JP2002363344A - Crosslinkable polymer composition for sole of shoe, and sole of shoe - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a crosslinkable polymer composition for the sole of a shoe, containing an oil-extended 1,2-polybutadiene and having excellent functions inherent in conventional 1,2-polybutadienes and excellent in processability, moldability and colorability (high image sharpness), and its molded article. SOLUTION: The crosslinkable polymer composition for the sole of a shoe contains (A) an oil-extended 1,2-polybutadiene, (B) a thermoplastic polymer other than the component (A), and (C) a crosslinking agent, or a crosslinking agent and a crosslinking aid. The molded article is obtained by crosslinking and molding the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel oil-extended 1, 2
The present invention relates to a cross-linkable polymer composition for soles used for non-foamed or foamed soles, using polybutadiene, and a sole obtained by cross-linking the composition.

[0002]

2. Description of the Related Art Sole materials tend to be lightweight, and foams are often used for the purpose of weight reduction. At present, as a method for producing a shoe sole material from a foam, a vulcanizing press machine which conventionally uses a foam is used. (1) A plate-shaped foam is produced using a plate-shaped mold. And (2) foaming using a shoe-shaped mold, and then further punching into a shoe-sole shape for the purpose of size adjustment. These methods are suitable for small-quantity multi-product production, but are not suitable for mass production. This causes an increase in the cost of the sole material.

As cross-linked foams used for shoe sole materials, ethylene-vinyl acetate copolymer (EVA),
A crosslinked foam using natural rubber, synthetic rubber, or the like is known. Among them, the crosslinked foam using EVA has a large deformation (set) during use, and at the same time does not have sufficient wet skid resistance, which is the most important material for shoe soles. On the other hand, rubber-based cross-linked foams using synthetic rubbers such as natural rubber, styrene-butadiene rubber, and polybutadiene rubber have better settling and wet skid resistance than EVA foams, but the products after cross-linking and foaming have good properties. The shrinkage is large, the defect rate due to the variation in the size of the product is high, and this is a factor for increasing the cost of shoe sole materials, and it is required to reduce the cost.

[0004] By the way, 1,2-polybutadiene has come to be used as a material which is excellent in wet skid property and has a small shrinkage ratio of a product after cross-linking and foaming, and is suitable as a shoe sole material. The 1,2-polybutadiene has excellent wet skid resistance, in addition shrinkage after crosslinking foaming is small, the mechanical strength (T _B, E _B), an interlayer tear strength, such as a permanent compressive strain good soles It is widely used as a material. Since 1,2-polybutadiene controlled to such an appropriate degree of crystallinity has a structure composed of a region rich in crystallinity and an amorphous portion, it has not only a function as a thermoplastic elastomer but also a molecule in the molecule. Since it has a carbon-carbon double bond rich in chemical reactivity, it also functions as a conventional vulcanizate or a thermosetting resin or rubber having an increased crosslink density. Also, this 1,2-polybutadiene is
It has also been applied as a modifier for other resins, thermoplastic elastomers, thermosetting elastomers, and medical polymer materials. However, when this 1,2-polybutadiene is used for various new applications such as shoe soles, workability and formability are insufficient, and low colorability has been pointed out.

[0005]

SUMMARY OF THE INVENTION The present invention relates to a conventional 1
2-Crosslinkable polymer composition for shoe soles using oil-extended 1,2-polybutadiene having excellent functions which are characteristic of polybutadiene, and further excellent in processability, moldability and coloring property (high definition). An object of the present invention is to provide an article and a shoe sole obtained by crosslinking the article.

[0006]

The present invention relates to (A) oil-extended 1,2-polybutadiene, (B) a thermoplastic polymer other than the above (A) component, and (C) a crosslinking agent or a crosslinking agent and a crosslinking agent. The present invention relates to a crosslinkable polymer composition for shoe soles containing an auxiliary. Here, the proportions of the components (A) to (C) are as follows:
(A) 1 to 99 parts by weight of component, (B) 99 to 1 part by weight of component (provided that (A) + (B) = 100 parts by weight) 1
Component (C) is 0.001 to 50 parts by weight based on 00 parts by weight. As the component (B), at least one selected from the group consisting of a thermoplastic resin, a thermoplastic elastomer, a natural rubber, and a synthetic rubber other than the component (A) is exemplified. As the component (C), at least one selected from the group consisting of sulfur, a compound capable of generating sulfur upon heating, an organic peroxide, a polyfunctional monomer, and a silanol compound is exemplified. The crosslinkable polymer composition for shoe soles of the present invention,
(D) 0 to 300 parts by weight of a softening agent, (E) 0 to 300 parts by weight of an inorganic filler, (F) a flame retardant, an oxidizing agent, based on 100 parts by weight of the total amount of the components (A) and (B). At least one selected from the group consisting of an inhibitor, a softener, a lubricant, a coloring agent, a foaming agent, an ultraviolet absorber, an antistatic agent, a heat stabilizer, an antioxidant, a processing aid, a light-fast (weather) agent, and an antibacterial agent. 0 to 20 parts by weight of other additives, and the total amount of these components (D), (E) and (F) is 1 to 60
0 parts by weight may be blended. Further, the crosslinkable polymer composition for shoe soles of the present invention further comprises (G) a foaming agent in an amount of 1 to 3 parts by weight based on 100 parts by weight of the total of the components (A) and (B).
You may mix | blend 00 weight part. Next, the present invention relates to a shoe sole obtained by cross-linking the crosslinkable polymer composition for a shoe sole.

[0007]

DETAILED DESCRIPTION OF THE INVENTION (A) Oil-extended 1,2-polybutadier
Emissions 1,2-polybutadiene; 1,2-polybutadiene used in the component (A) of the present invention, for example, as long as 1,2-bond content of 70% or more, any 1,2
Polybutadiene may be used, but preferably, in the presence of a catalyst containing a cobalt compound and an aluminoxane,
It is obtained by polymerizing butadiene.

The 1,2-polybutadiene of the present invention has a 1,2-bond content of 70% or more, preferably 80% or more, more preferably 90% or more, in the butadiene-binding unit. When the 1,2-bond content is 70% or more, the 1,2-polybutadiene of the present invention exhibits good properties as a thermoplastic elastomer.

The 1,2-polybutadiene of the present invention is preferably 1,2-polybutadiene having crystallinity, and its melting point is preferably in the range of 50 to 130 ° C, more preferably 60 to 120 ° C. When the melting point is in this range, the result is excellent in balance between mechanical strength such as tensile strength and tear strength and flexibility.

In the 1,2-polybutadiene of the present invention, a small amount of a conjugated diene other than butadiene may be copolymerized.
Examples of the conjugated diene other than butadiene include 1,3-pentadiene, 1,3-butadiene derivatives substituted with a higher alkyl group, and 2-alkyl-substituted-1,3-butadiene. Among them, 1,3-butadiene derivatives substituted with higher alkyl groups include 1-pentyl-
Examples thereof include 1,3-butadiene, 1-hexyl-1,3-butadiene, 1-heptyl-1,3-butadiene, and 1-octyl 1,3-butadiene.

Here, typical 2-alkyl-substituted-1,3-butadiene is 2-methyl-1,3-butadiene (isoprene), 2-ethyl-1,3-butadiene, 2-propyl-butadiene. 1,3-butadiene, 2-isopropyl-1,3-butadiene, 2-butyl-1,3-butadiene, 2-isobutyl-1,3-butadiene, 2-amyl-1,3-butadiene, 2-isoamyl- 1,3-
Butadiene, 2-hexyl-1,3-butadiene, 2-
Cyclohexyl-1,3-butadiene, 2-isohexyl-1,3-butadiene, 2-heptyl-1,3-butadiene, 2-isoheptyl-1,3-butadiene, 2-
Octyl-1,3-butadiene, 2-isooctyl-
1,3-butadiene and the like can be mentioned. Among these conjugated dienes, preferred conjugated dienes copolymerized with butadiene include isoprene and 1,3-pentadiene. The content of butadiene in the monomer component used for the polymerization is preferably at least 50 mol%, particularly preferably at least 70 mol%.

