Title of Invention

A PROCESS FOR PREPARING A URETHANE FOAM FOR SHOE SOLES

Abstract

424/MAS/97 "A process for preparing a urethane foam for shoe soles" The invention relates to a process for preparing a urethane foam for shoe soles reacting a compound having at least two isocyanate-reactive hydrogen atoms in a molecule and a molecular weight of 400 to 10000 with a polyisocyanate in the presence of a foam stabilizer, water and a catalyst. The foam prepared has a mean skin cell diameter r1 to a mean core cell diameter r2 in a ratio of 0.02 to 0.80, wherein the mean skin cell diameter r1 is defined as the mean diameter of the cells diameter r1 is defined as the mean diameter of the cells which form the skin portion of a urethane foam extending from the surface to a depth of 5% of the foam thickness and the mean core cell diameter r2 is defined as the mean diameter of the cells which form the core portion of a urethane foam extending from a depth of 40% to a depth of 60% of the foam thickness.

Full Text

DESCRIPTION URETHANE FOAM FOR SHOE SOLES TECHNICAL FIELD The present invention relates to a urethane foam for shoe soles where the sizes of skin and core cells are markedly different. BACKGROUND ART Usually, a polyurethane foam is prepared by mixing and stirring a polyisocyanate and a polyol mixture comprising a polyol, a catalyst, a blowing agent, a foam stabilizer (a surfactant), and other optional auxiliaries, and thereby allowing the starting components to react. Shoe soles made of polyurethane foam are characterized by such excellent properties as lightness, impact resistance, chemical resistance, abrasion resistance, and bending resistance. As for midsoles, in particular, there has recently been a rapid trend toward density reduction for the purposes of reduction in cost and weight. Density reduction in a water-blown polyurethane foam for shoe soles is normally achieved by increasing the relative amount of water in the polyol mixture to increase the expansion ratio. However, increasing the relative amount of water as a blowing agent markedly deteriorates the foam's mechanical )roperties due to increased urea linkage. Deterioration of 5plit tear strength, a particularly important mechanical property of midsoles, is a problem. Although many attempts have been made to improve split tear strength through Investigation of polyols, prepolymers, catalysts, etc., no useful means have been found. Also, as a molding method without affecting the foam's mechanical properties, the integral skin foam, based on differences between surface and core densities, is used to mold automobile interiors. It is characterized in that skin layer and inner foam are simultaneously molded. This can be achieved by suppressing the expansion of the skin portion which comes into contact with the mold's inner wall during the reaction. However, because the skin layer is a high-density elastomer, there is a limit in reducing the molded density of the foam as a whole. Also, a chlorofluorocarbon-type blowing agent is required for the integral skin method, which causes various problems in a process where water is used as a blowing agent. DISCLOSURE OF THE INVENTION The object of the present invention is to solve the above problems. Accordingly, the present invention is to provide a polyurethane foam possessing excellent moldability which maintains a high split tear strength even when the relative amount of water is increased to reduce the molded density. In order to solve the above problem, the present inventors made intensive studies and found that a polyurethane foam with a certain cell diameter distribution can solve the above problem and have completed the present invention. Accordingly, the gist of the invention is: (1) A urethane foam for shoe soles prepared by reacting a compound having at least two isocyanate-reactive hydrogen atoms in a molecule and a molecular weight of 400 to 10000 with a polyisocyanate in the presence of a foam stabilizer, water and a catalyst, characterized in that the ratio r1/r2 of a mean skin cell diameter r1 to a mean core cell diameter r2 is 0.02 to 0.80, wherein the mean skin cell diameter r1 is defined as the mean diameter of the cells which form the skin portion of a urethane foam extending from the surface to a depth of 5% of the foam thickness and the mean core cell diameter r1 is defined as the mean diameter of the cells which form the core portion of a urethane.foam extending from a depth of 40% to a depth of 60% of the foam thickness; (2) The urethane foam for shoe soles described in Item (1) above, wherein the ratio r1/r2 of the mean skin cell diameter r1 to the mean core cell diameter r2 is 0.02 to 0.40; (3) The urethane foam for shoe soles described in Item (1) or (2) above, wherein the