WO2020082484A1 - Method for preparing multi-color, multi-density sole having different materials, and multi-color, multi-density sole prepared using the method - Google Patents

Abstract

Disclosed are a method for preparing a multi-color, multi-density sole of different materials, and a multi-color, multi-density sole prepared using the method. The method employs a one-step formation process which involves free, moldless, and three-dimensional foam formation using a supercritical fluid injected under a high-temperature, high-pressure condition, thus obtaining a multi-color, multi-density foamed sole of different materials formed in one step without the need for adhesion with an adhesive, the sole having an enlarged size consistent with a profile. The foamed sole prepared using the method has multiple materials, colors and densities. By using a foaming tank to conduct foaming, the pressure release rate can be easily controlled, cell nucleation rate is high, and the resulting microporous foamed material has smaller cells and higher cell density. The sole prepared is a three-dimensional microporous foamed product with controlled morphology and precise dimensions. The sole has high resilience, toughness, abrasion resistance and skid resistance. Moreover, the sole is more comfortable, light, corrosion resistant and water resistant. Functional components are integrally formed with the main part of the sole, which provides a stronger connection that effectively prevents separation.

Description

Preparation method of multi-color multi-density soles of different materials and multi-color multi-density soles adopting the method Technical field

The technical field of the invention and the method for preparing a shoe sole, more specifically, relates to a method for preparing a multi-color multi-density sole with different materials and a multi-color multi-density sole using the method.

Background technique

China is the world's largest footwear producer and exporter. Footwear has become a major pillar of China's economy. With the development of society, the demand for footwear functions in various industries has become more diversified, especially for footwear products. Performance requirements are getting higher and higher. Because polymer foam products have soft, lightweight, good elasticity, anti-skid resistance, friction resistance and chemical corrosion resistance, they are widely used as shoe materials in sports shoes, slippers, sandals, casual shoes and other shoes. However, with the improvement of people's living standards and personalized requirements, to improve wearing comfort and meet different functional needs, shoe soles usually use different color and different hardness of the sole body and functional parts.

In order to solve this technical problem, in the prior art, the side or bottom surface of the sole body part is usually set as a depression in advance, and a functional part or a decoration piece is provided corresponding to the depression. The hardness ratio and color of the functional part or the decoration piece are different from the sole body part . This technology has two commonly used molding methods: (1) pre-foaming to prepare the sole body part, functional parts or decorative sheets of multi-colors with different densities, and then bonding them together with an adhesive to make molding different materials Multi-color multi-density foam shoe material or shoes. However, the sole products obtained by this manufacturing method are easy to delaminate and delaminate, and the operation is complicated and cumbersome, the labor intensity of workers is high, the production cost is high, and the adhesive has a great impact on workers' health and serious environmental pollution. (2) Preparing foam shoe material preforms of various colors and densities separately, and then laminating the pre-foamed shoe blanks constituting multi-color and multi-density, and then molding and foaming to produce multi-color and multi-density shoe products of different materials However, due to the difference in the foaming efficiency of the pre-foamed shoe blanks of various colors and densities in the foam molding process, the foaming synchronization rate is not high, which affects the appearance quality of shoe products, and scrap products are prone to appear, reducing production efficiency. Practicality is low.

Summary of the invention

The purpose of the present invention is to overcome the above-mentioned shortcomings in the prior art, and to provide a multi-color multi-density sole with different materials that can form an enlarged size foam sole with multi-material, multi-color, multi-density and profiling compatible at one time的 制备 方法。 Preparation method.

To achieve the above object, the present invention provides a method for preparing a multi-color multi-density sole of different materials, including the following steps:

(1) According to the foaming rate of the product, injection-molded shoe sole blanks of reduced size are prepared by injection molding. The injection molded shoe sole blanks include a midsole, an outsole, and functional components. The outsole is a second polymer material, and the functional component is a third polymer material;

(2) Send the injection-molded shoe sole blank to the foaming high-pressure tank;

(3) Fill the injection-molded shoe sole blank with a supercritical fluid in a state free of molds;

(4) Heating and pressurizing the foaming tank to adjust the temperature and pressure in the foaming tank to the target temperature and pressure;

(5) The supercritical fluid penetrates into the injection molded shoe sole blank and swells and diffuses for a period of time;

(6) Open the foaming high-pressure tank for pressure relief foaming to obtain multi-color and multi-density foam soles with different materials formed at one time.

