CN101678577B - Foam articles and methods of producing the same - Google Patents

Abstract

A method for producing a foam sheet comprises: forming a foamed material, casting the foamed material, impinging the cast material with a fluid at a sufficient pressure to form a hole, and curing the impinged material. If the foamed material comprises a thermoset, the foamed material is uncured or partially cured. If the foamed material comprises a thermoplastic, the foamed material is unset or partially set. A foam sheet comprises: a first surface and an opposite second surface, and a plurality of holes extending through the first surface toward the second surface. The holes comprise a skin cover, the holes having a conical geometry, and/or each of the holes has a diameter larger than the largest pore diameter of the foam, as well as combinations comprising at least one of the foregoing characteristics.

Description

Foam articles and preparation method thereof

The cross reference of related application

The application requires the rights and interests of the U.S. Provisional Application sequence number 60/910,986 of submission on April 10th, 2007, by reference this application integral body is incorporated to this paper.

Background technology

Foam articles and preparation method thereof is disclosed herein.

Polyurethane foamed material for example is used in the extensive use from the automotive seat to the carpet backing.The polyurethane foamed material plate has many can be used in footwear product as the favourable character in upper construction.Footwear product generally includes upper construction and footwear sole construction.Upper of a shoe cosily receives pin fixing feet in footwear sole construction.Footwear sole construction provides the durable medium of support foot and can comprise a plurality of parts.Modern footwear are the multipart combinations of being permitted with specific function, and all these parts must be cooperated to support and protect pin and obtain aesthetic property.

For function and/or purpose attractive in appearance, wishing to prepare in foamed material has depression in (" hole ") and run through in some cases the polyurethane foamed material goods of the opening (" through hole ") of foam.But in foamed material and/or not produce a large amount of waste materials and/or do not make the complicated process of preparation of foam for panel through foamed material forms hole be much a major challenge.Depression and/or through hole can form with card punch, but will produce waste material (it will increase the cost of foamed material and must be disposed), also can produce exposed abscess in addition.Exposed abscess may change the outward appearance of foam articles, for example the aberration between exposed abscess and foamed material surface.In addition, exposed abscess may affect the washability of goods, because of exposed abscess fluid-absorbing, changes potentially goods character.Depression and/or through hole also available suitable mould provide, but the manufacturing expense of this class mould is high, once and make and can not change the depression or clear size of opening or the pattern that provide different.

Soft foam articles and to prepare the method that goods wherein have the foam articles in the hole that is formed in goods and/or runs through goods be that people seek.

General introduction

Herein disclosed is foam articles and preparation method thereof.

In one embodiment, the method for preparing the polyurethane foamed material plate comprises: the composition that forms polyurethane is bubbled, to the reactive composition of the formation polyurethane of the described foaming of the first carrier top casting to form plate, impact this plate with fluid to form hole under enough pressure, and solidify the plate that the reactive composition of the formation polyurethane bubbled comprises hole with formation.The composition of described formation polyurethane can comprise component containing isocyanates, containing reactive hydrogen and component, surfactant and the catalyst system described component reaction containing isocyanates.

In another embodiment, the method for preparing foam for panel comprises: the material that forms foaming, the material of described foaming is cast on the first carrier, impacts this cast material to form hole under enough pressure with fluid, and solidify the plate that the described material through impacting comprises hole with formation.If the material of described foaming comprises thermosets, the material of described foaming is without solidifying or through partly solidified.If the material of described foaming comprises thermoplastic, the material of described foaming is without solidifying or through partial coagulation, and may also need cooling step.

In one embodiment, foam for panel comprises: first surface and relative second surface and a plurality of hole of extending to described second surface through described first surface.Described hole can have be selected from maximum diameter of hole that epidermis, conical geometry, diameter are foamed material at least twice characteristic and comprise at least one the combination in afore-mentioned characteristics.

Above-mentioned and other feature is explained by following accompanying drawing and detailed description.

The accompanying drawing summary

With reference now to accompanying drawing,, these accompanying drawings are exemplary and nonrestrictive, and wherein similar part has identical Reference numeral.

Fig. 1-4 are the schematic diagram with the exemplary foamed board in the hole that is formed in foam and/or runs through foam.

The cross sectional representation of the example foam plate of material that Fig. 5 is preparation as described herein.

Describe in detail

Foam articles (as can be used for various application comprise the foam for panel in footwear etc.) can have desirable pore size distribution, geometry and the degree of depth by using fluid jet be prepared as in foam for panel preparation technology.Fluid jet can foamed material partly solidified/use before solidifying, in process and/or afterwards.Can regulate in addition and/or Control Nozzle size, geometry and fluid pressure to produce sectional hole patterns, hole design and/or hole geometry and to obtain desirable structural intergrity and/or aesthetic property.

Foamed material can be mechanically and/or chemical mode (as by physical blowing (as mechanical foaming), chemical blowing and comprise at least one the combination in aforementioned) preparation.For example, then polymeric blends (comprise isocyanate component, containing component and other additives of reactive hydrogen) can solidify through mechanical foaming.Foamed material can form plate by casting.

Foam for panel can for example, be formed as thermoplastic foam and/or thermosetting foams material by various foamed materials (perforate or closed pore).Some possible foamed materials comprise silicone, polyurethane, polyolefin (such as polyethylene, low density polyethylene (LDPE), high density polyethylene (HDPE), polypropylene, ethylene-propylene copolymer etc.), polyester, polyamide, fluorinated polymer, polyalkylene oxide (as PEO and PPOX), polyvinyl alcohol, ionomer (as the ethylene-methacrylic acid copolymer with the alkali neutralization), cellulose acetate, polystyrene etc. and comprise at least one the combination in aforementioned.

Polymer for foamed material can be selected from blend or the thermosetting resin of thermoplastic resin, thermoplastic resin widely.The example of available thermoplastic resin comprises polyacetals, polyacrylic, styrene-acrylonitrile, polyolefin, acrylonitrile-butadiene-styrene (ABS), Merlon, polystyrene, PETG, polybutylene terephthalate (PBT), polyamide is (such as but not limited to nylon 6, nylon 6, 6, nylon 6, 10, nylon 6, 12, nylon 11 or nylon 12), polyamidoimide, polyarylate, polyurethane, EP rubbers (EPR), polyarylsulfone (PAS), polyether sulfone, polyphenylene sulfide, polyvinyl chloride, polysulfones, PEI, polytetrafluoroethylene (PTFE), PEP, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, polyether-ketone, polyether-ether-ketone, polyether-ketone, ketone etc. or comprise at least one the combination in aforementioned thermoplastic resin.

The example that can be used for the blend of the thermoplastic resin in polymer foams comprises acrylonitrile-butadiene-styrene (ABS)/nylon, PC/Abs, acrylonitrile-butadiene-styrene (ABS)/polyvinyl chloride, polyphenyl ether/styrene, polyphenyl ether/nylon, polysulfones/acrylonitrile-butadiene-styrene (ABS), Merlon/thermoplasticity ammonia ester, Merlon/PETG, Merlon/polybutylene terephthalate (PBT), thermoplastic elastomer alloy, PETG/polybutylene terephthalate (PBT), phenylethylene-maleic anhydride/acrylonitrile-butadiene-styrene (ABS), polyether-ether-ketone/polyether sulfone, SBR styrene butadiene rubbers, polyethylene/nylon, polyethylene/polyacetals, EP rubbers (EPR) etc. or comprise at least one the combination in aforementioned blend.

The example that can be used for the heat of polymerization thermosetting resin in polymer foams comprises polyurethane, epoxy resin, phenolic resins, polyester, polyamide, silicone etc. or comprises at least one the combination in the aforementioned hot thermosetting resin.Also can use the blend of thermosetting resin and the blend of thermoplastic resin and thermosetting resin.

Other additives that become known in foamed material preparation can be present in foam composition of the present invention, for example other fillers as reinforcer as woven webs, silica, glass particle, glass microballoon, the filler that is used to provide heat management or fire retardant filler or additive.Suitable fire retardant comprises the metal hydroxides that for example contains aluminium, magnesium, zinc, boron, calcium, nickel, cobalt, tin, molybdenum, copper, iron, titanium or its combination, such as aluminium hydroxide, magnesium hydroxide, calcium hydroxide, iron hydroxide etc.; Metal oxide is as antimony oxide, antimony trioxide, antimony pentaoxide, iron oxide, titanium oxide, manganese oxide, magnesia, zirconia, zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, chromium oxide, tin oxide, nickel oxide, cupric oxide, tungsten oxide etc.; Metal borate is as Firebrake ZB, zinc metaborate, barium metaborate etc.; Metal carbonate is as zinc carbonate, magnesium carbonate, calcium carbonate, brium carbonate etc.; Melamine cyanurate, melamine phosphate etc.; Carbon black, expansible graphite sheet (for example can be from GrafTech International, those that Ltd. obtains with trade name GRAFGUARD) etc.; Nanoclay; And brominated compound.Exemplary flame retardant materials is magnesium hydroxide, nanoclay and brominated compound.In one embodiment, the anti-flammability of polymer foams meets some Underwriters Laboratory (Underwriter ' s Laboratory, the UL) standard about anti-flammability.For example, polymer foams is V-0 by the grade of UL standard 94.

