Low density, low compression set, long recovery time polyurethane foam

Abstract

Flexible polyurethane foams are characterized by slow recovery times, low foam densities, and very low compression sets, making them useful in human comfort applications such as pillows and mattresses.

Description

[Technical field]

[0001] The present invention relates to polyurethane foams characterized by low density, low compression set, and long recovery time. Summary of the Invention [Problem to be solved by the invention]

[0002] A rapidly growing segment of the polyurethane foam industry is the so-called "viscoelastic" foams. These foams are characterized by having low resiliency and slow recovery when compression forces are released. These properties have been recognized as highly desirable in many human cushioning applications, such as bedding. Products such as mattresses and pillows are increasingly being made from viscoelastic polyurethane foams.

[0003] To avoid shipping and storing large amounts of air, these products are usually packaged in a compressed form. When the consumer removes the product from the package, the foam is allowed to re-expand to approximately its original dimensions. Thus, one requirement of a foam is that it can be compressed to a small fraction of its original volume, but still be able to re-expand when the compressive force is removed, even after being so compressed for a significant period of time. This attribute is measured using the compression set test of ISO 1856 Method A. The compression set should be as low as possible so that the foam can be packaged in a highly compressed form, but still be able to re-expand completely or nearly completely. Additionally, the foam should retain its properties even after repeated compression during use.

[0004] Sufficiently low compression set: about 35 kg / m 3 This can be achieved with core foam densities of 32 kg / m 3 Below, especially 28kg / m 3Lower foam densities, such as the following, are difficult to obtain in slow recovery foams, especially when the polyisocyanate is MDI or based on MDI and the foam is blown mainly or exclusively with water. These very low foam densities are usually produced by increasing the amount of water in the foam formulation, thus resulting in more urea bonds in the polymer structure. The presence of a large proportion of urea bonds is known to increase compression set. Lower densities are also associated with poorer properties, such as poorer compression set.

[0005] U.S. Patent No. 9,441,068 describes slow recovery foams made using a large proportion of a 1300-1700 equivalent weight polyether polyol containing 80-95% primary hydroxyl groups and in which the oxyethylene units constitute 75-95% of the total combined weight of the oxyethylene and oxypropylene units. This selection of polyol is reported to provide a desirable set of surface tactile properties. As an example, a polyether polyol containing 3.1-3.35 parts water and having a viscosity of 44-46 kg / m 3 Formulations which produce foams with densities in the range of 100 to 2000 have been reported.

[0006] WO2013 / 182527 describes slow recovery foams made using as the primary polyol an equivalent weight of about 1516, an oxyethylene content of 71.1 mole % (about 65 weight percent), and about 83% primary hydroxyl groups. A specific embodiment is shown in which the water level is 3.5 weight percent based on the weight of the polyol side of the formulation. No physical properties of the foam are reported.

[0007] What is desired is a strength of at most 33 kg / m2 when measured according to ISO 1856 method A. 3 and a 90% compression set of at most 10%. The foam has desirable surface tactile properties, in particular a very smooth surface. A method for making such a foam is also desired.

[0008] In one embodiment, the present invention provides a method for producing a coating composition comprising: 3 and b) a 90% compression set of 10% or less, when measured according to ISO 1856 Method A, and a recovery time of 0.5 to 20 seconds, measured as follows:

[0009] The flexible foam of the present invention comprises a reaction mixture comprising: a) an aromatic polyisocyanate having an isocyanate content of 20 to 33% by weight in an amount that produces an isocyanate index of 50 to 90; b) a polyether comprising: i) at least one polyether having a hydroxyl equivalent weight of 500 to 2000, a nominal hydroxyl functionality of 1 to 4, and an oxyethylene content of 40 to 95% by weight, wherein at least 60% of the hydroxyl groups are primary; and ii) at least one homopolymer or copolymer of propylene oxide having a hydroxyl equivalent weight of 80 to 2000, a nominal hydroxyl functionality of 1 to 6, and at least 80% of the hydroxyl groups are secondary, wherein polyether ii) is present in an amount such that polyether i) is at least partially incompatible with polyether i); c) water in an amount of 4.5 to 6.5 weight percent, based on the combined weight of components b) through f); and d) at least one catalyst for the reaction of isocyanate groups with alcohols and / or water; e) at least one silicone foam stabilizing surfactant; f) 0 to 25 weight percent, based on the combined weight of components b) through f), of an isocyanate-reactive compound different from components b), c), d), and e); provided that the reaction mixture contains no more than 5 weight percent, based on the combined weight of components b) through f), of an ethylene oxide-capped poly(propylene oxide) polyol having an oxyethylene content of up to 30 percent, based on the weight of the ethylene oxide-capped poly(propylene oxide) polyol.

[0010] Further, the flexible foam of the present invention comprises a reaction mixture comprising: a) an aromatic polyisocyanate having an isocyanate content of 20 to 33% by weight in an amount that produces an isocyanate index of 50 to 90; b) a polyether, b-1) at least one polyether having a hydroxyl equivalent weight of 500 to 2000, a nominal hydroxyl functionality of 1 to 4, and an oxyethylene content of 40 to 95% by weight, wherein at least 60% of the hydroxyl groups are primary; b-2) at least one homopolymer or copolymer of propylene oxide having a hydroxyl equivalent weight of 600 to 2000 and a nominal hydroxyl functionality of 1 to 6, wherein at least 80% of the hydroxyl groups are secondary; and b-3) optionally at least one homopolymer or copolymer of propylene oxide having a hydroxyl equivalent weight of 80 to 599 and a nominal hydroxyl functionality of 1 to 6, wherein at least 80% of the hydroxyl groups are secondary; i) the ratio of hydroxyl equivalents provided by component b-1) to the hydroxyl equivalents provided by components b-2) and b-3) is from 1 to 2.5; ii) component b-1 constitutes 65 to 85 weight percent of the combined weight of components b) through f); iii) component b-2) constitutes 1 to 30 weight percent of the combined weight of components b) through f); iii) component b-3) constitutes 0 to 20 weight percent of the combined weight of components b) through f); and iv) the combined weight of components b-1), b-2), and b-3) constitutes at least 70% of the combined weight of components b) through f); c) water in an amount of 4.5 to 6.5 weight percent, based on the combined weight of components b) to f) above; d) at least one catalyst for the reaction of isocyanate groups with alcohols and / or water; e) at least one silicone foam stabilizing surfactant; f) 0 to 25 weight percent, based on the combined weight of components b) through f), of an isocyanate-reactive compound different from components b), c), d), and e); provided that the reaction mixture contains no more than 5 weight percent, based on the combined weight of components b) through f), of an ethylene oxide-capped poly(propylene oxide) polyol having an oxyethylene content of up to 30 percent, based on the weight of the ethylene oxide-capped poly(propylene oxide) polyol.

