JP5859769B2 - Shoes-like material - Google Patents

Description

  The present invention relates to a sheet material for shoes, and more particularly to a sheet material for shoes having a high anti-slip effect when wet.

  2. Description of the Related Art Conventionally, in sports shoes that require the ball to be controlled by shoes, grip performance between the ball and the shoes has been particularly emphasized. Above all, soccer competition is a sport that uses the foot to perform actions such as shooting, dribbling, and passing, so shoes are considered to be the most important tool to bring out the player's ability to control the ball. The gripping force of the shoe on the ball greatly affects the accuracy and effectiveness of soccer players' shooting, dribbling, and passing.

  By the way, soccer is one of the competitions that are not usually stopped even in rainy weather. That is, high grip performance is required not only when it is dry, such as when it is sunny, but also when it is wet when it is raining. In addition, when shooting or dribbling, the ball is close to the ground and easily wetted, so there is a water layer between the shoe surface and the ball, making it slippery and the accuracy of ball control is more likely to be lost. .

  A number of techniques have been proposed in the past to prevent such wet grip degradation. For example, to improve the wet grip by attaching an uneven texture pattern to the sheet material used as the surface material of shoes, or by attaching protrusions with a polymer material such as rubber on the surface to improve the flow of water. (Patent Document 1, etc.). However, wet grip performance is limited only by these changes in the texture pattern, and satisfactory satisfaction cannot be obtained. Furthermore, changing the texture on the surface or attaching protrusions causes a difference in appearance from other parts, which limits the design design of the shoe and is disadvantageous from a commercial standpoint.

  In addition, on a clear day, when the grip performance is extremely high, the right foot shoes and the left foot shoes are caught at the moment of touching and may even cause a fall. In other words, in the case of a sport shoe sheet-like material, a grip performance that is not too high is required even in the case of dry weather. In other words, as an ideal shoe sheet, high grip performance and performance with little change were required in both dry and wet situations.

JP-A-9-140402

  The object is to obtain a shoe sheet having high and little change in grip performance in both dry and wet situations.

The shoe-like material for shoes of the present invention is a shoe-like material for shoes in which an outermost surface layer mainly composed of a polymer elastic body is present on a substrate, and contains a gel method silica in the outermost surface layer. It is characterized by.
Further, the polymer elastic body is a polyurethane resin, the surface layer contains a rosin resin or a terpene resin, and the secondary particle diameter of the gel method silica is in the range of 0.01 μm to 10 μm. It is preferable that the thickness of the outermost surface layer is 5 to 30 μm.
Another shoe according to the present invention uses the above-described shoe sheet-like material according to the present invention, and further, the shoe sheet-like material has any shape of a logo, a letter, a symbol, or a mark. Preferably it is shoes.

  ADVANTAGE OF THE INVENTION According to this invention, the sheet-like article for shoes which has the grip performance which is high and has few changes in the scene of both the time of drying and wet.

Hereinafter, the present invention will be described in detail.
The shoe-like material for shoes of the present invention is a shoe-like material for shoes in which an outermost surface layer mainly composed of a polymer elastic body is present on a substrate, and contains gel silica in the outermost surface layer. It is. “Mainly a polymer elastic body” means that it is the most abundant component constituting the outermost skin layer, and more preferably 50% by weight or more.

  Here, the substrate that can be used in the present invention is preferably made of a fiber and a polymer elastic body widely used for artificial leather and the like. Further, it is preferable that the substrate is composed of a fibrous substrate composed of fibers and a polymer elastic body, and a skin layer mainly composed of the polymer elastic body on the surface thereof. The surface skin layer made of a polymer elastic body on the surface is preferably a porous layer from the viewpoint of emphasizing the texture, and is preferably a solid layer in order to ensure stronger physical properties. In particular, a sheet-like material in which a porous layer is disposed at a portion in contact with the fibrous base layer, a solid layer is further disposed on the surface of the porous layer, and an outermost surface layer is disposed on the solid layer is most preferable.

