JPH0838201A - Member for a footwear - Google Patents

Abstract

PURPOSE:To provide a member for a footwear with excellent shock absorption properties by using a high polymer composition with specific physical properties, which contains a low molecular weight material holding composite comprising a low molecular material and a medium, and a high molecular weight material. CONSTITUTION:This member for a footwear employs a high molecular weight composition with specific physical properties, which contains a low molecular weight material holding composite comprising a low molecular material and a medium, and a high molecular weight material as constituting materials. The low molecular weight material contained in the polymer composition has viscosity of 5X10<5>cps or lower at 100 deg.C, and the difference between solubility parameter of the low molecular weight material and that of the medium is 3.0 or lower. The weight ratio of the low molecular weight material to the medium in the polymer composition is 1.0 or higher, and the difference between solubility parameter of the low molecular weight material and that of the polymer material is 4.0 or lower. The weight ratio of the low molecular weight material to the high molecular weight material in the polymer composition is 0.5 or higher. This high polymer composition 5, for example, is used for the tread part of an insole 2 of a shoe 1.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a footwear member such as various sports shoes, and more particularly to a footwear member which is extremely comfortable to wear.

[0002]

2. Description of the Related Art Insoles such as leather shoes (men's shoes, women's shoes), sports shoes, chemical shoes, and footwear made of rubber or other materials such as sandals absorb the impact of walking or running. A variety of shapes and materials are provided so that the wearer does not easily get tired and is comfortable to wear.

Further, especially for sports shoes,
For the purpose of safety, not only the insole but also the tip of the shoe (toe), heel, ankle, and instep are provided with materials for shock absorption. Heretofore, as a shock absorbing material for such an insole of such shoes, a material in which a lightweight filler such as cork is mixed with rubber, or urethane, silicone or the like is used.

[0004]

As a shock absorbing material for the insole etc. of the above shoes, it is required that the shock absorbing material has sufficient shock absorption, is lightweight, is excellent in productivity and is inexpensive. To be done. Therefore, these characteristics and physical properties,
It is desired to develop footwear members such as shoes that use impact absorbing materials with improved productivity.

The present invention has been made in view of the above-mentioned conventional circumstances, and uses an impact absorbing material which has excellent impact resistance, can be reduced in weight, and can be manufactured at low cost with high productivity. An object is to provide a footwear member such as a pair of shoes.

[0006]

In footwear such as shoes for which the impact absorbing material of claim 1 is useful, the member used as the impact absorbing material is a low molecular weight material holding composite containing a low molecular weight material and a medium material. And a low molecular weight material in the high molecular weight composition having a viscosity of 5 × 10 ⁵ centipoise or less at 100 ° C., The difference between the solubility parameter values of the low molecular weight material and the medium material is 3.0 or less, and the weight ratio of the low molecular weight material and the medium material in the polymer composition is 1.0 or more. A polymer having a solubility parameter value difference of 4.0 or less between the polymer and the polymer material, and a weight ratio of the low molecular weight material and the polymer material in the polymer composition is 0.5 or more. It is characterized by including a composition as a constituent material.

Further, in claim 2 of the present invention, the footwear member is formed by using the polymer composition according to claim 1 in which the polymer material is a thermosetting material as a main component. Is characterized by.

That is, the inventors of the present invention have conducted extensive studies on shock absorbing materials having excellent shock absorbing performance, and as a result, the polymer composition according to the present invention has various characteristics such as shock absorbing characteristics and hardness. As for the insole, midsole, outsole, etc. of the footwear member as described above, it is possible to obtain an extremely excellent footwear article by using this polymer composition as a shock absorber. They found out and completed the present invention.

The present invention will be described in detail below.

First, as the low molecular weight material which is one of the constituent elements of the present invention, the following materials are preferable.

