WO2010050628A2

WO2010050628A2 - Foamed rubber composition for shoe sole and outersole

Info

Publication number: WO2010050628A2
Application number: PCT/JP2010/051833
Authority: WO
Inventors: 毅仲島; 恒夫田中; ▲徐▼善柳
Original assignee: 宇部興産株式会社
Priority date: 2009-06-22
Filing date: 2010-02-08
Publication date: 2010-05-06
Also published as: WO2010050628A3; JP5565313B2; JPWO2010050628A1

Abstract

Provided is a foamed rubber composition for a shoe sole that is lightweight, has suitable hardness, and has excellent tensile strength, tearing strength, and impact absorbance, and an outersole that uses the same. The foamed rubber composition for a shoe sole uses (A) a vulcanizable rubber, (B) a vinyl cis-butadiene rubber (VCR) that is not (A) and that has a boiling n-hexane-insoluble content of 1 to 25 wt% and a boiling n-hexane-soluble content of 99 to 75 wt%, and (C) a thermoplastic resin, in combination with a foaming agent composed of (D1) a thermal expanding foaming agent and (D2) a pyrolyzing foaming agent such that there are 0.5 to 3.0 parts by weight of (D1) and 0.5 to 7.0 parts by weight of (D2) per 100 parts by weight of the total rubber components consisting of (A) + (B) + (C).

Description

Foam rubber composition for shoe sole and outsole

The present invention is a rubber foam composition for a shoe sole, which is lightweight and has an appropriate hardness, and excellent in tensile strength, tear strength, impact absorbability, in-mold fluidity, and dimensional stability after foaming, and further its rubber The present invention relates to an outsole using the composition.

In the footwear field, there is a need for strength to support the weight of the wearer, withstand the load and impact force associated with exercise, weight reduction and grip to enhance the comfort and safety of shoes. Among them, in recent years, low hardness and light weight and dimensional stability (low shrinkage) of molded products are required, and it is necessary to improve these characteristics.

In order to achieve low hardness and light weight, a chemical foaming agent (Patent Document 1) and a physical foaming agent (Patent Document 2) are used, and low hardness and light weight are achieved by mixing bubbles in the product. However, when a large amount of a chemical foaming agent is added alone to reduce the weight, there are problems such as destruction of the foam due to abnormal foaming, deterioration of the surface of the foamed product, and unstable product dimensions.

In order to solve the above problems, a thermoplastic resin having a glass transition temperature (Tg) lower than that of conventional 1,2-polybutadiene and vinyl cis polybutadiene (VCR) are used together and crosslinked with an organic oxide to increase the thickness accuracy. Excellent, moderate hardness, excellent smoothness, and further improved workability (Patent Document 3). In

Patent Document

4, 1,2-polybutadiene, polyethylene-based polymer, ethylene-vinyl acetate polymer resin is blended with natural rubber (isoprene) as a third component, which is rich in rubber elasticity, light weight and excellent hardness, Improves impact resistance and tear strength.

Japanese Patent Laid-Open No. 10-174601 Japanese Patent Laid-Open No. 10-152575 JP 2006-16518 A JP-A 61-55126

The present invention relates to a foam rubber composition for a shoe sole having a tensile strength, a tear strength, and an impact absorption property with a light weight and an appropriate hardness by using a pyrolytic foaming agent and a thermal expansion foaming agent in combination. The outsole used is provided. In particular, the flowability in the mold (because the temperature dependency during pressurization is low, the viscosity is low and there is no air bubble inclusion. Hereafter referred to as air voids), the product is free from chipping and becomes a molded product. There is provided a foam rubber composition for a shoe sole which is free from defects and excellent in dimensional stability after foaming.

In the present invention, (A) vulcanizable rubber, (B) other than (A) (B) boiling n-hexane insoluble content: 1 to 25% by weight, boiling n-hexane soluble content: 99 to 75% by weight A vinyl cis-butadiene rubber (VCR) and a thermoplastic resin (C) are combined with a foaming agent comprising (D1) a thermal expansion foaming agent and (D2) a thermal decomposition foaming agent, and (A) + (B) + A shoe characterized in that (D1) is 0.5 to 3.0 parts by weight and (D2) is 0.5 to 7.0 parts by weight with respect to 100 parts by weight of the total rubber component comprising (C). The present invention relates to a foam rubber composition for a bottom.

The present invention also relates to an outsole characterized by using the foam rubber composition for a shoe sole.

The foam rubber composition for shoe soles and the outsole using the same obtained in the present invention are lightweight and have an appropriate hardness, and have tensile strength, tear strength, and impact absorption. In particular, in the manufacturing process, the fluidity in the mold is improved (because the temperature dependency at the time of pressurization is low, the viscosity decrease is small and the air void is also improved). Therefore, it is possible to provide a foam rubber composition for a shoe sole that is free from defects in the product, has no defects in the molded product, and is excellent in dimensional stability after foaming.

FIG. 4 shows the relationship between the foaming pressure in the reactor and the time at the initial stage of vulcanization (heating and pressurization) in Examples 1 to 4. FIG. FIG. 6 is a relationship between the foaming pressure in the reactor and the time at the initial stage of vulcanization (heating and pressurization) in Examples 5 to 8. FIG. FIG. 5 is a relationship between the foaming pressure in the reactor and the time at the initial stage of vulcanization (heating and pressurization) in Comparative Examples 1 to 5. FIG. FIG. 4 is a relationship between the foaming pressure in the reactor and the time at the initial stage of vulcanization (heating and pressurization) in Comparative Examples 6 to 10. FIG. This is the foam pressure in the reactor from the start to the end of vulcanization in Examples 1 to 4. The in-reactor foaming pressure from the start to the end of vulcanization in Examples 5 to 8. This is the foaming pressure in the reactor from the start to the end of vulcanization in Comparative Examples 1 to 5. This is the foaming pressure in the reactor from the start to the end of vulcanization in Comparative Examples 6 to 10.

FIG. 4 is a relationship between the foaming pressure in the reactor and the time at the initial stage of vulcanization (heating and pressurization) in Examples 9 to 12. FIG. FIG. 6 shows the relationship between the foaming pressure in the reactor and the time at the initial stage of vulcanization (heating and pressurization) in Examples 13 to 15. FIG. FIG. 6 is a relationship between the foaming pressure in the reactor and the time at the initial stage of vulcanization (heating and pressurization) in Comparative Examples 11 to 14. FIG. It is a relationship between the foaming pressure in a reactor in the initial stage of vulcanization (heating and pressurization) in Comparative Example 15 and time. The in-reactor foaming pressure from the start to the end of vulcanization in Examples 9-12. This is the foam pressure in the reactor from the start to the end of vulcanization in Examples 13-15. This is the foam pressure in the reactor from the start to the end of vulcanization in Comparative Examples 11-14. This is the foam pressure in the reactor from the start to the end of vulcanization in Comparative Example 15.

FIG. 6 shows the relationship between the in-reactor foaming pressure and time at the initial stage of vulcanization (heating and pressurization) in Examples 16 to 18 and Comparative Example 16. FIG.

