USOO8501838B2
(12) United States Patent (10) Patent No.: US 8,501,838 B2 Jackson et al. (45) Date of Patent: Aug. 6, 2013
(54) COMPOSITE WOOD BOARD 1,886,353 A 1 1/1932 Novotny et al. 2,198,874 A 4, 1940 Holmes (75) Inventors: RE so St. E. Tony 2,392,1052,215,825 A 9,1/1946 1940 WallaceSussman indow, St. Helens (GB); George 2,442,989 A 6/1948 Sussman Baybutt, St. Helens (GB) 2,518,956 A 8/1950 Sussman 2,875,073. A 2/1959 Gogek (73) Assignee: Knauf Insulation SPRL (BE) 3,232,821 A 2f1966 Moore et al. 3,297,419 A * 1/1967 Eyre, Jr...... 44,534 (*)c Notice:- r Subject to any distic the t 3,513,0013,791,807 A 2,5/1970 1974 WorthingtonEtzel et al. patent is extended or adjusted under 35 3,802,897 A 4/1974 Voigt et al. U.S.C. 154(b) by 235 days. 3,809,664 A 5, 1974 Fanta 3,826,767 A 7, 1974 Hoover et al. (21) Appl. No.: 12/524,522 3,856,606 A 12/1974 Fan et al. 3,867,119 A 2/1975 Kasuga et al. (22) PCT Filed:1-1. Jan. 25, 2007 4,014,7263,911,048 A 10/19753/1977 VargiuFargo et al. 4,028,290 A 6, 1977 Reid (86). PCT No.: PCT/EP2007/050746 4,048,127 A 9/1977 Gibbons et al. S371 (c)(1), (Continued) (2), (4) Date: Nov. 12, 2009 FOREIGN PATENT DOCUMENTS (87) PCT Pub. No.: WO2008/089847 AU 2003237324 A1 12/2003 CA 1090026. A 11, 1980 PCT Pub. Date: Jul. 31, 2008 (Continued) (65) Prior Publication Data OTHER PUBLICATIONS US 201O/OO87571 A1 Apr. 8, 2010 International Search Report and Written Opinion for PCT/EP2007/ (51) Int. Cl. 050747, completed Jun. 27, 2007. C08L 97/02 (2006.01) (Continued) (52) U.S. Cl. USPC ...... 524/13:524/14: 524/18: 524/33 Primary Examiner — Robert D. Harlan (58) Field of Classification Search (74) Attorney, Agent, or Firm — Barnes & Thornburg LLP USPC ...... 524/13, 14, 18, 33 See application file for complete search history. (57) ABSTRACT (56) References Cited In a stack of composite wood boards, the wood boards com U.S. PATENT DOCUMENTS prise wood particles and an organic binder. 1,801,052 A 4/1931 Meigs 1,801,053 A 4/1931 Meigs 20 Claims, 5 Drawing Sheets
*Omino compound Aldose Sugar N-substituted glycosylamine '4' Amadori-rearrangement Amadori rearrangement product (ARP) 1-Gmino-4-deoxy-2-ketose
Fission products Schiff's base of (aceto, diocely, Pyruvaldehyde, etc.) hydroxymethylfurfural -2 R Or furfural Dehydroreductones C0, - Gmino to Omino acid Srecker degradation compound Aldehydes HMF or furfural
s Adols and + amino Gmino N-free polymers compound
compound Aldimines and Kelines Melanoidins (brown nitrogenous polymers) US 8,501,838 B2 Page 2
(56) References Cited 5,977,232 A 11/1999 Arkens et al. 5,981,719 A 11/1999 WoiSZwillo et al. U.S. PATENT DOCUMENTS 5,983,5865.990,216 A 1 1/1999 CaietBerdan, al. II et al. 4,054,713. A 10/1977 Sakaguchi et al. 6,072,086 A 6/2000 James et al. 4,085,076 A 4, 1978 Gibbons et al. 6,077,883. A 6/2000 Taylor et al. 4,097.427 A 6, 1978 Aitken et al. 6,090,925 A 7/2000 WoiSZwillo et al. 4,107,379 A 8, 1978 Stofko 6,114,033 A 9, 2000 Ikemoto et al. 4,148,765 A 4, 1979 Nelson 6,114,464 A 9, 2000 Recket al. 4,183,997 A 1, 1980 Stofko 6,136,916 A 10/2000 Arkens et al. 4,184,986 A 1/1980 Krasnobajew etal. 6,143,243 A 1 1/2000 Gershun et al. 4,186,053 A 1/1980 Krasnobajew etal. 6,171444 B1 1/2001 Nigam 4,201,857 A 5/1980 Krasnobajew etal. 6,171,654 B1 1/2001 Salsman et al. 4,233,432 A 1 1/1980 Curtis, Jr. 6,210,472 B1 4/2001 Kwan et al. 4,246,367 A 1/1981 Curtis, Jr. 6,221,973 B1 4/2001 Arkens et al. 4.278,573 A 7, 1981 Tessler 6,274,661 B1 8/2001 Chen et al. 4.296,173 A 10/1981 Fahey 6,299,936 B1 10/2001 Recket al. 4,301.310 A 1 1/1981 Wagner 6,310,227 B1 10/2001 Sarama et al. 4,330,443 A 5, 1982 Rankin 6,313,102 B1 1 1/2001 Colaco et al. 4,357,194. A 1 1/1982 Stofko 6,319,683 B1 1 1/2001 James et al. 4,396,430 A 8, 1983 Matalon 6,331,350 B1 12/2001 Taylor et al. 4400,496 A 8, 1983 Butler 6,348,530 B1 2/2002 Recket al. 4,464,523 A 8/1984 Neigel 6,379,739 B1 4/2002 Formanek et al. 4,506,684 A 3, 1985 Keritsis 6,395,856 B1 5/2002 Petty et al. 4,668,716 A 5/1987 Pepe et al. 6,440.204 B1 8/2002 Rogols 4,754,056 A 6, 1988 Ansel et al. 6,468.442 B2 10/2002 Bytnar 4,845,162 A 7, 1989 Schmitt et al. 6,468,730 B2 10/2002 Fujiwara et al. 4,906,237 A 3, 1990 Johansson et al. 6,482,875 B2 11/2002 Lorenz et al. 4,912, 147 A 3, 1990 Pfoehler et al. 6,495,656 B1 12/2002 Haile et al. 4,923,980 A 5/1990 Blomberg 6,525,009 B2 2/2003 Sachdev et al. 5,037,930 A 8, 1991 Shih 6,638,884 B2 10/2003 Quicket al. 5,041,595 A 8/1991 Yang 6,699.945 B1 3/2004 Chen et al. 5,095,054 A 3/1992 Lay 6,730,730 B1 5/2004 Hansen et al. 5,106,615 A 4, 1992 Dikstein 6,753,361 B2 6/2004 Kroner et al. 5,114,004 A 5, 1992 Isono et al. 6,818,694 B2 11/2004 Hindi et al. 5,124.369 A 6, 1992 Vandichel et al. 6,852.247 B2 2/2005 Bytnar 5,143,582 A 9, 1992 Arkens et al. 6,858,074 B2 2, 2005 Anderson et al. 5,151.465 A 9, 1992 Le-Khac 6,861,495 B2 3/2005 Barsotti et al. 5,308,896 A 5, 1994 Hansen et al. 6,864.044 B2 3/2005 Ishikawa et al. 5,318,990 A 6, 1994 Strauss 6,878,800 B2 4/2005 Husemoen et al. 5,336,753 A 8/1994 Jung et al. 6.955,844 B2 10/2005 Tagge et al. 5,336,755 A 8/1994 Pape 7,029,717 B1 4/2006 Ojima et al. 5,340,868 A 8, 1994 Strauss et al. 7,067,579 B2 6/2006 Taylor et al. 5,387,665 A 2f1995 Misawa et al. 7,083,831 B1 8, 2006 Koch et al. 5,393,849 A 2f1995 Srinivasan et al. 7,090,745 B2 8, 2006 Beckman 5.434,233 A 7/1995 Kiely et al. 7,141,626 B2 11/2006 Rodrigues et al. 5,480,973 A 1/1996 Goodladet al. 7, 195,792 B2 3/2007 Boston et al. 5,498,662 A 3, 1996 Tanaka et al. 7,201,778 B2 4/2007 Smith et al. 5,536,766 A 7/1996 Seyffer et al. 7,458,235 B2 12/2008 Beaufils et al. 5,547,541 A 8, 1996 Hansen et al. 7,514,027 B2 4/2009 Horres et al. 5,571,618 A 1 1/1996 Hansen et al. 7,655,711 B2 2/2010 Swift et al. 5,578,678 A 1 1/1996 Hartmann 7,772,347 B2 8/2010 Swift et al. 5,582,682 A 12/1996 Ferretti 7,807,771 B2 10/2010 Swift et al. 5,583,193 A 12/1996 Aravindakshan et al. 7,888.445 B2 2/2011 Swift et al. 5,589,536 A 12/1996 Golino et al. 7,947,765 B2 5/2011 Swift et al. 5,609,727 A 3, 1997 Hansen et al. 8,114,210 B2 2/2012 Hampson et al. 5,614,570 A 3, 1997 Hansen et al. 8, 182,648 B2 5/2012 Swift et al. 5,620,940 A 4/1997 Birbara et al. 2002/0032253 A1 3/2002 Lorenz et al. 5,621,026 A 4/1997 Tanaka et al. 2002/0091185 A1 7/2002 Taylor 5,633,298 A 5, 1997 Arfaei et al. 2002/0130439 A1 9, 2002 Kroner et al. 5,643,978 A 7, 1997 Darwin et al. 2002fO161108 A1 10, 2002 Schultz et al. 5,645,756 A 7, 1997 Dubin et al. 2003,0005857 A1 1/2003 Minami et al. 5,661.213 A 8, 1997 Arkens et al. 2003.0153690 A1 8/2003 Husemoen et al. 5,690,715 A 1 1/1997 Schiwek 2004/00 19168 A1 1/2004 Soerens et al. 5,691,060 A 11/1997 Levy 2004.0024170 A1 2/2004 Husemoen et al. 5,693.411. A 12/1997 Hansen et al. 2004/0033747 A1 2/2004 Miller et al. 5,756,580 A 5, 1998 Natori et al. 2004/0038,017 A1 2/2004 Tutin et al. 5,788,243 A 8, 1998 Harshaw et al...... 273/.363 2004/OO77055 A1 4, 2004 Fosdick et al. 5,855.987 A 1/1999 Margel et al. 2004/O12216.6 A1 6/2004 O'Brien-Bernini et al. 5,885,337 A 3, 1999 Nohr et al. 2004/0152824 A1 8/2004 Dobrowolski 5,895,804 A 4/1999 Lee et al. 2004/0249066 A1 12/2004 Heinzman et al. 5,919,831 A 7/1999 Philipp 2004/0254285 Al 12/2004 Rodrigues et al. 5,925,722 A 7, 1999 Exner 2005/0020224 A1 1/2005 Locatelli et al. 5,929, 184 A 7/1999 Holmes-Farley et al. 2005/005977O A1 3/2005 Srinivasan 5,932,344 A 8, 1999 Ikemoto et al. 2005, 0171085 A1 8, 2005 Pinto et al. 5,932,665 A 8, 1999 DePorter et al. 2005/0196421 A1 9, 2005 Hunter et al. 5,932,689 A 8, 1999 Arkens et al. 2005/0215153 A1 9, 2005 Cossement et al. 5,942,123 A 8, 1999 McArdle 2005/0275133 A1 12/2005 Cabel1 et al. 5,977.224. A 1 1/1999 Cheung et al. 2006/0005580 A1 1/2006 Espiard et al. US 8,501,838 B2 Page 3
2006, OO44302 A1 3, 2006 Chen Kwasi Agyei-Aye et al., The role of the anion in the reaction of 2006/009.987O A1 5, 2006 Garcia et al. reducing Sugars with ammonium salts, Carbohydrate Research 337 2006/011 1480 A1 5, 2006 Hansen et al. (2002) 2273-2277. Accepted for publication Jul. 19, 2002, 5 pages. 2006, O135433 A1 6/2006 Murray et al. Johan Bjorkstenet al., Polyester Resin-Glass Fiber Laminates, Indus 2006/0252855 A1 11/2006 Pisanova trial and Engineering Chemistry, vol. 46, No. 8, 1632-1634. Accepted 2006/0281622 A1 12/2006 Maricourt et al. for publication Jun. 5, 1954, 3 pages. 2007/OOO6390 A1 1/2007 Clamen et al. Non-final Office Action issued Sep. 7, 2012 by the USPTO from 2007/OOO9582 A1 1/2007 Madsen et al. re-examination of U.S. Patent No. 7,888,445. 2007/0027281 A1 2/2007 Michl et al. Response filed Nov. 7, 2012 by Patent Owner in response to Non-final 2007. O184740 A1 8, 2007 Keller et al. Office Action issued Sep. 7, 2012 by the USPTO from re-examination 2008. O108741 A1 5/2008 Van Herwijnen of U.S. Patent No. 7,888,445. 2009/030 1972 A1 12/2009 Hines et al. Non-final Office Action issued Sep. 7, 2012 by the USPTO from 2009/0324915 A1 12/2009 Swift et al. re-examination of U.S. Patent No. 7,807,771. 2010/032O113 A1 12, 2010 Swift Response filed Nov. 7, 2012 by Patent Owner in response to Non-final 2011/O190425 A1 8, 2011 Swift Office Action issued Sep. 7, 2012 by the USPTO from re-examination of U.S. Patent No. 7,807,771. FOREIGN PATENT DOCUMENTS Non-final Office Action issued Sep. 19, 2012 by the USPTO from CA 2O37214 A1 9, 1991 re-examination of U.S. Patent No. 7,854,980. DE 43O8089 A1 9, 1994 Response filed Nov. 19, 2012 by Patent Owner in response to Non EP 0044 614 A2 1, 1982 final Office Action issued Sep. 19, 2012 by the USPTO from re EP 0911361 A1 1, 1993 examination of U.S. Patent No. 7,854,980. EP O 5478.19 6, 1993 Non-final Office Action issued Sep. 25, 2012 by the USPTO from EP O 583 086 2, 1994 re-examination of U.S. Patent No. 7,772,347. EP O 672 720 9, 1995 Response filed Nov. 26, 2012 by Patent Owner in response to Non EP 0 714754 6, 1996 final Office Action issued Sep. 25, 2012 by the USPTO from re EP O 826 710 4f1998 examination of U.S. Patent No. 7,772,347. EP O 873 976 10, 1998 95000672 Third Party Reexam Request = Third Party Request for EP 1382642 A1 12, 1998 Inter Partes Reexamination of U.S. Patent No. 7,888,445 filed Jun. EP O 911361 4f1999 30, 2012. EP O 990 729 4/2000 95000672 Exhibit A Reexam Request = Exhibit A submitted with EP 1038 433 9, 2000 Third Party Request for Inter Partes Reexamination of U.S. Patent EP 1 193288 4/2002 No. 7,888.445. EP 1382 642 1, 2004 95000672 Exhibit B Reexam Request = Exhibit B submitted with EP 1486547 A2 6, 2004 Third Party Request for Inter Partes Reexamination of U.S. Patent EP 1486 547 12, 2004 No. 7,888.445. FR 2 614 388 10, 1988 95000672 Third Party Reply = Third Party Comments filed Dec. 7, FR 2614388 A1 10, 1988 2012 After Patent Owner Response to Non-final Office Action issued GB 809645 3, 1959 by the USPTO from re-examination of U.S. Patent No. 7,888,445. GB 1391172 4, 1975 95000673 Third Party Reexam Request = Third Party Request for GB 1512066 5, 1978 Inter Partes Reexamination of U.S. Patent No. 7,807,771 filed Jun. GB 2047258 A 11, 1980 30, 2012. GB 2078805 1, 1982 95000673 Exhibit A Reexam Request = Exhibit A submitted with JP 57-101100 6, 1982 Third Party Request for Inter Partes Reexamination of U.S. Patent JP 2002-293576 9, 2002 No. 7,807,771. JP 2004-60058 2, 2004 95000673 Exhibit B Reexam Request = Exhibit B submitted with SU 37.4400 3, 1973 Third Party Request for Inter Partes Reexamination of U.S. Patent WO 9936368 A1 7, 1999 No. 7,807,771. WO 99/47765 9, 1999 95000673 Third Party Reply = Third Party Comments filed Dec. 7, WO OOf 62628 10, 2000 WO O3,O71879 9, 2003 2012 After Patent Owner Response to Non-final Office Action issued WO O3106561 A1 12/2003 by the USPTO from re-examination of U.S. Patent No. 7,807,771. WO 2004/076734 9, 2004 95000674. Third Party Reexam Request = Third Party Request for WO 2006/044302 4/2006 Inter Partes Reexamination of U.S. Patent No. 7,854,980 filed Jun. WO 2006O443O2 A1 4/2006 30, 2012. WO WO2007/O14236 2, 2007 95000674 Exhibit A Reexam Request = Exhibit A submitted with WO 2011 138459 A1 11 2011 Third Party Request for Inter Partes Reexamination of U.S. Patent No. 7,854,980. OTHER PUBLICATIONS 95000674 Exhibit B Reexam Request = Exhibit B submitted with Third Party Request for Inter Partes Reexamination of U.S. Patent English Translation of Japanese Abstract for 5801 1193, Jan. 21. No. 7,854,980. 1983, 1 page. 95000674. Third Party Reply = Third Party Comments filed Dec. 19, 2012 After Patent Owner Response to Non-final Office Action English Translation of Japanese Abstract for 03173680, Jul. 26, 1991, issued by the USPTO from re-examination of U.S. Patent No. 1 page. 7,854,980. English Translation of Japanese Abstract for 07034023, Feb. 3, 1995, 95000675. Third Party Reexam Request = Third Party Request for 1 page. Inter Partes Reexamination of U.S. Patent No. 7,772,347 filed Jun. English Translation of Russian Abstract for 374400, Mar. 20, 1973, 1 30, 2012. page. 95000675. Exhibit a Reexam Request = Exhibit a submitted with Ames, J. M.. “The Maillard Browning Reaction—an Update'. Third Party Request for Inter Partes Reexamination of U.S. Patent Chemistry & Industry, No. 17, 1988, 4 pages. No. 7,772,347. "Gamma-aminopropyltrimethoxysilane'. Hawley's Condensed 95000675. Exhibit B Reexam Request = Exhibit B submitted with Chemical Dictionary, 14th Edition, John Wiley & Sons, Inc., 2002, 1 Third Party Request for Inter Partes Reexamination of U.S. Patent page. No. 7,772,347. Dow Corning, A Guide to Silane Solutions, Copyright 2005 bro 95000675. Third Party Reply = Third Party Comments filed Dec. chure, 30 pages, Form No. 26-132801. 19, 2012 After Patent Owner Response to Non-final Office Action Guy Clamen et al. Acrylic Thermosets: A Safe Alternative to Form issued by the USPTO from re-examination of U.S. Patent No. aldehyde Resins, Nonwovens World Apr.-May 2004, 7 pages. 7,772,347. Knauf Insulation, Amber Blanket Insulation brochure, undated, 4 pageS. * cited by examiner U.S. Patent Aug. 6, 2013 Sheet 1 of 5 US 8,501,838 B2
