CN114921048A - Cold-resistant midsole material, preparation method thereof and shoes - Google Patents
Cold-resistant midsole material, preparation method thereof and shoes Download PDFInfo
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- CN114921048A CN114921048A CN202210264438.5A CN202210264438A CN114921048A CN 114921048 A CN114921048 A CN 114921048A CN 202210264438 A CN202210264438 A CN 202210264438A CN 114921048 A CN114921048 A CN 114921048A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
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- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/04—Plastics, rubber or vulcanised fibre
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2353/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2407/00—Characterised by the use of natural rubber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
Abstract
The invention discloses a cold-resistant midsole material, a preparation method thereof and shoes, which comprise the following raw materials in parts by weight: 10-25 parts of natural rubber, 10-25 parts of olefin block copolymer, 60-80 parts of silicone rubber and hydrogenated acetonitrile modified styrene-ethylene/propylene block copolymer, 0.3-0.8 part of stearic acid, 1-2 parts of cell stabilizer, 3-8 parts of activator, 3-8 parts of nucleating agent, 4-8 parts of AC foaming agent and 1-2 parts of cross-linking agent. The cold-resistant midsole material can ensure that the hardness change is small under the low-temperature environment of minus 20 ℃, and has proper hardness and lower density.
Description
Technical Field
The invention relates to the technical field of soles, in particular to a cold-resistant midsole material, a preparation method thereof and shoes.
Background
The shoes are a tool for protecting feet from being injured, with the continuous progress of the society, the requirements of people on the shoes are higher and higher, and the midsoles are one of the important components of the shoes and play a great decisive role in the performance of the shoes.
In cold regions, particularly outdoor sports, there is a particular need for a midsole material that has cold resistance, and that retains its original properties at low temperatures, thereby providing the wearer with a better wearing experience.
Disclosure of Invention
The invention aims to provide a cold-resistant midsole material, a preparation method thereof and shoes aiming at the defects in the prior art, wherein the cold-resistant midsole material can ensure that the hardness change is small under the low-temperature environment of-20 ℃, and has proper hardness and low density.
Therefore, the invention adopts the following technical scheme:
a cold-resistant midsole material comprises the following raw materials in parts by weight: 10-25 parts of natural rubber, 10-25 parts of olefin block copolymer, 60-80 parts of silicone rubber and hydrogenated acetonitrile modified styrene-ethylene/propylene block copolymer, 0.3-0.8 part of stearic acid, 1-2 parts of cell stabilizer, 3-8 parts of activator, 3-8 parts of nucleating agent, 4-8 parts of AC foaming agent and 1-2 parts of cross-linking agent.
Preferably, the mass fraction of the silicon rubber in the silicon rubber and hydrogenated acetonitrile modified styrene-ethylene/propylene block copolymer is 5-10%, and the mass fraction of the hydrogenated acetonitrile is 10-25%.
Preferably, the number average molecular weight of the silicone rubber and the hydrogenated acetonitrile modified styrene-ethylene/propylene block copolymer is 15 to 20 ten thousand.
Preferably, the cell stabilizer is at least one of zinc oxide, zinc stearate, magnesium stearate and zinc carbonate, the active agent is diethylene glycol, the nucleating agent is titanium dioxide, and the crosslinking agent is dicumyl peroxide.
Preferably, the natural rubber is selected from the model 3L, the olefin block copolymer is selected from the model 9107, and the silicone rubber and hydrogenated acetonitrile modified styrene-ethylene/propylene block copolymer is selected from the model SBC 1553.
Based on the same inventive concept, the invention also provides a method for preparing the cold-resistant midsole material, which adopts a one-time injection foaming process.
Preferably, the preparation method comprises the following steps: weighing various raw materials according to the parts by weight, mixing and banburying the raw materials on a banbury mixer, and then discharging the materials to obtain a mixture; cooling, dispersing and mixing the mixture on an open mill, and then granulating to obtain material particles; and injecting the material particles once by a once injection machine, and injecting the material particles into a mould to obtain a product.
Preferably, banburying on an internal mixer at the temperature of 115-125 ℃ for 10-15 min; mixing on an open mill at 65-75 ℃ for 5-6 min; the temperature of a gun of the primary injection machine is 90-130 ℃, and the temperature of the die is 175-185 ℃.
Based on the same inventive concept, the invention also provides a shoe, which comprises a midsole, wherein the midsole is made of the cold-resistant midsole material.
