CN106319683B - A kind of EVA combined insoles materials of ventilative moisture absorption and preparation method thereof - Google Patents

A kind of EVA combined insoles materials of ventilative moisture absorption and preparation method thereof Download PDF

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Publication number
CN106319683B
CN106319683B CN201610639504.7A CN201610639504A CN106319683B CN 106319683 B CN106319683 B CN 106319683B CN 201610639504 A CN201610639504 A CN 201610639504A CN 106319683 B CN106319683 B CN 106319683B
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eva
moisture absorption
grain
materials
preparation
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CN106319683A (en
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叶剑
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Jiangmen Xinhui District Meilisai Non Woven Fabrics Fiber Product Co ltd
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Jiangmen Xinhui Meili Sai Nonwoven Fabric Products Co Ltd
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B17/00—Insoles for insertion, e.g. footbeds or inlays, for attachment to the shoe after the upper has been joined
    • A43B17/003—Insoles for insertion, e.g. footbeds or inlays, for attachment to the shoe after the upper has been joined characterised by the material
    • A43B17/006—Insoles for insertion, e.g. footbeds or inlays, for attachment to the shoe after the upper has been joined characterised by the material multilayered
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B17/00—Insoles for insertion, e.g. footbeds or inlays, for attachment to the shoe after the upper has been joined
    • A43B17/14—Insoles for insertion, e.g. footbeds or inlays, for attachment to the shoe after the upper has been joined made of sponge, rubber, or plastic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/02—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising animal or vegetable substances, e.g. cork, bamboo, starch
    • 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
    • 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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • 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
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/06—Wet spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/14—Applications used for foams

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Textile Engineering (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)

Abstract

The present invention provides EVA combined insoles materials of a kind of ventilative moisture absorption and preparation method thereof, and substantially steps are as follows：(1) grain on orange peel, fragrant citrus pericarp is sheared off, by washing, alkalization, is acidified, breaks up obtained grain crude fibre；(2) grain crude fibre is passed through into pectase degumming, grain fiber is made；(3) grain fiber and EVA lotions are carried out being crosslinked obtained spinning solution, then composite fibre is made in wet spinning；(4) EVA and other auxiliary agent mixer mixings are obtained into mixing sheet stock with open mill slice；(5) composite fibrofelt is made in composite fibre, is molded by vulcanizing press with sheet stock is mixed, obtain the EVA combined insoles materials of ventilative moisture absorption.The insole material that the present invention prepares has preferable hygroscopicity and gas permeability.

Description

A kind of EVA combined insoles materials of ventilative moisture absorption and preparation method thereof
Technical field
The present invention relates to a kind of insole materials, more particularly to the EVA combined insoles material and its system of a kind of ventilative moisture absorption Preparation Method.
Background technology
EVA, full name are Ethylene/vinyl acetate, Chinese entitled ethylene-vinyl acetate copolymer, that is, low Polyethylene foamed foam.EVA products of rubber and plastic are novel environment friendly plastics, have good buffering, antidetonation, heat-insulated, moisture-proof, anti- The advantages that ecsomatics corrode is nontoxic, do not absorb water.EVA products of rubber and plastic can be shaped through design, and shockproof properties are better than polyphenyl second The traditional materials such as alkene (foam), and meet environmental requirement, it is the optimal selection of exported product.
The density of EVA is in 0.91~0.93 (g/cm3) between, the density of EVA is mainly restricted by VA contents, with copolymer Middle VA contents are increased to 40% by 5%, and density is by 0.929g/cm3Increase to 0.974g/cm3, when being less than 5%, density is minimum.EVA Resin applications are very wide.Under normal circumstances, vinyl acetate content is in 5% EVA below, major product be film, electric wire, LDPE modifying agent, adhesive etc.；Vinyl acetate content is elastic film etc. in 5%~10% EVA products；Vinyl acetate content In 20~28% EVA, it is mainly used for hotmelt and coated article；Vinyl acetate content is 5%~45%, major product For film (including agricultural film) and sheet material, injection molding, moulding article, foaming product, hotmelt etc..
Insole material is the important application of EVA expanded materials, it is advantageous that good flexibility, elasticity, pliability, anti- Aging, but there is also certain disadvantages：Itself have the characteristics that not absorb water, instead at scarce when for insole material Point, i.e., hygroscopicity is poor, in addition, its gas permeability is also bad, therefore is not easy to keep dry state when use, is brought to user Harmful effect.
