WO2018023095A1 - Procédés de fabrication de produits composites avec des liants contenant des isocyanates bloqués - Google Patents

Procédés de fabrication de produits composites avec des liants contenant des isocyanates bloqués Download PDF

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Publication number
WO2018023095A1
WO2018023095A1 PCT/US2017/044552 US2017044552W WO2018023095A1 WO 2018023095 A1 WO2018023095 A1 WO 2018023095A1 US 2017044552 W US2017044552 W US 2017044552W WO 2018023095 A1 WO2018023095 A1 WO 2018023095A1
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WIPO (PCT)
Prior art keywords
binder
aldehyde
blocked isocyanate
group
based resin
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PCT/US2017/044552
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English (en)
Inventor
Arun Narayan
Jack W. TRIEU
David F. Townsend
Shahid P. Qureshi
Charles Chan
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Georgia-Pacific Chemicals Llc
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Publication of WO2018023095A1 publication Critical patent/WO2018023095A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/8096—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with two or more compounds having only one group containing active hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/54—Polycondensates of aldehydes
    • C08G18/542—Polycondensates of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds
    • C08G18/8067—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds phenolic compounds

Definitions

  • Embodiments described generally relate to processes for making composite products. More particularly, such embodiments relate to processes for making composite products with a binder that can include one or more aldehyde-based resins and one or more blocked isocyanates, resinated furnishes that include the binder, and the composite products made with the binder.
  • Sheets or mats of non-woven fibers have many applications in the building materials industry.
  • Fiberglass mats are typically used in, among others, insulation materials, flooring products, wall panel products, and roofing products. Fiberglass mats are usually made commercially by a wet-laid process that involves the addition of a binder or adhesive solution to a glass fiber mat to bind and hold the fibers together.
  • Tear strength provides an estimate as to the ability of a roofing product, such as a shingle incorporating the fiberglass mat, to resist wind forces. As the tear strength of a fiberglass mat increases, the level of wind forces the roofing product can resist also increases, thereby providing a more reliable and durable roofing product. Frequently, binders used to make fiberglass mats do not produce fiberglass mats that meet minimum tear strength specifications required for use in roofing applications.
  • the process for making a composite product can include combining a plurality of substrates and a binder to produce a resinated furnish.
  • the binder can include an aldehyde-based resin and a blocked isocyanate.
  • the blocked isocyanate can have a diisocyanate base structure with a first urethane group and a second urethane group.
  • the first urethane group can include a polyoxyalkylene group.
  • the second urethane group can include an aryloxy group.
  • the process can also include curing the binder in the resinated furnish to produce a composite product.
  • the resinated furnish can include a plurality of substrates, and a binder that can include an aldehyde-based resin and a blocked isocyanate.
  • the blocked isocyanate can have a diisocyanate base structure with a first urethane group and a second urethane group.
  • the first urethane group can include a polyoxyalkylene group and the second urethane group can include an aryloxy group.
  • the composite product can include a plurality of substrates and a cured binder.
  • the binder Prior curing, can include an aldehyde-based resin and a blocked isocyanate.
  • the blocked isocyanate can have a diisocyanate base structure with a first urethane group and a second urethane group.
  • the first urethane group can include a polyoxyalkylene group and the second urethane group can include an aryloxy group.
  • the binder can include one or more aldehyde-based resins and one or more blocked isocyanates.
  • the blocked isocyanate can have a diisocyanate base structure with a first urethane group and a second urethane group.
  • the first urethane group can be, include, or contain a polyoxyalkylene group and the second urethane group can be, include, or contain an aryloxy group.
  • the binder can be produced by mixing, blending, or otherwise combining one or more blocked isocyanates and one or more aldehyde-based resins.
  • the binder can also include one or more solvents or diluents.
  • the binder can be produced by mixing, blending, or otherwise combining one or more blocked isocyanates, one or more aldehyde-based resins, and one or more solvents.
  • a plurality of substrates and the binder can be mixed, blended, or otherwise combined to produce a resinated furnish.
  • the binder in the resinated furnish can be cured to produce a composite product.
  • the polyoxyalkylene group in the first urethane group of the blocked isocyanate can be a relatively long and flexible unit within the overall binder, which can decrease the crosslinking density and, hence, can increase the elasticity and/or impact resistance capability.
  • the aryloxy group in the second urethane group of the blocked isocyanate can be removed to provide an unblocked isocyanate group that is reactive with the aldehyde-based resin when the binder is cured.
  • the blocked isocyanate Prior to curing the binder, can be relatively inert to water as opposed to traditional "non-blocked" isocyanates that are typically highly reactive to water. The blocked isocyanate, therefore, is more stable than the traditional isocyanates when mixed with the aldehyde-based resin and, if present, the solvent and stored as a component of the binder.
  • the blocked isocyanate when mixed, blended, or otherwise combined with the aldehyde-based resin and, if present, the solvent, is compatible with and does not change or does not substantially change the storage stability of the aldehyde-based resin.
  • the storage stability of the binder that includes the aldehyde-based resin, the blocked isocyanate, and, optionally, the solvent can have the same storage stability as a comparative binder that includes that same aldehyde-based resin and, optionally, the same solvent, but no blocked isocyanate.
  • the storage stability of the binder that includes the aldehyde-based resin, the blocked isocyanate, and, optionally, the solvent can be reduced by less than 30%, less than 25%, less than 20%, less than 15%), less than 10%>, less than 8%>, less than 6%>, less than 5%, less than 4%, less than 3%, less than 2%, or less than 1% as compared to the comparative binder that includes that same aldehyde-based resin and, optionally, the same solvent, but no blocked isocyanate.
  • the first urethane group can be or include a reaction product between a first isocyanate group on the diisocyanate base structure and a polyalkylene glycol.
  • Illustrative polyalkylene glycols that can be used to produce the blocked isocyanate can be or include, but are not limited to, one or more of: a polymethylene glycol, a polyethylene glycol, a polypropylene glycol, a copolymer of ethylene oxide and propylene oxide, a polybutylene glycol, a polypentylene glycol, copolymers thereof, or any mixture thereof.
  • the polyalkylene glycol can have or include, but is not limited to, one or more of: oxym ethylene units, oxy ethylene units, oxypropylene units, oxybutylene units, oxypentylene units, isomers thereof, or any mixture thereof.
  • the polyalkylene glycol can be or include one or more compounds having the chemical formula: H[-OR 1 -] n OR 2 , where each R 1 can be a C1-C5 alkylene; R 2 can be hydrogen or a C1-C20 alkyl; and n can be a number of 1 to about 100.
  • each R 1 can be a C1-C4 alkylene, such as methylene, ethylene, propylene, or butylene;
  • R 2 can be hydrogen or a C1-C4 alkyl, such as methyl, ethyl, propyl, or butyl;
  • n can be a number of 5 to about 50.
  • R 1 can be propylene and n can be a number of 5, 8, or 10 to about 15, about 20, about 30, or about 40.
  • the number n can be of 5 to about 40, 6 to about 37, 6 to about 24, 6 to about 12, or 6 to about 10.
  • the second urethane group can be or include a reaction product between a second isocyanate group on the diisocyanate base structure and a phenolic compound.
  • Illustrative phenolic compounds that can be used to produce the blocked isocyanate can be or include, but are limited to, one or more of: phenol; methylphenol, including 2-methylphenol (o-cresol), 3- methylphenol (m-cresol), or 4-methylphenol (p-cresol); dimethylphenol, including 2,3- dimethylphenol, 2,4-dimethylphenol, 2, 5 -dimethylphenol, 2,6-dimethylphenol, 3,4- dimethylphenol, or 3,6-dimethylphenol; benzenediol, including, 1,2-benzenediol, 1,3- benzenediol (resorcinol), 1,4-benzenediol; or any mixture thereof.
  • the phenolic compound can be or include one or more compounds having the chemical formula: HOC6HxR 3 (5-x), where each R 3 can be a substituted or unsubstituted linear, branched, cyclic, heterocyclic, or aromatic hydrocarbyl group; and x can be an integer of 0, 1, 2, 3, 4, or 5.
  • R 3 can be alkyl, alkenyl, alkynyl, phenyl, aryl, alkanol, alkoxyl, silyl, or halogen substitutes thereof. For example, if R 3 is an alkyl group, then R 3 can be a C1-C5 alkyl.
  • each R 3 can be a C1-C5 alkyl; and x can be 0, 1, or 2. In other examples, each R 3 can be methyl, ethyl, propyl, butyl, isomers thereof, or halogen substitutes thereof; and x can be 1 or 2.