Preferably, the first polymer material is EVA or TPU or PEBAX or TPE or TPO or TPV or TPEE or TPAE or natural rubber or synthetic rubber, and the second polymer material is PU or PEBAX or TPE or TPV or TPEE or TPAE or natural rubber or synthetic rubber, and the third polymer material is PEBAX or TPU or natural rubber or synthetic rubber.

Preferably, a barrier material is added on the surface of the functional component, and the barrier material is aluminum foil or tin foil or barrier plastic EVOH or vinylidene chloride copolymer or acrylonitrile copolymer or aromatic nylon or poly Vinyl alcohol.

Preferably, the supercritical fluid is carbon dioxide or nitrogen or a mixture of carbon dioxide and nitrogen.

Preferably, the supercritical fluid penetrates into the injection-molded profile sole blank and swells and diffuses for 60 to 120 minutes.

Preferably, the pressure relief rate is 1 to 1000 MPa / s.

Preferably, the foaming rate of the midsole is 10 to 40 times, the cell diameter is 1 to 100 μm, the foaming rate of the outsole is 2-15 times, the cell diameter is 1 to 60 μm, the function The components are not foamed or the expansion ratio is 0.1-2 times.

Preferably, a foaming nucleus agent and a grafting agent are added to the first polymer, the second polymer, and the third polymer. The foaming nucleus agent is talc or citric acid or calcium carbonate whiskers. The added amount of the foaming nucleating agent is 0.1 to 10%, the grafting agent is maleic anhydride or benzoyl peroxide BPO or diethylpropylbenzene peroxide DCP or the crosslinking agent TAIC, the addition of the grafting agent The amount is 0.001-3%.

Preferably, the target temperature during operation in the foaming tank is 1 to 50 ° C lower than the melting temperature or melting point temperature of the polymer, and the working pressure in the foaming tank is 5-30 MPa.

The invention provides a multi-color multi-density sole, which includes a midsole, an outsole and a functional component. The midsole is installed on the top surface of the outsole, and the functional component is installed on the bottom surface of the outsole. The bottom, outsole and functional components are injection-molded and foamed at one time, and the density of the midsole, outsole and functional components is different.

Compared with the prior art, the beneficial effects of the present invention are:

The preparation method of the sole provided by the present invention adopts a one-step molding method, is filled with supercritical fluid under the condition of high temperature and high pressure, and freely moldless three-dimensional structure foam molding to obtain a multi-material, multi-color, multi-density and profiling phase in one molding The foamed sole of the enlarged size of the volume does not need to be bonded by an adhesive. The foamed sole obtained by the present invention has a variety of materials, a variety of colors and a variety of different densities, and is foamed by a foaming tank. It is easy to control the pressure relief rate, the cell nucleation rate is high, the formed microcellular foam material has smaller cells, higher cell density, and more excellent performance. At the same time, the manufactured soles are micropores with controllable shape and accurate size The three-dimensional foam product has excellent functions of high resilience, toughness and wear resistance and anti-skid performance, and is more comfortable and lightweight, and has better corrosion resistance and water resistance. The main body parts of the sole and the functional components are formed as a whole, and the connection is more firm , Effectively avoid separation, the main parts of the sole are not easy to crack, and can be used to make shoe materials with high quality requirements. The manufactured sole is light in weight, resistant to wear and twists, and cost Suitable for industrial scale production.

BRIEF DESCRIPTION

In order to more clearly explain the embodiments of the present invention or the technical solutions in the prior art, the following will briefly introduce the drawings required in the embodiments or the description of the prior art. Obviously, the drawings in the following description are For some embodiments of the present invention, for those of ordinary skill in the art, without paying any creative work, other drawings may be obtained based on these drawings.

FIG. 1 is a schematic structural diagram of a multi-color multi-density sole provided by the present invention.

detailed description

To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be described clearly and completely in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments It is a part of the embodiments of the present invention, but not all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by a person of ordinary skill in the art without creative work fall within the protection scope of the present invention.

