The present invention relates to a high resilience flexible polyurethane foam using methylene diphenyl diisocyanate (MDI), including a high resilience flexible slabstock polyurethane foam made using MDI, its formulation, and the process for the making thereof.
Flexible slabstock polyurethane foam for furniture and bedding has traditionally been produced using toluene diisocyanate (TDI) as a basic raw material.
In the United States, methylene diphenyl diisocyanate (MDI) has predominantly been used in polyurethane foam applications other than flexible slabstock polyurethane foam applications such as furniture and bedding. MDI has been used in, for example, molded polyurethane foam such as automotive applications; rigid polyurethane foam such as insulation, construction and packaging; microcellular froth polyurethane foam such as footwear and gasketing; and viscoelastic (“memory”) polyurethane foam chemistries. Due in part to the inherently different chemical reaction kinetics as well as the differences in foam stabilization requirements for processing using MDI as opposed to TDI, MDI does not readily fit the criteria for use in continuous flexible slabstock foam formulations. In Europe, MDI has been utilized to produce high density, namely greater than 2.5 pounds per cubic foot (PCF) high resilience slabstock foams. In general terms, the complexity of formulation, speed of reactivity and mechanical processing limitations have prevented the commercialization of low density, soft MDI-based foams since the advent of the flexible polyurethane foam industry in the 1950s.
In the wake of Hurricane Katrina in the United States, many of the necessary flexible polyurethane foam raw materials became temporarily but seriously unavailable due to unplanned chemical plant shutdowns and transportation problems. More recently, a similar situation with TDI specifically, due to global demand exceeding current supply, resulted in allocated supply and significant price increases.
The cost of polyurethane foam, whether TDI or MDI based, is driven almost solely by chemical cost. Lower density foams cost less per unit than higher density foams, making them more attractive to end users, given acceptable performance. In the United States market, where foam is considered commodity-like, due to similarity of product and aggressive pricing, high-density European-style MDI foams have never widely gained acceptance.
Thus, there is a need to reduce dependence on potentially scarce raw materials to produce a MDI-based high resilience flexible polyurethane foam, more particularly one that is acceptable to the particular needs of the furniture, bedding and other industries. Accordingly, there is a need for an alternative high resilience flexible slabstock polyurethane foam.
The present invention is directed to a high resilience flexible polyurethane foam, made using methylene diphenyl diisocyanate (MDI), having a bulk foam density of 2.5 pounds per cubic foot or lower and having a foam hardness or Indentation Force Deflection (IFD) in a range of 10 to 40 lb/50 in2.
In an aspect of the present invention, the high resilience flexible polyurethane foam having a bulk foam density of 2.5 pounds per cubic foot or lower and having a foam hardness or Indentation Force Deflection (IFD) in a range of 10 to 40 lb/50 in2 is measured in accordance with test method ASTM 3574—Test B1.
In another aspect of the present invention, the high resilience flexible polyurethane foam passes the requirements of State of California Technical Bulletin 117 without the use of a flame retardant additive.
It is also a feature of the foam of the present invention that the foam is made without or substantially free of toluene diisocyanate (TDI).
The present invention is also directed to a method of making a high resilience flexible polyurethane foam. The method comprises reacting methylene diphenyl diisocyanate (MDI) with a high resilience polyol in the presence of a blowing agent.
In an another aspect of the method of the present invention, the foam is made without or substantially free of toluene diisocyanate (TDI).
In still yet another aspect of the method of the present invention, the method of making a high resilience flexible polyurethane foam comprises reacting a high resilience polyol with methylene diphenyl diisocyanate (MDI) in the presence of a blowing agent in a one-shot continuous process.
Further areas of applicability of the present invention will become apparent from the detailed description provided hereinafter. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
The present invention will become more fully understood from the detailed description and the accompanying drawings, not necessarily to scale, wherein:
The following detailed description of the embodiment(s) is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses.
The polyurethane foam of the present invention is of the high resilience flexible polyurethane foam type. High resilience foam typically has a cell structure that is less uniform, thus having a more randomly distributed cell size often described as a bimodal distribution, than conventional polyurethane foam products. The difference in cell structure provides additional support, comfort, and resilience. High resilience foams typically have a high support factor and a greater resilience than conventional polyurethane foams. Furthermore, the high resilience flexible polyurethane foam of the present invention is made using methylene diphenyl diisocyanate, also commonly referred to as diphenyl methane diisocyanate, (MDI).
