CN106009028B - A kind of preparation method of colored or double-colored TPU expanded beads molding bonded body - Google Patents
A kind of preparation method of colored or double-colored TPU expanded beads molding bonded body Download PDFInfo
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- CN106009028B CN106009028B CN201610332964.5A CN201610332964A CN106009028B CN 106009028 B CN106009028 B CN 106009028B CN 201610332964 A CN201610332964 A CN 201610332964A CN 106009028 B CN106009028 B CN 106009028B
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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
- C08J9/22—After-treatment of expandable particles; Forming foamed products
- C08J9/224—Surface treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/16—Making multilayered or multicoloured articles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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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
- C08J9/22—After-treatment of expandable particles; Forming foamed products
- C08J9/228—Forming foamed products
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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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/06—Polyurethanes from polyesters
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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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
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- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
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Abstract
The present invention discloses the preparation method of a kind of colored or double-colored TPU expanded beads molding bonded body, and the preparation method of colored TPU expanded beads molding bonded body comprises the following steps：1. the PPG that constitutes the isocyanates being made up of component A, chain extender, water, catalyst, cell modifiers and B component, PEPA obtain PU performed polymers in mixing chamber mixed at high speed；2. PU performed polymers are injected into the mixing chamber for filling TPU expanded beads, mixed at high speed is quantitatively injected into mould by Melt Pump；3. closed die, mould is positioned in circulation drying tunnel and is heating and curing；4. mould is opened, molding bonded body material is taken out, and be placed in drying chamber and further solidify；Pigment is added in the component A of step 1. or the TPU expanded beads are colour TPU expanded beads.
Description
Technical field
The present invention relates to a kind of painting methods of TPU expanded beads formed body, by the way that TPU expanded beads or surface are contaminated
Base polyurethane prepolymer for use as mixed at high speed of the TPU expanded beads of color with base polyurethane prepolymer for use as or comprising pigment is uniform, injects mould,
Base polyurethane prepolymer for use as is set to crosslink reaction through baking oven heat treatment, so as to be prepared into colorful various colors, controlled shape, can answer
Close the TPU expanded bead molding bonded body materials of cloth and plastics/rubber parts, the sport footwear shoe-pad/midsole that is particularly suitable for use in, ground cushion,
The fields such as sport protection material.
Background technology
Resilient foam material such as EVA expanded materials are widely used in the fields such as footwear material, athletic protective.Ethene-vinyl acetate
Copolymer (EVA) birds of the same feather flock together compound expanded material be used to making the features such as there is lightweight, elasticity the shoe-pad of sport footwear, midsole and
Outer bottom.Colored EVA expanded materials assign the abundant colour match of sport footwear and good designed capacity.Prepare colour EVA hairs
The technique of bubble footwear material is disclosed.A kind of method is low temperature such as pigment and EVA particles, auxiliary agent, filler, foaming agent, crosslinking agents
Height is mixed, mill, extruding pelletization, particulate material foamable and/or secondary mould shape in a mold, so as to prepare colored EVA hairs
Steep footwear material.Another method is that pigment is combined into EVA foaming systems, by the one-shot forming of injection foaming technique into colored EVA
Foaming shoe material, especially EVA foaming sandals.
EVA resin for preparing EVA foam shoe material is thermoplasticity, can be by way of melt-processed to be prepared into
Need shape.But, need to be chemically crosslinked when EVA resin foams.EVA Foamexes with cross-linked structure are one big point
Son, 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 is generally carried out using chemical blowing mode, and chemical blowing process produces toxic and harmful gas, CBA point
Solution not exclusively causes Material Manufacturing Process not environmentally, and material property is unstable.
ETPU is a kind of new flexible macromolecule expanded material, and its rebound performance is excellent, Compression Set is low,
It is applied to high-end sport footwear midsole shoe material.ETPU is, using TPU resins as raw material, TPU foaming to be prepared by physical foaming technology
Bead material, TPU expanded bead materials are molded by vapor, so as to be prepared into ETPU formed body materials.