Example one

Embodiment 1 of the present invention provides a method for preparing a multi-color multi-density sole of different materials, including the following steps:

(1) According to the foaming rate of the product, the injection-molded sole blank is reduced in size according to the injection molding. The injection-molded sole blank includes a midsole 1, a large sole 2 and a functional component 3, and the midsole 1 is a first polymer material. The outsole 2 is a second polymer material, and the functional component 3 is a third polymer material;

(2) Send the injection-molded shoe sole blank to the foaming high-pressure tank;

(3) Fill the injection-molded shoe sole blank with a supercritical fluid in a state free of molds;

(4) Heating and pressurizing the foaming tank to adjust the temperature and pressure in the foaming tank to the target temperature and pressure;

(5) The supercritical fluid penetrates into the injection molded shoe sole blank and swells and diffuses for a period of time;

(6) Open the foaming high-pressure tank for pressure relief foaming to obtain multi-color and multi-density foam soles with different materials formed at one time.

Preferably, the first polymer is a soft and flexible elastic polymer material suitable for foaming, the second polymer is a non-slip and wear-resistant elastic flexible polymer material suitable for foaming, and the third polymer It is a non-slip, abrasion-resistant, tear-resistant polymer material that is abrasion-resistant, non-foamed or slightly foamed.

Among them, the first polymer material is EVA or TPU or PEBAX or TPE or TPO or TPV or TPEE or TPAE or natural rubber or synthetic rubber, the second polymer material is PU or PEBAX or TPE or TPV or TPEE or TPAE or natural rubber Or synthetic rubber, the third polymer material is PEBAX or TPU or natural rubber or synthetic rubber, and can be processed and injection molded according to actual needs.

Preferably, a barrier material is added to the surface of the functional component 3, the barrier material is aluminum foil or tin foil or barrier plastic EVOH or vinylidene chloride copolymer or acrylonitrile copolymer or aromatic nylon or polyvinyl alcohol, Processing injection can be selected according to actual needs.

Among them, the first polymer, the second polymer and the third polymer are added a foaming nucleus agent and a grafting agent, the foaming nucleus agent is talc or citric acid or calcium carbonate whiskers, and the amount of the foaming nucleus agent is 0.1 to 10%, the grafting agent is maleic anhydride or benzoyl peroxide BPO or diethylpropylbenzene peroxide DCP or cross-linking agent TAIC. The amount of grafting agent added is 0.001-3%. Core agent and grafting agent to adjust the different foaming rate of the sole.

In this embodiment, the supercritical fluid is carbon dioxide or nitrogen or a mixture of carbon dioxide and nitrogen, which can be selected according to actual conditions.

In this embodiment, the supercritical fluid penetrates into the injection molded shoe sole blank to swell and diffuse for 60 minutes.

In this embodiment, the pressure relief rate is 1 MPa / s.

In this example, in the manufactured shoe sole blank, the foaming magnification of the midsole is 10 times, the cell diameter is 1 μm, the foaming magnification of the outsole is 2 times, the cell diameter is 1 μm, and the functional components are not foamed Or the expansion ratio is 0.1 times.

In this embodiment, the target temperature during operation in the foaming tank is 1 ° C lower than the melting temperature or melting point temperature of the polymer, and the working pressure in the foaming tank is 5 MPa, which can be selected according to actual conditions.

Preferably, the midsole 1, the outsole 2 and the functional component 3 can be respectively set to different colors and different density polymer materials, which can be selected according to actual conditions.

Example 2

Embodiment 2 of the present invention provides a method for preparing a multi-color multi-density shoe sole of different materials, including the following steps:

(1) According to the foaming rate of the product, the injection-molded sole blank is reduced in size according to the injection molding. The injection-molded sole blank includes a midsole 1, a large sole 2 and a functional component 3, and the midsole 1 is a first polymer material. The outsole 2 is a second polymer material, and the functional component 3 is a third polymer material;

(2) Send the injection-molded shoe sole blank to the foaming high-pressure tank;

(3) Fill the injection-molded shoe sole blank with a supercritical fluid in a state free of molds;

(4) Heating and pressurizing the foaming tank to adjust the temperature and pressure in the foaming tank to the target temperature and pressure;

(5) The supercritical fluid penetrates into the injection molded shoe sole blank and swells and diffuses for a period of time;

(6) Open the foaming high-pressure tank for pressure relief foaming to obtain multi-color and multi-density foam soles with different materials formed at one time.