  More specifically, examples of the fiber base that is preferably used include a fiber aggregate or a composite fiber aggregate obtained by impregnating a polymer elastic body into the fiber aggregate. The fiber is preferably thin in terms of both the texture and physical properties, and the fiber diameter is particularly preferably an ultrafine fiber having a diameter of 0.001 to 0.2 dtex. The thickness of the substrate is preferably 0.2 to 5 mm, more preferably 0.4 to 2 mm. Examples of the fiber assembly include non-woven fabrics and woven and knitted fabrics. Examples of the fibers constituting them include synthetic fibers such as polyester and polyamide, natural fibers such as cotton, hemp, and wool, or semi-synthetic fibers such as rayon. Moreover, these may be mixed 2 or more types.

  As a specific example of the case where the fibrous substrate is a composite fiber assembly composed of a fiber assembly and a polymer elastic body, a fiber assembly impregnated with a polymer elastic body, solidified, and dried can be exemplified. . Examples of the polymer elastic body include polyurethane, polyester elastomer, polyamide elastomer, polyolefin elastomer, and synthetic rubber such as polybutadiene and polyisoprene. Among these, polyurethane is preferably used from the viewpoints of wear resistance, elastic recovery, flexibility and the like. In the production process, these polymer elastic bodies are subjected to impregnation as a solution or dispersion in an organic solvent. Preferably, these polymers are used for impregnation as an aqueous solution or water dispersion for the protection of the global environment and the working environment.

  In a preferred embodiment, when the substrate is a fibrous substrate composed of fibers and a polymer elastic body and a skin layer mainly composed of a polymer elastic body on the surface thereof, the skin layer composed of the polymer elastic body is Although it may be nonporous, it is preferably a porous layer, and in particular, the substrate layer is preferably a so-called leather-like sheet-like material in which a polymer porous layer is present on the surface of a fibrous substrate. In particular, the polymer elastic body forming this layer is preferably composed mainly of polyurethane. Furthermore, the polymer elastic body constituting the fibrous base is also preferably porous, like the polymer elastic body of the surface layer.

  As the polyurethane that can be used for such a porous material, those used for artificial leather can be used, and conventionally known thermoplastic polyurethanes obtained by polymerization reaction of organic diisocyanate, polymer diol and chain extender are exemplified. be able to. Organic diisocyanates include aliphatic, alicyclic or aromatic diisocyanates containing two isocyanate groups in the molecule, especially 4,4′-diphenylmethane diisocyanate, P-phenylene diisocyanate, tolylene diisocyanate, 1,5-naphthalene diisocyanate, Examples include xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, and the like. Examples of the polymer diol include at least one of polyester glycol obtained by condensation polymerization of glycol and aliphatic dicarboxylic acid, polylactone glycol obtained by ring-opening polymerization of lactone, aliphatic or aromatic polycarbonate glycol, or polyether glycol. Examples include polymer glycols having an average molecular weight of 500 to 4000 selected from seeds. Examples of chain extenders include diols having a molecular weight of 500 or less containing two hydrogen atoms capable of reacting with isocyanate, such as ethylene glycol, 1,4 butanediol, hexamethylene glycol, xylylene glycol, cyclohexanediol, and neopentyl glycol. Can be mentioned.

  As a method for obtaining a porous layer using such a polymer elastic body, a conventionally known method can be employed. For example, a so-called wet coagulation method in which polyurethane is dissolved in an organic solvent that is a good solvent for polyurethane and is compatible with water, and this polyurethane solution is coated on a support with an arbitrary thickness and is immersed in a water bath to be porously solidified. Or a solution in which polyurethane is not compatible with water but dissolved or dispersed in an organic solvent that can dissolve or disperse polyurethane, or a dispersion is coated on the support with an arbitrary thickness to prevent water evaporation. A dry porous molding method that selectively evaporates the solvent, or a thermally expandable fine particle capsule dispersed in an aqueous solution of polyurethane or an aqueous dispersion, coated on a support with an arbitrary thickness, and dried while being thermally expanded. A method of swelling, or a prepolymer having an alcoholic hydrogen at the molecular end of a polyurethane A method in which an anate and water are mixed and immediately coated on a support in an arbitrary thickness, or a method in which an inert gas is dispersed in molten polyurethane to coat and foam on a support in an arbitrary thickness, or Examples thereof include a method in which a polyurethane solution or dispersion mixed with a chemical foaming agent is coated on a support with an arbitrary thickness. Among these, the wet coagulation method is preferable for easily controlling the shape of the pores to obtain a porous material.