For example, Publication No. CN103275405A, publication date 2013.09.04, application artificial Jinjiang City of Fujian Province Shanxi hundred million The Chinese patent application of footwear material Co., Ltd discloses " a kind of modified EVA microporous foamed shoe-pad material and preparation method thereof ", carries For the physical property of microcellular foam material can be improved with meet a kind of modified EVA microporous foamed shoe-pad material of the needs of market and Preparation method, the modified EVA microporous foamed shoe-pad material group become：1st modifying agent 10~40, the 2nd modifying agent 20~30, 3rd modifying agent 20~30, crosslinking agent 0.5~1.0, assistant crosslinking agent 0.1~0.5, accelerating agent 0.5~1.3, foaming agent 5~9, hair Steep auxiliary agent 2~5, lubricant 0.7.Whole raw materials are put into mixing in mixer；Material after mixing is thick logical on a mill Afterwards, it is packaged, slice is cut into sheet material after material mixing；It weighs sheet material to be placed in mold, heating mould crosslinked foaming, after die sinking to obtain the final product Modified EVA microporous foamed shoe-pad material.The insole material equally exists hygroscopicity and the poor problem of gas permeability.
Invention content
The technical problem to be solved in the present invention is to provide a kind of EVA combined insoles material of ventilative moisture absorption and its preparation sides Method, the insole material prepared have preferable hygroscopicity and gas permeability.
In order to solve the above technical problems, the technical scheme is that：
A kind of preparation method of the EVA combined insoles materials of ventilative moisture absorption, its step are as follows：
(1) 30 minutes wash with distilled water after shearing off the grain on orange peel, fragrant citrus pericarp, 10% matter is added after crushing In the sodium hydroxide solution for measuring concentration, it is 12 to adjust ph values, is heated to 55 DEG C and stirs 2 hours, is washed with deionized after taking-up It to neutrality, is then added in the dilution heat of sulfuric acid of 10% mass concentration, it is 4 to adjust ph values, is heated to 55 DEG C and stirs 2 hours, takes It is washed with distilled water to neutrality after going out, is placed in baking oven at 60 DEG C and dries to constant weight, grain crude fibre is obtained after breaing up；
(2) grain crude fibre is added in distilled water, adds citric acid, pectase, stirring adjusts ph to being uniformly mixed Value is 5.5, is heated to 55 DEG C, and constant temperature stirs 2 hours, takes out postcooling to room temperature, is washed with deionized to neutrality, is placed in baking It is dried to constant weight at 60 DEG C in case, obtains grain fiber；
(3) grain fiber is added in EVA lotions, is heated to 60 DEG C and stirs 30 minutes, it is 3 to adjust ph values, is then added TAC continues stirring 4 hours, and the press filtration under 0.6MPa pressure after taking-up obtains spinning solution after deaeration, spinning solution is added wet Method spinning-drawing machine wet spinning obtains composite fibre, and using sodium sulphate as coagulator when wet spinning, spinning temperature is 60 DEG C, coagulating bath Temperature is 40 DEG C；
(4) EVA, foaming agent, foamed promoter, antioxidant, filler, crosslinking agent, releasing agent are added in mixer, 100 DEG C, be kneaded to being uniformly mixed under the conditions of 40 revs/min of rotor speeds, open mill is transferred to after discharging immediately, is in 100 DEG C, roll spacing Slice under the conditions of 1mm is parked 24 hours at room temperature, obtains mixing sheet stock；
(5) composite fibrofelt is made in composite fibre, is 1 by volume ratio:1 composite fibrofelt mixes sheet stock according to one Layer composite fibrofelt, one layer of alternation method for mixing sheet stock are put into mold, are put into vulcanizing press, are adjusted after closed die Its temperature is 130 DEG C, and pressure 1MPa, heat-insulation pressure keeping demoulds after five minutes, and the EVA that ventilative moisture absorption is obtained after being cooled to room temperature is multiple Close insole material.
Preferably, in step (2) of the present invention, grain crude fibre, distilled water, citric acid, pectase weight ratio be 1:6:0.05:0.1。
Preferably, in step (3) of the present invention, grain fiber, EVA lotions, the weight ratio of TAC are 1:1.2:0.04.
Preferably, in step (4) of the present invention, by weight, 70-76 parts of EVA, 2-5 parts of foaming agent, foaming rush Into 4 parts of agent, 0.1-0.6 parts of antioxidant, 12-16 parts of filler, 0.5-1 parts of crosslinking agent, 3-4 parts of releasing agent.