Preferably, the shoe further comprises a support stabilizing member provided to a sidewall at a heel of the outsole, and an outsole extending to an arch of the outsole.
The technical scheme has the advantages that:
1. the cold-resistant midsole material provided by the invention can ensure that the hardness change is small under the low-temperature environment of-20 ℃, and has proper hardness and low density, and the prepared shoes can provide portability, comfort and shock absorption functions, so that good wearing and movement experience is provided for a wearer;
2. the cold-resistant midsole material provided by the invention is prepared by adopting a primary injection foaming process, the traditional process of amplifying the foaming ratio and then carrying out secondary mould pressing is replaced, and the preparation flow is simplified;
3. the cold resistance of the composite material is improved by using the silicone rubber and the hydrogenated acetonitrile modified styrene-ethylene/propylene block copolymer.
Drawings
Fig. 1 is a schematic structural view of an outsole of a shoe provided by the present invention.
Detailed Description
In order that the objects, features and advantages of the invention will be more clearly understood, a more particular description of the invention will be rendered by reference to the appended drawings, which are illustrated in detail in order to provide a thorough understanding of the invention, but which may be carried out in other ways than those described. Accordingly, the invention is not limited by the specific implementations disclosed below.
The invention provides a cold-resistant midsole material which comprises the following raw materials in parts by weight: 10-25 parts of natural rubber, 10-25 parts of olefin block copolymer, 60-80 parts of silicone rubber and hydrogenated acetonitrile modified styrene-ethylene/propylene block copolymer, 0.3-0.8 part of stearic acid, 1-2 parts of cell stabilizer, 3-8 parts of activator, 3-8 parts of nucleating agent, 4-8 parts of AC foaming agent and 1-2 parts of cross-linking agent.
The formulation of the traditional midsole material takes ethylene vinyl acetate copolymer (EVA) as a main raw material. In the formula of the cold-resistant midsole material provided by the invention, the EVA is replaced by the styrene-ethylene/propylene block copolymer modified by the silicon rubber and the hydrogenated acetonitrile.
The silicone rubber and the hydrogenated acetonitrile modified styrene-ethylene/propylene block copolymer are polymerized by adding the silicone rubber and the hydrogenated acetonitrile in a synthesis process, and the styrene-ethylene/propylene block copolymer (SEP) is modified, so that the cold resistance and resilience effects of the composite material are ensured, and the defect that the traditional midsole material is very easy to harden greatly in a cold environment can be effectively overcome.
In the embodiment of the present invention, silicone rubber having a number average molecular weight of 15 to 20 ten thousand and hydrogenated acetonitrile-modified styrene-ethylene/propylene block copolymer may be used. When the number average molecular weight of the used silicone rubber and the hydrogenated acetonitrile modified styrene-ethylene/propylene block copolymer is less than 15 ten thousand, the prepared composite material has poor cold resistance. When the number average molecular weight of the silicone rubber and the hydrogenated acetonitrile modified styrene-ethylene/propylene block copolymer is more than 20 ten thousand, the preparation difficulty of the composite material is increased.
In the embodiment of the invention, the preferable model is SBC1553, wherein the mass fraction of the silicon rubber is 5-10%, the mass fraction of the hydrogenated acetonitrile is 10-25%, and the silicon rubber and the hydrogenated acetonitrile modified styrene-ethylene/propylene block copolymer are used.
In the formula of the cold-resistant midsole material provided by the invention, the natural rubber is used for improving the cold-resistant effect of the composite material, and the preferred model is 3L.
In the embodiment of the present invention, the weight part of the natural rubber is set to 10 to 25 parts, and the composite material having the best cold resistance effect can be prepared.
The Olefin Block Copolymer (OBC) is used for ensuring the rebound and permanent compression deformation resistant effect of the composite material, and the hardness change of the OBC is obviously smaller than that of EVA under the subzero temperature environment, and the preferred model is 9107.
In the embodiment of the invention, stearic acid is used as an elastic additive for improving the shaping stability of the composite material, so that the composite material has a good deformation resistant effect.
In the embodiment of the present invention, at least one of zinc oxide, zinc stearate, magnesium stearate, and zinc carbonate may be used as the cell stabilizer. The cell stabilizer used in the invention also serves as a heating aid and has a heating auxiliary function.
The preferred type of AC blowing agent is AC 3000H. The foam stabilizer and the AC foaming agent are matched to improve the dispersion effect among the raw materials and stabilize the pH value.
In an embodiment of the present invention, diethylene glycol may be used as the active agent, with the preferred model number YC 100.
