CN108485143A - Shoes expanded material and preparation method thereof - Google Patents
Shoes expanded material and preparation method thereof Download PDFInfo
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- CN108485143A CN108485143A CN201810265292.XA CN201810265292A CN108485143A CN 108485143 A CN108485143 A CN 108485143A CN 201810265292 A CN201810265292 A CN 201810265292A CN 108485143 A CN108485143 A CN 108485143A
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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
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
-
- 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
- C08J9/0066—Use of inorganic compounding ingredients
-
- 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
- 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
- C08J2331/00—Characterised by the use of copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, or carbonic acid, or of a haloformic acid
- C08J2331/02—Characterised by the use of omopolymers or copolymers of esters of monocarboxylic acids
- C08J2331/04—Homopolymers or copolymers of vinyl acetate
-
- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—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
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
- C08J2423/28—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by reaction with halogens or halogen-containing 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
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Emergency Medicine (AREA)
- Inorganic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of shoes expanded materials and preparation method thereof.In terms of the weight percent of the shoes expanded material, including：Base-material, foaming agent, crosslinking agent, assistant crosslinking agent, activator and filler；Wherein, it is in terms of 100% by the gross mass of the base-material, the base-material includes：Ethylene vinyl acetate rubber：30 49.9%, preferably 35 45%；Ethylene vinyl acetate resin：10 30%, preferably 15 25%；Styrene ethylene butylene styrene block copolymer：20 40%, preferably 25 35%；Brombutyl：5 30%, preferably 5 20%.The foam structure of the shoes expanded material of the present invention is uniform, has a preferable shock absorption, deformation resistant, light weight and at low cost, and according to the difference of each component material mixture ratio, the controllable purpose of density, elasticity, hardness, percent thermal shrinkage may be implemented.
Description
Technical field
The present invention relates to a kind of shoes expanded materials and preparation method thereof, belong to field of new materials.
Background technology
In order to reduce physical consumption, improve snugness of fit, the high-elastic shock-absorbing foamed material of lightweight has become Sports shoe sole
The Main way of development.Meanwhile Chinese as world sports shoes big producer, low gear during most products belong to, homogeneity,
Low price competition is quite serious.Footwear quality scale is promoted by footwear material performance, the price war of current kinetic shoes is reversed, has
Important realistic meaning.
Existing manufacture vibration absorptive material method is mainly with neoprene, acrylonitrile-butadiene rubber (NBR), styrene-
Isoprene-styrene block copolymer (SIS), thermoplastic elastomer (TPE) (TPE), polyurethane (PU)/thermoplastic polyurethane
(TPU) or the foamed molding of elastomeric materials such as the ethylene-vinyl acetate of the vinylacetate of low content (VA) (EVA)
After be made.
Patent application CN2699704Y provides a kind of urethane composition of environmental protection (PU gels) and thermoplastic polyurethane
(TPU) material preparation is used for the Shock absorbing cushion of sole；Patent application CN 103030842A provide a kind of wear-resisting suction for sole
Rubber material and preparation method thereof is shaken, wear-resisting shock-absorbing rubber material used is the combination of isoprene rubber and butadiene rubber
Object.Patent application CN2904707Y provides a kind of Shock absorption shoe-pad in internal setting shock suction body, which is crystallized by elasticity
Body and the protective layer composition for being coated on elastic crystalline solid, the elastic crystalline solid is by 4- butanediols, polyvinyl chloride, ethylene glycol
Certain temperature crystallizes after methyl ether, ethylenediamine component mixing.
Patent application CN102051003A provides a kind of by hydrogenated styrene-butadiene copolymer, ethylene-octene copolymerization
Object, haloflex mix the shock-absorbing rubber-plastic composite material of composition according to a certain percentage.Patent application CN102898738A is provided
A kind of manufacturing method of the continuous athletic shoe sole of memory bubble.The raw material of the sole is styrene-butadiene copolymer, polystyrene
Fiber and brombutyl form, and have prepared the sole sample that elasticity is less than 10%, with excellent damping and persistently
Anti- cushion performance.