  • Isocyanates that can be used to produce the blocked isocyanate can be or include one or more monoisocyanates and/or one or more polyisocyanates.
  • Polyisocyanates can be or include diisocyanates, triisocyanates, tetraisocyanates, or isocyanate compounds with five or more isocyanate groups.
  • Illustrative isocyanates can be or include, but are not limited to, toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexam ethylene diisocyanate, w-phenylene diisocyanate, /?-phenylene diisocyanate, bitolylene diisocyanate, cyclohexane diisocyanate (CUDI), bis(isocyanatom ethyl) cyclohexane (H 6 XDI), dicyclohexylmethane diisocyanate (H12MDI), dimer acid diisocyanate (DDI), trimethyl hexamethylene diisocyanate, lysine diisocyanate, methyl ester of lysine diisocyanate, methyl cyclohexane diisocyanate, 1,5-napthalene diisocyanate, xylylene diisocyanate, xylene
  • the blocked isocyanate can have the chemical formula:
  • OR 4 can be the polyoxyalkylene group and R 5 , R 6 , R 7 , R 8 , and R 9 can independently be hydrogen or a substituted or unsubstituted linear, branched, cyclic, heterocyclic, or aromatic hydrocarbyl group.
  • R 5 , R 6 , R 7 , R 8 , or R 9 is a substituted or unsubstituted linear, branched, cyclic, heterocyclic, or aromatic hydrocarbyl group
  • R 5 , R 6 , R 7 , R 8 , or R 9 can independently be alkyl, alkenyl, alkynyl, phenyl, aryl, alkanol, alkoxyl, or halogen substitutes thereof.
  • R 5 , R 6 , R 7 , R 8 , or R 9 is an alkyl group, then R 6 , R 7 , R 8 , or R 9 can independently be a C1-C5 alkyl.
  • R 5 , R 6 , R 7 , R 8 , and R 9 can independently be hydrogen or a C1-C5 alkyl.
  • each of R 5 , R 6 , R 7 , R 8 , and/or R 9 can independently be hydrogen, methyl, ethyl, propyl, butyl, pentyl, trifluoromethyl, trimethylsilyl, isomers thereof, or halogen substitutes thereof.
  • R 5 , R 6 , R 8 , or R 9 can be hydrogen; and R 7 can be methyl, ethyl, propyl, butyl, or trifluoromethyl.
  • the polyoxyalkylene group OR 4 can have the chemical formula: [-OR 1 -] n OR 2 , where each R 1 can independently be a C1 -C5 alkylene, and R 2 can be hydrogen or a C1-C20 alkyl, and n can be the number of oxyalkyene monomer units (OR 1 ), such as an integer of 1 to about 100.
  • n can be 1, 2, 3, 4, 5, 6, 7 8, 9, 10, 1 1, 12, 13, 14, or 15 to about 18, about 20, about 24, about 30, about 36, about 40, about 48, about 50, about 60, about 70 about 80, about 90, or about 100.
  • n can be 2 to about 100; 2 to about 50; 2 to about 40; 2 to about 38; 2 to about 34; 2 to about 30; 2 to about 24; 2 to about 20; 2 to about 14; 5 to about 50; 5 to about 40; 5 to about 38; 5 to about 30; 5 to about 24; 5 to about 20; 5 to about 14; 8 to about 40; 5 to about 38; 8 to about 30; 8 to about 24; 8 to about 18; about 10 to about 50; about 10 to about 40; about 10 to about 30; about 10 to about 20; about 20 to about 50; or about 30 to about 40.
  • the polyoxyalkylene group OR 4 and/or the oxyalkylene units OR 1 can be derived or otherwise produced from one or more polyalkylene glycols and/or one or more other types of polyoxyalkylenes.
  • the polyoxyalkylene group OR 4 can be derived or otherwise produced from a polyoxypropylene glycol (POPG) or a polyoxyethylene glycol (POEG).
  • POPG polyoxypropylene glycol
  • POEG polyoxyethylene glycol
  • the polyoxyalkylene group OR 4 and/or the oxyalkylene units OR 1 can be or include polyoxymethylene, polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxypentylene, or any mixture thereof.
  • each R 1 can independently be a C1 -C4 alkylene
  • R 2 can be hydrogen or a CI -CI 8 alkyl
  • n can be a number of 5 to about 50.
  • the polyoxyalkylene group OR 4 and/or the oxyalkylene units OR 1 contained in the first urethane group of the blocked isocyanate can be a relatively long and flexible group or unit.
  • the polyoxyalkylene group OR 4 contained in the first urethane group of the blocked isocyanate can stay bonded thereto during and after curing and can provide greater elasticity and/or impact resistance in the cured resin and the composite product containing the cured resin due having a relatively long and flexible length.
  • the aryloxy group OC 6 R 5 R 6 R 7 R 8 R 9 contained in the second urethane group of the blocked isocyanate can provide more stability to the diisocyanate base structure of the blocked isocyanate against water than if the isocyanate group remained unblocked.
  • the greater stability due to the aryloxy group blocking the isocyanate provides a longer shelf life for the binder that contains the blocked isocyanate mixed with the aldehyde-based resin and the solvent.
  • the blocked isocyanate can be relatively inert to water contained in the binder at ambient temperatures (e.g., about 20°C to about 30°C).
  • the aryloxy group can be removed by protonation via the amine group on the aldehyde-based resin to produce a phenolic compound product and the isocyanate bonded to the aldehyde-based resin as a portion of the cured resin.
  • the blocked isocyanate can have the chemical formula:
  • OR 4 can be the polyoxyalkylene group and R 7 can be the C1-C5 alkyl.
  • OR 4 can be a polyoxypropylene group and R 7 can be methyl.
  • the blocked isocyanate can be or include an isocyanate prepolymer derived or otherwise produced from one or more polyoxypropylene glycols (POPG) and toluene diisocyanate (TDI) that are blocked by an alkylphenol, such as DESMOCAP ® 11A and DESMOCAP ® 12 blocked isocyanates, commercially available from Covestro, AG, formerly known as Bayer Material Science, AG.
  • POPG polyoxypropylene glycols
  • TDI toluene diisocyanate
  • the blocked isocyanate can be or include blocked aliphatic polyisocyanates such as BAYHYDUR® BL XP 2706 and BAYHYDUR® BL 5335 blocked isocyanates, also commercially available from Covestro AG.
  • blocked aliphatic polyisocyanates such as BAYHYDUR® BL XP 2706 and BAYHYDUR® BL 5335 blocked isocyanates, also commercially available from Covestro AG.
  • the aldehyde-based resin can be or include, but is not limited to, one or more phenolic aldehyde resins, one or more melaminic aldehyde resins, one or more ureic aldehyde resins, one or more resorcinolic aldehyde resins, or any mixture thereof.
  • the aldehyde- based resin can be or include, but is not limited to, one or more of: a phenol-formaldehyde (PF) resin, a urea-formaldehyde (UF) resin, a phenol-urea-formaldehyde (PUF) resin, a melamine- formaldehyde (MF) resin, a melamine-urea-formaldehyde (MUF) resin, a phenol-melamine- formaldehyde (PMF) resin, a resorcinol-formaldehyde (RF) resin, a phenol-resorcinol- formaldehyde (PRF) resin, or any mixture thereof.
  • PF phenol-formaldehyde
  • UDF urea-formaldehyde
  • PEF phenol-urea-formaldehyde
  • MF melamine- formaldehyde
  • MRF melamine-urea-formaldehy
  • the aldehyde-based resin can include one or more PF resins, one or more UF resins, one or more PUF resins, or any mixture thereof. In other examples, the aldehyde-based resin can include one or more UF resins, one or more MF resins, one or more MUF resins, or any mixture thereof. In one or more examples, the aldehyde-based resin be or include one or more phenol-formaldehyde resole resins. In one or more examples, the aldehyde-based resin be or include one or more urea-formaldehyde resins.
  • Suitable processes for synthesizing the aldehyde-based resin can include both single step processes and multi-step or "programmed" processes (e.g., staged monomer/catalyst addition). While batch operations are generally the standard, continuous processes can also be used.
  • the aldehyde compound in the aldehyde-based resin can be or include one or more substituted aldehyde compounds, one or more unsubstituted aldehyde compounds, or any mixture of substituted and/or unsubstituted aldehyde compounds.
  • Illustrative aldehyde compounds can be or include, but are not limited to, aldehydes having the chemical formula RCHO, where R is hydrogen or a hydrocarbyl group.
