CN104262940A - Colorful TPU (thermoplastic polyurethane) foaming material, method for preparing shoe material by colorful TPU foaming material and application - Google Patents
Colorful TPU (thermoplastic polyurethane) foaming material, method for preparing shoe material by colorful TPU foaming material and application Download PDFInfo
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- CN104262940A CN104262940A CN201410538129.8A CN201410538129A CN104262940A CN 104262940 A CN104262940 A CN 104262940A CN 201410538129 A CN201410538129 A CN 201410538129A CN 104262940 A CN104262940 A CN 104262940A
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Abstract
The invention discloses a colorful TPU (thermoplastic polyurethane) foaming material, a preparation method and an application. The colorful TPU foaming material comprises colorful foaming particles or colorful foaming sheets, pigment concentration of the colorful foaming particles or the colorful foaming sheets is 0.01%-5% by weight, pigments inside and outside the colorful TPU foaming material have the same concentration, the hardness of the colorful TPU foaming material is HA 5-65, the density is 0.05-0.5 g/cm<3>, and the average cell size is smaller than 100 mu m. The colorful TPU foaming material has the characteristics of good inside and outside uniformity, absence of wrinkles on the surface and the like.
Description
Patent application of the present invention is the divisional application of Chinese Patent Application No. 201410196699.3, the application number of original application is 201410196699.3, the applying date is on 05 09th, 2014, and denomination of invention is colored TPU foam material, preparation method, purposes and utilizes this material to prepare the method for formed body, thin slice, footwear material.
Technical field
The present invention relates to a kind of method that high pressure fluid physical blowing prepares colored thermoplastic polyurethane (TPU) foam material of low density, low temperature is heated by the short period of time, colored TPU resin after high pressure fluid dipping, reduce the interfacial migration of organic molecule pigment, to obtain pigment homodisperse colored TPU foam material inside and outside foam structure, and one carries compression technology by high pressure gas, reduce the pressure difference inside and outside TPU foam material foam structure, thus suppress the ununiform shrinkage of colored TPU foam material, to obtain any surface finish, epidermis does not have the colored TPU foam material of the low density of obvious fold.The present invention relates to the shaping and TPU foam sheet of TPU expanded particle water vapour split cut, the method for compression molding, be applied to footwear material field to make prepared colored TPU foam material.
Background technology
Ethylene-vinyl acetate copolymer (EVA) base polymer foam material has the feature such as lightweight, elasticity and for the shoe-pad making sports shoes, the middle end and outer bottom.The colour match that colored EVA foam material imparting sports shoes enriches and good designed capacity.The technique preparing colored EVA foam shoe material is open.One method be the low temperature height such as pigment and EVA particle, auxiliary agent, filler, whipping agent, linking agent are mixed, open refine, extruding pelletization, particulate material foamable and/or secondary mould shape in a mold, thus prepare colored EVA foam shoe material.Another kind method is that pigment compound is entered EVA foaming system, becomes colored EVA foam shoe material by the once shaped of injection foaming technique, especially EVA foaming sandals.
EVA resin for the preparation of EVA foam shoe material is thermoplasticity, can be prepared into desired shape by the mode of melt-processed.But, need to carry out chemically crosslinked during EVA resin foaming.The EVA foamex with crosslinking structure is a macromole, and this material can not carry out melt-processed, and this causes EVA resin just to lose melting recovery ability after expanding.In addition, EVA resin foaming adopts chemical foaming mode to carry out usually, chemical foaming procedures produce toxic obnoxious flavour, and chemical foaming agent decomposes and not exclusively causes Material Manufacturing Process not environmentally, and material property is unstable.
Thermoplastic polyurethane (TPU) has the plurality of advantages such as high abrasion, snappiness, antifatigue, resistance to chemical attack and is widely used in footwear material.Be that the low-density foamed material of colour prepared by base material is expected to alternative EVA material foam material and is applied to high-performance footwear material field with TPU.
Prior art can not prepare that to have bright-colored abundant, that color is evenly distributed inside and outside material, density be 0.05-0.5g/cm
3, foam structure evenly and size be less than 100 μm, any surface finish and do not have the TPU foam material of obvious shrinkage creases.
The method adopting chemical foaming agent to prepare TPU foam material is known.In TPU chemical foaming system, add suitable pigment can give TPU foam material shades of colour, but there is similar problem to EVA resin foam material, as preparation process not environmentally with the problem etc. needing chemically crosslinked.In addition, also there is the problem that foam structure is coarse, density is large, expansion multiplying power is low in the TPU foam material adopting chemical foaming agent to prepare.
In order to eliminate this defect, patent documentation WO2000/44821A, WO2004/108811A disclose the method that expended microsphere prepares TPU foam material.The TPU of powder, particle form mixes with expended microsphere by the method, melt-processed prepares TPU foam material.Expended microsphere used is enclosed with the tackiness agent of low boiling point solvent (as pentane) or cured or thermoplastics pill, and the thermolysis in the TPU course of processing of the low boiling point solvent in expended microsphere becomes gas core, and the growth of gas core defines foam structure.The size of expended microsphere is being generally 20-40 μm, and it is not easily dispersed that it adds man-hour in TPU melting mixing, high-content expended microsphere add the formation being easy to cause uneven macroporous structure.Be 0.3-1.0g/cm for density
3tPU foam material, can observe sample surfaces and occur that visible caves in, meanwhile, the wear resisting property of this foam material is poor.By pigment being mixed into expended microsphere foaming TPU system, colored TPU foam material should be prepared, but the problem that prepared low density TPU foam material exists equally, and abscess-size is excessive, depression, wear resisting property difference appear in sample surfaces, secondly, there is color problem bright-coloured not in prepared low density TPU foam material.
