CN114921048B - 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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- CN114921048B CN114921048B CN202210264438.5A CN202210264438A CN114921048B CN 114921048 B CN114921048 B CN 114921048B CN 202210264438 A CN202210264438 A CN 202210264438A CN 114921048 B CN114921048 B CN 114921048B
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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
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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
- 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)
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- Polymers & Plastics (AREA)
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- 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 silicon 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 active agent, 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 in a low-temperature environment of-20 ℃, and has proper hardness and low 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
Shoes are a tool for protecting feet from injury, with the continuous progress of society, people have increasingly higher requirements on shoes, and midsoles are one of important components of shoes, which play a great decisive role in the performance of the shoes.
In cold areas, particularly in outdoor exercises, there is a particular need for cold resistance of midsole materials, which require that the materials retain their original properties at low temperatures, thereby providing a better wearing experience to the wearer.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a cold-resistant midsole material, a preparation method thereof and a shoe.
For this purpose, the invention adopts the following technical scheme:
the 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 silicon 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 active agent, 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 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 model 3L, the olefin block copolymer is selected from model 9107, and the silicone rubber and hydrogenated acetonitrile-modified styrene-ethylene/propylene block copolymer is selected from model SBC1553.
Based on the same inventive concept, the invention also provides a method for preparing the cold-resistant midsole material, which is prepared by adopting a one-time injection foaming process.
Preferably, the preparation method comprises the following steps: weighing various raw materials according to parts by weight, mixing and banburying the raw materials on an internal mixer, and then discharging the raw materials to obtain a mixture; cooling, dispersing and mixing the mixture on an open mill, and granulating to obtain granules; and injecting the material particles once through a primary injection molding machine, and injecting the material particles into a mold to obtain the product.
Preferably, the banburying temperature on an internal mixer is 115-125 ℃ and the time is 10-15 min; mixing in an open mill at 65-75 deg.c for 5-6 min; the temperature of the 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 prepared from the cold-resistant midsole material.
Preferably, the shoe further comprises a support stabilizing member disposed at a sidewall at a heel of the outsole and an outsole, the support stabilizing member 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 in a low-temperature environment at the temperature of minus 20 ℃, and meanwhile, 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 are provided for a wearer;
2. the cold-resistant midsole material provided by the invention is prepared by adopting a primary injection foaming process, replaces the traditional process of amplifying foaming multiplying power and then performing secondary mould pressing, and simplifies the preparation flow;
3. the cold resistance of the composite material is improved by using the silicone rubber and hydrogenated acetonitrile modified styrene-ethylene/propylene block copolymer.
Drawings
FIG. 1 is a schematic view of the structure of an outsole of a shoe provided by the present invention.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, and in order to provide a more thorough understanding of the present invention, reference is made to the following detailed description of the invention in connection with the accompanying drawings and examples, in which the invention may be practiced in other ways than those described. Therefore, 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 silicon 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 active agent, 3-8 parts of nucleating agent, 4-8 parts of AC foaming agent and 1-2 parts of cross-linking agent.
In the traditional formula of the midsole material, ethylene-vinyl acetate copolymer (EVA) is used as a main raw material. In the formula of the cold-resistant midsole material provided by the invention, the EVA is replaced by the silicon rubber and hydrogenated acetonitrile modified styrene-ethylene/propylene segmented copolymer.
The silicone rubber and the hydrogenated acetonitrile modified styrene-ethylene/propylene block copolymer are added in the synthesis process to polymerize, so that the styrene-ethylene/propylene block copolymer (SEP) is modified, the cold resistance and rebound effect of the composite material are ensured, and the defect that the traditional midsole material is extremely easy to harden greatly in a cold environment can be effectively overcome.
In embodiments of the present invention, silicone rubber having a number average molecular weight of 15 to 20 tens of thousands may be used with hydrogenated acetonitrile-modified styrene-ethylene/propylene block copolymer. When the number average molecular weight of the used silicone rubber and hydrogenated acetonitrile modified styrene-ethylene/propylene block copolymer is less than 15 ten thousand, the cold resistance of the prepared composite material is poor. When the number average molecular weight of the used silicon rubber and hydrogenated acetonitrile modified styrene-ethylene/propylene segmented copolymer is more than 20 ten thousand, the preparation difficulty of the composite material is increased.
In embodiments of the present invention, a silicone rubber and hydrogenated acetonitrile modified styrene-ethylene/propylene block copolymer having a mass fraction of silicone rubber of 5 to 10% and a mass fraction of hydrogenated acetonitrile of 10 to 25%, preferably model SBC1553, may be 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 model is 3L.
In the embodiment of the invention, the weight part of the natural rubber is set to be 10-25 parts, and the prepared composite material has the optimal cold resistance effect.