[0011] The ability to achieve a combination of slow recovery time, very low foam density, and very low compression set even after 90% compression is entirely unexpected and highly beneficial, and believed to have been previously unknown, especially for foams blown using such large amounts of water. The foams of the present invention having such a combination of properties are useful as pillows and other bedding and human cushioning applications, and for such applications have highly desirable tactile properties. The low density contributes greatly to these desirable tactile properties, while providing the additional benefit of reducing raw material costs.

[0012] The very low compression set allows the foam to be packaged, stored, and shipped in a highly compressed state. After removal from the package, the foam recovers to nearly its original dimensions. There is little to no permanent set. Similarly, the foam resists permanent set (such as from the weight of a human body or parts thereof) even after repeated compression during normal use.

[0013] The aromatic polyisocyanate is a single material or mixture of isocyanate compounds having an isocyanate content of 20-33% by weight and an average of at least two isocyanate groups per molecule. In some embodiments, the isocyanate content is at least 25%, at least 27%, or at least 28% by weight and up to 31% or up to 30% by weight. In some embodiments, the aromatic polyisocyanate has an average of up to 3, up to 2.7, up to 2.5, or up to 2.2 isocyanate groups per molecule.

[0014] Examples of useful aromatic polyisocyanates include m-phenylene diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, naphthylene-1,5-diisocyanate, methoxyphenyl-2,4-diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, diphenylmethane-2,2'-diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4' -biphenyl diisocyanate, 3,3'-dimethyl-4-4'-biphenyl diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4',4''-triphenylmethane triisocyanate, polymethylene polyphenylisocyanate (PMDI) with three or more phenylisocyanate groups, toluene-2,4,6-triisocyanate, and 4,4'-dimethyldiphenylmethane-2,2',5,5'-tetraisocyanate. Any of the foregoing aromatic isocyanates can be modified to include one or more urethane, urea, allophanate, biuret, carbodiimide or uretonimine linkages, or any combination of any two or more thereof.

[0015] Preferably, the polyisocyanate is diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, diphenylmethane-2,2'-diisocyanate, PMDI, or a mixture of any two or more thereof. Diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, and diphenylmethane-2,2'-diisocyanate, as well as mixtures thereof, are collectively referred to as MDI, and all of them can be used. As for the "polymeric MDI" which is a mixture of PMDI and MDI, a polymeric MDI containing 70% by weight or less of MDI, particularly 50 to 70% by weight of MDI, can be particularly used.

[0016] In some embodiments, the polyisocyanate is or comprises an MDI product containing up to 50 weight percent, preferably up to 30 weight percent, of the 2,4'-isomer and up to 5 weight percent of the 2,2'-isomer (the balance being the 4,4'-isomer), and / or a mixture thereof with PMDI, in each case having the isocyanate content and average isocyanate functionality described herein.

[0017] Another useful organic polyisocyanate is or comprises a urethane group-containing prepolymer made by reaction of one or more of the aforementioned aromatic isocyanates (especially those mentioned in the previous paragraph) with a monoalcohol or polyol, the prepolymer having an isocyanate content and functionality as described above. The monoalcohol or polyol may have one or more hydroxyl groups, especially 2-4 or 2-3 hydroxyl groups, and a hydroxyl equivalent weight of 30-2500. Particularly suitable polyols for making the prepolymer are polyether polyols having a hydroxyl equivalent weight of 500-2000, especially 1000-2000, or 1250-1750, and 2-4, especially 2-3 hydroxyl groups per molecule. Such polyether polyols may be, for example, homopolymers of ethylene oxide or propylene oxide, (random and / or block) copolymers of ethylene oxide and propylene oxide, or poly(tetramethylene glycol).

[0018] The aromatic isocyanate is provided in an amount sufficient to produce an Isocyanate Index of from 50 to 90, preferably from 60 to 90, or from 60 to 75.

[0019] The aromatic isocyanates are reacted with one or more polyethers (component b) and water to produce the foams of the present invention.

[0020] The polyether b) comprises at least one polyether b-1) having a hydroxyl equivalent weight of 500 to 2000, a nominal hydroxyl functionality of 1 to 4, preferably 2 to 3, and an oxyethylene content of 40 to 95% by weight (based on the total weight of the polyethers of component i), with at least 60%, preferably at least 80%, at least 85%, or at least 88% of the hydroxyl groups being primary. The hydroxyl equivalent weight may be at least 1200, or at least 1300, and in certain embodiments up to 1800 or up to 1700. In certain embodiments up to 95% or up to 90% of the hydroxyl groups may be primary. In certain embodiments, the oxyethylene content of each polyether of component i) may be at least 40%, at least 50%, or at least 70%, for example up to 93%, up to 90%, up to 85%, or up to 80%.

[0021] Component b-1) is preferably a copolymer of ethylene oxide and propylene oxide. In a particularly preferred embodiment, component i) is a random copolymer made by polymerizing a mixture of ethylene oxide and propylene oxide onto an initiator compound (or a mixture of initiator compounds). Such random copolymers may have poly(oxyethylene) end caps formed by homopolymerizing ethylene oxide at the ends of randomly polymerized ethylene oxide / propylene oxide chains.

[0022] Component b-2) of polyether mixture b) is at least one homopolymer or copolymer of propylene oxide having a hydroxyl equivalent weight of 600 to 2000. In some embodiments, the hydroxyl equivalent weight of component b-2) is at least 700, at least 750, at least 800, or at least 900, and in some embodiments up to 1500 or up to 1250. Component b-2) can have a nominal hydroxyl functionality of 1 to 6 or 1 to 3, with a nominal functionality of 2 to 3 being preferred.