As described above, the 1,2-polybutadiene of the present invention is preferably obtained by polymerizing butadiene in the presence of a catalyst containing a cobalt compound and an aluminoxane. As the cobalt compound, preferably, an organic acid salt of cobalt having 4 or more carbon atoms can be exemplified. Specific examples of the organic acid salts of cobalt include octylates such as butyrate, hexanoate, heptylate and 2-ethyl-hexyl acid, decanoates, and higher grades such as stearic acid, oleic acid and erucic acid. Examples thereof include fatty acid salts, benzoates, tolylates, xylates, alkyls such as ethylbenzoic acid, aralkyls, allyl-substituted benzoates and naphthoates, and alkyl, aralkyl or allyl-substituted naphthoates. Of these, two
The so-called octylates, stearates and benzoates of ethylhexylic acid are preferred for their excellent solubility in hydrocarbon solvents.

Examples of the aluminoxane include those represented by the following general formula (I) or (II).

[0014]

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In the aluminoxane represented by the general formula (I) or (II), R is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group and a butyl group, preferably a methyl group, an ethyl group. And particularly preferably a methyl group. M is an integer of 2 or more, preferably 5 or more, and more preferably 10 to 100. Specific examples of aluminoxane include methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, and the like.
Methylaluminoxane is particularly preferred.

It is extremely preferred that the polymerization catalyst contains a phosphine compound in addition to the above-mentioned cobalt compound and aluminoxane. The phosphine compound is a component effective for activating the polymerization catalyst, controlling the vinyl bond structure and crystallinity, and preferably includes an organic phosphorus compound represented by the following general formula (III).

P (Ar) _n (R ′) _3-n (III) In the general formula (III), Ar represents a group shown below.

[0018]

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(In the above groups, R ¹ , R ² and R ³ are the same or different and each have a hydrogen atom and a carbon number of preferably 1 to 1.
6 alkyl groups, halogen atoms, and preferably 1 carbon atom
And preferably 6 to 12 alkoxy groups or 6 to 12 carbon atoms.
Represents an aryl group. ) In addition, in the general formula (III), R ′
Represents a cycloalkyl group or an alkyl-substituted cycloalkyl group, and n is an integer of 0 to 3.

Specific examples of the phosphine compound represented by the general formula (III) include tri- (3-methylphenyl)
Phosphine, tri- (3-ethylphenyl) phosphine, tri- (3,5-dimethylphenyl) phosphine,
Tri- (3,4-dimethylphenyl) phosphine, tri- (3-isopropylphenyl) phosphine, tri-
(3-t-butylphenyl) phosphine, tri- (3,
5-diethylphenyl) phosphine, tri- (3-methyl-5-ethylphenyl) phosphine), tri- (3-
Phenylphenyl) phosphine, tri- (3,4,5-
Trimethylphenyl) phosphine, tri- (4-methoxy-3,5-dimethylphenyl) phosphine, tri-
(4-ethoxy-3,5-diethylphenyl) phosphine, tri- (4-butoxy-3,5-dibutylphenyl) phosphine, tri (p-methoxyphenylphosphine), tricyclohexylphosphine, dicyclohexylphenylphosphine, tribenzylphosphine , Tri (4-methylphenylphosphine), tri (4-ethylphenylphosphine) and the like. Of these, particularly preferred are triphenylphosphine, tri- (3-methylphenyl) phosphine,
Tri- (4-methoxy-3,5-dimethylphenyl) phosphine and the like.

Further, as the cobalt compound, a compound represented by the following general formula (IV) can be used.

[0022]

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The compound represented by the general formula (IV) is a complex having, as a ligand, a phosphine compound in which n is 3 in the general formula (III) with respect to cobalt chloride. When using this cobalt compound, a compound synthesized in advance may be used, or a method in which cobalt chloride and a phosphine compound are brought into contact in a polymerization system may be used. By selecting various phosphine compounds in the complex, it is possible to control the amount of 1,2-bonds and crystallinity of the obtained 1,2-polybutadiene.

Specific examples of the cobalt compound represented by the general formula (IV) include cobalt bis (triphenylphosphine) dichloride, cobalt bis [tris (3-methylphenylphosphine)] dichloride, and cobalt bis [tris (3 -Ethylphenylphosphine)] dichloride, cobalt bis [tris (4-methylphenylphosphine)] dichloride, cobalt bis [tris (3,5-dimethylphenylphosphine)] dichloride, cobalt bis [tris (3,4-dimethylphenylphosphine) )] Dichloride, cobalt bis [tris (3-isopropylphenylphosphine)] dichloride, cobalt bis [tris (3-t-butylphenylphosphine)] dichloride, cobalt bis [tris (3,5-diethylphenyl) Sphine)] dichloride, cobalt bis [tris (3-methyl-5-ethylphenylphosphine)] dichloride, cobalt bis [tris (3-phenylphenylphosphine)] dichloride, cobalt bis [tris (3,4,5-trimethylphenyl) Phosphine)] dichloride, cobalt bis [tris (4-methoxy-3,5-dimethylphenylphosphine)] dichloride, cobalt bis [tris (4-ethoxy-3,5-diethylphenylphosphine)] dichloride, cobalt bis [tris ( 4-butoxy-3,
5-dibutylphenylphosphine)] dichloride, cobalt bis [tris (4-methoxyphenylphosphine)] dichloride, cobalt bis [tris (3-methoxyphenylphosphine)] dichloride, cobalt bis [tris (4-dodecylphenylphosphine)] dichloride And cobalt bis [tris (4-ethylphenylphosphine)] dichloride.

Of these, cobalt bis (triphenylphosphine) dichloride, cobalt bis [tris (3-methylphenylphosphine)] dichloride, cobalt bis [tris (3,3)
5-dimethylphenylphosphine)] dichloride, cobalt bis [tris (4-methoxy-3,5-dimethylphenylphosphine)] dichloride and the like.

The amount of the catalyst used is as follows: in the case of homopolymerization of butadiene, per mole of butadiene;
Total amount of butadiene and conjugated diene other than butadiene 1
The amount of the cobalt compound per mole is 0.001 to 1 mmol, preferably 0.01 to 0.5 in terms of cobalt atom.
Use about millimoles. The amount of the phosphine compound used is determined by the ratio of the phosphorus atom to the cobalt atom (P / Co).
As 0.1 to 50, preferably 0.5 to 2
0, more preferably 1 to 20. Further, the amount of aluminoxane used is expressed as a ratio of aluminum atoms to cobalt atoms of the cobalt compound (Al / Co):
Usually, it is 4 to 10 ⁷ , preferably 10 to 10 ⁶ . When the complex represented by the general formula (IV) is used, the amount of the phosphine compound used is such that the ratio of the phosphorus atom to the cobalt atom (P / Co) is 2, and the amount of the aluminoxane is as described above. Follow the description in

Examples of the inert organic solvent used as the polymerization solvent include aromatic hydrocarbon solvents such as benzene, toluene, xylene and cumene; aliphatic hydrocarbon solvents such as n-pentane, n-hexane and n-butane; Examples include alicyclic hydrocarbon solvents such as cyclopentane, methylcyclopentane, and cyclohexane, and mixtures thereof.