Description of Component (A) As vulcanizable rubber of (A), natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR) ), Butyl rubber (IIR), acrylonitrile-chloroprene rubber, acrylonitrile-isoprene rubber, styrene-chloroprene rubber, styrene-isoprene rubber and other diene rubbers, ethylene-propylene rubber, ethylene-butene rubber, ethylene-vinyl acetate copolymer (EVA) And ethylene-α-olefin copolymer rubbers such as ethylene-propylene-diene rubber (EPDM). These may be used alone or in combination.

Preferred are rubber components selected from natural rubber, isoprene rubber, butadiene rubber, butyl rubber, acrylonitrile-butadiene rubber and styrene-butadiene rubber, and particularly preferred are (a-1) natural rubber (NR) and (a-2 ) Styrene-butadiene rubber (SBR) combination or (a-1) natural rubber.

(A-2) As the styrene-butadiene rubber, it is particularly preferable to use a water-added styrene-butadiene rubber. Further, as the (a-2) styrene-butadiene rubber, it is particularly preferable to use a styrene-butadiene rubber (S-SBR) obtained by solution polymerization. Use of SBR other than S-SBR is not preferable because it causes problems such as deterioration of shrinkage and deterioration of wear resistance (or use of S-SBR exhibits excellent characteristics in terms of shrinkage and wear resistance). Preferred to use).

The blending amount of (A) is 2 to 30 parts by weight, preferably 5 to 25 parts by weight, particularly preferably 7 to 17 parts by weight of vulcanizable rubber in 100 parts by weight of all rubber components. When blended within the above blending range, properties necessary for roll processability (sheet skin shape appearance) and various physical properties of footwear (tensile strength, elongation, tear strength) can be imparted. However, if the blending amount is less than 2 parts by weight, problems such as roughness of the sheet and workability occur, and conversely if it exceeds 30 parts by weight, problems such as an increase in specific gravity and deterioration of shrinkage occur.

When (a-1) natural rubber (NR) and (a-2) styrene-butadiene rubber are mixed and used as the component (A), the blending amount of (a-1) natural rubber (NR) is: It is preferable that 2 to 30 parts by weight, preferably 5 to 20 parts by weight, particularly preferably 7 to 15 parts by weight are blended in 100 parts by weight of the total rubber component. When blended, properties necessary for roll processability (sheet skin shape appearance) and various physical properties of footwear (tensile strength, elongation, tear strength) can be imparted.

(A-2) The amount of the solution-polymerized styrene butadiene rubber (S-SBR) is 2 to 30 parts by weight, preferably 5 to 25 parts by weight, particularly preferably 8 to 20 parts by weight based on 100 parts by weight of the total rubber. What mix | blends a part is preferable. When blended, properties necessary for roll processability (sheet skin shape appearance, viscosity adjustment) can be imparted.

When the blending amount of (a-1) natural rubber and (a-2) S-SBR are used, the blending ratio (a-1) / (a-2) is preferably 0.07 to 15 More preferably, it is 0.2 to 4, particularly preferably 0.35 to 1.88. Use within the above-mentioned ratio range is preferable because it exhibits excellent properties in terms of shrinkage and wear resistance.

(B) Explanation of Component The vinyl cis-butadiene rubber (hereinafter abbreviated as VCR) as the component (B) will be described. VCR is a boiling cis-butadiene rubber with a boiling n-hexane insoluble content of 1 to 25% by weight, a boiling n-hexane soluble content of 99 to 75% by weight, and a boiling n-hexane insoluble content is syndiotactic 1 , 2-polybutadiene resin (hereinafter abbreviated as SPB). The boiling n-hexane soluble content is high cis-1,4-polybutadiene, and the microstructure is 90% by weight or more of the cis-1,4 structure. The boiling n-hexane insoluble matter mentioned here means the part recovered as an insoluble matter when the VCR is refluxed in boiling n-hexane, and the boiling n-hexane soluble matter means that the VCR is refluxed in boiling n-hexane. It is the part that dissolves when The boiling n-hexane insoluble matter has a reduced viscosity (135 ° C, concentration 0.20 g / dl orthodichlorobenzene solution) measured with an orthodichlorobenzene solution of 0.5 to 4, preferably 0.8 to 3 is there. When the reduced viscosity of boiling n-hexane insolubles is less than 0.5, the die swell of the formulation is not improved sufficiently. On the other hand, when the reduced viscosity of boiling n-hexane insolubles is greater than 4, SPB will form agglomerates in high cis-1,4-polybutadiene during polymerization, resulting in poor dispersion and reduced workability and durability. Thus, the object of the present invention cannot be achieved. The boiling n-hexane insoluble matter is SPB having a melting point of preferably 170 ° C. or higher, particularly preferably 190 to 220 ° C. If the melting point of SPB is less than 170 ° C., problems such as deterioration in workability and mechanical strength (such as tensile stress and tensile strength) occur due to the decrease in SPB reinforcement. Further, the weight average molecular weight of the boiling n-hexane soluble part is preferably in the range of 300,000 to 800,000, and if it is less than 300,000, the durability and impact resilience of the vulcanizate are lowered, which is not preferred. Exceeding 800,000 is not preferable because the Mooney viscosity of the compound becomes too high and processing becomes difficult.

The above-mentioned VCR production methods are disclosed in, for example, JP-B-49-17666, JP-B-49-17667, JP-B-61-57858, JP-B-62-171, JP-B-63-36324, The methods described in JP-A-2-37927, JP-B-2-38081, JP-B-3-63566 and the like can be used. However, the manufacturing method of the VCR used in the present invention is not limited to these methods.

The blending amount of the VCR of the component (B) is preferably 40 to 80 parts by weight, and more preferably 50 to 70 parts by weight with respect to 100 parts by weight of all rubber components. When blended within the above range, various physical properties of the footwear (tensile strength, elongation, tear strength, abrasion resistance) can be imparted. However, if the blending amount is less than 40 parts by weight, the problem of deterioration of wear resistance occurs, and conversely if it exceeds 80 parts by weight, problems such as an increase in specific gravity and an increase in hardness occur.

(C) Explanation of Component (C) Examples of the thermoplastic resin include syndiotactic 1,2-polybutadiene resin (SPB), polyethylene and its maleic anhydride graft polymer, polyisobutylene, ethylene vinyl acetate copolymer, Ethylene acrylate, ethylene acrylic acid copolymer, polypropylene and its maleic anhydride graft polymer, chlorinated polypropylene, 4-methylpentene-1 resin, polystyrene, ABS resin, AS resin, acrylic resin, methacrylic resin, vinyl chloride resin, Examples include vinylidene chloride resin, polyamide resin, and polycarbonate. These thermoplastic resins (C) can be used alone or in combination of two or more.

(C) The thermoplastic resin is preferably a polyolefin resin. Examples of polyolefin resins include polyethylene (PE), particularly low density PE (LDPE), medium density PE (MDPE), high density PE (HDPE), and linear low density PE (LLDPE), ethylene-propylene elastomer copolymer. (EPM), ethylene-propylene-diene rubber (EPDM), ethylene-vinyl ester copolymers such as ethylene-vinyl acetate copolymer (EVA), ethylene-acrylate copolymers, and ethylene-α-olefin thermoplastic copolymers, as well as propylene, butene -1, and copolymers such as pentene-1. These polyolefin resins can be used alone or in combination of two or more.

(C) Particularly preferable examples of the thermoplastic resin include 1,2-polybutadiene resins having a melting point of 70 ° C. to 110 ° C., and ethylene-vinyl acetate copolymer (EVA).

