin, lignin, modified melamine resin, petroleum resin and other reinforcing agents, various grades of calcium carbonate, Fillers such as basic magnesium carbonate, clay, zinc white, diatomaceous earth, reclaimed rubber, powder rubber, ebonite powder, aldehydes, ammonia, aldehydes
Vulcanization accelerators such as amines, guanidines, thioureas, thiazoles, thiurams, dithiocarbamates and xanthates, vulcanization accelerators such as metal oxides and fatty acids, amine aldehydes, amine ketones , Amines, funols, imidazoles, sulfur-containing or phosphorus-containing anti-aging agents, naphthene-based or aromatic-based process oils and the like within a range that does not impair the effects of the present invention to prepare a composition. You can In particular, it is preferable to add 1 to 30 parts by weight of a thermosetting resin such as a novolac type phenolic resin to 100 parts by weight of the rubber in the rubber composition of the present invention.

The vulcanization temperature of the rubber composition of the present invention is 100-.
About 190 ° C is preferable. However, the vulcanization temperature needs to be lower than the melting point of the thermoplastic resin forming the fine fibers in the rubber composition. When vulcanization is performed at a temperature equal to or higher than the melting point of this thermoplastic resin, the fibers formed in the stage of preparing the bent-angle fiber-reinforced thermoplastic composition are melted, excellent in processability, and the vulcanized product has a tensile modulus of elasticity. This is because a large rubber composition cannot be obtained.

The rubber composition of the present invention is excellent in processability because of its low Mooney viscosity, moreover, the vulcanizate has an M ₅₀ of 30 kg / cm ² or more, a flexing number of 1000 or more, and a large elastic modulus. Flex crack growth resistance is excellent, instead of a conventionally known bead filler rubber composition, a passenger car,
It can be used as a tire member for buses, trucks, airplanes, etc. together with other tire members (sidewalls, treads, chafers, rims, etc.).

[0046]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples. In Examples and Comparative Examples,
Regarding the observation of the dispersion shape of ((3) component) in the fiber reinforced thermoplastic composition, and the Mooney viscosity, the tensile elastic modulus, the tensile strength, the hardness and the number of flexing of the obtained bead filler rubber composition, Was measured.

(1) (3) in the fiber-reinforced thermoplastic composition
Observation of dispersion form of components: Pellets of each sample were mixed with a mixed solvent of o-dichlorobenzene and xylene (volume ratio 50: 5).
The mixture was refluxed in 0) at 100 ° C. to extract and remove the polyolefin and elastomer therein, and the remaining fibers were observed with an electron microscope. (2) Mooney viscosity According to JIS K6300, Mooney viscosity M at 100 ° C.
L _{1 + 4} was measured. (3) Tensile Elastic Modulus, Tensile Strength, Hardness Tensile elastic modulus M ₅₀ , tensile strength, and hardness were measured according to JIS K6301. (4) Number of bends According to JIS K6301, the number of times when a 2 mm scratch grew to 15 mm was measured.

[Sample 1] As the component (1), polypropylene (Ube Polypro JI0 manufactured by Ube Industries, Ltd.)
9, melting point 165 to 170 ° C., melt flow index 9 g / 10 min), and natural rubber (N) as component (2)
R, SMR-L) as component (3), nylon 6 (manufactured by Ube Industries, Ube nylon 1030B, melting point 21)
5 to 220 ° C. and a molecular weight of 30,000) were used. (1)
The components are 0.5 parts by weight of γ-methacryloxypropyltrimethoxysilane and 0.1 parts by weight of 4,4-di-t-butylperoxyvaleric acid n based on 100 parts by weight of the component (1). -Modified by melt-kneading with butyl ether. The component (3) was modified by melt-kneading with 1.0 part by weight of N-β (aminoethyl) γ-aminopropyltrimethoxysilane with respect to 100 parts by weight of the component (3).
First, 100 parts by weight of the component (1) modified as described above was kneaded with 100 parts by weight of the component (2) in a Banbury mixer to prepare a matrix. This was dumped at 170 ° C. and pelletized. Next, this matrix and 100 parts by weight of the component (3) were kneaded with a biaxial kneader heated to 240 ° C. to pelletize the kneaded product. The obtained kneaded product is extruded into a string with a uniaxial extruder set at 245 ° C.,
The pellets were pelletized with a pelletizer while being collected at a draft ratio of 10. The obtained pellets were refluxed in a mixed solvent of o-dichlorobenzene and xylene to obtain polyolefin and NR.
When the shape and diameter of the remaining fibers were removed with an electron microscope, it was confirmed that the fibers had an average fiber diameter of 0.2 μm.

[Sample 2] Sample 2 was prepared in the same manner as in Sample 1, except that the proportion of nylon 6 as the component (3) was increased to 200 parts by weight relative to 100 parts by weight of the polypropylene as the component (1). , This was pelletized. The obtained pellets were refluxed in a mixed solvent of o-dichlorobenzene and xylene to remove polyolefin and NR, and the shape and diameter of the remaining fibers were observed with an electron microscope. It was confirmed that it was a fiber.