Preferably, in step (4) of the present invention, foaming agent ADC.
Preferably, in step (4) of the present invention, crosslinking agent DCP.
Preferably, in step (4) of the present invention, antioxidant is irgasfos 168.
Preferably, in step (4) of the present invention, filler is calcium carbonate.
Preferably, in step (4) of the present invention, releasing agent is zinc stearate.
Preferably, in step (4) of the present invention, foamed promoter is zinc oxide.
The EVA combined insoles materials of the above-mentioned preparation-obtained ventilative moisture absorption of preparation method.
Compared with prior art, the invention has the advantages that：
Grain on orange peel, fragrant citrus pericarp is often that people eat the part abandoned after orange, orange, in fact inside grain Containing a large amount of celluloses, hemicellulose, lignin and colloid, the present invention first shears off grain, after washing is clean by alkalization, It is acidified, breaks up obtained grain crude fibre, while eliminating part hemicellulose and lignin, then taken off by pectase Glue thoroughly eliminates hemicellulose, lignin and colloid, has obtained the preferable grain fiber of ventilative and hygroscopicity, while degumming Processing improves the mechanical property of grain fiber, but the compatibility between grain fiber and EVA groups is bad, therefore the present invention It cross-linking reaction is subjected to by crosslinking agent TAC with EVA lotions, spinning solution is made, then spinning solution is passed through into wet spinning The composite fibre that grain fiber is formed with EVA lotions has been obtained, has improved the compatibility between grain fiber and EVA groups, so It is combined with each other afterwards with EVA matrixes and other auxiliary agents by replacing mould pressing method by the form of fibrofelt, has obtained moisture absorption Property, the preferable combined insoles material of gas permeability.
Specific implementation mode
Below in conjunction with specific embodiment, the present invention will be described in detail, herein illustrative examples and explanation of the invention For explaining the present invention, but it is not as a limitation of the invention.
Embodiment 1
The EVA combined insoles materials for moisture absorption of breathing freely are prepared according to the following steps：
(1) 30 minutes wash with distilled water after shearing off the grain on orange peel, fragrant citrus pericarp, 10% matter is added after crushing In the sodium hydroxide solution for measuring concentration, it is 12 to adjust ph values, is heated to 55 DEG C and stirs 2 hours, is washed with deionized after taking-up It to neutrality, is then added in the dilution heat of sulfuric acid of 10% mass concentration, it is 4 to adjust ph values, is heated to 55 DEG C and stirs 2 hours, takes It is washed with distilled water to neutrality after going out, is placed in baking oven at 60 DEG C and dries to constant weight, grain crude fibre is obtained after breaing up；
(2) grain crude fibre is added in distilled water, adds citric acid, pectase, stirring adjusts ph to being uniformly mixed Value is 5.5, is heated to 55 DEG C, and constant temperature stirs 2 hours, takes out postcooling to room temperature, is washed with deionized to neutrality, is placed in baking In case at 60 DEG C dry to constant weight, obtain grain fiber, wherein grain crude fibre, distilled water, citric acid, pectase weight Than being 1:6:0.05:0.1；
(3) grain fiber is added in EVA lotions, is heated to 60 DEG C and stirs 30 minutes, it is 3 to adjust ph values, is then added TAC continues stirring 4 hours, and the press filtration under 0.6MPa pressure after taking-up obtains spinning solution after deaeration, spinning solution is added wet Method spinning-drawing machine wet spinning obtains composite fibre, and using sodium sulphate as coagulator when wet spinning, spinning temperature is 60 DEG C, coagulating bath Temperature is 40 DEG C, wherein grain fiber, EVA lotions, the weight ratio of TAC are 1:1.2:0.04；
(4) by 72 parts of EVA, 4.5 parts by weight ADC, 4 part by weight of zinc oxide, 0.6 parts by weight irgasfos 168,13 weight Part calcium carbonate, 0.6 parts by weight DCP, 3.4 parts by weight zinc stearates are added in mixer, in 100 DEG C, 40 revs/min of rotor speed items Under part be kneaded to be uniformly mixed, open mill is transferred to after discharging immediately, 100 DEG C, roll spacing be 1mm under the conditions of slice, stop at room temperature It puts 24 hours, obtains mixing sheet stock；
(5) composite fibrofelt is made in composite fibre, is 1 by volume ratio:1 composite fibrofelt mixes sheet stock according to one Layer composite fibrofelt, one layer of alternation method for mixing sheet stock are put into mold, are put into vulcanizing press, are adjusted after closed die Its temperature is 130 DEG C, and pressure 1MPa, heat-insulation pressure keeping demoulds after five minutes, and the EVA that ventilative moisture absorption is obtained after being cooled to room temperature is multiple Close insole material.