Patent document ZL201410196699.3 is described using colored TPU resins as raw material, supercritical CO2For foaming agent,
The migration of pigment is avoided using techniques such as high-pressure fluid low temperature dipping, short time foamables, so that it is uniform to be prepared for dyestuff
It is dispersed in the TPU expanded beads in polymer surfaces and matrix.The color of expanded material it is main by the concentration of its surface pigment Lai
Determine, and the pigment inside expanded material is not contributed significantly.Because pigment is expensive, hybrid pigment needs addition compatible
Agent, auxiliary agent, secondary granulation, which increase cost；Secondly, the foam structure, swollen of influence expanded material is tended in additions of pigment
Swollen multiplying power, accordingly, foaming process also result in the change of material surface color, uneven foam structure or uneven
Expansion multiplying power will cause material formation aberration, and this influences the lot stability of expanded material.
The vapor forming method of colored ETPU beads is known, the colored ETPU beads in vapor die forming machine
It is heated to expand, strand diffusion occurs between bead interface and tangles, the molecular chain structure of interface is made by cold water cooling
Cool down, so as to be prepared into colored ETPU bead moldings material.The steam temperature applied in forming process up to 120-
150 degree, heating process can cause pigment molecule to migrate, further, and the expansion process of ETPU beads also results in pigment
Molecule is different with the concentration of bead interface in bead body, so as to be easily caused aberration problem.
When ETPU beads are used to make shoe-pad, it is necessary to which material and cloth are combined, high-temperature vapor meeting when vapor is molded
Cause the colour fading of cloth, meanwhile, it is difficult to be accurately positioned in a mold that cloth is excessively soft, therefore, is difficult to using vapor moulding process
The ETPU shoe-pads for adding cloth are prepared, particularly when shoe-pad has radian and flank.
The content of the invention
It is an object of the invention to provide a kind of molding bonded painting methods of TPU expanded beads, from cleaning, cheap, ring
The friendly high pressure CO in border2Fluid is physical blowing agent, prepares and is foamed with superficial cortical layers, foam structure for the TPU of 100% closed pore
Bead.
By the isocyanates being made up of component A, chain extender, water, catalyst, cell modifiers and gathering for being made up of B component
The performed polymer and TPU expanded beads mixed at high speed that ester polyol, PPG are mixed with are uniform, will be mixed by Melt Pump
In material injection mould, by curing process, the TPU expanded bead compression molding body materials of structure-controllable are obtained.
Pigment is added by the TPU expanded beads dyeing of white or in performed polymer, the dyeing of formed body can be realized.
It is possible to further which the TPU expanded particle mix and match with different colours, the formed body with camouflage color effect can be prepared
Material.
Cloth or working of plastics can be pre-placed in a mold, and TPU expanded beads and PU pre-polymer mixtures are poured into a mould
It is molded thereon, thus this technique is highly convenient for preparing the composite article for posting cloth or working of plastics.
Selected performed polymer formula has good flexibility and elasticity, and this causes prepared TPU expanded beads to glue
Knot formed body sense of touch is good, excellent in mechanical performance, is suitably employed in sport footwear shoe-pad/multiple fields such as midsole and athletic protective.
TPU is the class thermoplastic elastic synthesized by polyisocyanates, PEPA or PPG, chain extender etc.
Body material.The various types of polyisocyanates, but yield maximum only two kinds, i.e. methyl diphenylene diisocyanate (MDI)
With toluene di-isocyanate(TDI) (TDI).The species of polyalcohol is various, mainly including PEPA, PPG, polycarbonate
Polyalcohol, polyolefin polyhydric alcohol, polyacrylate polyol etc..Glycol such as butanediol, ethylene glycol, propane diols etc. are chain extender.
