CN113929953A - High-flexibility foaming sole material and preparation method of sole - Google Patents
High-flexibility foaming sole material and preparation method of sole Download PDFInfo
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- CN113929953A CN113929953A CN202111151094.9A CN202111151094A CN113929953A CN 113929953 A CN113929953 A CN 113929953A CN 202111151094 A CN202111151094 A CN 202111151094A CN 113929953 A CN113929953 A CN 113929953A
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- 239000000463 material Substances 0.000 title claims abstract description 55
- 238000005187 foaming Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229920002725 thermoplastic elastomer Polymers 0.000 claims abstract description 34
- 229920001971 elastomer Polymers 0.000 claims abstract description 32
- 239000005060 rubber Substances 0.000 claims abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 17
- 239000004711 α-olefin Substances 0.000 claims abstract description 14
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 13
- 239000004088 foaming agent Substances 0.000 claims abstract description 13
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 13
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920006132 styrene block copolymer Polymers 0.000 claims abstract description 8
- 229920006346 thermoplastic polyester elastomer Polymers 0.000 claims abstract description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000004513 sizing Methods 0.000 claims description 7
- 235000021355 Stearic acid Nutrition 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 6
- 238000009998 heat setting Methods 0.000 claims description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 6
- 239000008117 stearic acid Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 6
- 238000003801 milling Methods 0.000 claims description 5
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 229920001400 block copolymer Polymers 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000004073 vulcanization Methods 0.000 claims description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- 239000004156 Azodicarbonamide Substances 0.000 claims description 2
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 claims description 2
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 claims description 2
- 239000004944 Liquid Silicone Rubber Substances 0.000 claims description 2
- 229920000459 Nitrile rubber Polymers 0.000 claims description 2
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 2
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- 229920001021 polysulfide Polymers 0.000 claims description 2
- 239000005077 polysulfide Substances 0.000 claims description 2
- 150000008117 polysulfides Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920005604 random copolymer Polymers 0.000 claims description 2
- 229920002545 silicone oil Polymers 0.000 claims description 2
- 229920002379 silicone rubber Polymers 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- WXCZUWHSJWOTRV-UHFFFAOYSA-N but-1-ene;ethene Chemical compound C=C.CCC=C WXCZUWHSJWOTRV-UHFFFAOYSA-N 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 claims 2
- 229920002521 macromolecule Polymers 0.000 description 5
- 238000005096 rolling process Methods 0.000 description 4
- 235000010215 titanium dioxide Nutrition 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- -1 polybutylene terephthalate Polymers 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 229920003232 aliphatic polyester Polymers 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000007906 compression Methods 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
Classifications
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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
-
- 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
-
- 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
-
- 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
- C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
-
- 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
- C08J9/104—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof
- C08J9/105—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof containing sulfur
-
- 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
- C08J9/107—Nitroso compounds
-
- 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
-
- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
-
- 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
- C08J2453/02—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
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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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
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
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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 high-flexibility foaming sole material which is prepared from the following raw materials in parts by mass: 25-55 parts of ethylene-vinyl acetate copolymer, 20-35 parts of composite flexible thermoplastic elastomer, 15-30 parts of alpha-olefin thermoplastic elastomer, 5-10 parts of talcum powder, 2-15 parts of wear-resisting agent, 0.3-1.5 parts of crosslinking agent and 2.5-10 parts of foaming agent; the composite flexible thermoplastic elastomer is prepared from a styrene-ethylene-styrene block copolymer, a thermoplastic polyester elastomer and liquid rubber in a mass ratio of (5-15): (20-30): (20-45) blending. The invention also discloses a preparation method of the sole made of the material. The high-flexibility foamed sole material disclosed by the invention is good in wear resistance, soft and comfortable in texture, excellent in resilience, light and comfortable. The high-flexibility foamed sole prepared by the preparation method of the sole has the advantages of stable preparation process and high yield of finished products.
Description
Technical Field
The invention relates to a sole, in particular to a high-flexibility foaming sole material and a preparation method of the sole.
Background
Sports shoes can be simply divided into professional sports shoes and daily leisure sports shoes, the professional sports shoes can provide sufficient support and mechanical feedback for feet, and therefore the soles are always heavier and harder overall.