The polymerization temperature is usually -50 to 120 ° C.
Preferably it is -20 to 100 ° C. The polymerization reaction may be a batch type or a continuous type. The concentration of the monomer in the solvent is usually 5 to 50% by weight, preferably 10 to 35% by weight. In addition, in order to prevent the deactivation of the catalyst and the polymer of the present invention in producing the polymer, consideration must be given to minimizing the incorporation of a compound having a deactivating effect such as oxygen, water or carbon dioxide gas into the polymerization system. is necessary. When the polymerization reaction has progressed to the desired stage, the reaction mixture is added with an alcohol, other polymerization terminators, an antioxidant, an antioxidant, an ultraviolet absorber, and the like, and then the produced polymer is separated, washed, and dried according to a conventional method. 1,2- used in the present invention
Polybutadiene can be obtained.

The weight average molecular weight of (A) 1,2-polybutadiene used in the present invention is preferably 10,000 to 500.
10,000, more preferably 10,000 to 1.5 million, particularly preferably 50,000 to 1,000,000. If the weight average molecular weight is less than 10,000, the fluidity after oil extension is extremely high, and subsequent processing becomes extremely difficult. On the other hand, if the weight average molecular weight exceeds 5,000,000, the fluidity after oil extension is extremely low, and the processing is extremely difficult. It is difficult and not preferable.

The 1,2-polybutadiene used in the present invention alone can provide sufficient strength even without cross-linking, so that non-cross-linked molding for industrial parts such as injection molding and extrusion molding and film applications can be obtained. Suitable for use.
At this time, there is no particular limitation on the processing method, and it is possible to mix by a usual resin, a roll used in rubber processing, a kneader, a Banbury mixer, a screw extruder, a melt kneading using a feeder ruder extruder, or the like. .

Extending oil: The above-described 1,2-polybutadiene is oil-extended to prepare (A) the oil-extended 1,2-polybutadiene of the present invention. There is no particular limitation as long as it is a commonly used extender oil or softener. For example, a mineral oil-based extender oil can be mentioned as a preferred example.

The mineral oil-based extender oil is preferably a viscosity specific gravity constant (or a viscosity specific gravity constant; hereinafter, referred to as V.V.
G. FIG. C. Abbreviated. ) Is 0.790 to 0.999, and more preferably V.I. G. FIG. C. Is 0.790 to 0.949, particularly preferably V.I. G. FIG. C. Is 0.790 to 0.912. As the extender oil, generally, an aromatic extender oil, a naphthenic extender oil, and a paraffin extender oil are known.

Among them, aromatic extender oils satisfying the above viscosity specific gravity constants include Diana Process Oil AC-12, AC460 and AH-1 manufactured by Idemitsu Kosan Co., Ltd.
6, AH-58, manufactured by Esso Mobile, Mobilzol K, 22 and 130, manufactured by Nippon Kyoishi Co., Ltd., manufactured by Kyoishi Process X50, X100, X140, manufactured by Shell Chemical Co.,
Resox No. 3. Deuterex 729UK, manufactured by Nippon Oil Co., Ltd., Komorix 200, 300, 500,
700, Esso Process Oil 110, 120 manufactured by Esso Mobile, Mitsubishi 34 Heavy Process Oil, Mitsubishi 44 Heavy Process Oil, Mitsubishi 38 Heavy Process Oil, Mitsubishi 39 Heavy Process Oil manufactured by Mitsubishi Petroleum. .

The naphthenic extender oil satisfying the above viscosity specific gravity constant is Diana Process Oil NS-24, NS-100, NM-26, NM-, manufactured by Idemitsu Kosan Co., Ltd.
280, NP-24, Naplex 38 manufactured by Esso Mobile, Fukkol FLEX # 10 manufactured by Fujikosan
60N, # 1150N, # 1400N, # 2040N,
# 2050N, Kyoishi process R25, manufactured by Nikko Kyoishi Co., Ltd.
R50, R200, R1000, Shell Flex 371JY, 371N, 451, N-40, 22, 22, 22R, 32R, 100R, manufactured by Shell Chemical Co., Ltd.
100S, 100SA, 220RS, 220
S, 260, 320R, 680, Komorex No. 2 process oil manufactured by Nippon Oil Co., Ltd., Esso Process Oil L-2, 765 manufactured by Esso Mobile, Mitsubishi 20 Light Process Oil manufactured by Mitsubishi Petroleum And the like.

Further, as the paraffinic extender oil satisfying the above viscosity specific gravity constant, Diana Process Oil PW-90, PW-380, PS-32, P-32, manufactured by Idemitsu Kosan Co., Ltd.
S-90, PS-430, FUKKOR processes P-100, P-200, P-300, P40 manufactured by Fujikosan Co., Ltd.
K-stone process P-2, manufactured by Nikko Kyoishi Co., Ltd.
00, P-300, P-500, Kyoishi EPT750, Kyoishi 1000, Kyoishi Process S90, Lubrex 26, 100, 460 manufactured by Shell Chemical Co., Ltd., Esso Process Oil 815 manufactured by Esso Mobile Co., Ltd. No. 845, No. B-1, Naplex 32 manufactured by Esso Mobile, and Mitsubishi 10 light process oil manufactured by Mitsubishi Petroleum.

As described above, since the 1,2-polybutadiene is oil-extended by the extending oil, the filler such as carbon black and silica can be finely dispersed uniformly in the 1,2-polybutadiene. Workability and various properties of the molded shoe sole can be remarkably improved.
Moreover, thereby, surprisingly, it is possible to improve the mechanical strength, particularly the abrasion resistance of (A) the obtained oil-extended 1,2-polybutadiene and the shoe sole as a molded product.

The compounding amount of the extender oil used in the present invention is as follows:
1-2 parts per 100 parts by weight of 1,2-polybutadiene
00 parts by weight, preferably 10 to 100 parts by weight, more preferably 15 to 80 parts by weight, particularly preferably 20 to 70 parts by weight.
Parts by weight. If the amount is less than 1 part by weight, the effect of improving wear resistance and workability are poor, while if it exceeds 200 parts by weight, the material becomes extremely soft and poor in workability.

The oil-extending method is not particularly limited, and examples thereof include a method in which an extending oil is added to a polymerization solution of 1,2-polybutadiene and mixed in a solution state. This method is preferable in that the step of mixing the 1,2-polybutadiene and the extension oil can be omitted from the operation, and the mixing uniformity of the two is excellent. When the extender oil is added to the polymer solution, it is preferable after the end of the polymerization, for example, after the addition of a terminal modifier or after the addition of a polymerization terminator. A required amount of extender oil is added to a polymer solution containing an organic solvent and mixed well in a solution state (first step). Next, a crumb is obtained by a steam stripping method in which steam is blown into the polymer solution containing the extender oil, or the polymer solution containing the extender oil is directly desolvated by means of an extruder, a devolatizer, or the like. Go, oil exhibition 1, 2-
The polybutadiene and the solvent are separated (second step). The obtained oil-extended 1,2-polybutadiene is dried by a vacuum dryer, a hot air dryer, a roll, or the like as necessary (third
Step), the desired (A) oil-extended 1,2-polybutadiene can be isolated. In addition, as oil extension method,
(A) Oil-extended 1,2-polybutadiene can also be prepared by blending 2-polybutadiene and extender oil in a molten state. In this case, as a blending method, a single-screw extruder, a twin-screw extruder, a banbury, a roll, a kneader, a plast mill, or the like is employed.
0-160 ° C is preferred.

The polymer composition obtained by combining (A) the oil-extended 1,2-polybutadiene with a thermoplastic polymer other than the component (A), which is the component (B) described below, is a fluid composition. Since the composition is excellent, the composition can be smoothly filled in a mold using an injection molding machine or a transfer molding machine. Moreover, the crosslinked foam obtained by heating the mold has a high expansion ratio and a uniform and fine foam structure. The sole material made of such a crosslinked (foamed) body has a mechanical strength (TB, E).
B), excellent in interlayer tear strength, compression set, and wet skid resistance.