At present, in the market can be provided TPU resin types are a lot, different hardness, different melt flow index, different chemical structures,
Different physical property etc., this provides convenience to prepare suitable TPU expanded materials.
By the isocyanates being made up of component A, chain extender, water, catalyst, cell modifiers with being made up of B component
PEPA and PPG mixing, through heat cure can prepare PU elastomeric materials.Come for TPU expanded beads
Say, PU elastomeric materials can serve as binding agent, because TPU and PU have similar chemical constitution, both have fabulous phase
Capacitive, therefore prepared molding bonded body material has excellent mechanical property.By regulate and control A, B component chemical constitution with
And the proportioning of A/B components, it can prepare with the appropriate TPU expanded bead molding bonded body materials of pliability, elasticity.
According to wikipedia, so-called pigment is exactly the material for making material catch color.Pigment why can display color,
The color of the visible ray of some wavelength can be reflected or absorb in them.Pigment is broadly divided into organic pigment and inorganic pigment.Nothing
Machine pigment is usually mineral material, and organic pigment is typically derived from plant, marine animal or organic synthesis.TPU resins are main
It is known for being dyed using organic molecule pigment.The processing temperature of TPU resins is typically not less than 180 DEG C, and this requires organic
The temperature tolerance of small molecule pigment typically will be more than 180 DEG C.Inorganic pigment typically has a very high temperature tolerance, but often containing lead,
, there is environmental issue in the heavy metals such as mercury, chromium, cadmium, secondly inorganic pigment has the problem of dyeing not vivid enough.Carbon black is organic
The carbon black of modification is the conventional black pigment of TPU resins, and it does not contain the heavy metals such as lead, mercury, chromium, cadmium, in the absence of environmental issue.
The titanium dioxide of titanium dioxide or organic decoration is the conventional Chinese white of TPU resins, and it does not contain the huge sum of money such as lead, mercury, chromium, cadmium
Category, also in the absence of environmental issue.
Our research finds that reaction temperature of the PU prepolymers when solidifying crosslinking is only 30-60 degree, the mould temperature of preheating
Degree is also only 40-80 degree, and therefore, pigment need not necessarily select resistant to elevated temperatures organic pigment, the bad organic fluorescence of temperature tolerance
Pigment can also meet the coloring process of the present invention.By adding pigment in PU performed polymers, it is possible to achieve white TPU expanded beads
The dyeing of grain molding bonded body material.
Our research finds that the oil color molecule in the solution prepared by oil color/inorganic agent/solvent is easy
In absorption in the outer surface of white TPU expanded beads, this absorption general satisfaction mono layer adsorption or multi-molecular absorption.
Further find, by washing, drying and other steps, oil color molecule of the uniform adsorption in TPU expanded beads outer surface
There are good color fastness, the mechanical friction of water-fastness, resistance to some strength.TPU expanded beads after dyeing and PU performed polymers is high
Speed mixing and solidification, can prepare the TPU expanded bead molding bonded body materials of colour.It is possible to further which difference will be infected with
The TPU expanded beads of color it is two kinds or more of mixing cured with PU performed polymers, can prepare with camouflage color effect TPU hair
Steep bead bond formed body material.It is possible to further by TPU expanded beads/PU pre-polymer mixtures with different colours
The privileged site of mould is sequentially placed into, double-colored or polychrome TPU expanded beads molding bonded body material can be prepared.
The problem of being positioned due to mould, vapor moulding process be difficult to ETPU bead moldings carry out Compound Fabric or
Other working of plastics of person, our research finds that TPU expanded beads/PU pre-polymer mixtures have preferable mobility, Ke Yitong
Cross Melt Pump and realize cast in situs and curing molding.Therefore, this technique be especially suitable for a molding bonded body and cloth or other
Working of plastics is combined, so as to prepare shoe-pad and midsole shoe material.