But the material used in above method either contains chlorine to environmentally friendly unfavorable or higher price, is not appropriate for using
In footwear material.Meanwhile above method is mostly crosslinked with sulfide, has certain limitation.Also useful low acetic acid in the market
The ethylene-vinyl acetate of ethylene ester content carries out foaming and prepares vibration absorptive material, and this method can effectively reduce cost, but make
Standby material impact rebound value is higher, when carrying out damping performance test, it is found that its deceleration is big, and rebound rate is high, reach compared with
Scheduled shock-absorbing effect could be obtained when big buffer distance.
In addition, gas permeability that the ethylene-vinyl acetate rubber (EVM) containing high vinyl acetate content has had and resistance to
Oiliness, low impact rebound degree and compression set rate and high damping capacity, are ideal vibration-absorptive materials.Patent
CN101293386A describes a kind of ethylene-vinyl acetate rubber (VA with high vinyl acetate content：Based on 70-90%)
The manufacturing method of the shock absorption foamed plastic of base-material is prepared for the foaming material of low bounce-back rate and short buffer distance by hot-pressing and foaming molding
Material.However, with the increase of vinyl acetate content, the processing viscosity of ethylene-vinyl acetate rubber is low, and the low temperature of material is tough
Property be deteriorated, dimensional stability is bad, therefore, has to prepare shock-absorbing foaming shoe material using ethylene-vinyl acetate rubber as base-material
Certain limitation.
As it can be seen that material used in the prior art, larger containing the chlorine or density for polluting larger.Separately
Outside, polyurethane material the problem of there is also not hydrolysis, the application in footwear material have larger drawback.Therefore, one is researched and developed
There is kind excellent vibration absorption and pressure resistance to become performance, and the shoes expanded material of good stability of the dimension, the technology for becoming urgently to be resolved hurrily are asked
Topic.
Invention content
Problems to be solved by the invention
For the technical problems in the prior art, the present invention provides with excellent vibration absorption and pressure resistance become performance, and
Good stability of the dimension, light-weighted shoes expanded material.Overcome that processing viscosity is low, and the low-temperature flexibility of material is deteriorated, size is steady
It is qualitative bad；When carrying out damping performance test, deceleration is big, and impact rebound degree is higher, when reaching larger buffer distance
The technical issues of scheduled shock-absorbing effect could be obtained.
Further, the present invention also provides a kind of preparation methods of shoes expanded material.
The solution to the problem
The present invention provides a kind of shoes composition, foam, including：Base-material, foaming agent, crosslinking agent, assistant crosslinking agent, activator
And filler；Wherein,
It is in terms of 100% by the gross mass of the base-material, the base-material includes：
Ethylene-vinyl acetate rubber：30-49.9%, preferably 35-45%；
Ethylene-vinyl acetate resin：10-30%, preferably 15-25%；
Styrene-ethylene-butylene-styrene block copolymer：20-40%, preferably 25-35%；
Brombutyl：5-30%, preferably 5-20%.
Shoes composition, foam according to the present invention, wherein vinylacetate list in the ethylene-vinyl acetate rubber
The content of body unit is 40-80 mass %, preferably 55-80 mass %.
Shoes composition, foam according to the present invention, wherein vinylacetate list in the ethylene-vinyl acetate resin
The content of body unit is 14-28 mass %, preferably 20-28 mass %.
Shoes composition, foam according to the present invention, wherein by the gross mass of the base-material be 100% in terms of, the foaming
The addition of agent is 3-5%, and the addition of the crosslinking agent is 0.5-1.5%, and the addition of the assistant crosslinking agent is 0.3-
1%, the addition of the activator is 1-6%, and the addition of the filler is 10-30%.
Shoes composition, foam according to the present invention, wherein the foaming agent includes azodicarbonamide, N, bis- nitrous of N-
Base pentamethylene tetramine, 4,4 '-oxybis-benzenesulfonyl hydrazides, sodium bicarbonate, ammonium carbonate, ammonium hydrogen carbonate and one kind in ammonium nilrite or
Two or more combinations.
Shoes composition, foam according to the present invention, wherein the crosslinking agent includes peroxide cross-linking agent, the peroxide
Compound crosslinking agent is preferably one or two kinds of in cumyl peroxide and 1,4 bis tert butyl peroxy isopropyl benzene；It is described to help friendship
It includes Triallyl isocyanurate, trimethylol-propane trimethacrylate and trimethylolpropane trimethacrylate to join agent
One or more of combination.
