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    • 专利摘要:
    REACTION SYSTEM FOR PREPARING A VISCOELASTIC POLYURETHANE FOAM AND POLYURETHANE FOAM. Embodiments of the invention describe viscoelastic polyurethane foams. Foams are prepared with a reaction system that includes (a) a reactive isocyanate component, (b) an isocyanate component, (c) one or more blowing agents, (d) a catalyst component, and (e) a surfactant silicone based. The reactive isocyanate component includes at least (i) 25 to 80% by weight of that of at least one polyoxypropylene / polyoxyethylene polyol capped with polyoxyethylene, having a numerical equivalent numerical weight of 1300 to 1700, a percentage of polyoxyethylene between 75% and 95% by weight of the combined amounts of polyoxypropylene and polyoxyethylene, and a percentage of primary OH between 80 and 95% of the total number of OH groups of the polyoxypropylene / polyoxyethylene polyol capped with polyoxyethylene; and (ii) from 5 to 30% by weight of the isocyanate reactive component of at least one low functionality polyol having a functionality between 1.5 and 2.5, a combined equivalent average numerical weight of 500 to 1500 and an OH index from 40 to 70.
    公开号:BR112014007095B1
    申请号:R112014007095-4
    申请日:2012-09-20
    公开日:2020-11-17
    发明作者:Francois M. Casati；Elisa Corinti；Andrea Benvenuti；Alessio Sabadini；Jean-Paul Masy；Brian Dickie
    申请人:Dow Global Technologies Llc；
    IPC主号:
    专利说明:

    Technical field
    [001] The embodiments of the present invention relate to polyurethane foams. More particularly, the embodiments of the present invention relate to polyurethane foams having viscoelastic properties. History of the Invention
    [002] Polyurethane foams are used in a wide variety of applications, ranging from cushioning (such as mattresses, pillows and seat cushions) to packaging, shoe soles, thermal insulation and medical and automotive applications. One category of polyurethane foam is known as viscoelastic (VE) or "memory" foam. Viscoelastic foams respond to an applied voltage that is dependent on speed and time delay. They have low resilience, open cells and recover slowly when pressed. These properties are often associated with the glass transition temperature (Tg) of the polyurethane. Viscoelasticity often manifests itself when the polymer has a Tg equal to or close to the temperature of use, which in this case is the ambient temperature for many applications, such as acoustics in automotive applications or comfort in furniture applications.
    [003] Viscoelastic foam can be produced as a block ("slabstock") or in molding, either as a foam block or as part of a composite, for example, a heavy layer. One type of viscoelastic foam includes molded viscoelastic foams with foamed inner parts and compact outer skin layers used directly with thin fabric lining in furniture applications such as mattresses, pillows and medical devices.
    [004] Polyurethane molded viscoelastic foams can be formed in an open or closed mold process. In the open mold process, two reactive components are mixed and poured into an open mold and well dispersed on the mold surface. The mold is then closed and the mixture allowed to expand and cure. With the closed mold process, the mixed components are injected into a closed mold through an injection point, thus allowing the foam mass to flow well into the mold. In both cases, a release agent can be applied by spraying or brushing over the mold surface, including the lid, before the foam injection (between 10 seconds and 1 minute, depending on the process conditions) prevents the foam sticks to the mold and also to obtain a foam skin without superficial or subsurface defects, such as holes, gaps, local collapses, blisters, blisters, and skin peeling, which can be harmful for the application, both for aesthetic reasons as well as comfort.
    [005] Two types of release agent can be used: a solvent-based system in which a solvent is evaporated when in contact with the heat of the mold, thereby releasing a waxy layer on the foam surface, or a release agent water-based, in which most of the water has no evaporation time before foam injection; in this case the release agent needs to be formulated properly to prevent this residual water from reacting with the isocyanate, thus leading to the formation of undesirable local gas. For environmental reasons, water-based release agents are currently preferred to reduce volatile organic compounds. In addition to the effect of release agents, skin formation and the quality of viscoelastic foams is governed by foam formulation, nucleation control, cell formation, cell stabilization and gelation. Preferably, the skin is smooth and flexible, while being resistant to avoid tears in demoulding and during handling and storage.
    [006] As with most polyurethane foams, in the VE polyurethane foams the two reactive components are a polyol component and a polyisocyanate component. The two components can be reacted in the presence of a blowing agent. The blowing agent is generally water or, less preferably, a mixture of water and another material. The predominant polyol used in these formulations has a functionality of about 2 hydroxyl groups / molecule and a molecular weight in the range of 400-1500. This polyol composition is basically the main determinant of the Tg (glass transition temperature) of the polyurethane foam, although other factors, such as water level and type and isocyanate index also play important roles. However, as mentioned above, the skin of the molded viscoelastic blocks may have surface defects and / or sticky surfaces at the time of demoulding, with solvent and water based demolding agents, resulting in a high scrap rate.