Other additives that also can exist comprise dyestuff, pigment (such as titanium dioxide and iron oxide), antioxidant, antiozonant, ultraviolet (UV) stabilizing agent, conductive filler, catalyst, crosslinking agent etc. and comprise at least one the combination in aforementioned additive for polymer cure.

The particular polymers that is used for the preparation of foamed material comprises polyurethane foamed material and silicone foam material.For example, generally speaking, polyurethane foamed material is formed by reactive composition, and described reactive composition comprises organic isocyanate component, surfactant and the catalyst with the component reaction that contains reactive hydrogen.The organic isocyanate component of using in the preparation of polyurethane foamed material usually comprises and has general formula Q (NCO) _ipolyisocyanates, the integer that wherein " i " is greater than 2 for mean value, Q is the organic group that chemical valence is " i ".Q can be and replaces or unsubstituted alkyl (as suitable valent alkyl or aryl).Q can be has formula Q ¹-Z-Q ¹group, Q wherein ¹for alkylidene or arlydene, Z is-O-,-O-Q ¹-S ,-CO-, S-,-S-Q ¹-S-,-SO-or-SO ₂-.Exemplary isocyanates comprises hexamethylene diisocyanate, 1, 8-bis-isocyanate groups are to methane, the xylyl vulcabond, two isocyanate group cyclohexanes, phenylene vulcabond, toluene di-isocyanate(TDI) (comprises toluene 2, the 4-vulcabond, toluene 2, 6-vulcabond and crude toluene diisocynate), two (4-isocyanate group phenyl) methane, the chloro phenylene vulcabond, diphenyl methane-4, 4 '-vulcabond is (also referred to as 4, 4 '-methyl diphenylene diisocyanate or MDI) and adduct, naphthylene-1, the 5-vulcabond, triphenyl methane-4, 4 ', 4 "-triisocyanate, isopropylbenzene-α-4-vulcabond, the aggretion type isocyanates is as polymethylene polyphenyl isocyanate and comprise at least one the combination in aforementioned isocyanates.

Q also can mean the polyurethanyl group that chemical valence is " i ", in this case Q (NCO) _ifor being known as the composition of prepolymer.Such prepolymer by make polyisocyanates as excessive as described stoichiometry above and hereinafter with as the described component containing reactive hydrogen is especially described below hereinafter containing polyhydric material or polyol reaction, forms.Usually, polyisocyanates is for example approximately 30% to arrive the approximately excessive ratio use of 200% stoichiometry, the isocyanate groups equivalents of stoichiometry based on every equivalent hydroxyl in polyalcohol.The consumption of polyisocyanates will be according to the character slight modification of prepared polyurethane.

Component containing reactive hydrogen can comprise PPG and PEPA.Exemplary PEPA comprise polyalcohol and dicarboxylic acids or its become the polycondensation product of ester derivant (as acid anhydrides, ester and halide), the poly-lactone polyol that can obtain by the ring-opening polymerisation of lactone under existing at polyalcohol, can be by carbonic diester the polycarbonate polyol and the castor oil polyhydric alcohol that react acquisition with polyalcohol.The exemplary dicarboxylic acids and the dicarboxylic acid derivatives that can be used for preparing the polycondensation PEPA have aliphatic series or cycloaliphatic dicarboxylic acid as glutaric acid, adipic acid, decanedioic acid, fumaric acid and maleic acid; Dimeric dibasic acid; Aromatic dicarboxylic acid is as phthalic acid, M-phthalic acid and terephthalic acid (TPA); Ternary or higher official energy polybasic carboxylic acid are as PMA; And acid anhydrides and secondary Arrcostab are as maleic anhydride, phthalic anhydride and dimethyl terephthalate (DMT).

Other components containing reactive hydrogen have the polymer of cyclic ester.By at least one cyclic ester monomer prepare the cyclic ester polymer at patent documentation as United States Patent (USP) 3,021, be documented in 309 to 3,021,317,3,169,945 and 2,962,524.Exemplary cyclic ester monomer comprise δ-valerolactone, 6-caprolactone, ξ-heptalactone and monoalkyl-valerolactone (as monomethyl-, single ethyl-and single hexyl-valerolactone).Generally speaking, PEPA can comprise PEPA, aromatic polyester polyols, the polyalcohol based on ethylene glycol adipate based on caprolactone and comprise at least one the combination in aforementioned PEPA, the PEPA especially made by 6-caprolactone, adipic acid, phthalic anhydride, terephthalic acid (TPA) and/or dimethyl terephthalate (DMT).

PPG passes through epoxyalkane (as oxirane, expoxy propane etc. and comprise at least one the combination in aforementioned) with water or polyhydroxy organic component (as ethylene glycol, propane diols, trimethylene glycol, 1,2-butanediol, 1,3-BDO, BDO, 1,5-PD, 1,2-hexylene glycol, 1,10-decanediol, 1,2-cyclohexanediol, the 2-butene-1, the 4-glycol, 3-cyclohexene-1, the 1-dimethanol, 4-methyl-3-cyclohexene-1, the 1-dimethanol, 3-methylene-1,5-PD, diethylene glycol, (2-hydroxyl-oxethyl)-1-propyl alcohol, 4-(2-hydroxyl-oxethyl)-n-butyl alcohol, 5-(2-hydroxyl propoxyl group)-1-amylalcohol, 1-(2-hydroxyl methoxyl group)-2-hexanol, 1-(2-hydroxyl propoxyl group)-sec-n-octyl alcohol, 3-allyloxy-1,5-PD, 2-allyloxy methyl-2-methyl isophthalic acid, ammediol, [(4,4-amoxy)-methyl]-1,3-PD, 3-(o-acrylic phenoxy group)-1,2-PD, 2, two (to the inferior phenoxy group) diethanol of 2 '-diisopropylidene, glycerine, 1,2,6-hexanetriol, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, 3-(2-hydroxyl-oxethyl)-1,2-PD, 3-(2-hydroxyl propoxyl group)-1,2-PD, 2,4-dimethyl-2-(2-hydroxyl-oxethyl)-methyl pentanediol-1,5, 1,1,1-tri-[the 2-hydroxyl-oxethyl) methyl]-ethane, 1,1,1-tri-[2-hydroxyl propoxyl group)-methyl] propane), diethylene glycol, DPG, pentaerythrite, D-sorbite, sucrose, lactose, α-methylglucopyranoside, the Alpha-hydroxy alkyl glucoside, novolac resin, phosphoric acid, benzenephosphonic acid, polyphosphoric acid (as tripolyphosphate and four polyphosphoric acids), ternary polycondensation product etc. and comprise at least one the combination in aforementioned) chemical addition obtain.Epoxyalkane used in the preparation of polyalkylene oxide polyalcohol is usually containing 2-4 carbon atom.The mixture of preferred expoxy propane and expoxy propane and oxirane.Polyalcohol listed above itself can be used as active hydrogen component.

The useful PPG of one class is expressed from the next usually: R[(OCH _nh _2n) _zoH] _a, wherein R is hydrogen or multivalence alkyl; " a " for equaling valent integer of R, and each " n " is the integer of 2-4 (comprising 2 and 4) (particularly 3), and each " z " is for being worth for the integer of 2-200 or 15-100 more especially.Wish that PPG comprises DPG, BDO and 2-methyl isophthalic acid, the mixture of one or more in ammediol etc.

The spendable another kind of material containing reactive hydrogen is as United States Patent (USP) 3,383, the polymer polyol composition obtained by polymerization ethylenically unsaturated monomers in polyalcohol described in 351.Exemplary monomer for the preparation of this based composition comprises acrylonitrile, vinyl chloride, styrene, butadiene, vinylidene chloride and other ethylenically unsaturated monomers.Polymer polyol composition can be containing 1 % by weight (wt%)-70wt% or more particularly 5wt%-50wt%, the monomer of 10wt%-40wt% polymerization in polyalcohol even more particularly, the gross weight of wherein said percetage by weight based on polyalcohol.Such composition easily by selected polyalcohol under the existence of the temperature of 40-150 ℃ and catalysts for radical polymerization (as peroxide, persulfate, percarbonate, perborate, azo-compound and comprise at least one the combination in aforementioned) polymerization single polymerization monomer prepare.