Patent documentation WO2005/066250A, WO2007/082838A, WO2010/136398A and CN103642200A to describe with organic solvent or rare gas element as pneumatogen, are prepared the method for TPU foam material by suspension process.The abscess of prepared TPU foam material is little and be evenly distributed, and density can be low to moderate 0.1-0.5g/cm
3, which solve expended microsphere technology and prepare Problems existing in TPU foam material.But, it is boil 0.5-10 hour in the water of 100-150 DEG C in temperature that the method relates to TPU particle, particularly polyester type TPU resin is easy to be hydrolyzed this fact to TPU resin is a problem, long-time poach easily causes TPU resin generation chemical degradation and xanthochromia problem, have impact on the performance of TPU foam material and follow-up use.What is more important, the pigment that TPU resin is conventional is mainly small molecule organic compound, small molecule organic compound is easy to interfacial migration occurs under the environment of high-pressure foam agent plasticizing, the long-time poach of high temperature, there is the problems such as the even foam material surface color of pigment skewness inside and outside foam material fades.
Patent documentation WO2007/082838A discloses and adopts saturated aliphatic hydrocrbon to be whipping agent, the method for preparation TPU expanded particle under continuous expressed water.There is environmental issue and production safety problem in whipping agent used.Secondly, organic molecule pigment can remarkable plasticising TPU matrix, and viscosity and this fact of melt strength of reducing TPU melt are individual problems, cause the foam structure of TPU foam material restive.In addition, it is also a problem that TPU foam material prepared by continuous extrusion foaming exists percentage of open area this fact high, causes TPU expanded particle to occur in water vapour moulding process the problem that shrinking percentage is high.
High pressure fluid is as high pressure CO
2fluid is a kind of clean, cheap, eco-friendly pneumatogen, according to demand, and high pressure CO
2fluid can be high-pressure gas flow body, highly pressurised liquid fluid and supercutical fluid.CO
2supercritical state can realize under comparatively gentle condition, if pressure is 7.31MPa, temperature is 31.0 DEG C.
Patent documentation WO2002/4628A describes with high pressure fluid or supercutical fluid as the method for high-density TPU foam material prepared by whipping agent.The hardness of TPU foam material prepared by the method is not less than 90, and density is 0.5-1.0g/cm
3, prepared TPU foam material is mainly used in the polishing pad of semiconductor crystal wafer, and is not suitable for the buffering shoe material of sports shoes.
Patent documentation CN102229709A describes with supercritical CO
2for whipping agent, moulded from foam technique is adopted to prepare the method for TPU foam material.The pressure of the supercutical fluid that the method is used is 5-25MPa, and the temperature of supercutical fluid is 100-250 DEG C, and the treatment time of supercutical fluid is 1-60 minute.This know-why can be prepared colored TPU foam material, but organic molecule pigment resistance toheat is poor, is easy to interfacial migration and volatilization occur under the environment of high temperature, high pressure, cause foam material to there is dyeing problem of non-uniform.In addition, the hypertonia required for this technology, causes the high and production safety problem of equipment cost.Secondly, this technology does not use dispersion medium, and TPU particle is easily out of shape under high temperature, high pressure, appearance becomes sticky, and preparation appearance is bright and clean, shape is spherical or the TPU expanded particle of elliposoidal to cause this technology to be unsuitable for.
International literature (Journal of Applied Polymer Science, 2010,116,1994.; Journal of Applied Polymer Science, 2013,128,2245.) report with high pressure CO
2fluid is the method that thermoplastic elastomer foam material prepared by whipping agent.The method adopts high pressure CO
2fluid, low temperature dipping thermoplastic elastomer resin, make thermoplastic elastomer realize foaming by water-bath or water vapour heating.But, the free volume size of thermoplastic elastomer is large, high pressure CO
2fluid can go out polymeric matrix by convenient in rapid escape when thermoplastic elastomer foams, and the quality again due to thermoplastic elastomer is soft, and material, when foaming, serious contraction (dimensional contraction is up to 40-50%) easily occurs.The generation of this significant shrinkage not only significantly can increase the density of thermoplastic elastomer foam material, foam material epidermis also can be caused to occur obvious fold and foam material overall dimensions instability, have a strong impact on the follow-up use of thermoplastic elastomer foam material.