    [007] There is, therefore, a need for block foam without internal collapses, to maximize production yield. Summary of the Invention
    [008] Embodiments of the invention provide viscoelastic polyurethane foams. Foams are prepared with a reaction system that includes: (a) an isocyanate reactive component, (b) an isocyanate component, (c) one or more blowing agents, (d) a catalyst component, and (e) a silicone-based surfactant. The reactive isocyanate component includes at least (i) from 25 to 80% by weight of at least one polyoxypropylene / polyoxyethylene polyol capped with polyoxyethylene, having an equivalent average combined numerical weight of 1300 to 1700, a percentage of polyoxyethylene between 75% and 95% by weight of the combined amounts of polyoxypropylene and polyoxyethylene, and a primary OH percentage between 80 and 95% of the total number of OH groups of the polyoxypropylene / polyoxyethylene polyol capped with polyoxyethylene, and (ii) 5 to 30% by weight of the component reactive isocyanate of at least one polyol of low functionality between 1.5 and 2.5, an average combined weight equivalent of 500 to 1500 and an OH index of 40 to 70. Description of Embodiments of the Invention
    [009] Embodiments of the present invention provide viscoelastic foams with improved skin formation. These foams do not collapse, do not peel skin or form gaps in demoulding, while maintaining excellent physical properties, such as uniform cell sizes, viscoelasticity, and high-quality surface appearance.
    [010] The embodiments include polyurethane foams that include the reaction products of a reaction system that includes at least: (a) an isocyanate reactive component, (b) a polyisocyanate component, (c) water, and (d ) a catalyst component, (e) a surfactant component.
    [011] The reactive isocyanate components (a) used in the production of polyurethane are generally compounds that contain at least two hydroxyl groups. Such compounds are referred to herein as polyols. Polyols include those obtained by the alkoxylation of suitable starting molecules (initiators) with an alkylene oxide, such as ethylene oxide, propylene oxide, or butylene oxide. Examples of initiator molecules containing 2 to 4 reactive sites include water, ammonia, or polyhydric alcohols, such as dihydric alcohols with a molecular weight of 62 to 399, especially alkane polyols, such as ethylene glycol, propylene glycol, hexamethylene diol, glycerol, trimethylol propane or trimethylol ethane, or low molecular weight alcohols containing ether groups, such as diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol or butylene glycols. These polyols are conventional materials prepared using conventional methods. For polyols, the use of the term "triol" or "monol" proposes the functionality of the starter (such as glycerin for triols and n-butanol for monols). The catalysis for this polymerization can be anionic or cationic, with catalysts such as potassium hydroxide (KOH), cesium hydroxide (CsOH), boron trifluoride, or a complex double metal cyanide (DMC) catalyst, such as hexacyanocobaltate zinc or the quaternary phosphazene compound. In the case of alkaline catalysts, these alkaline catalysts are preferably removed from the polyol at the end of production through an appropriate finishing step, such as coalescence, magnesium silicate separation or acid neutralization.
    [012] Component (a) can be an isocyanate reactive component comprising (i) from 25 to 80% by weight of the isocyanate reactive component of one or more polyoxyethylene-rich polyols.
    [013] In certain embodiments, the one or more polyols rich in polyoxyethylene ((a) (i)) may comprise at least 25% by weight, 30% by weight, 35% by weight, 40% by weight, 45% by weight. weight, 50% by weight, 55% by weight, 60% by weight, 65% by weight, 70% by weight, or 75% by weight of the reactive isocyanate component (a). In certain embodiments, the one or more polyols rich in polyoxyethylene ((a) (i)) may comprise up to 50% by weight, 55% by weight, 60% by weight, 65% by weight, 70% by weight, or 80 % by weight. The one or more polyols rich in polyoxyethylene ((a) (i)) may comprise from 50% by weight to 80% by weight or from 55% by weight to 75% by weight of the total isocyanate reactive component (a).
    [014] In certain embodiments, the one or more polyoxyethylene-rich polyols ((a) (i)) have an equivalent combined numerical average weight of 1300 to 1700. In certain embodiments, the one or more polyoxyethylene-rich polyols ((a ) (i)) have an equivalent combined numerical average weight of at least 1300, 1350, 1400, 1450, 1500, 1550 or 1600. In certain embodiments, the one or more polyols rich in polyoxyethylene ((a) (i)) have an equivalent average combined numerical weight of up to 1350, 1400, 1450, 1500, 1550, 1600, 1650 or 1700.
    [015] In certain embodiments, the one or more polyoxyethylene-rich polyols ((a) (i)) have a functionality between 2 and 6. In certain embodiments, the one or more polyoxyethylene-rich polyols ((a) (ii) have a functionality between 2.5 and 4.