The blending amount of the thermoplastic resin (C) is preferably 10 to 35 parts by weight, more preferably 15 to 30 parts by weight, and more preferably 18 to 28 parts by weight based on 100 parts by weight of the total rubber component. It is particularly preferred. When blending within this range, various physical properties (gas barrier properties, dimensional stability) of footwear can be imparted. On the other hand, if the blending amount is less than 10 parts by weight, problems such as an increase in specific gravity and dimensional stability (shrinkage) due to a decrease in gas barrier properties occur, and conversely, if it exceeds 35 parts by weight, a problem of an increase in hardness will occur. Absent.

Here, the total rubber component means (A) + (B) + (C).

(D1) Thermal expansion type foaming agent (physical foaming agent)
The thermal expansion type foaming agent is not particularly limited as long as it is a foaming agent that expands by heat, but it is preferable to use thermally expandable microcapsules. A heat-expandable microcapsule is an encapsulated liquid or gas that expands when heated in a synthetic resin capsule, and is encapsulated by heat of kneading and melting by a screw or the like during extrusion molding or injection molding. The microcapsules that form the outer shell are expanded by the expansion of the liquid or gas. However, depending on the temperature conditions during molding, a microcapsule that melts and completes without bursting is used.

As a material of the microcapsule, a copolymer having acrylonitrile as one of monomer components is used, and other monomer components that may be copolymerized with acrylonitrile include, for example, acrylic acid, methacrylic acid, acrylate ester, methacrylic ester, and the like. Examples thereof include, but are not limited to, acid esters, styrene, vinyl acetate, and vinylidene chloride.

The liquid or gas encapsulated in the microcapsule is one that expands as a gas at a temperature below the softening point of the microcapsule. For example, propane, propylene, butene, normal butane, isobutane, isopentane, neopentane, normal pentane, hexane Low boiling point liquids such as methane halides such as heptane, petroleum ether, methyl chloride and methylene chloride, chlorofluorocarbons such as CCl ₃ F and CCl ₂ F ₂ , and tetraalkylsilanes such as tetramethylsilane and trimethylethylsilane In addition, a compound such as AIBN that is thermally decomposed by heating and becomes gaseous can be mentioned.

In addition, in extrusion molding and injection molding, since the raw material introduced from the hopper by the extruder or the injection machine is kneaded by a screw or the like, shearing force due to the kneading is applied to the thermally expandable microcapsule, and the die or metal Since a pushing force and a radiant force are applied when being extruded into the mold, the microcapsule needs to be unbreakable even when these forces are applied, and the size is selected.

Therefore, in the foamed molded product formed by such extrusion molding or injection molding, the amount and size of the bubbles are determined by the number (mixing amount) and the particle size of the thermally expandable microcapsules after expansion, and the molding is performed from these. Since the specific gravity of the body is determined, by predicting the number of unexpanded thermally expandable microcapsules (mixed amount) to be mixed with the thermoplastic resin raw material and the particle size of the thermally expandable microcapsules after expansion by the heating amount during molding The foaming state can be controlled, and only the gas does not escape to the outside as compared with the case where the conventional gas is directly expanded, and the target specific gravity can be easily achieved.

In this way, a foam can be formed in a state where the thermally expandable microcapsule is expanded and contained in the thermoplastic resin by extrusion molding or injection molding, and each bubble is stable in a state of being encapsulated in the microcapsule. In the case of extrusion molding, even when the pressure is released by being extruded from a die, the gas does not escape directly to the outside of the molded product, and a foam having a good surface appearance can be obtained.

Also, commercially available heat-expandable microcapsules (for example, EXPANCEL 920DU40, EXPANCEL 920DU80, EXPANCEL009DU80, EXPANCEL920DU40 master batch products 920MB40 and 920MB50, Matsumoto Yushi Pharmaceutical Matsumoto Microsphere F-D, etc.) are used. Can do. However, the particle size of the thermally expandable microcapsule is preferably 8 to 30 μm, more preferably 8 to 17 μm, and even more preferably 10 to 16 μm. In the said range, the effect of low specific gravity and the smoothness of the surface skin of a molded article can be expected. If a microcapsule smaller than the above range is used, there is a problem that the effect of reducing the specific gravity is reduced. On the other hand, if a microcapsule larger than the above range is used, there is a problem of surface roughness (smoothness) of the molded product. Arise.

The compounding amount of the thermal expansion foaming agent is 0.5 to 3.0 parts by weight, preferably 0.75 to 3.0 parts by weight, more preferably 0.80 to 2. It is 5 parts by weight, more preferably 0.85 to 2.5 parts by weight, still more preferably 0.90 to 2.0 parts by weight, and particularly preferably 1.2 to 2.0 parts by weight. In the above blending range, air removal, appearance of molded products (surface state smoothness and dimensional stability) with increasing foaming pressure in the initial stage of vulcanization, and various physical properties (tensile strength, elongation at break and tear strength) associated with lower specific gravity. Can be suppressed. On the other hand, if the blending amount is less than 0.5 parts by weight, there is a problem that the effect of lowering the specific gravity is reduced. Conversely, if the blending amount is more than 3.0 parts by weight, the surface roughness of the molded product (smoothness) is reduced. Problems arise.

(D2) Pyrolytic foaming agent (chemical foaming agent)
Examples of the thermally decomposable foaming agent include organic foaming agents such as azocicarbonamide complex (ADCA), azobisisobutyronitrile (AIBN), dinitrosopentamethylenetetramine (DPT), N, N′-dimethyl. -N, N'-dinitrosotephthalamide, benzenesulfonyl hydrazide (BSH), p-toluenesulfonyl hydrazide (TSH), 4,4'-oxybis (benzenesulfonyl hydrazide) (OBSH), 3,3'-disulfone hydrazide diphenyl Sulfone, toluene disulfonyl hydrazine, p-toluene disulfonyl hydrazide, p-toluene sulfonyl semi strength rubazide, diethyl azodicarboxylate and the like can be used.

Furthermore, an inorganic foaming agent can also be used as the thermally decomposable foaming agent. For example, sodium bicarbonate or ammonium bicarbonate can be used.

These thermal decomposable foaming agents may be used alone or in combination.

An organic foaming agent having a decomposition temperature of about 195 to 210 ° C. and a generated gas amount of 190 to 240 (ml / g) is preferable for use as a thermally decomposable foaming agent. In particular, azodicarbonamide complex (ADCA) or 4,4′-oxybis (benzenesulfonylhydrazide) (OBSH) is preferable.

When the thermal decomposable foaming agent having the above-described characteristics is used, the foaming effect with the combined thermal expansion foaming agent (D1) can be maximized, and the air accompanying the increase in foaming pressure at the initial stage of vulcanization can be completely removed. In addition, it is possible to suppress a decrease in appearance of a molded product (smoothness and dimensional stability of the surface state) and various physical properties (tensile strength, elongation at break and tear strength) associated with a decrease in specific gravity.