Component containing reactive hydrogen also can comprise containing polyhydric compound as hydroxy-end capped poly-hydrocarbon (United States Patent (USP) 2, 877, 212), hydroxy-end capped polyformal (United States Patent (USP) 2, 870, 097), fatty acid glyceryl ester (United States Patent (USP) 2, 833, 730 and 2, 878, 601), hydroxy-terminated polyester (United States Patent (USP) 2, 698, 838, 2, 921, 915, 2, 591, 884, 2, 866, 762, 2, 850, 476, 2, 602, 783, 2, 729, 618, 2, 779, 689, 2, 811, 493, 2, 621, 166 and 3, 169, 945), methylol end-blocking perfluor methylene (United States Patent (USP) 2, 911, 390 and 2, 902, 473), hydroxy-end capped polyalkylene ether glycols (United States Patent (USP) 2, 808, 391, BP 733,624), hydroxy-end capped polyalkylene arylene ether glycol (United States Patent (USP) 2,808,391) and hydroxy-end capped polyalkylene ether triol (United States Patent (USP) 2,866,774).

In one embodiment, can be basically clear consistent with 53-8735 with Japanese Patent Publication for the preparation of the reactive composition of foamed material.The polyalcohol wish used has respectively for the repetitive (being called " unit ") of PO (expoxy propane) and/or PTMG (through the oxolane of ring-opening polymerisation) etc.In a specific embodiment, EO (oxirane; (CH ₂cH ₂o) _n) amount be minimized to improve the hygroscopicity of foam.Especially, in polyalcohol, the percentage of EO unit (or EO unit ratio) can be less than or equal to approximately 20%.For example, when polyalcohol used only is comprised of PO-unit and EO-unit, set this polyalcohol in [PO unit]: [EO unit]=100: in the 0-scope of approximately 80: 20.The percentage of EO unit is called as " EO content ".

The hydroxyl value of polyalcohol can change in wide region.Generally speaking, polyalcohol (comprise other crosslinking additives, hydroxyl value if you are using) can be approximately 28 to approximately 1,000 and Geng Gao, or more particularly approximately 100 to approximately 800.Hydroxyl value is defined as and neutralizes by 1 gram polyalcohol fully or polyol blends adds or do not add the required potassium hydroxide milligram number of hydrolysate of the full acetylated derivative that other crosslinking additives make.Hydroxyl value also can be defined by following equation:

$\mathrm{OH}=\frac{56.1\×1000\×f}{M_w}$

Wherein: the hydroxyl value that OH is polyalcohol,

F is average functionality, i.e. the average number of hydroxyl of per molecule polyalcohol, and

The mean molecule quantity that Mw is polyalcohol.

As mentioned above, foamed material can chemical mode foaming and/or with physics mode foaming (as mechanical foaming).When using, can use blowing agent widely in reactive composition, comprise chemistry and/or physical blowing agent.CBA comprises for example water and the compound decomposed with high gas yield as interior as narrow temperature range under given conditions.Wish not efflorescence of catabolite or the foamed material product do not had to decolorization.Exemplary CBA comprises water, azo isobutyronitrile, azo dicarbonamide (being azobisformamide (ABFA)) and barium azodicarboxylate; The hydrazine (as diphenyl sulfone-3,3 '-disulfonyl hydrazide, 4,4 '-hydroxyl-bis--(benzene sulfonyl hydrazide), trihydrazinotriazine and aryl-bis--(sulfohydrazide)) replaced; Semicarbazides (as p-toluene sulfonylsemicarbazide and 4,4 '-hydroxyl-bis--(benzenesulfonamido-urea)); Triazole (as 5-morpholinyl-1,2,3, the 4-thiatriazole); N-nitroso compound (as N, N '-dinitrosopentamethylene tetramine and N, N-dimethyl-N, N '-dinitroso phthalic amide); Benzoxazine (as isatoic anhydride); And comprise at least one combination in aforementioned as sodium carbonate/citric acid mixture.

The amount of blowing agent will change according to blowing agent and desirable foam densities.Generally speaking, the consumption of these blowing agents accounts for the approximately 0.1wt% of gross weight of reactive composition to about 10wt%.When water, during as at least one (as amount accounts for the approximately 0.1wt% of gross weight of reactive composition to about 8wt%) in blowing agent, usually wish by optionally with catalyst, controlling curing reaction.

Also (or as an alternative) can use physical blowing agent.These blowing agents can be from selecting material widely, comprises hydrocarbon, ether, ester (comprising partially halogenated hydrocarbon, ether and ester) etc. and comprise at least one the combination in aforementioned.Exemplary physical blowing agent comprises CFC (CFC) 1-fluoroethane as chloro-as 1,1-bis-, 1, and 1-bis-is chloro-2,2,2-HFC-143a, monochloro difluoromethane and 1-chlorine-1,1-difluoroethane, FC (fluorohydrocarbon) is as 1, 1, 1, 3, 3, the 3-HFC-236fa, 2, 2, 4, 4-tetrafluoro butane, 1, 1, 1, 3, 3, 3-hexafluoro-2-methylpropane, 1, 1, 1, 3, the 3-pentafluoropropane, 1, 1, 1, 2, the 2-pentafluoropropane, 1, 1, 1, 2, the 3-pentafluoropropane, 1, 1, 2, 3, the 3-pentafluoropropane, 1, 1, 2, 2, the 3-pentafluoropropane, 1, 1, 1, 3, 3, the 4-hexafluoro butane, 1, 1, 1, 3, the 3-3-pentafluorobutane, 1, 1, 1, 4, 4, the 4-hexafluoro butane, 1, 1, 1, 4, the 4-3-pentafluorobutane, 1, 1, 2, 2, 3, the 3-HFC-236fa, 1, 1, 1, 2, 3, the 3-HFC-236fa, 1, the 1-Difluoroethane, 1, 1, 1, 2-HFC-134a and pentafluoroethane, FE (fluoro-ether) is as methyl isophthalic acid, 1,1-trifluoroethyl ether and difluoromethyl-1,1,1-trifluoroethyl ether, hydrocarbon is as pentane, isopentane and pentamethylene, and comprise at least one the combination in aforementioned.The same with CBA, physical blowing agent is used with the amount of the desirable bulk density of foamed material that is enough to give gained.The consumption of physical blowing agent can be the approximately 5wt% of reactive composition to about 50wt%, or more particularly about 10wt% is to about 30wt%.

Many can all can be used in the foamed material preparation with the catalyst reacted of the component that contains reactive hydrogen by the catalysis isocyanate component.Exemplary catalyst comprises phosphine; Trimethylamine; Organic and inorganic acid salt and the Organometallic derivatives of bismuth, lead, tin, iron, antimony, uranium, cadmium, cobalt, thorium, aluminium, mercury, zinc, nickel, cerium, molybdenum, vanadium, copper, manganese and zirconium; And comprise at least one the combination in aforementioned.The instantiation of this class catalyst comprises dibutyl tin laurate, dibutyltin diacetate, stannous octoate, lead octoate, cobalt naphthenate, triethylamine, triethylenediamine, N, N, N ', N '-tetramethylethylenediamine, 1, 1, 3, the 3-TMG, N, N, N ', N '-tetramethyl-1, the 3-butanediamine, N, the N-dimethylethanolamine, N, the N-diethyl ethylene diamine, 1, 3, 5-tri-(N, the N-dimethylaminopropyl)-s-hexahydrotriazine, o-and p-(dimethylaminomethyl) phenol, 2, 4, 6-tri-(dimethylaminomethyl) phenol, N, the N-dimethyl cyclohexyl amine, five methyl diethylentriamine, 1, 4-bis-azo dicyclo [2.2.2] octanes, carboxylic acid N-hydroxyl-alkyl quaternary ammonium salts and tetramethyl-ammonium formate, the acetic acid tetramethylammonium, 2 ethyl hexanoic acid tetramethylammonium etc. and comprise at least one the combination in aforementioned catalyst.Other catalyst provide in the commonly assigned u.s. patent application serial number 11/200,536 of submitting on August 9th, 2005.

Can use the acetyl acetone salt as aluminium, barium, cadmium, calcium, cerium (III), chromium (III), cobalt (II), cobalt (III), copper (II), indium, iron (II), lanthanum, lead (II), manganese (II), manganese (III), neodymium, nickel (II), palladium (II), potassium, samarium, sodium, terbium, titanium, vanadium, yttrium, zinc and zirconium based on metal.Common catalyst is that two (2,4-pentanedione) nickel (II) (also claiming nickel acetylacetonate or diacetyl acetone nickel) and derivative thereof are as diacetonitrile diacetyl acetone nickel, two cyanophenyl diacetyl acetone nickel, two (triphenylphosphine) diacetyl nickel acetylacetonate etc.Due to its relative stability, good catalytic activity and nontoxicity, therefore ferric acetyl acetonade (FeAA) particularly preferably.

As authorize in the commonly assigned United States Patent (USP) 5,733,945 of Simpson disclosedly, can in acetyl acetone salt, add acetylacetone,2,4-pentanedione (2,4-pentanedione).Bound by theory not, acetylacetone,2,4-pentanedione will provide latent heat and be that required mixing, casting and other programs sets apart and avoid premature setting harmful in the low temperature process process.But solidify the rising that reaches ammonia ester admixture temperature in some thermals treatment zone along with material, acetylacetone,2,4-pentanedione will be dispersed.Along with acetylacetone,2,4-pentanedione, together with the removing of its correlation delay function, acetyl acetone salt can recover its normal high response and very high catalytic levels will be provided when polyurethane reaction finishes.This high response in later stage process-cycle is favourable and provides improved physical property as compression set.Generally speaking, the ratio of acetyl acetone salt and acetylacetone,2,4-pentanedione is approximately 2: 1 (by weight).