[Sample 3] Sample 1 except that the polypropylene as the component (1) was 100 parts by weight, the natural rubber as the component (2) was 75 parts by weight, and the nylon 6 as the component (3) was 87.5 parts by weight. Sample 3 was prepared in the same manner as in 1. and pelletized. The obtained pellets were refluxed in a mixed solvent of o-dichlorobenzene and xylene to remove polyolefin and NR, and the shape and diameter of the remaining fibers were observed with an electron microscope. It was confirmed that it was a fiber. Table 1 shows the ratio of each component of Samples 1 to 3 and the shape of the nylon 6 fiber.

Example 1 A B-type Banbury (capacity: 1.7 liters) set at 100 ° C. and 77 rpm was used. Sample 1 was used as the fiber-reinforced thermoplastic composition. The compounding agents except the accelerator and sulfur were kneaded to obtain a kneaded material which was a bead filler rubber composition. At this time, the maximum kneading temperature was adjusted to 170 to 180 ° C. Next, this kneaded product was kneaded with a vulcanization accelerator and sulfur on a 10-inch roll, rolled out into a sheet, and then placed in a mold for vulcanization to obtain a vulcanized product. Vulcanization is 1
It was carried out at 45 ° C. for 40 minutes. The results are summarized in Table 2.

[Examples 2 and 3] A bead filler rubber composition was obtained in the same manner as in Example 1 except that the fiber-reinforced thermoplastic composition used was changed to the samples shown in Table 2. The results are summarized in Table 2.

[Examples 4 to 8] Table 2 shows the blending ratio of each component.
A bead filler rubber composition was obtained in the same manner as in Example 1 except that the bead filler rubber composition was changed as shown in FIG. The results are summarized in Table 2.

[Examples 9 to 11] The same procedure as in Example 1 was carried out except that the kind of carbon black to be blended was changed. The results are summarized in Table 2.

[Comparative Examples 1 and 2] A bead filler rubber composition was obtained in the same manner as in Example 1 except that the ratio of each component was changed as shown in Table 2 without using the fiber reinforced thermoplastic composition. It was The results are summarized in Table 2.

[0056]

[Table 1]

[0057]

[Table 2]

(Note 1) BR: polybutadiene (UBEP
OL-BR100, manufactured by Ube Industries, Ltd. (Note 2) SBR: styrene-butadiene copolymer rubber (SBR-1500, manufactured by Nippon Synthetic Rubber Co., Ltd.) (Note 3) N-330: HAF, particle diameter 30 mμ , DBP
Oil absorption 110ml / 100g N-440: FF, particle size 38mμ, DBP oil absorption
75ml / 100g N-550: FEF, particle size 41mμ, DBP oil absorption 1
22ml / 100g N-660: GPF, particle size 84mμ, DBP oil absorption
81ml / 100g (Note 4) Other compounding agents Zinc white: 5 parts, stearic acid: 2 parts, anti-aging agent N-
Phenyl-N'-isopropyl-p-phenylenediamine: 1 part, vulcanization accelerator N-oxydiethylenebenzothiazyl-2-sulfenamide: 0.8 part, sulfur: 3
Parts (Comparative Example 1 only, 4 parts)

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location C08L 23/20 LCV 77/00 LQS

Claims (4)

[Claims] 1. A fiber reinforced thermoplastic composition, that is, (1) polyolefin (hereinafter referred to as (1) component) (2) vulcanizable rubber (hereinafter referred to as (2) component) (3) main chain Thermoplastic Polymer Having Amido Group
(Hereinafter, referred to as (3) component), wherein the (1) component and the (2) component form a matrix, and the (3) is contained in the matrix.
A composition in which the components are dispersed as fine fibers, and the component (3) is combined with the components (1) and (2), natural rubber, polyisoprene, or a mixture of both (B). ), A diene rubber (C) excluding natural rubber and polyisoprene, and carbon black (D), and satisfying the following conditions (i) to (iv): Rubber composition. (I) The amount of the thermoplastic polymer (component (3)) is 2 to 20 parts by weight based on 100 parts by weight of the total rubber component, and (ii) the natural rubber in the component (A) in the rubber component. Alternatively, the total amount of polyisoprene and the component (B) is 100 to 5
5% by weight, (iii) the amount of carbon black (D) is 50 to 70 parts by weight based on 100 parts by weight of the total of the rubber components, and (iv) the vulcanized product has a 50% tensile modulus. M ₅₀ is 30 kg / cm ² or more. 2. Fine fibers of a thermoplastic polymer (component (3)) having an amide group in its main chain in the fiber-reinforced thermoplastic composition (A) have an average diameter of 0.05 to 1.0 μm. The bead filler rubber composition according to claim 1, which comprises: 3. The polyolefin (component (1)) in the fiber-reinforced thermoplastic composition (A) has a softening point of 50 ° C. or higher or a melting point in the range of 80 to 250 ° C.
Alternatively, the bead filler rubber composition according to claim 2. 4. The vulcanizable rubber ((2 components) in the fiber reinforced thermoplastic composition (A) is a polyolefin ((1)
Component) The bead filler rubber composition according to claims 1 to 3, which is 10 to 400 parts by weight with respect to 100 parts by weight.