Ordinary once jet forming sole is because need the full palm contact ground, in order to improve the insole wearability, on the one hand will increase hardness, on the other hand will add too much wear-resisting agent or powder to make the insole harden, its soft comfort performance reduces by a wide margin, gives other people not good wearing experience. Therefore, in order to solve the problems of hard sole and poor foot feel in one-time injection molding, it is necessary to develop a highly comfortable and soft foamed midsole material, which can meet the daily exercise requirements of most sports enthusiasts.
Disclosure of Invention
The invention aims to provide a high-flexibility foaming sole material, and a sole prepared from the high-flexibility foaming sole material is wear-resistant, has high flexibility and is suitable for being used on sports shoes. In order to achieve the purpose, the invention adopts the following technical scheme:
the invention discloses a high-flexibility foaming sole material which is prepared from the following raw materials in parts by mass: 25-55 parts of ethylene-vinyl acetate copolymer, 20-35 parts of composite flexible thermoplastic elastomer, 15-30 parts of alpha-olefin thermoplastic elastomer, 5-10 parts of talcum powder, 2-15 parts of wear-resisting agent, 0.3-1.5 parts of crosslinking agent and 2.5-10 parts of foaming agent; the composite flexible thermoplastic elastomer is prepared from a styrene-ethylene-styrene block copolymer, a thermoplastic polyester elastomer and liquid rubber in a mass ratio of (5-15): (20-30): (20-45) blending.
Preferably, the feed also comprises the following raw materials in parts by mass: 2.5-3 parts of titanium dioxide, 2-2.5 parts of zinc oxide, 0.5-0.8 part of stearic acid and 0.8-1 part of zinc stearate.
Furthermore, the mass content of VA in the ethylene-vinyl acetate copolymer is 22-35%. The liquid rubber is liquid rubber with the relative molecular weight of 1000-35000.
The liquid rubber is one or more of hydroxyl-terminated polybutadiene, mercapto-terminated liquid polysulfide rubber, liquid nitrile rubber, liquid styrene-butadiene rubber, liquid silicone rubber and cast polyurethane.
Wherein the alpha-olefin thermoplastic elastomer is one or more of ethylene-butyl/octene random copolymer, ethylene-butyl/octene block copolymer and ethylene-propylene-non-conjugated diene copolymer.
Preferably, the particle size of the talcum powder is 4000-6500 meshes; the wear-resisting agent is a blend compounded by ethylene-vinyl acetate copolymer and silicone oil; the cross-linking agent is one or two of dicumyl peroxide or 1, 4-di-tert-butylperoxyisopropyl benzene; the foaming agent is selected from one or more of azodicarbonamide, 4 '-oxo-bis-benzenesulfonyl hydrazide and N, N' -dinitrosopentamethylenetetramine.
The invention also discloses a preparation method of the sole, which comprises the following steps:
s1, weighing raw materials, and weighing the raw materials according to the proportion of the high-flexibility foamed sole material.
S2, mixing the rubber material, namely banburying the other raw materials except the cross-linking agent and the foaming agent, and adding the cross-linking agent and the foaming agent for mixing when the temperature is raised to 100-110 ℃.
S3, sizing material open milling, wherein the mixed sizing material is added into an open mill for open milling, and the temperature of a front roller of the open mill is set to be 65-75 ℃; the temperature of the rear roller is set to be 35-45 ℃.
And S4, granulating, namely putting the milled rubber material into a granulator for granulation, wherein the temperature of the granulator is 80-85 ℃.
S5, foaming, namely pouring the manufactured material into a foaming forming machine for foaming and mold vulcanization forming, wherein the foaming temperature is 90-95 ℃, and the mold temperature is 170-185 ℃; the vulcanizing time is 300-500s, and the molded sole is obtained.
And S6, drying, namely drying and heat setting the formed sole.
Preferably, in the step S3, adjusting the gap between a front roller and a rear roller of the open mill to be 5-10 mm, rolling the rubber material for a plurality of times by using a roller, adjusting the gap between the front roller and the rear roller to be 2-3 mm, and rolling the rubber material for a plurality of times by using the roller; in the step S4, the temperatures of a hopper, a screw heating area and a die head in the granulator are respectively 80 +/-5 ℃, 80 +/-5 ℃ and 85 +/-5 ℃, the rotation speed of the screw is adjusted to 40-50 r/min, and the rotation speed of the cutting machine is adjusted to 15-20 r/min.