The amount of the catalyst existed in reactive composition can be the about 3.0wt% of approximately 0.03wt%-containing the weight of the component of reactive hydrogen.

In one embodiment, when making water as blowing agent, select ferric acetyl acetonade (FeAA) as catalyst.Can regulate the relative reaction rate of water and ammonia ester as amine with other catalyst or auxiliary agent.Water and isocyanate reaction discharge CO ₂.FeAA and acetylacetone,2,4-pentanedione will be with the mode catalytic curing reactions simultaneously postponed, and such delayed mode prevents premature setting, therefore makes chemistry (with optional physics) foaming continue unimpededly.Catalyst finally can make polyurethane foamed material fully curing.Acetyl acetone salt most convenient ground is by being dissolved in solvent and adding in advance.Exemplary solvent is the component of DPG or other hydroxyls for example, and then it will participate in reaction and become the part of end product.

For stabilizing polyurethane foams material before polyurethane foamed material solidifies, can use surfactant widely, comprise the mixture of surfactant.Organic silicon surfactant is particularly useful, as substantially by SiO ₂(silicate) unit and (CH ₃) ₃siO _0.5(trimethylsiloxy) unit is with approximately 0.8: 1-approximately 2.2: 1 or more especially approximately 1: the copolymer that the 1-silicate of approximately 2.0: 1/trimethylsiloxy mol ratio forms.Another organic silicon surfactant stabilizing agent is partial cross-linked siloxanes-polyalkylene block copolymers and composition thereof, and wherein siloxane blocks is connected with carbon or is connected with oxygen-carbon bond by silicon by silicon with polyoxyalkylene block.Each block that siloxane blocks comprises combination in hydrocarbon-siloxane group and connection on average has at least silicon of divalence.Polyoxyalkylene block comprises the epoxyalkane group and is multivalence at least partly, and in described connection, each block of combination has at least carbon and/or the bond with carbon oxygen of divalence.Any remaining polyoxyalkylene block all comprises the epoxyalkane group and is unit price, and in described connection, each block of combination only has carbon or the bond with carbon oxygen of monovalence.Other organopolysiloxane-polyalkylene block copolymers comprise United States Patent (USP) 2,834,748,2,846,458,2,868,824,2,917,480 and 3,057, and those described in 901.Also can adopt at least one the combination comprised in aforementioned surfactants.Can variation within the tolerance as the amount of the organosilicon polymer of foam stabiliser, as be the about 10wt% of approximately 0.5wt%-of amount of active hydrogen component or more, or the about 6.0wt% of about 1.0wt%-more especially.

Can be in preparation process to reactive composition as added other optional additives in the polyurethane foam mixture.For example, also can use additive as filler (hibbsite, silica, talcum, calcium carbonate, clay etc.), dyestuff, pigment (as titanium dioxide and iron oxide), antioxidant, antiozonant, fire retardant, UV stabilizing agent, conductive filler, conducting polymer etc. and comprise at least one the combination in aforementioned additive.

In one embodiment, foamed material can be by mechanically prepared by the reactive composition of mix predetermined quantities (being isocyanate component, the component containing reactive hydrogen, surfactant, catalyst and any optional additive of stable foam) and the gas of formation foam.Carry out mode a kind of, first make the component of reactive composition mix, then bubble by aero-mechanical.As an alternative, in can in the mechanical foaming process, component being added to liquid phase successively.Since inexpensive and be easy to obtain, therefore the gas phase of foam can be air.But if necessary, can use under environmental condition as gaseous state and basic inertia or other gases of not reacting with all components in liquid phase.Other gases comprise for example nitrogen, carbon dioxide and are generally at ambient temperature the fluorocarbon of gaseous state.

Inert gas by High shear device as Hobart blender or Oakes blender in machinery beat during liquid phase is incorporated into liquid phase.Gas can under pressure, introduce or its can as in the Hobart blender beat or whipping action under from covering atmosphere, suck.Machinery beat operation can normal pressure according to appointment 100 pound per square inches (psi) to about 200psi, (689 kPas (kPa) to 1, carries out under 379kPa).Can use the mixing apparatus be easy to get.Throw the amount of the inert gas in liquid phase into and control to produce the foam of desired density by the air-flow measuring equipment.Machinery beats and carries out the suitable time to obtain required foam density, for example in the Oakes blender, carries out the several seconds or carry out 3-30 minute in the Hobart blender.When beat operation from machinery, while occurring, foam is basic chemically stable and constitutionally stable, but be easy to environment temperature according to appointment 10 ℃ to approximately processing under 40 ℃.

After foaming, reactive mixture is deposited on the first carrier.For simplicity, this first carrier can be called as " bottom carrier ", it typically is and can easily or not allow the mobile vehicle of changing places from the cured foam material is peeled off.Optionally at the foam top, place Second support (in this article also referred to as " sealer " or " roof carrier ").Optional roof carrier is not for can easily or allow the mobile vehicle of changing places from the cured foam material is peeled off yet, and condition is that at least one carrier is easy to peel off from foamed material.Roof carrier can almost apply with foam simultaneously.Apply before roof carrier and can sprawl equipment by for example scraper or other and foamed material is sprawled into to the layer of desired thickness.As an alternative, the placement of roof carrier can be used to sprawl foamed material and regulates foaming layer to desirable thickness.In another embodiment, can after placing roof carrier, with spreader, regulate the height of foamed material.After reaching desirable height, the foamed material of foaming also can foam under the impact of physics or CBA.

In practice, carrier can emit and finally again be wound up on takers-in the polyurethane foamed material with curing separates from feed rolls.The selection of the material of roof carrier and bottom carrier depends on that factor supports degree and pliability, desirable from the cured foam material is peeled off degree, cost and aesthetic property etc. as desired.Can make thin plate or polymer film (as PETG) and the silicone etc. of paper using, metal (as stainless steel).Described material can be coated with release coating.In one embodiment, carrier can be coated with to be intended to transfer to the basilar memebrane of material as peeled off from carrier on the surface of curing urethane foamed material.Can on carrier surface, arrange fibre web or other filler materials, thereby finally be incorporated in the foamed material solidified.In another embodiment, on curable one or two in carrier of foamed material.Therefore, carrier can form the part of final products rather than separate with foamed material.As an alternative or in addition, can use conveyer belt as bottom carrier.Carrier can have matting or grain surface.In a specific embodiment, the surface of foamed material has epidermal area.

In another example, prepared because between water and hydride group in the polysiloxane polymer precursor composition, reacting and separate out subsequently hydrogen by silicone foam material.This reaction is platinum catalyst catalysis by noble metal usually especially.In one embodiment, the viscosity of polysiloxane polymer under 25 ℃ is about 100 to 1,000,000 pool and the chain substituent that is selected from hydride, methyl, ethyl, propyl group, vinyl, phenyl and trifluoro propyl arranged.End group on polysiloxane polymer can be hydride, hydroxyl, vinyl, the organic siloxy of vinyl two, alkoxyl, acyloxy, pi-allyl, oxime, aminooxy group, different propenyloxy group, epoxy radicals, sulfydryl or other known reactive terminal groups.The suitable silicone foam material also available some polysiloxane polymers that have separately different molecular weight (as bimodal or three peak shape molecular weight distribution) produces, as long as in the superincumbent designated value of viscosity of combination.Also can use have different officials can or the some polysiloxanes basis polymer of reactive group to produce desirable foamed material.In one embodiment, polysiloxane polymer comprises the approximately every mole of water of 0.2 moles of hydrogen compound (Si-H) group.

According to the chemical property of polysiloxane polymer used, can use catalyst (being generally platinum or catalyst made from platonic) to come catalysis foaming and curing reaction.Can be by catalyst deposit to inert carrier as on silica gel, aluminium oxide or carbon black.In one embodiment, use be selected from chloroplatinic acid, its hexahydrate form, its alkali metal salt and with the unsupported catalyst of the complex of organic derivative.Exemplary catalyst has chloroplatinic acid and the vinyl polysiloxanes product as 1,3-divinyl tetramethyl disiloxane, and it is treated or come partially or completely except the dechlorination atom with alkaline reagent; The product of chloroplatinic acid and alcohol, ether and aldehyde; The platinum chelate reaches with phosphine, phosphine oxide, alkene as ethene, propylene and cinnamic platinous chloride complex.According to the chemical property of polysiloxane polymer, may also wish to replace the catalyst based on platinum with other catalyst as dibutyl tin laurate.