Summary of the invention
The object of this invention is to provide a kind of preparation method of colored TPU foam material, select clean, cheap, eco-friendly high pressure CO
2fluid is pneumatogen, by continuous fusion extruding pelletization/slab, high pressure fluid dipping, dissolution equilibrium, foamable, second-heating foaming, carry the techniques such as pressure process, prepare that shrinkage degree is little, outside surface is bright and clean, neat appearance, foam structure are 100% closed pore, abscess-size is less than 100 μm, the colored TPU expanded particle material that is evenly distributed inside and outside foam material of pigment and colored TPU foam sheet material.Adopt expanded particle forming machine, make to form bonding between expanded particle by water vapour heating, obtained colored TPU expanded particle formed body material, this formed body has the features such as density is low, shrinkage degree is low, formed body outward appearance good, bead interfacial adhesion is good.Adopt silicon rubber sponge chopper, can split cut colored TPU foam sheet, because prepared colored TPU foams, size is little, pigment is evenly distributed inside and outside foam material, and prepared colored TPU splits that sheet is homogeneous, color distribution is even.Adopt mould pressing process, colored TPU foam sheet generation viscous deformation can be made by hot pressing, prepare complex-shaped TPU Foamed article.Sheet is split in prepared colored TPU expanded particle formed body, colored TPU foaming, colored TPU foaming mould plastic can be applied to sports shoes material field.
TPU is a class Thermoplastic Elastic Material Used of being synthesized by polyisocyanates, polyester polyol or polyether glycol, chainextender etc.The kind of polyisocyanates is a lot, but output maximum only have two kinds, i.e. diphenylmethanediisocyanate (MDI) and tolylene diisocyanate (TDI).Polyvalent alcohol of a great variety, mainly comprises polyester polyol, polyether glycol, polycarbonate polyvalent alcohol, polyolefin polyhydric alcohol, polyacrylate polyol etc.Glycol such as butyleneglycol, ethylene glycol, propylene glycol etc. are chainextender.At present, the TPU resin types that market can provide is a lot, different hardness, different melt flow index, different chemical structures, different physical property etc., and this is that the suitable colored TPU foam material of preparation is provided convenience.
According to wikipedia, so-called pigment is exactly the material making material catch color.Pigment why can Show Color, is that they can reflect or absorb the color of the visible ray of some wavelength.Pigment is mainly divided into pigment dyestuff and mineral dye.Mineral dye is generally mineral material, and pigment dyestuff generally takes from plant, marine animal or organic synthesis.It is known that TPU resin mainly uses organic molecule pigment to dye.The processing temperature of TPU resin is generally not less than 180 DEG C, and this requires that the temperature tolerance of organic molecule pigment generally will more than 180 DEG C.Mineral dye generally has very high temperature tolerance, but often containing heavy metals such as lead, mercury, chromium, cadmiums, there is environmental issue, and secondly mineral dye exists dyeing problem vivid not.The carbon black of carbon black or organic decoration is the black pigment that TPU resin is conventional, and it containing heavy metals such as lead, mercury, chromium, cadmiums, does not exist environmental issue.The titanium dioxide of titanium dioxide or organic decoration is the white pigment that TPU resin is conventional, and it containing heavy metals such as lead, mercury, chromium, cadmiums, does not also exist environmental issue.
Pigment dyestuff is generally small-molecule substance, it is mainly present in polymkeric substance non-crystalline areas with the form of pigment molecule, and the size of polymeric matrix free volume size, the characteristic of pigment molecule, pigment are subject to influence degree of water effect etc. to determine the look migratory behaviour of pigment dyestuff.Temperature rising can increase the size of polymer free volume and improve the motor capacity of pigment molecule, and pigment dyestuff molecule is easier to color transfer occurs at high ambient temperatures.High pressure fluid has strong plastification as the whipping agent of TPU resin to TPU matrix, which increases the mobility of TPU molecular resin chain, too increases the ability of pigment dyestuff molecule to interfacial diffusion.Pigment dyestuff is generally easy to water suction, and the pigment in TPU resin is easy to when poach interfacial migration occurs.Above-mentioned reason causes suspension process to be difficult to the uniform colored TPU foam material of preparation color distribution.
Our research finds, pigment molecule color transfer can not occur when low temperature, high pressure fluid dipping.Find further, also can not there is obvious color transfer when short period of time poach or water vapour boiling in the colored TPU resin after low temperature, high pressure fluid dipping, colored TPU foam material prepared by this method has uniform color distribution inside and outside foam structure.
TPU resin exists with rubbery state at a lower temperature, the free volume size of polymkeric substance is large, and the TPU after high pressure fluid dipping is when by heat foamable, and inner high pressure fluid rapid diffusion can go out polymeric matrix, meanwhile, extraneous air starts to be diffused in formed foam structure.Due to the speed that high pressure fluid spreads to the speed of external diffusion far above outside air in TPU foam structure, thus make pressure in foam structure lower than the normal atmosphere outside abscess, mineralization pressure is poor.It is partially soft that TPU resin is in rubbery state matrix at normal temperatures, causes TPU foam material that seriously shrinkage strain occurs under the effect of pressure difference, causes sample surfaces to occur large-area indenture.Polymeric foamable material as expandable polystyrene (EPS), expansioning polypropylene (EPP) shrinks in the preparation is common, the contraction being eliminated foam material by the method for long-time slaking, drying and processing is known.But, research finds, TPU foam material surface is once occur serious indenture, and the method for long-time slaking, drying and processing all effectively can not eliminate the contraction trace of TPU foam material.This studies surprised discovery, effectively can be suppressed the ununiform shrinkage of TPU foam material by the method passing into high-pressure air or high pressure nitrogen in the TPU material that also do not shrink after expanding, obtained TPU foam material any surface finish, significantly not shrink trace.