[0023] At least 80% of the hydroxyl groups of component b-2) are secondary. In some embodiments, at least 90% of the hydroxyl groups are secondary.

[0024] The optional component b-3) of the polyether mixture b) is at least one homopolymer or copolymer of propylene oxide having a hydroxyl equivalent weight of 80 to 599. In some embodiments, the hydroxyl equivalent weight of component b-3) is at least 100, at least 125, at least 150, at least 175, or at least 190, and in some embodiments, the hydroxyl equivalent weight is up to 550 or up to 500. Component b-3) can have a nominal hydroxyl functionality of 1 to 6, or 1 to 3, preferably 2 to 3. At least 80%, preferably at least 90%, of the hydroxyl groups of component b-3) are secondary.

[0025] Components b-2) and b-3) (if present) are each preferably a homopolymer of propylene oxide or a copolymer of propylene oxide and ethylene oxide containing not more than 20% by weight, preferably not more than 10% by weight, or not more than 5% by weight, of oxyethylene groups.

[0026] In some embodiments, polyether b) comprises at least one polyether b-2) and at least one polyether b-3).

[0027] Each of components b-1) and b-2) preferably contains no primary, secondary amine groups, and more preferably no tertiary amine groups. Furthermore, each of components b-1), b-2), and b-3) is devoid of siloxane groups.

[0028] Components b-1), b-2), and b-3) (if present) are present in relative amounts such that the ratio of hydroxyl equivalents provided by component b-1) to hydroxyl equivalents provided by components b-2) and b-3 is from 1 to 2.5, 1.5 to 1.75. This ratio can be at least 1.5, or at least 1.55, or at least 1.58, and in certain embodiments can be up to 2.25, up to 2.0, up to 1.75, up to 1.70, up to 1.68, or up to 1.65.

[0029] Further, component b-1) comprises 65 to 85 weight percent of the combined weight of components b)-f). In some embodiments, component b-1) may comprise up to 80%, or up to 82%, or up to 80%, or up to 78% of the combined weight of components b)-f).

[0030] Component b-2) comprises 1 to 30 weight percent of the combined weight of components b)-f), in some embodiments, component b-2) comprises at least 5, at least 6, at least 8, at least 10 weight percent, and in some embodiments, up to 28, up to 25, up to 20, or up to 18 weight percent of the combined weight of components b)-f).

[0031] Component b-3) may comprise 0 to 20 weight percent of the combined weight of components b)-f). When present, component b-3) may comprise at least 1, at least 2.5, or at least 5 weight percent of the combined weight of components b)-f). In some embodiments, component b-3) comprises up to 18, up to 15, or up to 12.5 weight percent of the combined weight of components b)-f).

[0032] Components b-2) and b-3) together may comprise up to 30 weight percent of the combined weight of components b)-f).

[0033] The combined weight of components b-1), b-2), and b-3) constitutes at least 75% of the combined weight of components b)-f), preferably at least 80%, at least 85%, at least 90%, at least 93%, or 93.5% of the combined weight.

[0034] Component c) is water and is present in an amount of 4.5 to 6.5 percent by weight of the combined weight of components b)-f). In some embodiments, water may comprise at least 4.75 or at least 4.9 percent by weight of the combined weight of components b)-f), and in some embodiments, up to 6.0, up to 5.75, or up to 5.5 percent by weight of the combined weight of components b)-f).

[0035] Component d) is at least one urethane catalyst, i.e., a catalyst for the reaction of isocyanate groups with alcohols and / or water. The urethane catalyst catalyzes either or both the water-isocyanate reaction and the alcohol-isocyanate reaction, and is not a polyether corresponding to any of components b-1), b-2), or b-3). Suitable catalysts include, for example, tertiary amines, cyclic amidines, tertiary phosphines, various metal chelates, acidic metal salts, strong bases, various metal alcoholates and phenolates, and metal salts of organic acids. Examples of metal-containing catalysts are salts of tin, bismuth, cobalt, and zinc. The most important catalysts are tertiary amine catalysts, cyclic amidines, zinc catalysts, and tin catalysts. Examples of tertiary amine catalysts include trimethylamine, triethylamine, N-methylmorpholine, N-ethylmorpholine, N,N-dimethylbenzylamine, N,N-dimethylethanolamine, N,N,N',N'-tetramethyl-1,4-butanediamine, N,N-dimethylpiperazine, 1,4-diazobicyclo-2,2,2-octane, bis(dimethylaminoethyl)ether, triethylenediamine, and dimethylalkylamines in which the alkyl group contains 4 to 18 carbon atoms. Mixtures of these tertiary amine catalysts are often used.

[0036] Reactive amine catalysts such as DMEA (dimethylethanolamine), DMAPA (dimethylaminopropylamine), or amine-initiated polyols different from components b-1), b-2), and b-3) may also be used.

[0037] Tin catalysts include stannic chloride, stannous chloride, stannous octoate, stannous oleate, dimethyltin dilaurate, dibutyltin dilaurate, stannous ricinoleate, and stannous mercury compounds represented by the formula SnR n (OR) 4-n Other tin compounds of the formula (where R is alkyl or aryl and n is 0-4), dialkyltin mercaptides, dialkyl tin thioglycolates, etc. Tin carboxylates, in which the carboxylate group has 6-18 carbon atoms, are sometimes associated with lower VOCs in VE foams. Zinc and tin catalysts, if used at all, are generally used in conjunction with one or more tertiary amine catalysts.

[0038] Catalysts are typically used in small amounts, with the combined amount of all catalysts suitably comprising 0.0015 to 4.5 percent of the total weight of components b) through f). Preferred amounts are up to 2 percent, up to 1.5 percent, or up to 1.0 percent on the same basis. Zinc and tin catalysts are generally used in very small amounts within this range, such as 0.0015 to 0.25 weight percent on the same basis.