Preferably, the first polymer is a soft and flexible elastic polymer material suitable for foaming, the second polymer is a non-slip and wear-resistant elastic flexible polymer material suitable for foaming, and the third polymer It is a non-slip, abrasion-resistant, tear-resistant polymer material that is abrasion-resistant, non-foamed or slightly foamed.

Among them, the first polymer material is EVA or TPU or PEBAX or TPE or TPO or TPV or TPEE or TPAE or natural rubber or synthetic rubber, the second polymer material is PU or PEBAX or TPE or TPV or TPEE or TPAE or natural rubber Or synthetic rubber, the third polymer material is PEBAX or TPU or natural rubber or synthetic rubber, and can be processed and injection molded according to actual needs.

Preferably, a barrier material is added to the surface of the functional component 3, the barrier material is aluminum foil or tin foil or barrier plastic EVOH or vinylidene chloride copolymer or acrylonitrile copolymer or aromatic nylon or polyvinyl alcohol, Processing injection can be selected according to actual needs.

Among them, the first polymer, the second polymer and the third polymer are added a foaming nucleus agent and a grafting agent, the foaming nucleus agent is talc or citric acid or calcium carbonate whiskers, and the amount of the foaming nucleus agent is 0.1 to 10%, the grafting agent is maleic anhydride or benzoyl peroxide BPO or diethylpropylbenzene peroxide DCP or cross-linking agent TAIC. The amount of grafting agent added is 0.001-3%. Core agent and grafting agent to adjust the different foaming rate of the sole.

In this embodiment, the supercritical fluid is carbon dioxide or nitrogen or a mixture of carbon dioxide and nitrogen, which can be selected according to actual conditions.

In this embodiment, the supercritical fluid penetrates into the injection molded shoe sole blank and swells and diffuses for 90 minutes, which can be selected according to the actual situation.

In this embodiment, the pressure relief rate is 500 MPa / s.

In this example, in the manufactured shoe sole blank, the foaming magnification of the midsole is 25 times, the cell diameter is 50 μm, the foaming magnification of the outsole is 8 times, the cell diameter is 30 μm, and the functional component does not foam Or the expansion ratio is double.

In this embodiment, the target temperature in the operation of the foaming tank is 25 ° C lower than the melting temperature or melting temperature of the polymer, and the working pressure in the foaming tank is 15 MPa, which can be selected according to the actual situation.

Preferably, the midsole 1, the outsole 2 and the functional component 3 can be respectively set to different colors and different density polymer materials, which can be selected according to actual conditions.

Example Three

Embodiment 3 of the present invention provides a method for preparing a multi-color multi-density sole of different materials, including the following steps:

(1) According to the foaming rate of the product, the injection-molded sole blank is reduced in size according to the injection molding. The injection-molded sole blank includes a midsole 1, a large sole 2 and a functional component 3, the midsole 1 is a first polymer material The outsole 2 is a second polymer material, and the functional component 3 is a third polymer material;

(2) Send the injection-molded shoe sole blank to the foaming high-pressure tank;

(3) Fill the injection-molded shoe sole blank with a supercritical fluid in a state free of molds;

(4) Heating and pressurizing the foaming tank to adjust the temperature and pressure in the foaming tank to the target temperature and pressure;

(5) The supercritical fluid penetrates into the injection molded shoe sole blank and swells and diffuses for a period of time;

(6) Open the foaming high-pressure tank for pressure relief foaming to obtain multi-color and multi-density foam soles with different materials formed at one time.

Preferably, the first polymer is a soft and flexible elastic polymer material suitable for foaming, the second polymer is a non-slip and wear-resistant elastic flexible polymer material suitable for foaming, and the third polymer It is a non-slip, abrasion-resistant, tear-resistant polymer material that is abrasion-resistant, non-foamed or slightly foamed.