Fig 1 (52)
Centre line
O.5 BS1 resin
0.4
0.3
0.2
0.1
0.0 4. 5 6 7 8 9 10 11 PB-1 PB-2 PB-3-9 Pressing times, min U.S. Patent Aug. 6, 2013 Sheet 2 of 5 US 8,501,838 B2
BS-SOK resin
s 6 7 8 9 10 11 PB-12 PB-13 PB-14 Pressing times, min
Sample U.S. Patent Aug. 6, 2013 Sheet 3 of 5 US 8,501,838 B2
120
100
80 4060
2O
Sample
0.32
0.28
0.24
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8 9 10 11 12 13 14 15 16 OSB-1, OSB-2 OSB-3 OSB-4 Pressing times U.S. Patent Aug 6 , 2013 Sheet 4 of 5 US 8,501,838 B2
|NBNOdW00ENIWW U.S. Patent Aug. 6, 2013 Sheet 5 of 5 US 8,501,838 B2
tamino compound Aldose Sugar ON-substituted glycosylamine +HO Amadori-rearrangement Amadori rearrangement product (ARP) 1-amino-1-deoxy-2-ketose 2,0>pH7 Fission products Schiff's base of (ocetol, diocely, pyruvaldehyde, etc.) hydroxymethylfurfural -2H +2H (HMF) or furfural Dehydroreductones +H.0 -C0, + Omino - Omino +comino acid Strecker degradation compound compound Aldehydes HMF or furfural Aldols and + ami -- (minoO N-free polymers CompoundOO COmpound Aldimines Ond Ketimes Melanoidins (brown nitrogenous polymers) US 8,501,838 B2 1. 2 COMPOSITE WOOD BOARD mentally friendly resins that are competitive in price, perfor mance and adaptable to existing composite manufacturing CROSS-REFERENCE TO RELATED processes. APPLICATIONS SUMMARY This application is a U.S. national counterpart application of international application serial no. PCT/EP2007/050746 According to one aspect, the present invention provide a filed Jan. 25, 2007. composite wood board as defined in claim 1. Other aspects are defined in other independent claims. Preferred and/or FIELD OF THE INVENTION 10 alternative features are defined in the dependent claims. This invention relates to composite wood boards, for DETAILED DESCRIPTION example particle boards, orientated Strand boards and wood fibre boards, and particularly to composite wood board com 15 The composite wood board is preferably an industrially prising a bioresin and/or having a low formaldehyde or form manufactured composite wood board, as opposed to a labo aldehyde free binder. ratory test manufactured wood board. The composite wood board may have dimensions of at least 30 cmx30 cm; it may BACKGROUND have dimensions of at least 50 cmx80 cm, possibly at least 1 mx2 m. Bioresin is a term coined to describe a resin or resin for The composite wood board may have edges which are mulation derived from a biological source. Thus, many tradi trimmed and/or cut and/or machined. tional resins such as protein-based soybean, collagen or The composite wood board may be provided as a package casein, or carbohydrate-derivatives from cellulose or starch, comprises a plurality or wood boards arranged and/or bound natural rubber based adhesives and natural phenolic adhe 25 together, for example to facilitate transport; it may comprise sives such as tannin or lignin may all be classed as bioresins. an enveloping film, for example of a plastics material. The They are renewable polymers and, with low environmental package may comprise a pallet; it may be adapted by handling impact, represent an alternative to existing petroleum-driven by mechanical lifting equipment and/or a forklift truck. systems. The composite board may have a nominal thickness of at Interest in bio-resin systems stems largely from increasing 30 least 11 mm, at least 12 mm or at least 15 mm. regulation and public concern for a pollution-free environ The curing time of the composite woodboard is preferably ment, and the need for sustainable alternatives to products less than 25 minutes. based upon a finite petrochemical resource. Commercial ther moset resin production and use is subject to Such regulation The binder may: largely due to the monomer components that form the basis of 35 be based on a reducing Sugar, and/or the formulation. Overwhelmingly, these resins are based on be based on reductosis; and/or melamine, phenol, urea, formaldehyde, Styrene or isocyanate be based on an aldehyde containing SugarS/and/or starting materials. include at least one reaction product of a carbohydrate Emissions of formaldehyde, phenol and isocyanate are 40 reactant and an amine reactant; and/or generally regulated; they are governed in England and Wales include at least one reaction product of a reducing Sugar under the Pollution Prevention and Control Regulations and an amine reactant; and/or (2000), SI 19, for installations involved in the manufacture of include at least one reaction product of a carbohydrate particleboard (PB), oriented strandboard (OSB), medium reactant and a polycarboxylic acid ammonium salt reac density fibreboard (MDF) and wood fibreboard. Emissions to 45 tant; and/or air are limited to 5 mg/m. In particular, the guidance notes include at least one reaction product from a Maillard reac that operators should use resins which minimise emissions tion. of formaldehyde wherever possible. The choice of resins used Non-limiting examples of laboratory scale tests relating to should be continually reviewed to ensure minimum emissions the invention are described below with reference to the occur. Problems may exist concerning both high formalde 50 accompanying drawings of which: hyde levels in the workplace and with the slow release of formaldehyde from the panel products themselves, particu FIG. 1 shows the cutting pattern for boards in Example 2 larly at the beginning of the product’s lifetime. FIG.2 shows the effects of pressing times on IB for particle Bioresin products may offer an alternative, renewable boards with BS1 resin in Example 2 Source of thermosetting resins that will begin to address the 55 FIG. 3 shows the effects on pressing times on IB for par depletion of finite resources and have better emissions pro ticle boards with BS1-SOK resin in Example 2 files, particularly when formulated without formaldehyde. FIG. 4 shows thickness swelling after 24 hours at 20°C. in Though formaldehyde-free materials such as siisocyanate relation to Example 2 and tannin resins have become available, about 85% of MDF FIG. 5 shows water absorption swelling after 24 hours at produced today uses formaldehyde resin, corresponding to a 60 European market of approximately 2 million tonnes per 20°C. in relation to Example 2 annum. In those resins, whilst a reduction in formaldehyde FIG. 6 shows effects of pressing times on IB for orientated content has been achieved in recent years, it has been at the strand board with BS1 resin in relation to Example 2 cost of longer processing times, and decreases in internal FIG. 7 shows a number of illustrative reactants for produc bond and bending strengths and an increase in Swelling and 65 ing melanoidins; water absorption of panel products made therefrom. There is, FIG. 8 illustrates a Maillard reaction schematic when react thus, a clear place in the market now for new more environ ing a reducing Sugar with an amino compound. US 8,501,838 B2 3 4 EXAMPLE 1 a Several methods were used to produce wood fiber boards/ sheets bonded with this triammonium citrate-dextrose (1:6) Preparation of Ammonium Polycarboxylate-Sugar binder. A representative method, which method produced Binders Used to Construct Wood Fiber Board strong, uniform samples, is as follows: Wood in the form of Compositions assorted pine wood shavings and sawdust was purchased from a local farm supply store. Wood fiber board samples Aqueous triammonium citrate-dextrose (1:6) binders were were made with the as received wood and also material prepared by the following general procedure: Powdered dex segregated into the shavings and sawdust components. Wood trose monohydrate (91.5 g) and powdered anhydrous citric was first dried in an oven at approximately 200°F. over night, acid (152.5 g) were combined in a 1-gallon reaction vessel to 10 which drying resulted in moisture removal of 14-15% for the which 880 g of distilled water was added. To this mixture wood shavings and about 11% for the sawdust. Thereafter, were added 265 g of 19% aqueous ammonia with agitation, dried wood was placed in an 8 inch highx12 inch widex 10.5 and agitation was continued for several minutes to achieve inch deep plastic container (approximate dimensions). Tri complete dissolution of solids. To the resulting solution were ammonium citrate-dextrose (1:6) binder was prepared (36% in binder solids) as described above, and then 160 g of binder added 3.3 g of SILOUEST A-1 101 silane to produce a pH 15 ~8-9 solution (using pH paper), which solution contained was sprayed via an hydraulic nozzle onto a 400-g sample of approximately 50% dissolved dextrose monohydrate and dis wood in the plastic container while the container was inclined Solved ammonium citrate Solids (as a percentage of total 30-40 degrees from the vertical and rotated slowly (approxi weight of solution); a 2-g sample of this solution, upon ther mately 5-15 rpm). During this treatment, the wood was gently mal curing at 400°F. for 30 minutes, would yield 30% solids tumbled while becoming uniformly coated. (the weight loss being attributed to dehydration during ther Samples of resinated wood were placed in a collapsible frame and compressed in between heated platens under the moset binder formation). Where a silane other than following conditions: resinated wood shavings, 300 psi; SILOUEST A-1 101 was included in the triammonium cit resinated sawdust, 600 psi. For each resinated sample, the rate-dextrose (1:6) binder, substitutions were made with cure conditions were 350° F for 25 to 30 minutes. The result SILOUEST A-187 Silane, HYDROSIL 2627 Silane, or 25 Z-6020 Silane. When additives were included in the triam ing sample boards were approximately 10 inches longx10 inches wide, and about 0.4 inches thick before trimming, monium citrate-dextrose (1:6) binder to produce binder vari well-bonded internally, Smooth Surfaced and made a clean cut ants, the standard solution was distributed among bottles in when trimmed on the band saw. Trimmed sample density and 300-galiquots to which individual additives were then Sup the size of each trimmed sample board produced were as plied. 30 The FT-IR spectrum of a dried (uncured) triammonium follows: sample board from wood shavings, density ~54pcf. citrate-dextrose (1:6) binder, which spectrum was obtained as size -8.3 inches longx9 inches widex0.36 inches thick; a microscopic thin film from a 10-g sample of a 30% (dis sample board from sawdust, density ~44pcf, size -8.7inches longx8.8 inches widex0.41 inches thick. The estimated solved binder solids) binder dried in vacuo, is shown in FIG. binder content of each sample board was ~12.6%. 