[0039] The reaction mixture further comprises e) at least one silicone foam stabilizing surfactant. Foam stabilizing surfactants are materials that help stabilize the bubbles formed by the blowing agent during the foaming process until the polymer cures. A wide variety of silicone surfactants, such as those typically used to make polyurethane foams, can be used in the formulated polyol composition of the present invention. The silicone surfactant can include polyether chains, such as poly(ethylene oxide), poly(propylene oxide), or random or block chains of copolymerized ethylene oxide and propylene oxide. Examples of such silicone surfactants are commercially available under the trade names Tegostab™ (Evonik Industries AG), Niax™ (Momentive Performance Materials), Dabco™ (Air Products and Chemicals), and VORASURF® (The Dow Chemical Company).

[0040] The silicone foam stabilizing surfactant may, for example, constitute 0.01 to 2.5 weight percent of the combined weight of components b) through f), with preferred amounts being at least 0.05 weight percent, or at least 0.1 weight percent, and up to 1 weight percent, up to 0.5 weight percent, or up to 0.25 weight percent, on the same basis.

[0041] The reaction mixture may contain from 0 to 25 weight percent, based on the combined weight of components b) through f), of an isocyanate-reactive compound different from components b), c), d), and e). When component f) is present, the preferred amount is up to 20, up to 15, or up to 10 weight percent, on the same basis. For purposes of this invention, monoalcohol impurities formed in the production of components b-1), b-2), and b-3) are considered to be part of components b-1), b-2), and b-3), respectively, and the weights of such monoalcohol impurities are included in the weights of their respective components.

[0042] Among the optional isocyanate-reactive components are one or more monoalcohols or polyols different from components b) to e). Examples of such other monoalcohols or polyols include compounds having a hydroxyl equivalent weight of 30 to 79 and 2 to 6 hydroxyl groups per molecule. Among such polyols are propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, erythritol, triethanolamine, diethanolamine, mannitol, sucrose, sorbitol, and the like. Other optional polyols include polyether polyols, polyester polyols, and one or more natural oil polyols, such as castor oil, "blown" soybean oil, and the like, having a hydroxyl equivalent weight of more than 2000.

[0043] Component f) may comprise monoalcohols (monols, i.e. compounds with exactly one hydroxyl group per molecule) having a hydroxyl equivalent weight of up to 79 or even more than 2000. Such monools may be polyethers such as homopolymers of propylene oxide, homopolymers of ethylene oxide, or random and / or block copolymers of propylene oxide and ethylene oxide.

[0044] Still other examples of component f) materials are primary or secondary amine compounds such as phenylenediamine, diethyltoluenediamine, ethylenediamine, diethylenetriamine, aminated polyethers, and the like, as well as alkanolamines, such as, for example, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, and triisopropanolamine, etc. However, these amine and alkanolamine compounds, if used, are used in very small amounts, such as up to 2 weight percent, preferably up to 1 weight percent, up to 0.5 weight percent, or up to 0.25 weight percent, based on the combined weight of components b)-f).

[0045] The materials of component f) are optional and may be omitted. In particular, the reaction mixture contains 5 weight percent or less, 2 weight percent or less, 1 weight percent or less, or 0.5 weight percent or less of an ethylene oxide-capped poly(propylene oxide) polyol having an oxyethylene content of up to 30%, based on the weight of the ethylene oxide-capped poly(propylene oxide) polyol.

[0046] In certain embodiments, the reaction mixture also has the following characteristics, in each case the weight percentages being based on the total weight of components b) through f): i) less than or equal to 5 weight percent, less than or equal to 3 weight percent, less than or equal to 2 weight percent, less than or equal to 1 weight percent, or less than or equal to 0.5 weight percent of compounds having one or more primary and / or secondary amine groups; ii) 15 weight percent or less, 10 weight percent or less, 8 weight percent or less, or 5 weight percent or less, of polyether polyols having an oxyethylene content of 50% or more and less than 40% of the hydroxyl groups being primary; iii) less than or equal to 5 weight percent, less than or equal to 3 weight percent, less than or equal to 2 weight percent, less than or equal to 1 weight percent, or less than or equal to 0.5 weight percent of polyols and alkanolamines having a hydroxyl equivalent weight of 149 or less; iv) 5 weight percent or less, 3 weight percent or less, 2 weight percent or less, or 1 weight percent or less of any isocyanate-reactive material different from components b)-e); In some embodiments, the reaction mixture consists of components a), b-1), b-2), c), d), and e), while in other embodiments, the reaction mixture consists of components a), b-1), b-2), b-3), c), d), and e), in each case in the aforementioned ratios.

[0047] Further, in any of the foregoing embodiments, the reaction mixture contains less than 0.5 weight percent, less than 0.25 weight percent, or less than 0.1 weight percent urea (NH 2 CONH 2 ).

[0048] The Isocyanate Index is 100 times the ratio of the number of equivalents of isocyanate groups provided by component a) to the total number of equivalents of isocyanate-reactive groups provided by components b), c), and f) (if present). For purposes of calculating the Isocyanate Index, water is considered to have two isocyanate-reactive groups and any primary amino group is considered to be only one isocyanate-reactive group.

[0049] The reaction mixture may include one or more optional ingredients in addition to those already described.

[0050] The reaction mixture (or any of its components) may contain dispersed polymer particles. The dispersed polymer particles may be, for example, polyureas, polyurethanes, and / or polyhydrazides, or polymers of one or more vinyl monomers. Useful vinyl monomers include, for example, various polyolefins (such as polymers and copolymers of ethylene), various polyesters, various polyamides, various polycarbonates, various polymers and copolymers of acrylic and / or methacrylic acid esters, homopolymers or copolymers of styrene, homopolymers or copolymers of acrylonitrile, and the like. In some embodiments, the dispersed particles are styrene-acrylonitrile copolymer particles.

[0051] In some embodiments, the dispersed polymer particles have a particle size of from 100 nm to 25 μm, more typically from 250 nm to 10 μm, as measured by laser diffraction using an instrument such as a Beckman-Coulter LX 13320 laser diffraction particle sizer.

[0052] It may be desirable to include an auxiliary blowing agent in the reaction mixture. Such auxiliary blowing agents include physical (endothermic) blowing agents such as various low boiling chlorofluorocarbons, fluorocarbons, and hydrocarbons, as well as chemical (exothermic) blowing agents (other than water) that decompose or react under the conditions of the polyurethane-forming reaction. Additionally, gases such as carbon dioxide, air, nitrogen, or argon may be used as auxiliary blowing agents in the frothing process. Carbon dioxide may also be used as a liquid or as a supercritical fluid.