mean skin cell diameter r^^ is not more than 0.20 mm and the mean core cell diameter rj is 0.25 to 1.20 mm; (4) The urethane foam for shoe soles described in any one of Items (1) to (3) above, wherein the ratio d2/d1 of a mean core foam density d2 to a mean skin foam density d1 is 0.2 to 0.8, wherein the mean skin foam density d1 is defined as the mean density of foam in the skin portion extending from the surface to a depth of 12% of the foam thickness, and the mean core foam density d2 is defined as the mean density of foam in the core portion extending from a depth of 40% to a depth of 60% of the foam thickness; (5) The urethane foam for shoe soles described in any one of Items (1) to (4) above, wherein the mean skin foam density d^ is 0.20 to 0.80 g/cm^ and the mean core foam density dj is 0.05 to 0.60 g/cm^; and (6) The urethane foam for shoe soles described in any one of Items (1) to (5) above, wherein the molded density of the urethane foam is 0.15 to 0.50 g/cm3. BRIEF DESCRIPTION OF THE DRAWING Figure 1 is a perspective of a polyurethane foam test piece for the determination of split tear value. BEST MODE FOR CARRYING OUT THE INVENTION The urethane foam for shoe soles of the present invention is obtained by reacting a compound having at least two isocyanate-reactive hydrogen atoms in each molecule and having a molecular weight of 400 to 10000 (hereinafter referred to as "isocyanate-reactive compound") and a polyisocyanate in the presence of a foam stabilizer, water and a catalyst, and is characterized in that the ratio r1/r2 of the mean skin cell diameter r1 to the mean core cell diameter r2 is 0.02 to 0.80, preferably 0.02 to 0.60, more preferably 0.02 to 0.40, and still more preferably 0.03 to 0.30. Here, "the mean skin cell diameter r1" is defined as the mean diameter of the cells which form the skin portion of a urethane foam extending from the surface to a depth of 5% of the foam thickness. On the other hand, "the mean core cell diameter r2" is defined as the mean diameter of the cells which form the core portion of a urethanefoam extending from a depth of 40% of the foam thickness to a depth of 60% of the foam thickness. In the case of a urethane foam sheet with a 10-mm thickness, for example, "r^" is obtained with the cells which form the portion of the urethanefoam extending from the surface to a depth of 0.5 mm, while "r2" is obtained with the cells which form the portion extending from a depth of 4 mm to a depth of 6 mm of the foam sheet. Also, the mean cell diameters r1 and rj are obtained by taking a cross-sectional photomicrograph of the urethane foam using a scanning electron microscope (SEM), and calculating number (arithmetic) average the maximum diametersin a given direction (also referred to as Krummbein diameter). When the ratio of the mean skin cell diameter r1 to the mean core cell diameter r1 (r1/r2) is less than 0.02, cushion quality, an essential property of foams, may be impaired. When the ratio exceeds 0.80, the foam surface's cosmetic appearance and moldability may be impaired. Considering the above points, it is desired in the present invention that the mean skin cell diameter (r1) is not more than 0.20 mm, preferably 0.03 to 0.20 mm, more preferably 0.03 to 0.16 mm, particularly preferably 0.03 to 0.12 mm. Also, the mean core cell diameter (r1) is preferably 0.25 to 1.20 mm, more preferably 0.30 to 1.00 mm, still more preferably 0.35 to 0.90 mm. When the mean skin cell diameter r1 exceeds 0.20 mm, smoothness of the foam surface may be impaired. When the mean core cell diameter is less than 0.25 mm, it tends to become difficult to improve the split tear strength. When it exceeds 1.20 mm, void may occur, thereby impairing the product quality. * as described in "Silikattechik" 20 (6) 189-192 (1969) A preferred embodiment is that r1/R2 is 0.02 to 0.60, wherein r1 is 0.25 to 1.20 mm; a more preferred embodiment is that r1/r2 is 0.02 to 0.60, wherein r2 is 0.30 to 1.00 mm ; and a still more preferred embodiment is that r1/r2 is 0.02 to 0.40, wherein r2 is 0.30 to 1.00 mm. In a still more preferable embodiment, r1/r2 is 0-02 to 0.40, wherein r2 is 0.35 to 0.90 mm. In these embodiments, r1 is not particularly limited as long as it is in the above numerical ranges. Here, "the mean skin foam density d1" is defined as the mean density of foam in the skin portion extending from the surface to a depth of 12% of the foam thickness, while "the mean core foam density d2" is defined as the mean density of foam in the core portion extending from a depth of 40% of the foam thickness to a depth of 60% of the foam thickness. In the case of a urethane foam sheet with a 10-mm thickness, for example, "the mean skin foam density d1" is obtained with the foam portion extending from the