The step suppressing TPU foam material to shrink generally is carried out in pressure-pot or autoclave pressure.Because the volume of pressure-pot or autoclave pressure is large, temperature is adopted to be the high-pressure air of room temperature or high pressure nitrogen convenient operation often.Research finds, when room temperature is 0 ~ 40 DEG C, high-pressure air carries the ununiform shrinkage that pressure all can suppress TPU foam material effectively.
The object of this invention is to provide colored TPU foam material, especially the hardness of foam material is Shao A5 ~ 65, and density is 0.05 ~ 0.5g/cm
3, abscess-size is less than those of 100 μm, and they have soft sense of touch and good rebound resilience, and especially apparent bright and cleanly do not have fold, pigment to be evenly distributed inside and outside foam material and can be applied to the colored TPU foam material of footwear material.
Colored TPU foam material in the present invention comprises colored TPU expanded particle material and colored TPU foam sheet material.
Described pigment is the pigment of the different colourities formed containing red, yellow, Lan Sanse and has the pigment of the different colourities be made up of red, yellow, Lan Sanse of fluorescent effect.
Described pigment is organic molecule pigment and mineral dye, and be preferably organic molecule pigment, wherein the thermostability of organic molecule pigment is higher than 180 DEG C.
When described pigment is black, preferred carbon black is as pigment, and if necessary, the carbon black of preferred organic decoration is pigment; When described pigment is white, preferred titanium dioxide is pigment, and if necessary, the carbon black of preferred organic decoration is pigment.
Described pigment has identical/close concentration inside and outside colored TPU foam material.
The content of described pigment in TPU foam material is 0.01 ~ 5wt%, is preferably 0.1 ~ 3wt%, is more preferably 0.2 ~ 2wt%.
The present invention relates to a kind of preparation method of colored TPU expanded particle material, comprise the following steps:
1) by pigment and TPU particle premix, then the particle after premix is extruded through forcing machine, granulation underwater makes colored TPU particle.
2) colored TPU particle is flooded in high pressure fluid, make high pressure fluid reach dissolution equilibrium in colored TPU matrix;
3) the colored TPU particle after high pressure fluid dissolution equilibrium is placed in water-bath or water vapour foamable, obtains colored TPU expanded particle B1;
4) colored TPU expanded particle B1 is inserted in closed container, and high-pressure air or high pressure nitrogen is passed in container, extraneous high-pressure air or nitrogen are replaced with the high pressure fluid in colored TPU expanded particle, obtained contraction are even, the colored TPU expanded particle B2 of any surface finish;
Described colored TPU particle is spherical and elliposoidal, and the ratio of major axis and short-axis direction is 1 ~ 3, and wherein the diameter of minor axis is 0.5 ~ 5.0mm.
Step 2) in, described high pressure fluid is CO
2fluid.The pressure of described high pressure fluid is 1 ~ 10MPa, and the temperature of described high pressure fluid is 0 ~ 60 DEG C, and the solubleness of described high pressure fluid in colored TPU is 8 ~ 30wt%.
Step 3) in, the heat-up time of described water vapour is 1 ~ 60s.
Due in air 75% composition be nitrogen, research finds, is loaded into high-pressure air or high pressure nitrogen has similar effect in colored TPU foam material, considers running cost, preferred high-pressure air.Step 4) in, the pressure of described high-pressure air is 0.15 ~ 0.5MPa, and the temperature of high-pressure air is room temperature.
In order to obtain the higher colored TPU expanded particle material of expansion multiplying power, the method that can also be foamed by second-heating is implemented, and comprises the steps:
1) by pigment and TPU particle premix, then the particle after premix is made colored TPU particle through forcing machine granulation, granulation underwater.
2) colored TPU particle is flooded in high pressure fluid, make high pressure fluid reach dissolution equilibrium in colored TPU matrix;
3) the colored TPU particle after high pressure fluid dissolution equilibrium is placed in foamable under water-bath or water vapour, obtains colored TPU expanded particle B1 ';
4) TPU expanded particle B1 is placed in warm air to heat, make it to continue foaming and obtain colored TPU expanded particle B2 ', the temperature of this warm air is 100-140 DEG C;
5) colored TPU expanded particle B2 ' is inserted in closed container, and high-pressure air is passed in container, extraneous high-pressure air is replaced with the high pressure fluid in colored TPU expanded particle, obtains that shrinkage degree is little, the colored TPU expanded particle B3 ' of any surface finish;
Described colored TPU particle is spherical and elliposoidal, and the ratio of major axis and short-axis direction is 1 ~ 3, and wherein the diameter of minor axis is 0.5 ~ 5.0mm.
Step 2) in, described high pressure fluid is CO
2fluid.The pressure of described high pressure fluid is 1 ~ 10MPa, and the temperature of described high pressure fluid is 0 ~ 60 DEG C, and the solubleness of described high pressure fluid in colored TPU is 8 ~ 30wt%.
Step 3) in, the heat-up time of described water vapour is 1 ~ 60s.