  • Illustrative hydrocarbyl groups can include 1 carbon atom to about 8 carbon atoms.
  • Suitable aldehyde compounds can also include the so-called masked aldehydes or aldehyde equivalents, such as acetals or hemiacetals.
  • Illustrative aldehyde compounds can be or include, but are not limited to, formaldehyde, paraformaldehyde, cinnamaldehyde, tolualdehyde, acetaldehyde, propionaldehyde, butyraldehyde, furfural, benzaldehyde, retinaldehyde, glyoxal, malondi aldehyde, succindialdehyde, glutaraldehyde, phthaldehyde, derivatives thereof, or any mixture thereof.
  • Still other suitable formaldehyde compounds can include formaldehyde present in a prepolymer or precondensate, such as urea-formaldehyde condensate (UFC) or UF precondensate.
  • the phenolic compound when present in the aldehyde-based resin, can be or include phenol (also known as monohydroxybenzene), one or more substituted phenol compounds, one or more unsubstituted phenol compounds, or any combination or mixture of substituted and/or unsubstituted phenol compounds.
  • phenol also known as monohydroxybenzene
  • substituted phenol compounds one or more substituted phenol compounds
  • unsubstituted phenol compounds or any combination or mixture of substituted and/or unsubstituted phenol compounds.
  • Illustrative substituted phenolic compounds can include, but are not limited to, alkyl-substituted phenols such as the cresols and xylenols; cycloalkyl- substituted phenols such as cyclohexyl phenol; alkenyl-substituted phenols; aryl- substituted phenols such as p-phenyl phenol; alkoxy-substituted phenols such as 3,5-dimethyoxyphenol; aryloxy phenols such as p-phenoxy phenol; halogen-substituted phenols such as p- chlorophenol, or any mixture thereof.
  • Dihydric phenols such as catechol, resorcinol, hydroquinone, bisphenol A and bisphenol F also can also be used.
  • the phenolic compound can be or include, but is not limited to, resorcinol, phenol, catechol, hydroquinone, pyrogallol, 5-methylresorcinol, 5-ethylresorcinol, 5-propylresorcinol, 4-methylresorcinol, 4- ethylresorcinol, 4-propylresorcinol, resorcinol monobenzoate, resorcinol monosinate, resorcinol diphenyl ether, resorcinol monomethyl ether, resorcinol monoacetate, resorcinol dimethyl ether, phloroglucinol, benzoylresorcinol, resorcinol rosinate, alkyl substituted resorcinol, aralkyl substituted re
  • the aldehyde-based resin can be or include phenol, resorcinol, or a mixture thereof.
  • the aldehyde-based resin can include any combination or mixture of two or more phenolic compounds combined with one another and/or added independent of one another to the reaction mixture.
  • the phenol-aldehyde resin that can have an aldehyde, e.g., formaldehyde, to phenolic compound, e.g., phenol, molar ratio of about 0.5: 1, about 0.6: 1, about 0.7: 1, about 0.8: 1, about 0.85: 1, about 0.9: 1, about 0.95: 1, about 0.99: 1, or about 1 : 1 to about 1.1 : 1, about 1.3 : 1, about 1.5: 1, about 1.7: 1, about 1.9: 1, about 2: 1, about 2.1 : 1, about 2.3 : 1, about 2.5: 1, about 2.7: 1, or about 3 : 1.
  • aldehyde e.g., formaldehyde
  • phenol molar ratio of about 0.5: 1, about 0.6: 1, about 0.7: 1, about 0.8: 1, about 0.85: 1, about 0.9: 1, about 0.95: 1, about 0.99: 1, or about 1 : 1 to about 1.1 : 1, about 1.3 : 1, about 1.5: 1, about 1.7: 1, about 1.9
  • the phenol-formaldehyde resin can have a formaldehyde to phenol molar ratio of about 0.8: 1 to about 2.5: 1, about 0.8: 1 to about 2: 1, about 0.8: 1 to about 1.9: 1, about 0.8: 1 to about 1.5: 1, about 0.8: 1 to about 1.1 : 1, about 0.8: 1 to about 1 : 1, about 0.8: 1 to about 0.95: 1, about 0.8: 1 to about 0.9: 1, about 0.9: 1 to about 2.3 : 1, about 0.9: 1 to about 2: 1, about 0.9: 1 to about 1.9: 1, about 0.9: 1 to about 1.5: 1, about 0.9: 1 to about 1.1 : 1, about 0.9: 1 to about 1 : 1, about 1 : 1 to about 2.5: l, about 1 : 1 to about 2: l, about 1 : 1 to about 1.5: 1, about 1.1 : 1 to about 2.5 : 1, about 1.1 : 1 to about 2: l, about 1.1 : 1 to about 1.5: 1, about 1.1
  • the ureic compound when present in the aldehyde-based resin, can be or include urea.
  • the urea can be provided in many forms.
  • solid urea such as prill, and/or urea solutions, typically aqueous solutions, can be used to prepare the aldehyde-based resin.
  • the urea can be combined with another moiety, for example, formaldehyde and/or urea-formaldehyde adducts that can be in an aqueous solution. Any form of urea or urea in combination with formaldehyde can be used to make a urea-formaldehyde resin.
  • urea-formaldehyde resins can be prepared from urea and formaldehyde monomers or from urea-formaldehyde precondensates.
  • Illustrative urea-formaldehyde products can include, but are not limited to, UFC and UF precondensate. These types of UF products are discussed and described in U.S. Patent Nos. 5,362,842 and 5,389,716. Any of these forms of urea, alone or in any combination, can be used to prepare any of the urea-aldehyde resins.
  • Suitable urea-aldehyde resins can have a molar ratio of formaldehyde to urea of about 1.1 : 1, about 1.3 : 1, about 1.5: 1, about 1.7: 1, about 2: 1, or about 2.2: 1 to about 2.4: 1, about 2.6: 1, about 2.8: 1, about 3 : 1, about 3.3 : 1, about 3.5: 1, about 3.7: 1, or about 4: 1.
  • the urea-aldehyde resin can have a solids content of about 40 wt%, about 45 wt%, about 50 wt%, or about 55 wt% to about 60 wt%, about 65 wt%, about 70 wt%, or about 75 wt%.
  • the urea-aldehyde resin can have a viscosity of about 50 cps, about 100 cps, about 200 cps, about 300 cps, about 400 cps, or about 500 cps to about 700 cps, about 900 cps, about 1,200 cps, about 1,500 cps, about 1,800 cps, or about 2,000 cps at a solids content of about 60 wt% and at a temperature of about 25°C.
  • the urea-aldehyde resin can have a pH of about 7, about 7.5, about 8, about 8.5, or about 9 to about 9.5, about 10, about 11, or about 12.
  • the urea-aldehyde resin can have a free aldehyde content of less than 5 wt%, less than 4 wt%, less than 3 wt%, less than 2 wt%, or less than 1 wt%.
  • the urea-aldehyde resin can have a water dilutability of about 1 : 1, about 5: 1, about 10: 1, or about 20: 1 to about 50: 1, about 65: 1, about 85: 1, about 100: 1 or greater.
  • the reactants for making a urea-aldehyde resin can also include one or more resin modifiers.
  • resin modifiers can include, but are not limited to, ammonia, alkanolamines, polyamines, such as an alkyl primary diamine, e.g., ethyl enediamine (EDA), or any mixture thereof.
  • Additional resin modifiers such as melamine, ethylene ureas, primary amines, secondary amines, and tertiary amines, for example, dicyanodi amide, can also be incorporated into the urea-aldehyde resin.
  • the amount of each resin modifier in the reaction mixture can be from about 0.05 wt%, about 0.1 wt%, about 0.5 wt%, or about 0.7 wt% to about 1 wt%, about 3 wt%, about 5 wt%, about 10 wt%, about 15 wt%, or about 20 wt%, based on a solids weight of the urea-aldehyde resin.
  • These modifiers can promote hydrolysis resistance, polymer flexibility, and/or lower aldehyde emissions in the cured binder. Further urea additions for purposes of scavenging free aldehydes or as a diluent also can also be used.
  • the melaminic compound when present can be provided in many forms.
  • solid melamine such as prill, and/or melamine solutions can be used.
  • melamine is specifically mentioned, the melamine can be totally or partially replaced with other aminotriazine compounds.
  • suitable aminotriazine compounds can include substituted melamines, or cycloaliphatic guanamines, or mixtures thereof.