    [016] In certain embodiments, the one or more polyoxyethylene-rich polyols ((a) (i)) have a polyoxyethylene content of at least 75% by weight, 80% by weight, 82% by weight, 85% by weight , 87% by weight, 90% by weight, or 92% by weight of the total weight of one or more polyoxyethylene-rich polyols. In certain embodiments, the one or more polyols rich in polyoxyethylene ((a) (i)) have a polyoxyethylene content of up to 80% by weight, 82% by weight, 85% by weight, 87% by weight, 90% by weight. weight, 92% by weight, or 95% by weight of the total mass of the one or more polyoxy rich polyols. One or more polyoxyethylene-rich polyols ((a) (i)) may have a polyoxyethylene content greater than 80%, but less than 95% of the total mass of one or more polyoxyethylene-rich polyols or 85% by weight at 90% by weight of the total mass of the one or more polyols rich in polyoxyethylene.
    [017] In certain embodiments, the one or more polyols rich in polyoxyethylene ((a) (i)) have a primary OH content of at least 80%, 82%, 85%, 87%, 90% or 92% of the total number of OH groups of polyoxyethylene-rich polyols ((a) (i)). In certain embodiments, the one or more polyols rich in polyoxyethylene ((a) (i)) have a primary OH content of up to 85%, 87%, 90%, 92% or 95% of the total number of OH groups of the polyols rich in polyoxyethylene ((a) (i)).
    [018] In certain embodiments, polyoxyethylene-rich polyols may comprise at least one polyoxypropylene / polyoxyethylene polyol capped with polyoxyethylene having an equivalent combined numerical weight of 1300 to 1700, a percentage of polyoxyethylene between 75% and 95% by weight of the combined amounts polyoxypropylene and polyoxyethylene, and a percentage of primary OH between 80 to 95% of the total number of OH groups of polyoxypropylene / polyoxyethylene polyol capped with polyoxyethylene, which may, in certain embodiments, be a triol. An example of such a polyol is VORANOL 1477, from Dow Chemical Company.
    [019] Component (a) may also include an isocyanate reactive component comprising (ii) from 5 to 30% by weight of the isocyanate reactive component of one or more low functionality polyols. In certain embodiments, the one or more low-functional polyols ((a) (ii)) have a functionality between 1.5 to 2.5. In certain embodiments, the one or more low-functional polyols ((a) (ii)) have a functionality between 1.7 and 2.3. In certain embodiments, the one or more low-functional polyols ((a) (ii)) can be diols.
    [020] In certain embodiments, the one or more low-functional polyols ((a) (ii)) may comprise at least 5% by weight, 10% by weight, 15% by weight, 20% by weight, or 25% by weight of the total isocyanate reactive component (a). In certain embodiments, the one or more low-functional polyols ((a) (ii)) may comprise up to 10% by weight, 15% by weight, 20% by weight, 25% by weight, or 30% by weight. The one or more low functionality polyols ((a) (ii)) may comprise from 5% by weight to 30% by weight or from 10% by weight to 20% by weight of the total isocyanate reactive component (a).
    [021] In certain embodiments, the one or more low functionality polyols ((a) (ii)) have an equivalent combined numerical average weight of 500 to 1500. In certain embodiments, the one or more low functionality polyols ((a ) (ii)) have an equivalent combined numerical average weight of at least 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1350 or 1400. In certain embodiments, the one or more low functionality polyols ( (a) (ii)) have an average combined numerical weight of up to 700, 800, 900, 950, 1000, 1050, 1100, 1200, 1300, 1350, 1400, 1450 or 1500.
    [022] In certain embodiments, the one or more low-functional polyols ((a) (ii)) have an OH index of at least 40, 45, 50, 60 or 65. In certain embodiments, the one or more polyols low functionality ((a) (ii)) have an OH index of up to 45, 50, 60, 65 or 70.
    [023] Examples of suitable diols may include VORANOL P 2000, from The Dow Chemical Company.
    [024] Component (a) may also include an isocyanate reactive component (iii) of 5 to 30% by weight of the isocyanate reactive component of one or more high functionality polyols. In certain embodiments, the one or more high functionality polyols ((a) (iii)) have a functionality between 4 and 6. In certain embodiments, the one or more high functionality polyols ((a) (iii)) have a functionality functionality between 4.5 and 5. In certain embodiments, the one or more high functionality polyols ((a) (iii)) may have a functionality of 4.7.
    [025] In certain embodiments, the one or more highly functional polyols ((a) (iii)) may comprise at least 5% by weight, 10% by weight, 15% by weight, 20% by weight, or 25% by weight of the total isocyanate reactive component (a). In certain embodiments, the one or more high-functional polyols ((a) (iii)) may comprise up to 10% by weight, 15% by weight, 20% by weight, 25% by weight, or 30% by weight. The one or more high functionality polyols ((a) (iii)) can comprise from 5% by weight to 30% by weight or from 10% by weight to 20% by weight of the total isocyanate reactive component (a).