Also can control the dynamics of foaming and curing reaction to control porosity and the density of silicone foam material with various platinum catalyst inhibitor.The example of such inhibitor comprises poly-ethylene methacrylic radical siloxane cyclic compound and alkynol.These inhibitor should not disturb foaming and solidify in the mode of destroying foamed material.

Useful physics or CBA produce silicone foam material, the physics and chemistry blowing agent of listing about polyurethane above comprising.Other examples of CBA comprise benzylalcohol, methyl alcohol, ethanol, isopropyl alcohol, butanediol and silanol.In one embodiment, obtain the foamed material with desirable characteristics with the combination of foaming method.For example can to add in reactive mixture physical blowing agent as CFC as auxiliary blowing agent, wherein the Main Patterns of foaming is because of the hydrogen discharged that reacts between water and hydride substituting group on polysiloxanes.

In the preparation of silicone foam material, the reactive component of precursor composition is stored in two packings, a catalyst made from platonic, and the polysiloxane polymer that another contains hydride group, thus prevent premature reaction.In another preparation method, polysiloxane polymer is introduced in extruder together with water, physical blowing agent (if necessary) and other desired additives.Then the platinum catalyst metering is introduced in extruder to start foaming and curing reaction.Physical blowing agent can produce density much lower foamed material together with CBA as the use of water as liquid carbon dioxide or supercritical carbon dioxide.In a method again, the liquid silicone component is measured, mixes and be assigned to equipment as mould or continuously in paint line.Then foam and carry out on paint line in mould or continuously.

As an alternative, the reaction of precursor composition that can be by comprising the liquid silicone composition forms soft silicon-ketone composition, wherein said liquid silicone composition comprise per molecule containing the polysiloxanes of at least two thiazolinyls, effectively the amount of hardening composition the polysiloxanes containing at least two silicon bonded hydrogen atoms, catalyst and optionally viscosity be approximately 100 to the about reactive or non-reacted polysiloxane fluid of 1000 centipoises.Suitable reactive silicon one compositions has 1: 1 liquid silicones rubber (LSR) or LIM (LIM) composition of soft.Because its intrinsic viscosity is low, therefore the use of soft LSR or LIM will facilitate the more formation that adds and cause soft foamed material of a large amount filler.

Reactive or non-reacted polysiloxane fluid can make more substantial filler be incorporated in curing silicon-ketone composition, thereby reduces the volume and the surface resistivity values that obtain.In one embodiment, polysiloxane fluid is retained in curing silicone and is not extracted out or removes.Therefore the reactive silicone fluid becomes the part of polymeric matrix, thereby causes in low outgas and use procedure seldom or not to surperficial migration.In one embodiment, the enough height of the boiling point of non-reacted silicone fluid do not evaporate while making in being dispersed in polymeric matrix in solidification process or afterwards, do not move to surface or outgas yet.

In one embodiment, LSR or LIM system provide with the bi-component formula that approximately ratio of 1: 1 volume mixes being suitable for." A " of this formula partly comprises one or more polysiloxanes with two or more thiazolinyls and rate of extrusion lower than about 500g/ minute.The example of suitable thiazolinyl has vinyl, pi-allyl, cyclobutenyl, pentenyl, hexenyl and heptenyl, and vinyl is suitable especially.Thiazolinyl can be connected to side group position or the two place on molecular chain-end place, strand.Have the example of other silicon bonding organic groups in the polysiloxanes of two or more thiazolinyls for replacing and unsubstituted univalence hydrocarbyl, for example alkyl is as methyl, ethyl, propyl group, butyl, amyl group and hexyl; Aryl is as phenyl, tolyl and xylyl; Aralkyl is as benzyl and phenethyl; And haloalkyl is as 3-chloropropyl and 3,3,3-trifluoro propyl.Exemplary substituting group is methyl and phenyl.

Polysiloxanes containing thiazolinyl can have straight chain, side chain or the network molecule structure of straight chain, part branching, or can be the mixture that two or more are selected from the candidate of the polysiloxanes with exemplified molecular structure.The example that contains the polysiloxanes of thiazolinyl has the dimethyl siloxane of trimethylsiloxy end-blocking-methyl ethylene silicone copolymers, the ethylene methacrylic radical siloxane of trimethylsiloxy end-blocking-methyl phenyl siloxane copolymer, the dimethyl siloxane of trimethylsiloxy end-blocking-ethylene methacrylic radical siloxane-methyl phenyl siloxane copolymer, the dimethyl polysiloxane of dimethylvinylsiloxy end-blocking, the methylvinyl-polysiloxane of dimethylvinylsiloxy end-blocking, the methyl ethylene phenyl siloxane of dimethylvinylsiloxy end-blocking, the dimethyl vinylsiloxane of dimethylvinylsiloxy end-blocking-methyl ethylene silicone copolymers, the dimethyl siloxane of dimethylvinylsiloxy end-blocking-methyl phenyl siloxane copolymer, the dimethyl siloxane of dimethylvinylsiloxy end-blocking-diphenyl siloxane copolymer, comprise R ₃siO _1/2and SiO _4/2the polysiloxanes of unit, comprise RSiO _3/2the polysiloxanes of unit, comprise R ₂siO _2/2and RSiO _3/2the polysiloxanes of unit, comprise R ₂siO _2/2, RSiO _3/2and SiO _4/2the polysiloxanes of unit, and aforementioned polysiloxanes in both or more persons' mixture.R means to replace and unsubstituted univalence hydrocarbyl, and for example alkyl is as methyl, ethyl, propyl group, butyl, amyl group and hexyl; Aryl is as phenyl, tolyl and xylyl; Aralkyl is as benzyl and phenethyl; Reach haloalkyl as 3-chloropropyl and 3,3,3-trifluoro propyl, condition is that in per molecule, at least two R groups are thiazolinyl.

" B " component in LSR or LIM system comprise one or more per molecules containing the polysiloxanes of at least two silicon bonded hydrogen atoms and rate of extrusion lower than about 500g/ minute.Hydrogen can be connected to side group position or the two place on molecular chain-end place, strand.Other silicon binding groups are organic group, the replacement that example is non-thiazolinyl and unsubstituted univalence hydrocarbyl, and for example alkyl is as methyl, ethyl, propyl group, butyl, amyl group and hexyl; Aryl is as phenyl, tolyl and xylyl; Aralkyl is as benzyl and phenethyl; And haloalkyl is as 3-chloropropyl and 3,3,3-trifluoro propyl.Exemplary substituting group is methyl and phenyl.

Hydrogeneous polysiloxanes component can have straight chain, side chain, ring-type, the network molecule structure of straight chain, part branching, or can be the mixture that two or more are selected from the candidate of the polysiloxanes with exemplified molecular structure.The example of hydrogeneous polysiloxanes has the methylhydrogenpolysi,oxane of trimethylsiloxy end-blocking, dimethyl siloxane-the methylhydrogensiloxacopolymer copolymer of trimethylsiloxy end-blocking, the methyl hydrogen siloxane of trimethylsiloxy end-blocking-methyl phenyl siloxane copolymer, dimethyl siloxane-the methyl hydrogen siloxane of trimethylsiloxy end-blocking-methyl phenyl siloxane copolymer, the dimethyl polysiloxane of dimethyl hydrogen siloxy end-blocking, the methylhydrogenpolysi,oxane of dimethyl hydrogen siloxy end-blocking, dimethyl siloxane-the methylhydrogensiloxacopolymer copolymer of dimethyl hydrogen siloxy end-blocking, the dimethyl siloxane of dimethyl hydrogen siloxy end-blocking-methyl phenyl siloxane copolymer, methyl phenyl silicone with dimethyl hydrogen siloxy end-blocking.

Hydrogeneous polysiloxanes component with the amount that is enough to hardening composition, especially containing the about 0.5-of each thiazolinyl in the polysiloxanes of thiazolinyl approximately the amount of 10 silicon bonded hydrogen atoms add.

Silicon-ketone composition also comprises usually used as the catalyst of the part of component " A " and solidifies accelerating as platinum.Can use the platinum that is called catalyst for addition reaction of hydrogen and silicon and platinum compounds as the alcoholic solution of platinum black, alumina load platinum powder, silicon dioxide carried platinum powder, carbon load platinum powder, chloroplatinic acid, chloroplatinic acid, platinum-olefin complex, platinum-alkenyl siloxane complex and the catalyst that provides as the micronize of the dispersion in methyl methacrylate, Merlon, polystyrene, silicone etc. at thermoplastic resin by platinum addition reaction catalyst as mentioned above.Also can use the mixture of catalyst.The amount of effectively solidifying the catalyst of composition of the present invention is generally 1,000,000/0.1-1 of the merging amount of thiazolinyl and hydrogen component, the platinum of 000 (by weight).