[0053] In addition to the aforementioned components, the reaction mixture may contain fillers such as melamine and calcium carbonate, pigments and / or colorants such as titanium dioxide, iron oxide, chromium oxide, azo / diazo dyes, phthalocyanines, dioxazines, and carbon black, reinforcing agents such as glass fiber, carbon fiber, flaked glass, mica, talc, flame retardants, biocides, preservatives, antioxidants, plasticizers, paraffin oil, vegetable or animal fats and oils, epoxidized vegetable oils and / or animal fats, wax particles, gel particles, and the like.

[0054] The foams are prepared by forming a reaction mixture containing components a) through e), component f), if used, and any other optional formulation ingredients as needed, and curing the reaction mixture to produce the foam.

[0055] If desired, all of the formulation ingredients except the polyisocyanate can be blended into the blended polyol composition and subsequently combined with the aromatic polyisocyanate to form the reaction mixture which reacts to produce the foam. Alternatively, the various formulation ingredients can be combined all at once or in any other order, with it generally being preferred to add the aromatic polyisocyanate last or at the same time as the other formulation ingredients are combined. Blend ingredients b) through f) can be formed into various subcombinations which are then combined with the other formulation ingredients to produce the reaction mixture.

[0056] The reaction mixture is then foamed and cured. The process of the present invention does not require special processing conditions, and therefore the processing conditions and equipment described in the art for making flexible polyurethane foams are entirely appropriate. In general, the isocyanate compound spontaneously reacts with water and polyol b) in the presence of a urethane catalyst, even at room temperature (22°C). If necessary, heat can be applied to the reaction mixture to accelerate the curing reaction. This can be done by heating some or all of the ingredients before combining them, by applying heat to the reaction mixture, or by some combination of each. This heating can be at least partially due to the exothermic heat of reaction that is released as the reaction mixture cures.

[0057] Curing is continued until the reaction mixture has expanded and cured sufficiently to form a stable foam.

[0058] In some embodiments, the curing step is carried out in a closed mold. In such a process, the reactive mixture is either formed within the mold itself or formed outside the mold and then injected into the mold where it cures. Thus, its expansion as the reactive mixture cures is limited by the inner surfaces of the mold, as well as the dimensions and shape of the molded part.

[0059] In a preferred molding process, the mold is maintained at a temperature of 60° C. or less, preferably 50° C. or less, during the curing step. Lower mold temperatures favor the formation of an attached skin, i.e., a compact outer surface that is primarily non-cellular. Such attached skins often impart desirable tactile properties to the foam. These tactile properties are particularly beneficial when the foam is used in human cushioning applications such as pillows and bedding.

[0060] In the molding process, the amount of reaction mixture charged to the mold is such that a foam having a core density as described below is produced.

[0061] In other embodiments, the curing step is carried out in a free rise (or slabstock) process. In a free rise process, the reacting mixture is poured into an open vessel such that expansion in at least one direction (usually perpendicular) occurs against the atmosphere or a lightweight surface (such as a film) that offers little resistance to the expansion of the foam. In a free rise process, the reacting mixture expands essentially unrestrained in at least one direction, except by its own weight. A free rise process may be carried out by forming the reacting mixture and distributing it in a trough or on a conveyor, where the reacting mixture expands and cures.

[0062] The flexible polyurethane foams obtained by this process are characterized by a particular combination of core foam density, 90% compression set, resiliency, and recovery time.

[0063] The core foam density (measured according to ISO 845 after removal of the densified skin) is 20 kg / m 3 ~Up to 33kg / m 3 In some embodiments, the core foam density is at least 22 kg / m 3 , or at least 24 kg / m 3 In some embodiments, the core foam density is up to 32 kg / m 3 , up to 30kg / m 3 , up to 29kg / m 3 , up to 28kg / m 3 , up to 26kg / m 3 , or up to 25 kg / m 3 The ability to produce such low density foams that still have excellent compression set behavior, as well as good viscoelastic properties, is highly surprising and is a significant advantage of the present invention.

[0064] The foams of the present invention have a 90% compression set of up to 10% when measured according to ISO 1856 Method A. The 90% compression set is measured in that test by compressing the foam sample by only 90%, i.e., to 10% of its original thickness.

[0065] The foams of the present invention preferably have a resilience of less than 20%, less than 15%, or less than 10% as measured by ASTM D-3574.

[0066] The foams of the present invention have a recovery time of, for example, at least 0.5 seconds, at least 1 second, at least 1.5 seconds, or at least 2 seconds, and at most 20 seconds, at most 10 seconds, at most 8 seconds, or at most 5 seconds. Recovery time is measured by compressing the foam. A test specimen having a size of 4 inches by 4 inches by 2 inches (10.16 cm by 10.16 cm by 5.08 cm) and with all skin removed is compressed to 25% of its initial thickness and held under compression for 100 seconds. The compressive force is then released, and the time it takes for the foam to regain 90% of its original thickness is measured as the recovery time. A suitable device for performing recovery time measurements is the RESIMAT 150 viscoelastic foam testing device (Format Messtechnik GmbH, Germany).

[0067] The foams of the present invention may exhibit a 40% compressive load deflection of at least 0.3 when measured by ISO 3386-1 without pre-compression and without measurements on the first cycle.

[0068] Flexible polyurethane foam may meet one or more FR (flame retardant) standards, such as the British Standard flammability test (BS 5852-Ignition Source 5) which uses a collection of wood (called a crib) as an ignition source.

[0069] The foam of the present invention is useful in cushioning applications such as pillows, mattresses, backrests (for bed headboards, seats, etc.), automotive armrests, seat cushions for home and / or vehicle seats, packaging, protective cushioning, etc. It can be used as a sound and / or vibration (i.e., NVH) damping means or as a component thereof. For example, it is useful in acoustic applications for noise, vibration, and / or harshness reduction for earplugs, as well as other applications where previous slow recovery polyurethane foams are useful. It is useful in other applications where slow recovery after foam compression is desired. In general, the slow recovery foam of the present invention can be used in the same applications and in the same manner as conventionally made slow recovery foams.