It is an object of the invention to provide a kind of molding bonded painting methods of TPU expanded beads, by PU performed polymers
Disperse pigment or using the TPU expanded beads for being infected with pigment, can realize and TPU expanded bead molding bondeds body is realized
Color, TPU expanded beads/PU pre-polymer mixture viscosity is low, can carry out cast in situs curing molding by Melt Pump, very just
In mixture and cloth either working of plastics are carried out into compoiste adhering shaping, sport footwear shoe-pad and midsole product are prepared.
TPU expanded beads are adopted in the present invention realizes dyeing with the following method, comprises the following steps：
1) by TPU expanded bead pickling, the dispersant that is added in the grease of its outer surface, foaming process, absorption are removed
Dust etc.；
2) pigment, inorganic agent, stirring solvent are prepared by mixing into pigment solution；
3) TPU expanded beads are put into pigment solution, stirring makes TPU expanded beads be sufficiently mixed with pigment solution；
4) the TPU expanded beads after dyeing are isolated with screen cloth, scrubbed, low temperature drying is prepared into pigment and uniformly divided
The TPU expanded beads of cloth.
Step 1) described in TPU expanded particles size be 1-8mm, preferably 1-5mm.
Step 1) described in the hardness of TPU expanded particles be Shao's C5-60 degree, when applied to soft shoe-pad, preferred Shao
C10-30 degree, when applied to motion midsole, preferred Shao C30-60 degree.
Step 1) described in TPU expanded beads multiplying power be 4-10 times, preferably 4-8 times.
Step 1) described in TPU expanded beads there is fine and close epidermis, wherein skin thickness is less than 50 microns, excellent selection
There are the TPU expanded beads of minimum fold on surface.
Step 2) described in pigment concentration in the solution be 1-10000ppm.
Step 2) described in solvent in methanol, methyl ether, toluene, ethanol, ether, propyl alcohol, butanol, amylalcohol, hexanol etc.
One or more.
In order to further improve the thickness that pigment improves coat of colo(u)r in the adhesive force of TPU expanded beads outer surface and further
Degree, can also by step 2) in add the method for resin and realize.Described resin be low molecule amount TPU resins, low point
Son measures EVA resin, acrylic resin, preferably SEBS grafted maleic anhydride resins, low molecule amount TPU resins, and its middle-molecular-weihydroxyethyl is
1000-20000.This promotes the pigment thickness increase of dyeing TPU expanded beads outer surface.
The present invention adopts with the following method to prepare colored TPU expanded beads molding bonded body material, comprises the following steps：
1. by gathering that the isocyanates being made up of component A, chain extender, water, catalyst, cell modifiers and B component are constituted
Ethoxylated polyhydric alcohol, PEPA are obtained in mixing chamber mixed at high speed (mixed at high speed refers to that mixing rate reaches 1000-10000rpm)
PU performed polymers；
2. PU performed polymers are injected into the mixing chamber for filling TPU expanded beads, (mixed at high speed refers to mixing speed to mixed at high speed
Rate reaches 1000-10000rpm), quantitatively it is injected into by Melt Pump in mould；
3. closed die, mould is positioned in circulation drying tunnel and is heating and curing；
4. mould is opened, molding bonded body material is taken out, and be placed in drying chamber and further solidify；Pigment is added to
In the component A of step 1. or the TPU expanded beads be colour TPU expanded beads.
Further, 1. described component A includes 100 parts of isocyanates, 1-5 parts of chain extenders, 1-3 parts of water, 0.2-1.0 to step
0-5 parts of part catalyst, 0.5-2 parts of cell modifiers and pigment；Described B component includes 40-60 parts of PEPAs and 60-
40 parts of PPGs.
Further, the viscosity of step 1. described PU performed polymers is 300-3000mPa.s.
Further, 1. described pigment is inorganic or organic pigment to step, and inorganic pigment is carbon black or titanium dioxide, You Jiyan
Material is selected and the good pigment of PU resin compatibles, and organic pigment is the iridescent pigment of heat resistance difference.