    [026] In certain embodiments, the one or more high-functionality polyols ((a) (iii)) have a combined numerical average molecular weight of 4000 to 5500. In certain embodiments, the one or more high-functionality polyols ((a ) (iii)) have a combined numerical average molecular weight of at least 4000, 4500, 5000 or 5500. In certain embodiments, the one or more highly functional polyols ((a) (iii)) have a combined numerical average molecular weight up to 4500, 5000 or 5500 or 5000.
    [027] In certain embodiments, the one or more highly functional polyols ((a) (iii)) have an OH index of at least 25, 30, 35, or 40. In certain embodiments, the one or more polyols of high functionality ((a) (iii)) have an OH index of up to 30, 35 or 40 or 45.
    [028] In certain embodiments, the one or more high functionality polyols ((a) (iii)) can be a polyoxypropylene polyol capped with polyoxyethylene having an average functionality between 4 and 6, a combined numerical average molecular weight of 4000 to 6000 , and an OH index of 25 to 45. Suitable examples are SPECFLEX NC 632, from The Dow Chemical Company.
    [029] Component (a) may further include an isocyanate reactive component comprising (iv) from 5 to 30% by weight of the isocyanate reactive component of one or more triols.
    [030] In certain embodiments, the one or more triols ((a) (iv)) may comprise at least 5% by weight, 10% by weight, 15% by weight, 20% by weight or 25% by weight of the component total isocyanate reactive (a). In certain embodiments, the one or more triols ((a) (iv)) may comprise up to 10% by weight, 15% by weight, 20% by weight, 25% by weight, or 30% by weight. The one or more triols ((a) (iv)) may comprise from 5% by weight to 30% by weight, or from 10% by weight to 20% by weight of the total isocyanate reactive component (a).
    [031] In certain embodiments, the one or more triols ((a) (iv)) have a combined average numerical weight of 200 to 400. In certain embodiments, the one or more triols ((a) (iv)) have a combined equivalent average numerical weight of at least 200, 250, 300 or 350. In certain embodiments, the one or more triols ((a) (iv)) have a combined equivalent average numerical weight of up to 250, 300, 350 or 400 .
    [032] In certain embodiments, the one or more triols ((a) (iv)) have an OH index of at least 175, 200, 225 or 250. In certain embodiments, the one or more triols ((a) ( iv)) have an OH index of up to 200, 225, 250 or 275.
    [033] In certain embodiments, the one or more triols ((a) (iv)) can be a glycerin-initiated polyoxypropylene having a combined average numerical weight of 200 to 400 and an OH index of 175 to 275. Suitable examples they are, for example, VORANOL CP 755, from The Dow Chemical Company.
    [034] One or more components ((a) (i)) - ((a) (iv)) can be a polymeric polyol that contains a dispersed polymeric phase. The dispersed polymeric phase can be particles of an ethylenically unsaturated monomer (whose styrene, acrylonitrile and styrene-acrylonitrile copolymers are of particular interest), polyurea particles, or polyurethane particles. The dispersed phase can comprise 5 to 60% by weight of the polymeric polyol. The embodiments comprise grafted polyether polyols containing 30 to 50% copolymerized styrene and acrylonitrile (SAN).
    [035] Alternatively, the polymeric polyol can be a separate copolymer polyol ((a) (v)). Products available on the market of this type include SPECFLEX NC 700, from The Dow Chemical Company.
    [036] One or more components (a) can be polyols based on renewable resources, such as epoxidized or hydroformylated seed oil, such as soybean oil, or linear chain castor oil.
    [037] Component (b) can comprise one or more organic polyisocyanate components having an average of 1.8 or more isocyanate groups per molecule. The isocyanate functionality is preferably from about 1.9 to 4, and more preferably from 1.9 to 3.5 and especially from 2.0 to 3.3.
    [038] The one or more components of organic polyisocyanate can be a polymeric polyisocyanate, aromatic isocyanate, cycloaliphatic isocyanate, or aliphatic isocyanate. Representative polyisocyanates include m-phenylene diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, hexamethylene-1,6-diisocyanate, tetramethylene-1,4-diisocyanate, cyclohexane-1,4-diisocyanate, diisocyanate hexahydrotoluene, naphthylene-1,5-diisocyanate, methoxyphenyl-2,4-diisocyanate, diphenylmethane-4,4'-diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4 'diisocyanate 1- biphenyl, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, 3,3'-dimethyldiphenyl methane-4,4'-diisocyanate, 4,4 ', 4 "-triphenyl triisocyanate, a polyphenylisocyanate polymethylene (PMDI), toluene-2,4,6-triisocyanate and 4,4'-dimethyldiphenylmethane-2,2 ', 5'-tetraisocyanate. Preferred polyisocyanates include MDI and MDI derivatives, such as liquid "MDI products "modified with biuret and polymeric MDI. Preferred polyisocyanates are the so-called polymeric MDI products, a mixture of polyethylene polyphenylene polyisocyanates in monomeric MDI. In one embodiment, MDI po limeric comprises 70% by weight or more of the total isocyanate. Especially suitable polymeric MDI products have a free MDI content of 5 to 50% by weight, more preferably 10 to 40% by weight. Such polymeric MDI products are from The Dow Chemical Company under the PAPI and VORANATE brands.