That is, the viscosity at 100 ° C. is 5 × 10 ^5.
It is preferably not more than 1 centipoise, particularly not more than 1 × 10 ⁵ centipoise, and from the viewpoint of molecular weight, the number average molecular weight of the low molecular weight material is not more than 20,000, especially 10.0.
It is preferably 00 or less, and particularly preferably 5,000 or less. As such a low molecular weight material, a liquid or liquid material at room temperature is usually preferably used. Further, both hydrophilic and hydrophobic low molecular weight materials can be used. The low molecular weight material is not particularly limited, but the following materials are suitable.

Further, the low molecular weight material has a difference of 3.0 or less between the solubility parameter value of the medium material and the solubility parameter value of the medium material described later, and a difference of 4.0 or less between the solubility parameter value of the polymer material. Use something.

As the low molecular weight material, any material can be used as long as it satisfies the above conditions, and it is not particularly limited, but specifically, the following materials can be mentioned.

Softening agent: A softening agent for various rubbers or resins such as mineral oils, vegetable oils and synthetics. Examples of the mineral oil-based oil include process oils such as aromatic oils, naphthene oils, and paraffin oils. Vegetable oils include castor oil, cottonseed oil, linseed oil, rapeseed oil, soybean oil, palm oil,
Examples include coconut oil, peanut oil, wood wax, pine oil, olive oil and the like.

Plasticizers: various ester plasticizers such as phthalic acid esters, mixed phthalic acid esters, aliphatic dibasic acid esters, glycol esters, fatty acid esters, phosphoric acid esters, stearic acid esters, epoxy plasticizers, etc. Plasticizer for plastics or phthalate type,
Adipate-based, sebacate-based, phosphate-based, polyether-based, polyester-based, etc. plasticizers for NBR.

Tackifier: Various tackifiers (tackifier) such as coumarone resin, coumarone-indene resin, phenol terpene resin, petroleum hydrocarbon, rosin derivative and the like.

Oligomer: Crown ether, fluorine-containing oligomer, polyisobutylene, xylene resin, chlorinated rubber, polyethylene wax, petroleum resin, rosin ester rubber, polyalkylene glycol diacrylate,
Liquid rubber (polybutadiene, styrene-butadiene rubber, butadiene-acrylonitrile rubber, polychloroprene, etc.), silicone-based oligomers, various oligomers such as poly-α-olefins.

Lubricants: Hydrocarbon lubricants such as paraffin and wax, fatty acid lubricants such as higher fatty acids and oxyfatty acids, fatty acid amide lubricants such as fatty acid amides and alkylenebisfatty acid amides, fatty acid lower alcohol esters, fatty acid polyhydric alcohol esters. , Ester-based lubricants such as fatty acid polyglycol esters, alcohol-based lubricants such as fatty alcohols, polyhydric alcohols, polyglycols and polyglycerols, various lubricants such as metal soaps and mixed lubricants.

In addition, latex, emulsion, liquid crystal, bituminous composition, viscosity, natural starch, sugar, inorganic silicone oil, phosphazene and the like are also suitable as the low molecular weight material. Further, hydrocarbon-based, halogenated hydrocarbon-based, alcohol-based, phenol-based, ether-based, acetal-based, ketone-based, fatty acid-based, ester-based, nitrogen compound-based, sulfur compound-based organic solvents: or various medicinal effects Ingredients, soil modifiers, fertilizers, petroleum, water, aqueous solutions, etc. are also used.

These low molecular weight materials may be used alone or in combination of two or more, and the required properties of the obtained polymer composition, the use as a vibration damping material, and The optimum material is selected by taking into consideration the compatibility with the medium material, which is another component of the invention, and the polymer material, and the optimum amount is used.

On the other hand, the medium material in the present invention is a material having a function as a medium of the low molecular weight material and the polymer material described later, and is an important component for achieving the object of the present invention.
Specifically, in order to realize a uniform composition of a large amount of low molecular weight material and a high molecular weight material, a large amount of low molecular weight material and a medium material are used to hold a large amount of low molecular weight material. The purpose is to obtain a composite first, and then to combine it with a polymer material to obtain a target polymer composition holding a large amount of a low-molecular material.