Preferably, MDI is either pure MDI or in the form of a mixture including, but not limited to, any amount or ratio of isomers 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 2,2′-diphenylmethane diisocyanate and optionally blended with any polymeric, modified, or prepolymer MDI species. The isomers may be in any ratio or in any blend of these isomer polyisocyanates with a blend average isocyanate functionality of ≧2. Examples of commercially available MDI products pertaining to the description above include, but are not limited to: No. 280 Isocyanate, No. 278 Isocyanate—BASF Corp.; MONDUR® 1488—Bayer Material Science LLC; PAPI® 20, PAPI® 27, PAPI® 94, PAPI® 95, PAPI® 580N, PAPI® 901—DOW Chemical Co.; SUPRASEC® 5005, SUPRASEC® 6521, SUPRASEC® 6522, SUPRASEC® 9597, SUPRASEC® 7050—Huntsman Petrochemical Corporation.
Thus, the high resilience flexible polyurethane foam made using MDI of the present invention serves as an alternative to the high resilience polyurethane foam made using toluene diisocyanate (TDI). TDI has become a relatively expensive foam ingredient of which the supply remains unstable. Thus, the high resilience flexible polyurethane foam of the present invention provides the potential to introduce a new flexible polyurethane foam with features unique to the application of MDI foam chemistry.
A high resilience flexible polyurethane foam to be useful for furniture and bedding is required in its industry to have a bulk foam density in the range of 2.5 pounds per cubic foot (PCF) or lower, more preferably ≦1.8 PCF, and a foam hardness or Indentation Force Deflection (IFD) in the range of 10 to 40 lb/50 in2, as measured in accordance with ASTM 3574.
As indicated previously, MDI, however, does not lend itself to achieve products in this density range and until the present invention has prevented products in the desired IFD range. However, in the method of the present invention, MDI is used to make a high resilience foam wherein both the desired foam density and the desired foam hardness are achieved independently of one another. Furthermore, the high resilience flexible polyurethane foam of the present invention is achieved without or substantially free of TDI. The high resilience flexible polyurethane foam of the present invention is achieved with or without the use of load-bearing (support-enhancing) polyols including, but not limited to, copolymer polyol, polymer polyol, graft polyol, PIPA polyol, crosslinker, and polyharnstoff dispersion (PHD) polyol, and a combination thereof, which have been historically required to impart high resilience flexible foam physical properties and performance.
The present invention relates to a process for preparing a high resilience flexible slabstock polyurethane foam. In particular, the present invention relates to a process for preparing a high resilience flexible slabstock polyurethane foam using MDI to achieve a foam with a density in a range of 2.5 pounds per cubic foot (PCF) or lower, more preferably ≦1.8 PCF, as measured in accordance with ASTM 3574.
Referring now to the Figures,
As shown in
With reference to the high resilience polyether polyol, the polyol is a polyalkyleneoxide polyether glycol having a molecular weight in a range from about 4,500 to 6,000 g/mol with the weight percent content of ethylene oxide groups being from about 12 to 20 weight percent of the total alkylene oxide group content (therefore, the remaining 80 to 88 weight percent of the total alkylene oxide groups being propylene oxide groups) while having a hydroxyl functionality ranging from about 2 to 8, preferably from about 2 to 3. Examples of commercialized high resilience slabstock foam polyols include, but are not limited to, PLURACOL® P-945, P-2090, P-2100, P-2115, P-2120, P-2130—BASF Corp., VORANOL® 3512A and VORANOL® 4701—Dow Chemical Co.