    [039] An especially preferred polyisocyanate is a polymeric MDI product having an average isocyanate functionality of 2.3 to 3.3 isocyanate groups / molecule and an isocyanate equivalent weight of 120 to 170, preferably 125 to 135. Suitable products available such markets include PAPI PB-219, PAPI 27, VORANATE M229, VORANATE 220, VORANATE 290, VORANATE M595 and VORANATE M600, all from The Dow Chemical Company.
    [040] Component (b) may alternatively or additionally comprise one or more isocyanate-terminated prepolymers, in which the stoichiometric excess of any of the above isocyanates or mixture of isocyanates is first reacted with any of the aforementioned polyols or others polyols to form a prepolymer. In certain embodiments, the prepolymer can be prepared using a mixture of 4'-methylene diphenyl isocyanate, 4,4'-methylene diphenyl diisocyanate and polymeric methylene diphenyl diisocyanate. In certain embodiments, the prepolymer can be prepared using polyoxypropylene polyol capped with polyoxyethylene / polyoxypropylene having a functionality between 2 and 4, a percentage of polyoxyethylene between 60 and 90 and an OH index between 25 and 40 mg KOH / g.
    [041] In certain embodiments, the reaction system further comprises (c) a blowing agent. In certain embodiments, the blowing agent content is 1% to 5% by weight of the total weight of the reaction system. In certain embodiments, the blowing agent content is 3% to 4% by weight of the total weight of the reaction system. In certain embodiments, the blowing agent is water.
    [042] In certain embodiments, the reaction system further comprises (d) one or more catalysts. Catalysts are typically used in small amounts, for example, each catalyst being employed from 0.0015 to 5% by weight of the total reaction system. The amount depends on the catalyst or mixture of catalysts, the desired balance of gelling and blowing reactions for specific equipment, the reactivity of polyols and isocyanate, as well as other factors familiar to those skilled in the art.
    [043] A wide variety of materials are known to catalyze polyurethane formation reactions, including tertiary amines; tertiary phosphines such as trialkylphosphines and dialkylbenzylphosphines; various metal chelates such as those obtainable from acetylacetone, benzoylacetone, trifluoroacetyl acetone, ethyl acetoacetate and the like, with metals such as Be, Mg, Zn, Cd, Pd, Ti, Zr, Sn, As, Bi, Cr, Mo, Mn, Fe, Co and Ni; acidic metallic salts of strong acids, such as ferric chloride, stannous chloride, stannous chloride, antimony trichloride, bismuth nitrate and bismuth chloride; strong bases such as alkali and alkaline earth metal hydroxides, alkoxides and phenoxides, various metal alcoholates and phenolates, such as Ti (OR) 4, Sn (OR) 4 and Al (OR) 3, where R is alkyl or aryl, and products reaction of alcoholates with carboxylic acids, beta-diketones and 2- (N, N-dialkylamino) alcohols; alkaline earth metal, carboxylate salts of Bi, Pb, Sn or Al; and tetravalent tin and tri or pentavalent bismuth compounds, antimony or arsenic compounds. Examples of commercially available tertiary amine catalysts include: trimethylamine, triethylamine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethylbenzylamine, N, N-dimethylethanolamine, N, N-dimethylaminoethyl, N, N, N ', N' -tetratmeil-1,4-butanediamine, N, N-dimethylpiperazine, 1,4-diazobicyclo-2,2,2-octane, bis (dimethylaminoethyl) ether, triethylenediamine and dimethylalkylamines, where the alkyl group contains from 4 to 18 atoms carbon. Mixtures of these tertiary amine catalysts are often used.
    [044] Examples of commercially available amine catalysts include NIAX Al and NIAXA99 (bis (dimethylaminoethyl) propylene glycol ether distributed by Momentive Performance Materials), NIAXB9 (N, N-dimethylpiperazine and N, N-dimethylhexadecylamine in an oxide polyol polyalkylene from Momentive Performance Materials), DABCO 82 64 (a mixture of bis (dimethylaminoethyl) ether, triethylenediamine and dimethylhydroxyethylamine in dipropylene glycol from Air Products and Chemicals), DABCO 33LV (triethylene diamine in dipropylene glycol, from Air Products and Chemicals), DABCO BL-11 (a 70% solution of bis-dimethylaminoethyl ether in dipropylene glycol from Air Products and Chemicals, Inc.), NIAXA -400 (a tertiary amine / carboxylic salt and exclusive bis (2-dimethylaminoethyl) ether) and an exclusive hydroxyl compound, from Momentive Performance Materials); NIAXA-300 (a tertiary / carboxylic amine salt and triethylenediamine in water, from Momentive Performance Materials); POLYCAT 58 (an exclusive amine catalyst from Air Products and Chemicals), POLYCAT 5 (pentamethyl diethylene triamine from Air Products and Chemicals) and POLYCAT 8 (N, N-dimethyl cyclohexylamine from Air Products and Chemicals). Autocatalytic polyols can also be used to reduce VOCs.