That is, even if the low molecular weight material, the medium material, and the high molecular weight material are mixed at the same time, a uniform polymer composition having a low elastic modulus cannot be obtained. Further, even if a large amount of a low molecular weight material and a high molecular weight material are directly mixed to obtain a polymer composition containing a large amount of a low molecular weight material, the low molecular weight material cannot be uniformly mixed, and bleeding often occurs. However, the intended polymer composition having a low elastic modulus cannot be obtained.

In the present invention, the medium material "holds" the low molecular weight material or "blends" the low molecular weight material-holding composite with the polymer material means that the low molecular weight material is the medium material and the polymer. It means that the material is uniformly dispersed and does not bleed, or bleeding is suppressed. Of course, the degree of bleeding can be easily controlled depending on the purpose of the polymer composition. Finally, the uniform mechanism by which the low molecular weight material-holding composite is uniformly dispersed in the polymer material when mixed with the polymer material is not always clear. It is considered that this is because the polymer is stably held in the polymer material in the state of being dispersed in the polymer.

The medium material used in the present invention has the above-mentioned function. That is, any material that can form a low molecular weight material-holding composite that holds a large amount of low molecular weight material can be used, but normally, a thermoplastic polymer compound or this polymer compound is used as a constituent element. can do.

The medium material has a number average molecular weight of 20,0.
00 or more, especially 30,000 or more, especially 40,000
A thermoplastic high molecular weight organic material of 0 or more is preferable, and examples thereof include styrene (butadiene styrene, isoprene styrene, etc.), vinyl chloride, olefin (butadiene, isoprene, ethylene propylene, etc.), ester, Amide-based, urethane-based and other thermoplastic elastomers, and their hydrogenated and other modified products, styrene-based, ABS-based, olefin-based (ethylene-based, propylene-based, ethylene-propylene-based, ethylene-styrene-based, propylene-styrene-based) Etc.), acrylic acid ester type (methyl acrylate type, etc.), vinyl chloride type, methacrylic acid ester type (methyl methacrylate type, etc.), carbonate type, acetal type, nylon type, halogenated polyether type (chlorinated polyether type) Etc.), halogenated olefins (tetrafluoride) Thermoplastics such as ren series, fluorinated-ethylene chloride series, fluorinated ethylene propylene series), cellulose series (acetyl cellulose series, ethyl cellulose series), vinylidene series, vinyl butyral series, alkylene oxide series (propylene oxide series, etc.) resin,
And rubber modified products of these resins.

As the thermoplastic polymer material, it is particularly preferable to use a material in which a portion which easily forms a hard block such as a crystal structure or an agglomerate structure and a soft block such as an amorphous structure are mixed together. Specifically,
The following (i) to (iii) are mentioned.

(I) A block copolymer of polyethylene / butylene and an ethylene-styrene random copolymer obtained by hydrogenating a block copolymer of polybutadiene and a butadiene-styrene random copolymer (ii) Polybutadiene Block copolymer with polystyrene, or block copolymer of polyethylene / butylene and polystyrene obtained by hydrogenating a block copolymer of polystyrene with polybutadiene or ethylene-butadiene random copolymer (iii) ethylene- Propylene rubber (EPM) or ethylene-propylene-diene terpolymer (EPDM) Incidentally, the low molecular weight material, the medium material and the low molecular weight material-holding composite according to the present invention are partially disclosed in JP-A-5-239256. It is described in JP-A-5-194763. As the medium material, those having a three-dimensional continuous net-like skeleton structure disclosed in these publications are preferably used as a representative one in the present invention.

The medium material in the present invention is not particularly limited, but it may be in a usual bulk state, a granular state, a gel state, a foam state, a non-woven fabric state or the like. It can also be used in a form in which a capsule containing a low molecular weight material is incorporated. These various thermoplastic polymer organic materials are mainly used alone, but two or more kinds may be blended and used.