The compounding amount of the thermally decomposable foaming agent is 0.5 to 7.0 parts by weight, preferably 0.75 to 7.0 parts by weight, more preferably 0.8 to 7. 0 parts by weight, more preferably 0.85 to 7.0 parts by weight, still more preferably 0.85 to 6.0 parts by weight, and particularly preferably 1.0 to 4.5 parts by weight. In the above blending range, air removal, appearance of molded products (surface state smoothness and dimensional stability) with increasing foaming pressure in the initial stage of vulcanization, and various physical properties (tensile strength, elongation at break and tear strength) associated with lower specific gravity. Can be suppressed. On the other hand, if the blending amount is less than 0.5 parts by weight, there is a problem that the effect of reducing the specific gravity and the hardness is reduced. Conversely, if the blending amount is more than 7.0 parts by weight, the dimensional stability is reduced due to high foaming. Problem arises.

(E) Rubber Reinforcing Agent Examples of the rubber reinforcing agent (E) blended in the rubber composition according to the present invention include various types of carbon black, white carbon, silica, activated calcium carbonate, and ultrafine magnesium silicate. . Of these, silica and / or carbon black are preferred. Above all, silica having an average primary particle size of 5 to 100 nm, such as silicic anhydride by a dry method, hydrous silicic acid by a wet method, and synthetic silicate, and a particle size of 90 nm or less and a dibutyl phthalate (DBP) oil supply amount of 70 ml / 100 g or more. Carbon black is preferred. Examples of carbon black include furnace black, channel black, thermal black, and the like. 110, 212, N242, S315, N330, N550, N660, N765 and the like.

Silica can be either wet silica or dry silica, and can be used in combination. Further, silica can be used alone. Moreover, it is preferable that the silica to be used has a silica purity of 97% or more. Further, pulverized natural quartz having a silica purity of 97% or more can be used. Furthermore, particles obtained by hydrolyzing an organosilicon compound such as silane are also preferably used. Silica having a purity of less than 97% does not have a sufficient rubber reinforcing effect, so that a rubber composition blended with such silica does not have sufficient wear resistance.

The average particle diameter of the silica particles is preferably in the range of 0.1 to 50 μm, more preferably 1 to 50 μm, and particularly preferably 5 to 50 μm. Such a silica particle size can be obtained, for example, by a method of pulverizing a completely melted quartz glass so as to have an appropriate particle size. On the other hand, if the average particle size is smaller than 0.1 μm, it is difficult to mix in the rubber, causing problems such as loss and poor dispersion, and conversely if larger than 50 μm, the reinforcing effect is low, which is not preferable.

The amount of the rubber reinforcing agent used is 10 to 30 parts by weight, preferably 12 to 25 parts by weight, more preferably 15 to 20 parts by weight based on 100 parts by weight of the total rubber components. Within the above-mentioned range, a sufficient reinforcing effect can be obtained, and an effect of improving wear resistance can be obtained. On the other hand, if the amount is less than 10 parts by weight, the reinforcing effect is low, causing problems of deterioration in various physical properties (mechanical strength and wear resistance). Conversely, if the amount is more than 30 parts by weight, the workability is lowered due to the increase in viscosity. This is not preferable because it causes problems.

(F) Vulcanization accelerator Examples of the vulcanization accelerator used in the present invention include aldehydes, ammonia, amines, guanidines, thioureas, thiazoles, thiurams, dithiocarbamates, xanthates and the like. More specifically, tetramethylthiuram disulfide (TMTD), N-oxydiethylene-2-benzothiazolylsulfenamide (OBS), N-cyclohexyl-2-benzothiazylsulfenamide (CBS), dibenzo Thiazyl sulfide (MBTS), zinc di-n-butyldithiocarbide (ZnBDC), zinc dimethyldithiocarbide (ZnMDC) and the like can be mentioned. Of these, dibenzothiazyl sulfide (MBTS) and diortolyl guanidine (DOTG) are particularly preferable.

The amount of the vulcanization accelerator is 0.5 to 1.5 parts by weight, preferably 0.7 to 1.3 parts by weight, more preferably 0.8 to 1.2 parts by weight based on 100 parts by weight of the total rubber component. Part. Within the above range, a sufficient vulcanization effect can be obtained. On the other hand, if the amount is less than 0.5 parts by weight, problems such as a delay in vulcanization time and various physical properties due to a decrease in crosslink density are caused. This is not preferable.

(G) Vulcanizing agent Further, as the vulcanizing agent used in the present invention, sulfur, a compound that generates sulfur by heating, an organic peroxide, a metal oxide such as magnesium oxide, a polyfunctional monomer, a silanol compound, and the like Is mentioned. Examples of the compound that generates sulfur by heating include tetramethyl thiuram disulfide and tetraethyl thiuram disulfide. Among these, sulfur is particularly preferable.

The amount of the vulcanizing agent is 0.3 to 2.2 parts by weight, preferably 0.5 to 1.7 parts by weight, more preferably 1.0 to 1.5 parts by weight, based on 100 parts by weight of all rubber components. It is. Within the above range, a sufficient vulcanization effect can be obtained. On the other hand, if the amount is less than 0.3 parts by weight, problems such as a delay in vulcanization time and a decrease in physical properties due to a decrease in crosslink density are caused. This is not preferable.

(H) Other additives Various chemicals usually used in the rubber industry, for example, anti-aging agents, processing aids, process oils, scorch inhibitors, zinc white, stearin as long as the object of the present invention is not impaired. An acid etc. can be contained.

(H1) Anti-aging agent Examples of the anti-aging agent include amine / ketone-based, imidazole-based, amine-based, phenol-based, sulfur-based and phosphorus-based anti-aging agents.

(H2) Vulcanization aids As vulcanization aids, known vulcanization aids such as aldehydes, ammonia, amines, guanidines, thioureas, thiazoles, thiurams, dithiocarbamates, and xanthates Etc. are used.

(H3) Scorch inhibitor (retarder)
As the scorch inhibitor, organic acids, nitroso compounds, N-cyclohexylthiophthalimide, sulfonamide derivatives and the like are used.

(H4) Process oil Process oil may be any of aromatic, naphthenic, and paraffinic.

(Processing method)
(A) Vulcanizable rubber other than (A) (B) Boiling n-hexane insoluble content: 1 to 25% by weight, boiling n-hexane soluble content: 99 to 75% by weight vinyl cisbutadiene The rubber (VCR) and (C) thermoplastic resin are used in combination with a foaming agent comprising (D1) a thermal expansion type foaming agent and (D2) a thermal decomposition type foaming agent. (E) The rubber reinforcing agent is an open type such as a roll. It can be obtained by kneading using a kneader such as a closed kneader such as a kneader or Banbury mixer, and can be vulcanized after molding and applied to various rubber products.

Another main point of the present invention is the adjustment of the pressure in the reactor in the vulcanization process. In particular, by adjusting the foaming pressure in the reactor at the initial stage of vulcanization (after heating and pressurization 30 seconds) to 2000 kPa or more, preferably 2200 kPa, air voids are not generated, and there is no chipping in the product. It is possible to provide a method for producing a rubber foam composition for a shoe sole that is excellent in dimensional stability after foaming.

If the foaming pressure in the reactor in the initial stage of vulcanization (after heating and pressurization 30 seconds) is less than 2000 kP, sufficient deaeration cannot be performed in the initial stage of vulcanization, causing air voids. Therefore, the foaming pressure in the reactor in the initial stage of vulcanization (after 30 seconds of heating and pressurization) is a major factor for improving the product.

However, it is not only necessary that the foaming pressure in the reactor is larger than 2000 kPa, and the roles of the two types of foaming agents at the initial stage of vulcanization and the final stage of vulcanization are greatly affected.