Referring to the conventional polyether polyol, the polyol has a molecular weight in a range from about 3,000 to 3,900 g/mol with the weight percent content of ethylene oxide groups being from about zero to 15 percent of the total alkylene oxide group content (therefore, the remaining 85 to 100 weight percent of the total alkylene oxide groups being propylene oxide groups) while having a hydroxyl functionality ranging from about 2 to 8, preferably from about 2 to 3. Examples of commercially available conventional slabstock polyether polyols include, but are not limited to, PLURACOL® P-1385, P-1388, P-4150 and P-4156—BASF Corp., ARCOL® F-3022, ACCLAIM® F-3040, ACCLAIM® 3300N—Bayer Corp., VORANOL® 3136 and VORANOL® 3137—Dow Chemical Co. The present invention uses a high resilience polyether polyol with or without the use of a conventional polyether polyol, preferably without the use of a conventional polyether polyol.
Referring to the graft polyol, the polyol has a molecular weight in a range from about 1,500 to 8,500 g/mol and a solids level ranging up to about 75 percent by weight of the graft polyol as realized through chain growth copolymer polyol chemistry such as wherein the free-radical polymerization of styrene and acrylonitrile copolymerized with a polyol itself to produce a grafted polyol of the SAN type, or through step-growth polyol polymerization chemistry such as wherein polyurea particles resulting from the reaction of diamines with diisocyanate in the presence of polyol thereby being dispersed in polyol, or through PIPA polyol chemistry such as wherein an alkanolamine has been reacted with a diisocyanate in the presence of a polyol to produce a dispersion of polyurethane particles in polyol. Examples of commercialized graft polyols, polymer polyols or copolymer polyols include, but are not limited to, PLURACOL® P-637, P-1365, P-1441, P-1442, P-1443, P-1543, P-4600, P-4800, P-4815, P-4830, P-4850—BASF Corp., ARCOL® E-919, ARCOL® HS-100 and ULTRACELL® U-3000—Bayer Corp., VORANOL® 3943A—Dow Chemical Co. The present invention uses a high resilience polyether polyol with or without the use of a graft polyol, preferably without a graft polyol.
In accordance with the present invention, these polyols may have either randomly distributed ethylene oxide and propylene oxide groups or may be of the blocked type of polymer polyol wherein the ethylene oxide and propylene oxide is sequentially incorporated into the polyol structure. These polyols may also be either primary or secondary hydroxyl group terminated.
In the process of the present invention, the polyol or polyols optionally pass through a static or dynamic mixer 40 before reaching the additives manifold 50 and, if after having passed through the mixer 40, proceeds to the additives manifold 50. Alternatively, the polyol(s) 10 may bypass the static or dynamic mixer 40 and is fed to the additives manifold 50. Prior to the junction A at which the polyol(s) 10 either bypasses the mixer 40 or enters the mixer 40, a silicone surfactant 20 may be optionally added. Another optional addition to the polyol 10 prior to arriving at the junction is the optional addition of a nucleating gas 30 such as nitrogen or air in feed stream 30a.
At the additives manifold 50, several components are continuously fed and mixed. One or more silicone surfactants 20 are added. The additives manifold 50 is the standard point of addition for the silicone surfactant(s) 20. Amine catalyst(s) 22 is also added at this point in the process. An auxiliary blowing agent (ABA) 24 is added. Water 26 is optionally added at the additives manifold 50, although water is preferably added later at the dynamic mixer 80. Other chemical components that are optionally added at the additives manifold 50 include, but are not limited to, an organometallic catalyst 27, alkanolamine(s) 28, and a flame retardant additive(s) 29. Examples of suitable polyurethane foam flame retardants include, but are not limited to, halogen-containing phosphate esters such as brominated or chlorinated phosphate esters, chlorinated paraffins, melamine powders or phosphorous flame retardant compounds. Examples of such commercially available flame retardants for use in the present invention include, but are not limited to: AB-117HF—Albermarle Corp.; DE-60E-Special and FIREMASTER® 500, 550, and 600—Chemtura Corp.; CP-2—Gulbrandsen Chemicals; FR-2, FR-38, HF-4—ICL, Limited; DISFLAMOLL® DPK—Lanxess Corp. Although a flame retardant may be optionally added, Applicant has surprisingly found that high resilience flexible foam of the present invention does not require the use of a flame retardant chemical additive to satisfy the requirements of the State of California's Technical Bulletin 117 for “Requirements, Test Procedure and Apparatus for Testing the Flame Retardance of Resilient Filling Materials Used in Upholstered Furniture,” which is the standard in the furniture industry.