surface to a depth of 1.2 mm, while "the mean core foam density d2" is obtained with the foam portion extending from a depth of 4 mm to a depth of 6 mm. Also, the mean foam densities d1 and d2 are obtained by cutting pieces of a given size from the skin and core portions of the foam and weighing the pieces. The ratio d2/d1 of the mean core foam density d2 to the mean skin foam density d1 is preferably 0.2 to 0.8, more preferably Considering the above points, it is desired in the present invention that the mean skin foam density (d1) is 0.20 to 0.80 g/cm3, particularly 0.25 to 0.70 g/cm1, while the mean core foam density (d2) is 0.05 to 0.60 g/cm3, particularly 0.12 to 0.50 g/cm3. Also, in view of the fact that foam shrinkage tends to occur at low density, it is desired in the present invention that the cells be open cells. Any method can be used without limitation to prepare a urethane foam having a particular cell diameter and density for the present invention, and such a urethane foam can be obtained by optimizing molding conditions, such as mold temperature and mixer stirring rate, and choosing and controlling catalysts and/or foam stabilizers. For example, as foam stabilizers, a polyalkylsiloxane and a polysiloxane-polyoxyalkylene copolymer may be combinedly used. Examples of polyalkylsiloxanes for the present invention include polydimethylsiloxanes and polymethylphenylsiloxanes, with preference given to the polydimethylsiloxanes represented by formula (1) below. Of the polydimethylsiloxane compounds represented by the formula, those wherein X4 is 0 to 20 are particularly preferred. The above-described polyalkylsiloxanes are commercially available in various kinds, which may be optionally used. On the other hand, any polysiloxane-polyoxyalkylene copolymer can be used for the present invention, as long as it is normally used as a foam stabilizer for urethane foam production. Examples of such polysiloxane-polyoxyalkylene copolymers include copolymers mainly comprising one or more polysiloxane components, such as polydimethylsiloxane and polymethylphenylsiloxane, and one or more polyoxyalkylene components, such as polyoxyethylene and polyoxypropylene. Here, the components of such copolymers may be polymerized by block polymerization, random polymerization and other methods, with preference given to block polymerization. Among the above, one or more copolymers represented by formulas (2) through (4) below are preferably used. n the formula, X1 is a number of 40 to 60; Yl is a number of to 10; ml is a number of 5 to 15; and nl is a number of 10 to .) (In the formula, X2 is a number of 40 to 60; Y2 is a number of 5 to 15; m2 is a number of 4 to 10; and n2 is a number of 10 to 20. ) (In the formula, X3 is a number of 40 to 60; Y3 is a number of 5 to 10; m3 is a number of 5 to 15; and n3 is a number of 5 to 15. ) The above-described polysiloxane-polyoxyalkylene copolymers are commercially available in various kinds, and they can easily be synthesized, for example, by the method described in Japanese Patent Laid-Open No. 7/90102. When the above-described two kinds of foam stabilizers are used in combination, the ratio by weight B/A of polysiloxane-polyoxyalkylene copolymer (B) to polyalkylsiloxane (A) is preferably 0.02 to 1.00, more preferably 0.02 to 0.50. When the ratio by weight B/A is less than 0.02, demold time tends to be extended, when it exceeds 1.00, the foam surface tends to become rough. The total amount of these foam stabilizers used is preferably 0.2 to 3.0 parts by weight, more preferably 0.5 to 2.0 parts by weight, based on 100 parts by weight of isocyanate-reactive compound. If the amount is less than 0.2 parts by weight, foam-stabilizing power for cell shape control is insufficient; if it exceeds 3.0 parts by weight, foam strength tends to be decreased by plasticizing action. In addition to the above foam stabilizers, such foam stabilizers as fluorine-based foam stabilizers and ordinary silicone- or fluorine-free surfactants may be optionally used. The amount of such foam stabilizer used is preferably 0.2 to 3.0 parts by weight based on 100 parts by weight of isocyanate-reactive compound- Mold temperature is normally 40 to 60°C. Isocyanate-reactive compounds which can be used for the present invention, i.e., compounds having at least two isocyanate-reactive hydrogen atoms in the molecule, include polyester polyols, polyether polyols and polymer polyols having a molecular weight of 400 to 10000, preferably 1000 to 3000. Examples of such polyester polyols include condensation polymers formed between polyhydric alcohols, such as ethylene glycol, propylene glycol, 1,4-butanediol, diethylene glycol, neopentyl glycol and trimethylolpropane, and polybasic acids, such as phthalic acid, maleic