Further, in obtaining the low molecular weight material holding composite containing a large amount of the low molecular weight material and the medium material, as described above, the difference in solubility parameter value between the low molecular weight material and the medium material used is 3.0. Below, both materials are selected so as to be preferably 2.5 or less. If this difference exceeds 3.0, from the viewpoint of compatibility, it is difficult for the medium material to hold a large amount of low molecular weight material, which is an obstacle to lowering the elastic modulus of the high molecular weight material, and bleeding of the low molecular weight material occurs. It is not preferable because it is easy to do.

In the present invention, the weight ratio of the low molecular weight material to the medium material is 1.0 or more, particularly 2.0 or more, and especially 3.
It is preferably 0 or more. If this weight ratio is less than 1.0, it may be difficult to obtain a polymer composition having a low elastic modulus, and the object of the present invention may not be achieved.

The low molecular weight material-holding composite containing the low molecular weight material and the medium material can be produced by an optimum method including a known method depending on the types, characteristics, mixing ratios of the low molecular weight material and the medium material to be used. Good and not particularly limited. Japanese Patent Laid-Open No. 5-2 mentioned above
The method described in Japanese Patent No. 39256 is also one method.

As a particularly preferable method, a method using a high-shear type special mixer previously proposed by the present applicant, that is, a thermoplastic polymer material as a medium material and a low-molecular material are sheared at a rotor speed of 5. Kneading with a special high-shear type mixer having a capacity of 0 × 10 ² (sec ⁻¹ ) or more allows a large amount of low-molecular weight material to be uniformly contained and the low-molecular weight material to retain little bleeding. A method for obtaining a composite (Japanese Patent Application No. 5-316461) can be mentioned.

The polymer material to be blended with such a low molecular weight material holding composite is not particularly limited, and a usual thermoplastic material or thermosetting material can be used.

Among these, examples of the thermoplastic material include the above-mentioned thermoplastic resins exemplified as specific examples of the medium material, and rubber modified products of these resins.

On the other hand, examples of the thermosetting material, that is, a material which is thermoset in the presence or absence of a curing agent, include ethylene propylene rubber (EPM, EPDM), nitrile rubber (NBR), butyl rubber and halogenated materials. Butyl rubber,
Chloroprene rubber (CR), natural rubber (NR), isoprene rubber (IR), styrene butadiene rubber (SB
R), butadiene rubber (BR), acrylic rubber, ethylene-vinyl acetate rubber (EVA), general rubber such as polyurethane,
Silicone rubber, fluorine rubber, ethylene acrylic rubber,
Polyester elastomer, epichlorohydrin rubber,
Specific rubbers such as polysulfide rubber, hypalon and chlorinated polyethylene, and various cured resins such as phenol, urea, melamine, aniline, unsaturated polyester, diallyl phthalate, epoxy alkyd, silicon and polyimide can be used.

These thermosetting materials may be used alone or in a blend of two or more.

As the curing agent for these thermosetting materials, known ones such as sulfur, organic peroxides and nitroso compounds are widely used. Further, if necessary, various vulcanization accelerators, antioxidants, antioxidants, ultraviolet absorbers and other rubber chemicals can be used. Further, various tackifiers, plasticizers, rubber softeners, rubber reinforcing agents, and fillers can be added depending on the purpose. Furthermore, a foaming agent, a flame retardant, an antistatic agent,
A colorant or the like can be added.

In the present invention, both materials are selected so that the difference in solubility parameter value between the low molecular weight material and the high molecular weight material is 4.0 or less, preferably 3.0 or less. That is, the low molecular weight material is mixed with the high molecular weight material in the form of a low molecular weight material-holding composite, and in this case, the compatibility between the low molecular weight material and the high molecular weight material becomes a problem. If this difference exceeds 4.0, from the viewpoint of compatibility, the low molecular weight material held in a large amount in the low molecular weight material-holding composite is difficult to be retained by the high molecular weight material, and the low elastic modulus of the high molecular weight material is reduced. It becomes an obstacle and bleeding of the low molecular weight material is likely to occur, which is not preferable.

The weight ratio of the low molecular weight material and the high molecular weight material in the low molecular weight material holding composite is 0.5 or more, preferably 0.8 or more, and particularly preferably 1.0 or more. If this weight ratio is less than 0.5, it is difficult to obtain a polymer composition having a low elastic modulus, which is not preferable.