All components fed in and added at the additives manifold 50 are next fed to the dynamic mixer 80. Additional nucleating gas 30 (such as, but not limited to, nitrogen or air) is optionally fed in feed stream 30b to the feed stream of isocyanate 70 prior to entering the main dynamic mixer 80. At the main dynamic mixer 80 is also the preferred point of addition for water 26. It is at this point in the process, wherein the foaming reaction begins to take place as the isocyanate begins to simultaneously react with both the polyol(s) and the water in this foam formulation.
There are at least two dispensing methods suitable for use in the present invention for dispensing the mixed stream from the main dynamic mixer 80, namely trough-pouring 90a or, stationary or traversing direct wet laydown 90b.
In accordance with the method of the present invention, high resilience polyether polyol(s) are reacted with isocyanate in the presence of water in the range from about 0.1 to 8.0 based on parts per hundred polyol (pphp), preferably about 2.5 to 5.0 pphp. The reaction of the polyol(s) with the isocyanate proceeds to form polyurethane, considered to compose the primary soft-segment portion of the final skeletal framework of the foam. Simultaneously, the water reacts to form polyurea considered to compose the hard-segment portion of the foam's final skeletal framework while also liberating carbon dioxide as a bi-product gas. It is this evolution of the carbon dioxide gas via the reaction of water and isocyanate which thereby “blows” the foam hence expanding it into a cellular structure. Therefore, water serves also in this chemistry as the primary blowing agent. In addition to water being the primary blowing agent, an auxiliary blowing agent is added in the range of from 0 to 20 pphp, more preferably from about 2 to 10 pphp. Suitable auxiliary blowing agents include, but are not limited to, acetone, pentane, methylene chloride, methyl-formate, water, and CO2. A preferred auxiliary blowing agent is acetone. Such auxiliary blowing agent is commercially available from Sasol Chemicals North America LLC.
In accordance with the present invention, a silicone surfactant is added in the range from about 0.01 to 5.0 pphp, preferably from about 0.1 to 1.0 pphp. These surfactants include, but are not limited to, unmodified polydimethylsiloxane polymers, modified polydimethylsiloxane copolymers such as of the polyalkyleneoxide polydimethylsiloxane copolymer type, and a combination thereof. Examples of suitable surfactants for use in the present invention include, but are not limited to, high resilience surfactants, high resilience molded surfactants and high resilience slabstock foam surfactants. Examples of commercially available products include, but are not limited to: DABCO® DC-5043—Air Products & Chemicals Inc; TEGOSTAB® B-4113, B-4690, B-8636, B-8681, B-8715LF, B-8716LF, —Evonik Industries; NIAX® U-2000, L-3001, L-3002, L-3184—Momentive Performance Materials.
The balance of these components, along with a use of a catalyst(s), produces a foam product made using MDI that is suitable for furniture and bedding applications. Examples of suitable catalysts for use in the present invention, include but are not limited to, tertiary amine catalysts and organometallic catalysts. Preferred catalysts are amine catalysts and tin catalysts. Examples of commercially available amine catalysts include, but are not limited to: bis-Dimethylaminoethylether amine blends known as DABCO BL-13—Air Products & Chemicals Inc., JEFFCAT® ZF-24—Huntsman Petrochemical Corp. and Niax A-133—Momentive Performance Materials; dibutylaminoethanol (DBAE); dimethylethanolamine (DMEA); 1,2-Dimethylimidazole amine blends known as DM-70—Tosoh USA Inc., DABCO® 2039—Air Products & Chemicals Inc.; tributylamine (TBA); triethylenediamine (TEDA) blend known as TEGOAMIN® 33—Evonik Industries, DABCO® 33LV—Air Products & Chemicals Inc., Niax® A-33—Momentive Performance Materials. Examples of commercially available polyurethane foam tin catalysts include, but are not limited to: stannous octoate blends known as Kosmos 29—Evonik Industries, DABCO® T-9—Air Products & Chemicals Inc.; dibutyltin dilaurate blends known as DABCO® T-12—Air Products & Chemicals Inc., Kosmos 19—Evonik Industries.