(B) Thermoplastic polymer ; Here, as the (B) thermoplastic polymer used in the present invention, other than the component (A), thermoplastic resins, thermoplastic elastomers, natural rubbers and synthetic rubbers At least one selected from the group is included.

Among them, as the thermoplastic resin other than the component (A), any thermoplastic resin having a plasticizing temperature of 50 to 450 ° C. can be used without any particular limitation. For example, a styrene resin (for example, polystyrene) , Butadiene / styrene copolymer, acrylonitrile / styrene copolymer,
Acrylonitrile-butadiene-styrene copolymer, etc.), ABS resin, AES resin, AAS resin, polyethylene, polypropylene, ethylene-propylene resin, ethylene-ethyl acrylate resin, polyvinyl chloride, polyvinylidene chloride, polybutene, polycarbonate, polyacetal, polyphenylene Oxide, polymethyl methacrylate, saturated polyester resin (eg, condensate of hydroxycarboxylic acid such as polylactic acid, condensate of diol and dicarboxylic acid such as polybutylene succinate), polyamide resin, fluororesin, polysulfone, polyether One or a mixture of two or more of sulfone, polyarylate, polyetheretherketone, liquid crystal polymer and the like can be mentioned. Preferred thermoplastic resins are polystyrene, butadiene / styrene copolymer, acrylonitrile / styrene copolymer, ABS
Resin, AES resin, AAS resin, polyethylene, polypropylene, polyvinyl chloride, saturated polyester resin, and polyamide resin.

As the thermoplastic elastomer, for example, according to the classification based on the chemical composition of the hard segment, styrene-based thermoplastic elastomer (abbreviated as SBC; hereinafter, the abbreviations are shown in parentheses), olefin-based thermoplastic elastomers Thermoplastic elastomer (TPO), urethane-based thermoplastic elastomer (TPU), ester-based thermoplastic elastomer (TPEE), amide-based thermoplastic elastomer (TP
AE) and the like. In addition, there are other thermoplastic thermoplastic elastomers (TPVC), ion-cluster-type thermoplastic elastomers (ionomers), and fluoroplastic elastomers containing a fluororesin as a constraining block. Among them, TPO by dynamic crosslinking, which improves the performance by reducing the rubber dispersion particle diameter by kneading while kneading the rubber component serving as a soft segment, is sometimes referred to as TPV). These thermoplastic elastomers are:
Species or a mixture of two or more species.

Preferred as SBC is styrene-
Butadiene-styrene block copolymer (SBS),
Styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene / butylene-styrene block copolymer (SEBS), functionalized SEB
S (f-SEBS), styrene-ethylene propylene-styrene block copolymer (SEPS), random hydrogenated styrene-butadiene polymer (H
SBR).

Preferred as TPO are PP, PE
EP, EPDM, EBM, EB for polyolefins such as
Simple blend type T mixed with elastomer such as DM and compounded with a mixer such as Banbury or Plastmill
PO (s-TPO), polymerizing the olefin monomer which is a hard segment, and then polymerizing the olefin monomer which is a soft segment in the same plant or the same reactor (the order may be reversed).
It is a dynamically vulcanized TPO (TPV) made by vulcanizing rubber simultaneously with mixing with a mixer such as PO (i-TPO), Banbury or Plastmill. Further, as the TPV, preferably, PP-EPDM in which PP is combined with a hard segment and EPDM is combined with a soft segment (hereinafter, a hard segment is described on the left and a soft segment is described on the right), PP-nitrile rubber (NBR), PP-acryl rubber (ACM), PP-natural rubber (NR), PP-butyl rubber (IIR), PE-EPDM, PE-NR, nylon-NBR, nylon-ACM, polyester-chloroprene (CR), PVC-NBR.

Preferred TPUs are those in which the diisocyanate used for the hard segment is toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4 ( 2,4,4)
-Trimethylhexamethylene diisocyanate, p-phenylene diisocyanate, 4,
4′-dicyclohexylmethane diisocyanate, 3,3′-dimethyldiphenyl-4,4′-disissocyanate, 1,5′-naphthalene diisocyanate, trans-1,4-cyclohexyl diisocyanate Some are lysine diisocyanates, and some are mixtures of two or more of these.

Preferred as TPEE are polyester-polyether type TPEE in which the hard segment is an aromatic crystalline polyester and a polyether is used as the soft segment, and the hard segment is an aromatic crystalline polyester and the soft segment is aliphatic. Polyester-type TPEE using polyester based, liquid crystalline TPEE in which hard segments are liquid crystal molecules and soft segments are aliphatic polyester
It is. More preferably, as the polyester / polyether type TPEE, the hard segment is a polycondensate of butanediol and dimethyl terephthalate, a polycondensate of ethylene glycol and dimethyl terephthalate, or a polycondensation of butanediol and 2,6-naphthalenedicarboxylic acid. A polycondensate of ethylene glycol and 2,6-naphthalenedicarboxylic acid, or a mixture thereof, wherein the soft segment is polytetramethylene ether glycol, poly (1,2-propylene oxide) glycol, poly (ethylene oxide) glycol. Either or a mixture. More preferably, the hard segment is polyester / polyester type TPEE.
Same as polyether type TPEE, except that the soft segment is a polylactone type aliphatic polyester. Further, as the liquid crystalline TPEE, more preferably, the hard segment is a thermotropic liquid crystal polymer, particularly a multi-block copolymer using a low-molecular liquid crystal compound such as dihydroxy-paraquarterphenyl and using an aliphatic polyester for the soft segment. It is.

As the TPAE, the hard segment is preferably a polyamide, the soft segment is a multi-block copolymer using a low ether Tg polyether or polyester, and more preferably the hard segment is nylon-6, nylon-6,6, Nylon-6,1
0, nylon-11 and nylon-12, and the soft segments are polyether diols and polyester diols. Particularly preferably, the soft segments are diol poly (oxytetramethylene) glycol, poly (oxypropylene) glycol, poly (ethylene adipate). ) Glycols and poly (butylene-1,4-adipate) glycols.

As the TPVC, it is preferable to use high-molecular-weight polyvinyl chloride (hereinafter abbreviated as PVC) for the hard segment to have a function of a cross-linking point in the microcrystal part, and to make the soft segment a PVC plasticized with a plasticizer. What used, the thing which used the PVC which plasticized with the plasticizer in the soft segment using the PVC which introduced the partial bridge | crosslinking or the branched structure in the hard segment, the rubber such as NBR etc. in the soft segment using the PVC in the hard segment and the soft segment And / or those using TPE such as TPU or TPEE alone or as a mixture of two or more.

The natural rubber can be used without any particular limitation, and examples thereof include one or a mixture of two or more of gum arabic and indian rubber. The synthetic rubber can be used without any particular limitation. For example, polybutadiene rubber, polyisoprene rubber, isobutylene / isoprene rubber, ethylene-α-olefin- (diene) copolymer (eg, EPM, EBM, EOM, EP
DM, EBDM, etc.), aromatic vinyl compound-conjugated diene compound- (α-olefin) copolymer (for example, SB
R, SBS, SEBS, etc.), acrylonitrile-butadiene rubber, fluorine rubber, silicone rubber, halogenated butyl rubber (for example, chlorinated butyl rubber, brominated butyl rubber, etc.) or a mixture of two or more thereof. The above-mentioned thermoplastic resins, thermoplastic elastomers, natural rubbers, synthetic rubbers and the like can be used alone or as a mixture of two or more.