Embodiment 2
The EVA combined insoles materials for moisture absorption of breathing freely are prepared according to the following steps：
(1) 30 minutes wash with distilled water after shearing off the grain on orange peel, fragrant citrus pericarp, 10% matter is added after crushing In the sodium hydroxide solution for measuring concentration, it is 12 to adjust ph values, is heated to 55 DEG C and stirs 2 hours, is washed with deionized after taking-up It to neutrality, is then added in the dilution heat of sulfuric acid of 10% mass concentration, it is 4 to adjust ph values, is heated to 55 DEG C and stirs 2 hours, takes It is washed with distilled water to neutrality after going out, is placed in baking oven at 60 DEG C and dries to constant weight, grain crude fibre is obtained after breaing up；
(2) grain crude fibre is added in distilled water, adds citric acid, pectase, stirring adjusts ph to being uniformly mixed Value is 5.5, is heated to 55 DEG C, and constant temperature stirs 2 hours, takes out postcooling to room temperature, is washed with deionized to neutrality, is placed in baking In case at 60 DEG C dry to constant weight, obtain grain fiber, wherein grain crude fibre, distilled water, citric acid, pectase weight Than being 1:6:0.05:0.1；
(3) grain fiber is added in EVA lotions, is heated to 60 DEG C and stirs 30 minutes, it is 3 to adjust ph values, is then added TAC continues stirring 4 hours, and the press filtration under 0.6MPa pressure after taking-up obtains spinning solution after deaeration, spinning solution is added wet Method spinning-drawing machine wet spinning obtains composite fibre, and using sodium sulphate as coagulator when wet spinning, spinning temperature is 60 DEG C, coagulating bath Temperature is 40 DEG C, wherein grain fiber, EVA lotions, the weight ratio of TAC are 1:1.2:0.04；
(4) by 70 parts of EVA, 3 parts by weight ADC, 4 part by weight of zinc oxide, 0.4 parts by weight irgasfos 168,12.5 weight Part calcium carbonate, 0.8 parts by weight DCP, 3.2 parts by weight zinc stearates are added in mixer, in 100 DEG C, 40 revs/min of rotor speed items Under part be kneaded to be uniformly mixed, open mill is transferred to after discharging immediately, 100 DEG C, roll spacing be 1mm under the conditions of slice, stop at room temperature It puts 24 hours, obtains mixing sheet stock；
(5) composite fibrofelt is made in composite fibre, is 1 by volume ratio:1 composite fibrofelt mixes sheet stock according to one Layer composite fibrofelt, one layer of alternation method for mixing sheet stock are put into mold, are put into vulcanizing press, are adjusted after closed die Its temperature is 130 DEG C, and pressure 1MPa, heat-insulation pressure keeping demoulds after five minutes, and the EVA that ventilative moisture absorption is obtained after being cooled to room temperature is multiple Close insole material.