In the vulcanization initial stage (after heating and pressurization 30 seconds), the foaming effect of (D1) thermal expansion type foaming agent affects the rapid increase of the foaming pressure in the reactor. Here, at the initial stage of vulcanization (D1), by increasing the foaming pressure in the reactor due to foaming of the thermal expansion type foaming agent, the air void in the reactor is not generated, and there is a problem of heat shrinkage of the molded product. Can also be prevented. Next, at the end of vulcanization, the foaming effect of (D2) pyrolytic foaming agent is affected. At this stage, when the vulcanization is sufficiently advanced, (D2) the foaming effect by the pyrolytic foaming agent can suppress the increase in the hardness of the resin and realize weight reduction. Therefore, the combined use of (D1) and (D2) is important.

FIGS. 1 and 2 show the relationship between the vulcanization time (especially at the initial stage of vulcanization) and the foaming pressure in the reactor of Examples 1 to 8. In Examples 1 to 8, the pressure inside the reactor was higher than 2000 kPa at the time of 0.5 minutes from the start of vulcanization (start of vulcanization: 30 seconds after heating and pressurization). On the other hand, in FIGS. 3 to 4 where Comparative Examples 1 to 10 are shown, the pressure inside the reactor is less than 2000 kPa at the time of vulcanization start 0.5 minutes (vulcanization start: after 30 seconds of heating and pressurization). There are many things.

Figures 5 to 8 show the relationship between the foaming pressure in the reactor from the start to the end of vulcanization. As shown in FIGS. 5 to 6, in Examples 1 to 8, the initial pressure of vulcanization (after 30 seconds of heating and pressurization) was maintained even after the in-reactor foaming pressure exceeded 2000 kPa. It can be seen that, even at the end of vulcanization, the in-reactor foaming pressure still exceeds 1000 kPa and the pressure is maintained. It is desirable to take such a course that there is no sudden pressure decrease, and the foaming effect of the pyrolytic foaming agent (D2) is greatly influenced particularly in the late vulcanization stage.

Table 3 shows that no air void occurred in Examples 1 to 8.

FIGS. 9 to 10 show the relationship between the vulcanization time (particularly at the initial stage of vulcanization) and the foaming pressure in the reactor of Examples 9 to 15 in the present invention. 9 to 10, in Examples 9 to 15, the pressure in the reactor was higher than 2000 kPa at the time of vulcanization start 0.5 minutes (vulcanization start: after 30 seconds of heating and pressurization).

11 to 12 show the relationship between the foaming pressure in the reactor from the start to the end of vulcanization in Comparative Examples 11 to 15. Here, when the reaction pressure decreases to 2000 kPa or less from the start to the end of vulcanization, there arises a problem of an increase in specific gravity and hardness accompanying a decrease in the reaction pressure.

From Table 7, it can be seen that no air voids occurred in Examples 9 to 15.

FIG. 17 shows the relationship between the vulcanization time (especially at the initial stage of vulcanization) and the foam pressure in the reactor of Examples 16 to 18 and Comparative Example 16 in the present invention. As shown in FIG. 17, in Examples 16 to 18, the pressure in the reactor was higher than 2000 kPa at the time of vulcanization start 0.5 minutes (vulcanization start: 30 seconds after heating and pressurization). On the other hand, in Comparative Example 16, the pressure in the reactor was less than 2000 kPa at the time of vulcanization start 0.5 minutes (vulcanization start: after 30 seconds of heating and pressurization).

From Table 10, it can be seen that in Examples 16 to 18, no air void occurred.

The specific gravity value at 2 mm is preferably 0.450 to 0.950 (g / cm ³ ), more preferably 0.500 to 0.800 (g / cm ³ ), and 0.550 to More preferably, it is 0.750 (g / cm ³ ). When the specific gravity is large, there arises a problem that the hardness cannot be increased and the weight cannot be reduced. Moreover, when specific gravity is small, the problem of deterioration of various physical properties (mechanical strength, abrasion resistance, shrinkage | contraction) will arise.

In all the comparative examples, when workability and air void are improved, there is a tendency for weight reduction, low hardness, water absorption, etc. to deteriorate, and conversely, for weight reduction purposes, workability and air void deteriorate. I understand that the balance is bad. Therefore, in consideration of the balance of overall physical properties and workability, the foaming pressure in the reactor is a combination of the constituent elements in the composition and the initial stage of vulcanization (after heating and pressurization 30 seconds) is 2000 kPa. It turns out that it is important to adjust so that it may become above, and to adjust so that specific gravity may become small.

The blending ratio of all rubber components (D1) and (D2) is also important in the present invention. As described above, the foaming pressure in the reactor at the initial stage of vulcanization (after heating and pressurization 30 seconds) is 2000 kPa or more. The amount of the foaming agent is necessary, and an appropriate amount of foaming agent is required to suppress the increase in the hardness of the resin at the end of vulcanization and to realize weight reduction. From such a viewpoint, the blending ratio of (D1) of 0.5 to 3.0 parts by weight and (D2) of 0.5 to 7.0 parts by weight is the optimum condition.

(Shoe sole foam rubber composition and outsole)
(A) Vulcanizable rubber other than (A) (B) Boiling n-hexane insoluble content: 1 to 25% by weight, boiling n-hexane soluble content: 99 to 75% by weight vinyl cisbutadiene (D1) 0.5 to 3.0 parts by weight of a thermal expansion foaming agent with respect to 100 parts by weight of the total rubber component (A) + (B) + (C) consisting of rubber (VCR) and (C) thermoplastic resin (D2) Low hardness, low specific gravity, and tensile strength compared to solid rubber sole material (specific gravity = 1 or more) -It has been found that a foam rubber composition for shoe soles having a large elongation at break, excellent shrinkage / appearance of a molded product after vulcanization, moldability, and balance thereof can be obtained.

The physical properties of the obtained rubber composition were measured as follows.
(1) Specific gravity (density): Measured by method A according to JIS K6268.

(2) Foaming pressure: Using ALPHA TECHNOLOGIES RPA2000 (rotorless type, rubber processability analyzer), the time to reach 10% and 160% vulcanization degree at 160 ° C. and the foaming pressure were measured according to JIS K6300. The higher the pressure value, the better.

(3) Hardness: Measured at room temperature using a type A durometer according to JIS K6253. Moreover, it measured at room temperature using Asker C type (sponge hardness meter) based on SR1S0101. The smaller the value, the softer and better.

(4) Tensile modulus, tensile strength, elongation at break; measured according to JIS K6251. The higher the value, the better the mechanical properties of the product, and the lower the value, the worse the wear resistance.

(5) Tear strength: measured in accordance with JIS K6252. The higher the value, the better it will be without tearing when the product is peeled from the mold.

(6) DIN wear; wear loss was measured according to JIS K6264. The smaller the value of DIN Index, the better the physical properties of DIN wear performance.

(7) Rebound resilience: measured according to JIS K6255 using a trypso type.

(8) Impact absorbability; measured according to JIS K6255 using a trypso type. The higher the value, the better the shock absorption performance.

(9) Shrinkage rate: Calculated from the length after 5 minutes at room temperature after molding (length after 30 minutes at room temperature). The smaller the value, the better the dimensional stability.