In the composition of the present invention, (A) oil-extended 1,
The mixing ratio of 2-polybutadiene and (B) the other thermoplastic polymer is such that the component (A) is 1 to 99 parts by weight, preferably 10 to 10 parts by weight.
To 90 parts by weight, the component (B) is 99 to 1 part by weight, preferably 90 to 10 parts by weight [however, (A) + (B) = 100
Parts by weight]. By using such another thermoplastic polymer (B) in the above range, it has excellent wet skid properties, small shrinkage after cross-linking firing, mechanical strength (T _B , E _B ), interlayer tear strength, The crosslinkable polymer composition for shoe soles of the present invention having good compression set and the like, good workability, good moldability and good colorability can be obtained.

(C) Crosslinking Agent or Crosslinking Agent and Crosslinking Aid As the component (C) of the present invention, sulfur, a compound capable of generating sulfur by heating, an organic peroxide, a polyfunctional monomer,
And at least one selected from the group of silanol compounds
Seeds. At the time of crosslinking, a combination of a polyfunctional monomer and electron beam irradiation, or a combination of a photosensitizer and ultraviolet irradiation can also be used.

As the sulfur, powdered sulfur, precipitated sulfur, colloidal sulfur, surface-treated sulfur and the like can be used, and as the compound that generates sulfur by heating, tetramethylthiuram disulfide, tetraethylthiuram disulfide and the like can be used. Examples of the vulcanization accelerator used in combination with sulfur or a compound that generates sulfur by heating include tetramethylthiuram disulfide (TMTD) N-oxydiethylene-2-benzothiazolyl sulfenamide (O
BS), N-cyclohexyl-2-benzothiazylsulfenamide (CBS), dibenzothiazyldisulfide (MBTS), 2-mercaptobenzothiazole (M
BT), zinc di-n-butyl dithiocarbite (Zn
BDC), zinc dimethyl dithiocarbide (ZnMD)
C).

In the case of the organic peroxide cross-linking compound, dicumyl peroxide, di-t-butylperoxy-3,3,5
-Trimethylcyclohexane, α, α'-di-t-butylperoxy-di-p-diisopropylbenzene, n-
Butyl-4,4-bis-t-butylperoxyvalerate, t-butylperoxybenzoate, t-butylperoxyisopropyl carbonate, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane Etc. can be used. In the case of organic peroxide crosslinking, various polyfunctional monomers may be added at the same time. Specific examples of the polyfunctional monomer include trimethylolpropane trimeacrylate, ethylene glycol dimethacrylate, triallyl isocyanate, diallyl phthalate and the like. The organic peroxide / polyfunctional monomer (molar ratio) in this case is usually 1/1 to 1/50, preferably 1 to 1/50.
/ 2 to 1/40.

These polyfunctional monomers can also be effectively used in an electron beam crosslinking system for obtaining the crosslinkable polymer composition for shoe soles of the present invention. As the electron beam device used in this case, for example, a scanning type (scan type), a curtain type (linear cathode type, ion plasma type)
Is used. The conditions for electron beam irradiation are as follows: processing capacity: 1 to 3000 Mrad · m / min;
KV to 3000 KV.

In the case of UV crosslinking, efficient crosslinking can be achieved by using a photosensitizer. As the photosensitizer, sensitized in the wavelength range of 260 to 400 nm of a high pressure mercury lamp, and natural rubber other than oil-extended 1,2-polybutadiene and oil-extended 1,2-polybutadiene, synthetic rubber, thermoplastic elastomer, Those having a good affinity with a thermoplastic resin or the like are preferable.
Specific examples of the photosensitizer include benzophenone, P, P '
-Aromatic ketones such as dimethoxybenzophenone, P, P'-dichlorobenzophenone P, P'-dimethylbenzophenone, acetophenone and acetonaphthone give good results, and other aromatic aldehydes such as terephthalaldehyde and quinones such as methylanthraquinone. Aromatic compounds are also included. The addition amount is 0.1 to 30 parts by weight, preferably 0.3 to 20 parts by weight. In addition, in the case of producing a sponge, the addition amount is 0.1 to 3.0 parts by weight, preferably 0.3 to 1.0. UV irradiation conditions are 2
UV rays from a 0 cm distance with a 1 kW high pressure mercury lamp
Minute irradiation. In the case of foaming, the above-mentioned ultraviolet treatment is applied to a thin sheet which has been subjected to a predetermined treatment with a foaming agent in advance, and the thin sheet is subjected to a temperature treatment at 150 to 250 ° C.

According to the combination of the silanol compound and the aqueous agent, there is an effect of water crosslinking. Here, examples of the silanol compound include vinylmethoxysilane, vinylethoxysilane, vinyltriacetoxysilane, vinyldimethoxymethylsilane, vinyldiethoxymethylsilane, vinylmethoxydimethylsilane, and vinylethoxydimethylsilane. , Water or steam. In a preferred case, the silanol compound / water-based agent (molar ratio) is usually from 1 / 0.01 to
It is 1/100, preferably 1 / 0.05 to 1/90.

The amount of the component (C) used is, for example, from (A) to (A) in terms of the weight of a compound such as sulfur or an organic peroxide.
0.001 to 100 parts by weight of the total amount of the component (C)
50 parts by weight, preferably 0.01 to 40 parts by weight,
Depending on the combination with a vulcanization accelerator, a polyfunctional monomer, electron irradiation, ultraviolet irradiation, or the like, the amount is appropriately increased or decreased within this range. If the amount is less than 0.001 part by weight, crosslinking is insufficient and heat resistance, mechanical strength and compression set (compression set) are not satisfied. On the other hand, if it exceeds 50 parts by weight, excessive crosslinking occurs and the crosslinked product is brittle and cannot be evaluated, and the molded article of the present invention cannot be obtained. The crosslinkable polymer composition for shoe soles of the present invention contains the above-mentioned components (A) to (C) as essential components.
The component (G) may be blended.

(D) Softener (D) The softener is an extender oil other than that used for (A) oil-extended 1,2-polybutadiene, and can be separately added to the composition of the present invention. As this extension oil,
The same kind as the extender oil used in the component (A) can be used. In this case, the amount of the extending oil
With respect to 100 parts by weight of the total amount of the components (A) and (B),
It is 300 parts by weight, preferably about 1 to 100 parts by weight.

(E) Inorganic Filler (E) Incorporated in the crosslinkable polymer composition for shoe soles of the present invention.
Examples of the inorganic filler include, for example, glass fiber, glass beads, potassium titanate, talc, mica, barium sulfate, carbon black, silica, carbon-silica dual phase filler, clay, calcium carbonate,
Examples include magnesium carbonate. (E) The compounding amount of the inorganic filler is 10 (the total amount of the components (A) and (B)).
0 to 300 parts by weight, preferably. It is 1 to 200 parts by weight. As the inorganic filler (E), use of a combination of carbon black and silica, use of a carbon-silica dual phase filler, or combination of a carbon-silica dual phase filler with carbon black and / or silica is preferable. .

The carbon black produced by the furnace method has a nitrogen adsorption specific surface area of 5%.
0-200 m ² / g, DBP oil absorption 80-200 ml
/ 100 g of carbon black is preferable.
Examples include EF, HAF, ISAF, and SAF classes. Among them, a highly cohesive type is preferred.

The compounding amount of carbon black ranges from (A)
It is preferably 2 to 100 parts by weight, more preferably 5 to 95 parts by weight, based on 100 parts by weight of the total amount of the component (B).

As silica, for example, wet silica,
Dry method silica, synthetic silicate-based silica, and the like can be given. The silica having a high reinforcing effect is silica having a small particle diameter, and a small particle / high agglomeration type (high surface area, high oil absorption) is preferable in terms of good dispersibility in a polymer and physical properties and workability. The average particle size of the silica is a primary particle size, preferably 5 to 60 μm, more preferably 10 to 3 μm.
5 μm. The specific surface area (BET method) is preferably 45 to 280 m ² / g.