The content of the polymer material in the polymer composition of the present invention is preferably 30% by weight or more.

In the present invention, the method of mixing the low molecular weight material-holding composite and the polymer material is not particularly limited, but an optimum method including a known method may be adopted depending on the characteristics of both and the mixing ratio.

The polymer composition according to the present invention can be easily obtained by mixing the low molecular weight material-holding composite and the polymer material, and then vulcanizing and curing the rubber if necessary.

If necessary, the polymer composition of the present invention may further contain the following fillers. That is, clay, diatomaceous earth, carbon black, silica, talc, barium sulfate, calcium carbonate, magnesium carbonate, metal oxides, mica, graphite, scale-like inorganic fillers such as aluminum hydroxide, various metal powders, wood chips, glass powders , Ceramic powder, granular or powdered solid filler such as granular or powdered polymer, and other various natural or artificial short fibers and long fibers (for example, straw, hair, glass fiber, metal fiber, other various polymer fibers, etc.) Etc. can be blended. Depending on the purpose, it is also possible to mix and dye a dye such as a fluorescent dye, a luminescent dye, and a phosphorescent dye.

Weight reduction can be achieved by blending a hollow filler, for example, an inorganic hollow filler such as a glass balloon or a silica balloon, or an organic hollow filler made of polyvinylidene fluoride, a polyvinylidene fluoride copolymer, or the like. . Further, in order to improve various physical properties such as weight reduction, it is possible to mix various foaming agents, and it is also possible to mechanically inject gas during mixing or the like.

By the way, the polymer composition constituting the shock absorbing material of the footwear member of the present invention has a loss tangent (tan).
δ) is preferably in the range of 0.01 to 1.0.
If this loss tangent is less than 0.01, for example, the impact absorption effect at the time of landing is not sufficient, and more than 1.0, the force for kicking up the ground or the like is required, and any force is required. In such a case, it is difficult to obtain a suitable footwear member.

The loss tangent is a value measured by a shear dynamic viscoelasticity tester (manufactured by Toyo Seiki Co., Ltd.) under the conditions of 25 ° C. and 5 Hz.

The structure of the footwear member of the present invention is not particularly limited and may be composed only of the above-mentioned polymer composition, and may be polyurethane, silicone, polyethylene, ABS, PP, nylon or the like. It may be used in combination with existing plastics or rubber materials (shock absorbers) such as or foams thereof and the like in a laminated structure. Furthermore,
It may be used in combination with metal materials such as iron, aluminum, copper, zinc, and stainless steel, and various ceramic materials.
Further, the surface layer of the polymer blend material may be coated with a urethane-based, polyvinyl acetate-based, silicone-based, EVA-based, nylon-based, or other organic material, cloth, leather, or the like.
It is also possible to use it in combination with a spring element such as an air spring or a spring-like structure such as metal.

In the footwear member of the present invention, there are no particular restrictions on the location of each footwear to be made, and any desired position, shape, or, for example, the inner side (insole) or middle part of the footwear ( For shock absorbers such as midsole),
Alternatively, the same member of the present invention or another member of the present invention can be selected or combined and used as required, for example, as a material for the outer side (outsole).

For example, as shown in FIG. 1 (cross-sectional view), a stepped portion of the insole 2 of the shoe 1, a part of the midsole 3 of the shoe 1 as shown in FIG. 2 (cross-sectional view), and further, FIG. As shown in (cross-sectional view), the polymer composition material 5 is disposed on a part of the outsole 4 of the shoe 1.
Further, as shown in FIG. 4 (cross-sectional view), the polymer composition material 5 can be arranged on each of the instep portion 5A, the toe portion 5B, the heel portion 5C, and the ankle portion 5D.