Described composition optionally also comprise one or more viscosity less than or equal to about 1000 centipoises, particularly less than or equal to about 750 centipoises, more especially less than or equal to about 600 centipoises, the most particularly less than or equal to the about polysiloxane fluid of 500 centipoises.The viscosity of polysiloxane fluid also can be greater than or equal to about 100 centipoises.The purpose that adds the polysiloxane fluid component is to reduce the viscosity of composition, thereby the curing composition that makes in the lump at least during realization increases the filler carrying capacity, reinforcement filler is wetting and reinforcement filler distributes has lower resistance and resistivity value.The use of polysiloxane fluid component also can reduce resistance value to the dependence of temperature and/or reduce resistance and resistivity value change in time.Outgas and diluent migration possible in the needs of the add-on step to removing fluid in process and use procedure have been avoided in the use of polysiloxane fluid component.Polysiloxane fluid should not suppress the addition reaction that curing reaction is composition, but it can participate in or can not participate in curing reaction.

The boiling point of non-reacted polysiloxane fluid is higher than approximately 500 °F (260 ℃), and can be side chain or straight chain.Non-reacted polysiloxane fluid comprises the non-thiazolinyl organic group of silicon bonding, and the example of described organic group has replacement and unsubstituted univalence hydrocarbyl, and for example alkyl is as methyl, ethyl, propyl group, butyl, amyl group and hexyl; Aryl is as phenyl, tolyl and xylyl; Aralkyl is as benzyl and phenethyl; With haloalkyl as 3-chloropropyl and 3,3,3-trifluoro propyl.Exemplary substituting group is methyl and phenyl.Therefore, non-reacted polysiloxane fluid can comprise R ₃siO _1/2and SiO _4/2unit, RSiO _3/2unit, R ₂siO _2/2and RSiO _3/2unit or R ₂siO _2/2, RSiO _3/2and SiO _4/2unit, wherein R means to be selected from alkyl, methyl, ethyl, propyl group, butyl, amyl group, hexyl, aryl, phenyl, tolyl, xylyl, aralkyl, benzyl, phenethyl, haloalkyl, 3-chloropropyl and 3, the replacement of 3,3-trifluoro propyl and do not replace univalence hydrocarbyl.Because described non-reacted polysiloxanes is fluid and significantly higher boiling point (higher than approximately 230 ℃ (500 °F)) is arranged, therefore it allows to introduce the filler of higher amount, but do not move or outgas.The example of non-reacted polysiloxane fluid comprises the DC 200 from Dow Corning Corporation.

The reactive polysiloxane fluid will with containing the polysiloxanes of thiazolinyl with containing the polysiloxanes co-curing of at least two silicon bonded hydrogen atoms, but therefore self containing thiazolinyl or hydrogen bonding by silicon group.Such compound can have with top about containing the polysiloxanes of thiazolinyl with containing the described identical structure of polysiloxanes of at least two silicon bonded hydrogen atoms, but have in addition less than or equal to about 1000 centipoises (cps), particularly less than or equal to about 750cps, more especially less than or equal to about 600cps, the most particularly less than or equal to the viscosity of about 500cps.In one embodiment, the boiling point of reactive polysiloxane fluid is higher than the solidification temperature of addition curing reaction.

Silicone foam material also optionally comprises curable silicon gel formula.The silicon gel is lightly crosslinked fluid or owes curing elastomer.Its unique distinction is that its sense of touch is from very soft and adhere to the soft only slightly sticky change of moderate.The use of gel formula will reduce the viscosity of composition, thus can realize increasing the filler carrying capacity, during reinforcement filler is wetting and/or reinforcement filler distributes one of at least, thereby make curing composition there is the softness of lower resistance and resistivity value and increase.Suitable gel formula can be two component curable formula or one pack system formula.The component of two component curable gel formula to top about LSR system described similar (being that per molecule contains the organopolysiloxane of at least two thiazolinyls and the per molecule organopolysiloxane containing at least two silicon bonded hydrogen atoms).Main difference is not exist the mol ratio of filler and hydrogen bonding by silicon group (Si-H) and thiazolinyl to be usually less than 1 and can change to produce the fact of " owing crosslinked " polymer of looseness with the gel solidified and softness.Especially, the ratio of silicon bonded hydrogen atom and thiazolinyl is less than or equal to approximately 1.0, particularly less than or equal to approximately 0.75, more especially less than or equal to approximately 0.6, the most particularly less than or equal to approximately 0.1.The example of suitable bi-component silicon gel formula is what can commercially obtain from Dow CorningCorporation

527 gels.

Silicone foam material can be as mentioned above only by bottom carrier or with bottom carrier and the two casting of roof carrier and processing.

In a specific embodiment, for strengthening the structural intergrity of goods, for example, for improving the operability of product, can for example, to cured substrate film on foam for panel (being adhered to plate).This basilar memebrane also can be used as the transfer equipment of the reactive composition that bubbles in preparation facilities.Therefore, basilar memebrane can comprise any resin with mechanical strength and heat that anti-heater (as stove, baking oven etc.) is applied of tension force that low thermal shrinkage behavior, the machine of anti-the roller apply.For example can use resin as polyolefin, polyester, polyamide, polyvinyl chloride, but, particularly from the cost angle, wish to use PETG (PET).The thickness of basilar memebrane can be approximately 10 microns (μ m) to 500 microns, more especially approximately 25 μ m, to about 125 μ m, depend on the quality of material.

The assembly of carrier and sponge layer (after optional foaming) can be passed to the thermal treatment zone with the cured foam material.Temperature remains in the scope that is suitable for the cured foam material, for example approximately 90 ℃ to approximately 220 ℃, depends on the composition of foamed material.Can create the temperature difference to form complete epidermis or increase thicker layer on the outer surface of foamed material on foamed material.

Foamed material be heated and solidify or partial melting after can be sent to ， cooling zone, cooling zone, its by any suitable cooling device as fan coolling.In the time of suitably, remove carrier, foamed material can be wound on roller.As an alternative, foamed material can be through further processing, and for example lamination (with heat and pressure bonding) is first-class to one or two in carrier layer.Plate through processing can be reeled to be collected on the product-collecting roller again.In such production model, the length of foam for panel can be up to 5 meters or longer.Manufacture the device of polyurethane foamed material plate states in u.s. patent application serial number 11/200,536.

Hole can the each point place in forming the technical process of plate form in material (if for example material comprises thermoplastic, before plate partly solidified, in process and/or afterwards; If material comprises thermosets, in the partial coagulation (as solidification) of plate before, in process and/or afterwards).In some embodiments, hole is after moulding plate but form before fully the solidifying of foamed material.In another embodiment, foamed material solidified at least partly to suppress in the foamed material run-in-hole and lipostomous before forming hole.In another embodiment, hole forms in curing process.In this embodiment, the hole of formation can keep by solidifying to reach desirable hole shape, the degree of depth and/or size at least partly.For example, hole can be in the extent of reaction when material (as state of cure; Or in the thermoplastic situation, coagulation grade) less than or equal to approximately 90% or more especially less than or equal to approximately 80% or also more especially less than or equal to approximately forming 60% the time.

Hole can form in plate by various technology, fluid jet for example, fluid jet used herein comprises liquid (as water) and gas jet (as inert gas as air, nitrogen, carbon dioxide, fluorohydrocarbon etc. and comprise at least one the combination in these gases).Depend on the desirable effect of each jet, can adopt various nozzles to reach desirable control, pressure, hole geometry etc.For example, jet pattern can be used in sub-thread shooting or multiply gunnery system.In one embodiment, jet pattern can be in a fixed position and the foam for panel composition crosses the fluid jet pattern continuously.In one embodiment, single jet pattern can form the opening that runs through plate, and in other embodiments, and the first jet pattern can make the foamed material displacement and one or more follow-up jet pattern can form the opening that runs through plate in some or all holes.As an alternative, the first jet pattern can apply some strikes to help to improve formation and the structure in hole to foam for panel in identical position.For example, but the first jet pattern impact fluid reached for the first duration on plate, and then impact fluid reached for the second duration in identical Board position.In another embodiment, the first jet pattern can apply in different positions a plurality of strikes and form pattern with the Huo Yong hole, hole that forms different size in plate.In an embodiment again, but the first jet pattern bump fluid is on foam for panel.An example of this embodiment can be the situation that the fluid jet pattern moves to form hole with plate and helps prevent material reflow.Another example can be foam for panel when fluid jet pattern impact fluid is on plate and keeps static situation.All can make fluid bump foam for panel until foamed material part, substantially or fully curing in arbitrary example.On foam for panel, continuous fluid impact and/or foam composition that viscosity low slow for solidification rate comes in handy, in the situation that the solidification rate of foam composition is slow and/or viscosity is low, material may be a problem to the backflow in formed hole.The same position of when in a further example, a plurality of jet rows or pattern can move through described a plurality of jet rows or pattern continuously in the position when plate, in a plurality of time, regularly impacting foam for panel.