Further, 2. described TPU expanded beads are the colored TPU expanded beads after white or dyeing to step, wherein
The size of TPU expanded particles is 1-8mm, preferably 1-5mm, and the hardness of TPU expanded particles is Shao's C5-60 degree, when applied to soft
Shoe-pad when, preferred Shao C10-40 degree, when applied to motion midsole, preferred Shao C30-60 degree.
Further, 2. described TPU expanded beads can be identical size to step, or various sizes of mixing
Thing, can be same color, or the mixture of two kinds or multiple color.
Further, step 2. described in the mixed proportion of PU performed polymers and TPU expanded beads be 1：0.2-1：10, preferably
1：0.5-1：5.
Further, 2. described mould needs preheating to step, and preheating temperature is 40-80 degree.
Further, 2. step can be pre-placed cloth or working of plastics in described mould.
Further, 3. described solidification temperature is 30-60 degree to step, and hardening time is 3-20 minutes.
Further, the temperature of step 4. described drying chamber is 30-40 degree, and drying time is 1-12h.
The present invention adopts with the following method to prepare double-colored TPU expanded bead molding bonded body materials, comprises the following steps：
1. by gathering that the isocyanates being made up of component A, chain extender, water, catalyst, cell modifiers and B component are constituted
Ethoxylated polyhydric alcohol, PEPA obtain PU performed polymers in mixing chamber mixed at high speed；
2. PU performed polymers are injected separately into the first mixing chamber and the second mixing chamber for filling TPU expanded beads, it is mixed at a high speed
Close, material in first mixing chamber is injected into mould by the way that Melt Pump is quantitative, it is with the first cope plate that material is flat；
3. closed die, is positioned over heating part in circulation drying tunnel by mould and solidifies；
4. mould is opened, the first cope plate is taken out, changes the second cope plate into, the material in the second mixing chamber is injected into mould
In, mould is positioned in circulation drying tunnel and is heating and curing by closed die.
5. mould is opened, molding bonded body material is taken out, and be placed in drying chamber and further solidify；Pigment is added to
In the component A of step 1. or the TPU expanded beads be colour TPU expanded beads.
Further, 1. described component A includes 100 parts of isocyanates, 1-5 parts of chain extenders, 1-3 parts of water, 0.2-1.0 to step
0-5 parts of part catalyst, 0.5-2 parts of cell modifiers and pigment；Described B component includes 40-60 parts of PEPAs and 60-
40 parts of PPGs.
Further, the viscosity of step 1. described PU performed polymers is 300-3000mPa.s.
Further, 1. described pigment is inorganic or organic pigment to step, and inorganic pigment is carbon black or titanium dioxide, You Jiyan
Material is selected and the good pigment of PU resin compatibles, and organic pigment is the iridescent pigment of heat resistance difference.
Further, 2. described TPU expanded beads are the colored TPU expanded beads after white or dyeing to step, wherein
The size of TPU expanded particles is 1-8mm, preferably 1-5mm, and the hardness of TPU expanded particles is Shao's C5-60 degree, when applied to soft
Shoe-pad when, preferred Shao C10-30 degree, when applied to motion midsole, preferred Shao C30-60 degree.
Further, 2. described TPU expanded beads can be identical size to step, or various sizes of mixing
Thing, can be same color, or the mixture of two kinds or multiple color.
Further, step 2. described in the mixed proportion of PU performed polymers and TPU expanded beads be 1：0.2-1：10, preferably
1：0.5-1：5.
Further, 2. step can be pre-placed cloth or working of plastics in described mould.