1. The FT-IR spectrum of a cured triammonium citrate-dex 35 trose (1:6) Maillard binder, which spectrum was obtained as a microscopic thin film from a 10-g sample of a 30% binder EXAMPLE1b. (dissolved binder solids) after curing, is shown in FIG. 2. The following samples were tested to compare the Flexural When polycarboxylic acids other than citric acid, Sugars other and Tensile strength of standard particle board and oriented than dextrose, and/or additives were used to prepare aqueous 40 Strand board with similar products made using a new test ammonium polycarboxylate Sugar binder variants, the same binder: general procedure was used as that described above for prepa Commercially available /2 in. particle board purchased ration of an aqueous triammonium citrate-dextrose (1:6) from Builders Lumber binder. For ammonium polycarboxylate-Sugar binder Vari Commercially available /2 in. oriented strand board (OSB) ants, adjustments were made as necessary to accommodate 45 purchased from Builders Lumber the inclusion of, for example, a dicarboxylic acid or a poly Test wood particle board made as described above 8.75x meric polycarboxylic acid instead of citric acid, or to accom 8.87x0.414 371.9 gm. 44.1 lbs 12.6% binder modate the inclusion of, for example, a triose instead of Test wood shavings board made as described above 8.37x dextrose, or to accommodate the inclusion of, for example, 9x0.336361.2 gm. 54.4 lbs 12.6% binder one or more additives. Such adjustments included, for 50 The test boards were each approximately 8% inches example, adjusting the Volume of aqueous ammonia neces square. The boards from builders were approximately 2 ftx4 sary to generate the ammonium salt, adjusting the gram ft when purchased. These boards were cut down to approxi amounts of reactants necessary to achieve a desired molar mately 8% inches square so that the samples would be col ratio of ammonium polycarboxylate to Sugar, and/or includ lected consistently from the various products. ing an additive in a desired weight percent. The test results are set out in tables 1 to 5: TABLE 1. Summary results Tensile Strength Flexural Strength Max Tensile Load (c) Thickness Density Load Strength. Thickness Density Break Modulus In. Lb/ft Ibs psi In. Lb/ft Ibs psi Particle 41.36 296.95 760.70 O.S2O 45.81 76.26 325295.1 Board (store bought) US 8,501,838 B2 5 TABLE 1-continued Summary results Tensile Strength Flexural Strength Max Tensile Load (c) Thickness Density Load Strength. Thickness Density Break Modulus In. Lb/ft Ibs psi In. Lb/ft Ibs psi Test- O416 42.82 270.55 868.44 0.445 45.OS 61.38 281499.6 Particle Board Oriented O463 36.66 293.92 848.92 O.495 37.05 87.82 293246.4 Strand Board (store bought) Test- O.331 51.64 274.2O 1124.94 O.386 50.67 77.02 322299.0 Oriented Strand Board TABLE 2 Detail Data - Standard Particle Board (store bought Tensile Strength Flexural Strength Max Tensile Load (c) Particle Thickness Density Load Strength. Thickness Density Break Modulus Board In. Lb/ft Ibs psi In. Lb/ft Ibs psi 1 O.S2O 41.4S 307. 63 788.80 O.S23 46.68 78.45 3.012546 2 O.S21 41.35 286.26 732.60 O.S21 46.93 78.9S 31.3865.3 3 O.S2O 46.64 73.8O 314028.9 4 O.S22 45.04 71.87 335869.O 5 O.S18 44.47 76.23 34O901.5 6 O.S16 45.08 78.24 345851.6 TABLE 3 Detail Data - Test Particle Board Tensile Strength Flexural Strength Test Max Tensile Load (c) Particle Thickness Density Load Strength. Thickness Density Break Modulus Board In. Lb/ft Ibs psi In. Lb/ft Ibs psi 1 O416 40.99 204.3O 654.82 0418 51.02 75.88 316852.8 2 O415 44.76 336.79 1082.06 0.431 49.89 72.45 329690.9 3 0.441 4172 S6.33 247OO6.3 4 O4SO 47.66 68.94 348970.7 5 O-463 44.37 59.02 281044.9 6 O468 35.62 35.62 165431.8 TABLE 4 Detail Data - Standard Oriented Strand Board (Store bought Tensile Strength Flexural Strength Oriented Max Tensile Load (c) Strand Thickness Density Load Strength. Thickness Density Break Modulus Board In. Lb/ft Ibs psi In. Lb/ft Ibs psi 1 O468 36.47 2SO.98 715.O3 O.475 38.67 41.02 1777O6.4 2 O.457 36.91 336.86 982.81 O.S12 36.03 79.96 23OO90.1 3 O495 36.57 S2.95 198956.O 4 O491 37.88 126.31 412893.2 5 O495 36.4S 115.87 375834.9 6 OSOO 36.68. 110.82 363997.5 US 8,501,838 B2 TABLE 5 Detail Data - Test Oriented Strand Board Test Tensile Strength Flexural Strength Oriented Max Tensile Load (c) Strand Thickness Density Load Strength. Thickness Density Break Modulus Board In. Lb/ft Ibs psi In. Lb/ft Ibs psi 1 O.317 54.39 382.26 16O7.84 O.351 56.57 53.61 241391.O 2 O.345 49.1O 166.13 642.04 O.380 54.20 78.17 363.683.1 3 O400 51.12 81.74 365485.3 4 O384 53.08 91.70 402491.O 5 O400 46.72 89.90 33821O.S 6 O400 42.34 67.00 222533.0 15 EXAMPLE 2 The boards information was shown in table 7. PB-1 to PB-11 were made with BS1 resin, PB12 to PB14 made with Two experimental resins were used, BS1 and BS1-SOK BS1-SOK resin. (solids content of 50%). Particle boards (PB), oriented strand boards (OSB) and medium density fibreboards (MDF) were TABLE 6 manufactured with those two resin Systems. Manufacture of Test Particle Boards: Particle boards information Single layer particleboards were manufactured. Wood Moisture chips for the manufacture of the particleboards were for com 25 Resin content, % Processing mercial particleboard manufacture, these chips would have Loading, Pre- Post- Temp, Time, consisted of a mixture of wood species and was thought to Type % blend blend o C. min Additives consist mainly of recycled timber. Prior to use the chips were PB-1 BS 2 3.22 2.1 220 5 No sieved to remove oversize material and shives. Before resina PB-2 BS 2 4.24 2.26 220 9 No tion, the chips were dried to constant moisture content (MC). 30 PB-3 BS 2 3.22 2.1 220 10 No Hereinafter, moisture content will be expressed as the weight PB-4 BS 2 3.54 2.32 220 10 No PB-5 BS 2 3.54 2.32 22O 10 No of water contained in wood as a percentage of the oven dry PB-6 BS 2 4.78 2.27 220 10 No weight of wood. PB-7 BS 2 3.36 2.25 220 10 No 12% or 14% resin was added to the wood chips (weight of PB-8 BS 2 4.24 2.92 220 10 No 35 PB-9 BS 2 4.24 2.92 220 10 No resin solids to weight of dry wood). The resin and chips were PB-10 BS 2 3.78 1.8 220 10 Wax blended together in a Kenwood or Drumblender. The dry chip PB-11 BS 4 3.22 2 220 10 No moisture content and the moisture content of the sprayed PB-12 BS1- 2 3.68 S.68 220 5 No SOK chips were all measured; the information is Summarised in PB-13 BS1- 2 3.68 4.44 220 9 No Table 6. The mass of chips per board was adjusted according 40 SOK to moisture content in order to achieve a target density of 650 PB-14 BS1- 2 3.47 2.86 220 10 No kg/m. SOK After blending the resin, additives and chips, the resultant “furnish' was transferred to a forming box and lightly com pacted before being hot pressed for final consolidation and 45 TABLE 7 resin curing. Boards were pressed using a target platen temperature of Oriented strand boards information 220° C. and a total press time of 5-12 minutes. Panels were Moisture 500mm by 500 mm or 300 mm by 300 mm square and 12 mm content, % Processing thick. On removal from the hot press the boards were labelled 50 and after cooling the edges were trimmed. Pre-blend Post-blend Temp, C. Time, min Manufacture of Test Orientated Strand Boards: OSB-1 Surface 4.84 12.1 220 9 Core 5.39 11.65 The flakes are sifted and separated into core and surface OSB-2 Surface 2.84 11.21 220 10 flakes. Large size flakes are used in Surface layers, Small size Core 2.86 10.03 in core layer. 55 OSB-3 Surface 3.71 12.04 220 12 The surface material is blended with 14% BS1 resin (resin Core 3.56 11.37 to timber, dry basis) and water in two benders. Resin is mixed OSB-4 Surface 3.22 9.89 220 15 with water through a static mixer. Water is added to reduce the Core 3.22 8.23 viscosity of the resin and increase the flake MC to 12%. The core material is blended with 12% BS1 resin and water 60 Manufacture of Test Medium Density Fibreboards: in a single bender. Target core flake MC is at 10-12%. A standard raw material was used: chipped softwood (pri The blended material is conveyed to three forming stations, marily spruce) obtained from Kronospan. Surface, core and Surface. The Surface formers align the flakes 12% BS1 resin was added to the MDF (weight of resin parallel to the machine direction, whilst the core former solids to weight of dry fibres). The MC before and post blend arranges the flakes perpendicular to the machine direction. 65 was 8.26 and 16.23%, respectively. Flake alignment is achieved by a series of paddles or rollers in Boards were pressed using a target platen temperature of the forming stations. 220° C. and a total press time of 10 minutes. US 8,501,838 B2 10 Preparation of Samples for Testing: There were no significant difference on thickness Swelling After cooling each board was cut to a specified pattern, see and water absorption between PB-8 and PB-9, both thickness FIG. 1 for details. Swelling and water absorption were much higher than the The sample size (from positions 1-12) was 50 mm by 50 requirement by standard, as indicated by solid line in FIG. 6. mm squares, sample width from positions 13 and 14 was 50 Significant difference were apparent in addition of wax, sample had the lowest thickness Swelling and water absorp From each board six samples (from positions 1, 3, 5, 8, 10 tion, which also was lower than the requirement by Standard. and 12) were tested for internal bond strength in accordance This suggested that use of wax helped to improve thickness with EN319, six (from positions 2, 4, 6, 7, 9 and 11) for thickness swelling and water absorption with EN317. Two Swelling and water absorption. from positions 13 and 14 were tested for modulus of elasticity 10 Modulus of Elasticity in Bending and of Bending Strength in bending and of bending strength according to EN310. Only the boards (PB-8 and PB-9) made at 220° C. for 10 Testing: min were tested for modulus of elasticity and bending Internal Bond Strength strength. The average for MOE was 2314 N/mm with STD of Transverse Internal Bond Strength. (EN319 for PB and EN 257.68, which was much higher than the requirement by 300 for OSB) 15 standard of 1800 N/mm. This means the board was much Moisture Absorption & Thickness Swelling stiffer. Average for MOR was 10.4 N/mm., which was lower Thickness Swelling after 24hrs in Water at 20°C. (EN317) than the requirement of 14 N/mm. To improve MOR to Water Absorption after 24 hrs in Water at 20° C. match the requirement, increasing the resin loading may be Modulus of Elasticity in Bending and of Bending Strength. the right way. Modulus of elasticity (MOE), (EN310) Results for Oriented Strand Boards (OSB) Bending strength (MOR) FIG. 6 summarises the results for internal bond of oriented Test Results for Particle Boards: strand board, the solid line indicated the requirement of 0.28 Table 8 summarises the results for internal bond strength N/mm by standard (EN300) for OSB. (IB) of particle boards. IB was always lower than the requirement; to improve the FIGS. 2 and 3 show the effects of pressing times on IB. It 25 bond strength for OSB boards with BS1 resin, the processing was noted that PB-3 to PB-9 shared the same processing parameters and/or the resin loading should be considered. (temperature and times) and IB varied within error, so the Modulus of Elasticity in Bending and of Bending Strength average at 0.43 N/mm with STD 0.03 was included in FIG.2. Boards OSB-2 and OSB-3 were tested for mor and moe, The general requirement of 0.4 N/mm for IB from standards the results are summarized in table 9. The requirements by was also indicated in FIGS. 2 and 3. 