In the embodiment of the invention, titanium dioxide can be used as the nucleating agent, the energy barrier between the nucleating agent particles and the polymer melt interface is low, and the nucleation of the foam cells is easy to occur around the particles, so that the nucleation process is promoted, the size of the foam cells is greatly reduced, and the density of the foam cells is improved.
In the embodiment of the invention, dicumyl peroxide (DCP) can be used as the crosslinking agent, and the crosslinking agent can reduce the tension between raw material interfaces, improve the compatibility effect between raw materials and improve the stability of the composite material.
In the embodiment of the invention, the raw materials can be added with color particles for adjusting the color of the insole finished product so as to meet the appearance requirements of different consumers.
The formula of the cold-resistant midsole material provided by the invention can be prepared by adopting a one-time injection foaming (IP) process.
The technical scheme of the traditional cold-resistant midsole material basically adopts an operation flow of amplifying foaming multiplying power and then carrying out secondary mould pressing, adopts an operation flow of primary injection foaming, belongs to the initiative in the technical field of cold-resistant midsole industry, directly simplifies the preparation flow, and can improve various properties of the prepared composite material.
The preparation method provided by the invention comprises the following steps:
weighing various raw materials in parts by weight, mixing and banburying the raw materials on a banbury mixer at the temperature of 115-125 ℃ for 10-15 min, and then discharging to obtain a mixture.
And cooling, dispersing and mixing the mixture on an open mill at 65-75 ℃ for 5-6 min, and granulating to obtain granules.
And injecting the material particles into a mold to form a product by a primary injection machine, wherein the temperature of a gun of the primary injection machine is 90-130 ℃, and the temperature of the mold is 175-185 ℃.
After the finished product is shrunk and stabilized, trimming and finishing can be carried out, and then the finished product is packaged and put in storage and is stored in a dark place for standby.
The cold-resistant midsole material prepared by the technical means has proper hardness of 42 +/-2C, provides support for a wearer and reduced sole pressure, provides a buffering effect, has hardness change of 5-8C at-20 ℃ low temperature environment, improves outdoor long-time wearing comfort, and has lower density of 0.22 +/-0.02 g/cm 3 The weight of the shoe can be reduced, and the load of the wearer can be reduced.
The invention also provides application of the cold-resistant midsole material in preparation of a midsole, namely a shoe, which comprises the midsole made of the cold-resistant midsole material. The structure of the midsole is not particularly limited in the present invention, and a conventional structure may be employed, and the type of shoe including the midsole may be not limited, and may be a sports shoe, a leisure shoe, or the like.
Referring to fig. 1, in order to improve the supporting effect including the shoe, a support stabilizer is provided at a sidewall of the outsole heel of the shoe, and the support stabilizer may extend to the arch of the outsole, based on the hardness of the midsole of the shoe being 42 ± 2C. The support stabilizing component is usually made of thermoplastic polyurethane elastomer (TPU) injection sheet, nylon injection sheet, carbon fiber sheet and the like.
Examples one to five
The cold-resistant midsole materials are respectively obtained according to the preparation of the corresponding formula in the table 1.
Table 1 formulations of examples one to five
Comparative example 1
The raw material SBC1553 in the formulation of example five was replaced with the same parts by weight of EVA, the model number selected was 7470M.
The cold-resistant midsole materials prepared in examples one to five and comparative example one were respectively subjected to performance tests, and the test results are shown in table 2. Wherein the hardness change at the temperature of minus 20 ℃ takes the hardness value of the material at the temperature of 23 ℃ as an initial value, and then the hardness value after the temperature is reduced to minus 20 ℃ and stabilized for 6 hours is a final value for calculation.
Table 2 performance data for examples one through five and comparative example one
Specific analysis:
with the increase of the mass fraction of the natural rubber in the formula, the hardness of the composite material at the temperature of-20 ℃ is changed, namely the cold resistance is not obviously increased, but the hardness and the density are obviously increased, so that the formula of the cold-resistant midsole material provided by the invention is optimally set to be 10-25 parts by weight of the natural rubber.
The formula of the first comparative example is a traditional formula, EVA is used in the formula, and the cold resistance performance of the prepared cold-resistant midsole material is obviously different from that of the cold-resistant midsole materials prepared in the first to fifth examples. Meanwhile, the cold-resistant midsole material prepared in the comparative example one has lower hardness at normal temperature than the cold-resistant midsole materials prepared in the examples one to five.