The invention has the advantages that：
The inventive method realizes the colouring of TPU bead moldings using the gluing method of PU performed polymers, PU performed polymers
Solidification temperature is low, is easy to by temperature tolerance is not high but color is more bright-coloured pigment such as fluorescent pigment composite diffusion into formed body,
TPU expanded bead mixtures are injected into mould by the modest viscosity of PU performed polymers, the method for conveniently implementing to pour, can in mould
To be pre-placed cloth and working of plastics, it is easy to prepare the shoe-pad and other complicated formed body materials of patch, can be by different colours
Expanded bead/pre-polymer mixture be implanted sequentially mould, be easy to prepare have double-colored TPU expanded bead formed body materials.
PU elastomer soft textures, tensile strength is high, wear-resisting, and not only performance is excellent for prepared TPU expanded bead molding bonded bodies material
It is different, and designability is strong.
As example, colored TPU expanded beads molding bonded body material of the invention can be with sheet material, Buffer Unit, sole
And other footwear are used with the form of part., according to the invention it is preferred to sole and shoe-pad etc..
The present invention is described in more detail in the examples below that.
Embodiment
In order to which technical scheme is explained further, the present invention is explained in detail below by specific embodiment
State.
Embodiment 1
By 100 parts of isocyanates, 2 parts of chain extenders, 2 parts of water, 0.5 part of catalyst, 0.5 part of cell modifiers, 50 parts of polyester
Polyalcohol, 50 parts of PPGs are stirred in mixing chamber high speed, are prepared into the PU performed polymers that viscosity is 900mPa.s.
PU performed polymers are injected into fill and are infected with the mixed of yellow TPU expanded particles (size is 2.0mm, and hardness is 30 degree of Shao)
Expect in room, the mixed proportion of PU performed polymers and TPU expanded particles is 1：1, material is passed through melt by high-speed stirred to well mixed
Pump is injected into the mould of 60 degree of preheatings, merges mould, mould is put into the circulation drying tunnel that temperature is 40 degree, hardening time is 10
Minute.
Mould is opened, molding bonded sample is taken out, the drying chamber that temperature is 35 degree is put into and continues to solidify 10 hours, obtain Huang
The TPU expanded bead molding bonded body materials of color.
Prepared molding bonded body texture material is soft, and stretching and tearing strength are high.
Embodiment 2
Except mould is the shoe-pad mould with flank, cloth is pre-placed in a mold, other be the same as Examples 1 are realized
Preparation with flank shoe-pad.
Prepared texture material is soft, stretching and tearing strength are high.
Embodiment 3
Except mould is motion midsole mould, big bottom sheet rubber is pre-placed in a mold, and other be the same as Examples 1 are real
Foaming midsole, the one-shot forming of sheet rubber are showed.Between prepared foaming materials layer soft texture, foaming layer and rubber slab
Peel strength is high.
Embodiment 4
Fluorescence green pigment except adding 1 part in component A, TPU expanded beads are white, prepared by other be the same as Examples 1
There is the TPU expanded bead molding bonded body materials of fluorescent green.Prepared formed body texture material is soft, stretches and tears
Resistance to spalling is high.
Embodiment 5
Except white TPU expanded beads include two kinds of sizes, respectively 2mm and 5mm, ratio is 2：1, other be the same as Examples
4, it is prepared for the TPU expanded bead molding bonded body materials with fluorescent green.Prepared formed body texture material is soft, draws
Stretch high with tearing strength.