30 standard were 18 N/mm and 2500 N/mm. Both OSB-2 and It was apparent that resins in PB-1 and PB-12 pressed for 5 OSB-3 had much higher morand moe than the requirements min had developed no significant bond strengths due to insuf for general purposeboards, though the IB was lower. Not only ficient press times, bond strengths were improved when the bonding strength between fibres and resin but also the increased the pressing times to 9 min (PB-2 and PB-13), bond fibre dimension and orientation would be of benefit to mor strength over standard value was obtained for PB with BS1 35 and moe. resin (PB-3 to PB-9) when further increased the pressing The current values also were greater than the requirements times to 10 min. However, with BS1-SOK resin system, IB for load bearing boards for use in both dry and humid condi (PB14) was lower than the standard requirement. tions which are 20 N/mm and 3500 N/mm. however, lower For PB-10, Wax was added in, it seems there was no sig than the requirement for heavy duty load bearing boards 28 nificant effects on IB. 40 N/mm and 4800 N/mm. IB for PB-11 which had a resin loading at 14%, 2% higher than the rest boards, was 0.5 N/mm. This suggested that the TABLE 9 increase of resin loading will increase the bond strengths. Morand moe results for OSB TABLE 8 45 MOR, N/mm. STD MOE, N/mm. STD OSB-2 26.47 4.11 4158.0 S64.58 Internal bond strength of panels OSB-3 24.89 2.42 3861.9 428.73 Density, Kg/m3 STD IB, N/mm2 STD PB-1 552 22.2 O.O2 O.O1 50 Results for Medium Density Board PB-2 598 18.75 0.37 O.O2 Internal Bond Strength PB-3 565 12.9 O46 O.O2 PB-4 617 1O.S O46 O.O3 Only one trial of medium density board was manifested. PB-5 592 8.3 0.44 O.O2 The pressing temperature was 220°C. and times 10 min. The PB-6 591 6.9 O43 O.04 average of IB was 0.43 N/mm with STD at 0.03, which was PB-7 610 15.8 O41 O.OS 55 higher than the requirement of 0.4 N/mm by standard. PB-8 615 23.4 O46 O.04 Modulus of Elasticity in Bending and of Bending Strength PB-9 613 39.4 O40 O.O7 PB-10 630 20.6 O.47 O.OS The average for MOR was 22.26 N/mm with STD of 1.31, PB-11 617 6.04 O.S O.O3 which was 60% higher than the requirement by standard of 14 PB-12 638 37.6 O.OS O.O2 N/mm. Average for MOE was 2771.62 N/mm. STD 204.17 PB-13 627 8.9 O.25 O.O6 60 which was over 50% greater than the requirement of 1800 PB-14 567 12.1 O.35 O.OS N/mm. Note that 14 N/mm and 1800 N/mm are the requirement The results of the tests for thickness swelling and water for general purpose boards of use in dry condition. The absorption are summarised in FIGS. 4 and 5. requirements for load-bearing boards of use in dry or humid PB-8, 9 and 10 were processed at same temperature and 65 conditions are 18 N/mm and 2500 N/mm. IB of 0.45 times, the only difference between PB-8, 9 and 10 was the N/mm. The current mor and moe were greater than this addition of wax, 0.8% wax was added in PB-10. requirements as well though IB was slighter lower. However, US 8,501,838 B2 11 12 with the optimisation of processing, MDF must achieve all Furthermore, the binders of the present invention may the requirements for load-bearing boards or even for heavy include a product of a Maillard reaction. For example, see duty load bearing ones. FIG.8. As shown in FIG. 8, Maillard reactions produce mel Discussion of Results from Example 2: anoidins, i.e., high molecular weight, furan ring and nitrogen The pressing times and resin loading played an important containing polymers that vary in structure depending on the role in IB of particle boards made with BS1 resin, IB reactants and conditions of their preparation. Melanoidins increased with the increase of pressing times and resin load display a CN ratio, degree of unsaturation, and chemical ing. However, for particle boards made with BS1-SOK resin, aromaticity that increase with temperature and time of heat IB varied with the increase of pressing time, and which was ing. (See, Ames, J.M. in The Maillard Browning Reaction— always lower than the requirement by standard. Optimisation 10 an update, Chemistry and Industry (Great Britain), 1988, 7. of process parameters would be expected to lead to improve 558-561, the disclosure of which is hereby incorporated mentS. herein by reference). Accordingly, the subject binders may be Thickness Swelling and water absorption was improved by made via a Maillard reaction and thus contain melanoidins. It the addition of wax in particle board, the values were lower should be appreciated that the Subject binders may contain than the requirement by standard. Optimisation should bring 15 melanoidins, or other Maillard reaction products, which improvements. products are generated by a separate process and then simply Oriented strand boards made by BS1 resin had lower IB but added to the composition that makes up the binder. The mel higher morand moe than the requirements by standards. IB anoidins in the binder may be water insoluble. Moreover, the strongly depended on the bonding strength between fibres binders may be thermoset binders. and matrix, however, morand moe would be benefited from The Maillard reactants to produce a melanoidin may the fibre dimension and orientation. include an amine reactant reacted with a reducing-Sugar car By using BS1 resin, medium density fibre boards showed bohydrate reactant. For example, an ammonium salt of a greater mechanical properties than the requirements of gen monomeric polycarboxylic acid may be reacted with (i) a eral purposes boards, with possibility to achieve the require monosaccharide in its aldose or ketose form or (ii) a polysac ments for load-bearing boards by optimising the processing. 25 charide or (iii) with combinations thereof. In another varia The problem for oriented strand boards with BS1 resin is tion, an ammonium salt of a polymeric polycarboxylic acid lower IB, to improve this, increasing resin loading may be the may be contacted with (i) a monosaccharide in its aldose or right way forward. ketose form or (ii) a polysaccharide, or (iii) with combina Medium density boards with BS1 resin showed great per tions thereof. In yet another variation, an amino acid may be formance; optimisation of the processing may meet the 30 contacted with (i) a monosaccharide in its aldose or ketose requirements for load-bearing boards or even heavy duty load form, or (ii) with a polysaccharide or (iii) with combinations bearing boards. thereof. Furthermore, a peptide may be contacted with (i) a Whilst particular binders have been used in the examples, monosaccharide in its aldose or ketose form or (ii) with a other binders particularly binders which are discussed below, polysaccharide or (iii) with combinations thereof. Moreover, may be used in the context of the invention. 35 a protein may be contacted with (i) a monosaccharide in its Discussion of Binders: aldose or ketose form or (ii) with a polysaccharide or (iii) with Cured or uncured binders useful in connection with the combinations thereof. present invention may comprise one or more of the following It should also be appreciated that the binders may include features or combinations thereof. In addition, materials in melanoidins produced in non-Sugar variants of Maillard reac accordance with the present invention may comprise one or 40 tions. In these reactions an amine reactant is contacted with a more of the following features or combinations thereof: non-carbohydrate carbonyl reactant. In one illustrative varia Initially it should be appreciated that the binders may be tion, an ammonium salt of a monomeric polycarboxylic acid utilized in a variety of fabrication applications to produce or is contacted with a non-carbohydrate carbonyl reactant Such promote cohesion in a collection of non or loosely assembled as, pyruvaldehyde, acetaldehyde, crotonaldehyde, 2-furalde matter. A collection includes two or more components. The 45 hyde, quinone, ascorbic acid, or the like, or with combina binders produce or promote cohesion in at least two of the tions thereof. In another variation, an ammonium salt of a components of the collection. For example, Subject binders polymeric polycarboxylic acid may be contacted with a non are capable of holding a collection of matter together Such carbohydrate carbonyl reactant Such as, pyruvaldehyde, that the matter adheres in a manner to resist separation. The acetaldehyde, crotonaldehyde, 2-furaldehyde, quinone, binders described herein can be utilized in the fabrication of 50 ascorbic acid, or the like, or with combinations thereof. In yet any material. another illustrative variation, an amino acid may be contacted One potential feature of the present binders is that they are with a non-carbohydrate carbonyl reactant such as, pyruval formaldehyde free. Accordingly, the materials the binders are dehyde, acetaldehyde, crotonaldehyde, 2-furaldehyde, disposed upon may also be formaldehyde free. In addition, quinone, ascorbic acid, or the like, or with combinations the present binders may have a reduced trimethylamine con 55 thereof. In another illustrative variation, a peptide may be tent as compared to other known binders. With respect to the contacted with a non-carbohydrate carbonyl reactant Such as, present binder's chemical constituents, they may include pyruvaldehyde, acetaldehyde, crotonaldehyde, 2-furalde ester and/or polyester compounds. The binders may include hyde, quinone, ascorbic acid, or the like, or with combina ester and/or polyester compounds in combination with a veg tions thereof. In still another illustrative variation, a protein etable oil, such as soybean oil. Furthermore, the binders may 60 may contacted with a non-carbohydrate carbonyl reactant include ester and/or polyester compounds in combination Such as, pyruvaldehyde, acetaldehyde, crotonaldehyde, with sodium salts of organic acids. The binders may include 2-furaldehyde, quinone, ascorbic acid, and the like, or with Sodium salts of inorganic acids. The binders may also include combinations thereof. potassium salts of organic acids. Moreover, the binders may The melanoidins discussed herein may be generated from include potassium salts of inorganic acids. The described 65 melanoidin reactant compounds. These reactant compounds binders may include ester and/or polyester compounds in are disposed in an aqueous solution at an alkaline pH and combination with a clay additive. Such as montmorillonite. therefore are not corrosive. That is, the alkaline solution pre US 8,501,838 B2 13 14 vents or inhibits the eating or wearing away of a Substance, the binder. These changes may increase the binder's durabil Such as metal, caused by chemical decomposition brought ity and solvent resistance as compared to the uncured binder. about by, for example, an acid. The reactant compounds may Curing a binder may result in the formation of a thermoset include a reducing-Sugar carbohydrate reactant and an amine material. Furthermore, curing may include the generation of reactant. In addition, the reactant compounds may include a melanoidins. These melanoidins may be generated from a non-carbohydrate carbonyl reactant and an amine reactant. Maillard reaction from melanoidin reactant compounds. In It should also be understood that the binders described addition, a cured binder may result in an increase in adhesion herein may be made from melanoidin reactant compounds between the matter in a collection as compared to an uncured themselves. That is, once the Maillard reactants are mixed, binder. Curing can be initiated by, for example, heat, electro this mixture can function as a binder of the present invention. 