Embodiment 3
The EVA combined insoles materials for moisture absorption of breathing freely are prepared according to the following steps：
(1) 30 minutes wash with distilled water after shearing off the grain on orange peel, fragrant citrus pericarp, 10% matter is added after crushing In the sodium hydroxide solution for measuring concentration, it is 12 to adjust ph values, is heated to 55 DEG C and stirs 2 hours, is washed with deionized after taking-up It to neutrality, is then added in the dilution heat of sulfuric acid of 10% mass concentration, it is 4 to adjust ph values, is heated to 55 DEG C and stirs 2 hours, takes It is washed with distilled water to neutrality after going out, is placed in baking oven at 60 DEG C and dries to constant weight, grain crude fibre is obtained after breaing up；
(2) grain crude fibre is added in distilled water, adds citric acid, pectase, stirring adjusts ph to being uniformly mixed Value is 5.5, is heated to 55 DEG C, and constant temperature stirs 2 hours, takes out postcooling to room temperature, is washed with deionized to neutrality, is placed in baking In case at 60 DEG C dry to constant weight, obtain grain fiber, wherein grain crude fibre, distilled water, citric acid, pectase weight Than being 1:6:0.05:0.1；
(3) grain fiber is added in EVA lotions, is heated to 60 DEG C and stirs 30 minutes, it is 3 to adjust ph values, is then added TAC continues stirring 4 hours, and the press filtration under 0.6MPa pressure after taking-up obtains spinning solution after deaeration, spinning solution is added wet Method spinning-drawing machine wet spinning obtains composite fibre, and using sodium sulphate as coagulator when wet spinning, spinning temperature is 60 DEG C, coagulating bath Temperature is 40 DEG C, wherein grain fiber, EVA lotions, the weight ratio of TAC are 1:1.2:0.04；
(4) by 75 parts of EVA, 3.5 parts by weight ADC, 4 part by weight of zinc oxide, 0.5 parts by weight irgasfos 168,15 weight Part calcium carbonate, 1 parts by weight DCP, 3.5 parts by weight zinc stearates are added in mixer, in 100 DEG C, 40 revs/min of rotor speed conditions It is lower be kneaded to be uniformly mixed, open mill is transferred to after discharging immediately, 100 DEG C, roll spacing be 1mm under the conditions of slice, park at room temperature 24 hours, obtain mixing sheet stock；
(5) composite fibrofelt is made in composite fibre, is 1 by volume ratio:1 composite fibrofelt mixes sheet stock according to one Layer composite fibrofelt, one layer of alternation method for mixing sheet stock are put into mold, are put into vulcanizing press, are adjusted after closed die Its temperature is 130 DEG C, and pressure 1MPa, heat-insulation pressure keeping demoulds after five minutes, and the EVA that ventilative moisture absorption is obtained after being cooled to room temperature is multiple Close insole material.
Embodiment 4
The EVA combined insoles materials for moisture absorption of breathing freely are prepared according to the following steps：
(1) 30 minutes wash with distilled water after shearing off the grain on orange peel, fragrant citrus pericarp, 10% matter is added after crushing In the sodium hydroxide solution for measuring concentration, it is 12 to adjust ph values, is heated to 55 DEG C and stirs 2 hours, is washed with deionized after taking-up It to neutrality, is then added in the dilution heat of sulfuric acid of 10% mass concentration, it is 4 to adjust ph values, is heated to 55 DEG C and stirs 2 hours, takes It is washed with distilled water to neutrality after going out, is placed in baking oven at 60 DEG C and dries to constant weight, grain crude fibre is obtained after breaing up；
(2) grain crude fibre is added in distilled water, adds citric acid, pectase, stirring adjusts ph to being uniformly mixed Value is 5.5, is heated to 55 DEG C, and constant temperature stirs 2 hours, takes out postcooling to room temperature, is washed with deionized to neutrality, is placed in baking In case at 60 DEG C dry to constant weight, obtain grain fiber, wherein grain crude fibre, distilled water, citric acid, pectase weight Than being 1:6:0.05:0.1；
(3) grain fiber is added in EVA lotions, is heated to 60 DEG C and stirs 30 minutes, it is 3 to adjust ph values, is then added TAC continues stirring 4 hours, and the press filtration under 0.6MPa pressure after taking-up obtains spinning solution after deaeration, spinning solution is added wet Method spinning-drawing machine wet spinning obtains composite fibre, and using sodium sulphate as coagulator when wet spinning, spinning temperature is 60 DEG C, coagulating bath Temperature is 40 DEG C, wherein grain fiber, EVA lotions, the weight ratio of TAC are 1:1.2:0.04；
(4) by 76 parts of EVA, 2 parts by weight ADC, 4 part by weight of zinc oxide, 0.3 parts by weight irgasfos 168,12 parts by weight Calcium carbonate, 0.5 parts by weight DCP, 4 parts by weight zinc stearates are added in mixer, under the conditions of 100 DEG C, 40 revs/min of rotor speed Be kneaded to be uniformly mixed, open mill is transferred to after discharging immediately, 100 DEG C, roll spacing be 1mm under the conditions of slice, park 24 at room temperature Hour, obtain mixing sheet stock；
(5) composite fibrofelt is made in composite fibre, is 1 by volume ratio:1 composite fibrofelt mixes sheet stock according to one Layer composite fibrofelt, one layer of alternation method for mixing sheet stock are put into mold, are put into vulcanizing press, are adjusted after closed die Its temperature is 130 DEG C, and pressure 1MPa, heat-insulation pressure keeping demoulds after five minutes, and the EVA that ventilative moisture absorption is obtained after being cooled to room temperature is multiple Close insole material.