The amount of silica is preferably 30 to 100 parts by weight based on 100 parts by weight of the total of components (A) and (B).
100 parts by weight, more preferably 30 to 95 parts by weight.

Further, it is also possible to mix carbon black and silica in combination, and the compounding amount at this time is (A) to (a) as the total amount of carbon black and silica.
With respect to 100 parts by weight of the total amount of the component (B), preferably,
It is 30 to 100 parts by weight, more preferably 30 to 95 parts by weight.

By blending the above-mentioned carbon black and silica with the composition of the present invention in the above-mentioned range, these fillers having a reinforcing effect are uniformly finely dispersed in the polymer, and are suitable for roll processability, extrudability and the like. Excellent in mechanical strength of the molded article, and furthermore, excellent in wear resistance.

In the above polymer composition, the carbon-silica dual phase filler (Dual
Phase Fi11er: a carbon-silica double-phase filler) alone or in combination with carbon black and / or silica. By blending the carbon-silica dual phase filler, the same excellent advantages as when carbon black and silica are used in combination can be obtained even when used alone. Carbon-silica dual phase filler is a so-called silica-coated carbon black in which silica is chemically bonded to the surface of carbon black.
000, CRX2002, CRX2006. The compounding amount of the carbon-silica dual phase filler is preferably 30 to 100 parts by weight, more preferably 30 to 95 parts by weight, based on 100 parts by weight of the total amount of the components (A) and (B). .

In the above polymer composition, carbon-
Silica dual phase fillers can be used in combination with other fillers. The filler that can be used in combination is not particularly limited, and examples thereof include the above-described carbon black and / or silica, clay, calcium carbonate, and magnesium carbonate. Among them, carbon black and / or silica are preferred. These fillers which can be used in combination, together with the carbon-silica dual phase filler, are preferably 3 to 100 parts by weight, more preferably 3 to 100 parts by weight, based on 100 parts by weight of the total of components (A) and (B). Is 5 to 95 parts by weight.

When silica is blended as the filler or when a carbon-silica dual phase filler is blended, it is preferable to blend a silane coupling agent. -Silica Dual Phase Filler-100
The amount is preferably 1 to 20 parts by weight, more preferably 5 to 15 parts by weight with respect to parts by weight.

As the silane coupling agent, a functional group capable of reacting with the silica surface such as an alkoxysilyl group in the molecule and a carbon-carbon double bond of a polymer such as a polysulfide, a mercapto group or an epoxy group can be used. Those having both functional groups are preferred. For example, bis- (3-triethoxysilylpropyl) tetrasulfide, bis-
(2-triethoxysilylethyl) tetrasulfide,
Examples thereof include 3-mercaptopropyltrimethoxysilane, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide, and 3-triethoxysilylpropylbenzothiazoletetrasulfide. By using such a silane coupling agent, when carbon black and silica are used together as a filler, or when a carbon-silica dual phase filler is used as a filler, its reinforcing effect is improved. Can be enhanced.

(F) Other Additives The composition of the present invention may contain a flame retardant, an antioxidant, a lubricant, a coloring agent, an ultraviolet absorber, an antistatic agent, Stabilizers, anti-aging agents, processing aids, light-fast (weather) agents, antibacterial agents and the like can be added.

Examples of the flame retardant which can be used in the present invention include a halogen-based flame retardant, a phosphorus-based flame retardant, and an inorganic flame retardant. Flame retardants are preferred. Phosphorus-based flame retardants include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, resorcinol-bis- (diphenyl phosphate), 2-ethylhexyl diphenyl phosphate, dimethyl methyl phosphate, Examples thereof include triallyl phosphate and the like, and condensates thereof, ammonium phosphate and the condensates thereof, and diethyl N, N-bis (2-hydroxyethyl) aminomethylphosphonate. Examples of the inorganic flame retardant include magnesium hydroxide, aluminum hydroxide, zinc borate, barium borate, kaolin clay, calcium carbonate, alunite, basic magnesium carbonate, calcium hydroxide and the like. The above-mentioned flame retardants include so-called flame retardant auxiliaries which have a low effect of exhibiting their own flame retardancy but exhibit a synergistically superior effect when used in combination with other flame retardants.

The composition of the present invention can extend the product life by using an antioxidant. Examples of the antioxidant used in this case include a phenolic antioxidant, a sulfur-based antioxidant, and an amine-based antioxidant, and a phenol-based antioxidant is particularly preferable. Specific examples of the phenolic antioxidant include styrenated phenol, 2,6-di-t-butyl-4-methylphenol, and 2,6-di-t-butyl-p.
-Ethylphenol, 2,4,6-tri-t-butylphenol, butylhydroxyanisole, 1-hydroxy-3-methyl-4-isopropylbenzene, mono-t
-Butyl-p-cresol, mono-t-butyl-m-cresol, 2,4-dimethyl-6-t-butylphenol, butylated bisphenol A, 2,2'-methylene-
Bis- (4-methyl-6-t-butylphenol),
2,2 'methylene-bis- (4-ethyl-6-t-butylphenol), 2,2'-methylene-bis (4-methyl-6-t-nonylphenol), 2,2'-isobutylidene-bis- ( 4,6-dimethylphenol), 4,
4'-butylidene-bis- (3-methyl-6-t-butylphenol), 4,4'-methylene-bis- (2,6
-Di-t-butylphenol), 2,2-thio-bis-
(4-methyl-6-t-butylphenol), 4,4 '
-Thio-bis- (3-methyl-6-t-butylphenol), 4,4'-thio-bis- (2-methyl-6-butylphenol), 4,4'-thio-bis- (6-t- Butyl-3-methylphenol), bis (3-methyl-4)
-Hydroxy-5-t-butylbenzene) sulfide;
2,2-thio [diethyl-bis-3- (3,5-di-t
-Butyl-4-hydroxyphenol) propionate], bis [3,3-bis (4'-hydroxy-3'-
t-butylphenol) butyric acid] glycol ester, bis [2- (2-hydroxy-5-methyl-3-t-butylbenzene) -4-methyl-6-t-butylphenyl] terephthalate, 1,3,5 -Tris (3 ', 5'-di-tert-butyl-4'-hydroxybenzyl) isocyanurate, N, N'-hexamethylene-
Bis (3,5-di-t-butyl-4-hydroxy-hydroxyamide), N-octadecyl-3- (4'-hydroxy-3 ', 5'-di-t-butylphenol) propionate, tetrakis [methylene- (3 ', 5'-di-t-butyl-4-hydroxyphenyl) propionate] methane, 1,1'-bis (4-hydroxyphenyl) cyclohexane, mono (α-methylbenzene) phenol, di (α-methyl Benzyl) phenol, tri (α-methylbenzyl) phenol, bis (2′-hydroxy-3′-t-butyl-5′-methylbenzyl) 4
-Methyl-phenol, 2,5-di-t-amylhydroquinone, 2,6-di-butyl-α-dimethylamino-
Examples thereof include p-cresol, 2,5-di-t-butylhydroquinone, and diethyl ester of 3,5-di-t-butyl-4-hydroxybenzylphosphoric acid. These antioxidants can be used alone or in combination of two or more. The compounding amount of the antioxidant is 0.1 to 100 parts by weight of the total of the components (A) and (B).
The amount is preferably 10 parts by weight, particularly preferably 0.2 to 5 parts by weight.

The lubricant usable in the present invention includes paraffinic and hydrocarbon resins generally used for imparting extrusion stability, metal soaps, fatty acids, fatty acid amides, fatty acid esters, aliphatic metal salts and the like. Is mentioned. As the colorant, an inorganic pigment or an organic pigment is appropriately selected and used.