Among them, the first polymer material is EVA or TPU or PEBAX or TPE or TPO or TPV or TPEE or TPAE or natural rubber or synthetic rubber, the second polymer material is PU or PEBAX or TPE or TPV or TPEE or TPAE or natural rubber Or synthetic rubber, the third polymer material is PEBAX or TPU or natural rubber or synthetic rubber, and can be processed and injection molded according to actual needs.

Preferably, a barrier material is added to the surface of the functional component 3, the barrier material is aluminum foil or tin foil or barrier plastic EVOH or vinylidene chloride copolymer or acrylonitrile copolymer or aromatic nylon or polyvinyl alcohol, Processing injection can be selected according to actual needs.

Among them, the first polymer, the second polymer and the third polymer are added a foaming nucleus agent and a grafting agent, the foaming nucleus agent is talc or citric acid or calcium carbonate whiskers, and the amount of the foaming nucleus agent is 0.1 to 10%, the grafting agent is maleic anhydride or benzoyl peroxide BPO or diethylpropylbenzene peroxide DCP or cross-linking agent TAIC. The amount of grafting agent added is 0.001-3%. Core agent and grafting agent to adjust the different foaming rate of the sole.

In this embodiment, the supercritical fluid is carbon dioxide or nitrogen or a mixture of carbon dioxide and nitrogen, which can be selected according to actual conditions.

In this embodiment, the supercritical fluid penetrates into the injection molded shoe sole blank and swells and diffuses for 120 minutes, which can be selected according to the actual situation.

In this embodiment, the pressure relief rate is 1000 MPa / s.

In this embodiment, in the manufactured shoe sole blank, the foaming magnification of the midsole is 40 times, the cell diameter is 100 μm, the foaming magnification of the outsole is 15 times, the cell diameter is 60 μm, and the functional component does not foam Or the expansion ratio is 2 times.

In this embodiment, the target temperature during the operation in the foaming tank is 50 ° C lower than the melting temperature or melting point temperature of the polymer, and the working pressure in the foaming tank is 30 MPa, which can be selected according to the actual situation.

Preferably, the midsole 1, the outsole 2 and the functional component 3 can be respectively set to different colors and different density polymer materials, which can be selected according to actual conditions.

Example 4

Please refer to FIG. 1, the fourth embodiment of the present invention provides a multi-color multi-density sole, including a midsole, outsole and functional components, the midsole is installed on the top surface of the outsole, the functional components are installed on the outsole The bottom surface, the midsole, the outsole and the functional components are injection-molded and foamed at one time. The density of the midsole, the outsole and the functional components are different. The following describes this embodiment in detail with reference to the drawings.

As shown in FIG. 1, the midsole 1 is installed on the top surface of the outsole 2, and the functional assembly 3 is installed on the bottom surface of the outsole 2. The midsole 1, the outsole 2 and the functional assembly 3 are integrally formed, through the midsole 1, The outsole 2 and the functional component 3 are injection-molded and foamed at one time, without the use of adhesive bonding, which effectively guarantees the firm connection of the sole, avoids the cracking or separation of the sole components, and has high resilience, flexibility and wear resistance Excellent function of anti-slip performance, light weight, wear resistance, resistance to twists and turns, low cost, suitable for industrial scale production.

In summary, the method for preparing shoe soles provided by the present invention adopts a one-step molding method, is filled with supercritical fluid under the condition of high temperature and high pressure, and is free of mold-free three-dimensional structure foam molding to obtain multi-material, multi-color and multi-molding in one time. Enlarged size foam sole with compatible density and profiling, no need to use adhesive bonding method, the foam sole obtained by the invention has multiple materials, multiple colors and different densities, through foaming The foaming of the tank makes it easy to control the pressure relief rate, the cell nucleation rate is high, the microcellular foamed material formed has smaller cells, higher cell density, and more excellent performance. At the same time, the resulting sole has a controllable shape. The microporous three-dimensional foam products with precise dimensions have the excellent functions of high resilience, toughness and wear-resistance and anti-skid performance, and are more comfortable and lightweight, and have better corrosion resistance and water resistance. Forming, the connection is more firm, effectively avoiding separation, the main parts of the sole are not easy to crack, and can be used to make shoe materials with high quality requirements. The resulting sole has light weight, wear resistance and resistance. Discount, low cost and suitable for industrial scale production.