Embodiment 5
The EVA combined insoles materials for moisture absorption of breathing freely are prepared according to the following steps：
(1) 30 minutes wash with distilled water after shearing off the grain on orange peel, fragrant citrus pericarp, 10% matter is added after crushing In the sodium hydroxide solution for measuring concentration, it is 12 to adjust ph values, is heated to 55 DEG C and stirs 2 hours, is washed with deionized after taking-up It to neutrality, is then added in the dilution heat of sulfuric acid of 10% mass concentration, it is 4 to adjust ph values, is heated to 55 DEG C and stirs 2 hours, takes It is washed with distilled water to neutrality after going out, is placed in baking oven at 60 DEG C and dries to constant weight, grain crude fibre is obtained after breaing up；
(2) grain crude fibre is added in distilled water, adds citric acid, pectase, stirring adjusts ph to being uniformly mixed Value is 5.5, is heated to 55 DEG C, and constant temperature stirs 2 hours, takes out postcooling to room temperature, is washed with deionized to neutrality, is placed in baking In case at 60 DEG C dry to constant weight, obtain grain fiber, wherein grain crude fibre, distilled water, citric acid, pectase weight Than being 1:6:0.05:0.1；
(3) grain fiber is added in EVA lotions, is heated to 60 DEG C and stirs 30 minutes, it is 3 to adjust ph values, is then added TAC continues stirring 4 hours, and the press filtration under 0.6MPa pressure after taking-up obtains spinning solution after deaeration, spinning solution is added wet Method spinning-drawing machine wet spinning obtains composite fibre, and using sodium sulphate as coagulator when wet spinning, spinning temperature is 60 DEG C, coagulating bath Temperature is 40 DEG C, wherein grain fiber, EVA lotions, the weight ratio of TAC are 1:1.2:0.04；
(4) by 73 parts of EVA, 5 parts by weight ADC, 4 part by weight of zinc oxide, 0.1 parts by weight irgasfos 168,14 parts by weight Calcium carbonate, 0.7 parts by weight DCP, 3.6 parts by weight zinc stearates are added in mixer, in 100 DEG C, 40 revs/min of rotor speed conditions It is lower be kneaded to be uniformly mixed, open mill is transferred to after discharging immediately, 100 DEG C, roll spacing be 1mm under the conditions of slice, park at room temperature 24 hours, obtain mixing sheet stock；
(5) composite fibrofelt is made in composite fibre, is 1 by volume ratio:1 composite fibrofelt mixes sheet stock according to one Layer composite fibrofelt, one layer of alternation method for mixing sheet stock are put into mold, are put into vulcanizing press, are adjusted after closed die Its temperature is 130 DEG C, and pressure 1MPa, heat-insulation pressure keeping demoulds after five minutes, and the EVA that ventilative moisture absorption is obtained after being cooled to room temperature is multiple Close insole material.
Embodiment 6
The EVA combined insoles materials of ventilative moisture absorption are prepared according to the following steps：
The EVA combined insoles materials for moisture absorption of breathing freely are prepared according to the following steps：
(1) 30 minutes wash with distilled water after shearing off the grain on orange peel, fragrant citrus pericarp, 10% matter is added after crushing In the sodium hydroxide solution for measuring concentration, it is 12 to adjust ph values, is heated to 55 DEG C and stirs 2 hours, is washed with deionized after taking-up It to neutrality, is then added in the dilution heat of sulfuric acid of 10% mass concentration, it is 4 to adjust ph values, is heated to 55 DEG C and stirs 2 hours, takes It is washed with distilled water to neutrality after going out, is placed in baking oven at 60 DEG C and dries to constant weight, grain crude fibre is obtained after breaing up；
(2) grain crude fibre is added in distilled water, adds citric acid, pectase, stirring adjusts ph to being uniformly mixed Value is 5.5, is heated to 55 DEG C, and constant temperature stirs 2 hours, takes out postcooling to room temperature, is washed with deionized to neutrality, is placed in baking In case at 60 DEG C dry to constant weight, obtain grain fiber, wherein grain crude fibre, distilled water, citric acid, pectase weight Than being 1:6:0.05:0.1；
(3) grain fiber is added in EVA lotions, is heated to 60 DEG C and stirs 30 minutes, it is 3 to adjust ph values, is then added TAC continues stirring 4 hours, and the press filtration under 0.6MPa pressure after taking-up obtains spinning solution after deaeration, spinning solution is added wet Method spinning-drawing machine wet spinning obtains composite fibre, and using sodium sulphate as coagulator when wet spinning, spinning temperature is 60 DEG C, coagulating bath Temperature is 40 DEG C, wherein grain fiber, EVA lotions, the weight ratio of TAC are 1:1.2:0.04；
(4) by 74 parts of EVA, 4 parts by weight ADC, 4 part by weight of zinc oxide, 0.2 parts by weight irgasfos 168,16 parts by weight Calcium carbonate, 0.9 parts by weight DCP, 3 parts by weight zinc stearates are added in mixer, under the conditions of 100 DEG C, 40 revs/min of rotor speed Be kneaded to be uniformly mixed, open mill is transferred to after discharging immediately, 100 DEG C, roll spacing be 1mm under the conditions of slice, park 24 at room temperature Hour, obtain mixing sheet stock；
(5) composite fibrofelt is made in composite fibre, is 1 by volume ratio:1 composite fibrofelt mixes sheet stock according to one Layer composite fibrofelt, one layer of alternation method for mixing sheet stock are put into mold, are put into vulcanizing press, are adjusted after closed die Its temperature is 130 DEG C, and pressure 1MPa, heat-insulation pressure keeping demoulds after five minutes, and the EVA that ventilative moisture absorption is obtained after being cooled to room temperature is multiple Close insole material.