10 magnetic radiation or, electron beams. These binders may be utilized to fabricate uncured, formal In a situation where the chemical change in the binder dehyde-free matter, such as fibrous materials. results in the release of water, e.g., polymerization and cross In the alternative, a binder made from the reactants of a linking, a cure can be determined by the amount of water Maillard reaction may be cured. These binders may be used to released above that would occur from drying alone. The tech fabricate cured formaldehyde free matter, such as, fibrous 15 niques used to measure the amount of water released during compositions. These compositions are water-resistant and, as drying as compared to when a binder is cured, are well known indicated above, include water-insoluble melanoidins. in the art. It should be appreciated that the binders described herein In accordance with the above paragraph, an uncured binder may be used in manufacturing products from a collection of is one that has not been cured. non or loosely assembled matter. For example, these binders As used herein, the term alkaline indicates a solution hav may be employed to fabricate fiber products. In one illustra ing a pH that is greater than or equal to about 7. For example, tive embodiment, the binders are used to make cellulosic the pH of the solution can be less than or equal to about 10. In compositions. With respect to cellulosic compositions, the addition, the solution may have a pH from about 7 to about 10, binders may be used to bind cellulosic matter to fabricate, for or from about 8 to about 10, or from about 9 to about 10. example, wood fiber board which has desirable physical 25 As used herein, the term ammonium. includes, but is not properties (e.g., mechanical strength). limited to, “NH, “NHR', and "NHR'R'', where R' and R' One embodiment of the invention is directed to a method are each independently selected in "NHR'R', and where R' for manufacturing products from a collection of non- or and Rare selected from alkyl, cycloalkyl, alkenyl, cycloalk loosely assembled matter. The method may include contact enyl, heterocyclyl, aryl, and heteroaryl. ing the fibers with a thermally-curable, aqueous binder. The 30 The term alkyl refers to a saturated monovalent chain of binder may include (i) an ammonium salt of a polycarboxylic carbon atoms, which may be optionally branched; the term acid reactant and (ii) a reducing-sugar carbohydrate reactant. cycloalkyl refers to a monovalent chain of carbon atoms, a These two reactants are melanoidin reactants (i.e., these reac portion of which forms a ring; the term alkenyl refers to an tants produce melanoidins when reacted under conditions to unsaturated monovalent chain of carbon atoms including at initiate a Maillard reaction.) The method can further include 35 least one double bond, which may be optionally branched; the removing water from the binder in contact with the fibers (i.e., term cycloalkenyl refers to an unsaturated monovalent chain the binder is dehydrated). The method can also include curing of carbon atoms, a portion of which forms a ring; the term the binder in contact with the fibers (e.g., thermally curing the heterocyclyl refers to a monovalent chain of carbon and het binder). eroatoms, wherein the heteroatoms are selected from nitro An example of utilizing this method is in the fabrication of 40 gen, oxygen, and Sulfur, a portion of which, including at least cellulosic materials. The method may include contacting the one heteroatom, form a ring; the term aryl refers to an aro cellulosic material (e.g., cellulose fibers) with a thermally matic mono or polycyclic ring of carbon atoms, such as phe curable, aqueous binder. The binder may include (i) an nyl, naphthyl, and the like; and the term heteroaryl refers to an ammonium salt of a polycarboxylic acid reactant and (ii) a aromatic mono or polycyclic ring of carbonatoms and at least reducing-Sugar carbohydrate reactant. As indicated above, 45 one heteroatom selected from nitrogen, oxygen, and Sulfur, these two reactants are melanoidin reactant compounds. The Such as pyridinyl, pyrimidinyl, indolyl, benzoxazolyl, and the method can also include removing water from the binder in like. It is to be understood that each of alkyl, cycloalkyl, contact with the cellulosic material. As before, the method alkenyl, cycloalkenyl, and heterocyclyl may be optionally can also include curing the binder (e.g., thermal curing). Substituted with independently selected groups such as alkyl, A fibrous product is described that includes a binder in 50 haloalkyl, hydroxyalkyl, aminoalkyl, carboxylic acid and contact with cellulose fibers, such as those in a mat of wood derivatives thereof, including esters, amides, and nitriles, shavings or sawdust. The mat may be processed to form one hydroxy, alkoxy, acyloxy, amino, alkyl and dialkylamino, of several types of wood fiber board products. In one varia acylamino, thio, and the like, and combinations thereof. It is tion, the binder is uncured. In this variation, the uncured further to be understood that each of aryland heteroaryl may binder may function to hold the cellulosic fibers together. In 55 be optionally substituted with one or more independently the alternative, the cured binder may function to hold the selected Substituents, such as halo, hydroxy, amino, alkyl or cellulosic fibers together. dialkylamino, alkoxy, alkylsulfonyl, cyano, nitro, and the As used herein, the phrase formaldehyde-free. means that like. a binder or a material that incorporates a binder liberates less As used herein, the term polycarboxylic acid indicates a than about 1 ppm formaldehyde as a result of drying and/or 60 dicarboxylic, tricarboxylic, tetracarboxylic, pentacarboxylic, curing. The 1 ppm is based on the weight of Sample being and like monomeric polycarboxylic acids, and anhydrides, measured for formaldehyde release. and combinations thereof, as well as polymeric polycarboxy Cured indicates that the binder has been exposed to condi lic acids, anhydrides, copolymers, and combinations thereof. tions to So as to initiate a chemical change. Examples of these In one aspect, the polycarboxylic acid ammonium salt reac chemical changes include, but are not limited to, (i) covalent 65 tant is sufficiently non-volatile to maximize its ability to bonding, (ii) hydrogen bonding of binder components, and remain available for reaction with the carbohydrate reactant chemically cross-linking the polymers and/or oligomers in of a Maillard reaction (discussed below). In another aspect, US 8,501,838 B2 15 16 the polycarboxylic acid ammonium salt reactant may be Sub homopolymer or copolymer prepared from unsaturated car stituted with other chemical functional groups. Illustratively, boxylic acids including, but not necessarily limited to, acrylic a monomeric polycarboxylic acid may be a dicarboxylic acid, acid, methacrylic acid, crotonic acid, isocrotonic acid, maleic including, but not limited to, unsaturated aliphatic dicarboxy acid, cinnamic acid, 2-methylmaleic acid, itaconic acid, lic acids, Saturated aliphatic dicarboxylic acids, aromatic 2-methylitaconic acid, C.B-methyleneglutaric acid, and the dicarboxylic acids, unsaturated cyclic dicarboxylic acids, like. Alternatively, the polymeric polycarboxylic acid may be saturated cyclic dicarboxylic acids, hydroxy-Substituted prepared from unsaturated anhydrides including, but not nec derivatives thereof, and the like. Or, illustratively, the poly essarily limited to, maleic anhydride, itaconic anhydride, carboxylic acid(s) itself may be a tricarboxylic acid, includ acrylic anhydride, methacrylic anhydride, and the like, as ing, but not limited to, unsaturated aliphatic tricarboxylic 10 well as mixtures thereof. Methods for polymerizing these acids, Saturated aliphatic tricarboxylic acids, aromatic tricar acids and anhydrides are well-known in the chemical art. The boxylic acids, unsaturated cyclic tricarboxylic acids, Satu polymeric polycarboxylic acid may additionally comprise a rated cyclic tricarboxylic acids, hydroxy-substituted deriva copolymer of one or more of the aforementioned unsaturated tives thereof, and the like. It is appreciated that any such carboxylic acids or anhydrides and one or more vinyl com polycarboxylic acids may be optionally Substituted, such as 15 pounds including, but not necessarily limited to, styrene, with hydroxy, halo, alkyl, alkoxy, and the like. In one varia C.-methylstyrene, acrylonitrile, methacrylonitrile, methyl tion, the polycarboxylic acid is the Saturated aliphatic tricar acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, boxylic acid, citric acid. Other suitable polycarboxylic acids methyl methacrylate, n-butyl methacrylate, isobutyl meth are contemplated to include, but are not limited to, aconitic acrylate, glycidyl methacrylate, vinyl methyl ether, vinyl acid, adipic acid, azelaic acid, butane tetracarboxylic acid acetate, and the like. Methods for preparing these copolymers dihydride, butane tricarboxylic acid, chlorendic acid, citra are well-known in the art. The polymeric polycarboxylic conic acid, dicyclopentadiene-maleic acid adducts, diethyl acids may comprise homopolymers and copolymers of poly enetriamine pentaacetic acid, adducts of dipentene and acrylic acid. The molecular weight of the polymeric polycar maleic acid, ethylenediamine tetraacetic acid (EDTA), fully boxylic acid, and in particular polyacrylic acid polymer, may maleated rosin, maleated tall-oil fatty acids, fumaric acid, 25 be is less than 10000, less than 5000, or about 3000 or less. glutaric acid, isophthalic acid, itaconic acid, maleated rosin For example, the molecular weight may be 2000. oxidized with potassium peroxide to alcohol then carboxylic As described in U.S. Pat. Nos. 5,318,990 and 6,331,350, acid, maleic acid, malic acid, mesaconic acid, biphenol A or the polyol (in a composition including a polymeric polycar bisphenol F reacted via the KOLBE-Schmidt reaction with boxylic acid) contains at least two hydroxyl groups. The carbon dioxide to introduce 3-4 carboxyl groups, oxalic acid, 30 polyol should be sufficiently nonvolatile such that it will phthalic acid, sebacic acid, Succinic acid, tartaric acid, tereph substantially remain available for reaction with the polymeric thalic acid, tetrabromophthalic acid, tetrachlorophthalic acid, polycarboxylic acid in the composition during heating and tetrahydrophthalic acid, trimellitic acid, trimesic acid, and the curing operations. The polyol may be a compound with a like, and anhydrides, and combinations thereof. molecular weight less than about 1000 bearing at least two Illustratively, a polymeric polycarboxylic acid may be an 35 hydroxyl groups such as, ethylene glycol, glycerol, pen acid, for example, polyacrylic acid, polymethacrylic acid, taerythritol, trimethylol propane, Sorbitol. Sucrose, glucose, polymaleic acid, and like polymeric polycarboxylic acids, resorcinol, catechol, pyrogallol, glycollated ureas, 1,4-cyclo copolymers thereof, anhydrides thereof, and mixtures hexane diol, diethanolamine, triethanolamine, and certain thereof. Examples of commercially available polyacrylic reactive polyols, for example, B-hydroxyalkylamides such as, acids include AQUASET-529 (Rohm & Haas, Philadelphia, 40 for example, bisN,N-di(B-hydroxyethyl)adipamide, or it Pa., USA), CRITERION 2000 (Kemira, Helsinki, Finland, may be an addition polymer containing at least two hydroxyl Europe), NF1 (H. B. Fuller, St. Paul, Minn., USA), and groups such as, polyvinyl alcohol, partially hydrolyzed poly SOKALAN (BASF, Ludwigshafen, Germany, Europe). With vinyl acetate, and homopolymers or copolymers of hydroxy respect to SOKALAN, this is a watersoluble polyacrylic ethyl(meth)acrylate, hydroxypropyl(meth)acrylate, and the copolymer of acrylic acid and maleic acid, having a molecu 45 like. lar weight of approximately 4000. AQUASET-529 is a com As described in U.S. Pat. Nos. 5,318,990 and 6,331,350, position containing polyacrylic acid cross-linked with glyc the catalyst (in a composition including a polymeric polycar erol, also containing sodium hypophosphite as a catalyst. boxylic acid) is a phosphorous-containing accelerator which CRITERION 2000 is an acidic solution of a partial salt of may be a compound with a molecular weight less than about polyacrylic acid, having a molecular weight of approximately 50 1000 such as, an alkali metal polyphosphate, an alkali metal 2000. With respect to NF1, this is a copolymer containing dihydrogen phosphate, a polyphosphoric acid, and an alkyl carboxylic acid functionality and hydroxy functionality, as phosphinic acid or it may be an oligomer or polymer bearing well as units with neither functionality; NF1 also contains phosphorous-containing groups, for example, addition poly chain transfer agents, such as Sodium hypophosphite or orga mers of acrylic and/or maleic acids formed in the presence of nophosphate catalysts. 55 Sodium hypophosphite, addition polymers prepared from eth Further, compositions including polymeric polycarboxylic ylenically unsaturated monomers in the presence of phospho acids are also contemplated to be useful in preparing the rous salt chain transfer agents or terminators, and addition binders described herein, such as those compositions polymers containing acid-functional monomer residues, for described in U.S. Pat. Nos. 5,318,990, 5,661,213, 6,136,916, example, copolymerized phosphoethyl methacrylate, and and 6.331,350, the disclosures of which are hereby incorpo 60 like phosphonic acid esters, and copolymerized vinyl Sulfonic rated herein by reference. In particular, in U.S. Pat. Nos. acid monomers, and their salts. The phosphorous-containing 5.318,990 and 6.331,350 an aqueous solution of a polymeric accelerator may be used at a level of from about 1% to about polycarboxylic acid, a polyol, and a catalyst is described. 