[0070] The following examples are provided to illustrate the present invention, but are not intended to limit the scope of the invention. All parts and percentages are by weight unless otherwise indicated. All molecular weights are number averages by gel permeation chromatography.

[0071] Polyol b-1) is a nominally trifunctional random copolymer of about 72% ethylene oxide and about 28% propylene oxide with an equivalent weight of 1500. 80-90% of its hydroxyl groups are primary.

[0072] Polyol b-2) is a nominally difunctional poly(propylene oxide) of number average molecular weight 2030. Greater than 90% of its hydroxyl groups are secondary.

[0073] Polyol b-3a) is a nominally difunctional poly(propylene oxide) of number average molecular weight 1020. Greater than 90% of its hydroxyl groups are secondary.

[0074] Polyol b-3b) is a nominally difunctional poly(propylene oxide) of number average molecular weight 430. Greater than 90% of its hydroxyl groups are secondary.

[0075] Polyol W is an ethylene oxide / propylene oxide copolymer containing 75% oxyethylene units. Polyol W has a hydroxyl equivalent weight of 1675, with 45% of its hydroxyl groups being primary.

[0076] Polyol X is an ethylene oxide-capped poly(propylene oxide) made by propoxylating and then ethoxylating a mixture of sucrose and glycerin. The oxyethylene content of Polyol X is less than 30%. Polyol X has an average functionality of 4.7 and a hydrogen equivalent weight of about 1750. About 77% of its hydroxyl groups are primary.

[0077] Monol Z is a 500 molecular weight n-butanol initiated random copolymer of ethylene oxide and butylene oxide sold by The Dow Chemical Company as Synalox™ 50-15B.

[0078] Prepolymer A is made by reacting 9.5 parts of a nominally trifunctional random copolymer of ethylene oxide and propylene oxide (45% primary hydroxyl) of 1675 equivalent weight with 63.7 parts of a mixture of about 32.5% 2,4'-MDI, 1-2% 2,2'-MDI, and the remainder 4,4'-MDI, and 26.8 parts of polymeric MDI having an isocyanate content of 31% and an isocyanate functionality of 2.7. Prepolymer A has an isocyanate content of about 29.5%.

[0079] Prepolymer B is made in the same manner as prepolymer A, replacing the polyol with the same weight of polyol b-1). Prepolymer B has an isocyanate content of about 29.5%.

[0080] Surfactant A is a silicone surfactant having a hydroxyl equivalent weight of about 1145.

[0081] Surfactant B is a commercially available silicone surfactant.

[0082] Surfactant C is a commercially available silicone surfactant. The catalyst is a mixture of i) an N,N-bis(dimethylaminopropyl)amine catalyst product and ii) a (dimethylaminoethyl)ether catalyst.

[0083] All foams are made by compounding all starting materials except the polyisocyanate into a compounded polyol. The compounded polyol and polyisocyanate are processed through a Cannon A40 or A60 foam machine equipped with an FLP 14 or FLP 18 mixhead at a throughput of 250-300 g / sec. The component temperature is 25°C. The component pressure is 160 atm. The mold is a 32 liter pillow mold and is kept at 45°C throughout the cure process. Demold time is 5 minutes. The isocyanate index for each case is as shown below:

[0084] Examples 1, 2 and Comparative Sample A These foams are made from the formulation ingredients shown in Table 1. [Table 1]

[0085] The resulting foams are measured for core density, recovery time, 90% compression set, and 40% compression load deflection, with the results shown in Table 2. [Table 2]

[0086] Comparative Sample A shows the effect of using 4.2 parts water and an isocyanate index of 60 or greater. Recovery time and 90% compression set are good, but the foam density is higher than desired.

[0087] Examples 1 and 2 have a very low density (30 kg / m3 ), very low compression set, and recovery time of greater than 1 second. Little to no loss in load-bearing capacity (as indicated by CLD measurements) is observed relative to Comparative Sample A.

[0088] Examples 3 to 6 and Comparative Sample B These foams are made from the formulation ingredients shown in Table 3. The foam properties are as shown in Table 4. [Table 3] [Table 4]

[0089] Very low compression set of 24.4 kg / m while retaining the good viscoelastic properties of the foam. 3 Low foam density is obtained.

[0090] Examples 7 and 8 and Comparative Sample C These foams are made from the formulation ingredients shown in Table 5. The foam properties are as shown in Table 6. [Table 5] [Table 6]

[0091] Very low compression set is obtained in all cases at low isocyanate index and low density.

[0092] Comparison samples D and E These foams are made from the formulation ingredients shown in Table 7. The foam properties are as shown in Table 8. [Table 7] [Table 8]

[0093] The presence of ethylene oxide capped poly(propylene oxide) (Polyol X) is seen to cause these foams to have very high compression set, even at high foam densities, at all Isocyanate Indexes evaluated.

[0094] Examples 9 and 10 These foams are made from the formulation ingredients shown in Table 9. The foam properties are as shown in Table 10. [Table 9] [Table 10]

[0095] These examples demonstrate that excellent results are obtained even when the foam formulation contains a certain amount of component f) material (i.e., Polyol W). In all cases, excellent recovery times and good load bearing properties are obtained. When Polyol W is present, compression set is affected at a very low isocyanate index of 60, but as the index increases to 70, very low compression set is obtained.