  • Substituted melamines include the alkyl melamines and aryl melamines which can be mono-, di-, or tri-substituted.
  • each alkyl group can be a C1-C6 alkyl, such as a C1-C4 alkyl.
  • Illustrative alkyl-substituted melamines can be or include, but are not limited to, monomethyl melamine, dimethyl melamine, trimethyl melamine, monoethyl melamine, and/or l-methyl-3- propyl-5-butyl melamine.
  • Illustrative aryl -substituted melamines can include one or two phenyl groups, such as, but not limited to, one or more monophenyl melamines and/or one or more diphenyl melamines.
  • the aldehyde and the melamine compounds can be reacted in an aqueous mixture under alkaline conditions.
  • the melamine-aldehyde resin can be made using a molar excess of formaldehyde (along with any other reactive aldehyde components) relative to the melaminic compound, e.g., melamine.
  • the molar ratio of formaldehyde to melamine (F:M) in the melamine-formaldehyde resin can be about 0.3 : l to about 6: l, about 0.5: l to about 4: l, about 0.8: l to about 5: l, about 1.1 : 1 to about 6: 1, about 1.3 to about 5: 1, or about 1.5: 1 to about 4: 1.
  • such resins can typically contain a low level of residual or "free" melamine and can have a greater amount of residual "free", i.e., unreacted aldehyde.
  • the melamine- aldehyde resin can have a free aldehyde content of about 0.2 wt% to about 18 wt% of the aqueous melamine-aldehyde resin.
  • a suitable melamine-formaldehyde resin can be or include GP 4878 MF resin, commercially available from Georgia Pacific Chemicals LLC.
  • Melamine-urea-formaldehyde resin can be prepared by reacting formaldehyde with urea and then with melamine, by reacting formaldehyde with melamine and then urea, or by reacting formaldehyde with urea and melamine under controlled molar ratios and reaction conditions.
  • the melamine-urea-formaldehyde resin can have a molar ratio of formaldehyde to the sum of moles for urea and melamine F:(U+M) of about 0.3 : 1, about 0.5: 1, or about 1 : 1 to about 2: 1, about 4: 1, or about 5: 1.
  • Illustrative melamine-urea-formaldehyde resins can be or include those discussed and described in U.S. Patent Nos.: 8,754,185; 9,133,374; 9, 169,364; and 9,217,065.
  • the aldehyde-based resins can have reactive methylol groups which upon curing can form methylene or ether linkages.
  • Illustrative methylol -containing adducts can be or include, but are not limited to, ⁇ , ⁇ '-dimethylol; dihydroxymethylolethylene; N,N'bis(methoxymethyl); ⁇ , ⁇ '-dimethylolpropylene; 5,5-dimethyl-N,N'dimethylolethylene; or N,N'-dimethylolethylene.
  • the aldehyde-based resin when mixed with water, can form an aqueous solution, dispersion, suspension, or other mixture that can have a pH of about 7, about 8, about 9, or about 10 to about 11, about 12, or about 13 at a temperature of about 25°C.
  • an aldehyde-based resin having a water content of about 40 wt% to about 70 wt% can form an aqueous solution, dispersion, suspension, or other mixture that can have a pH of about 8 to about 11, about 9 to about 10.5, about 9.5 to about 11.5, about 10 to about 12, about 10.5 to about 12.5, about 10.5 to about 11, about 10.6 to about 12, about 11 to about 12, or about 11.5 to about 12.5 at a temperature of about 25°C.
  • the aldehyde-based resin can be a thermosetting resin.
  • the phenol-formaldehyde resin can be a phenol-formaldehyde resole resin having a molar ratio of formaldehyde to phenol of 1 or greater.
  • the aldehyde-based resin can be a thermoplastic resin.
  • the aldehyde-based resin includes the phenol-formaldehyde resin
  • the phenol- formaldehyde resin can be a phenol-formaldehyde novolac resin having a molar ratio of formaldehyde to phenol of less than 1.
  • Phenol-formaldehyde resins that can be used to make the binder can include GPR 5815 resin and/or GP RESI-BO D ® 5772 plywood neat resin, both are commercially available from Georgia-Pacific Chemical LLC, a phenol-formaldehyde resin powder, such as WOOD WELD ® 190C42 spray-dried OSB binder, commercially available from Georgia-Pacific Chemical LLC, or a mixture thereof.
  • Urea-formaldehyde resins that can be used to make the binder can include GP ® 500A15, GP ® 245G93, and GP ® 6300, which are commercially available from Georgia-Pacific Chemicals LLC.
  • the optional solvent in part or in whole, can be added together or separately with the aldehyde-based resin and/or the blocked isocyanate to produce the binder.
  • the solvent, the aldehyde-based resin, and the blocked isocyanate can each be separately added to the plurality of substrates to produce the binder in the presence of the substrates.
  • a mixture of the aldehyde-based resin and at least a portion of the solvent can combined with the blocked isocyanate to produce the binder.
  • a mixture of the aldehyde-based resin and a first portion of the solvent can combined with a mixture of the blocked isocyanate and a second portion of the solvent to produce the binder.
  • the solvent can be or include one or more organic solvents, one or more aqueous solvents, or any mixture thereof.
  • the solvent can also include one or more solutes dissolved in the solvent and/or one or more undissolved compounds suspended, flocculated, or otherwise contained in the solvent.
  • the solvent can be or include water, one or more alcohols, one or more aromatic compounds, one or more glycols, one or more glycol ethers, one or more ethers, one or more alkanes, or any mixture thereof.
  • the solvent can be or include water, one or more alkanols, one or more cycloalkyl alcohols, one or more aromatic alcohols, one or more glycols, one or more glycol ethers, one or more ethers, one or more alkanes, one or more non-alchol aromatic compounds, or any mixture thereof.
  • the optional solvent can be or include solvents, precursors or reactants, products (including secondary products or byproducts), or other remnants from of the aldehyde-based resin and/or the blocked isocyanate.
  • the solvent can be or include one or more solvents and/or one or more monomer precursors used to produce, stabilize, or contain the aldehyde-based resin.
  • the solvent can also be or include one or more solvents and/or one or more reactants used to produce, stabilize, or contain the blocked isocyanate.
  • the alkanol can be or include one or more mono alcohols and/or one or more polyols.
  • the alkanol can be a primary alcohol, a secondary alcohol, and/or a tertiary alcohol.
  • Illustrative mono alcohols can be or include one or more CI -CIO alcohols, such as one or more C1-C8 alcohols or one or more C1-C5 alcohols.
  • Illustrative polyols can be or include one or more diols, one or more triols, and/or one or more glycol ethers.
  • Illustrative alkanols can be or include, but are not limited to, one or more of: methanol, ethanol, n-propanol, isopropanol, n- butanol, isobutanol, sec-butanol, tert-butanol, pentanol, hexanol, cyclohexanol, heptanol, octanol, nonanol, decanol, ethylene glycol, propylene glycol, butylene glycol, glycerol, erythritol, isomers thereof, or any mixture thereof.
  • Illustrative glycol ethers can include, but are not limited to, ethylene glycol methyle ether acetate (2-methoxyethyl acetate), ethylene glycol monoethyl ether acetate (2-ethoxy ethyl acetate), ethylene glycol monobutyl ether acetate (2-butoxyethyl acetate), propylene glycol methyl ether acetate (l-methoxy-2-propanol acetate or "MP A”), propylene glycol monom ethyl ether acetate (1,2-propanediol monom ethyl ether acetate or "PGMEA”), or any mixture thereof.
  • MP A propylene glycol monom ethyl ether acetate
  • PGMEA propylene glycol monom ethyl ether acetate
  • Aromatic alcohols can be or include unreacted monomers or free alcohols remaining after producing the aldehyde-based resin.
  • the aldehyde-based resin is or contains a phenolic aldehyde resin, such as a phenol formaldehyde resin, then the aromatic alcohol can be free phenol.
  • the aldehyde-based resin is or contains a resorcinolic aldehyde resin, such as a resorcinol formaldehyde resin, then the aromatic alcohol can be free resorcinol.
  • Illustrative aromatic alcohols can be or include, but are not limited to, one or more of: phenol; 1,2-benzenediol; 1,3-benzenediol (resorcinol); 1,4-benzenediol; 2- methylphenol (o-cresol); 3-methylphenol (m-cresol); 4-methylphenol (p-cresol); or any mixture thereof.
  • the alkanol can be or include isopropanol and the aromatic alcohol can be or include free phenol.