Fluid jet runs through the opening of plate with enough pressure alignment sheets to reach desirable hole depth and/or formation.Concrete pressure depends on foamed material formula, concrete plate composition, thickness and state of cure.Possible pressure is that approximately 0 pound per square inch (psi) arrives about 100psi, or more especially about 1psi arrives about 50psi, or even more especially about 5psi is to about 25psi, and also more especially about 10psi arrives about 15psi.Equally, the temperature of fluid can change and also depend on foamed material formula, concrete plate composition, thickness and state of cure.Fluid from jet also can be heated to help solidifying of foam for panel.Therefore fluid can be heated to the temperature range that is suitable for the cured foam material.Possible temperature can be approximately 50 ℃ to approximately 300 ℃, particularly approximately 90 ℃ to approximately 220 ℃.As an alternative or in addition, plate can be arranged as with grid and peel off carrier (mesh release carrier) operable communication.Here, lattice can design into peeling off in carrier in order to peel off carrier and can produce this design (individually or with fluid jet in combination).When by roof carrier and bottom carrier, producing foamed material, in one embodiment, one or both in carrier can comprise opening in desirable sectional hole patterns.

The character (as density, modulus, compression load deformation, hot strength, tearing strength etc.) of the foamed material formed as mentioned above can be regulated by the component that changes reactive composition.Generally speaking, when the parts as footwear, the density of foamed material can be about 50kg/m ³to about 500kg/m ³, about 70kg/m particularly ³to about 400kg/m ³, about 100kg/m more especially ³to about 350kg/m ³, about 200kg/m more especially also ³to about 300kg/m ³.The thickness of such foamed material also can be approximately 0.3 millimeter (mm) and arrives about 9mm to about 13mm, particularly about 0.3mm, and more especially about 0.3mm is to about 5mm, and even more especially about 0.3mm is to about 3mm.

Such foamed material has excellent physical property.For example, the incompressible permanent deformation of such foamed material can be less than or equal to approximately 10%, or more especially less than or equal to approximately 5%.

For the engineering properties that foamed material is good is provided, the average pore size of foamed material can be approximately 10 microns (μ m) to approximately 1 millimeter (mm), or more especially approximately 50 microns to approximately 500 microns.At least partly abscess extends through in the open-cell foam materials of plate therein, and through hole and such perforate can be of a size of basis and be distinguished.For example, in the foamed material bubbled at mechanical type, the minimum diameter of through hole is than at least ten times greatly of the maximum gauges of abscess.In the foamed material or non-microvesicle hole foamed material of foaming, the minimum diameter of through hole is at least twice of the maximum gauge of abscess.

Due to the Particular craft that forms hole in plate, therefore seldom or the waste material do not produced because forming hole.Another significant advantage that uses fluid jet to form hole in foam for panel is that quantity, arrangement, size and the structure in hole can easily regulate by position, pattern or the boot sequence of adjusting jet, the parameters such as power used.Such adjusting does not need the flower high price again to equip mould.For example, as shown in plate in Fig. 1 10, can on whole plate 10, form the regular pattern in the hole 12 of same size.In another embodiment, as shown in Figure 2, the hole 22 of irregular size can form in plate 20 or run through plate 20 by irregular pattern.Can produce the combination of hole dimension, the degree of depth and shape to obtain for example design of plate 30 mesopores 32 as shown in Figure 3.The example of design can include but not limited to letter, numeral, pattern, shape, sign etc.As shown in Figure 4, also can in plate 40, form hole 42 so that retain epidermis under depression.In one embodiment, the epidermal thickness of epidermis is less than or equal to approximately 5% of plate thickness in non-bore region.Whether the quantity in hole, hole dimension and distribution of sizes, hole shape, hole depth and hole form desirable function and the aesthetic property that the opening that runs through plate all depends on soleplate.

In yet another embodiment, hole can form on all surface that makes to form hole all epidermis.Can not there be epidermis in the hole formed in the foam for panel solidified with card punch for example.If foamed material is open-cell foam materials, such foamed material will be easier to dust stratification, moisture absorption or easily cracked or tear.On all surface of foamed material, provide epidermis will make foamed material be not easy to dust stratification and/or moisture absorption and/or tear/cracked.In addition, the appearance in hole and the appearance of foamed material coupling, thus make outward appearance more catchy than cross cutting hole, the cross cutting hole may have and the unmatched exposed foamed material of foamed material appearance.Equally, with the open-cell foam materials goods, compare, the goods that made by the closed-cell foam material with epidermis can more easily clean.

In addition, hole can form the unique texture had as shown in cross section in Fig. 5.In other words, through hole 52 can have the shape similar to punching, as drum jumpy from the plate body to the hole.Through hole 54 also can have cone shape.In other embodiments, the level and smooth depression that hole 56,58 changes in can be from the plate body to the hole gradually is as entered the inclined-plane in hole with the bowl sample loading mode, its mesopore can (hole 58) or not (with the hole 56 (not to scale (NTS)) of epidermis 60) extend through the complete opening of plate with the opposite side that is formed into plate.In other words, the bottom in hole can be the opening that runs through plate or can be epidermis (as thickness less than or equal to plate thickness in non-bore region approximately 3%).If hole is depression, the degree of depth of depression can be greater than or equal to approximately 75% of plate thickness, or more especially greater than or equal to approximately 85% of plate thickness, or even more especially greater than or equal to approximately 95% of plate thickness, also more especially greater than or equal to approximately 98% of plate thickness.

In a specific embodiment, foamed material (polyurethane) plate is provided, described plate comprises a plurality of cone-shaped holes, and the first surface of each cone-shaped hole slave plate extends through the relative second surface of plate.But other clear size of opening and geometry are also possible.Possible geometry comprises that various circles and polygon cross section are as circle (as cylindrical, conical etc.) or various rectangle and triangular cross section.Via hole geometry can by with one or more carrier boards in the hole that is complementary of geometry or with the fluid tip of definite shape, produce.Foam for panel can be used for function wherein can be by improving containing through hole and wherein the outward appearance, washability etc. of foamed material are in the multiple application of important Consideration in foam for panel.Exemplary application can include but not limited to article of footwear, garment component etc.The instantiation of article of footwear application can include but not limited to upper of a shoe, sole etc.The instantiation of garment component application can include but not limited to gym suit as for skiing, motor-cross, by motorcycle, the bedding and padding of the jacket of the motion of playing with water etc., trousers etc.These plates can provide buffering (as from foamed material) and gas permeability (because of the mesh opened).In addition, these plates can be and apply the uniform outer appearance that desirable U.S. is provided as footwear.

Below be intended to example and unrestriced embodiment has illustrated described foam for panel herein and prepare the method for the various embodiments of described foam for panel.In these embodiments, the polyurethane foamed material that foamed material bubbles with mechanical type is as United States Patent (USP) 5,733, those preparations described in 945.In addition in these embodiments will as the foam for panel for preparing by said method and the foam for panel prepared by additive method in addition relatively.

Comparative Examples

Foam for panel pore-forming technique to contrast is assessed, and result provides below in detail.The method of Comparative Examples adopts the recess spatula of vibration up and down to form hole in foam for panel before solidifying.The method adopt be configured to metering casting foamed material supplied materials control panel thickness first " dish upper slitter " (KOP).Then foam for panel passes through so that foamed material forms pattern under the recess spatula of shuttling movement in vertical direction.Then the foam for panel that has formed pattern is being configured to measure final plate thickness and is removing under the 2nd KOP of any accumulation material caused because of spatula and pass through.Calculate, for obtain 2-3 hole of per inch with 10 linear feet tinuous production speed per minute operation test production line the time, spatula responsiveness (being vertical circulation) need to be per minute for 200-300 circulation.Mechanical driving drives the recess spatula and adopts the motor with speed Control.

The solidification rate comparison of comparative sample 1 is than fast approximately one times of the solidification rate of sample 2.The viscosity of the foamed material of comparative sample 1 also is about the twice of comparative sample 2.It is believed that solidification rate and casting viscosity that comparative sample 1 is higher can more cleanly form through hole limiting material backflow.But result shows, although comparison has obtained than sample 2, better through hole forms and minimum material reflow, but foamed material is deposited in the recess spatula and on final foamed material panel products and causes follow-up blemish, particularly in long production run process.Accumulation can produce undesirable vestige and produce the thickness scrambling and affect the through hole uniformity to drippage deposit on surface on the plate surface.By comparison, lower casting viscosity and the slower solidification rate of comparative sample 2 formula reduced the accumulating amount of seeing in the spatula, but also for material reflow, advances in through hole to have created larger trend.Therefore the final foamed material panel products of comparative sample 2 shows depression rather than required real through hole.Test various spatulas and design the impact on the gained foam for panel of tooth pitch, size, shape and responsiveness.Do not have which change can effectively improve the foamed material panel products to being better than comparative sample 1 and 2.The spatula method of this Comparative Examples is not enough to produce the foam for panel that comprises the real through hole described in top specification.

Embodiment 1

The inventive method that forms through hole in foam for panel described in top whole specification is assessed and result and Comparative Examples are compared.