Moreover, with the increase of the mass fraction of the silicon rubber and the hydrogenated acetonitrile modified styrene-ethylene/propylene block copolymer in the formula, namely the increase of the content of the silicon rubber and the hydrogenated acetonitrile, the cold resistance of the composite material is obviously increased, which shows that the silicon rubber and the hydrogenated acetonitrile modified styrene-ethylene/propylene block copolymer can improve the cold resistance of the midsole material, reduce the abnormity of substantial hardening in a cold environment and improve the comfort of long-time wearing outdoors.
It will be understood that the above embodiments are merely exemplary embodiments adopted to illustrate the principles of the present invention, and the present invention is not limited thereto. It will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the spirit and scope of the invention, and such modifications and improvements are also considered to be within the scope of the invention.
Claims (10)
1. The cold-resistant midsole material is characterized by comprising the following raw materials in parts by weight: 10-25 parts of natural rubber, 10-25 parts of olefin block copolymer, 60-80 parts of silicone rubber and hydrogenated acetonitrile modified styrene-ethylene/propylene block copolymer, 0.3-0.8 part of stearic acid, 1-2 parts of cell stabilizer, 3-8 parts of activator, 3-8 parts of nucleating agent, 4-8 parts of AC foaming agent and 1-2 parts of cross-linking agent.
2. The cold-resistant midsole material according to claim 1, wherein the mass fraction of the silicone rubber in the silicone rubber and acetonitrile hydride modified styrene-ethylene/propylene block copolymer is 5 to 10%, and the mass fraction of the acetonitrile hydride is 10 to 25%.
3. The cold-resistant midsole material of claim 1, wherein the silicone rubber and the hydrogenated acetonitrile-modified styrene-ethylene/propylene block copolymer have a number average molecular weight of 15 to 20 ten thousand.
4. The cold-resistant midsole material of claim 1, wherein the cell stabilizer is at least one of zinc oxide, zinc stearate, magnesium stearate, zinc carbonate, the active agent is diethylene glycol, the nucleating agent is titanium dioxide, and the cross-linking agent is dicumyl peroxide.
5. The cold-resistant midsole material of claim 1, wherein the natural rubber is selected from the group consisting of model 3L, the olefin block copolymer is selected from the group consisting of model 9107, and the silicone rubber and hydrogenated acetonitrile-modified styrene-ethylene/propylene block copolymer is selected from the group consisting of model SBC 1553.
6. A method for preparing the cold-resistant midsole material as claimed in any one of claims 1 to 5, characterized by adopting a one-time injection foaming process.
7. The method of claim 6, comprising the steps of:
weighing various raw materials according to the parts by weight, mixing and banburying the raw materials on a banbury mixer, and then discharging the materials to obtain a mixture;
cooling, dispersing and mixing the mixture on an open mill, and then granulating to obtain material particles;
and injecting the material particles once by a once injection machine, and injecting the material particles into a mould to obtain a product.
8. The preparation method according to claim 7, characterized in that the temperature for banburying on an internal mixer is 115-125 ℃ and the time is 10-15 min;
mixing on an open mill at the temperature of 65-75 ℃ for 5-6 min;
the temperature of a gun of the primary injection machine is 90-130 ℃, and the temperature of the die is 175-185 ℃.
9. A shoe comprising a midsole made from a cold-resistant midsole material as claimed in any one of claims 1 to 5.
10. The shoe of claim 9, further comprising a support stabilizer disposed at a sidewall at a heel of the outsole and an outsole, the support stabilizer extending to an arch of the outsole.
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| CN202210264438.5A CN114921048B (en) | 2022-03-17 | 2022-03-17 | Cold-resistant midsole material, preparation method thereof and shoes |
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| JP2005125706A (en) * | 2003-10-27 | 2005-05-19 | Asahi Kasei Chemicals Corp | Multilayer film and sheet |
| US20090137708A1 (en) * | 2007-11-26 | 2009-05-28 | Hyundai Motor Company | Polypropylene resin composition for interior materials of vehicle |
| CN106147106A (en) * | 2015-03-27 | 2016-11-23 | 晋江凯基高分子材料有限公司 | A kind of styrene-ethylene-ethylene-propylene-based block copolymer modified foaming body and preparation method and application |
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| CN109897385A (en) * | 2019-03-11 | 2019-06-18 | 安踏（中国）有限公司 | A kind of vibration-damping foamed middle bottom material and preparation method thereof of width temperature range |
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| CN114921048B (en) | 2023-06-13 |
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