Shoes composition, foam according to the present invention, wherein the activator includes zinc oxide and/or zinc stearate；Institute
State the combination that filler includes one or more of talcum powder, calcium carbonate, white carbon and montmorillonite.
Shoes composition, foam according to the present invention, wherein the shoes further include with composition, foam：Compatilizer, antioxygen
A combination of one or more in agent, anti-wear agent, coupling agent and pigment；
It is in terms of 100% by the gross mass of the base-material, the addition of the compatilizer is 1-5%；The antioxidant
Addition is 0.5-3%；The addition of the anti-wear agent is 0.5-10%；The addition of the coupling agent is 0.5-6%；It is described
The addition of pigment is 1-6%.
Shoes composition, foam according to the present invention, wherein the compatilizer includes the ethylene-octene of maleic anhydride grafting
The ethylene-vinyl acetate tree that block copolymer, the ethylene-octene random copolymer of maleic anhydride grafting, maleic anhydride are grafted
The combination of one or more of the ldpe resin that fat and maleic anhydride are grafted.
The present invention also provides a kind of preparation methods of shoes composition, foam according to the present invention, wherein including will be described
The step of each component mixing of shoes composition, foam.
The effect of invention
The foam structure of the shoes expanded material of the present invention is uniform, has a preferable shock absorption, deformation resistant, light weight and at
This is low, and according to the difference of each component material mixture ratio, the controllable purpose of density, elasticity, hardness, percent thermal shrinkage may be implemented.
Further, the preparation method of shoes expanded material of the invention, the cost of the preparation method is low, processing method is simple
It is single, it is suitble to the production of industrial-scale.
Specific implementation mode
It will be detailed below various exemplary embodiments, feature and the aspect of the present invention.Dedicated word " example herein
Property " mean " being used as example, embodiment or illustrative ".Any embodiment here as illustrated by " exemplary " should not necessarily be construed as
Preferred or advantageous over other embodiments.
In addition, in order to better illustrate the present invention, numerous details is given in specific implementation mode below.
It will be appreciated by those skilled in the art that without certain details, the present invention can equally be implemented.In other example,
Method well known to those skilled in the art, means, equipment and step are not described in detail, in order to highlight the master of the present invention
Purport.
The present invention provides a kind of shoes composition, foam, including：Base-material, foaming agent, crosslinking agent, assistant crosslinking agent, activator
And filler；Wherein,
It is in terms of 100% by the gross mass of the base-material, the base-material includes：
Ethylene-vinyl acetate rubber：30-49.9%, preferably 35-45%；
Ethylene-vinyl acetate resin：10-30%, preferably 15-25%；
Styrene-ethylene-butylene-styrene block copolymer：20-40%, preferably 25-35%；
Brombutyl：5-30%, preferably 5-20%.
In general, each component of ethylene-vinyl acetate copolymer is also different with the different content of synthesis technology,
The difference of ethylene-vinyl acetate resin and ethylene-vinyl acetate rubber is Vinyl Acetate Monomer list in macromolecular
The content of member, when the content of Vinyl Acetate Monomer unit is less than 40%, what polymer embodied is plasticity, referred to as ethylene-vinegar
Vinyl acetate resin；When the content of Vinyl Acetate Monomer unit is 40% or more, what polymer embodied is the performance of rubber,
Referred to as ethylene-vinyl acetate rubber.
Specifically, the ethylene-vinyl acetate rubber (EVM) of the present invention can refer to vinylacetate (VA) monomer list
The content of member is a kind of ethylene-vinyl acetate copolymer of 40-80 mass %, and main chain is the nonpolar methylene base junction of saturation
Structure has excellent high temperature resistant, resistance to ozone and weather resistance so its chemical stability is good.Polar side chain vinylacetate
(VA) introducing destroys the regularity of main chain, reduces the crystal property of polymer (when vinylacetate (VA) content is higher than
When 55 mass %, copolymer is amorphous), while imparting the good compliance of copolymer.It was found by the inventors of the present invention that with
The increase of the content of vinylacetate (VA), the polarity of ethylene-vinyl acetate rubber increases, and shoes composition, foam rushes
It hits rebound degree and compression set rate then decreases.