[0096] Examples 11 and 12 These foams are made from the formulation ingredients shown in Table 11. The foam properties are as shown in Table 12. [Table 11] [Table 12]

[0097] These examples show the highly unusual and unexpected properties obtained at very high (6 parts) water loadings. The foam density is 21.9 kg / m 3 Although low, good viscoelastic properties are obtained while the compression set remains below 10%. The present application also relates to the following aspects: (1) a) 20-33 kg / m 3 a) a 90% compression set of 10% or less when measured in accordance with ISO 1856 Method A; and c) a recovery time of 0.5 to 20 seconds. (2) The foam is a reaction mixture comprising: a) an aromatic polyisocyanate having an isocyanate content of 20 to 33% by weight in an amount that produces an isocyanate index of 50 to 90; b) a polyether, b-1) at least one polyether having a hydroxyl equivalent weight of 500 to 2000, a nominal hydroxyl functionality of 1 to 4, and an oxyethylene content of 40 to 95% by weight, wherein at least 80% of the hydroxyl groups are primary; b-2) at least one homopolymer or copolymer of propylene oxide, said homopolymer or copolymer having a hydroxyl equivalent weight of 600 to 2000 and a nominal hydroxyl functionality of 1 to 6, wherein at least 80% of the hydroxyl groups are secondary; b-3) optionally at least one homopolymer or copolymer of propylene oxide, said homopolymer or copolymer having a hydroxyl equivalent weight of 80 to 599 and a nominal hydroxyl functionality of 1 to 6, wherein at least 80% of the hydroxyl groups are secondary; i) a ratio of hydroxyl equivalents provided by component b-1) to said hydroxyl equivalents provided by components b-2) and b-3) is from 1 to 2.5; ii) component b-1) constitutes 65 to 85 weight percent of the combined weight of components b) through f); iii) component b-2) constitutes 1 to 30 weight percent of the combined weight of components b) through f); iii) component b-3) constitutes 0 to 20 weight percent of the combined weight of components b) through f); and iv) the combined weight of components b-1), b-2), and b-3) constitutes at least 70% of the combined weight of components b) through f); c) water in an amount of 4.5 to 6.5 weight percent, based on the combined weight of components b) through f); d) at least one catalyst for the reaction of isocyanate groups with alcohols and / or water; e) at least one silicone foam stabilizing surfactant; f) 0 to 5 weight percent, based on the combined weight of components b) through f), of an isocyanate-reactive compound different from components b), c), d), and e); provided that said reaction mixture comprises an ethylene oxide-capped poly(propylene oxide) polyol having an oxyethylene content of up to 30%, based on the weight of the ethylene oxide-capped poly(propylene oxide) polyol, in said component The flexible polyurethane foam according to (1), which is a reaction product of a reaction mixture containing 5 weight percent or less of b) to f), based on the combined weight of the reaction mixture. (3) The flexible polyurethane foam according to (2) above, wherein the polyether b-3) constitutes 1 to 15 weight percent of the combined weight of the components b) to f). (4) The flexible polyurethane foam according to (2) or (3) above, wherein water constitutes at least 5 weight percent of the combined weight of components b) to f). (5) A flexible polyurethane foam according to any one of (2) to (4) above, wherein water constitutes 5.5 to 6 weight percent of the combined weight of components b) to f). (6) The flexible polyurethane foam according to any one of (2) to (5), wherein the reaction mixture contains 5 weight percent or less of a compound having one or more primary and / or secondary amine groups, based on the combined weight of components b) to f). (7) The flexible polyurethane foam according to any one of (2) to (6), wherein the reaction mixture contains 15 weight percent or less of a polyether polyol having an oxyethylene content of 50 percent or more and less than 50 percent of the hydroxyl groups are primary, based on the combined weight of components b) to f). (8) The flexible polyurethane foam according to any one of (2) to (7), wherein the reaction mixture contains 1 weight percent or less of a polyol having a hydroxyl equivalent weight of 79 or less, based on the combined weight of components b) to f). (9) The flexible polyurethane foam according to any one of (2) to (8), wherein the reaction mixture contains 5 weight percent or less of any isocyanate-reactive material different from components b) to e), based on the combined weight of components b) to f). (10) The flexible polyurethane foam according to any one of (2) to (9), wherein component a) comprises an MDI product containing up to 50 weight percent of the 2,4'-isomer and up to 5 weight percent of the 2,2'-isomer, the remainder being the 4,4'-isomer, and / or a mixture thereof with PMDI. (11) The flexible polyurethane foam according to any one of (2) to (9), wherein component a) comprises a urethane group-containing prepolymer prepared by reacting a polyol with an MDI product containing up to 50 weight percent of the 2,4'-isomer and up to 5 weight percent of the 2,2'-isomer, the remainder being the 4,4'-isomer, and / or a mixture thereof with PMDI. (12) The flexible polyurethane foam according to any one of (2) to (10), wherein the isocyanate index is 60 to 90. (13) 20~30kg / m 3 2. The flexible polyurethane foam of claim 1, having a core foam density of (14) 20~28kg / m 3 2. The flexible polyurethane foam of claim 1, having a core foam density of (15) The foam is a reaction mixture comprising: a) an aromatic polyisocyanate having an isocyanate content of 20 to 33% by weight in an amount that produces an isocyanate index of 50 to 90; b) a polyether comprising: i) at least one polyether having a hydroxyl equivalent weight of 500 to 2000, a nominal hydroxyl functionality of 1 to 4, and an oxyethylene content of 40 to 95% by weight, wherein at least 60% of the hydroxyl groups are primary; and ii) at least one homopolymer or copolymer of propylene oxide having a hydroxyl equivalent weight of 80 to 2000, a nominal hydroxyl functionality of 1 to 6, and wherein at least 80% of the hydroxyl groups are secondary, wherein polyether ii) is present in an amount such that polyether i) is at least partially incompatible with polyether i); c) water in an amount of 4.5 to 6.5 weight percent, based on the combined weight of components b) through f); d) at least one catalyst for the reaction of isocyanate groups with alcohols and / or water; e) at least one silicone foam stabilizing surfactant; f) 0 to 25 weight percent, based on the combined weight of components b) through f), of an isocyanate-reactive compound different from components b), c), d), and e); 1. The flexible polyurethane of claim 1, which is the reaction product of a reaction mixture, with the proviso that the reaction mixture contains no more than 5 weight percent, based on the combined weight of components b) through f), of an ethylene oxide-capped poly(propylene oxide) polyol having an oxyethylene content of up to 30%, based on the weight of the ethylene oxide-capped poly(propylene oxide) polyol.