40%, by weight based on the combined weight of the poly As described in U.S. Pat. Nos. 5,318,990 and 6,331,350, meric polycarboxylic acid and the polyol. A level of phos the polymeric polycarboxylic acid comprises an organic 65 phorous containing accelerator of from about 2.5% to about polymer or oligomer containing more than one pendant car 10%, by weight based on the combined weight of the poly boxy group. The polymeric polycarboxylic acid may be a meric polycarboxylic acid and the polyol may be used. US 8,501,838 B2 17 18 Examples of Such catalysts include, but are not limited to, pane, Sorbitol. Sucrose, glucose, resorcinol, catechol, pyro Sodium hypophosphite, sodium phosphite, potassium phos gallol, glycollated ureas, 1,4-cyclohexane diol, diethanola phite, disodium pyrophosphate, tetrasodium pyrophosphate, mine, triethanolamine, and certain reactive polyols, for Sodium tripolyphosphate, sodium hexametaphosphate, example, 3-hydroxyalkylamides, for example, bisN,N-di(B- potassium phosphate, potassium polymetaphosphate, potas hydroxyethyl)adipamide, bis(N.Ndi(B-hydroxypropyl) sium polyphosphate, potassium tripolyphosphate, Sodium tri azelamide, bisN-N-di(B-hydroxypropyl)adipamide, bisN metaphosphate, and sodium tetrametaphosphate, as well as Ndi (B-hydroxypropyl)glutaramide, bisN-N-di(B- mixtures thereof. Compositions including polymeric poly hydroxypropyl)succinamide, and bisN-methyl-N-(B- carboxylic acids described in U.S. Pat. Nos. 5,661.213 and hydroxyethyl)oxamide, or it may be an addition polymer 6,136,916 that are contemplated to be useful in preparing the 10 containing at least two hydroxyl groups such as, polyvinyl binders described herein comprise an aqueous solution of a polymeric polycarboxylic acid, a polyol containing at least alcohol, partially hydrolyzed polyvinyl acetate, and two hydroxyl groups, and a phosphorous-containing accel homopolymers or copolymers of hydroxyethyl(meth)acry erator, wherein the ratio of the number of equivalents of late, hydroxypropyl (meth)acrylate, and the like. carboxylic acid groups, to the number of equivalents of 15 As described in U.S. Pat. Nos. 5,661.213 and 6,136,916, hydroxyl groups is from about 1:0.01 to about 1:3. the phosphorous-containing accelerator (in a composition As disclosed in U.S. Pat. Nos. 5,661.213 and 6,136,916, including a polymeric polycarboxylic acid) may be a com the polymeric polycarboxylic acid may be, a polyester con pound with a molecular weight less than about 1000 such as, taining at least two carboxylic acid groups or an addition an alkali metal hypophosphite salt, an alkali metal phosphite, polymer or oligomer containing at least two copolymerized an alkali metal polyphosphate, an alkali metal dihydrogen carboxylic acid-functional monomers. The polymeric poly phosphate, a polyphosphoric acid, and an alkyl phosphinic carboxylic acid is preferably an addition polymer formed acid or it may be an oligomer or polymer bearing phospho from at least one ethylenically unsaturated monomer. The rous-containing groups such as, addition polymers of acrylic addition polymer may be in the form of a solution of the and/or maleic acids formed in the presence of Sodium hypo addition polymer in an aqueous medium Such as, an alkali 25 phosphite, addition polymers prepared from ethylenically soluble resin which has been solubilized in a basic medium; in unsaturated monomers in the presence of phosphorous salt the form of an aqueous dispersion, for example, an emulsion chain transfer agents or terminators, and addition polymers polymerized dispersion; or in the form of an aqueous Suspen containing acid-functional monomer residues such as, copo Sion. The addition polymer must contain at least two carboxy lymerized phosphoethyl methacrylate, and like phosphonic lic acid groups, anhydride groups, or salts thereof. 30 Ethylenically unsaturated carboxylic acids such as, meth acid esters, and copolymerized vinyl Sulfonic acid mono acrylic acid, acrylic acid, crotonic acid, fumaric acid, maleic mers, and their salts. The phosphorous-containing accelerator acid, 2-methyl maleic acid, itaconic acid, 2-methyl itaconic may be used at a level of from about 1% to about 40%, by acid, C.f3-methyleneglutaric acid, monoalkyl maleates, and weight based on the combined weight of the polyacid and the monoalkyl fumarates; ethylenically unsaturated anhydrides, 35 polyol. A level of phosphorous-containing accelerator of for example, maleic anhydride, itaconic anhydride, acrylic from about 2.5% to about 10%, by weight based on the anhydride, and methacrylic anhydride; and salts thereof, at a combined weight of the polyacid and the polyol, may be level of from about 1% to 100%, by weight, based on the utilized. weight of the addition polymer, may be used. Additional As used herein, the term amine base. includes, but is not ethylenically unsaturated monomer may include acrylic ester 40 limited to, ammonia, a primary amine, i.e., NHR', and a monomers including methyl acrylate, ethyl acrylate, butyl secondary amine, i.e., NHR'R'', where R' and R are each acrylate, 2-ethylhexyl acrylate, decyl acrylate, methyl meth independently selected in NHR'R', and where R' and Rare acrylate, butyl methacrylate, isodecyl methacrylate, selected from alkyl, cycloalkyl, alkenyl, cycloalkenyl, het hydroxyethyl acrylate, hydroxyethyl methacrylate, and erocyclyl, aryl, and heteroaryl, as defined herein. Illustra hydroxypropyl methacrylate; acrylamide or Substituted acry 45 tively, the amine base may be substantially volatile or sub lamides; styrene or Substituted styrenes; butadiene; vinyl stantially non-volatile under conditions sufficient to promote acetate or other vinyl esters; acrylonitrile or methacryloni formation of the thermoset binder during thermal curing. trile; and the like. The addition polymer containing at least Illustratively, the amine base may be a substantially volatile two carboxylic acid groups, anhydride groups, or salts thereof base. Such as, ammonia, ethylamine, diethylamine, dimethy may have a molecular weight from about 300 to about 10,000, 50 lamine, and ethylpropylamine. Alternatively, the amine base 000. A molecular weight from about 1000 to about 250,000 may be a Substantially non-volatile base, for example, aniline, may be used. When the addition polymer is an alkali-soluble 1-naphthylamine, 2-naphthylamine, and para-aminophenol. resin having a carboxylic acid, anhydride, or salt thereof, As used herein, reducing Sugar indicates one or more Sug content of from about 5% to about 30%, by weight based on ars that contain aldehyde groups, or that can isomerize, i.e., the total weight of the addition polymer, a molecular weight 55 tautomerize, to contain aldehyde groups, which groups are from about 10,000 to about 100,000 may be utilized Methods reactive with an amino group under Maillard reaction condi for preparing these additional polymers are well-known in the tions and which groups may be oxidized with, for example, art. Cu" to afford carboxylic acids. It is also appreciated that any As described in U.S. Pat. Nos. 5,661.213 and 6,136,916, Such carbohydrate reactant may be optionally Substituted, the polyol (in a composition including a polymeric polycar 60 Such as with hydroxy, halo, alkyl, alkoxy, and the like. It is boxylic acid) contains at least two hydroxyl groups and further appreciated that in any Such carbohydrate reactant, should be sufficiently nonvolatile that it remains substantially one or more chiral centers are present, and that both possible available for reaction with the polymeric polycarboxylic acid optical isomers at each chiral center are contemplated to be in the composition during heating and curing operations. The included in the invention described herein. Further, it is also polyol may be a compound with a molecular weight less than 65 to be understood that various mixtures, including racemic about 1000 bearing at least two hydroxyl groups, for example, mixtures, or other diastereomeric mixtures of the various ethylene glycol, glycerol, pentaerythritol, trimethylol pro optical isomers of any such carbohydrate reactant, as well as US 8,501,838 B2 19 20 various geometric isomers thereof, may be used in one or applying the binder to the fibers. Accordingly, corrosivity of more embodiments described herein. fiberglass fabrication (and the fabrication of other materials) FIG.7 shows examples of reactants for a Maillard reaction. is decreased. Examples of amine reactants include proteins, peptides, Without being bound to theory, covalent reaction of the polycarboxylic acid ammonium salt and reducing Sugar reac amino acids, ammonium salts of polymeric polycarboxylic tants of a Maillard reaction, which as described herein occurs acids, and ammonium salts of monomeric polycarboxylic Substantially during thermal curing to produce brown-col acids. As illustrated, ammonium. can be INHI NH ored nitrogenous polymeric and co-polymeric melanoidins of R', and NHRR), where x is at least about 1. With varying structure, is thought to involve initial Maillard reac respect to "NHRR, R and R are each independently tion of ammonia with the aldehyde moiety of a reducing selected. Moreover, R' and R are selected from alkyl, 10 Sugar carbohydrate reactant to afford N-Substituted glycosy cycloalkyl, alkenyl, cycloalkenyl, heterocyclyl, aryl, and het lamine, as shown in FIG.8. Consumption of ammonia in Such eroaryl, as described above. FIG. 1 also illustrates examples a way, with ammonia and a reducing Sugar carbohydrate of reducing-Sugar reactants for producing melanoidins, reactant combination functioning as a latent acid catalyst, would be expected to result in a decrease in pH, which including monosaccharides, in their aldose or ketose form, 15 decrease is believed to promote esterification processes and/ polysaccharides, or combinations thereof. Illustrative non or dehydration of the polycarboxylic acid to afford its corre carbohydrate carbonyl reactants for producing melanoidins sponding anhydride derivative. At pH-7, the Amadori rear are also shown in FIG. 1 and include various aldehydes, e.g., rangement product of N-Substituted glycosylamine, i.e., pyruvaldehyde and furfural, as well as compounds Such as 1-amino-1-deoxy-2-ketose, would be expected to undergo ascorbic acid and quinone. mainly 1.2-enolization with the formation of furfural when, FIG. 8 shows a schematic of a Maillard reaction, which for example, pentoses are involved, or hydroxymethylfur culminates in the production of melanoidins. In its initial fural when, for example, hexoses are involved, as a prelude to phase, a Maillard reaction involves a carbohydrate reactant, melanoidin production. Concurrently, contemporaneously, or for example, a reducing Sugar (note that the carbohydrate sequentially with the production of melanoidins, esterifica tion processes may occur involving melanoidins, polycar reactant may come from a substance capable of producing a 25 boxylic acid and/or its corresponding anhydride derivative, reducing Sugar under Maillard reaction conditions). The reac and residual carbohydrate, which processes lead to extensive tion also involves condensing the carbohydrate reactant (e.g., cross-linking. Accompanied by Sugar dehydration reactions, reducing Sugar) with an amine reactant, i.e., a compound whereupon conjugated double bonds are produced that may possessing an amino group. In other words, the carbohydrate undergo polymerization, a water-resistant thermoset binder is reactant and the amine reactant are the melanoidin reactants 30 produced consisting of polyester adducts interconnected by a for a Maillard reaction. The condensation of these two con network of carbon carbon single bonds. Consistent with the stituents produces an N-Substituted glycosylamine. For a above reaction scenario is a strong absorbance near 1734 more detailed description of the Maillard reaction see, cm-1 in the FT-IR spectrum of a cured binder described Hodge, J. E. Chemistry of Browning Reactions in Model herein, which absorbance is within the 1750-1730 cm-1 35 range expected for ester carbonyl C O vibrations. Systems J. Agric. Food Chem. 1953, 1928-943, the disclo The following discussion is directed to (i) examples of sure of which is hereby incorporated herein by reference. The carbohydrate and amine reactants, which can be used in a compound possessing a free amino group in a Maillard reac Maillard reaction and (ii) how these reactants can be com tion may be present in the form of an amino acid. The free bined. First, it should be understood that any carbohydrate amino group can also come from a protein where the free 40 and/or compound possessing a primary or secondary amino amino groups are available in the form of, for example, the group, that will act as a reactant in a Maillard reaction, can be C.