Preferably, in step S5, four continuous foaming zones are set in the foaming process, the temperature of the four zones is 95 ± 2 ℃, 90 ± 2 ℃ and 90 ± 2 ℃ in sequence, and the pressure of the four zones is 90 ± 5 Bar; in step S6, drying is carried out in an oven, the oven is provided with a front section, a middle section and a rear section, the temperatures are respectively set to be 100 +/-2 ℃, 90 +/-2 ℃ and 80 +/-2 ℃, and the heat setting time is 30 +/-5 minutes.
Due to the adoption of the scheme, the invention has the following beneficial effects: the high-flexibility foamed sole material disclosed by the invention is good in wear resistance, soft and comfortable in texture, excellent in resilience, light and comfortable. The high-flexibility foamed sole prepared by the preparation method of the sole is formed by one-time injection, the preparation process is stable, and the yield of finished products is high.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the present invention is further described in detail with reference to the specific embodiments below.
The invention discloses a high-flexibility foaming sole material which comprises the following raw materials in parts by mass: 25-55 parts of ethylene-vinyl acetate copolymer, 20-35 parts of composite flexible thermoplastic elastomer, 15-30 parts of alpha-olefin thermoplastic elastomer, 5-10 parts of talcum powder, 2-15 parts of wear-resisting agent, 0.3-1.5 parts of crosslinking agent, 2.5-10 parts of foaming agent, 2.5-3 parts of titanium dioxide, 2-2.5 parts of zinc oxide, 0.5-0.8 part of stearic acid and 0.8-1 part of zinc stearate.
The composite flexible thermoplastic elastomer is prepared from a styrene-ethylene-styrene block copolymer, a thermoplastic polyester elastomer and liquid rubber in a mass ratio of (5-15): (20-30): (20-45) blending.
The selection of specific materials was made according to the raw material composition, as shown in table 1 below.
Table 1 material selection of raw material components
The compounding ratios shown in Table 2 can be adjusted according to the compounding ratios of the raw materials.
TABLE 2 proportioning of the raw materials (parts by mass)
| Raw material composition/implementation group | A | B | C | D | E |
| Ethylene-vinyl acetate copolymer (EVA) | 45 | 40 | 35 | 25 | 55 |
| Composite flexible thermoplastic elastomer | 25 | 30 | 35 | 20 | 30 |
| Alpha-olefin thermoplastic elastomer (TPO) | 30 | 30 | 30 | 25 | 15 |
| Talcum powder | 5 | 5 | 5 | 8 | 10 |
| Wear-resisting agent | 10 | 10 | 10 | 15 | 4 |
| Crosslinking agent | 1.5 | 1.6 | 1.7 | 0.8 | 0.3 |
| Foaming agent | 3.5 | 3.4 | 3.8 | 5 | 2.5 |
| Titanium white powder | 2.5 | 2.5 | 2.5 | 3 | 2.8 |
| Zinc oxide | 2.1 | 2.1 | 2.5 | 2 | 2.4 |
| Stearic acid | 0.5 | 0.5 | 0.5 | 0.8 | 0.6 |
| Zinc stearate | 0.8 | 1.0 | 1.0 | 0.8 | 0.8 |
The composite flexible thermoplastic elastomer has the characteristics of soft elasticity, comfort, excellent elasticity, good support property and good fatigue resistance. The composite flexible thermoplastic elastomer consists of styrene-ethylene-styrene block copolymer (SBS), thermoplastic polyester elastomer (TPEE) and composite liquid rubber blend, and has excellent performance as detailed below:
(1) the polybutadiene block in the molecular structure of styrene-ethylene-styrene block copolymer (SBS) is used as a soft block, and the molecular chain of the styrene-ethylene-styrene block copolymer is more flexible to rotate due to the existence of C-C double bonds, so that the styrene-ethylene-styrene block copolymer has excellent flexibility and elasticity.
(2) Thermoplastic polyester elastomer (TPEE), also called polyester rubber, is a linear block copolymer containing PBT (polybutylene terephthalate) polyester hard segment and aliphatic polyester soft segment, has better flexibility and mechanical property, can improve the processing property of the material, and simultaneously combines the polyester hard segment and the aliphatic polyester soft segment to ensure that the material has excellent fatigue resistance, and the sole still keeps soft elastic property after long-time flexion.