  • Illustrative aromatics can be or include, but are not limited to, benzene, toluene, xylene, ethylbenzene, cumene, mesitylene, or any mixture thereof.
  • the weight of the aldehyde-based resin is the solids weight of the aldehyde-based resin and excludes the weights of any water, any other solvent, and any free or residual monomers used to make the aldehyde-based resin, unless otherwise noted.
  • the weight of the blocked isocyanate is the solids weight of the blocked isocyanate and excludes the weights of any water and any other solvent, unless otherwise noted.
  • a combined weight of the aldehyde-based resin and the blocked isocyanate means a sum of the solids weight of the aldehyde-based resin and the solids weight of the blocked isocyanate.
  • a combined weight of the aldehyde-based resin, the solvent, and the blocked isocyanate means a sum of the solids weight of the aldehyde-based resin, the weight of the solvent, and the solids weight of the blocked isocyanate. Accordingly, if any water or other liquid or solvent is present in the aldehyde-based resin, that water or other liquid or solvent would be considered part of the solvent once the aldehyde-based resin has been combined with the blocked isocyanate.
  • the solids weight, solids concentration, or solids content of a composition e.g., the aldehyde-based resin or the blocked isocyanate, as understood by those skilled in the art, can be measured by determining the weight loss upon heating a small sample, e.g., about 5 grams to about 8 grams, to a suitable temperature, e.g., about 105°C, and a time sufficient to remove the liquid therefrom. By measuring the weight of the sample before and after heating, the percent solids in the sample can be directly calculated or otherwise estimated.
  • the binder can also include one or more copolymers that includes one or more vinyl aromatic derived units and at least one of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride.
  • the copolymer can be or include a styrene maleic anhydride (SMA) copolymer.
  • SMA styrene maleic anhydride
  • Styrene-maleic anhydride copolymers are composed of alternating styrene and maleic anhydride monomer units, arranged in random, alternating, or block form.
  • suitable SMA copolymers can have the following generalized formula in the unneutralized form:
  • p and q are positive numbers in a ratio (p:q) that of about 0.5: 1 to about 5: 1.
  • Modified styrene-maleic anhydride copolymers such as copolymers that are partially esterified or copolymers containing sulfonate groups on the benzene ring, also can be used.
  • the styrene-maleic anhydride copolymers can have weight average molecular weight from about 1,000, about 20,000, about 60,000, about 80,000, about 100,000, or about 120,000 to about 200,000, about 300,000, about 400,000, or about 500,000.
  • Such unneutralized styrene-maleic anhydride (SMA) copolymers can generally be insoluble in water, however after a sufficient extent of neutralization using an alkaline substance, such as a hydroxide, e.g., sodium hydroxide, potassium hydroxide, ammonium hydroxide, lithium hydroxide, cesium hydroxide, or any mixture thereof; a carbonate, e.g., sodium carbonate, potassium carbonate, ammonium carbonate, or any mixture thereof; ammonia or an amine; or any mixture thereof, the styrene-maleic anhydride copolymers can become soluble in water.
  • an alkaline substance such as a hydroxide, e.g., sodium hydroxide, potassium hydroxide, ammonium hydroxide, lithium hydroxide, cesium hydroxide, or any mixture thereof
  • a carbonate e.g., sodium carbonate, potassium carbonate, ammonium carbonate, or any mixture thereof
  • Any strongly basic alkali metal compound can be used for neutralizing the styrene-maleic anhydride, such as ammonium hydroxide, potassium hydroxide, sodium hydroxide, lithium hydroxide, cesium hydroxide, ammonium carbonate, potassium carbonate and/or sodium carbonate.
  • Illustrative copolymers of one or more vinyl aromatic derived units and at least one of and unsaturated carboxylic acid and an unsaturated carboxylic anhydride can be or include, but are not limited to, those discussed and described in U.S. Patent Nos. 5,914,365; 9,217,065; and 9, 169,364; and U.S. Patent Application Publication Nos. : 2011/0165398 and 2012/0252937.
  • the amount of components in the binder can be based on a combined weight, i.e., a combined solids weight, of the aldehyde-based resin and the blocked isocyanate.
  • the binder can include about 0.1 wt%, about 0.3 wt%, about 0.5 wt%, about 0.7 wt%, about 1 wt%, about 1.5 wt%, about 2 wt%, about 2.5 wt%, about 3 wt%, about 3.5 wt%, about 4 wt%, about 4.5 wt%, about 5 wt%, about 10 wt%, about 15 wt%, about 20 wt%, or about 25 wt% to about 30 wt%, about 35 wt%, about 38 wt%, about 40 wt%, about 43 wt%, about 45 wt%, about 48 wt%, about 50 wt%, about 53 wt%, about 55 wt%, about
  • the binder can include about 5 wt% to about 60 wt%, about 10 wt% to about 60 wt%, about 5 wt% to about 18 wt%, about 30 wt% to about 55 wt%, about 50 wt% to about 60 wt%, or about 32 wt% to about 60 wt% of the blocked isocyanate, based on the combined solids weight of the aldehyde-based resin and the blocked isocyanate.
  • the binder can include about 35 wt%, about 40 wt%, about 42 wt%, about 45 wt%, or about 47 wt% to about 50 wt%, about 52 wt%, about 55 wt%, about 57 wt%, about 60 wt%, about 62 wt%, about 65 wt%, about 70 wt%, about 75 wt%, about 80 wt%, about 85 wt%, about 90 wt%, about 95 wt%, about 97 wt%, about 98 wt%, about 99 wt%, or about 99.9 wt% of the aldehyde-based resin, based on the combined solids weight of the aldehyde-based resin and the blocked isocyanate.
  • the binder can include about 40 wt% to about 95 wt%, about 40 wt% to about 80 wt%, about 40 wt% to about 60 wt%, about 40 wt% to about 50 wt%, about 55 wt% to about 95 wt%, about 75 wt% to about 95 wt%, or about 80 wt% to about 90 wt% of the aldehyde-based resin, based on the combined solids weight of the aldehyde-based resin and the blocked isocyanate.
  • the binder can include about 5 wt% to about 60 wt% of the blocked isocyanate and about 40 wt% to about 95 wt% of the aldehyde-based resin, based on the combined solids weight of the aldehyde-based resin and the blocked isocyanate. In some examples, the binder can include about 5 wt% to about 18 wt% of the blocked isocyanate and about 82 wt% to about 95 wt% of the aldehyde-based resin, based on a combined weight of the aldehyde-based resin and the blocked isocyanate.
  • the binder can include about 35 wt% to about 50 wt% of the blocked isocyanate and about 50 wt% to about 65 wt% of the aldehyde-based resin, based on a combined weight of the aldehyde-based resin and the blocked isocyanate. In other examples, the binder can include about 45 wt% to about 65 wt% of the blocked isocyanate and about 35 wt% to about 55 wt% of the aldehyde-based resin, based on a combined weight of the aldehyde-based resin and the blocked isocyanate.
  • the binder can include about 8 wt% to about 15 wt% of the blocked isocyanate and about 85 wt% to about 92 wt% of the aldehyde-based resin, based on a combined weight of the aldehyde-based resin and the blocked isocyanate.
  • the amount of each component in the binder can also be based on a combined or total weight of the aldehyde-based resin, the solvent, and the blocked isocyanate.
  • the binder can include about 0.5 wt%, about 1 wt%, about 2 wt%, about 3 wt%, about 4 wt%, about 5 wt%, about 6 wt%, about 8 wt%, about 10 wt%, or about 12 wt% to about 15 wt%, about 18 wt%, about 20 wt%, about 23 wt%, about 25 wt%, about 28 wt%, about 30 wt%, about 33 wt%, about 35 wt%, about 38 wt%, about 40 wt%, or about 45 wt% of the blocked isocyanate, based on a combined weight of the aldehyde-based resin, the solvent, and the blocked isocyanate.
  • the binder can include about 0.5 wt% to about 45 wt%, about 1 wt% to about 40 wt%, about 1 wt% to about 10 wt%, about 2 wt% to about 8 wt%, about 20 wt% to about 30 wt%, about 20 wt% to about 40 wt%, or about 25 wt% to about 35 wt% of the blocked isocyanate, based on a combined weight of the aldehyde-based resin, the solvent, and the blocked isocyanate.