acid, malonic acid, succinic acid, adipic acid and terephthalic acid, and having a hydroxyl group at its terminus. Useful polyether polyols include polyether polyols and polytetramethylene ether glycols obtained by addition polymerization of alkylene oxides to polyhydric alcohols, such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, glycerol, trimethylolpropane, 1,2,6-hexanetriol and pentaerythrito1. In carrying out the present invention, a polyhydroxy compound having a molecular weight of not less than 32 and less than 400 may of course be used as an ordinary chain extender and crosslinking agent according to necessity. By the use of such a polyhydroxy compound, the properties of the polyurethane foam for shoe soles obtained can optionally be changed. Examples of polyisocyanates for the present invention include tolylene diisocyanate, m-phenylene diisocyanate, P"phenylene diisocyanate, xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, polymethylenepolyphenyl isocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate compounds, or mixtures thereof, modified products thereof, or prepolymers thereof. Among them, toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, or mixtures thereof, modified products thereof, or prepolymers thereof are preferably used. The prepolymers are polymers prepared by previously reacting an excess of polyisocyanate with polyester polyol or the like. The amount of polyisocyanate used is normally 50 to 150 parts by weight, preferably 60 to 140 parts by weight based on 100 parts by weight of isocyanate-reactive compound. In producing a urethane foam for shoe soles, a blowing agent is used. The preferred blowing agent for the present invention is water, which generates carbon dioxide upon reaction with polyisocyanate. In the present invention, it is desired, from the viewpoint of density reduction of the polyurethane foam obtained, that the amount of water used be 0.4 to 2.0 parts by weight, more preferably 0.8 to 1.8 parts by weight, based on 100 parts by weight of isocyanate-reactive compound. Any catalyst can be used for the present invention, as long as it is normally used as a catalyst for urethane foam production. For example, amine catalysts, such as triethylenediamine, and 1,2-dimethylimidazole are preferably used, and 1,2-dimethylimidazole and an amine catalyst may be used in combination. The amount of catalyst used is normally 0.1 to 3 parts by weight, preferably 0.1 to 2.0 parts by weight, based on 100 parts by weight of isocyanate-reactive compound. In addition to the above-described components, such components as anti-discoloration agents, stabilizers, and antifungal agents may be optionally used as necessary in the present invention. In most cases, a urethane foam is prepared by a known one-shot method utilizing a prepolymer or a semi-prepolymer. According to the present invention, it is also possible to carry out the mixing in a closed mold to produce a foam. For this purpose, the reaction mixture is injected into a mold. Examples of suitable mold materials include metals. such as aluminum, and plastic materials, such as epoxy resin. The expandable reaction mixture forms a foam in the mold. Blowing in a mold is conducted so that the resulting foam has a cell structure on the surface thereof, and may also be conducted so that the foam has a high-density crust and a spongy core. In this regard, the present invention allows the expandable reaction mixture to be introduced into the mold in an amount such that the resulting foam just fills the mold. However, the expandable reaction mixture can also be introduced into the mold in an amount exceeding the minimum amount required to fill the mold with the resulting foam. In many cases, a known silicone-based release agent is used to ensure desired blowing in the mold. The present invention is hereinafter described in more detail by means of the following working examples, which are not to be construed as limitative. Synthesis Example To a 1 liter four-necked flask equipped with a mechanical stirrer, thermometer, refluxing condenser and nitrogen inlet, 170 g of a polyether represented by the formula: wherein the molar number of the oxyalkylene adduct is shown in mean value), 400 g of toluene and 0.15 g of a 10% solution of H2PtCl6*6H2O (solvent: isopropanol) were placed. Next, 199 g of a polydimethylsiloxane represented by the formula: H-[(CH3)2SiO]5i-Si(CH3)2"H wherein the molar number of the dimethylsiloxane adduct is shown in mean value was added drop by drop, while the reaction temperature was kept at 85 to 100°C. Then, reaction was carried out at 100 to 105°C for 5 hours. The reaction mixture was then neutralized with sodium hydrogen carbonate and filtered. Subsequently, the toluene was removed at 