-amino group of lysine residues, and/or the e-amino group utilized in the binders of the present invention. Such com of the terminal amino acid. pounds can be identified and utilized by one of ordinary skill Another aspect of conducting a Maillard reaction as in the art with the guidelines disclosed herein. With respect to exemplary reactants, it should also be described herein is that, initially, the aqueous Maillard reac 45 appreciated that using an ammonium salt of a polycarboxylic tant solution (which also is a binder), as described above, has acid as an amine reactant is an effective reactant in a Maillard an alkaline pH. However, once the Solution is disposed on a reaction. Ammonium salts of polycarboxylic acids can be collection of non or loosely assembled matter, and curing is generated by neutralizing the acid groups with an amine base, initiated, the pH decreases (i.e., the binder becomes acidic). It thereby producing polycarboxylic acid ammonium salt should be understood that when fabricating a material, the 50 groups. Complete neutralization, i.e., about 100% calculated amount of contact between the binder and components of on an equivalents basis, may eliminate any need to titrate or machinery used in the fabrication is greater prior to curing, partially neutralize acid groups in the polycarboxylic acid(s) (i.e., when the binder Solution is alkaline) as compared to prior to binder formation. However, it is expected that less after the binder is cured (i.e., when the binder is acidic). An than-complete neutralization would not inhibit formation of alkaline composition is less corrosive than an acidic compo 55 the binder. Note that neutralization of the acid groups of the sition. Accordingly, corrosivity of the fabrication process is polycarboxylic acid(s) may be carried out either before or decreased. after the polycarboxylic acid(s) is mixed with the carbohy It should be appreciated that by using the aqueous Maillard drate(s). reactant solution described herein, the machinery used to With respect to the carbohydrate reactant, it may include fabricate fiberglass is not exposed as much to an acidic solu 60 one or more reactants having one or more reducing Sugars. In tion because, as described above, the pH of the Maillard one aspect, any carbohydrate reactant should be sufficiently reactant Solution is alkaline. Furthermore, during the fabrica nonvolatile to maximize its ability to remain available for tion the only time an acidic condition develops is after the reaction with the polycarboxylic acid ammonium salt reac binder has been applied to fibers. Once the binder is applied to tant. The carbohydrate reactant may be a monosaccharide in the fibers, the binder and the material that incorporates the 65 its aldose or ketose form, including a triose, a tetrose, a binder, has relatively infrequent contacts with the compo pentose, a hexose, or a heptose; or a polysaccharide; or com nents of the machinery as compared to the time prior to binations thereof. A carbohydrate reactant may be a reducing US 8,501,838 B2 21 22 Sugar, or one that yields one or more reducing Sugars in situ 3-83, MOWIOL 4-88, MOWIOL 5-88, MOWIOL 8-88, under thermal curing conditions. For example, when a triose MOWIOL 18-88, MOWIOL 23-88, MOWIOL 26-88, serves as the carbohydrate reactant, or is used in combination MOWIOL 40-88, MOWIOL 47-88, and MOWIOL 30-92, as with other reducing Sugars and/or a polysaccharide, an aldot well as Celanese CELVOL. 203, CELVOL. 205, CELVOL riose Sugar or a ketotriose Sugar may be utilized. Such as 502,5 CELVOL504, CELVOL513, CELVOL523, CELVOL glyceraldehyde and dihydroxyacetone, respectively. When a 523TV, CELVOL 530, CELVOL 540, CELVOL 540TV, tetrose serves as the carbohydrate reactant, or is used in com CELVOL 418, CELVOL 425, and CELVOL 443. Also con bination with other reducing Sugars and/or a polysaccharide, templated to be useful are similar or analogous partially aldotetrose Sugars, such as erythrose and threose; and hydrolyzed polyvinyl acetates available from other commer ketotetrose Sugars, such as erythrulose, may be utilized. 10 cial Suppliers. When a pentose serves as the carbohydrate reactant, or is used When a fully hydrolyzed polyvinyl acetate serves as a in combination with other reducing Sugars and/or a polysac noncarbohydrate polyhydroxy reactant, Clariant MOWIOL charide, aldopentose Sugars, such as ribose, arabinose, 4-98, having a molecular weight of about 27,000 Da, may be Xylose, and lyxose; and ketopentose Sugars. Such as ribulose, utilized. Other fully hydrolyzed polyvinyl acetates contem arabulose, xylulose, and lyxulose, may be utilized. When a 15 plated to be useful include, but are not limited to, DuPont hexose serves as the carbohydrate reactant, or is used in ELVANOL 70-03 (98.0-98.8% hydrolyzed), ELVANOL combination with other reducing Sugars and/or a polysaccha 70-04 (98.0-98.8% hydrolyzed), ELVANOL 70-06 (98.5- ride, aldohexose Sugars, such as glucose (i.e., dextrose), man 99.2% hydrolyzed), ELVANOL 90-50 (99.0-99.8% hydro nose, galactose, allose, altrose, talose, gulose, and idose; and lyzed), ELVANOL 70-20 (98.5-99.2% hydrolyzed), ketohexose Sugars, such as fructose, psicose, Sorbose and ELVANOL 70-30 (98.5-99.2% hydrolyzed), ELVANOL tagatose, may be utilized. When a heptose serves as the car 71-30 (99.0-99.8% hydrolyzed), ELVANOL 70-62 (98.4- bohydrate reactant, or is used in combination with other 99.8% hydrolyzed), ELVANOL 70-63 (98.5-99.2% hydro reducing Sugars and/or a polysaccharide, a ketoheptose Sugar lyzed), ELVANOL 70-75 (98.5-99.2% hydrolyzed), Clariant such as sedoheptulose may be utilized. Other stereoisomers MOWIOL 3-98, MOWIOL 6-98, MOWIOL 10-98, of Such carbohydrate reactants not known to occur naturally 25 MOWIOL 20-98, MOWIOL 56-98, MOWIOL 28-99, and are also contemplated to be useful in preparing the binder Celanese CELVOL. 103, CELVOL. 107, CELVOL 305, CEL compositions as described herein. When a polysaccharide VOL 310, CELVOL 325, CELVOL 325LA, and CELVOL serves as the carbohydrate, or is used in combination with 350, as well as similar or analogous fully hydrolyzed polyvi monosaccharides. Sucrose, lactose, maltose, starch, and cel nyl acetates from other commercial Suppliers. lulose may be utilized. 30 The aforementioned Maillard reactants may be combined Furthermore, the carbohydrate reactant in the Maillard to make an aqueous composition that includes a carbohydrate reaction may be used in combination with a non-carbohydrate reactant and an amine reactant. These aqueous binders rep polyhydroxy reactant. Examples of non-carbohydrate poly resent examples of uncured binders. As discussed below, hydroxy reactants which can be used in combination with the these aqueous compositions can be used as binders of the carbohydrate reactant include, but are not limited to, trim 35 present invention. These binders are formaldehyde-free, cur ethylolpropane, glycerol, pentaerythritol, polyvinyl alcohol, able, alkaline, aqueous binder compositions. Furthermore, as partially hydrolyzed polyvinyl acetate, fully hydrolyzed indicated above, the carbohydrate reactant of the Maillard polyvinyl acetate, and mixtures thereof. In one aspect, the reactants may be used in combination with a non-carbohy noncarbohydrate polyhydroxy reactant is sufficiently non drate polyhydroxy reactant. Accordingly, any time the carbo volatile to maximize its ability to remain available for reac 40 hydrate reactant is mentioned it should be understood that it tion with a monomeric or polymeric polycarboxylic acid can be used in combination with a non-carbohydrate polyhy reactant. It is appreciated that the hydrophobicity of the non droxy reactant. carbohydrate polyhydroxy reactant may be a factor in deter In one illustrative embodiment, the aqueous solution of mining the physical properties of a binder prepared as Maillard reactants may include (i) an ammonium salt of one described herein. 45 or more polycarboxylic acid reactants and (ii) one or more When a partially hydrolyzed polyvinyl acetate serves as a carbohydrate reactants having a reducing Sugar. The pH of non carbohydrate polyhydroxy reactant, a commercially this solution prior to placing it in contact with the material to available compound such as an 87-89% hydrolyzed polyvinyl be bound can be greater than or equal to about 7. In addition, acetate may be utilized, such as, DuPont ELVANOL 51-05. this solution can have a pH of less than or equal to about 10. DuPont ELVANOL 51-05 has a molecular weight of about 50 The ratio of the number of moles of the polycarboxylic acid 22,000-26,000 Da and a viscosity of about 5.0-6.0 centi reactant(s) to the number of moles of the carbohydrate reac poises. Other partially hydrolyzed polyvinyl acetates con tant(s) can be in the range from about 1:4 to about 1:15. In one templated to be useful in preparing binder compositions as example, the ratio of the number of moles of the polycarboxy described herein include, but are not limited to, 87-89% lic acid reactant(s) to the number of moles of the carbohydrate hydrolyzed polyvinyl acetates differing in molecular weight 55 reactant(s) in the binder composition is about 1:5. In another and viscosity from ELVANOL 51-05, such as, for example, example, the ratio of the number of moles of the polycarboxy DuPont ELVANOL 51-04, ELVANOL 51-08, ELVANOL lic acid reactant(s) to the number of moles of the carbohydrate 50-14, ELVANOL 52-22, ELVANOL 50-26, ELVANOL reactant(s) is about 1:6. In yet another example, the ratio of 50-42; and partially hydrolyzed polyvinyl acetates differing the number of moles of the polycarboxylic acid reactant(s) to in molecular weight, viscosity, and/or degree of hydrolysis 60 the number of moles of the carbohydrate reactant(s) is about from ELVANOL 51-05, such as, DuPont ELVANOL 51-03 1:7. (86-89% hydrolyzed), ELVANOL 70-14 (95.0-97.0% hydro As described above, the aqueous binder composition lyzed), ELVANOL 70-27 (95.5-96.5% hydrolyzed), includes (i) an ammonium salt of one or more polycarboxylic ELVANOL 60-30 (90-93% hydrolyzed). Other partially acid reactants and (ii) one or more carbohydrate reactants hydrolyzed polyvinyl acetates contemplated to be useful in 65 having a reducing Sugar. It should be appreciated that when an preparing binder compositions as described herein include, ammonium salt of a monomeric or a polymeric polycarboxy but are not limited to, Clariant MOWIOL 15-79, MOWIOL lic acid is used as an amine reactant, the molar equivalents of US 8,501,838 B2 23 24 ammonium ion may or may not be equal to the molar equiva polycarboxylic acid reactant(s). In another variation, the lents of acid salt groups present on the polycarboxylic acid. In number of molar equivalents of hydroxyl groups present on one illustrative example, an ammonium salt may be monoba the carbohydrate reactant(s) is about ten-fold greater than the sic, dibasic, or tribasic when a tricarboxylic acid is used as a number of molar equivalents of acid salt groups present on the polycarboxylic acid reactant. Thus, the molar equivalents of 5 polycarboxylic acid reactant(s). In yet another variation, the the ammonium ion may be present in an amount less than or number of molar equivalents of hydroxyl groups present on about equal to the molar equivalents of acid salt groups the carbohydrate reactant(s) is about sixfold greater than the present in a polycarboxylic acid. Accordingly, the salt can be number of molar equivalents of acid salt groups present on the monobasic or dibasic when the polycarboxylic acid reactant polycarboxylic acid reactant(s). is a dicarboxylic acid. Further, the molar equivalents of 10 ammonium ion may be present in an amount less than, or In other embodiments of the invention, a binder that is about equal to, the molar equivalents of acid salt groups already cured can disposed on a material to be bound. As present in a polymeric polycarboxylic acid, and so on and so indicated above, most cured binders will typically contain