Embodiment 6
100 parts of isocyanates, 2 parts of chain extenders, 2 parts of water, 1 part of catalyst, 0.5 part of cell modifiers, 40 parts of polyester are more
First alcohol, 60 parts of PPGs are stirred in mixing chamber high speed, are prepared into the PU performed polymers that viscosity is 400mPa.s.By PU pre-polymerizations
Body is injected into the first mixing chamber for filling white TPU expanded particles (size is 3.0mm, and hardness is 40 degree of Shao), PU performed polymers
Mixed proportion with TPU expanded particles is 1：1, high-speed stirred is to well mixed；Performed polymer is injected into and is infected with purple TPU foaming
In second mixing chamber of particle (size is 3.0mm, and hardness is 30 degree of Shao), the mixed proportion of PU performed polymers and TPU expanded particles
For 1：2, high-speed stirred is to well mixed.Material in first mixing chamber is injected into the first mould, the first cope plate is covered,
Being put into circulation drying tunnel drying makes PU performed polymers partially cured.The first cope plate is removed, the material in the second mixing chamber is injected into
In first mould, the second cope plate is covered, being put into circulation drying tunnel solidifies PU performed polymers.Take out TPU expanded bead molding bondeds
Body material, is put into drying chamber and continues to solidify 5 hours, obtains white/purple double-colored TPU expanded bead molding bonded materials.It is prepared
Molding bonded body texture material it is soft, stretching and tearing strength are high.
Claims (10)
1. a kind of preparation method of colored TPU expanded beads molding bonded body, it is characterised in that comprise the following steps：
1. the polyethers constituted the isocyanates being made up of component A, chain extender, water, catalyst, cell modifiers and B component is more
First alcohol, PEPA obtain PU performed polymers in mixing chamber mixed at high speed；
2. PU performed polymers are injected into the mixing chamber for filling TPU expanded beads, mixed at high speed is quantitatively injected into mould by Melt Pump
In tool；
3. closed die, mould is positioned in circulation drying tunnel and is heating and curing；
4. mould is opened, molding bonded body material is taken out, and be placed in drying chamber and further solidify；Pigment is added to step
1. in component A or the TPU expanded beads be colour TPU expanded beads；The pigment is by oil color/inorganic agent/solvent
Oil color molecule in the solution of preparation；
The TPU expanded beads are adopted realizes dyeing with the following method, comprises the following steps：
1) by TPU expanded bead pickling, the dispersant added in the grease of its outer surface, foaming process, the dust of absorption are removed
Deng；
2) pigment, inorganic agent, stirring solvent are prepared by mixing into pigment solution；
3) TPU expanded beads are put into pigment solution, stirring makes TPU expanded beads be sufficiently mixed with pigment solution；
4) the TPU expanded beads after dyeing are isolated with screen cloth, scrubbed, low temperature drying is prepared into pigment equally distributed
TPU expanded beads.
2. a kind of preparation method of double-colored TPU expanded beads molding bonded body, it is characterised in that comprise the following steps：
1. the polyethers constituted the isocyanates being made up of component A, chain extender, water, catalyst, cell modifiers and B component is more
First alcohol, PEPA obtain PU performed polymers in mixing chamber mixed at high speed；
2. PU performed polymers are injected separately into the first mixing chamber and the second mixing chamber for filling TPU expanded beads, mixed at high speed is led to
Melt Pump is crossed quantitatively the material in the first mixing chamber is injected into mould, it is with the first cope plate that material is flat；
3. closed die, is positioned over heating part in circulation drying tunnel by mould and solidifies；
4. mould is opened, the first cope plate is taken out, changes the second cope plate into, the material in the second mixing chamber is injected in mould,
Closed die, mould is positioned in circulation drying tunnel and is heating and curing；
5. mould is opened, molding bonded body material is taken out, and be placed in drying chamber and further solidify；Pigment is added to step
1. in component A or the TPU expanded beads be colour TPU expanded beads；The pigment is by oil color/inorganic agent/solvent
Oil color molecule in the solution of preparation；
The TPU expanded beads are adopted realizes dyeing with the following method, comprises the following steps：
1) by TPU expanded bead pickling, the dispersant added in the grease of its outer surface, foaming process, the dust of absorption are removed
Deng；
2) pigment, inorganic agent, stirring solvent are prepared by mixing into pigment solution；
3) TPU expanded beads are put into pigment solution, stirring makes TPU expanded beads be sufficiently mixed with pigment solution；
4) the TPU expanded beads after dyeing are isolated with screen cloth, scrubbed, low temperature drying is prepared into pigment equally distributed
TPU expanded beads.