Olefin Block Copolymers (OBC) are used to ensure rebound and sustained compression set resistance of the composite, and the hardness change of the OBC is significantly less than that of EVA in a subzero temperature environment, preferably model 9107.
In the embodiment of the invention, stearic acid is used as an elastic additive for improving the molding stability of the composite material, so that the composite material has good deformation resistance effect.
In embodiments of the present invention, the cell stabilizer may use at least one of zinc oxide, zinc stearate, magnesium stearate, zinc carbonate. 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 AC3000H. The foam stabilizer and the AC foaming agent are matched to improve the dispersion effect between the raw materials and stabilize the pH value.
In an embodiment of the present invention, diethylene glycol, preferably model YC100, may be used as the active agent.
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 cell nucleation is easy to occur around the particles, so that the nucleation process is promoted, the cell size is greatly reduced, and the cell density is improved.
In the embodiment of the invention, dicumyl peroxide (DCP) can be used as the crosslinking agent, so that the tension between raw material interfaces can be reduced, the compatibility effect between raw materials can be improved, and the stability of the composite material can be improved.
In the embodiment of the invention, color particles can be added into the raw materials for adjusting the color of the midsole 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 the operation flow of amplifying the foaming ratio and then adopting the secondary mould pressing, the technical scheme of the invention adopts the operation flow of injecting and foaming once, belongs to the first creation in the technical field of the cold-resistant midsole industry, directly simplifies the preparation flow, and can also improve various performances of the prepared composite material.
The preparation method provided by the invention comprises the following steps:
weighing various raw materials according to parts by weight, mixing and banburying the raw materials on an internal mixer at the temperature of 115-125 ℃ for 10-15 min, and then discharging to obtain a mixture.
Cooling, dispersing and mixing the mixture on an open mill at 65-75 ℃ for 5-6 min, and granulating to obtain the granules.
The material particles are ejected once through a primary ejector, and are injected into a mould to be molded to obtain the product, the temperature of the ejection gun of the primary ejector is 90-130 ℃, and the temperature of the mould is 175-185 ℃.
After the finished product is contracted stably, trimming and finishing can be carried out, packaging and warehousing are carried out, and light-shielding storage is carried out for standby.
The cold-resistant middle-base material prepared by the technical means has proper hardness of 42+/-2 ℃ and reduced plantar pressure while providing support for a wearer, provides a buffering effect, has hardness change of 5-8 ℃ in a low-temperature environment of minus 20 ℃ and improves the comfort of wearing outdoors for a long time, and also 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 an application of the cold-resistant midsole material in preparing a midsole, namely a shoe, comprising the midsole prepared from the cold-resistant midsole material. The present invention is not particularly limited in the structure of the midsole, and may be of a conventional structure, and the type of shoe including the midsole is not limited, and may be of the type of sports shoe, casual shoe, or the like.
Referring to fig. 1, in order to enhance the supporting effect including the shoe, a support stabilizer is provided at a sidewall at the heel of the outsole of the shoe based on the hardness of the midsole of the shoe being 42±2c, and the support stabilizer may extend to the arch of the outsole. The material commonly used for the support stabilizing member is a thermoplastic polyurethane elastomer rubber (TPU) injection sheet, a nylon injection sheet, a carbon fiber sheet, etc.
Examples one to five
Prepared according to the corresponding formula of Table 1 to obtain the cold-resistant midsole materials respectively.
Table 1 formulations of examples one to five
Comparative example one
The raw material SBC1553 in the formulation of the fifth example is replaced by EVA with the same weight part, and the model is 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 minus 20 ℃ takes the hardness value of the material at 23 ℃ as an initial value, and then the hardness value after cooling to minus 20 ℃ and stabilizing for 6 hours is a final value, so as to calculate.
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 minus 20 ℃ is changed, namely the cold resistance is not obviously increased, but the hardness and the density of the composite material are obviously increased, so that the weight fraction of the natural rubber in the formula of the cold-resistant midsole material provided by the invention is optimally set to be 10-25 parts.
The formula of the first comparative example is a traditional formula, EVA is used in the formula, and the cold resistance of the prepared cold-resistant middle-base material is obviously different from that of the cold-resistant middle-base materials prepared in the first to fifth examples. Meanwhile, the hardness of the cold-resistant midsole material prepared in the first comparative example at normal temperature is not as high as that of the cold-resistant midsole materials prepared in the first to fifth examples.