water-insoluble melanoidins. Accordingly, these binders will forth. When a monobasic salt of a dicarboxylic acid is used, or also be water-resistant thermoset binders. when a dibasic salt of a tricarboxylic acid is used, or when the 15 molar equivalents of ammonium ions are present in an As discussed below, various additives can be incorporated amount less than the molar equivalents of acid salt groups into the binder composition. These additives give the binders present in a polymeric polycarboxylic acid, the pH of the of the present invention additional desirable characteristics. binder composition may require adjustment to achieve alka For example, the binder may include a silicon containing linity. coupling agent. Many silicon-containing coupling agents are The uncured, formaldehyde-free, thermally-curable, alka commercially available from the Dow-Corning Corporation, line, aqueous binder composition can be used to fabricate a Petrarch Systems, and by the General Electric Company. number of different materials. In particular, these binders can Illustratively, the silicon-containing coupling agent includes be used to produce or promote cohesion in non or loosely compounds Such as silylethers and alkylsilyl ethers, each of assembled matter by placing the binder in contact with the 25 which may be optionally Substituted, such as with halogen, matter to be bound. Any number of well known techniques alkoxy, amino, and the like. In one variation, the silicon can be employed to place the aqueous binder in contact with containing compound is an amino-Substituted silane, such as, the material to be bound. For example, the aqueous binder can gamma-aminopropyltriethoxy silane (General Electric Sili be sprayed on (for example during the binding glass fibers) or cones, SILOUESTA-1101: Wilton, Conn.; USA). In another applied via a roll-coat apparatus. These aqueous binders can 30 variation, the silicon-containing compound is an amino-Sub be applied to a mat of glass fibers (e.g., sprayed onto the mat), stituted silane, for example, aminoethylaminopropyltri during production offiberglass insulation products. Once the methoxy silane (Dow Z-6020: Dow Chemical, Midland, aqueous binder is in contact with the glass fibers the residual Mich.: USA). In another variation, the silicon containing heat from the glass fibers (note that the glass fibers are made compound is gamma-glycidoxypropyltrimethoxysilane from molten glass and thus contain residual heat) and the flow 35 (General Electric Silicones, SILOUEST A-187). In yet of air through the fibrous mat will evaporate (i.e., remove) another variation, the silicon-containing compound is an water from the binder. Removing the water leaves the remain n-propylamine silane (Creanova (formerly Huls America) ing components of the binder on the fibers as a coating of HYDROSIL 2627; Creanova: Somerset, N.J.; U.S.A.). Viscous or semi-Viscous high-solids liquid. This coating of The silicon-containing coupling agents are typically Viscous or semi-Viscous high-solids liquid functions as a 40 present in the binder in the range from about 0.1 percent to binder. At this point, the mat has not been cured. In other about 1 percent by weight based upon the dissolved binder words, the uncured binder functions to bind the glass fibers in Solids (i.e., about 0.1 percent to about 1 percent based upon the mat. the weight of the Solids added to the aqueous solution). In one Furthermore, it should be understood that the above application, one or more of these silicon-containing com described aqueous binders can be cured. For example, any of 45 pounds can be added to the aqueous uncured binder. The the above described aqueous binders can be disposed (e.g., binder is then applied to the material to be bound. Thereafter, sprayed) on the material to be bound, and then heated. For the binder may be cured if desired. These silicone containing example, in the case of making fiberglass insulation products, compounds enhance the ability of the binder to adhere to the after the aqueous binder has been applied to the mat, the matter the binder is disposed on, Such as glass fibers. Enhanc binder coated mat is transferred to a curing oven. In the curing 50 ing the binders ability to adhere to the matter improves, for oven the mat is heated (e.g., from about 300°F. to about 600° example, its ability to produce or promote cohesion in non or F.) and the binder cured. The cured binder is a formaldehyde loosely assembled Substance(s). free, water-resistant thermoset binder that attaches the glass A binder that includes a silicone containing coupling agent fibers of the mat together. Note that the drying and thermal can be prepared by admixing about 10 to about 50 weight curing may occur either sequentially, contemporaneously, or 55 percent aqueous solution of one or more polycarboxylic acid concurrently. reactants, already neutralized with an amine base or neutral With respect to making binders that are water-insoluble ized in situ, with about 10-50 weight percent aqueous solution when cured, it should be appreciated that the ratio of the of one or more carbohydrate reactants having reducing Sugar, number of molar equivalents of acid salt groups present on the and an effective amount of a silicon containing coupling polycarboxylic acid reactant(s) to the number of molar 60 agent. In one variation, one or more polycarboxylic acid equivalents of hydroxyl groups present on the carbohydrate reactants and one or more carbohydrate reactants, the latter reactant(s) may be in the range from about 0.04:1 to about having reducing Sugar, may be combined as Solids, mixed 0.15:1. After curing, these formulations result in a water with water, and the mixture then treated with aqueous amine resistant thermoset binder. In one variation, the number of base (to neutralize the one or more polycarboxylic acid reac molar equivalents of hydroxyl groups present on the carbo 65 tants) and a silicon-containing coupling agent to generate an hydrate reactant(s) is about twenty five-fold greater than the aqueous Solution 10-50 weight percent in each polycarboxy number of molar equivalents of acid salt groups present on the lic acid reactant and each carbohydrate reactant. US 8,501,838 B2 25 26 In another illustrative embodiment, a binder of the present where the composite wood board has one or more of the invention may include one or more corrosion inhibitors. following characteristics: These corrosion inhibitors prevent or inhibit the eating or a modulus of elasticity (MOE) of at least 1800 N/mm. wearing away of a Substance, such as, metal caused by chemi a bending strength (MOR) of at least 14 N/mm. cal decomposition brought about by an acid. When a corro an internal bond strength (IB) of at least 0.28 N/mm. sion inhibitor is included in a binder of the present invention, a thickness swelling after 24 hours in water at 20°C. of the binder's corrosivity is decreased as compared to the cor less than or equal to 12%, rosivity of the binder without the inhibitor present. In one a water absorption after 24 hours in water at 20° C. of embodiment, these corrosion inhibitors can be utilized to less than or equal to 40%. decrease the corrosivity of the glass fiber containing compo 10 2. The composite wood board of claim 1, wherein the sitions described herein. Illustratively, corrosion inhibitors composite wood board is formaldehyde free. include one or more of the following, a dedusting oil, or a 3. The composite wood board of claim 1, wherein the monoammonium phosphate, Sodium metasilicate pentahy composite wood board has a modulus of elasticity (MOE) of drate, melamine, tin(II) oxalate, and/or methylhydrogen sili at least about 1800 N/mm. cone fluid emulsion. When included in a binder of the present 15 4. The composite wood board of claim 3, wherein the invention, corrosion inhibitors are typically present in the modulus of elasticity (MOE) is at least about 2500 N/mm. binder in the range from about 0.5 percent to about 2 percent 5. The composite wood board of claim 1, wherein the by weight based upon the dissolved binder solids. composite wood board has a bending strength (MOR) of at By following the disclosed guidelines, one of ordinary skill least about 14 N/mm. in the art will be able to vary the concentrations of the reac 6. The composite wood board of claim 5, wherein the tants of the aqueous binder to produce a wide range of binder bending strength (MOR) is at least about 18 N/mm. compositions. In particular, aqueous binder compositions can 7. The composite wood board of claim 1, wherein the be formulated to have an alkaline pH. For example, a pH in composite woodboard has an internal bond strength (IB) of at the range from greater than or equal to about 7 to less than or least 0.28 N/mm. equal to about 10. Examples of the binder reactants that can be 25 8. The composite wood board of claim 7, wherein the manipulated include (i) the polycarboxylic acid reactant(s), internal bond strength (IB) is at least 0.4 N/mm. (ii) the amine base, (iii) the carbohydrate reactant(s), (iv) the 9. The composite wood board of claim 1, wherein the silicon-containing coupling agent, and (v) the corrosion composite woodboard swells less than or equal to about 12%, inhibitor compounds. Having the pH of the aqueous binders as measured by a change in thickness, after 24 hours in water (e.g. uncured binders) of the present invention in the alkaline 30 at 20° C. range inhibits the corrosion of materials the binder comes in 10. The composite wood board of claim 9, wherein the contact with, such as machines used in the manufacturing composite wood board has a water absorption after 24 hours process (e.g., in manufacturing fiberglass). Note this is espe in water at 20° C. of less than or equal to about 40%. cially true when the corrosivity of acidic binders is compared 11. The composite wood board of claim 1, wherein the to binders of the present invention. Accordingly, the lifespan. 35 composite wood board is a wood particleboard. of the machinery increases while the cost of maintaining 12. The composite wood board of claim 1, wherein the these machines decreases. composite wood board is an orientated Strandboard. Furthermore, standard equipment can be used with the 13. The composite wood board of claim 1, wherein the binders of the present invention, rather than having to utilize composite wood board is a medium density fiberboard. relatively corrosive resistant machine components that come 40 14. The composite wood board of claim 1, wherein the into contact with acidic binders. Such as stainless steel com organic binder comprises from about 8 to about 18% by ponents. Therefore, the binders disclosed herein decrease the weight (weight of dry resin to weight of dry wood particles) of cost of manufacturing bound materials. the composite wood board. What is claimed is: 15. The composite wood board of claim 1, wherein the 1. A composite wood board having dimensions of at least 45 organic binder comprises a product of a reaction including a 11.8 inchesx11.8 inches (30 cmx30 cm) comprising wood reducing Sugar. particles and an organic binder, wherein the organic binder is 16. The composite wood board of claim 15, wherein the substantially formaldehyde free and is selected from the organic binder comprises at least one Maillard reaction prod group consisting of uct. a binder based on a reducing Sugar, 50 17. The composite wood board of claim 1, wherein the a binder based on an aldehyde containing Sugar, organic binder comprises a product of a reaction of citric acid, a binder which includes at least one reaction product of a ammonia and dextrose. carbohydrate reactant and an amine reactant, 18. The composite wood board of claim 1, wherein the a binder which includes at least one reaction product of a composite wood board further comprises a wax. reducing Sugar and an amine reactant, 55 19. The composite wood board of claim 18, wherein the a binder which includes at least one reaction product of a wax comprises from about 0.1 to about 2% by weight of the carbohydrate reactant and a polycarboxylic acid ammo composite wood board. nium salt reactant, and 20. The composite wood board of claim 1, wherein the a binder which includes at least one reaction product from organic binder is a bioresin. a Maillard reaction; k k k k k