(10) Water absorption rate: The vulcanized rubber composition was immersed in a water bath manufactured by Yamato Kagaku Co. at 40 ° C for 24 hours, and the weight change before and after immersion was measured to calculate the water absorption rate. Larger numbers indicate larger bubbles.

Experimental example 1
Example 1
(A) natural rubber / (B) VCR / (C) 1,2 polybutadiene resin in Table 1 in a blending ratio of 7/70/23 parts by weight, and rubber reinforcing agents such as silica, zinc white and stearic acid Together with a 1.7 liter closed kneader. Thereafter, the vulcanization accelerator and sulfur, 1.0 part by weight of the thermal expansion foaming agent, and 1.5 parts by weight of the thermal decomposition foaming agent were mixed with an open roll. Next, press vulcanization was performed, and the physical properties were evaluated by the obtained vulcanized test pieces. The results are shown in Table 3.

(Example 2)
In Table 1, (A) natural rubber / (B) VCR / (C) 1,2 polybutadiene resin was blended in a ratio of 7/65/28 parts by weight, and a vulcanized test piece was prepared in the same manner as in Example 1 below. The physical properties were evaluated. The results are shown in Table 3.

(Example 3)
In Table 1, (A) natural rubber / (B) VCR / (C) 1,2 polybutadiene resin was blended in a ratio of 12/60/28 parts by weight, and a vulcanized test piece was prepared in the same manner as in Example 1 below. The physical properties were evaluated. The results are shown in Table 3.

Example 4
In Table 1, (a-1) natural rubber / (a-2) water-added styrene-butadiene rubber (manufactured by Asahi Kasei Chemicals Co., Ltd.) / (B) VCR / (C) 1,2 polybutadiene resin is blended in a ratio of 7/10/65. / 18 parts by weight, vulcanized test pieces were prepared in the same manner as in Example 1, and the physical properties were evaluated. The results are shown in Table 3.

(Example 5)
In Table 1, (A) natural rubber / (B) VCR / (C) 1,2 polybutadiene resin was blended in a blending ratio of 7/70/23 parts by weight, and then kneaded in the same manner as in Example 1. Thereafter, the vulcanization accelerator and sulfur, and 2.5 parts by weight of the thermal expansion foaming agent and 0.7 parts by weight of the thermal decomposition foaming agent were mixed with an open roll. Next, press vulcanization was performed, and the physical properties were evaluated by the obtained vulcanized test pieces. The results are shown in Table 3.

(Example 6)
In Table 1, (A) natural rubber / (B) VCR / (C) 1,2 polybutadiene resin was blended in a blending ratio of 7/70/23 parts by weight, and then kneaded in the same manner as in Example 1. Thereafter, the vulcanization accelerator, sulfur, 1.0 part by weight of the thermal expansion foaming agent, and 6.5 parts by weight of the thermal decomposition foaming agent were mixed with an open roll. Next, press vulcanization was performed, and the physical properties were evaluated by the obtained vulcanized test pieces. The results are shown in Table 3.

(Example 7)
In Table 1, (A) natural rubber / (B) VCR / (C) 1,2 polybutadiene resin was blended in a blending ratio of 7/70/23 parts by weight, and then kneaded in the same manner as in Example 1. Thereafter, the vulcanization accelerator and sulfur, 2.5 parts by weight of the thermal expansion foaming agent, and 6.5 parts by weight of the thermal decomposition foaming agent were mixed with an open roll. Next, press vulcanization was performed, and the physical properties were evaluated by the obtained vulcanized test pieces. The results are shown in Table 3.

(Example 8)
In Table 1, (A) natural rubber / (B) VCR / (C) 1,2 polybutadiene resin was blended in a blending ratio of 7/70/23 parts by weight, and then kneaded in the same manner as in Example 1. Thereafter, a vulcanization accelerator, sulfur, 2.5 parts by weight of a thermal expansion foaming agent, and 1.0 part by weight of a thermal decomposition foaming agent were mixed with an open roll. Next, press vulcanization was performed, and the physical properties were evaluated by the obtained vulcanized test pieces. The results are shown in Table 3.

(Comparative Example 1)
(A-1) natural rubber / (a-2) solution-polymerized styrene-butadiene rubber / (B) VCR / (C) 1,2 polybutadiene resin in Table 2 to a blending ratio of 7/18/55/20 parts by weight, Silica, which is a rubber reinforcing agent, and additives such as zinc white and stearic acid were kneaded using a 1.7 liter closed kneader. Thereafter, the vulcanization accelerator and sulfur were mixed with an open roll. Next, press vulcanization was performed, and the physical properties were evaluated by the obtained vulcanized test pieces. The results are shown in Table 4.

(Comparative Example 2)
In Table 2, (A) natural rubber / (B) VCR / (C) 1,2 polybutadiene resin was blended in a ratio of 7/70/23 parts by weight, and a vulcanized test piece was prepared in the same manner as in Comparative Example 1 below. The physical properties were evaluated. The results are shown in Table 4.

(Comparative Example 3)
In Table 2, (A) natural rubber / (B) VCR / (C) 1,2 polybutadiene resin was blended in a blending ratio of 7/70/23 parts by weight, and then kneaded by the same method as in Comparative Example 1. Thereafter, the vulcanization accelerator and sulfur, and 2.5 parts by weight of the thermal expansion foaming agent and 0.0 part by weight of the thermal decomposition foaming agent were mixed with an open roll. Next, press vulcanization was performed, and the physical properties were evaluated by the obtained vulcanized test pieces. The results are shown in Table 4.

(Comparative Example 4)
In Table 2, (A) natural rubber / (B) VCR / (C) 1,2 polybutadiene resin was blended in a blending ratio of 7/70/23 parts by weight, and then kneaded by the same method as in Comparative Example 1. Thereafter, the vulcanization accelerator, sulfur, 0.0 part by weight of the thermal expansion foaming agent, and 2.5 parts by weight of the thermal decomposition foaming agent were mixed with an open roll. Next, press vulcanization was performed, and the physical properties were evaluated by the obtained vulcanized test pieces. The results are shown in Table 4.

(Comparative Example 5)
In Table 2, (A) natural rubber / (B) VCR / (C) 1,2 polybutadiene resin was blended in a blending ratio of 7/70/23 parts by weight, and then kneaded by the same method as in Comparative Example 1. Thereafter, the vulcanization accelerator and sulfur, and 0.3 parts by weight of the thermal expansion foaming agent and 1.5 parts by weight of the thermal decomposition foaming agent were mixed with an open roll. Next, press vulcanization was performed, and the physical properties were evaluated by the obtained vulcanized test pieces. The results are shown in Table 4.

(Comparative Example 6)
In Table 2, (A) natural rubber / (B) VCR / (C) 1,2 polybutadiene resin was blended in a blending ratio of 7/70/23 parts by weight, and then kneaded by the same method as in Comparative Example 1. Thereafter, vulcanization accelerator and sulfur, and 5.0 parts by weight of thermal expansion type foaming agent and 1.5 parts by weight of thermal decomposition type foaming agent were mixed with an open roll. Next, press vulcanization was performed, and the physical properties were evaluated by the obtained vulcanized test pieces. The results are shown in Table 4.