Shoes composition, foam according to the present invention, Vinyl Acetate Monomer list in the ethylene-vinyl acetate rubber
The content of member is the 40 mass % of mass %~80, preferably 55 mass %-80 mass %, more preferably 70 mass %-80 matter
Measure %.In addition, ethylene-vinyl acetate rubber also has wider glass transition temperature range, as vinylacetate (VA)
When the content of monomeric unit is 70 mass %-80 mass %, glass transition temperature Tg is fallen in the range of -5~30 DEG C, and is hindered
The peak value of Buddhist nun factor t an δ is 0.93, shows that material has more preferably damping capacity.
In the present invention, it is in terms of 100% by the gross mass of the base-material, the addition of ethylene-vinyl acetate rubber exists
Between 30-49.9%, preferably between 35-45%.When the addition of ethylene-vinyl acetate rubber is between 30-49.9%
When, the preferable damping capacity of shoes composition, foam can be assigned, pressure resistance becomes performance.
Shoes composition, foam according to the present invention, with the total weight of the ethylene-vinyl acetate resin, the second
In alkene-vinyl acetate resin, the content of ethylene-vinyl acetate monomeric unit is 14 mass %-28 mass %, preferably 20
Quality %-28 mass %.Ethylene-vinyl acetate resin can provide the melt strength that composite material is suitble to foaming, while ethylene-
Vinyl acetate resin can match with the rate of cure after ethylene-vinyl acetate blend rubber with expansion rate, to make
It is standby to obtain the uniform expanded material of foam structure.
In the present invention, it is in terms of 100% by the gross mass of the base-material, the addition of ethylene-vinyl acetate resin exists
Between 10-30%, preferably between 15-25%.It, can be with when the addition of ethylene-vinyl acetate resin is between 10-30%
There is provided the melt strength for being suitble to foaming so that shoes composition, foam assigns shoes composition, foam more suitable for foaming
Preferably pressure resistance becomes performance.
Styrene-ethylene-butylene-styrene block copolymer (SEBS) is using polystyrene as end segment, with polybutadiene
The ethylene-butene copolymer that alkene adds hydrogen to obtain is the linear tri-block copolymer of intermediate elastic block.Styrene-ethylene-butadiene-benzene
Ethylene block copolymer is free of unsaturated double-bond, with good stability and resistance to ag(e)ing.
The inventors discovered that being applied in shoes expanded material when by styrene-ethylene-butylene-styrene block copolymer
When middle, the compression set rate of shoes expanded material, especially shrinking percentage etc. can be reduced, composite material can be effectively improved
Dimensional stability efficiently solves the bad defect of vibration-absorptive material dimensional stability.
In the present invention, it is in terms of 100% by the gross mass of the base-material, styrene-ethylene-butylene-styrene block is total
The addition of polymers is between 20-40%, preferably between 25-35%.When styrene-ethylene-butylene-styrene block copolymerization
When the addition of object is between 20-40%, shoes have preferable dimensional stability and compression set with composition, foam.
When the addition of styrene-ethylene-butylene-styrene block copolymer is less than 20%, preferable dimensional stability cannot be provided,
When the addition of styrene-ethylene-butylene-styrene block copolymer is more than 40%, and improve shoes composition, foam
Hardness and elasticity, damping effect are deteriorated.
Brombutyl (BIIR) is the isobutylene-isoprene copolymer elastomer containing active bromine.Due to bromination
Butyl rubber possesses the main chain that butyl rubber is substantially saturated, so its multiple performance characteristic with butyl polymer, such as higher
Physical strength, preferable hypotonicity, ageing-resistant, heat-proof aging and Weather-resistant etc..
The inventors discovered that by using a certain amount of brombutyl, tearing for shoes composition, foam can be improved
Fragility energy and elongation at break, and impact rebound degree, compression set rate can be further decreased etc..
In the present invention, be in terms of 100% by the gross mass of the base-material, the addition of brombutyl 5-30% it
Between, preferably between 5-20%.When the addition of brombutyl is between 5-30%, it is possible to provide shoes composition, foam compared with
Suitable melt strength and other physical mechanical properties.When the addition of brombutyl is less than 5%, it cannot provide enough
Melt strength；When the addition of brombutyl is more than 30%, it is not suitable for foaming, the density of material is bigger than normal, and damping performance subtracts
It is weak.