Claims

1. a) 20-33kg / m ３ and a core foam density of b) a 90% compression set of 10% or less as measured according to ISO 1856 Method A; c) a recovery time of 0.5 to 20 seconds; The present invention is characterized in that The recovery time is measured by compressing the foam: a test specimen having dimensions of 4 inches by 4 inches by 2 inches (10.16 cm by 10.16 cm by 5.08 cm) with all skin removed is compressed to 25% of its original thickness and held under compression for 100 seconds, then the compression force is released and the time it takes for the foam to regain 90% of its original thickness is measured as the recovery time. A flexible polyurethane foam, The foam is a reaction mixture comprising: a) an aromatic polyisocyanate having an isocyanate content of 20 to 33% by weight in an amount to provide an isocyanate index of 50 to 90; b) a polyether, b-1) at least one polyether having a hydroxyl equivalent weight of 500 to 2000, a nominal hydroxyl functionality of 1 to 4, and an oxyethylene content of 40 to 95% by weight, wherein at least 80% of the hydroxyl groups are primary; b-2) at least one homopolymer or copolymer of propylene oxide, said homopolymer or copolymer having a hydroxyl equivalent weight of 600 to 2000 and a nominal hydroxyl functionality of 1 to 6, wherein at least 80% of the hydroxyl groups are secondary; and b-3) optionally at least one homopolymer or copolymer of propylene oxide, said homopolymer or copolymer having a hydroxyl equivalent weight of 80 to 599 and a nominal hydroxyl functionality of 1 to 6, wherein at least 80% of the hydroxyl groups are secondary; i) the ratio of hydroxyl equivalents provided by component b-1) to said hydroxyl equivalents provided by components b-2) and b-3) is from 1 to 2.5; ii) component b-1) constitutes 65 to 85 weight percent of the combined weight of components b) through f); iii) component b-2) comprises 1 to 30 weight percent of the combined weight of components b) through f); iii) component b-3) comprises 0 to 20 weight percent of the combined weight of components b) through f); iv) a polyether, wherein the combined weight of components b-1), b-2), and b-3) constitutes at least 70% of the combined weight of components b)-f); c) water in an amount of 4.5 to 6.5 weight percent, based on the combined weight of components b) through f); and d) at least one catalyst for the reaction of isocyanate groups with alcohols and / or water; e) at least one silicone foam stabilizing surfactant; and f) 0 to 5 weight percent, based on the combined weight of components b) through f), of an isocyanate-reactive compound different from components b), c), d), and e); with the proviso that said reaction mixture contains no more than 5 weight percent, based on the combined weight of components b) through f), of said ethylene oxide-capped poly(propylene oxide) polyol having a maximum oxyethylene content of 30 percent, based on the weight of the ethylene oxide-capped poly(propylene oxide) polyol.

2. 2. The flexible polyurethane foam of claim 1, wherein the polyether b-3) comprises 1 to 15 weight percent of the combined weight of components b) through f).

3. 3. The flexible polyurethane foam of claim 1 or 2, wherein water comprises at least 5 weight percent of the combined weight of components b) through f).

4. 4. The flexible polyurethane foam according to any one of claims 1 to 3, wherein water comprises from 5.5 to 6 weight percent of the combined weight of components b) through f).

5. 5. The flexible polyurethane foam according to any one of claims 1 to 4, wherein the reaction mixture contains up to 5 weight percent of compounds having one or more primary and / or secondary amine groups, based on the combined weight of components b) through f).

6. 6. The flexible polyurethane foam according to any one of claims 1 to 5, wherein the reaction mixture contains up to 15 weight percent, based on the combined weight of components b) through f), of a polyether polyol having an oxyethylene content of 50 percent or more and less than 50 percent of the hydroxyl groups are primary.

7. 7. The flexible polyurethane foam according to any one of claims 1 to 6, wherein the reaction mixture contains no more than 1 weight percent of a polyol having a hydroxyl equivalent weight of 79 or less, based on the combined weight of components b) through f).

8. 8. The flexible polyurethane foam according to any one of claims 1 to 7, wherein the reaction mixture contains up to 5 weight percent of any isocyanate-reactive material different from components b) through e), based on the combined weight of components b) through f).

9. 9. Flexible polyurethane foam according to any one of claims 1 to 8, wherein component a) comprises an MDI product containing up to 50 weight percent of the 2,4'-isomer and up to 5 weight percent of the 2,2'-isomer, the remainder being the 4,4'-isomer, and / or mixtures thereof with PMDI.

10. 9. Flexible polyurethane foam according to any one of claims 1 to 8, wherein component a) comprises a urethane group-containing prepolymer made by reaction of a polyol with an MDI product containing up to 50 weight percent of the 2,4'-isomer and up to 5 weight percent of the 2,2'-isomer, the balance being the 4,4'-isomer, and / or mixtures thereof with PMDI.

11. 10. The flexible polyurethane foam according to any one of claims 1 to 9, wherein the isocyanate index is from 60 to 90.

12. 20-30 kg / m ３ 12. The flexible polyurethane foam of claim 1 having a core foam density of

13. 20-28kg / m ３ 13. The flexible polyurethane foam of claim 1 having a core foam density of

14. The foam is a reaction mixture comprising: a) an aromatic polyisocyanate having an isocyanate content of 20 to 33% by weight in an amount to provide an isocyanate index of 50 to 90; b) a polyether comprising: i) at least one polyether having a hydroxyl equivalent weight of 500 to 2000, a nominal hydroxyl functionality of 1 to 4, and an oxyethylene content of 40 to 95 weight percent, wherein at least 60% of the hydroxyl groups are primary; and ii) at least one homopolymer or copolymer of propylene oxide having a hydroxyl equivalent weight of 80 to 2000, a nominal hydroxyl functionality of 1 to 6, and wherein at least 80% of the hydroxyl groups are secondary, wherein polyether ii) is present in an amount such that polyether i) is at least partially incompatible with polyether i); c) water in an amount of 4.5 to 6.5 weight percent, based on the combined weight of components b) through f); and d) at least one catalyst for the reaction of isocyanate groups with alcohols and / or water; e) at least one silicone foam stabilizing surfactant; and f) 0 to 25 weight percent, based on the combined weight of components b) through f); and an isocyanate-reactive compound different from components b), c), d), and e), 2. The flexible polyurethane foam of claim 1, which is the reaction product of a reaction mixture containing no more than 5 weight percent, based on the combined weight of components b) through f), of an ethylene oxide-capped poly(propylene oxide) polyol having a maximum oxyethylene content of 30 percent, based on the weight of the ethylene oxide-capped poly(propylene oxide) polyol.

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