Step 4) in, adopt warm air to carry out second time of foaming, obtain colored TPU expanded particle B2 ', the described hot air treatment time is 1 ~ 60s, and the temperature of this warm air is 100-140 DEG C.
Due in air 75% composition be nitrogen, research finds, is loaded into high-pressure air or high pressure nitrogen has similar effect in colored TPU foam material, considers running cost, preferred high-pressure air.Step 4) in, the pressure of described high-pressure air or nitrogen is 0.15 ~ 0.5MPa, and the temperature of high-pressure air or nitrogen is room temperature.
The invention still further relates to a kind of preparation method of colored TPU expanded particle formed body.
It is known that EPS, EPP realize expanded particle shaping by water vapour, all can be implemented by water vapour forming machine, and their difference is that the latter needs higher water vapour forming pressure than the former.When EPS, EPP expanded particle material adopts water vapour forming machine shaping, water vapour is heating medium, to there is surface in EPS, EPP expanded particle softening under water vapour heating, the molecular chain generation interfacial diffusion on EPS, EPP expanded particle surface, thus form bonding between expanded particle.Our research finds, it is possible for adopting the shaping machine of EPP to prepare colored TPU expanded particle formed body material.The water vapour of colored TPU expanded particle is shaping to be comprised the following steps:
1) colored TPU expanded particle is injected the mould of expanded particle forming machine, adopt water vapour heat treated, after cold water cooling, draining, air-cooled, the demoulding, obtain colored thermoplastic expanded particle former body.
Our research finds, through the high-temperature vapor short period of time, heating can not cause color transfer to colored TPU expanded particle, and prepared colored TPU expanded particle formed body material has uniform color.
Described water vapour heat-up time is 10 ~ 60s, and described steam temperature is 120 ~ 149 DEG C.
In order to reach good product design effect, colored TPU expanded particle formed body material can comprise one or more colors.Described colored TPU foam material is by the TPU expanded particle mixture of one or more colors through the shaping formed body material made of water vapour, or is combined through the shaping formed body material made of water vapour with certain rule by the thermoplastic elastomer expanded particle of one or more colors.
Water vapour forming machine can realize multi-point mould and single shaping cycle is short, and shaping efficiency is very high.
Can prepare various colors, various informative TPU expanded particle formed body material by water vapour forming technique, prepared material is suitable for preparing cushioning material, is particularly suited for the footwear material preparing sports shoes, playshoes, sandals and slippers.
The hardness of described colored TPU expanded particle formed body material is Shao A5 ~ 65, and density is 0.05 ~ 0.5g/cm
3.
The invention still further relates to a kind of preparation method of colored TPU foam sheet material, comprise the following steps:
1) by pigment and TPU resin particle premix, then the particle after premix is extruded through forcing machine, curtain coating or mold pressing make colored TPU sheet material.
2) colored TPU sheet material is flooded in high pressure fluid, make high pressure fluid reach dissolution equilibrium in colored TPU sheet material;
3) the colored TPU sheet material after high pressure fluid dissolution equilibrium is placed in water-bath foamable, obtains colored TPU foam sheet B1 ";
4) by colored TPU foam sheet B1 " insert in closed container; and high-pressure air is passed in container; the high pressure fluid in extraneous high pressure gas and colored TPU foam sheet is replaced, the obtained colored TPU foam sheet B2 that shrinkage degree is little, surface does not have obvious indenture ".
The thickness of described colored TPU foam sheet is 0.5 ~ 30mm.
The hardness of described colored TPU foam sheet is Shao A5 ~ 65.
The foam structure of described colored TPU foam sheet is the unicellular structure of 100%, and abscess-size is less than 100 μm.
Step 2) in, described high pressure fluid is CO
2fluid.The pressure of described high pressure fluid is 1 ~ 10MPa, and the temperature of described high pressure fluid is 0 ~ 60 DEG C, and the solubleness of described high pressure fluid in colored TPU sheet material is 8 ~ 30wt%.
Step 3) in, the heat-up time of described water-bath is 1 ~ 60s.
Step 4) in, the pressure of described high-pressure air is 0.15 ~ 0.5MPa, and the temperature of high-pressure air is room temperature.
What the invention further relates to colored TPU foam sheet splits sheet.
The technology adopting sponge chopper to split sheet to sponge is known.Our research finds, the hardness of colored TPU foam sheet is Shao A5 ~ 65, and most suitable employing sponge chopper splits sheet processing to it.The foam structure of colored TPU prepared by the present invention is less than 100 μm and pigment has uniform dispersion inside and outside foam material, thus makes the colored TPU foam material of acquisition split sheet to have good outward appearance and uniform color distribution.Colored TPU foaming is split sheet material and is suitable for manufacturing shoe-pad.
It is 0.1 ~ 28mm that sheet thickness is split in described colored TPU foaming.
The invention further relates to the compression molding of colored TPU foam sheet.
Adopt compression molding to be known to the technique that the EVA after one step foaming shapes, this process relates to EVA foam material, under by the condition of hot moulding, viscous deformation and cooling and shaping step occurs, thus makes the footwear material of various style.Colored TPU foam material is thermoplasticity, and our research finds, can allow colored TPU foam material generation viscous deformation, make footwear material by the method for heating and mould pressing.