The inventors discovered that when the density for the composition being prepared is relatively low, can be formed abscess be connected and steep etc. it is existing
As compression set can become larger, and shock-absorbing effect weakens, and dimensional stability can also be deteriorated, but by the present invention in that be blended with EVM
EVA, SEBS and BIIR, to realize shoes composition, foam multiple performance balance.Therefore, shoes of the invention foaming group
Object is closed, while meeting required mechanical property, also there is low density, impact rebound degree and Compression Set rate
And higher dimensional stability, while shoes composition, foam itself is again with performances such as ventilative, heat-resisting, weather-proof and oil resistants.
The shoes composition, foam of the present invention is the addition of the foaming agent in terms of 100% by the gross mass of the base-material
For 3-5%, such as：Can be 4-5%.The foaming agent includes azodicarbonamide (AC), N, N- dinitroso pentamethylenes
In tetramine (blowing agent H), 4,4 '-oxybis-benzenesulfonyl hydrazides (OBSH), sodium bicarbonate, ammonium carbonate, ammonium hydrogen carbonate and ammonium nilrite
A combination of one or more.
The shoes composition, foam of the present invention is the addition of the crosslinking agent in terms of 100% by the gross mass of the base-material
For 0.5-1.5%, such as：Can be 0.8-1.2%.The crosslinking agent is peroxide cross-linking agent, the peroxide crosslinking
Agent is cumyl peroxide (DCP) and/or 1,4 bis tert butyl peroxy isopropyl benzene (BIPB).
The shoes composition, foam of the present invention is the addition of the assistant crosslinking agent in terms of 100% by the gross mass of the base-material
Amount is 0.3-1%, such as：Can be 0.5-0.8%.The assistant crosslinking agent can be Triallyl isocyanurate (TAIC),
One kind or two in trimethylol-propane trimethacrylate (TMPTMA) and trimethylolpropane triacrylate (TMPTA)
Kind or more combination, can be used for improve the present invention shoes composition, foam in crosslinking agent decomposition rate, be beneficial to foaming and
Crosslinked synchronous progress, to obtain the product of performance stabilization.
The activator of the present invention includes zinc oxide and/or zinc stearate.It is institute in terms of 100% by the gross mass of the base-material
The addition for stating activator is 1-6%, such as：It can be 2-5.5%, can also be 3-4%.Wherein, the addition of zinc oxide
Can be 0.5-5%, such as：0.5-2%；The addition of zinc stearate may be 0.5-5%, such as：0.5-2%.Pass through
Activator is added, the decomposition temperature of foaming agent in the shoes composition, foam of the present invention can be reduced, be beneficial to foam and is crosslinked
Be smoothed out, to obtain performance stabilization product.
The shoes composition, foam of the present invention is in terms of 100% by the gross mass of the base-material, and the addition of the filler is
10-30%, such as：It can be 15-25%, can also be 18-22%.The filler is to be selected from and talcum powder, calcium carbonate, hard charcoal
The black and one such or two or more composition of montmorillonite, the shoes that can be used for increasing the present invention are strong with composition, foam melt
Degree and the mechanical property for improving product.
The shoes composition, foam of the present invention, the shoes composition, foam can also include compatilizer.With the base-material
Gross mass be 100% meter, the addition of the compatilizer is 1-5%, such as can be 2-4%.Compatilizer is added, by means of
Intermolecular bonding force makes base-material realize compounding faster, and production efficiency is high, and the blend more stablized.
The shoes composition, foam of the present invention, the compatilizer are the ethylene-octene block copolymer of maleic anhydride grafting
(OBCs-g-MAH), the ethylene-that the ethylene-octene random copolymer (POE-g-MAH), maleic anhydride of maleic anhydride grafting are grafted
One kind in vinyl acetate resin (EVA-g-MAH) and the ldpe resin (LDPE-g-MAH) of maleic anhydride grafting
Or two or more combination.Compatilizer by maleic anhydride grafting makes material have height by introducing strongly polar reactive group
Polarity and reactivity, the compatibility of composite material can be greatly improved, to improve composite material machinery intensity.