The hygroscopicity and gas permeability of insole material and comparative example made from embodiment 1-6 are tested, comparative example is The Chinese patent application of Publication No. CN103275405A；Hygroscopicity refers to GB/T 1690-2010 standards, by 25 DEG C of each material Under be soaked in water, after 24 hours take out measure water absorption rate, water absorption rate is higher to show that hygroscopicity is better；Permeability test is using saturating Gas tester tests the Air permenbility of each material, and test gas is nitrogen, and the testing time is 24 hours, and test pressure is 0.2MPa, Air permenbility show that more greatly gas permeability is better.
Test result is as follows shown in table：
As seen from the above table, the water absorption rate of insole material made from 1-6 of the embodiment of the present invention and Air permenbility are far above Comparative example has preferable hygroscopicity and gas permeability.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe The personage for knowing this technology can all carry out modifications and changes to above-described embodiment without violating the spirit and scope of the present invention.Cause This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as At all equivalent modifications or change, should by the present invention claim be covered.

Claims (10)

1. a kind of preparation method of the EVA combined insoles materials of ventilative moisture absorption, which is characterized in that its step is：
(1) 30 minutes wash with distilled water after shearing off the grain on orange peel, fragrant citrus pericarp, it is dense that 10% mass is added after crushing In the sodium hydroxide solution of degree, it is 12 to adjust pH value, is heated to 55 DEG C and stirs 2 hours, is washed with deionized into after taking-up Property, it is then added in the dilution heat of sulfuric acid of 10% mass concentration, it is 4 to adjust pH value, is heated to 55 DEG C and stirs 2 hours, after taking-up It is washed with distilled water to neutrality, is placed in baking oven at 60 DEG C and dries to constant weight, grain crude fibre is obtained after breaing up；
(2) grain crude fibre is added in distilled water, adds citric acid, pectase, to being uniformly mixed, adjusting pH value is for stirring 5.5,55 DEG C are heated to, constant temperature stirs 2 hours, takes out postcooling to room temperature, is washed with deionized to neutrality, is placed in baking oven It is dried to constant weight at 60 DEG C, obtains grain fiber；
(3) will grain fiber be added EVA lotions in, be heated to 60 DEG C stir 30 minutes, adjust pH value be 3, then be added TAC after Continuous stirring 4 hours, the press filtration under 0.6MPa pressure after taking-up obtains spinning solution after deaeration, Wet-spinning is added in spinning solution Silk machine wet spinning obtains composite fibre, and using sodium sulphate as coagulator when wet spinning, spinning temperature is 60 DEG C, coagulation bath temperature It is 40 DEG C；
(4) by EVA, foaming agent, foamed promoter, antioxidant, filler, crosslinking agent, releasing agent be added mixer in, 100 DEG C, It is kneaded under the conditions of 40 revs/min of rotor speeds to being uniformly mixed, is transferred to open mill after discharging immediately, be 1mm items in 100 DEG C, roll spacing Slice under part is parked 24 hours at room temperature, obtains mixing sheet stock；
(5) composite fibrofelt is made in composite fibre, is 1 by volume ratio:1 composite fibrofelt, mixing sheet stock are multiple according to one layer Condensating fiber felt, one layer of alternation method for mixing sheet stock are put into mold, are put into vulcanizing press after closed die, its temperature is adjusted Degree is 130 DEG C, and pressure 1MPa, heat-insulation pressure keeping demoulds after five minutes, and the EVA composite shoes of ventilative moisture absorption are obtained after being cooled to room temperature Cushion material.