    [045] In another embodiment, the reaction system further comprises (e) one or more surfactants to help stabilize the foam as it expands and cures. Surfactants are typically in small amounts, for example, each catalyst always employed from about 0.0015 to about 5% by weight of the total reaction system. The amount depends on the surfactants or the mixture of surfactants, as well as other factors familiar to those skilled in the art.
    [046] Examples of surfactants include nonionic surfactants and wetting agents, such as those prepared by the sequential addition of propylene oxide and then ethylene oxide in propylene glycol, solid or liquid organosilicones, and polyethylene glycol ethers of chain alcohols long. Ion surfactants such as tertiary amine salts or alkanolamine of long chain acid alkyl sulfate esters, alkyl sulfonic esters and alkyl aryl sulfonic acids can also be used. Surfactants prepared by the sequential addition of propylene oxide and then ethylene oxide in propylene glycol are preferred, as are solid or liquid organosilicones. Examples of useful organosilicone surfactants include commercially available polysiloxane / polyether copolymers, such as TEGOSTAB B-8462, B-8404, B-8715 LF2 and B-8871 (from Evonik AG); surfactants DC-198 and DC-5043 from Dow Corning; and NIAX L-627, L-620, L-618, L-6633 and L-6900 from Momentive Performance Materials.
    [047] In another embodiment, to improve processing and allow the use of higher isocyanate levels, additional additives, such as those described in WO 2008/021034, can be added to the reaction mixture. Such additives include 1) alkali metal or transition metal salts of carboxylic acids; 2) 1,3,5-tris alkyl or 1,3,5-tris (N, N-dialkyl amino alkyl), hexahydro-s-triazine compounds; and 3) carboxylate salts of quaternary ammonium compounds. When used, such additives are generally used in an amount of about 0.01 to 1 part per 100 total polyol. The additional additive is usually dissolved in at least one other component of the reaction mixture. It is generally not preferred to dissolve it in the polyisocyanate.
    [048] Several additional components can be included in the viscoelastic foam formulation. These include, for example, crosslinkers, plasticizers, fillers, smoke suppressants, fragrances, reinforcements, dyes, dyes, pigments, preservatives, odor masks, physical blowing agents, chemical blowing agents, flame retardants, internal release agents , biocides, antioxidants, UV stabilizers, antistatic agents, thixotropic agents, adhesion promoters, cell openers, and combinations thereof.
    [049] The foaming composition may contain a cell opener or a crosslinker. When these materials are used, they are typically employed in small amounts such as up to 10 parts, especially up to 2 parts, by weight per 100 parts by weight of the total reactive system. A crosslinker is a material that contains, on average, more than two isocyanate reactive groups per molecule. In either case, the equivalent weight per reactive group with isocyanate can vary from about 30 to less than 100, being generally from 30 to 75. The reactive groups with isocyanate are preferably aliphatic alcohol groups, primary or secondary amine groups, with aliphatic alcohol groups being particularly preferred. Examples of chain extenders and crosslinkers include alkylene glycols such as ethylene glycol, 1,2- or 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol and the like; glycol ethers such as diethylene glycol.
    [050] One or more fillers may also be present in the viscoelastic foam formulation. A filler can help modify the composition's rheological properties in a beneficial way, reduce costs and confer beneficial physical properties to the foam. Suitable fillers include particulate inorganic or organic materials that are stable and do not melt at temperatures encountered during the polyurethane formation reaction. Examples of suitable fillers include recycled foam, kaolin, montmorillonite, calcium carbonate, mica, wolastonite, talc, high melting thermoplastics, glass, fly ash, carbon black, titanium dioxide, iron oxide, chromium oxide, azo / diazo dyes, phthalocyanines, dioxazins and the like. The filler can impart thixotropic properties to the foamed polyurethane composition. Pyrogenic silica is an example of such a charge.
    [051] Reactive particles can also be included in the reaction system to modify the properties of the viscoelastic foam. Such reactive systems include copolymer polyols, such as those containing styrene / acrylonitrile (SAN), Polyharnstoff dispersion (PHD), polyols and polyisocyanate polyaddition products (PIPA), for example as described in Chemistry and Technology of Polyols for Polyurethanes , Rapra Technology Limited (2005) p.185-227.
    [052] When used, the charges advantageously comprise from about 0.5 to about 30%, especially from about 0.5 to about 10% by weight of the reaction system.
    [053] Although no additional blowing agent (other than water) in the foamed polyurethane composition is generally used, it is within the scope of the embodiments described herein to include an additional physical or chemical blowing agent. Physical blowing agents can be, although not restricted to liquid carbon dioxide (CO2), supercritical CO2 and various hydrocarbons, fluorocarbons, hydrofluorocarbons, chlorocarbons, chlorofluorocarbons, hydrochlorofluorocarbons and acetone. Chemical blowing agents are materials that decompose or react (other than with isocyanate groups) at elevated temperatures to produce carbon dioxide and / or nitrogen.