The shoes composition, foam of the present invention, the composition further includes in antioxidant, anti-wear agent, coupling agent and pigment
At least one, be in terms of 100% by the gross mass of the base-material, the content of the antioxidant is 0.5-3%, such as：It can be with
It is 1-2%；The content of the anti-wear agent is 0.5-10%, such as：Can be 1-5%；The content of the coupling agent is 0.5-
6%, such as：Can be 1-3%；The content of the pigment is 1-6%, such as：Can be 1-4%.
The antioxidant can be the one or more of antioxidant 1010, irgasfos 168 and antioxidant B215
Combination, can be used for preventing the present invention shoes composition, foam aoxidized；The pigment can be various Masterbatch, according to need
It wants, the shoes composition, foam of the present invention can be prepared as a variety of different colors.
The coupling agent can be tetra-sulfurized pair (triethoxy propyl) silane, γ-methacryl azyloxy propyl three
The one or two of methoxy silane, 3- aminopropyl trimethoxysilanes and 3- glycidyl ether oxypropyltrimethoxysilanes
Above combination can be used for improving the dispersibility of filler in shoes composition, foam of the invention, composition, foam physical property
It is more stable.
The anti-wear agent is vinyltrimethoxysilane and resin copolymer, β-(3,4- epoxycyclohexylethyls) front three
The one or two of oxysilane and resin copolymer and γ-glycidyl ether oxygen propyl trimethoxy silicane and resin copolymer
Above combination, the resin can be ethylene-vinyl acetate resins.It can be used for improving the shoes composition, foam of the present invention
Wear-resisting property；The antioxidant, pigment, coupling agent and anti-wear agent content can be according to situation depending on.
The present invention also provides a kind of preparation methods of shoes composition, foam according to the present invention comprising will be described
The step of each component mixing of shoes composition, foam.
Specifically, preparation method of the invention includes the following steps：
(1) base-material is uniformly mixed using high-speed mixer, melt blending 3- is carried out in 100-140 DEG C in mixer
5min；Activator, foaming agent, assistant crosslinking agent and filler, mixing 3-5min is added, is eventually adding after crosslinking agent is kneaded 2-3min again
Discharging；
(2) raw material after mixing is extruded, reprocessing is sliced into the germule raw material with predetermined volume size；
(3) germule raw material is put into mold, at 10-15MPa and 160-175 DEG C of temperature condition, carries out moulded from foam,
Foaming body is made in pressure release after 5-15min, can be obtained finished product after cooling.
The preparation method of the shoes composition, foam of the present invention, step can also include in (1)：Base-material and compatilizer are adopted
It is uniformly mixed with high-speed mixer.
Mixer can be used in the present invention and open mill is blended, and moulded from foam can directly be carried out by being cut after slice, also may be used
It is granulated by screw extruder.It is processed using the methods of injection molding, molding, injection, application field is related to insole, midsole and damping
Piece or other need field, such as Safety protector, ground cushion, packaging material of damping etc..
Specifically, the shoes expanded material of the present invention can be used for producing medium-to-high grade athletic shoe sole building block, top grade
Leather shoe sole component materials；Other field is applied also for, in Safety protector, ground cushion, Yoga mat, packaging material.
Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
It can be with conventional products that are commercially available.
Embodiment 1-3
According to the mass fraction of each component in the following table 1, and the shoes foaming of embodiment 1-3 is prepared by the following method
Composition.
The preparation method of embodiment 1-3 is：
(1) by base-material (ethylene-vinyl acetate rubber (EVM), ethylene-vinyl acetate resin (EVA), styrene-second
Alkene-butylene-styrene block copolymer (SEBS) and brombutyl (BIIR)) and the maleic anhydride grafted ethylene-of compatilizer
Octene random copolymer (POE-g-MAH) is pre-mixed uniformly using high-speed mixer, then in 120 ± 3 DEG C in mixer
Carry out melt blending 3min.
(2) it sequentially adds foaming agent azodicarbonamide (AC), activator zinc stearate, activator, help crosslinking
Agent Triallyl isocyanurate (TAIC) and filler white carbon, mixing 5min are eventually adding crosslinking agent Isosorbide-5-Nitrae-dual-tert-butyl mistake
Oxygen cumene (BIPB) discharges after being kneaded 2min again.