Moreover, as the mass fraction of the silicon rubber and the hydrogenated acetonitrile modified styrene-ethylene/propylene block copolymer in the formula is increased, namely the content of the silicon rubber and the hydrogenated acetonitrile is increased, the cold resistance of the composite material is obviously increased, which indicates that the silicon rubber and the hydrogenated acetonitrile modified styrene-ethylene/propylene block copolymer can improve the cold resistance of a midsole material, reduce the abnormal hardening in cold environment and improve the comfort of wearing outdoors for a long time.
It is to be understood that the above embodiments are merely illustrative of the application of the principles of the present invention, but not in limitation thereof. Various modifications and improvements may be made by those skilled in the art without departing from the spirit and substance of the invention, and are also considered to be within the scope of the invention.
Claims (8)
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 silicon 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 active agent, 3-8 parts of nucleating agent, 4-8 parts of AC foaming agent and 1-2 parts of cross-linking agent, wherein the mass fraction of the silicon rubber in the silicon rubber and hydrogenated acetonitrile modified styrene-ethylene/propylene block copolymer is 5-10%, the mass fraction of the hydrogenated acetonitrile is 10-25%, the number average molecular weight of the silicon rubber and hydrogenated acetonitrile modified styrene-ethylene/propylene block copolymer is 15-20 ten thousand, and the silicon rubber and the hydrogenated acetonitrile modified styrene-ethylene/propylene block copolymer are prepared by adding the silicon rubber and the hydrogenated acetonitrile in a synthesis process for polymerization, and modifying the styrene-ethylene/propylene block copolymer.
2. 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 crosslinking agent is dicumyl peroxide.
3. The cold resistant midsole material of claim 1, wherein the natural rubber is selected from model 3L, the olefin block copolymer is selected from model 9107, and the silicone rubber and hydrogenated acetonitrile-modified styrene-ethylene/propylene block copolymer is selected from model SBC1553.
4. A method for preparing the cold-resistant midsole material according to any one of claims 1 to 3, which is prepared by a one-shot foaming process.
5. The method of manufacturing according to claim 4, comprising the steps of:
weighing various raw materials according to parts by weight, mixing and banburying the raw materials on an internal mixer, and then discharging the raw materials to obtain a mixture;
cooling, dispersing and mixing the mixture on an open mill, and granulating to obtain granules;
and injecting the material particles once through a primary injection molding machine, and injecting the material particles into a mold to obtain the product.
6. The preparation method according to claim 5, wherein the banburying is carried out on an internal mixer at 115-125 ℃ for 10-15 min;
mixing in an open mill at 65-75 deg.c for 5-6 min;
the temperature of the gun of the primary injection machine is 90-130 ℃, and the temperature of the die is 175-185 ℃.
7. A shoe comprising a midsole made from the cold resistant midsole material of any one of claims 1-3.
8. The shoe of claim 7, further comprising a support stabilization member disposed at a sidewall at a heel of the outsole and an outsole, the support stabilization member extending to an arch of the outsole.
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| 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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| CN110527235A (en) * | 2019-09-07 | 2019-12-03 | 黄伟斌 | A kind of cold tolerance foamed material formula and the method using its production footwear material |
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| JP4443186B2 (en) * | 2003-10-27 | 2010-03-31 | 旭化成ケミカルズ株式会社 | Multilayer film and sheet |
| KR100957303B1 (en) * | 2007-11-26 | 2010-05-12 | 현대자동차주식회사 | Poly propylene resin composition for interior materials of automobile |
| CN104804297B (en) * | 2015-04-24 | 2018-08-28 | 茂泰(福建)鞋材有限公司 | A kind of light weight high-elastic EVA sole and preparation method thereof |
| CN109897385B (en) * | 2019-03-11 | 2021-08-17 | 安踏（中国）有限公司 | Wide-temperature-range shock-absorption foaming insole material and preparation method thereof |
| CN110016180A (en) * | 2019-05-08 | 2019-07-16 | 福建五持恒科技发展有限公司 | Rubber-plastic foamed insole of graphene and preparation method thereof |
| CN111320790A (en) * | 2020-03-19 | 2020-06-23 | 许宝华 | Rubber composite material and ultralight high-elastic sole |
| CN112592461B (en) * | 2020-12-14 | 2022-02-11 | 北京化工大学 | Modified hydrogenated nitrile rubber material and preparation method and application thereof |
| CN112778621B (en) * | 2020-12-31 | 2023-01-10 | 安踏（中国）有限公司 | Composition for preparing high-elasticity memory EVA composite foaming material for sneaker sole and preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN110527235A (en) * | 2019-09-07 | 2019-12-03 | 黄伟斌 | A kind of cold tolerance foamed material formula and the method using its production footwear material |
| CN110511451A (en) * | 2019-10-12 | 2019-11-29 | 福建五持恒科技发展有限公司 | A kind of graphene arctic rubber polymeric composition and preparation method thereof |
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