80°C and 20 mmHg to yield 320 g of a polysiloxane-polyoxyalkylene block copolymer having a molecular weight of about 50000 and represented by the formula: wherein the molar numbers of the oxyalkylene and dimethylsiloxane adducts are shown in mean value. Examples 1 through 15 The starting components for polyurethane foam production were mixed according to the formulas in Tables 1 . and 2. The polyester polyols used * were that with OHv (hydroxyl value)= 52 and MW = 2160, that with OHV = 86 and MW = 1300, and that with OHV = 75 and MW = 1500. The foam stabilizers used were a polyalkylsiloxane mixture represented by the following formula and the EO.PO linear block modified silicone obtained in Synthesis Example, which were used in a 90/10 ratio by weight. The prepolymer used was EDDYFOAM B-2009 (manufactured by Kao Corporation, prepolymer of polyester polyol and 4,4-diphenylmethane diisocyanate, NCO = 18.5%)• Using the MU-203S molding machine (manufactured by Polyurethane Engineering K.K.), the above starting components were reacted to yield a 200 x 150 x 10 mm * ethyleneglycol-diethyleneglycdl adipate polyurethane foam sheet. All the products obtained in Examples 1 through 15 had a open cell structure. The molding conditions used are as follows: Mold temperature: 50 ± 2°C Polyol mixture and prepolymer retention temperature: 40 ± 2°C Demold time: 5 minutes The urethane foam obtained in each example was evaluated as follows: Mean cell diameter (r1, r2): The mean cell diameters r1 and r2 are obtained by taking a cross-sectional photomicrograph of the urethane foam using a scanning electron microscope (SEM), and calculating number (arithmetic) average diameters using the value of maximum diameter in a given direction (also referred to as Krummbein diameter). Mean foam density (d1, d2): Using a splitting machine (LEATHER SPLITTING MACHINE M0D-443M, manufactured by OMSA Company, Italy), a 70 x 30 x 1.2 mm foam section (for skin foam density) and a 70 x 30 x 2.0 mm foam section (for core foam density) were prepared from the relevant portions of a foam, respectively, and their d1 and d2 values were determined • Overall molded density: A 200 X 150 X 10 mm polyurethane foam sheet was weighed, and the weight obtained was divided by a volume of 300 cm3 to obtain overall molded density. Split tear strength: Split tear value was determined in accordance with the method of ASTM D-3574. Specifically, a 25.4 x 150 x 10 mm test piece was cut out from a 200 x 150 x 10 mm sheet and horizontally cut over a distance of 50 mm at a 5 mm depth from the surface (see Figure 1), Using the autograph DCS-50M (manufactured by Shimadzu Corporation), the split tear value was determined at a speed of 50 mm/min, and the actual measurement was divided by 2.54 to obtain the split tear value. Moldabilitv: Moldability was evaluated by visually assessing the sheet surface voids, skin condition, bubble size, shrinkage, etc., using a 3-grade rating system: good (O), single defect (A), and two or more defects (x). The results obtained are shown in Tables 3 and 4. Comparative Examples 1 and 2 The starting components for preparing a polyurethane foam were mixed according to the formulas shown in Table 2. The polyester polyol with OHV = 75 and MW = 1500 was used. The foam stabilizers used were commercially available side chain EG.PC modified silicone (Comparative Example 1) and the EG.PC linear block modified silicone obtained in Synthesis Example (Comparative Example 2), and each of the stabilizers above was used singly. The prepolymer used was EDDYFGAM B-2009 (manufactured by Kao Corporation), which was the same kind as that used in the above Examples. The molding and evaluation conditions used were the same as those used in Examples 1 through 15. The results are shown in Table 4. As shown in Tables 3 and 4, the urethane foam for shoe soles of the present invention has a good moldability and a high split tear value. In contrast, the urethane foam obtained in Comparative Example 1, having an r1/r2 ratio exceeding 0.80 and a low rj value, had poor moldability and a low split tear value for the molded density. Also, the urethane foam obtained in Comparative Example 2, having an r1/r2 ratio lower than 0.02, had poor moldability. Examples 16 and 17 A polyurethane foam was prepared by mixing the starting components according to the formulas in Table 5. The above mentioned EDDYFOAM B-2009 was used as prepolymer. The molding and evaluation conditions were the same as those used in Examples 1 to 15. The results are shown in Table 6. Examples 18 to 21 Using a polyether polyol as the starting material for polyols, a polyurethane foam was prepared under the same conditions as in Examples 1 to 15 according to the formulas shown in Table 7. The same foam