The mixing ratio of the above-mentioned (F) other additives is not particularly limited.
0 to 20 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of the total amount of the component (B). (D),
The total amount of the components (E) and (F) is 1 to 600 parts by weight, preferably 3 to 500 parts by weight, based on 100 parts by weight of the total amount of the components (A) and (B).

(G) Foaming agent The foaming agent varies depending on the composition of the crosslinkable polymer composition for shoe soles of the present invention. For example, the foaming agent may be a known inorganic or organic foaming agent. Can be used. Specific examples of the foaming agent include sodium bicarbonate, ammonium bicarbonate, sodium carbonate, ammonium carbonate, azodicarbonamide, dinitrosopentamethylenetetramine, dinitrosoterephthalamide, azobisisobutyronitrile, barium azodicarboxylate, and toluenesulfonyl. Sulfonyl hydrazides such as hydrazide and the like can be mentioned. Among them, azodicarbonamide, dinitrosopentamethylenetetramine, and sulfonyl hydrazides are more preferable. These foaming agents may be used in combination with known foaming aids such as urea and urea derivatives. The amount of the foaming agent varies depending on the type of the polymer of the molding material and the use of the molded product.
(B) 1 to 300 with respect to 100 parts by weight of the total amount of the components.
Parts by weight, preferably 2 to 300 parts by weight. If the amount of the foaming agent is small, only a foam having a low expansion ratio can be obtained,
On the other hand, if the amount is more than 300 parts by weight, the amount of gas generated by the decomposition of the foaming agent increases, and the gas pressure becomes excessively high, so that the obtained foam may be cracked. Also,
As a method of foaming the composition, there is a method in which a predetermined amount of carbon dioxide gas, water, or the like is contained, and a foamed molded body is obtained by various molding methods. For example, in the case of injection molding, carbon dioxide is added in an amount of 0.1 parts by weight based on 100 parts by weight of the total amount of the components (A) and (B).
The composition containing about 5 parts by weight does not foam due to high temperature and high pressure when it is in the measuring section in a plasticized and molten state, but is contained due to a decrease in pressure when filled into a mold by injection molding. The carbon dioxide gas which has been evaporated is vaporized, and a molded product in which the inside of the molded product is foamed can be obtained.

The method for preparing the crosslinkable polymer composition for shoe soles by mixing the above components (A) to (C) of the present invention and other components is not particularly limited. A mixing method using a kneading apparatus used for general rubber compounding such as a needle roll and an open roll may be used.
It is preferred to mix at a temperature in the range of 130 ° C.

In general, injection molding or transfer molding is employed for molding. The shape of the composition supplied to the injection molding machine or the transfer molding machine is not particularly limited, and may be a shape suitable for a molding machine used, for example, in a ribbon shape, a square pellet shape, a round pellet shape, or the like.

The molding machine is not particularly limited. For example, an injection molding machine or a transfer molding machine having a temperature controller in each of a cylinder, a nozzle, and a mold used for thermoplastic resin or rubber. Is used. The temperature conditions of these molding machines differ depending on the composition, but usually, the cylinder part is set at 70 to 100 ° C and the nozzle part is set at 80 to 12 ° C.
It is preferable to set the mold part at 0 ° C and the mold part at 140 to 200 ° C.

Cross-linking and foaming are performed by setting the mold portion within the above temperature range.
By heating for 3 to 10 minutes, the foaming agent is decomposed in a mold having a predetermined shape to generate gas, and the composition is crosslinked to proceed. The mold clamping pressure needs to exceed the expansion pressure of the gas generated by the decomposition of the foaming agent,
Usually, the specific pressure applied to the cavity of the mold is preferably 7 Mpa or more. If the specific pressure is low, the cell diameter of the molded product becomes large, and burrs are generated on the foam, resulting in poor appearance. After heating and pressurizing for a predetermined time, the mold is opened to obtain a crosslinked foam as a product. In the case of a foam molded product (foamed sole), the density is usually 0.1 to 1.1.
Mg / m ^3, preferably 0.1~0.9Mg / m ^3.

The crosslinked (foamed) body produced in this manner is used as a sole material, specifically, men's shoes, women's shoes, casual shoes, running shoes, jogging shoes, tracking shoes, various sports shoes, mountain climbing. It is useful as a sole material for shoes, dress shoes, golf shoes, indoor shoes, slippers, beach sandals, and other general footwear. In addition, the composition and the molded article of the present invention may be used, if necessary, in various molded articles such as automobile parts, building material parts, industrial parts, toys and miscellaneous parts, sports and health parts, various sheets, films, and other industrial products. It can be used for articles, cushioning materials, packaging materials and the like. The crosslinked foam of the present invention has excellent dimensional accuracy,
It has excellent durability and cushioning properties, and can be applied to thermoformed sponges. Here, the thermoformed sponge is used for foaming by preliminarily cutting the foam into a required shape (A).
-The melting point of the component (B) or higher, preferably 100-150 ° C
After heating and pressurizing in a mold heated to form a strong molten film on the outer surface of the foam, the mold is cooled and the foam is taken out.

[0081]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. The various measurements in the examples were based on the following methods.

(1) 1,2-vinyl bond content The content was determined by an infrared absorption spectrum method (Morello method). (2) Weight average molecular weight Gel permeation chromatography (GPC)
(Waters Company, Model 244) was used to determine the weight average molecular weight (Mw) in terms of polystyrene. (3) Melt flow index (MI) According to ASTM D1238 (conditions: 150 ° C, 2
1.2N)

(4) Workability The roll winding property was evaluated. Roll used: Lab 10 inch test roll machine Surface temperature = 90 ± 5 ° C. Roll interval = 2.0 mm, rubber guard width = 250 mm Number of rotations Front roll: back roll = 24: 20 rp
m The evaluation criteria were evaluated based on the time until 1 kg of the compound cooled to room temperature was tightly wound around a roll. ◎ It wraps within 5 minutes. ○ Wrap over 5 minutes and within 7 minutes. △ Winds over 7 minutes and within 10 minutes. × It takes more than 10 minutes.

(5) Formability 2 mm (thickness) × 150 mm (width) × 150 mm (length)
The evaluation was based on the thickness of the burr when cross-linking was performed using the mold. ◎ 0.02 mm or less ○ Exceeds 0.02 mm and 0.05 mm or less △ Exceeds 0.05 mm and 0.08 mm or less × Exceeds 0.08 mm.

(6) Colorability 1% of cobalt blue (manufactured by Kyoritsu Chemical Co., Ltd.) is added to polystyrene having excellent transparency (G120K manufactured by Nippon Polystyrene).
The mixed rolled 2 mm thick sheet was used as a standard color, and the color difference from the Example and Comparative Example sheets was measured. Colorability conforms to the following criteria: ○: color difference from standard color is less than 1.5 △: color difference from standard color is 1.5 to 3.0 ×; color difference from standard color exceeds 3.0

(7) Foaming Ratio The crosslinked and foamed products were compared with each other in the width direction after day and night. Mold used: 8 × 120 × 220 mm (8) Density Based on JIS K7112. (9) Abrasion resistance Akron abrasion method Solid evaluation: 6 Lbs, angle 15 degrees, 1000
Times Evaluation of sponge: 2Lbs, angle 15 degrees, 2000
The wear resistance was determined according to the following criteria. Solid evaluation (CC / 1000 times) Sponge evaluation (CC / 2000 times) ：: Less than 0.3 Less than 0.4 ：: 0.3-0.49 0.4-0.49 Δ: 0.5-0. 69 0.5 to 0.69 ×: 0.7 or more 0.7 or more