(3) The liquid rubber is low molecular weight liquid rubber with relative molecular weight within the range of 1000-35000, is viscous liquid at room temperature, and can form a three-dimensional network structure through proper chemical reaction, so that the oligomer with physical and mechanical properties similar to those of common vulcanized rubber is obtained.
The preparation method comprises the following steps of (1) mixing the three raw materials in a mass ratio of (5-15): (20-30): (20-45) the blend provides a material having good support properties and a certain flexibility without causing excessive hardness.
In the invention, the ethylene-vinyl ester copolymer (EVA) has a VA mass content of 22-35% and a higher VA mass content. The ethylene-vinyl acetate copolymer mainly comprises two parts, wherein one part is a crystallizable polyethylene hard segment with high chain structure regularity and symmetrical structure, and the other part is a polyvinyl acetate soft segment which contains ester side groups and has asymmetric molecular structure. The crystallizable polyethylene section is used as a physical entanglement point and mainly plays a role in crosslinking, so that macromolecular chains are entangled more tightly and have relaxation, excessive slippage of macromolecules can not cause sole deformation, and sole support is endowed; the polyvinyl acetate soft segment containing the ester side group is a flexible chain and mainly exists in a random agglomeration mode in macromolecules, so that the softness and resilience of the material can be improved, and better wearing experience is provided for a wearer.
The alpha-olefin thermoplastic elastomer is adopted in the invention, the molecular structure of the elastomer is special, the elastomer has excellent ageing resistance due to the existence of a C-C single bond, a side methyl group and a side vinyl group, macromolecular chains are intertwined due to the existence of hard segment and soft segment alternation/blocks to form a structure similar to a coil, so that the material shows excellent soft elastic performance, and the alpha-olefin thermoplastic elastomer is lighter in density and lighter and more comfortable to wear compared with other materials.
The stearic acid is added to improve the fluidity of the material and prevent the adhesion of a machine table during preparation, and the zinc stearate and the zinc oxide are added to promote the foaming process during preparation.
Example one
The embodiment discloses a high-flexibility foamed sole material, which comprises the following raw material components in parts by mass as shown in table 3.
Table 3 example a feedstock
The preparation of the soles was carried out according to the formulation as in table 3 above, the preparation steps of which are detailed below.
S1, weighing raw materials
Weighing the raw materials according to the proportion of the high-flexibility foaming sole material. The raw materials are divided into two groups: the first group is a cross-linking agent and a foaming agent, and the second group is the rest raw materials, namely: ethylene-vinyl acetate copolymer, composite flexible thermoplastic elastomer, alpha-olefin thermoplastic elastomer, talcum powder, wear-resisting agent, titanium dioxide, zinc oxide, stearic acid and zinc stearate.
S2, mixing the rubber materials
Firstly banburying the second group of raw materials, pouring the second group of raw materials into a banbury mixer, starting the machine, lowering a dust cover, then lowering a pressure roller, opening the dust cover when the temperature rises to about 85 ℃, cleaning surrounding powder, pouring the first group of raw materials when the temperature rises to 100-110 ℃, banburying for about 1 minute, opening the pressure roller, and cleaning residual odorless DCP and foaming agent in the inner cavity of the mixing chamber; when the temperature rises to 115 ℃, pouring out the mixed rubber material and entering the next step.
S3, sizing material open milling
The open mill is preheated two hours in advance, the temperature of a front roller of the open mill is set to be 65-75 ℃, the temperature of a rear roller of the open mill is set to be 35-45 ℃, and the gap between the front roller and the rear roller of the open mill is 5-10 mm. And (4) rolling the mixed rubber material in the step S2 for 2 times by using a roller, adjusting the gap between the front roller and the rear roller to be 2-3 mm, and rolling the rubber material for 2 times by using the roller. The purpose of the sizing mill is on the one hand to mix the sizing more evenly and on the other hand to reduce the temperature of the sizing and to prevent premature foaming during the granulation process.
S4, granulating
Open temperature switch in advance and preheat the board of granulator, transfer hopper, screw rod zone of heating, die head temperature respectively: adjusting the rotation speed of a screw to 40-50 r/min at 80 ℃ and 85 ℃, adjusting the rotation speed of a stock cutter to 15-20 r/min, cleaning a die head, the screw and accumulated materials in an air duct for granulation, sleeving a bag at the tail end of the air duct, locking the die head for granulation, and labeling the prepared particles for later use.
And (4) putting the milled rubber material into a granulator for granulation.