(Comparative Example 7)
In Table 2, (A) natural rubber / (B) VCR / (C) 1,2 polybutadiene resin was blended in a blending ratio of 7/70/23 parts by weight, and then kneaded by the same method as in Comparative Example 1. Thereafter, the vulcanization accelerator and sulfur, 1.0 part by weight of the thermal expansion foaming agent, and 0.3 part by weight of the thermal decomposition foaming agent were mixed with an open roll. Next, press vulcanization was performed, and the physical properties were evaluated by the obtained vulcanized test pieces. The results are shown in Table 4.

(Comparative Example 8)
In Table 2, (A) natural rubber / (B) VCR / (C) 1,2 polybutadiene resin was blended in a blending ratio of 7/70/23 parts by weight, and then kneaded by the same method as in Comparative Example 1. Thereafter, a vulcanization accelerator, sulfur, 1.0 part by weight of a thermal expansion foaming agent, and 10.0 parts by weight of a thermal decomposition foaming agent were mixed with an open roll. Next, press vulcanization was performed, and the physical properties were evaluated by the obtained vulcanized test pieces. The results are shown in Table 4.

(Comparative Example 9)
In Table 2, (A) natural rubber / (B) VCR / (C) 1,2 polybutadiene resin was blended in a blending ratio of 7/70/23 parts by weight, and then kneaded by the same method as in Comparative Example 1. Thereafter, a vulcanization accelerator, sulfur, 3.0 parts by weight of a thermal expansion foaming agent, and 0.0 part by weight of a thermal decomposition foaming agent were mixed with an open roll. Next, press vulcanization was performed, and the physical properties were evaluated by the obtained vulcanized test pieces. The results are shown in Table 4.

(Comparative Example 10)
In Table 2, (A) natural rubber / (B) VCR / (C) 1,2 polybutadiene resin was blended in a blending ratio of 7/70/23 parts by weight, and then kneaded by the same method as in Comparative Example 1. Thereafter, the vulcanization accelerator and sulfur, and 0.0 parts by weight of the thermal expansion type foaming agent and 7.0 parts by weight of the thermal decomposition type foaming agent were mixed with an open roll. Next, press vulcanization was performed, and the physical properties were evaluated by the obtained vulcanized test pieces. The results are shown in Table 4.

Experimental example 2
Example 9
In Table 5, (a-1) natural rubber / (a-2) styrene-butadiene rubber (SBR) / (B) VCR / (C) olefin resin is blended to 7/18/55/20 parts by weight, and rubber It knead | mixed using the 1.7-liter closed-type kneading apparatus with additives, such as silica which is a reinforcing agent, zinc white, and stearic acid. Thereafter, 0.95 parts by weight of vulcanization accelerator, 1.2 parts by weight of sulfur, 1.00 parts by weight of thermal expansion foaming agent EXPANCEL DU092-40, and 4.50 parts by weight of thermal decomposition foaming agent CAP-500 Were mixed in an open roll. Next, press vulcanization was performed, and the physical properties were evaluated by the obtained vulcanized test pieces. The results are shown in Table 7.

(Example 10)
(A-1) Natural rubber / (a-2) Styrene-butadiene rubber (SBR) / (B) VCR / (C) Olefin resin in Table 5 to a blending ratio of 7/18/55/20 parts by weight, rubber It knead | mixed using the 1.7-liter closed-type kneading apparatus with additives, such as silica which is a reinforcing agent, zinc white, and stearic acid. Thereafter, 0.95 parts by weight of a vulcanization accelerator, 1.2 parts by weight of sulfur, 1.25 parts by weight of a thermal expansion foaming agent EXPANCEL DU092-40, and 4.50 parts by weight of a thermal decomposition foaming agent CAP-500 Were mixed in an open roll. Next, press vulcanization was carried out, and the physical properties were evaluated by the obtained vulcanized test pieces. The results are shown in Table 7.

Example 11
In Table 5, (a-1) natural rubber / (a-2) styrene-butadiene rubber (SBR) / (B) VCR / (C) olefin resin is blended to 7/18/55/20 parts by weight, and rubber It knead | mixed using the 1.7-liter closed-type kneading apparatus with additives, such as silica which is a reinforcing agent, zinc white, and stearic acid. Thereafter, 0.95 parts by weight of a vulcanization accelerator, 1.2 parts by weight of sulfur, 1.50 parts by weight of a thermal expansion foaming agent EXPANCEL DU092-40, and 4.50 parts by weight of a thermal decomposition foaming agent CAP-500 Were mixed in an open roll. Next, press vulcanization was performed, and the physical properties were evaluated by the obtained vulcanized test pieces. The results are shown in Table 7.

(Example 12)
In Table 5, (a-1) natural rubber / (a-2) styrene-butadiene rubber (SBR) / (B) VCR / (C) olefin resin is blended to 7/18/55/20 parts by weight, and rubber It knead | mixed using the 1.7-liter closed-type kneading apparatus with additives, such as silica which is a reinforcing agent, zinc white, and stearic acid. Thereafter, 0.95 parts by weight of vulcanization accelerator, 1.2 parts by weight of sulfur, 2.00 parts by weight of thermal expansion foaming agent EXPANCEL DU092-40, and 4.50 parts by weight of thermal decomposition foaming agent CAP-500 Were mixed in an open roll. Next, press vulcanization was performed, and the physical properties were evaluated by the obtained vulcanized test pieces. The results are shown in Table 7.

(Example 13)
In Table 5, (a-1) natural rubber / (a-2) styrene-butadiene rubber (SBR) / (B) VCR / (C) olefin resin is blended to 7/18/55/20 parts by weight, and rubber It knead | mixed using the 1.7-liter closed-type kneading apparatus with additives, such as silica which is a reinforcing agent, zinc white, and stearic acid. Thereafter, 0.95 parts by weight of a vulcanization accelerator, 1.2 parts by weight of sulfur, 1.0 part by weight of a thermal expansion foaming agent EXPANCEL DU092-40, and 1.5 parts by weight of a thermal decomposition foaming agent CAP-500 Were mixed in an open roll. Next, press vulcanization was performed, and the physical properties were evaluated by the obtained vulcanized test pieces. The results are shown in Table 7.

(Example 14)
In Table 5, (a-1) natural rubber / (a-2) styrene-butadiene rubber (SBR) / (B) VCR / (C) olefin resin is blended to 7/18/55/20 parts by weight, and rubber It knead | mixed using the 1.7-liter closed-type kneading apparatus with additives, such as silica which is a reinforcing agent, zinc white, and stearic acid. Thereafter, 0.95 parts by weight of vulcanization accelerator, 1.2 parts by weight of sulfur, 1.0 part by weight of thermal expansion foaming agent EXPANCEL DU092-40, and 6.5 parts by weight of thermal decomposition foaming agent CAP-500 Were mixed in an open roll. Next, press vulcanization was performed, and the physical properties were evaluated by the obtained vulcanized test pieces. The results are shown in Table 7.

(Example 15)
In Table 5, (a-1) natural rubber / (a-2) styrene-butadiene rubber (SBR) / (B) VCR / (C) olefin resin is blended to 7/18/55/20 parts by weight, and rubber It knead | mixed using the 1.7-liter closed-type kneading apparatus with additives, such as silica which is a reinforcing agent, zinc white, and stearic acid. Thereafter, 0.95 parts by weight of a vulcanization accelerator, 1.2 parts by weight of sulfur, 2.5 parts by weight of a thermal expansion foaming agent EXPANCEL DU092-40, and 1.5 parts by weight of a thermal decomposition foaming agent CAP-500 Were mixed in an open roll. Next, press vulcanization was performed, and the physical properties were evaluated by the obtained vulcanized test pieces. The results are shown in Table 7.