(3) raw material after mixing is extruded, reprocessing is sliced into the germule raw material with predetermined volume size.
(4) germule raw material is put into mold, under 10MPa and 165 ± 5 DEG C of temperature condition, carries out moulded from foam, 5-
Foaming body is made in pressure release after 15min, can be obtained product shoes composition, foam after cooling.
Wherein, it is 26% that the Vinyl Acetate Monomer unit content in EVM, which is the vinyl acetate content in 80%, EVA,.
Table 1
The embodiment 1-3 compositions being prepared are tested for the property respectively, the results are shown in Table 2：
Table 2
As can be seen from Table 2, EVA, SEBS and BIIR are blended by using EVM and are remarkably improved its mechanical property, processing
Viscosity, melt strength and low-temperature flexibility.Therefore, the mechanics of shoes composition, foam of the invention required by meeting material for shoes
While performance, have lower density, impact rebound degree and compression set rate, while also there is preferable dimensionally stable
Property.
Comparative example 1-5
It is prepared according to the mass fraction of each component in the following table 3, and according to identical as embodiment 1-3 or corresponding preparation method
Obtain the shoes composition, foam of comparative example 1-5, wherein the vinyl acetate content in EVM is the vinyl acetate in 80%, EVA
Content is 26%.
Table 3
The comparative example 1-5 compositions being prepared are tested for the property respectively, the results are shown in Table 4：
Table 4
As can be seen from Table 4, comparative example 1 uses EVM as base-material, the impact rebound degree of the composition being prepared compared with
Height, and compressed shape variability and shrinking percentage are also higher, illustrates to be used only base-materials of the EVM as shoes composition, foam, mutability and
Dimensional stability is bad.
Comparative example 2 and comparative example 3, add EVA and are blended with EVM, while respectively using SEBS and BIIR as improvement
The modifying agent of matrix melt strength and processability.Comparative example 2 is due to the introducing of SEBS, and the density of foaming, impact rebound degree is
It reduces, so that dimensional stability is increased, but be insufficient for the requirement of the application, and elongation at break is relatively low；Comparative example 3 by
There is different degrees of raising in the physical mechanical property of the introducing of BIIR, compound system, but density is higher, shrinking percentage is higher,
It is slightly poor for the improvement of system dimensional stability.
Comparative example 4 and comparative example 5 are not added with BIIR and SEBS, although having preferable physical mechanical property, rebound degree
Relatively low, pressure resistance becomes better performances, but shrinking percentage is higher, and dimensional stability is poor.
Therefore, the shoes composition, foam prepared by the present invention also has while meeting required mechanical property
There are low density, impact rebound degree and Compression Set rate and excellent dimensional stability, while shoes composition, foam
Itself can be used as insole, midsole with performances, shoes of the invention such as ventilative, heat-resisting, weather-proof and oil resistants with composition, foam again
Damping shoe parts are needed with other.Meanwhile according to the above performance test, shoes of the invention apply also for it with composition, foam
He needs the field of damping, such as Safety protector, ground cushion, Yoga mat, packaging material.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
Those familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all contain
Lid is within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (10)
1. a kind of shoes composition, foam, which is characterized in that including：Base-material, foaming agent, crosslinking agent, assistant crosslinking agent, activator and
Filler；Wherein,
It is in terms of 100% by the gross mass of the base-material, the base-material includes：
Ethylene-vinyl acetate rubber：30-49.9%, preferably 35-45%；
Ethylene-vinyl acetate resin：10-30%, preferably 15-25%；
Styrene-ethylene-butylene-styrene block copolymer：20-40%, preferably 25-35%；
Brombutyl：5-30%, preferably 5-20%.
2. shoes composition, foam according to claim 1, which is characterized in that in the ethylene-vinyl acetate rubber
The content of Vinyl Acetate Monomer unit is 40-80 mass %, preferably 55-80 mass %.
3. shoes composition, foam according to claim 1 or 2, which is characterized in that the ethylene-vinyl acetate resin
The content of middle Vinyl Acetate Monomer unit is 14-28 mass %, preferably 20-28 mass %.
4. according to claim 1-3 any one of them shoes composition, foams, which is characterized in that with the gross mass of the base-material
Addition for 100% meter, the foaming agent is 3-5%, and the addition of the crosslinking agent is 0.5-1.5%, described to help crosslinking
The addition of agent is 0.3-1%, and the addition of the activator is 1-6%, and the addition of the filler is 10-30%.