In accordance with the present invention, alkanolamines may optionally be added in a range of from about 0 to 5 pphp, preferably from about 0 to 3 pphp in order to catalytically balance the stability of the foam while rising or expanding. Suitable alkanolamines include, but are not limited to, diethanolamine (DEOA). An example of a commercially available DEOA is DABCO® DEOA-LF, an 85% diethanolamine solution in 15% water, Air Products & Chemicals Inc.
A measure of the stoichiometry between the reactive ingredients of the foam hardness is referred to as the formulation index. The amount of isocyanate used relative to the theoretical equivalent amount is known as the Isocyanate Index:
As known to those skilled in the art, the Isocyanate Index is one of several methods, but a key method, for affecting the foam's hardness or Indentation Force Deflection (IFD) for the desired application.
The MDI index for the foam of the present invention is maintained in the range of 70 to 130, preferably 90 to 110. The process comprises reacting, at an isocyanate index of 70 to 130, the following components: MDI, polyether polyol(s) as set forth in Table 1, a catalyst(s), a surfactant(s) and water.
Unlike known processes for making high resilience polyurethane foams, the high resilience flexible slabstock polyurethane foam of the present invention made using MDI is made with or without a graft polyol. Representative molecular weight ranges, relative compositional weight percent ranges for the ratio of ethylene oxide to propylene oxide, and solids content (as it pertains to graft polyols) for the various types of polyol are set forth in Table 1.
Other additives and chemical components which are not necessary to the present invention but may optionally be used include, but are not limited to, flame retardant chemical additives, cross-linking agents, chain-extending agents, melamine, fillers, pigments, dyes, antimicrobials (biocides), antioxidants and the like.
An advantage of the foam of the present invention to the furniture and bedding industry is that it should bridge the technological gap that has prevented the widespread production of MDI slabstock foam in the United States and throughout the world by enabling lower density high resilience flexible foams across a wide range of hardness.
Several examples were conducted to make laboratory “bench” foams. Each sample's components (wherein the proportions and exact amounts for which being based on the total amount of polyol being used, 100 pphp, and as set forth in Table 2) were combined into a container as follows: a high resilience polyether polyol, diethanolamine, a polyurethane foam catalyst, flame retardant, silicone surfactant and acetone. These components were pre-mixed via a mixing-prop powered by a drill press at 2000 RPM's for 30 seconds. After this first 30 seconds of pre-mix, water was added to the pre-mix container with mixing continuing during the addition. Thereafter, five seconds after the water addition, the MDI was added to the mixing container (at which point the reactions between the MDI and both water and polyol simultaneously began) and mixing was continued for an additional 10 seconds after the MDI addition. Immediately following, the drill press/mixing was ceased and the mixture immediately poured into a square cardboard container wherein foam reaction kinetic data (via a thermocouple inserted in through the base of the box) and foam rise profile data (wherein the rate and extent of the foam rise was measured via a level detecting transducer affixed directly above the rising foam) were collected. Per each bench foam example, from the time at which the mixing cycle was completed a period of five minutes was realized during which time this data was collected, the foam reached a maximum height, carbon dioxide gas bubbles were observed to de-gas (“blow-off”) at the top surface of the foam, and a maximum internal foam reaction temperature was observed and recorded. Thereafter, the bench foam was removed and placed into a curing oven for ten minutes at 150 degrees Fahrenheit. After having initially cured in the oven, the foam sample was removed from the oven and allowed to further cure at ambient room temperatures for twenty-four hours. At this point, the foam was cut and measured in accordance with industry standard ASTM D3574 for the properties listed as in Table 3.
Several examples were also carried out on full scale production equipment in order to demonstrate utility on this level. Each sample's components and exact metered amounts as a ratio of the total polyol being used, 100 pphp are illustrated in Table 4. All the components were independently and simultaneously metered through a mixing head via the one-shot method and continuously poured as illustrated in
It will therefore be readily understood by those persons skilled in the art that the present invention is susceptible of broad utility and application. Many embodiments and adaptations of the present invention other than those herein described, as well as many variations, modifications and equivalent arrangements, will be apparent from or reasonably suggested by the present invention and the foregoing description thereof, without departing from the substance or scope of the present invention. Accordingly, while the present invention has been described herein in detail in relation to its preferred embodiment, it is to be understood that this disclosure is only illustrative and exemplary of the present invention and is made merely for purposes of providing a full and enabling disclosure of the invention. The foregoing disclosure is not intended or to be construed to limit the present invention or otherwise to exclude any such other embodiments, adaptations, variations, modifications and equivalent arrangements.