    [054] Polyurethane viscoelastic foams can be produced by combining isocyanate component and at least polyol components, together with any optional additives. The polyol isocyanate components can be reacted at isocyanate indices from 60 to 110. All individual values and sub-ranges from 60 to 110 are included and described here; for example, the index can range from a minimum of 60, 65, 70, 75, 80, 85, 90 or 95 to a maximum of around 75, 80, 85, 90, 95, 99, 100, 105 or 110.
    [055] The foam block is conveniently prepared by mixing the foam ingredients and dispensing them into a channel or other region where the reaction mixture reacts, increases freely against the atmosphere (sometimes under a film or another flexible coating) and curing. In conventional commercial foaming block production, the foam ingredients (or various mixtures thereof) are pumped independently to a mixing head where they are mixed and dispensed on a conveyor lined with paper or plastic. Foaming and curing takes place on the conveyor forming a foam roller. The resulting foams have densities below 100 kg / m3. All values and individual sub-ranges below 100 kg / m3 are included and described here; for example, density can be at a minimum limit of 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, or 80, at a maximum limit of 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 or 95.
    [056] The molded foam can be prepared according to embodiments of the invention by transferring the reagents to a closed mold where the defoaming reaction takes place producing a molded foam. Either process, be it "cold molding", which the mold is not preheated significantly above room temperature, or "hot molding", in which the mold is heated to activate the cure, are optionally used . Molded foams can have densities below 100 kg / m3. All values and sub-ranges below 100 kg / m3 are included and described here; for example, the density can be in a minimum limit of 30, 35, 40, 45, 50, 55, 60, 65, 70, 75 or 80 up to a maximum limit of 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 or 95. In certain embodiments, molded foams can have densities between 40 and 55 kg / m3, or between 45 and 50, 55 kg / m3.
    [057] The embodiments cover both cold molding and hot molding processes. However, surprisingly, it was found that improved skin formation can be achieved by using the reaction system described here. The skin may include superficial skin about 12-25pm thick and having small cell sizes (50-150pm). This makes the skin thicker and / or much stronger and resistant to demolding forces, resulting in the elimination of demolding defects. In addition, the presence of these smaller subsurface cells very close together provides a smoother surface, which results in better haptic (or tactile) properties of the foam. EXAMPLES
    [058] The following examples are provided to illustrate the embodiments of the invention, although they are not restricted to its scope. All parts and percentages are by weight, unless otherwise stated. The following materials are used:
    * ISONATE, SPECFLEX, VORANATE and VORANOL are trademarks of The Dow Chemical Company. Isocyanate component
    [059] An isocyanate component is prepared first by combining ISONATE 125 M (27.5 parts by weight), ISONATE OP50 (36.2 parts by weight) and VORANATE M229 (26.8 parts by weight) and mixing on a roller compactor for 30 minutes. The prepolymers are then formed by adding a polyol, VORANOL * CP 1421 (9.5 parts by weight) under mixing. The reaction is completed by internally heating a reactor to 70 ° C for 60 minutes. Examples 1 and 2 and Comparative Examples A and B
    [060] Foams are prepared by combining the Isocyanate Component with a Polyol Component listed in Table 2. Polyurethane foams are prepared through a one-step process using high pressure machines for weighing and proper dispensing of the Polyurethane Component. Isocyanate and the Polyol Component. The components are kept at 25 ° C and transferred to a mixing head (mixing head FPL 14 ") at 160 bar, and to a mold at 250 g / s. The foams are produced at an isocyanate index of 70. They are aluminum and epoxy molds are used which are heated by recirculating water adjusted to a temperature of 35-50 ° C and treated with solvent-based release agent to allow release. The release time is set at 4 -5 minutes The physical-mechanical properties were tested according to the test methods in Table 1: Table 1
    Table 2
    cell. The cells just below the surface are smaller than the volume, but in many cases, they are flattened. bA layer about three cells thick just below the surface has a smaller cell size: 0.75-1.2 mm. cIt is not really a surface, due to the large number of openings. However, the surface is again just below the thickness of the cell walls. Smaller subsurface cells extend further below the surface than in Comparative Example B. dThe final surface is also just a cell wall thickness, although there is a thin subsurface layer (homogeneous skin, 150-250 pm thick) with small cell sizes (50-150 pm). This makes the "skin" thicker and / or much stronger and resistant to demolding forces. The presence of these smaller subsurface cells very close together provides a smoother surface, which plays an important role in improving the tactile properties of this foam. The samples have two very similar Tgs, measured using DSC: first around -60 ° C and the second around -30 ° C.