  • the binder can include about 10 wt%, about 15 wt%, about 20 wt%, about 22 wt%, or about 25 wt% to about 28 wt%, about 30 wt%, about 32 wt%, about 35 wt%, about 36 wt%, about 38 wt%, about 40 wt%, about 42 wt%, about 45 wt%, about 50 wt%, about 55 wt%, or about 60 wt% of the aldehyde-based resin, based on a combined weight of the aldehyde-based resin, the solvent, and the blocked isocyanate.
  • the binder can include about 10 wt% to about 60 wt%, about 20 wt% to about 50 wt%, about 20 wt% to about 30 wt%, about 25 wt% to about 45 wt%, about 25 wt% to about 35 wt%, about 30 wt% to about 40 wt% of the aldehyde-based resin, based on a combined weight of the aldehyde-based resin, the solvent, and the blocked isocyanate.
  • the binder can include about 20 wt%, about 25 wt%, about 30 wt%, about 35 wt%, about 37 wt%, or about 40 wt% to about 42 wt%, about 45 wt%, about 47 wt%, about 50 wt%, about 52 wt%, about 55 wt%, about 57 wt%, about 60 wt%, about 62 wt%, about 65 wt%, about 67 wt%, about 70 wt%, about 75 wt%, or about 80 wt% of the solvent, based on a combined weight of the aldehyde-based resin, the solvent, and the blocked isocyanate.
  • the binder can include about 20 wt% to about 80 wt%, about 30 wt% to about 70 wt%, about 30 wt% to about 60 wt%, about 30 wt% to about 50 wt%, about 40 wt% to about 60 wt%, about 40 wt% to about 50 wt%, or about 45 wt% to about 65 wt% of the solvent, based on a combined weight of the aldehyde-based resin, the solvent, and the blocked isocyanate.
  • the binder can include about 1 wt% to about 40 wt% of the blocked isocyanate, about 20 wt% to about 60 wt% of the aldehyde-based resin, and about 30 wt% to about 70 wt% of the solvent, based on a combined weight of the aldehyde-based resin, the solvent, and the blocked isocyanate.
  • the binder can include about 2 wt% to about 38 wt% of the blocked isocyanate, about 22 wt% to about 45 wt% of the aldehyde-based resin, and about 35 wt% to about 65 wt% of the solvent, based on a combined weight of the aldehyde-based resin, the solvent, and the blocked isocyanate.
  • the binder can include about 4 wt% to about 35 wt% of the blocked isocyanate, about 25 wt% to about 40 wt% of the aldehyde-based resin, and about 40 wt% to about 60 wt% of the solvent, based on a combined weight of the aldehyde-based resin, the solvent, and the blocked isocyanate.
  • the binder can include about 2 wt% to about 15 wt% of the blocked isocyanate, about 40 wt% to about 60 wt% of the aldehyde-based resin, and about 35 wt% to about 55 wt% of the solvent, based on a combined weight of the aldehyde-based resin, the solvent, and the blocked isocyanate.
  • the binder can include about 3 wt% to about 7 wt% of the blocked isocyanate, about 35 wt% to about 42 wt% of the aldehyde-based resin, and about 50 wt% to about 65 wt% of the solvent, based on a combined weight of the aldehyde-based resin, the solvent, and the blocked isocyanate.
  • the binder can include about 20 wt% to about 26 wt% of the blocked isocyanate, about 25 wt% to about 32 wt% of the aldehyde- based resin, and about 37 wt% to about 55 wt% of the solvent, based on a combined weight of the aldehyde-based resin, the solvent, and the blocked isocyanate.
  • the binder can include about 28 wt% to about 38 wt% of the blocked isocyanate, about 20 wt% to about 35 wt% of the aldehyde-based resin, and about 30 wt% to about 50 wt% of the solvent, based on a combined weight of the aldehyde-based resin, the solvent, and the blocked isocyanate.
  • the binder can include about 1 wt% to about 10 wt% of the blocked isocyanate, about 9 wt% to about 40 wt% of the aldehyde-based resin, and about 50 wt% to about 90 wt% of the solvent, based on a combined weight of the aldehyde-based resin, the solvent, and the blocked isocyanate.
  • the binder can include about 2 wt% to about 8 wt% of the blocked isocyanate, about 9 wt% to about 30 wt% of the aldehyde-based resin, and about 62 wt% to about 89 wt% of the solvent, based on a combined weight of the aldehyde-based resin, the solvent, and the blocked isocyanate.
  • the binder includes the copolymer of one or more vinyl aromatic derived units and at least one of: one or more unsaturated carboxylic acids and one or more unsaturated carboxylic anhydrides, e.g., a styrene-maleic anhydride copolymer
  • the binder can include about 0.1 wt%, about 2 wt%, about 5 wt%, about 7 wt%, or about 10 wt% to about 12 wt%, about 15 wt%, about 17 wt%, about 20 wt%, about 22 wt%, about 25 wt%, about 27 wt%, about 30 wt%, or greater of the copolymer, based on the combined solids weight of the aldehyde-based resin and the blocked isocyanate.
  • the binder can include about 0.1 wt% to about 15 wt%, about 0.5 wt% to about 5 wt%, about 1 wt% to about 8 wt%, about 1 wt% to about 20 wt%, about 3 wt% to about 10 wt%, about 5 wt% to about 20 wt%, about 10 wt% to about 25 wt%, or about 15 wt% to about 30 wt% of the copolymer, e.g., a styrene-maleic anhydride copolymer, based on the combined solids weight of the aldehyde-based resin and the blocked isocyanate.
  • the copolymer e.g., a styrene-maleic anhydride copolymer
  • the binder can include about 1 wt% to about 15 wt% of the blocked isocyanate, about 30 wt% to about 70 wt% of the aldehyde-based resin, about 5 wt% to about 59 wt% of the solvent, and about 0.1 wt% to about 10 wt% of the copolymer, e.g., a styrene- maleic anhydride copolymer, based on a combined weight of the aldehyde-based resin, the solvent, the blocked isocyanate, and the copolymer.
  • the copolymer e.g., a styrene- maleic anhydride copolymer
  • the binder can include about 1 wt% to about 10 wt% of the blocked isocyanate, about 40 wt% to about 65 wt% of the aldehyde-based resin, about 17 wt% to about 60 wt% of the solvent, and about 1 wt% to about 8 wt% of copolymer, e.g., a styrene-maleic anhydride copolymer, based on a combined weight of the aldehyde-based resin, the solvent, the blocked isocyanate, and the copolymer.
  • copolymer e.g., a styrene-maleic anhydride copolymer
  • the binder can include about 1 wt% to about 8 wt% of the blocked isocyanate, about 45 wt% to about 60 wt% of the aldehyde-based resin, about 26 wt% to about 54 wt% of the solvent, and about 1 wt% to about 6 wt% of copolymer, e.g., a styrene-maleic anhydride copolymer, based on a combined weight of the aldehyde-based resin, the solvent, the blocked isocyanate, and the copolymer.
  • copolymer e.g., a styrene-maleic anhydride copolymer
  • the binder can include about 5 wt% to about 20 wt% of the blocked isocyanate, about 40 wt% to about 70 wt% of the aldehyde-based resin, about 10 wt% to about 45 wt% of the solvent, and about 0.5 wt% to about 10 wt% of copolymer, e.g., a styrene-maleic anhydride copolymer, based on the combined solids weight of the aldehyde-based resin and the blocked isocyanate.
  • copolymer e.g., a styrene-maleic anhydride copolymer
  • the binder can include about 5 wt% to about 15 wt% of the blocked isocyanate, about 45 wt% to about 70 wt% of the aldehyde-based resin, about 5 wt% to about 45 wt% of the solvent, and about 5 wt% to about 10 wt% of copolymer, e.g., a styrene-maleic anhydride copolymer, based on the combined solids weight of the aldehyde-based resin and the blocked isocyanate.
  • copolymer e.g., a styrene-maleic anhydride copolymer
  • the binder can include about 10 wt% to about 20 wt% of the blocked isocyanate, about 40 wt% to about 65 wt% of the aldehyde-based resin, about 10 wt% to about 40 wt% of the solvent, and about 0.5 wt% to about 5 wt% of copolymer, e.g., a styrene-maleic anhydride copolymer, based on the combined solids weight of the aldehyde-based resin and the blocked isocyanate.
  • copolymer e.g., a styrene-maleic anhydride copolymer
  • the solvent can be or include water.
  • the solvent can be or include water, an alkanol, an aromatic alcohol, or any mixture thereof.
  • the solvent can include the alkanol, the aromatic alcohol, and the water.