This application claims priority from U.S. patent application Ser. No. 61/203,168 filed on Dec. 19, 2008. The disclosure of which is incorporated herein by reference.
Number | Name | Date | Kind |
---|---|---|---|
3741917 | Morehouse | Jun 1973 | A |
4167612 | Tucker et al. | Sep 1979 | A |
4205136 | Ohashi et al. | May 1980 | A |
4239856 | Rowton | Dec 1980 | A |
4365025 | Murch et al. | Dec 1982 | A |
4525490 | Smith | Jun 1985 | A |
4605684 | Pcolinsky, Jr. | Aug 1986 | A |
4722942 | Nichols et al. | Feb 1988 | A |
4833176 | Wolf et al. | May 1989 | A |
4845133 | Priester, Jr. et al. | Jul 1989 | A |
4910231 | Pham et al. | Mar 1990 | A |
4950694 | Hager | Aug 1990 | A |
4994502 | Markovs et al. | Feb 1991 | A |
5010117 | Herrington et al. | Apr 1991 | A |
5043360 | Pham et al. | Aug 1991 | A |
5104907 | Yoshimura et al. | Apr 1992 | A |
5145882 | Samaritter et al. | Sep 1992 | A |
5171759 | Hager | Dec 1992 | A |
5175195 | Tani et al. | Dec 1992 | A |
5182314 | Tani et al. | Jan 1993 | A |
5194453 | Jourquin et al. | Mar 1993 | A |
5236964 | Savoca et al. | Aug 1993 | A |
5270348 | Muller et al. | Dec 1993 | A |
5332764 | Tairaka et al. | Jul 1994 | A |
5334689 | Muller et al. | Aug 1994 | A |
5367050 | Tairaka et al. | Nov 1994 | A |
5369138 | Gansen | Nov 1994 | A |
5436277 | Narayan et al. | Jul 1995 | A |
5441993 | Maretti | Aug 1995 | A |
5459170 | Bleys et al. | Oct 1995 | A |
5482980 | Pcolinsky | Jan 1996 | A |
5491177 | De Witte | Feb 1996 | A |
5500452 | Baker et al. | Mar 1996 | A |
5506278 | Walmsley | Apr 1996 | A |
5521226 | Bleys | May 1996 | A |
5530034 | Narayan et al. | Jun 1996 | A |
5536757 | Walmsley | Jul 1996 | A |
5538779 | Mispreuve et al. | Jul 1996 | A |
5539011 | Hilker et al. | Jul 1996 | A |
5565498 | Chaffanjon et al. | Oct 1996 | A |
5594039 | Gerber et al. | Jan 1997 | A |
5594097 | Chaffanjon et al. | Jan 1997 | A |
5607982 | Heyman et al. | Mar 1997 | A |
5618854 | Skorpenske et al. | Apr 1997 | A |
5621016 | Murty et al. | Apr 1997 | A |
5686187 | Turnbach | Nov 1997 | A |
5686526 | Turnbach | Nov 1997 | A |
5698609 | Lockwood et al. | Dec 1997 | A |
5700390 | Turnbach | Dec 1997 | A |
5700869 | Turnbach | Dec 1997 | A |
5716439 | Turnbach | Feb 1998 | A |
5877227 | Murty | Mar 1999 | A |
6020391 | Leenslag | Feb 2000 | A |
6063825 | Isobe et al. | May 2000 | A |
6080800 | Frey et al. | Jun 2000 | A |
6096237 | Narayan et al. | Aug 2000 | A |
6096238 | Lutter et al. | Aug 2000 | A |
6133481 | Singh et al. | Oct 2000 | A |
6136878 | Free et al. | Oct 2000 | A |
6158815 | Sugie et al. | Dec 2000 | A |
6180686 | Kurth | Jan 2001 | B1 |
6201035 | Tuinman et al. | Mar 2001 | B1 |
6239186 | Mansfield et al. | May 2001 | B1 |
6245825 | Bleys | Jun 2001 | B1 |
6316514 | Falke et al. | Nov 2001 | B1 |