stabilizer as that used in Examples 1 to 15 was used. EDDYFOAM B-6106M (manufactured by Kao Corporation, a prepolymer formed between a polyether polyol and 4,4-diphenylmethane diisocyanate, NC0=16%) was used as a prepolymer. The molding and evaluation conditions were the same as those in Examples 1 to 15. The results are shown in Table 8. Comparative Examples 3 and 4 A polyurethane foam was prepared according to the formulas shown in Table 7. The foam stabilizer used was the side chain EO.PO modified silicone. The prepolymer used was EDDYFOAM B-6106M manufactured by Kao Corporation, which was the same prepolymer as used in Examples 18 to 21. The molding and evaluation conditions were the same as those in Examples 1 to 15. The results are shown in Table 8. As shown in Table 8, the urethane foam for shoe soles of the present invention has a good moldability and a high split tear value. In contrast, the urethane foam obtained In Comparative Examples 3 and 4, having an r1/r2 ratio exceeding 0.80, had a low split tear value. Examples 22 to 29 Using the MU-203S molding machine (manufactured by Polyurethane Engineering K.K.)/ the starting components were mixed according to the formulas in Table 9 to yield a 200 x 150 X 10 mm polyurethane foam sheet. The molding conditions used are as follows: Mold temperature: 50 ± 2oC Polyol mixture and prepolymer retention temperature: 40 ± 2oC Demold time: 7 minutes The tensile strength soon after demolding was determined with an apparatus for the Schopper tensile test. The other evaluation conditions were the same as those used in Examples 1 to 15. The results of the above evaluations are shown in Tables 10 and 11. In the tables, foam stabilizer A is a mixture of polyalkylsiloxanes represented by the following formula: and foam stabilizer B is a copolymer prepared in Synthesis Example. As shown in Tables 10 and 11, the urethane foam for shoe soles obtained by the present invention has a good moldability. Also, the tensile strength soon after demolding is large. INDUSTRIAL APPLICABILITY According to the present invention, even when the water amount is increased in order to reduce the molded density in the preparation of a urethane foam, a polyurethane foam with a good moldability can be obtained with maintaining a high split tear strength. We Claim 1. A urethane foam for shoe soles prepared by reacting a compound having at least two isocyanate-reactive hydrogen atoms in a molecule and a molecular weight of 400 to 10000 with a polyisocyanate in the presence of a foam stabilizer, water and a catalyst, characterized in that the ratio r1/r2 of a mean skin cell diameter r1 to a mean core cell diameter r2 is 0.02 to 0.80, wherein the mean skin cell diameter r1 is defined as the mean diameter of the cells which form the skin portion of a urethane foam extending from the surface to a depth of 5% of the foam thickness and the mean core cell diameter r2 is defined as the mean diameter of the cells which form the core portion of a urethan foam extending from a depth of 40% to a depth of 60% of the foam thickness, 2. The urethane foam for shoe soles according to claim 1, wherein the ratio r1/r2 of the mean skin cell diameter r2 to the mean core cell diameter r2 is 0.02 to 0.40. 3. The urethane foam for shoe soles according to claim 1 or 2, wherein the mean skin cell diameter r1 is not more than 0.20 mm and the mean core cell diameter r2 is 0.25 to 1.20 mm. 4. The urethane foam for shoe soles according to any one of claims 1 to 3, wherein the ratio d2/d1 of a mean core foam density d2 to a mean skin foam density d1 is 0.2 to 0.8, wherein the mean skin foam density d1 is defined as the mean density of foam in the skin portion extending from the surface to a depth of 12% of the foam thickness, and the mean core foam density d2 is defined as the mean density of foam in the core portion extending from a depth of 40% to a depth of 60% of the foam thickness. 5. The urethane foam for shoe soles according to any one of claims 1 to 4, wherein the mean skin foam density d1 is 0.20 to 0.80 g/cm2 and the mean core foam density d2 is 0.05 to 0.60 g/cm3. 6. The urethane foam for shoe soles according to any one of claims 1 to 5, wherein the molded density of the urethane foam is 0.15 to 0.50 g/cm3. 7. A urethane foam for shoe soles, substantially as herein described, with reference to the accompanying drawings.

Documents:

424-mas-1997- abstract.pdf

424-mas-1997- claims duplicate.pdf

424-mas-1997- claims original.pdf

424-mas-1997- correspondence others.pdf

424-mas-1997- correspondence po.pdf

424-mas-1997- description complete duplicate.pdf

424-mas-1997- description complete original.pdf

424-mas-1997- drawings.pdf

424-mas-1997- form 1.pdf

424-mas-1997- form 26.pdf

424-mas-1997- form 4.pdf