S5, foaming
And (5) pouring the granulated material obtained in the step S4 into an injection foaming forming machine for foaming and die vulcanization forming.
Four continuous foaming areas are arranged in the foaming process, the temperature of the four areas is 95 +/-2 ℃, 90 +/-2 ℃ and 90 +/-2 ℃, and the pressure of the four areas is 90 +/-5 Bar. The reason for setting up the temperature gradient is that the hot plate temperature can receive many factors influence, such as ambient temperature, mould thickness etc. through setting up the temperature gradient, makes screw rod feeding region and compression zone temperature higher than homogenization district, so be favorable to the abundant melt-mixing of material.
The upper and lower templates of the die can be adjusted as follows: 170-185 ℃. The material amount and the injection speed are set according to the using amount of the mold, and the vulcanizing time is set to be 300-500 seconds.
S6, drying
And (4) putting the formed sole into an oven for drying and heat setting. The oven is provided with a front section, a middle section and a rear section, the temperatures are respectively set to be 100 +/-2 ℃, 90 +/-2 ℃ and 80 +/-2 ℃, and the heat setting time is 30 +/-5 minutes. And drying to obtain a finished product. Set up temperature gradient and mainly be the dimensional stability who improves the insole, increase the yields, at first the anterior segment temperature is higher, and macromolecule vibration aggravation can release the internal stress between the macromolecule chain, and rear end temperature is lower, mainly makes macromolecule chain vibration tend to stably to better design.
Example two
The embodiment discloses a high-flexibility foamed sole material, which comprises the following raw material components in parts by mass as shown in table 4 below.
Table 4 example two starting materials
The preparation process of this example is the same as that of the first example.
EXAMPLE III
The embodiment discloses a high-flexibility foamed sole material, which comprises the following raw material components in parts by mass as shown in table 5.
Table 5 example three feedstocks
The preparation process of this example is the same as that of the first example.
The following experiments demonstrate the effects of the present invention.
To verify the effect of the present invention, three control examples were prepared: comparison example one adopted formula compared with the example, the common thermoplastic elastomer is adopted to replace the composite flexible thermoplastic elastomer and the alpha-olefin thermoplastic elastomer. The formula adopted by the second comparison example is compared with that adopted by the second comparison example, and the common thermoplastic elastomer is adopted to replace the composite flexible thermoplastic elastomer and the alpha-olefin thermoplastic elastomer. The formula adopted in the third comparative example is compared with that adopted in the third example, and the common thermoplastic elastomer is adopted to replace the composite flexible thermoplastic elastomer and the alpha-olefin thermoplastic elastomer.
The prepared soles of the three groups of examples and the three groups of comparative examples were subjected to performance tests, and the test results are shown in table 6 below.
TABLE 6 results of Performance testing
As is clear from table 6, the composite type flexible thermoplastic elastomer and the α -olefin type thermoplastic elastomer of the present invention are not used in the comparative examples one to three, and therefore, the whole hardness is relatively high and the rebound resilience is low. The sole has high resilience rate, certain softness and good wear resistance under the condition of standard hardness, is suitable for being used as the sole of sports shoes, and can meet the daily sports requirements of most sports enthusiasts.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (10)
1. The high-flexibility foaming sole material is characterized by comprising the following raw materials in parts by mass:
25-55 parts of ethylene-vinyl acetate copolymer,
20-35 parts of a composite flexible thermoplastic elastomer,
15 to 30 parts of an alpha-olefin thermoplastic elastomer,
5-10 parts of talcum powder,
2-15 parts of a wear-resisting agent,
0.3 to 1.5 parts of a crosslinking agent,
2.5-10 parts of a foaming agent;
the composite flexible thermoplastic elastomer is prepared from a styrene-ethylene-styrene block copolymer, a thermoplastic polyester elastomer and liquid rubber in a mass ratio of (5-15): (20-30): (20-45) blending.
2. The high-flexibility foamed sole material according to claim 1, further comprising the following raw materials in parts by mass:
2.5 to 3 parts of titanium dioxide,
2 to 2.5 parts of zinc oxide,
0.5 to 0.8 part of stearic acid,
0.8-1 part of zinc stearate.
3. The high-flexibility foamed sole material according to claim 1 or 2, wherein the ethylene-vinyl acetate copolymer has a VA content of 22 to 35% by mass.