The temperature of described compression molding is 130 ~ 170 DEG C.
Tool of the present invention has the following advantages:
The inventive method adopts low temperature, high pressure CO
2the technique of fluid impregnated, short period of time foamable, effectively prevent the interfacial migration of pigment, the technique means such as pressure are carried by high-pressure air, restrained effectively the ununiform shrinkage of TPU foam material, thus obtain any surface finish obviously shrink trace, color is evenly distributed inside and outside foam structure, degrees of expansion is high, colored TPU foam material that abscess-size is little.
The present invention adopts high pressure fluid to be whipping agent, production process environmental protection, preparation technology be simple, workable, be easy to suitability for industrialized production, the colored TPU expanded particle formed body density of material of preparation is low, shrinking percentage is low, good stability of the dimension, the colored TPU foaming of preparation splits that sheet material quality is smooth, color distribution even, and obtained colored TPU pressing has steady and audible contour structures.
Colored TPU foam material prepared by the inventive method not only has abundant collocation of colour, low density, soft sense of touch, also has the distinctive attribute of TPU resin as the rebound resilience of excellence, low permanentset, excellent wear resistance and good chemical stability etc.
As an example, colored TPU foam material of the present invention can use with the form of film, sheet material, Buffer Unit, sole and other footwear parts.According to the present invention, preferred sole and shoe-pad etc.
Illustrate in greater detail the present invention in the examples below that.
Accompanying drawing explanation
Fig. 1 is the optical schematic diagram of the yellow TPU expanded particle of preparation in embodiment 1.
Fig. 2 is the optical schematic diagram of the yellow TPU expanded particle section of preparation in embodiment 1.
Fig. 3 is the Electronic Speculum schematic diagram of the yellow TPU expanded particle section of preparation in embodiment 1.
Fig. 4 is the optical schematic diagram of the yellow TPU expanded particle of preparation in comparative example 1.
Fig. 5 is the optical schematic diagram of the yellow TPU expanded particle of preparation in comparative example 3.
Fig. 6 is the optical schematic diagram of the yellow TPU expanded particle molding of preparation in embodiment 5.
Fig. 7 is the optical schematic diagram of the yellow/white mixing TPU expanded particle molding of preparation in embodiment 6.
Fig. 8 is the optical schematic diagram of the colored TPU foaming disk implementing preparation in reason 7.
Embodiment
In order to explain technical scheme of the present invention further, below by specific embodiment, the present invention will be described in detail.
Embodiment 1
The yellow organic pigment (permanent yellow HR) of TPU particle (production of Ningbo gold fringe company) and 1wt% is dry mixed, extrudes through forcing machine, granulation underwater makes the elliposoidal TPU particle that diameter is 2mm, length-to-diameter ratio is 1.5.Particle is put into autoclave, adopts low temperature, high pressure CO
2fluid impregnated TPU particle, makes high pressure CO
2fluid reaches dissolution equilibrium in TPU resin particle.TPU particle after dipping is put into water-bath or water vapour foams, obtains yellow TPU expanded particle B1.TPU expanded particle B1 being put into temperature is room temperature, high-pressure air year pressure, obtains yellow TPU expanded particle B2.Table 1 is processing parameter relevant in embodiment 1.Research shows, the density of the yellow TPU expanded particle obtained is 0.18g/cm
3, hardness is Shao A15.As shown in Figure 1, the yellow TPU expanded particle obtained is single ellipsoid shape, and any surface finish, not discovery significantly shrink trace.As shown in Figure 2, the yellow TPU expanded particle obtained is the unicellular structure of 100 %, and average cell size is 15 microns.As shown in Figure 3, the interface section of the yellow TPU expanded particle obtained is also for yellow, and yellow ultramarine is uniformly distributed inside and outside material.
Comparative example 1
Except TPU expanded particle not being carried out carrying pressure process, other operation is with embodiment 1, and the final densities of obtained yellow TPU expanded particle is 0.45g/cm
3.As shown in Figure 4, there is obvious gauffer and large-area depression in prepared TPU expanded particle surface.
Comparative example 2
Technique with reference to CN10229709A prepares colored TPU expanded particle.Yellow TPU particle is put into the autoclave that temperature is 120 DEG C, is the high pressure CO of 8MPa by pressure
2fluid, dipping TPU particle is respectively 1h, 2h, 3h, 4h, 6h, 12h, and then fast pressure relief obtains TPU foam material.The TPU foam material obtained is bulk or the sheet of irregularity, can not tell single TPU expanded particle, observes the surface that large-sized foam structure appears at sample simultaneously.Wherein 1h, 2h, 3h, 4h dip treating irregular TPU foam obtained that foams is light yellow, density is respectively 0.52,0.54,0.48,0.45g/cm
3; Wherein 6h, 12h dip treating irregular TPU foam obtained that foams is dark yellow, and illustrate that TPU resin chemical degradation may occur, the density of the TPU foam obtained is 0.61 g/cm
3.