(10) Preparation of Samples The samples used in the examples and comparative examples are as follows. Oil-extended RB-A 1,2-vinyl bond content = 90%, weight average molecular weight = 4
Extension oil amount = 30% by weight, extension oil type = paraffin-based process oil [Diana Process Oil P, manufactured by Idemitsu Kosan Co., Ltd.
S-32], MI = 1.6 oil-extended RB-B 1,2-vinyl bond content = 90%, weight average molecular weight = 3
0,000, extension oil amount = 20 wt%, extension oil type = naphthenic process oil [Fukor Flex # 20, manufactured by Fujikosan Co., Ltd.
50PN] MI = 4.5 RB830 JSR, 1,2-polybutadiene (1,2-vinyl bond content = 93%, weight average molecular weight = 180,000, MI =
2.8) IR2200 Polyisoprene rubber manufactured by JSR (weight average molecular weight = 8)
100,000) BR01 Polybutadiene rubber manufactured by JSR (cis 1,4 bond content)
= 96% by weight, average molecular weight = 580,000)

Zinc oxide manufactured by Sakai Chemical Industry Co., Ltd., zinc oxide No. 2 silica manufactured by Nippon Silica Industry Co., Ltd., Nip Seal VN3 hard clay manufactured by Vanderbilt (USA), Dixie Cl
ay Anti-aging agent TNP: Ouchi Shinko Chemical Co., Ltd., Nocrack TNP BHT: Ouchi Shinko Chemical Co., Ltd., Nocrack 200 organic peroxide park mill D: Nihon Yushi Co., Ltd., dicumyl peroxide foaming assistant Eiwa Chemical Co., Ltd. Paste, K5 foaming agent ADCA, manufactured by Eiwa Kasei Kogyo Co., Ltd., Vinyl Hall AC # 3 DNPT, manufactured by Eiwa Kasei Kogyo Co., Ltd., cellular D

Examples 1-2, Comparative Examples 1-2 (above, solid blend), Example 3, Comparative Examples 3 (above, sponge blend) According to the blending recipe shown in Tables 1-2, crosslinking agent / vulcanization After kneading the compounding agent except the accelerator and the (foaming agent) at a temperature of 90 to 130 ° C. for 5 minutes using a Banbury mixer,
A predetermined amount was added using a 10-inch test roll machine set at ± 5 ° C. to prepare an uncrosslinked compound. The produced uncrosslinked product was molded into a predetermined shape, and crosslinked with a steam vulcanizing 150T press under the conditions shown in Tables 1 and 2 to obtain a crosslinked molded product. The results are shown in Tables 1 and 2.

Table 1 is an example of a solid blend. Examples 1-2, which are compositions of the present invention, are oil-extended RB-A of the present invention.
In comparison with the conventional RB 830, the workability is longer than that of the conventional RB 830, and the time required for tightly winding the compound cooled to room temperature around the roll machine is reduced, and the processing time is longer. Also, regarding the cross-linking moldability, the dimensional accuracy of the molded product is improved because the burr of the molded product is greatly reduced. Further, the molded product has excellent coloring properties, and can be applied to products requiring a vivid color. The abrasion resistance improved by crosslinking is good in both Examples 1 and 2 and Comparative Examples 1 and 2, and there is no difference. Table 2 shows examples of sponge formulations. Example 3 shows the oil-extended RB- of the present invention.
This is an example using B. Like the solid blend, the sponge blend also has less workability than the conventional RB830 in terms of workability, and the time required to tightly wind the compound cooled to room temperature around a roll machine is reduced. The conventional disadvantage of long time can be solved. As for the cross-linking moldability, as in the case of the solid composition, the burrs of the molded product are greatly reduced, so that the dimensional accuracy of the molded product is improved. Further, the oil-extended RB-B of the present invention is excellent in foaming properties, and the foaming ratio is increased with the same amount of the foaming agent added. This makes it possible to reduce the amount of the expensive foaming agent and to lower the unit price of the compound. The abrasion resistance, in which the strength is improved by crosslinking, was excellent in the examples.

[0091]

[Table 1]

[0092]

[Table 2]

[0093]

According to the crosslinkable polymer composition for soles of the present invention containing the oil-extended 1,2-polybutadiene of the present invention, it has the excellent functions characteristic of the conventional 1,2-polybutadiene, It is excellent in processability, moldability, and colorability (high sharpness), and can be suitably used as a molded product for shoe sole materials by molding means such as injection molding and transfer molding. The crosslinked (foamed) body produced in this manner is used as a sole material, specifically, men's shoes, women's shoes, casual shoes, running shoes, jogging shoes, tracking shoes, various sports shoes, mountain climbing shoes, dresses. It is useful as a sole material for shoes, golf shoes, indoor shoes, slippers, beach sandals, and other general footwear. In addition, the composition and the molded article of the present invention may be used, if necessary, in various molded articles such as automobile parts, building material parts, industrial parts, toys and miscellaneous parts, sports and health parts, various sheets, films, and other industrial products. It can be used for articles, cushioning materials, packaging materials and the like. The crosslinked foam of the present invention has excellent dimensional accuracy,
It has excellent durability and cushioning properties and can be applied to thermoformed sponge.

Continuing from the front page (72) Inventor Katsuaki Morino 2-11-24 Tsukiji, Chuo-ku, Tokyo Inside JSR Co., Ltd. (72) Inventor Junji Shinjuku 2-11-24 Tsukiji, Chuo-ku, Tokyo JSR shares In-house F-term (reference) 4F050 AA01 AA06 BA01 BA04 HA37 HA53 HA67 HA69 HA73 4F071 AA12 AA21 AB04 AB26 AE02 AE05 AE17 BB01 BB05 BC07 4F074 AA10 AA13 AA26 AC03 AC32 AD08 AG03 AG06 BA13 BA16 AC17 BB01 AC04 DA046 EK006 EV166 FD010 FD020 FD030 FD090 FD146 GC00

Claims (7)

[Claims] (A) oil-extended 1,2-polybutadiene;
(B) A crosslinkable polymer composition for shoe soles, comprising a thermoplastic polymer other than the component (A) and (C) a crosslinking agent. 2. A total of 100 parts by weight of (A) 1 to 99 parts by weight of component (B) and 99 to 1 part by weight of component (B) (100 parts by weight of (A) + (B)) is added to (C) ) Component is 0.0
2. The crosslinkable polymer composition for a shoe sole according to claim 1, wherein the amount is from 01 to 50 parts by weight. 3. The shoe according to claim 1, wherein the component (B) is at least one selected from the group consisting of a thermoplastic resin, a thermoplastic elastomer, a natural rubber and a synthetic rubber, other than the component (A). Crosslinkable polymer composition for bottom. 4. The method according to claim 1, wherein the crosslinking agent is at least one selected from the group consisting of sulfur, a compound capable of generating sulfur upon heating, an organic peroxide, a polyfunctional monomer, and a silanol compound. 3. The crosslinkable polymer composition for shoe sole according to any one of 3). 5. A total amount of component (A) and component (B) of 1
(D) 0 to 300 parts by weight of a softener, (E) 0 to 300 parts by weight of an inorganic filler, (F) a flame retardant, an antioxidant, a softener, a lubricant, a coloring agent, and foaming. 0 to 20 parts by weight of at least one other additive selected from the group consisting of an agent, an ultraviolet absorber, an antistatic agent, a heat stabilizer, an antioxidant, a processing aid, a lightfast (weather) agent and an antibacterial agent. Blended,
The crosslinkable polymer composition for shoe soles according to any one of claims 1 to 4, wherein the total amount of the components (D), (E) and (F) is 1 to 600 parts by weight. 6. The total amount of the components (A) and (B) is 1
Further, (G) a foaming agent is added in an amount of 1 to 300
The crosslinkable polymer composition for a shoe sole according to any one of claims 1 to 5, which is blended in parts by weight. 7. A shoe sole obtained by molding and crosslinking the crosslinkable polymer composition for a shoe sole according to any one of claims 1 to 6.