4. The foamed sole material of claim 1 or 2, wherein the liquid rubber is a liquid rubber having a relative molecular weight of 1000 to 35000.
5. The high-flexibility foamed sole material according to claim 4, wherein said liquid rubber is one or more of hydroxyl-terminated polybutadiene, thiol-terminated liquid polysulfide rubber, liquid nitrile rubber, liquid styrene-butadiene rubber, liquid silicone rubber, and cast polyurethane.
6. A high-flexibility foamed sole material according to claim 1 or 2, wherein said α -olefin-based thermoplastic elastomer is one or more of an ethylene-butene/octene random copolymer, an ethylene-butene/octene block copolymer, and an ethylene-propylene-nonconjugated diene copolymer.
7. The high-flexibility foamed sole material according to claim 1 or 2, wherein the particle size of the talc powder is 4000-6500 mesh; the wear-resisting agent is a blend compounded by ethylene-vinyl acetate copolymer and silicone oil; the cross-linking agent is one or two of dicumyl peroxide or 1, 4-di-tert-butylperoxyisopropyl benzene; the foaming agent is selected from one or more of azodicarbonamide, 4 '-oxo-bis-benzenesulfonyl hydrazide and N, N' -dinitrosopentamethylenetetramine.
8. A preparation method of a sole is characterized by comprising the following steps:
s1, weighing raw materials
Weighing the raw materials according to the proportion of the high-flexibility foamed sole material of any one of claims 1 to 7;
s2, mixing the rubber materials
Banburying the other raw materials except the cross-linking agent and the foaming agent, and adding the cross-linking agent and the foaming agent for mixing when the temperature is raised to 100-110 ℃;
s3, sizing material open milling
Adding the mixed rubber material into an open mill for open milling, wherein the temperature of a front roller of the open mill is set to be 65-75 ℃; setting the temperature of a rear roller to be 35-45 ℃;
s4, granulating
Putting the milled rubber material into a granulator for granulation, wherein the temperature of the granulator is 80-85 ℃;
s5, foaming
Pouring the manufactured material into a foaming forming machine for foaming and mold vulcanization forming, wherein the foaming temperature is 90-95 ℃, and the mold temperature is 170-185 ℃; the vulcanizing time is 300-500s, and the molded sole is obtained;
s6, drying
And drying and heat setting the formed sole.
9. The method for preparing the shoe sole according to claim 8, wherein in step S3, the gap between the front roller and the rear roller of the open mill is adjusted to 5 to 10mm, the rubber compound is rolled for several times by the rollers, then the gap between the front roller and the rear roller is adjusted to 2 to 3mm, and the rubber compound is rolled for several times by the rollers; in the step S4, the temperatures of a hopper, a screw heating area and a die head in the granulator are respectively 80 +/-5 ℃, 80 +/-5 ℃ and 85 +/-5 ℃, the rotation speed of the screw is adjusted to 40-50 r/min, and the rotation speed of the cutting machine is adjusted to 15-20 r/min.
10. The method of claim 8, wherein in step S5, four consecutive foaming zones are provided for the foaming process, the four zones having a temperature of 95 ± 2 ℃, 90 ± 2 ℃ and a pressure of 90 ± 5 Bar; in step S6, drying is carried out in an oven, the oven is provided with a front section, a middle section and a rear section, the temperatures are respectively set to be 100 +/-2 ℃, 90 +/-2 ℃ and 80 +/-2 ℃, and the heat setting time is 30 +/-5 minutes.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114702750A (en) * | 2022-04-24 | 2022-07-05 | 安踏（中国）有限公司 | EVA composite foaming material for sports shoe sole and preparation method thereof |
| CN114716756A (en) * | 2022-03-17 | 2022-07-08 | 三六一度(中国)有限公司 | High-resilience sole material, preparation method thereof and shoe |