Comparative example 3
Colored TPU expanded particle is prepared with reference to WO2005/066250, WO2007/082838, WO2010/136398.Yellow TPU particle, dispersion agent are put into the water-bath autoclave of stirring, yellow TPU particle is suspended in a water bath, and bath temperature is 120 DEG C.Be whipping agent by the butane of 20wt%, under the state stirred, flood yellow TPU particle 1h, 2h, 3h, 4h respectively, then fast pressure relief obtains TPU expanded particle material.As shown in Figure 5, the TPU expanded particle that wherein 1h and 2h dip treating obtains is the light yellow of uneven color, and density is 0.20g/cm
3; Obtain the dark yellow that TPU expanded particle is uneven color after 3h, 4h dip treating, illustrate that TPU resin chemical degradation may occur, the density of the TPU foam obtained is 0.18 g/cm
3.
Comparative example 4
Colored TPU expanded particle is prepared with reference to CN103642200A.Yellow TPU particle, dispersion agent are put into the water-bath autoclave of stirring, yellow TPU particle is suspended in a water bath, and bath temperature is 120 degree.Be the high pressure CO of 8MPa by pressure
2fluid foaming agent, under the state stirred, flood yellow TPU particle 1h, 2h, 3h, 4h respectively, then fast pressure relief obtains TPU expanded particle material.The TPU expanded particle that wherein 1h and 2h dip treating obtains is the light yellow of uneven color, and density is 0.47g/cm
3; Obtain the dark yellow that TPU expanded particle is uneven color after 3h, 4h dip treating, illustrate that TPU resin chemical degradation may occur, the density of the TPU foam obtained is 0.51 g/cm
3.
Embodiment 2
Except changing the source (purchasing from Ningbo gold fringe, Yantai ten thousand China, Dow Chemical company, German Bayer AG) of TPU resin, granulation size and operating procedure condition, other operate with embodiment 1.The yellow TPU expanded particle material that the TPU expanded particle material obtained is any surface finish, does not obviously shrink.Otch expanded particle can be observed inside and outside colored TPU expanded particle has uniform pigment distribution.Concrete data are in table 1.
Embodiment 3
Be 0.1 except changing the content of yellow organic pigment, 0.5,1,2,5wt%, other operations are with embodiment 1.The yellow TPU expanded particle material that the TPU foam material obtained is any surface finish, does not obviously shrink.Otch expanded particle can be observed inside and outside colored TPU expanded particle has uniform pigment distribution.Concrete data are in table 2.
Embodiment 4
Except the content pigment brings up to 3wt%, TPU expanded particle B1 ' is proceeded warm air foaming 30s, and the temperature of this warm air is 100-140 DEG C, obtains B2 ', obtains B3 ' after high-pressure air carries pressure, and other operations are with embodiment 1.The yellow TPU expanded particle material that the TPU expanded particle material obtained is any surface finish, does not obviously shrink.Otch expanded particle can be observed inside and outside colored TPU expanded particle has uniform pigment distribution.Concrete data are in table 3.
Embodiment 5
Yellow TPU expanded particle B2 or B3 ' is injected the footwear mould of EPP expanded particle forming machine, closing molding, passes into water vapour and heats mould in mould, carries out cold water cooling, draining, blowing to mould, open mould, obtained yellow TPU expanded particle formed body sole.Wherein the temperature of water vapour is 138 degree, and the heat-up time of water vapour is 40s.As shown in Figure 6, yellow TPU expanded particle formed body material interface bonding is good, and pigment is even in formed body surface arrangement.Test shows: the mean density of yellow TPU expanded particle formed body sole is 0.29g/cm
3, hardness is Shao A42.
Embodiment 6
The TPU expanded particle red and white of yellow for 20wt% TPU expanded particle and 80wt% is injected the footwear mould of EPP expanded particle forming machine, closing molding, in mould, pass into water vapour heat mould, cold water cooling, draining, blowing are carried out to mould, open mould, obtained yellow TPU expanded particle formed body sole.Wherein, wherein the temperature of water vapour is 145 degree, and the heat-up time of water vapour is 10s.As shown in Figure 7, mixture colors TPU expanded particle formed body material interface bonding is good, and pigment, in TPU expanded particle, obviously migration does not occur.Test shows: the density of mixture colors TPU expanded particle formed body sole is 0.36g/cm
3, hardness is Shao A45.
Embodiment 7
The pigment of TPU particle (production of Dow Chemical company), 1wt% is dry mixed, extrudes through forcing machine, mold pressing makes the colored TPU sheet material that thickness is 2mm, cut into the disk that diameter is 20mm.Colored TPU disk is put into autoclave, adopts low temperature, high pressure CO
2fluid impregnated TPU particle, makes high pressure CO
2fluid reaches dissolution equilibrium in TPU resin particle.TPU particle after dipping is put into water-bath foam, obtain yellow TPU expanded particle B1.It is room temperature, high-pressure air year pressure that the disk B1 that foamed by TPU puts into temperature, obtains yellow TPU foaming disk B2.Except changing the kind of the color of pigment, the content of titanium dioxide is 3wt%, and other processing parameters are with embodiment 1.Figure 8 shows that the optical photograph of the colored TPU foam material that interpolation titanium dioxide, carbon black, phthalocyanine blue, everbright fast red, permanent yellow pigment, fluorescyanine obtain.As shown in Figure 8, the TPU foam material obtained all significantly does not shrink trace.Otch expanded particle can be observed inside and outside colored TPU expanded particle has uniform pigment distribution.Table 4 is depicted as the performance index of colored TPU disk.