  • the solvent can include about 40 wt%, about 50 wt%, about 55 wt%, about 60 wt%, about 65 wt%, about 67 wt%, or about 70 wt% to about 75 wt%, about 80 wt%, about 85 wt%, about 90 wt%, about 95 wt%, or about 98 wt% of the alkanol, based on a combined weight of the alkanol, the aromatic alcohol, and the water.
  • the solvent can include about 50 wt% to about 90 wt%, about 50 wt% to about 85 wt%, about 50 wt% to about 75 wt%, about 60 wt% to about 80 wt%, about 60 wt% to about 70 wt%, about 64 wt% to about 75 wt%, about 67 wt% to about 80 wt%, or about 75 wt% to about 90 wt% of the alkanol, based on a combined weight of the alkanol, the aromatic alcohol, and the water.
  • the solvent can include about 5 wt%, about 10 wt%, about 15 wt%, about 18 wt%, about 20 wt%, about 22 wt%, or about 24 wt% to about 25 wt%, about 26 wt%, about 28 wt%, about 30 wt%, about 35 wt%, about 40 wt%, about 45 wt%, or about 50 wt% of the aromatic alcohol, based on a combined weight of the alkanol, the aromatic alcohol, and the water.
  • the solvent can include about 5 wt% to about 50 wt%, about 10 wt% to about 40 wt%, about 10 wt% to about 30 wt%, about 10 wt% to about 25 wt%, about 10 wt% to about 20 wt%, about 15 wt% to about 40 wt%, about 15 wt% to about 30 wt%, or about 15 wt% to about 25 wt% of the aromatic alcohol, based on a combined weight of the alkanol, the aromatic alcohol, and the water.
  • the solvent can include about 1 ppm, about 10 ppm, about 100 ppm, about 500 ppm, about 0.1 wt%, about 0.5 wt%, about 1 wt%, about 2 wt%, about 3 wt%, about 4 wt%, or about 5 wt% to about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, about 10 wt%, about 12 wt%, about 15 wt%, about 18 wt%, or about 20 wt% of water, based on a combined weight of the alkanol, the aromatic alcohol, and the water.
  • the solvent can include about 1 ppm to about 20 wt%, about 0.1 wt% to about 15 wt%, about 0.1 wt% to about 10 wt%, about 1 wt% to about 20 wt%, about 1 wt% to about 15 wt%, about 1 wt% to about 12 wt%, about 1 wt% to about 10 wt%, about 1 wt% to about 5 wt%, about 1 wt% to about 3 wt%, about 5 wt% to about 15 wt%, about 5 wt% to about 12 wt%, about 5 wt% to about 8 wt%, or about 7 wt% to about 9 wt% of the water, based on a combined weight of the alkanol, the aromatic alcohol, and the water.
  • the solvent can include about 50 wt% to about 85 wt% of the alkanol, about 10 wt% to about 40 wt% of the aromatic alcohol, and about 0.1 wt% to about 15 wt% of the water, based on a combined weight of the alkanol, the aromatic alcohol, and the water.
  • the solvent can include about 60 wt% to about 75 wt% of the alkanol, about 20 wt% to about 30 wt% of the aromatic alcohol, and about 1 wt% to about 12 wt% of the water, based on a combined weight of the alkanol, the aromatic alcohol, and the water.
  • the solvent can include about 64 wt% to about 70 wt% of the alkanol, about 22 wt% to about 28 wt% of the aromatic alcohol, and about 5 wt% to about 10 wt% of the water, based on a combined weight of the alkanol, the aromatic alcohol, and the water.
  • the solvent can be or include a mixture of water, one or more aromatic compounds, and one or more glycol ethers.
  • the solvent can include about 60 wt% to about 95 wt% of water, about 1 wt% to about 20 wt% of the aromatic compound, and about 1 wt% to about 20 wt% of the glycol ether, based on a combined weight of the water, the aromatic compound, and the glycol ether.
  • the solvent can include about 80 wt% to about 95 wt% of water, about 1 wt% to about 10 wt% of the aromatic compound, and about 1 wt% to about 10 wt% of the glycol ether, based on a combined weight of the water, the aromatic compound, and the glycol ether.
  • the amounts of individual components of the solvent contained in the binder can be based on the combined solids weight of the aldehyde-based resin and the blocked isocyanate.
  • the binder can include about 30 wt%, about 35 wt%, about 40 wt%, about 45 wt%, about 50 wt%, about 55 wt%, about 60 wt%, about 65 wt%, about 67 wt%, or about 70 wt% to about 75 wt%, about 80 wt%, about 85 wt%, about 90 wt%, or about 95 wt% of the alkanol, based on the combined solids weight of the aldehyde-based resin and the blocked isocyanate.
  • the binder can include about 30 wt% to about 95 wt%, about 40 wt% to about 90 wt%, about 80 wt% to about 95 wt%, about 35 wt% to about 55 wt%, or about 47 wt% to about 67 wt% of the alkanol, based on the combined solids weight of the aldehyde-based resin and the blocked isocyanate.
  • the binder can include about 10 wt%, about 15 wt%, about 18 wt%, about 20 wt%, or about 22 wt% to about 25 wt%, about 28 wt%, about 30 wt%, about 35 wt%, or about 40 wt% of the aromatic alcohol, based on the combined solids weight of the aldehyde-based resin and the blocked isocyanate.
  • the binder can include about 10 wt% to about 40 wt%, about 10 wt% to about 24 wt%, about 15 wt% to about 35 wt%, about 15 wt% to about 26 wt%, or about 24 wt% to about 40 wt% of the aromatic alcohol, based on the combined solids weight of the aldehyde-based resin and the blocked isocyanate.
  • the binder can include about 1 ppm, about 10 ppm, about 100 ppm, about 0.1 wt%, about 0.5 wt%, about 1 wt%, about 2 wt%, about 3 wt%, about 4 wt%, about 5 wt%, or about 6 wt% to about 7 wt%, about 8 wt%, about 9 wt%, about 10 wt%, about 11 wt%, about 12 wt%, about 13 wt%, about 14 wt%, about 15 wt%, or about 18 wt% of water, based on the combined solids weight of the aldehyde-based resin and the blocked isocyanate.
  • the binder can include about 1 ppm to about 18 wt%, about 1 wt% to about 18 wt%, about 1 wt% to about 10 wt%, about 2 wt% to about 8 wt%, about 3 wt% to about 12 wt%, about 5 wt% to about 18 wt%, about 5 wt% to about 9 wt%, or about 7 wt% to about 15 wt% of the water, based on the combined solids weight of the aldehyde-based resin and the blocked isocyanate.
  • the binder can include about 10 wt%, about 15 wt%, about 20 wt%, about 25 wt%, or about 30 wt% to about 35 wt%, about 40 wt%, about 45 wt%, or about 50 wt% of water, based on the combined solids weight of the aldehyde-based resin and the blocked isocyanate.
  • the binder can include about 40 wt% to about 70 wt% of the aldehyde-based binder, about 5 wt% to about 20 wt% of the blocked isocyanate, and about 10 wt% to about 55 wt% of water, based on the solids weight of the aldehyde-based resin, the solids weight of the blocked isocyanate, and the weight of the water.
  • the binder can include about 40 wt% to about 70 wt% of the aldehyde-based binder, about 1 wt% to about 15 wt% of the blocked isocyanate, about 25 wt% to about 58 wt% of water, and about 1 wt% to about 10 wt% of the copolymer, e.g., a styrene-maleic anhydride copolymer, based on the solids weight of the aldehyde-based resin, the solids weight of the blocked isocyanate, the solids weight of the copolymer, and the weight of the water.
  • the copolymer e.g., a styrene-maleic anhydride copolymer
  • the binder can include about 35 wt% to about 95 wt% of the alkanol, about 10 wt% to about 40 wt% of the aromatic alcohol, and about 0.1 wt% to about 15 wt% of the water, based on the combined solids weight of the aldehyde-based resin and the blocked isocyanate.
  • the binder can include about 40 wt% to about 92 wt% of the alkanol, about 15 wt% to about 36 wt% of the aromatic alcohol, and about 2 wt% to about 13 wt% of the water, based on the combined solids weight of the aldehyde-based resin and the blocked isocyanate.
  • the binder can include about 44 wt% to about 89 wt% of the alkanol, about 17 wt% to about 33 wt% of the aromatic alcohol, and about 5.5 wt% to about 11 wt% of the water, based on the combined solids weight of the aldehyde-based resin and the blocked isocyanate.