3. preparation method as claimed in claim 1 or 2, it is characterised in that 1. described component A includes 100 parts of isocyanides to step
Acid esters, 1-5 parts of chain extenders, 0-5 parts of 1-3 parts of water, 0.2-1.0 parts of catalyst, 0.5-2 parts of cell modifiers and pigment；Described
B component includes 40-60 parts of PEPAs and 60-40 parts of PPGs.
4. preparation method as claimed in claim 1 or 2, it is characterised in that the viscosity of step 1. described PU performed polymers is
300-3000mPa.s。
5. preparation method as claimed in claim 1 or 2, it is characterised in that 1. described pigment is inorganic or organic face to step
Material, inorganic pigment is carbon black or titanium dioxide, and organic pigment is selected and the good pigment of PU resin compatibles, and organic pigment is temperature tolerance
The iridescent pigment of energy difference.
6. preparation method as claimed in claim 1 or 2, it is characterised in that step 2. described TPU expanded beads for white or
Colored TPU expanded beads after person's dyeing, the wherein size of TPU expanded particles are 1-8mm, when applied to soft shoe-pad,
The hardness of TPU expanded particles is Shao's C10-40 degree, and when applied to motion midsole, the hardness of TPU expanded particles is Shao C30-
60 degree.
7. preparation method as claimed in claim 1 or 2, it is characterised in that step 2. described in PU performed polymers foamed with TPU
The mixed proportion of bead is 1：0.2-1：10.
8. preparation method as claimed in claim 1 or 2, it is characterised in that 2. described mould needs preheating, preheating temperature to step
Spend for 40-80 degree.
9. preparation method as claimed in claim 1 or 2, it is characterised in that step be 2. pre-placed in described mould cloth or
Person's working of plastics.
10. preparation method as claimed in claim 1 or 2, it is characterised in that solidification temperature is 30-60 degree, and hardening time is 3-
20 minutes；The temperature of drying chamber is 30-40 degree, and drying time is 1-12h.
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| CN106497009A (en) * | 2016-10-28 | 2017-03-15 | 丁钰 | A kind of manufacture method of movement cushioning element |
| CN107353428A (en) * | 2017-08-08 | 2017-11-17 | 陈茂双 | The manufacture craft of TPU puffed rice footwear materials |
| CN108794797A (en) * | 2018-05-11 | 2018-11-13 | 美瑞新材料股份有限公司 | A kind of preparation method of the colored thermoplastic polyurethane foam particle with low aberration |
| CN111150174A (en) * | 2018-11-08 | 2020-05-15 | 冠颉股份有限公司 | Shoe pad and its regulating and making method |
| CN109676860A (en) * | 2018-12-21 | 2019-04-26 | 中山市政兴塑料制品有限公司 | A kind of production technology of insole |
| CN111086121A (en) * | 2019-11-20 | 2020-05-01 | 晋江兴迅新材料科技有限公司 | Manufacturing process of luminous etpu popcorn shoes |
| CN111469365A (en) * | 2020-03-30 | 2020-07-31 | 广东维杰汽车部件制造有限公司 | Reaction injection molding process of automobile spoiler |
| CN116003869A (en) * | 2022-11-09 | 2023-04-25 | 宁波聚泰新材料科技有限公司 | Preparation method of antifouling foaming polyurethane elastomer |
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| AR075000A1 (en) * | 2009-01-24 | 2011-03-02 | Bayer Materialscience Ag | POLYURETHANE FOAMS STABILIZED WITH POLYURETHANE TENSIOACTIVE |
| KR101332433B1 (en) * | 2010-08-24 | 2013-11-22 | 제일모직주식회사 | Rigid polyurethane foam having good insulation property and method for preparing the same |
| US9498927B2 (en) * | 2013-03-15 | 2016-11-22 | Nike, Inc. | Decorative foam and method |
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