6352658 | Chang et al. | Mar 2002 | B1 |
6372812 | Niederoest et al. | Apr 2002 | B1 |
6376698 | Bleys | Apr 2002 | B1 |
6417241 | Huygens et al. | Jul 2002 | B1 |
6432543 | Harrison et al. | Aug 2002 | B2 |
6457777 | Kazuno et al. | Oct 2002 | B1 |
6465569 | Kurth | Oct 2002 | B1 |
6521674 | Haley et al. | Feb 2003 | B1 |
6579912 | Parfondry et al. | Jun 2003 | B2 |
6583192 | Falke et al. | Jun 2003 | B2 |
6586486 | Falke et al. | Jul 2003 | B2 |
6590008 | Parfondry et al. | Jul 2003 | B1 |
6593387 | Parfondry et al. | Jul 2003 | B2 |
6617369 | Parfondry et al. | Sep 2003 | B2 |
6649107 | Harrison et al. | Nov 2003 | B2 |
6660783 | Arlt et al. | Dec 2003 | B2 |
6734220 | Niederoest et al. | May 2004 | B2 |
6747068 | Kelly | Jun 2004 | B2 |
6759448 | Toyota et al. | Jul 2004 | B2 |
6765034 | Nishida et al. | Jul 2004 | B2 |
6774153 | Parfondry et al. | Aug 2004 | B2 |
6784217 | Parfondry et al. | Aug 2004 | B2 |
6784218 | Apichatachutapan et al. | Aug 2004 | B1 |
6797736 | Smiecinski et al. | Sep 2004 | B1 |
6852403 | Harrison et al. | Feb 2005 | B2 |
6855742 | Hager et al. | Feb 2005 | B2 |
6858655 | Hofmann et al. | Feb 2005 | B1 |
6864296 | Kurth | Mar 2005 | B2 |
6867239 | Kurth | Mar 2005 | B2 |
6881763 | Kurth | Apr 2005 | B2 |
6884825 | Daunch et al. | Apr 2005 | B2 |
6919384 | Yu | Jul 2005 | B2 |
7169824 | Bleys et al. | Jan 2007 | B2 |
7238730 | Apichatachutapan et al. | Jul 2007 | B2 |
7268170 | Anderson et al. | Sep 2007 | B2 |
7456229 | Hager et al. | Nov 2008 | B2 |
8058343 | Liu et al. | Nov 2011 | B2 |
8097675 | Finder et al. | Jan 2012 | B2 |
20020058774 | Kurth et al. | May 2002 | A1 |
20030060528 | Parfondry et al. | Mar 2003 | A1 |
20030087977 | Parfondry et al. | May 2003 | A1 |
20030105178 | Kurth | Jun 2003 | A1 |
20030143910 | Mashburn et al. | Jul 2003 | A1 |
20030158280 | Daunch et al. | Aug 2003 | A1 |
20030212155 | Parfondry et al. | Nov 2003 | A1 |
20040029988 | Kurth | Feb 2004 | A1 |
20040034163 | Kurth | Feb 2004 | A1 |
20040102596 | Kurth | May 2004 | A1 |
20040147627 | Hager et al. | Jul 2004 | A1 |
20040152796 | Muller et al. | Aug 2004 | A1 |
20040162385 | Krebs | Aug 2004 | A1 |
20040186192 | Smiecinski et al. | Sep 2004 | A1 |
20040254256 | Lockwood et al. | Dec 2004 | A1 |
20040259968 | Krebs | Dec 2004 | A1 |
20050032973 | Krebs et al. | Feb 2005 | A1 |
20050070620 | Herrington et al. | Mar 2005 | A1 |
20050101681 | Kaushiva et al. | May 2005 | A1 |
20050176840 | Chan et al. | Aug 2005 | A1 |
20050182228 | Kurth | Aug 2005 | A1 |
20050222291 | Pirkl et al. | Oct 2005 | A1 |
20060060486 | Castleberry | Mar 2006 | A1 |
20060073321 | Kaushiva et al. | Apr 2006 | A1 |
20060084710 | Meyer-Ahrens et al. | Apr 2006 | A1 |
20060128928 | Wershofen et al. | Jun 2006 | A1 |