  A skin layer made of a high molecular polymer can be directly formed on a fibrous substrate by a coating method as described above. Another method is a film made of polyurethane or the like formed on a peelable support. The layer may be bonded to the fibrous substrate with an adhesive. Furthermore, the first skin layer may be formed on the fibrous substrate by a wet coagulation method or the like, and the second skin layer may be formed thereon by a lamination method or the like. In this case, generally, the wet coagulation layer becomes a porous layer, the laminate layer becomes a solid layer, and the substrate of the present invention has a porous layer (wet coagulation layer) and a solid layer (laminate layer) in this order on the fibrous layer. It becomes the thing which has.

  The shoe-like material for shoes of the present invention has an outermost surface layer containing gel silica on the base as described above. Preferably, the outermost layer mainly composed of the polymer elastic body on the substrate has a thickness of 5 to 30 μm. As for the thickness of the outermost layer, if it is thin, the time for the effect to be manifested will be shortened. It tends to be difficult to put out.

  In general, synthetic silica is roughly classified into dry process silica and wet process silica, and wet process silica is divided into precipitation process (precipitation process) silica and gel process silica. The silica used in the present invention needs to be gel method silica among such synthetic silicas. The gel method silica used in the present invention causes aggregation in a state where the neutralization reaction between sodium silicate and mineral acid (usually sulfuric acid) proceeds in an acidic pH region and the growth of primary particles is suppressed. It is manufactured through the gel state of the three-dimensional network structure to be formed.

  The gel method silica used in the present invention generally has hard secondary particles, and the silica particles present in the outermost surface layer can exhibit their characteristics in both wet and dry states due to the unevenness. Further, the gel method silica is hard and effective as an additive, and its content can be increased as compared with the case of using ordinary silica. The secondary particle diameter is preferably in the range of 0.01 to 10 μm, more preferably 2 to 8 μm. Moreover, as a primary particle, the range of 1-20 nm is preferable. Further, the content of the gel method silica in the outermost surface layer is preferably in the range of 10 to 50% by weight, and particularly preferably in the range of 20 to 40% by weight. Thus, by making the content larger than usual, it has become possible to further exhibit the effect of surface micro unevenness.

  As the polymer elastic body used for the outermost surface layer, the same material as that used in the above-mentioned substrate can be used, but from the viewpoint of physical properties, a polyurethane resin is most preferable. Furthermore, the polyurethane resin of the outermost surface layer preferably contains a polyoxyethylene chain, and the content of the polyoxyethylene chain in the polyurethane resin is particularly preferably 2 to 20% by weight. By containing such a polyoxyethylene chain, the surface becomes hydrophilic, and when it gets wet, water can be moved in a short time, and the water film on the surface of the sheet can be made thin. The polyoxyethylene chain is preferably polyethylene glycol (PEG) having high hydrophilicity, and more preferably a PEG-modified polyurethane resin using polyethylene glycol having a molecular weight of 400 to 4000 as a raw material for the polyurethane resin. However, if the content of the polyoxyethylene chain is too large, the strength of the polyurethane resin tends to decrease.

Further, the outermost surface layer preferably contains a rosin resin or terpene resin as a tackifier as an additive. The content of the rosin resin or terpene resin is preferably in the range of 10 to 50% by weight. Examples of rosin resins include gum rosin and polymerized rosin. Examples of the terpene resin include a terpene phenol resin, a terpene styrene resin, and an aromatic modified terpene resin. Grip properties can be improved by adding these materials having tackiness. If the content of these tackifiers is small, the gripping effect tends to be small. Conversely, if the content is too large, the strength of the outermost surface layer decreases, especially when used as shoes, and wear durability decreases. There is a tendency.
This outermost surface layer can be formed by a method such as known gravure coating on the substrate.