5. according to claim 1-4 any one of them shoes composition, foams, which is characterized in that the foaming agent includes azo
Diformamide, N, N- dinitrosopentamethylene tetramines, 4,4 '-oxybis-benzenesulfonyl hydrazides, sodium bicarbonate, ammonium carbonate, ammonium hydrogen carbonate
With the combination of one or more of ammonium nilrite.
6. according to claim 1-5 any one of them shoes composition, foams, which is characterized in that the crosslinking agent includes peroxide
Compound crosslinking agent, the peroxide cross-linking agent are preferably in cumyl peroxide and Isosorbide-5-Nitrae-dual-tert-butyl peroxy isopropyl base benzene
It is one or two kinds of；The assistant crosslinking agent includes Triallyl isocyanurate, trimethylol-propane trimethacrylate and three
The combination of one or more of hydroxymethyl-propane triacrylate.
7. according to claim 1-6 any one of them shoes composition, foams, which is characterized in that the activator includes oxidation
Zinc and/or zinc stearate；The filler includes one or more of talcum powder, calcium carbonate, white carbon and montmorillonite
Combination.
8. according to claim 1-7 any one of them shoes composition, foams, which is characterized in that the shoes composition, foam
Further include：A combination of one or more in compatilizer, antioxidant, anti-wear agent, coupling agent and pigment；
It is in terms of 100% by the gross mass of the base-material, the addition of the compatilizer is 1-5%；The addition of the antioxidant
Amount is 0.5-3%；The addition of the anti-wear agent is 0.5-10%；The addition of the coupling agent is 0.5-6%；The pigment
Addition be 1-6%.
9. shoes composition, foam according to claim 8, which is characterized in that the compatilizer includes maleic anhydride grafting
Ethylene-octene block copolymer, maleic anhydride grafting ethylene-octene random copolymer, maleic anhydride grafting ethylene-vinegar
The combination of one or more of the ldpe resin that vinyl acetate resin and maleic anhydride are grafted.
10. a kind of preparation method according to claim 1-9 any one of them shoes composition, foams, which is characterized in that packet
Include the step of mixing each component of the shoes composition, foam.
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| CN115536922A (en) * | 2022-10-29 | 2022-12-30 | 福建省莆田富邦实业有限公司 | Lightweight high-resilience sole material and sports shoes |
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| CN109897385B (en) * | 2019-03-11 | 2021-08-17 | 安踏（中国）有限公司 | Wide-temperature-range shock-absorption foaming insole material and preparation method thereof |
| CN110372926A (en) * | 2019-08-28 | 2019-10-25 | 张皓丽 | One kind resists cold ageing-resistant acrylonitrile butadiene packing material and preparation method thereof |
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| CN111100369A (en) * | 2020-01-02 | 2020-05-05 | 李宁（中国）体育用品有限公司 | Foaming material for shoes, preparation method and shoes |
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| CN111286110A (en) * | 2020-02-18 | 2020-06-16 | 安踏（中国）有限公司 | High-comfort cushioning foaming insole material, preparation method thereof and sports shoes |
| CN112321935A (en) * | 2020-11-24 | 2021-02-05 | 安踏（中国）有限公司 | Thermotropic memory foaming insole material and preparation method thereof |
| CN112321935B (en) * | 2020-11-24 | 2022-11-18 | 安踏（中国）有限公司 | Thermotropic memory foaming insole material and preparation method thereof |
| CN112662043A (en) * | 2020-12-21 | 2021-04-16 | 郑忠利 | Preparation and implementation method of impact force protection foaming shoe material |
| WO2022184597A1 (en) * | 2021-03-02 | 2022-09-09 | Inoveight Limited | A shoe sole formed from a polymeric foam compound with enhanced perfomance characteristics |
| CN114683603A (en) * | 2022-03-16 | 2022-07-01 | 达州市嘉源体育用品有限公司 | Preparation method of ultralight breathable sole |
| CN115536922A (en) * | 2022-10-29 | 2022-12-30 | 福建省莆田富邦实业有限公司 | Lightweight high-resilience sole material and sports shoes |
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