The above embodiments are preferred embodiments of the invention, but the embodiments of the invention are not limited by the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications made without departing from the spirit and principles of the invention , Should be equivalent replacement methods, all included in the scope of protection of the amplifier.

Claims (10)

1. A preparation method of multi-color multi-density soles of different materials is characterized by the following steps:

   (1) According to the foaming rate of the product, injection-molded shoe sole blanks of reduced size are prepared by injection molding. The injection molded shoe sole blanks include a midsole, an outsole, and functional components. The midsole is a first polymer material. The outsole is a second polymer material, and the functional component is a third polymer material;

   (2) Send the injection-molded shoe sole blank to the foaming high-pressure tank;

   (3) Fill the injection-molded shoe sole blank with a supercritical fluid in a state free of molds;

   (4) Heating and pressurizing the foaming tank to adjust the temperature and pressure in the foaming tank to the target temperature and pressure;

   (5) The supercritical fluid penetrates into the injection molded shoe sole blank and swells and diffuses for a period of time;

   (6) Open the foaming high-pressure tank for pressure relief foaming to obtain multi-color and multi-density foam soles with different materials formed at one time.
2. The method for preparing a multi-color multi-density sole with different materials according to claim 1, wherein the first polymer material is EVA or TPU or PEBAX or TPE or TPO or TPO or TPV or TPEE or TPAE or natural For rubber or synthetic rubber, the second polymer material is PU or PEBAX or TPE or TPV or TPEE or TPAE or natural rubber or synthetic rubber, and the third polymer material is PEBAX or TPU or natural rubber or synthetic rubber.
3. The method for preparing a multi-color multi-density sole with different materials according to claim 1, wherein a barrier material is added to the surface of the functional component, and the barrier material is aluminum foil or tin foil or barrier Permeable plastic EVOH or vinylidene chloride copolymer or acrylonitrile copolymer or aromatic nylon or polyvinyl alcohol.
4. The method for preparing a multi-color multi-density sole of different materials according to claim 1, wherein the supercritical fluid is carbon dioxide or nitrogen or a mixture of carbon dioxide and nitrogen.
5. The method for preparing a multi-color multi-density sole of different materials according to claim 1, characterized in that: the supercritical fluid penetrates into the injection-molded copy sole blank and swells and diffuses for 60 to 120 minutes.
6. The method for preparing a multi-color multi-density sole of different materials according to claim 1, wherein the pressure relief rate is 1 to 1000 MPa / s.
7. The method for preparing a multi-color multi-density sole of different materials according to claim 1, characterized in that: the foaming ratio of the midsole is 10 to 40 times, the cell diameter is 1 to 100 μm, and the large The expansion ratio of the bottom is 2-15 times, the cell diameter is 1-60 μm, the functional component is not foamed or the expansion ratio is 0.1-2 times.
8. The method for preparing a multi-color multi-density sole of different materials according to claim 1, characterized in that: a foaming nucleus agent and a graft are added to the first polymer, the second polymer and the third polymer Agent, the foaming nucleus agent is talc or citric acid or calcium carbonate whiskers, the foaming nucleus agent is added in an amount of 0.1 to 10%, and the grafting agent is maleic anhydride or benzoyl peroxide BPO Or diethylpropylbenzene peroxide DCP or cross-linking agent TAIC, the addition amount of the grafting agent is 0.001-3%.
9. The method for preparing a multi-color multi-density sole of different materials according to claim 1, characterized in that the target temperature during operation in the foaming tank is 1 to 50 ° C lower than the melting temperature or melting point of the polymer The working pressure in the foaming tank is 5-30MPa.
10. A multi-color multi-density sole using the method according to any one of claims 1 to 9, characterized in that it includes a midsole, an outsole, and a functional component, and the midsole is installed on the top surface of the outsole. The functional components are installed on the bottom surface of the outsole, and the midsole, outsole and functional components are injection-molded and foamed at one time, and the density of the midsole, outsole and functional components is different.

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