  Furthermore, it is preferable that the sheet material for shoes of the present invention has a convexity on the surface by embossing or the like. In particular, it is preferable that the convex portions form any one of a logo, characters, symbols, and marks, which is excellent not only in terms of function but also in design. Due to the presence of the large convex portion, it is easy to drop off when foreign matter such as rain or mud adheres, and the performance can be maintained at a high level.

  The sheet material for shoes of the present invention as described above has a sufficient grip property not only in the dry state but also in the wet state, and is suitable for shoes, particularly soccer shoes. In addition to the shoe body, this shoe sheet can also be used only for the logo, characters, symbols, and marks on the front and side of the shoe, reducing the area used and reducing the cost. It becomes possible to reduce.

  The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to these examples. In the examples and comparative examples, “parts” and “%” are based on weight unless otherwise specified. Moreover, each measured value in an Example was measured with the following method.

(1) Grip feeling at the time of wet The sensory evaluation was performed on the grip property of the obtained sheet-like material in a wet state (at the time of wet). From the one with the most excellent grip, a four-step evaluation was performed: excellent, good, acceptable, and impossible.
(2) Dynamic friction coefficient at the time of wet and dry Using the obtained sheet-like material, the dynamic friction coefficient at a load of 1000 g in each of a wet state (at the time of wet) and a dry state (at the time of dry). It was measured.

[Example 1]
<Preparation of a fibrous substrate having a porous layer on its surface>
Nylon and low-density polyethylene were mixed and spun, and entangled, and a fiber assembly (nonwoven fabric) having a thickness of 1.6 mm and an apparent density of 0.28 g / cm ³ was obtained. The fiber assembly was impregnated with a polyurethane resin, coated, wet coagulated, and the polyethylene component in the mixed spun fiber was extracted and removed in hot toluene, thereby producing a fibrous substrate composed of ultrafine fibers and polyurethane. . The fiber diameter of the ultrafine fiber was 0.003 dtex. Further, a wet porous layer made of polyurethane is formed on the surface of the fibrous base, and the weight per unit area (weight) is 460 g / m ² , the thickness is 1.3 mm, and the apparent density is 0.35 g / cm ^3. The ratio (R / F) of the polymer elastic body to the fiber in the fibrous base material was 48%.

<Creation of substrate>
100 parts of Rezamin LU-2109HV (polyurethane concentration 22%, manufactured by Dainichi Seika Co., Ltd., melting point 150 ° C.), 15 parts of DMF, 15 parts of isopropyl alcohol on the release paper at a transfer bonding line at a line speed of 10 m / min. The mixed solution was applied at a basis weight of 120 g / m ² . The film layer which consists of a polymeric elastic body with a thickness of 0.01 mm was formed by drying at 110 degreeC for 2 minute (s). Further, 100 parts of polyurethane adhesive was coated on the film layer with a preparation of 10 parts of resamine NE cross-linking agent, 10 parts of DMF, and 10 parts of MEK at a basis weight of 180 g / m ² to form an adhesive layer. Next, the release paper coated with the polymer elastic body of the film layer and the adhesive layer is dried at a temperature of 90 ° C. for 2 minutes, and then the fibrous layer having the above porous layer on the surface of the polymer elastic body of the release paper. The substrate was superposed and passed through a roll with a gap of 0.6 mm on the surface of a heated cylinder having a temperature of 110 ° C. and pressed. Then, after leaving for 2 days in an atmosphere at a temperature of 70 ° C., the release paper was peeled off to obtain a substrate for a sheet.

<Creation of a sheet for shoes having an outermost surface layer>
On this substrate, gravure PEG-modified polyurethane resin (Dainippon Ink Co., Ltd., Chrisbon S517, solid content concentration 30% by weight) 100 parts, DMF 75 parts, methyl ethyl ketone (MEK) 160 parts, and gel synthetic silica (average Using a # 110 mesh gravure roll, apply a solution of 15 parts of silicon dioxide having a particle size of 6.6 μm) and apply a coating weight of 25 g / m ² four times as the outermost surface layer to obtain a sheet for shoes. It was. The solid content ratio of the outermost surface layer at this time is a polyurethane: silica ratio of 67:33. This was excellent in grip feeling during wet, there was little difference in coefficient of friction between dry and wet, and ball controllability was excellent in both rain and rain. The evaluation results are shown in Table 1.