| CN114773658A (en) * | 2022-05-24 | 2022-07-22 | 安踏（中国）有限公司 | Wear-resistant, light and anti-slip high-softness-elasticity cushioning EVA (ethylene-vinyl acetate copolymer) foamed sole material and preparation method and application thereof |
| CN115746440A (en) * | 2022-11-23 | 2023-03-07 | 莆田市百合鞋业有限公司 | EVA wear-resistant sole and preparation method thereof |
| CN115850790A (en) * | 2022-12-23 | 2023-03-28 | 晋江国盛新材料科技有限公司 | Foamed thermoplastic elastomer yoga mat with skin layer structure and preparation method thereof |
| CN115847698A (en) * | 2022-12-09 | 2023-03-28 | 安踏（中国）有限公司 | Preparation method of multifunctional sole |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050027025A1 (en) * | 2003-06-26 | 2005-02-03 | Taylor Made Golf Company, Inc. | Shoe components and methods of manufacture |
| US20050148727A1 (en) * | 2004-01-06 | 2005-07-07 | Manoj Ajbani | Thermoplastic elastomer composition |
| CN109251511A (en) * | 2018-09-20 | 2019-01-22 | 安踏（中国）有限公司 | A kind of sport footwear shock-absorbing foamed material, preparation method and its application |
| CN110372951A (en) * | 2019-07-31 | 2019-10-25 | 特步(中国)有限公司 | A kind of high-elastic compression resistant modified shoe material copolymer and preparation method thereof |
| CN111213958A (en) * | 2020-02-18 | 2020-06-02 | 李宁（中国）体育用品有限公司 | Sole and shoe for improving boosting force |
-
2021
- 2021-09-29 CN CN202111151094.9A patent/CN113929953A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050027025A1 (en) * | 2003-06-26 | 2005-02-03 | Taylor Made Golf Company, Inc. | Shoe components and methods of manufacture |
| US20050148727A1 (en) * | 2004-01-06 | 2005-07-07 | Manoj Ajbani | Thermoplastic elastomer composition |
| CN109251511A (en) * | 2018-09-20 | 2019-01-22 | 安踏（中国）有限公司 | A kind of sport footwear shock-absorbing foamed material, preparation method and its application |
| CN110372951A (en) * | 2019-07-31 | 2019-10-25 | 特步(中国)有限公司 | A kind of high-elastic compression resistant modified shoe material copolymer and preparation method thereof |
| CN111213958A (en) * | 2020-02-18 | 2020-06-02 | 李宁（中国）体育用品有限公司 | Sole and shoe for improving boosting force |
Non-Patent Citations (1)
| Title |
|---|
| 中国优质化工产品大辞典编委会: "《中国优质化工产品大辞典》", 31 December 1991, 长春出版社 * |
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|---|---|---|---|---|
| CN114716756A (en) * | 2022-03-17 | 2022-07-08 | 三六一度(中国)有限公司 | High-resilience sole material, preparation method thereof and shoe |
| CN114716756B (en) * | 2022-03-17 | 2023-12-26 | 三六一度(中国)有限公司 | High-resilience sole material, preparation method thereof and shoe |
| CN114702750A (en) * | 2022-04-24 | 2022-07-05 | 安踏（中国）有限公司 | EVA composite foaming material for sports shoe sole and preparation method thereof |
| CN114702750B (en) * | 2022-04-24 | 2023-12-19 | 安踏（中国）有限公司 | EVA composite foaming material for sports shoe sole and preparation method thereof |
| CN114773658A (en) * | 2022-05-24 | 2022-07-22 | 安踏（中国）有限公司 | Wear-resistant, light and anti-slip high-softness-elasticity cushioning EVA (ethylene-vinyl acetate copolymer) foamed sole material and preparation method and application thereof |
| CN114773658B (en) * | 2022-05-24 | 2023-09-08 | 安踏（中国）有限公司 | Wear-resistant, light and anti-slip high-soft-elasticity cushioning EVA (ethylene-vinyl acetate) foam sole material and preparation method and application thereof |
| CN115746440A (en) * | 2022-11-23 | 2023-03-07 | 莆田市百合鞋业有限公司 | EVA wear-resistant sole and preparation method thereof |
| CN115746440B (en) * | 2022-11-23 | 2024-02-09 | 莆田市百合鞋业有限公司 | EVA wear-resistant sole and preparation method thereof |
| CN115847698A (en) * | 2022-12-09 | 2023-03-28 | 安踏（中国）有限公司 | Preparation method of multifunctional sole |
| CN115850790A (en) * | 2022-12-23 | 2023-03-28 | 晋江国盛新材料科技有限公司 | Foamed thermoplastic elastomer yoga mat with skin layer structure and preparation method thereof |
| CN115850790B (en) * | 2022-12-23 | 2024-05-17 | 晋江国盛新材料科技有限公司 | Foaming thermoplastic elastomer yoga mat with cortex structure and preparation method thereof |
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