2. a kind of preparation method of the EVA combined insoles materials of ventilative moisture absorption according to claim 1, it is characterised in that： In the step (2), grain crude fibre, distilled water, citric acid, pectase weight ratio be 1:6:0.05:0.1.
3. a kind of preparation method of the EVA combined insoles materials of ventilative moisture absorption according to claim 1, it is characterised in that： In the step (3), grain fiber, EVA lotions, the weight ratio of TAC are 1:1.2:0.04.
4. a kind of preparation method of the EVA combined insoles materials of ventilative moisture absorption according to claim 1, it is characterised in that： In the step (4), by weight, 70-76 parts of EVA, 2-5 parts of foaming agent, 4 parts of foamed promoter, antioxidant 0.1-0.6 Part, 12-16 parts of filler, 0.5-1 parts of crosslinking agent, 3-4 parts of releasing agent.
5. a kind of preparation method of the EVA combined insoles materials of ventilative moisture absorption according to claim 1, it is characterised in that： In the step (4), foaming agent ADC.
6. a kind of preparation method of the EVA combined insoles materials of ventilative moisture absorption according to claim 1, it is characterised in that： In the step (4), crosslinking agent DCP.
7. a kind of preparation method of the EVA combined insoles materials of ventilative moisture absorption according to claim 1, it is characterised in that： In the step (4), antioxidant is irgasfos 168.
8. a kind of preparation method of the EVA combined insoles materials of ventilative moisture absorption according to claim 1, it is characterised in that： In the step (4), filler is calcium carbonate.
9. a kind of preparation method of the EVA combined insoles materials of ventilative moisture absorption according to claim 1, it is characterised in that： In the step (4), releasing agent is zinc stearate, and foamed promoter is zinc oxide.
10. a kind of preparation method of the EVA combined insoles materials of ventilative moisture absorption described in claim 1 is preparation-obtained ventilative The EVA combined insoles materials of moisture absorption.
CN201610639504.7A 2016-08-04 2016-08-04 A kind of EVA combined insoles materials of ventilative moisture absorption and preparation method thereof Active CN106319683B (en)

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Publication number Priority date Publication date Assignee Title
US4461099A (en) * 1983-02-28 1984-07-24 Bailly Richard Louis Molded odor-absorbing laminate
EP0664970A1 (en) * 1993-12-28 1995-08-02 Mizuno Corporation Cup-like insole
US6346210B1 (en) * 1997-02-14 2002-02-12 The Rockport Company, Llc Method of shaping susceptor-based polymeric materials
CN1865334A (en) * 2006-05-23 2006-11-22 福州大学 Preparation method of EVA/plant fiber foamed composite material for shoes
CN204682658U (en) * 2015-04-29 2015-10-07 庄景平 A kind of anticancer taxad sole
CN103910925B (en) * 2014-04-21 2016-02-03 南京东亚橡塑制品有限公司 A kind of tasteless EVA material as sole and preparation method thereof
CN105623066A (en) * 2016-02-25 2016-06-01 苏州市景荣科技有限公司 Manufacturing method of antibacterial air-permeable foaming insole material

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4461099A (en) * 1983-02-28 1984-07-24 Bailly Richard Louis Molded odor-absorbing laminate
EP0664970A1 (en) * 1993-12-28 1995-08-02 Mizuno Corporation Cup-like insole
US6346210B1 (en) * 1997-02-14 2002-02-12 The Rockport Company, Llc Method of shaping susceptor-based polymeric materials
CN1865334A (en) * 2006-05-23 2006-11-22 福州大学 Preparation method of EVA/plant fiber foamed composite material for shoes
CN103910925B (en) * 2014-04-21 2016-02-03 南京东亚橡塑制品有限公司 A kind of tasteless EVA material as sole and preparation method thereof
CN204682658U (en) * 2015-04-29 2015-10-07 庄景平 A kind of anticancer taxad sole
CN105623066A (en) * 2016-02-25 2016-06-01 苏州市景荣科技有限公司 Manufacturing method of antibacterial air-permeable foaming insole material

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