[Example 2]
A shoe sheet was obtained in the same manner as in Example 1 except that the outermost surface layer was formed by gravure and was changed to contain a terpene resin as an additive. Specifically, as a gravure solution, polyurethane resin (Dainippon Ink Co., Ltd., Chrisbon S517) 100 parts, DMF 75 parts, methyl ethyl ketone (MEK) 160 parts, gel method synthetic silica (silicon dioxide having an average particle size of 6.6 μm) ) And 15 parts of a terpene resin (YShara Chemical Co., Ltd., YS Resin CP) mixed solution was used. At this time, the solid content ratio of the outermost surface layer is such that the ratio of polyurethane: silica: terpene resin is 55:27:18. This was also excellent in grip feeling at the time of wet, in particular, there was little difference in coefficient of friction between dry and wet, and the ball controllability was excellent in both rain and rain. The evaluation results are shown in Table 1.

[Example 3]
A sheet material for shoes was obtained in the same manner as in Example 1 except that the solution for forming the outermost surface layer by gravure was changed to contain a rosin-modified resin as an additive. Specifically, as a gravure solution, polyurethane resin (Dainippon Ink Co., Ltd., Chrisbon S517) 100 parts, DMF 75 parts, methyl ethyl ketone (MEK) 160 parts, gel method synthetic silica (silicon dioxide having an average particle size of 6.6 μm) ) And 15 parts of a rosin resin (Harima Kasei Co., Ltd., rosin-modified resin “Hari Star”) was used. At this time, the solid content ratio of the outermost surface layer is such that the ratio of polyurethane: silica: rosin ester is 55:27:18. This was also excellent in grip feeling at the time of wet, and excellent in ball control performance in any rainy weather. The evaluation results are shown in Table 1.

[Comparative Example 1]
A sheet-like material was obtained in the same manner as in Example 1 except that the gel method silica was not used in the outermost surface layer. The outermost surface layer of this material was composed only of a polyurethane resin, and although there was a tackiness during Dry, no grip effect was felt. In addition, the grip effect was small and slippery at the time of wet. Numerically, the dynamic friction coefficient at the time of Dry was too high, and the dynamic friction coefficient at the time of Wet was low. The evaluation results are also shown in Table 1.

[Comparative Example 2]
A sheet-like material was obtained in the same manner as in Example 2 except that the gel method silica was not used in the outermost surface layer. The outermost layer of this material was composed of a polyurethane resin and a terpene resin, and had a tack feeling when dry and had a slight grip effect, but had little grip effect when wet and was slippery. Numerically, the dynamic friction coefficient at the time of Dry was too high, and the dynamic friction coefficient at the time of Wet was low. The evaluation results are also shown in Table 1.

[Comparative Example 3]
A sheet-like material was obtained in the same manner as in Example 1 except that dry silica (manufactured by Nippon Aerosil Co., Ltd., fumed silica, primary particle size 16 nm) was used instead of the gel method silica in the outermost surface layer. At the time of Dry, the grip effect was not felt. In addition, although a slight anti-slip effect was felt at the time of wet, the grip force was inferior to that of the example and the result was slightly slippery. Numerically, the coefficient of dynamic friction at the time of wet was low. The evaluation results are also shown in Table 1.

Claims (7)

  A shoe sheet having an outermost surface layer mainly composed of a polymer elastic body on a substrate, the gel surface silica being contained in the outermost surface layer.   The sheet-like article for shoes according to claim 1, wherein the polymer elastic body is a polyurethane resin.   The shoe-like material according to claim 1 or 2, wherein the outermost surface layer contains a rosin resin or a terpene resin.   The shoe-like material according to any one of claims 1 to 3, wherein the gel method silica has a secondary particle diameter in the range of 0.01 µm to 10 µm.   The sheet-like article for shoes according to any one of claims 1 to 4, wherein the outermost surface layer has a thickness of 5 to 30 µm.   A shoe using the sheet-like material for shoes according to any one of claims 1 to 5.   The shoe according to claim 6, wherein the shoe sheet has a shape of any one of a logo, a character, a symbol, and a mark.