(Comparative Example 11)
The same procedure as in Example 9 was conducted except that the thermal expansion foaming agent EXPANCEL DU092-40 was not used. The results are shown in Table 8.

(Comparative Example 12)
The same procedure as in Example 9 was conducted except that the thermal expansion foaming agent EXPANCEL DU092-40 was not used and the thermal decomposition foaming agent CAP-500 was used in an amount of 5.50 parts by weight. The results are shown in Table 8.

(Comparative Example 13)
The same procedure as in Example 9 was conducted except that the thermal expansion foaming agent EXPANCEL DU092-40 was not used and the thermal decomposition foaming agent CAP-500 was used in an amount of 6.50 parts by weight. The results are shown in Table 8.

(Comparative Example 14)
The same procedure as in Example 9 was conducted, except that 5.00 parts by weight of the thermal expansion foaming agent EXPANCEL DU092-40 was used, and the thermal decomposition foaming agent CAP-500 was not used. The results are shown in Table 8.

(Comparative Example 15)
In Table 6, (a-1) natural rubber / (a-2) styrene-butadiene rubber (SBR) / (B) VCR / (C) olefin resin is blended in a ratio of 7/18/75/0 parts by weight. It knead | mixed using the 1.7-liter closed-type kneading apparatus with additives, such as silica which is a reinforcing agent, zinc white, and stearic acid. Thereafter, 0.95 parts by weight of vulcanization accelerator, 1.2 parts by weight of sulfur, 2.00 parts by weight of thermal expansion foaming agent EXPANCEL DU092-40, and 4.50 parts by weight of thermal decomposition foaming agent CAP-500 Were mixed in an open roll. Next, press vulcanization was performed, and the physical properties were evaluated by the obtained vulcanized test pieces. The results are shown in Table 8.

Experimental example 3
(Example 16)
(A-1) Natural rubber / (a-2) Styrene-butadiene rubber (SBR) / (B) VCR / (C) Olefin resin in Table 9 to a blending ratio of 7/10/65/18 parts by weight It knead | mixed using the 1.7-liter closed-type kneading apparatus with additives, such as silica which is a reinforcing agent, zinc white, and stearic acid. Thereafter, 0.95 parts by weight of a vulcanization accelerator, 1.2 parts by weight of sulfur, 1.00 parts by weight of a thermal expansion foaming agent EXPANCEL DU092-40 having an average particle size of 10 to 16 μm, and a thermal decomposition foaming agent 4.50 parts by weight of CAP-500 was mixed with an open roll. Next, press vulcanization was performed, and the physical properties were evaluated by the obtained vulcanized test pieces. The results are shown in Table 10.

(Example 17)
(A-1) Natural rubber / (a-2) Styrene-butadiene rubber (SBR) / (B) VCR / (C) Olefin resin in Table 9 to a blending ratio of 7/10/65/18 parts by weight It knead | mixed using the 1.7-liter closed-type kneading apparatus with additives, such as silica which is a reinforcing agent, zinc white, and stearic acid. Thereafter, 0.95 parts by weight of a vulcanization accelerator, 1.2 parts by weight of sulfur, 1.00 parts by weight of a thermal expansion foaming agent EXPANCEL DU092-80 having an average particle size of 18 to 24 μm, and a thermal decomposition foaming agent 4.50 parts by weight of CAP-500 was mixed with an open roll. Next, press vulcanization was performed, and the physical properties were evaluated by the obtained vulcanized test pieces. The results are shown in Table 10.

(Example 18)
(A-1) Natural rubber / (a-2) Styrene-butadiene rubber (SBR) / (B) VCR / (C) Olefin resin in Table 9 to a blending ratio of 7/10/65/18 parts by weight It knead | mixed using the 1.7-liter closed-type kneading apparatus with additives, such as silica which is a reinforcing agent, zinc white, and stearic acid. Thereafter, 0.95 parts by weight of a vulcanization accelerator, 1.2 parts by weight of sulfur, 1.00 parts by weight of a thermal expansion type foaming agent EXPANCEL DU009-80 having an average particle size of 18 to 24 μm, and a thermal decomposition type foaming agent 4.50 parts by weight of CAP-500 was mixed with an open roll. Next, press vulcanization was performed, and the physical properties were evaluated by the obtained vulcanized test pieces. The results are shown in Table 10.

(Comparative Example 16)
The same procedure as in Example 16 was performed except that the thermal expansion foaming agent was not used. The results are shown in Table 10.

As the use of the foam rubber composition obtained in the present invention, it is useful as a sole material in the sole field, in particular, footwear in general such as sports shoes, running shoes, and casual shoes.

Claims

(A) Vulcanizable rubber other than (A) (B) Boiling n-hexane insoluble content: 1 to 25% by weight, boiling n-hexane soluble content; 99 to 75% by weight vinyl cisbutadiene From (A) + (B) + (C), a rubber (VCR) and (C) thermoplastic resin are combined with a foaming agent comprising (D1) a thermal expansion type foaming agent and (D2) a thermal decomposition type foaming agent. A foam for a shoe sole, wherein (D1) is 0.5 to 3.0 parts by weight and (D2) is 0.5 to 7.0 parts by weight with respect to 100 parts by weight of the total rubber component. Rubber composition.
The vulcanizable rubber (A) is a combination of (a-1) natural rubber and (a-2) styrene-butadiene rubber (SBR), or (a-1) natural rubber. Item 1. A foam rubber composition for a shoe sole according to Item 1.
3. The foam rubber composition for a shoe sole according to claim 2, wherein the (a-2) styrene-butadiene rubber (SBR) is a water-added styrene-butadiene rubber.
3. The foam rubber composition for a shoe sole according to claim 2, wherein (a-2) the styrene-butadiene rubber (SBR) is a solution-polymerized styrene-butadiene rubber (S-SBR).
5. The foam rubber composition for a shoe sole according to any one of claims 1 to 4, which is syndiotactic 1,2-polybutadiene having a melting point of (B) insoluble in boiling n-hexane of 170 ° C. or higher.
6. The foam rubber composition for a shoe sole according to any one of claims 1 to 5, wherein the thermoplastic resin (C) is a polyolefin resin.
The foam rubber composition for a shoe sole according to claim 6, wherein the polyolefin resin is a 1,2-polybutadiene resin having a melting point of 70 ° C to 110 ° C.
The shoe rubber foam composition according to claim 6, wherein the polyolefin resin is an ethylene-vinyl acetate copolymer (EVA).
(D1) The foam rubber composition for a shoe sole according to any one of claims 1 to 8, wherein the thermally expandable foaming agent is a thermally expandable microcapsule.
10. The foam rubber composition for a shoe sole according to claim 9, wherein a particle diameter of the thermally expandable microcapsule is 8 to 30 μm.
The foam rubber composition for a shoe sole according to any one of claims 1 to 10, wherein the pyrolytic foaming agent (D2) is an azodicarbonamide composite foaming agent.
An outsole comprising the foam rubber composition for a shoe sole according to any one of claims 1 to 11.