In the present invention, for example, the following steps may be taken to dispose the footwear member, which is made of the polymer composition material and which utilizes the impact absorbing performance, at the desired place of the shoe. That is, a sheet having a predetermined thickness is prepared from the polymer composition material, and then the sheet is punched or cut into an appropriate size or shape and placed at a desired position. Alternatively, the polymer composition material is poured into a mold having a predetermined shape, cooled, molded, and then placed. Alternatively, many methods can be applied, such as directly casting the polymer composition material into a place where a predetermined void is provided and using it as an integrated body.

The footwear member of the present invention is suitable for all shoes such as leather shoes, sports shoes, chemical shoes, etc., and other footwear such as sandals, etc., and due to its excellent shock absorption performance, it is comfortable or durable. Will be provided.

[0052]

That is, the member for footwear constituted by using the polymer composition containing the low molecular weight material holding composite containing the low molecular weight material and the medium material according to the present invention and the polymer material is soft and has a proper degree. It exhibits excellent properties as a footwear member in terms of elasticity, compression properties, hardness, shock absorption properties, etc., and is economically producible with high productivity. In particular, when a thermoplastic polymer organic material is used, a footwear member excellent in moldability and recyclability is provided.

[0053]

EXAMPLE An example of the present invention will be described below in more detail. [Examples 1 to 4] A high-shear type special mixer ("TK Auto Homomixer") in which the low molecular weight material and the medium material shown in Table 1 below are mixed in the proportions shown in Table 1 under the kneading conditions shown in Table 2. A low molecular weight material-holding composite was obtained by kneading using a Tokushu Kika Kogyo Co., Ltd. When the produced low molecular weight material-holding composite was confirmed by an electron microscope, it was found that it had a three-dimensional continuous network skeleton structure and held the low molecular weight material therein.

[Table 1]

[Table 2]

Next, a polymer composition was obtained by using the Brabender under the kneading conditions shown in Table 4 at the ratio of the obtained low molecular weight material holding composite and the following polymer materials in Table 3. The loss tangents (tan δ) of the polymer compositions of Examples 1 to 4 obtained by the above method were all 0.1.

[Table 3]

[Table 4]

The polymer composition obtained as described above was placed on the insole, midsole, and outsole of the shoe 1 and evaluated. As a result, as the insole, those of Examples 1 and 2 and the midsole were used. When using the ones of Examples 3 and 4 and the one of Example 4 for the outsole, it is excellent in shock absorption of the sole of the foot, very comfortable to wear, and foot fatigue after walking for a long time, It was very small compared to the conventional one.

[0056]

As described above in detail, according to the footwear member of the present invention, since the shock absorbing performance of the shock absorbing material is remarkably good, the comfort is good and the shock during walking is reduced.
It is a member for which footwear such as shoes is provided, in which the foot is less tired even after walking for a long time. Moreover, the polymer composition according to the present invention can be produced with high productivity and is economically excellent.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of a shoe showing an example of a location where a footwear member of the present invention is disposed.

FIG. 2 is a cross-sectional view of a shoe showing an example of the location of the footwear member of the present invention.

FIG. 3 is a cross-sectional view of a shoe showing an example of the location of the footwear member of the present invention.

FIG. 4 is a cross-sectional view of a shoe showing an example of the location of the footwear member of the present invention.

[Explanation of symbols]

 1 shoes 2 insole 3 midsole 4 outsole 5 polymer composition

Claims (2)

[Claims] 1. A footwear member comprising, as a constituent material, a polymer composition containing a low molecular weight material-holding composite containing a low molecular weight material and a medium material, and a polymer material. The low molecular weight material has a viscosity of 5 × 10 ⁵ centipoise or less at 100 ° C., and the difference in solubility parameter value between the low molecular weight material and the medium material is 3.0 or less. The weight ratio of the low molecular weight material to the medium material is 1.0 or more, the difference in solubility parameter value between each of the low molecular weight material and the polymer material is 4.0 or less, and further, in the polymer composition 2. A footwear member, comprising as a constituent material a polymer composition in which the weight ratio of the low molecular weight material to the polymer material is 0.5 or more. 2. A footwear member, characterized in that the polymer material is formed by using the polymer composition according to claim 1 containing a thermosetting material as a main component.