The method advantageously adopts the air blowing through hole to form technique.Air use gas bar (air bar) impacts on foam composition.The method adopts the single KOP that is configured to metering casting foamed material supplied materials control panel thickness.Foam for panel then under the gas bar by so that foamed material forms the pattern with through hole.The gas bar consists of the stainless steel tube of 0.375 inch of external diameter, 0.050 inch of diameter is arranged on the gas pole length and separate the approximately pore of 0.190 inch.But under the distance, the distortion of contiguous pore has stoped the consistent through-hole pattern of generation in the plate during this time.Therefore spacing between each pore increases.Two kinds of different formulas are used to two kinds of different pore spacings, and this will illustrate in greater detail below.In addition, air hole structure is straight, and in other words, it does not have tapering.In addition, do not use nozzle on pore, further to change the characteristic curve from the blast in hole.Solenoid and gas bar operable communication are also driven by digital clock, so that the gas bar is with speed " startup " blast of appointment.The cycle rate that changes this appointment is to obtain desirable outward appearance (as the hole count of per inch foam for panel) (based on 10 linear feet per minute line speed).Air pressure is set to from approximately 10 to about 15 pound per square inches (psi) (the casting foamed material layer thickness based on 0.125 inch).The surface that the gas bar is located at its below casting sponge layer of advancing is 0.200 inch approximately.

Select two kinds of different foamed materials to fill a prescription to determine how viscosity and solidification rate affect formation and the maintenance of pattern hole.Sample A has the casting viscosity of solidification rate and Lve Gao faster than sample B.But the solidification rate of two kinds of sample recipe ratio comparative sample 1 using in air blowing technique and 2 formula is slightly slow.For the pore of the gas bar of sample A every one by shutoff, so that pitch of holes is 0.38 inch but not 0.19 inch.But the gained foam for panel still has and leans on to obtain the sign of the bore deformation that very closely causes because of contiguous pore.For improving the ventilating hole plate pattern, larger pitch of holes or the hole diameter reduced by needs.Due to the result of sample A, only open in every four holes one for the gas bar of sample B, thereby the spacing of 0.76 inch is provided.The foam for panel of sample B has minimum through hole distortion and best outward appearance in all samples.

Except above-mentioned bore deformation, sample A has minimum material reflow, good hole depth (with the thickness of casting foam for panel, compare and measure) and hole and keep its shape in solidifying.Sample A approximately has through hole completely in the plate of 0.100 inch in casting thickness.The casting viscosity of formula and solidification rate make when can form the clean through hole limited when the air blowing pore-forming technique is combined.The solidification rate of sample B is slightly slower than sample A, this can allow good through hole to form and when foamed material solidifies " smoothly " to the plate surface act on.What described " smoothly " effect was described usually herein is the effect of blast to material.Smoothing effect is that the slow solidification rate of foamed material can reflux into the result of filling and leading up in the hole, hole air diffusion in all directions causes when forming through hole hole, hole before solidifying along with foamed material.Result to cured plate is depression level and smooth except through hole, wherein from the air of gas bar, along with hole, is blown and wears foamed material and diffusion in all directions.Smoothing effect needs, because it can make foam for panel have level and smooth uniform outer surface around through hole and more give happiness and aesthetic feeling.In conjunction with the change of pore spacing, the air blowing pore-forming technique has produced the consistent material of pattern with good appearance.The foam for panel produced as the air blowing pore-forming technique used in embodiment 1 will have minimum defect and can be conditioned to produce different Some Aspects on Foamed Materials surfaces, comprise multiple hole dimension (as diameter), shape, spacing, frequency etc.In addition, different from the spatula method of contrast, the noncontact character of air blowing technique will greatly reduce the worry of effects on surface defect and there is no the material stacking relevant issues.In addition, air blowing technique and viscosity higher and very fast being combined with of solidification rate formula help be locked in foam for panel by sectional hole patterns and prevent material reflow.By comparison, the air blowing pore-forming technique has more effectively produced the foam for panel with required surface and through hole quality than the spatula method adopted in Comparative Examples.

Scope disclosed herein comprise mentioned end points and be capable of being combined (such as scope " high to about 25wt% or more especially about 5wt% to about 20wt% " comprise all medians etc. of end points and scope " about 5wt% arrives about 25wt% ")." combination " comprises blend, mixture, alloy, product etc.In addition, " comprise at least one the combination in aforementioned " and show the combination of the combination that comprises each independent key element, cited two or more key elements of compiling a name list and cited one or more key elements and the key element of not enumerating.In addition, term herein " first " " second " etc. does not mean any order, quantity or importance, but is used for distinguishing each key element, and the usage quantity vocabulary does not show at least one mentioned project that exists herein.The modifier of using about quantity " approximately " comprises described value and has the implication of context defined (for example comprising the degree of error of following specific quantity to measure)." embodiment " " another embodiment " fingers such as " embodiments " of mentioning in whole specification comprises about the described specific factor of this embodiment (as feature, structure and/or characteristic) in described at least one embodiment in this article.Should be understood that in addition described key element can combine in any suitable manner in various embodiments.Term plate used herein, film, dish and layer can be used instead and non-ly be intended to indicate size.

All patents of quoting, patent application and other lists of references are incorporated into herein by quoting in full.But if the term in the application contradicts or conflict with the term in list of references that institute is combined, from the application's term, have precedence over the term from the conflict of the list of references of combination.

Although invention has been described in conjunction with its some embodiments, it will be understood by those skilled in the art that and can do various changes and can replace its key element and not depart from scope of the present invention by equivalent.In addition, can do many changes to instruction of the present invention and not depart from its essential scope to adapt to specific situation or material.Therefore, the invention is not restricted to the disclosed particular of enforcement best mode of the present invention as expection, but comprise all embodiments that drop in appended claim scope.

Claims (19)

1. a method for preparing the polyurethane foamed material plate, described method comprises:

The composition that makes to form polyurethane bubbles, the composition of described formation polyurethane comprise component containing isocyanates, with component, surfactant and the catalyst system containing reactive hydrogen of the described component reaction containing isocyanates;

To the reactive composition of the formation polyurethane of the described foaming of the first carrier top casting to form plate;

Impact described plate with fluid to form hole under enough pressure, the curing degree of wherein said plate or degree of solidifying are less than or equal to 90%; With

The cured plate that the reactive composition of the formation polyurethane of curing described foaming comprises hole with formation.

2. the process of claim 1 wherein described foaming formation polyurethane reactive composition with before fluid impact described plate by partly solidified, and wherein said fluid is gas.

3. the method for claim 1, described method also is included on casting foamed material one side relative with described the first carrier and places Second support; With in the situation that with blowing at the reactive composition of the described Second support polyurethane of the formation to described foaming in place before the described plate of fluid impact; Wherein said Second support comprises opening.

4. the process of claim 1 wherein that described the first carrier comprises peel ply on the side contacted with described foamed material.

5. the method for claim 1, described method also comprises makes described the first carrier, foam and Second support pass through thickness adjusting apparatus.

6. the process of claim 1 wherein that described curing polyurethane foamed material layer contains the abscess that average pore size is 20 to 500 microns.

7. the process of claim 1 wherein that described fluid impacts described plate continuously until partially or completely solidify.

8. the method for claim 1, described method also comprises the described fluid of heating.

9. the process of claim 1 wherein that described fluid impacts described plate in primary importance and reached for the first duration, then described fluid impacts described plate in described primary importance and reached for the second duration.

10. the process of claim 1 wherein that described plate repeatedly impacts a position experience.

11. the process of claim 1 wherein that the bottom in described hole comprises epidermis.

Form opening 12. the process of claim 1 wherein described hole to extend through described plate.

13. a method for preparing foam for panel, described method comprises:

Form the material of foaming, wherein

If the material of described foaming comprises thermosets, the material of described foaming is without solidifying or through partly solidified;

If the material of described foaming comprises thermoplastic, the material of described foaming is without solidifying or through partial coagulation;

Material to the described foaming of the first carrier top casting;

Impact cast material with fluid to form hole under enough pressure, the curing degree of wherein said plate or degree of solidifying are less than or equal to 90%; With

Solidify the plate that the described material through impacting comprises described hole with formation.

14. the method for claim 13, the curing degree of wherein said foamed material or degree of solidifying are less than or equal to 90%.

15. the method for claim 13, wherein said material is selected from silicone, polyolefin, polyester, polyamide, fluorinated polymer, polyalkylene oxide, polyvinyl alcohol, ionomer, cellulose acetate, polystyrene and comprises at least one the combination in aforementioned.

16. the method for claim 13, the described cast material of wherein said fluid bump is until foamed material partially or completely solidifies, and wherein said foamed material is polyurethane.

17. the method for claim 13, wherein said fluid is gas.

18. the method for claim 13, wherein said fluid is produced as the hole of level and smooth concave form in described curing material.

19. the method for claim 13, the bottom in wherein said hole comprises 3% the epidermis of thickness lower than plate thickness in non-bore region.

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