    [061] SEM images of the foam's outer skin and foam core (1 cm under the skin) are illustrated in Figures 1 to 6. The differences between Example 1 and Comparative Examples A and B can be seen in the cell morphology of the foam, as well as the morphology of the skin surface. The observed differences may explain some of the differences in the tactile property of foam surfaces, although the difference in haptics is also dependent on differences in viscoelastic behavior.
    [062] Figures 1, 3 and 5 show the differences in the cross sections of the interfacial skin foam and foam core for Comparative Example A, Comparative Example B and Example 1, respectively. It can be seen that the cell size just below the skin is larger in the foam of Comparative Example A and Comparative Example B than in the foam of Example 1. As a result, the skin layer is much thinner in the two Comparative Examples resulting much more fragile and much easier to damage during demoulding. Even though the skin of Example 1 still has a foam structure, it has very small cell sizes, thus having a significantly higher density than the underlying foam. Higher foam skin thickness and density provide better release properties, as can be seen.
    [063] Figures 2, 4 and 6 show the morphologies of top surfaces for Comparative Example A, Comparative Example B and Example 1, respectively. All foams have surfaces with some holes as a result of the underlying cellular structure emerging to the surface. This phenomenon predominates more in Comparative Example A, being less prevalent in Comparative Example B. Because Example 1 has the thickest skin and the smallest cell size close to the surface, it has a waxy surface with a higher frequency. The result of this surface is that the human hand / finger experiences a smoother surface, with a more velvety touch. The observed effect may simply be caused by the surface morphology, although some influence of the viscoelastic behavior of the material may play a role in this case. Considering that comparative foams have thin skin layers with larger cell sizes close to the surface, the skins have a larger waxy surface, but with a lower frequency. However, a greater roughness gives these foams poor haptic (or tactile) characteristics. In addition, these blocks cannot be used with light fabric lining.
    [064] Although the aforementioned is directed to embodiments of the present invention, other embodiments of the invention can be contemplated without departing from its basic scope, such scope being determined by the claims described below.
    权利要求:
    Claims (10)
    [0001]
    1. Reaction system for the preparation of a viscoelastic polyurethane foam, characterized by the fact that it comprises: (a) an isocyanate reactive component comprising: (i) from 25 to 80% by weight of the isocyanate reactive component of at least one polyoxypropylene / polyoxyethylene polyol capped with polyoxyethylene, having a combined average numerical weight of 1300 to 1700, a percentage of polyoxyethylene between 75% and 95% by weight of the combined amounts of polyoxypropylene and polyoxyethylene, and a percentage of primary OH between 80 and 95 % of the total number of OH groups of the polyoxypropylene / polyoxyethylene polyol capped with polyoxyethylene; (ii) from 5 to 30% by weight of the reactive isocyanate component of at least one low-functional polyol having a functionality between 1.5 and 2.5, a combined numerical average weight of 500 to 1500 and an OH index of 40 to 70; (b) an isocyanate component; (c) one or more blowing agents; (d) a catalyst component; and (e) a silicone-based surfactant.
    [0002]
    2. System according to claim 1, characterized in that the reactive isocyanate component further comprises: (111) from 5 to 30% by weight of the isocyanate reactive component of at least one polyoxypropylene polyol capped with polyoxyethylene having a functionality average between 4 and 6, a combined numerical average molecular weight of 4000 to 6000, and an OH index of 25 to 45.
    [0003]
    System according to either of claims 1 or 2, characterized in that the reactive isocyanate component further comprises: (iv) from 2 to 20% by weight of the reactive isocyanate component of at least one triol containing a weight equivalent numerical average of 200 to 400 and an OH index of 175 to 275.
    [0004]
    System according to any one of claims 1 to 3, characterized in that the one or more blowing agents comprises water.
    [0005]
    System according to any one of claims 1 to 4, characterized in that the polyisocyanate component (b) comprises an isocyanate-terminated prepolymer.
    [0006]
    6. System according to claim 5, characterized in that the prepolymer comprises the reaction product of a polyol and a mixture of 2,4'-methylene diphenyl isocyanate, 4,4'- diphenyl diisocyanate methylene, and polymeric methylene diphenyl diisocyanate.
    [0007]
    7. Polyurethane foam, characterized by the fact that it comprises a reaction product from any of the reaction systems, as defined in any of claims 1 to 6.
    [0008]
    8. Foam according to claim 7, characterized in that it is shaped and comprises a skin having a thickness of 100-300 pm.
    [0009]
    9. Foam according to claim 8, characterized in that the skin is 150-250 pm thick.
    [0010]
    10. Foam according to any one of claims 8 and 9, characterized in that the skin comprises polyurethane cells having diameters of 50-150 pm
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    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-09-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-08-04| B09A| Decision: intention to grant|
    2020-11-17| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 20/09/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    ITMI20111750|2011-09-29|
    ITMI2011A001750|2011-09-29|
    PCT/EP2012/068508|WO2013045336A1|2011-09-29|2012-09-20|Viscoelastic foam|
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