20060142529 | Tiede et al. | Jun 2006 | A1 |
20070155941 | Nefzger et al. | Jul 2007 | A1 |
20070282028 | Harre et al. | Dec 2007 | A1 |
20070293594 | Heisler et al. | Dec 2007 | A1 |
20100160470 | Smiecinski et al. | Jun 2010 | A1 |
20100160473 | Neff et al. | Jun 2010 | A1 |
20100249260 | Casati et al. | Sep 2010 | A1 |
Number | Date | Country |
---|---|---|
0 257 441 | Mar 1988 | EP |
0547765 | Jun 1993 | EP |
0 608 626 | Aug 1994 | EP |
0 765 355 | Apr 1997 | EP |
1164153 | Dec 2001 | EP |
1174453 | Jan 2002 | EP |
1178061 | Feb 2002 | EP |
1234843 | Aug 2002 | EP |
1 471 086 | Oct 2004 | EP |
1 529 792 | May 2005 | EP |
1305352 | Aug 2005 | EP |
2 109 803 | Jun 1983 | GB |
2308373 | Jun 1997 | GB |
2 329 642 | Mar 1999 | GB |
59-166537 | Sep 1984 | JP |
60-181115 | Sep 1985 | JP |
1-104611 | Apr 1989 | JP |
3-45618 | Feb 1991 | JP |
7-3062 | Jan 1995 | JP |
11-171963 | Jun 1999 | JP |
2003-342343 | Dec 2003 | JP |
2006-45267 | Feb 2006 | JP |
9424183 | Oct 1994 | WO |
9534591 | Dec 1995 | WO |
9606874 | Mar 1996 | WO |
WO 0008083 | Feb 2000 | WO |
0015684 | Mar 2000 | WO |
WO 0055232 | Sep 2000 | WO |
0073368 | Dec 2000 | WO |
WO 0073362 | Dec 2000 | WO |
WO 0073363 | Dec 2000 | WO |
WO 0107521 | Feb 2001 | WO |
WO 0132735 | May 2001 | WO |
WO 0132736 | May 2001 | WO |
WO 0160884 | Aug 2001 | WO |
WO 0210245 | Feb 2002 | WO |
WO 0210246 | Feb 2002 | WO |
WO 02059175 | Aug 2002 | WO |
2004011518 | Feb 2004 | WO |
WO 2004014976 | Feb 2004 | WO |
WO 2004014980 | Feb 2004 | WO |
2004071281 | Aug 2004 | WO |
2004096883 | Nov 2004 | WO |
WO 2005003205 | Jan 2005 | WO |
2006116456 | Nov 2006 | WO |
2007042407 | Apr 2007 | WO |
WO 2011106377 | Sep 2011 | WO |
Entry |
---|
ASTM Designation: D 3574-05 “Standard Test Methods for Flexible Cellular Materials—Slab, Bonded, and Molded Urethane Foams,” Copyright ASTM International, 100 Barr Harbor Drive, West Conshohocken, PA 19428-2959; Aug. 2005, pp. 1-25. |
Article, “A New Era for MDI:Flexible Polyurethane Slabstock Foam,” Knaub et al. Journal of Cellular Plastics, vol. 33—Mar. 1997, pp. 159-184. |
Technical Bulletin 117, “Requirements, Test Procedure and Apparatus for Testing the Flame Retardance of Resilient Filling Materials Used in Upholstered Furniture,” State of California Department of Consumer Affairs, Bureau of Home Furnishings and Thermal Insulation, 3485 Orange Grove Avenue, North Highlands, CA 95660, Mar. 2000, pp. 1-8. |
U.S. Appl. No. 12/701,356, filed 2010, Dounis. |
European Patent Office International Search Report for WO2011/106377, (2011). |
Publication: Smiecinski et al., BASF Corp., Michigan, “Visco-Elastic Polyurethane Foam: The Impact of Isocyanate Upon Foam Morphology”, Sep. 26, 2006, p. 405-416. |
Number | Date | Country | |
---|---|---|---|
61203168 | Dec 2008 | US |