Comparative example 5
Except not adding pigment, other operations are with embodiment 7.The white TPU expanded particle material that the TPU foam material obtained is any surface finish, does not obviously shrink.Compare with the TPU foam sheet adding titanium dioxide in embodiment 7, the color of the TPU foam sheet that comparative example 5 obtains is partially dark.
Embodiment 8
Thickness except yellow TPU cast sheet is 15mm, and other operations are with embodiment 7.The thickness of the yellow TPU foam sheet obtained is 30mm.Further, the TPU foam material obtained significantly does not shrink trace, has uniform pigment distribution inside and outside colored TPU foam sheet.
Embodiment 9
Adopt the chopper of silicon rubber sponge, to hardness be Shao A20, thickness is that the yellow TPU foam sheet of 30mm is split and cut, prepare thickness be respectively 0.2,0.5,1,2,5,10mm split sheet.It is even that sheet appearance color is split in the yellow TPU foaming obtained, and smooth texture is smooth.
Embodiment 10
Be that the yellow TPU foam sheet of 8mm puts into the shoe-pad mould that temperature is 155 DEG C by thickness, merge mould heat pressure, water cooling mold, die sinking, obtained yellow TPU foamed shoe-pad.Obtained yellow TPU foaming shoe material is bright in luster, homogeneous, does not significantly shrink trace.
Embodiment 11
Be 10mm by upper thickness, lower thickness is that to put into temperature be 175 DEG C of shoe moulds to the trapezoidal fluorescence cyan foam sheet of 3mm, merges mould heat pressure, water cooling mold, die sinking, and obtained fluorescence cyan TPU foams at the end in sports shoes.Obtained fluorescence cyan TPU foaming shoe material is bright in luster, homogeneous, does not significantly shrink trace.
The preparation technology parameter of the colored TPU expanded particle of table 1. and performance index
The performance index of the colored TPU expanded particle of the different yellow ultramarine content of table 2.
The impact of table 3. warm air second time of foaming whether on TPU expanded particle performance perameter
Table 4. adopts different sorts pigment to make the parameter of colored TPU foam sheet
Above-described embodiment and graphic and non-limiting product form of the present invention and style, any person of an ordinary skill in the technical field, to its suitable change done or modification, all should be considered as not departing from patent category of the present invention.
Claims (9)
1. colored TPU foam material, it is characterized in that, described colored TPU foam material is made up of colored expanded particle or colored foam sheet, in described colored expanded particle or colored foam sheet, the concentration of pigment is 0.01 ~ 5wt%, described pigment has identical concentration inside and outside colored TPU foam material, and the hardness of described colored TPU foam material is Shao A5-65, density is 0.05-0.5g/cm
3, average cell size is less than 100 μm.
2. colored TPU foam material as claimed in claim 1, is characterized in that, described colored expanded particle is spherical or elliposoidal, and wherein the ratio of major axis and short-axis direction is 1 ~ 3, and wherein minor axis is of a size of 0.5 ~ 5.0mm.
3. colored TPU foam material as claimed in claim 1, is characterized in that, the thickness of described foam sheet is 0.5 ~ 30mm.
4. a kind of colored TPU foam material as claimed in claim 1, is characterized in that, in described colored expanded particle or colored foam sheet, the concentration of pigment is 0.1 ~ 3wt%.
5. colored TPU foam material as claimed in claim 1, is characterized in that, in described colored expanded particle or colored foam sheet, the concentration of pigment is 0.2 ~ 2wt%.
6. colored TPU foam material as claimed in claim 1, is characterized in that, described pigment is organic molecule pigment, and the thermostability of this organic molecule pigment is higher than 180 DEG C.
7. colored TPU foam material as claimed in claim 1, is characterized in that, described pigment is mineral dye, and described mineral dye is carbon black or titanium dioxide.
8. utilize colored TPU foam sheet described in any one of claim 1 to 7 to prepare a method for footwear material, it is characterized in that, comprise the steps:
1. allow colored TPU foam sheet produce viscous deformation by the mode of compression molding and make footwear material, the temperature of compression molding is 130 ~ 170 DEG C.
9. the purposes of colored TPU foam material as described in any one of claim 1 to 7, it is characterized in that, described colored TPU foam material is applied to footwear material, crash helmet, bumper inner core, bicycle tyre and sports equipment cushion mat field.
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| CN105085968A (en) * | 2015-06-30 | 2015-11-25 | 上海高裕家居科技有限公司 | Polyurethane material with irregular grains and production process for polyurethane material |
| CN105968403A (en) * | 2016-05-19 | 2016-09-28 | 晋江国盛新材料科技有限公司 | Method for preparing colored TPU (thermoplastic polyurethanes) molding body through co-molding |
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| CN108948722A (en) * | 2018-07-24 | 2018-12-07 | 泉州泰亚鞋业有限公司 | High-elastic endurance foaming shoe material and its manufacturing method |
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| CN111808354A (en) * | 2019-04-10 | 2020-10-23 | 东莞市龙奕实业有限公司 | Production process of supercritical physical foaming coarse-pore sports equipment |
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