  • the binder prior to being cured, can have a viscosity of about 100 cP, about 200 cP, about 300 cP, about 400 cP, about 500 cP, about 600 cP, about 700 cP to about 800 cP, about 900 cP, about 1,000 cP, about 1,100 cP, about 1,200 cP, about 1,500 cP, about 1,800 cP, about 2,000 cP, about 2,200 cP, about 2,500 cP, about 2,800 cP, about 3,000 cP, or greater at a temperature of about 25°C.
  • the binder can have a viscosity of about 100 cP to about 3,000 cP, about 100 cP to about 2,000 cP, about 100 cP to about 1,000 cP, about 100 cP to about 500 cP, about 400 cP to about 2,000 cP, about 400 cP to about 1,800 cP, about 400 cP to about 1,300 cP, about 400 cP to about 800 cP, about 600 cP to about 2,000 cP, or about 600 cP to about 1,000 cP at a temperature of about 25°C.
  • the binder can have a viscosity of about 100 cP, about 200 cP, about 300 cP, about 400 cP, about 500 cP, about 600 cP, about 700 cP to about 800 cP, about 900 cP, about 1,000 cP, about 1,100 cP, about 1,200 cP, about 1,500 cP, about 1,800 cP, about 2,000 cP, about 2,200 cP, about 2,500 cP, about 2,800 cP, about 3,000 cP, or greater at a temperature of about 25°C and a solids content of about 63 wt%.
  • the viscosity of the binder can be measured using a Model DV-II+ viscometer, commercially available from Brookfield Company, Inc., with a small sample adapter, for example, a number 3 spindle.
  • the small sample adapter can allow the sample to be cooled or heated by the chamber jacket to maintain the temperature of the sample surrounding the spindle at a temperature of about 25°C.
  • the binder can have an initial viscosity of about 500 cP to about 800 cP, at a temperature of about 25°C, and can be stored for a period of time of about 1 day, about 2 days, about 5 days, or about 8 days to about 10 days, about 15 days, about 20 days, about 30 days, or longer, where the period of time starts when the binder is initially produced.
  • the binder can be maintained at a temperature of about 10°C to about 40°C or about 20°C to about 30°C, such as about 25°C, during the period of time.
  • the binder can be continuously or intermediary stirred when in storage to reduce or prevent phase separation of the binder.
  • the binder can have a pH of greater than 7.
  • the binder prior to curing can have a pH of about 7.5, about 8, about 9, about 9.5, about 10, about 10.5, about 11 to about 11.2, about 11.5, about 11.7, about 12, about 12.2, about 12.5, or about 13 at 25°C.
  • the binder can have a pH of about 8 to about 13, about 9 to about 13, about 10 to about 13, about 11 to about 13, about 12 to about 13, about 9 to about 12.5, about 10 to about 12.5, about 11 to about 12.5, about 12 to about 12.5, about 9 to about 12, about 10 to about 12, about 11 to about 12, about 11.5 to about 12, about 11.2 to about 12.5, about 11.5 to about 12.5, or about 11.7 to about 12.5 at 25°C.
  • the binder can have a pH of about 10.5 to about 13 at 25°C.
  • the binder can be used as or included in a variety of different products.
  • the binder can be used as or included in, but is not limited to, adhesives, binders, glues, coatings, moldings, or other similar products.
  • the binder can also be used as or included in, but is not limited to, adhesives, binders, glues, or similar products that can be used to bind, adhere, or otherwise hold a plurality of substrates together to produce one or more composite products.
  • the plurality of substrates can be or include a plurality of fibers and the binder can be mixed, blended, or otherwise combined with therewith to produce resin coated fibers or a resinated furnish.
  • the binder can be at least partially coated on the surface of the plurality of fibers and/or impregnated within the fibers.
  • the binder in the resinated furnish can be cured to produce a composite fiber product.
  • the composite products and other compositions can be employed with any fibers or fiber webs which can be formed into mats or other products in any suitable manner.
  • the terms "fiber”, “fibrous”, “fiberglass”, “fiber glass”, “fiber web”, and “glass fibers” are referred to as materials that have an elongated morphology exhibiting an aspect ratio (length to thickness) of greater than 100, and generally greater than 500, such as, for example, about 1,000 or greater, about 5,000 or greater, or about 10,000 or greater.
  • the fibers or fiber webs can be or include natural fibers, synthetic fibers, inorganic fibers, organic fibers, or any mixture or combination thereof.
  • Inorganic fibers can be or include, but are not limited to, glass fibers, mineral fibers, ceramic fibers, carbon fibers, graphite fibers, metal fibers, metal coated glass fibers, organic coated glass fibers, or asbestos fibers, or any mixture or combination thereof.
  • Illustrative glass fibers can be or include, but are not limited to, A-type glass fibers, C-type glass fibers, E-type glass fibers, S-type glass fibers, ECR-type glass fibers, wet use chopped strand ("WUCS") glass fibers, wool glass fibers, or any mixture thereof.
  • the fibers can be glass fibers that are WUCS glass fibers that can have a moisture content of about 5%, about 8%, or about 10% to about 20%, about 25%, or about 30%.
  • Organic fibers can be or include, but are not limited to, acrylic, aromatic polyamide, polyester, cellulosic including cellulose, polyolefin fibers, or any mixture thereof.
  • natural fibers refers to plant fibers extracted from any part of a plant, including, but not limited to, the stem, seeds, leaves, roots, or phloem.
  • Illustrative natural fibers can be or include, but are not limited to, cotton, jute, bamboo, ramie, bagasse, hemp, coir, linen, kenaf, sisal, flax, henequen, or any mixture thereof.
  • Illustrative synthetic fibers can be or include, but are not limited to, synthetic polymers, such as polyester, polyamide, aramid, or any mixture thereof.
  • the fibers or fiber webs can be or include, but are not limited to, carbon fibers, glass fibers, polymeric fibers, cellulosic fibers, mineral fibers, plastic fibers, fiber sheets, fiber mats, fabric, a fiber web, or any combination thereof.
  • fiber mats e.g., glass fiber mats, can be manufactured in a wet-laid or dry-laid process.
  • chopped bundles of fibers having suitable length and diameter, can be introduced to an aqueous dispersant medium to produce an aqueous fiber slurry, known in the art as "white water".
  • the white water generally contains about 0.1 wt% to about 1 wt% of fibers, e.g., about 0.5 wt% of fibers.
  • the fibers can be sized or unsized and wet or dry, as long as the fibers can be suitably dispersed within the aqueous fiber slurry.
  • the aqueous fiber slurry can be introduced to a mat-forming machine that can include a mat forming screen, e.g., a wire screen or sheet of fabric, which can form a fiber mat and can allow excess water to drain therefrom, thereby forming a wet or damp fiber mat.
  • a mat forming screen e.g., a wire screen or sheet of fabric
  • the fibers can be collected on the screen in the form of a wet fiber mat and excess water can be removed by gravity and/or by vacuum assist.
  • the removal of excess water via vacuum assist can include one or a series of vacuums.
  • the binder can be applied to the non-woven mat or other fiber substrate, such as by a curtain coating, spraying, or dipping, onto fibers, such as glass fibers. Excess binder can be removed, for example via vacuum.
  • the binder can include about 1 wt% to about 99 wt% solids when applied to the fiber substrate.
  • the binder can have a solids content of about 1 wt%, about 3 wt%, about 5 wt%, or about 7 wt% to about 10 wt%, about 12 wt%, about 15 wt%, about 20 wt%, about 25 wt%, about 35 wt%, or about 50 wt%, based on a total weight of the binder, when applied to the fiber substrate.
  • the binder composition can be blended with other additives or ingredients commonly used in binder compositions for preparing fiber products and diluted with additional water to a desired concentration that can be applied onto the fibers, such as by a curtain coater.
  • additives can include, but are not limited to, dispersants, biocides, viscosity modifiers, pH adjusters, coupling agents, surfactants, lubricants, defoamers, and the like.
  • the binder composition can be diluted to a desired solids content with an aqueous solution (white water) of polyacrylamide (PAA), amine oxide (AO), or hydroxyethylcellulose (HEC) and applied to a plurality of substrates, e.g., a plurality of fibers such as glass fibers.
  • the binder can be diluted to any desired solids content with white water, e.g., the aqueous solution of polyacrylamide, the aqueous solution of amine oxide, or the aqueous solution of hydroxyethylcellulose.
  • the plurality of substrates can be or include a plurality of lignocellulose substrates and the binder can be mixed, blended, or otherwise combined therewith to produce binder coated lignocellulose substrates, another resinated furnish.
  • the binder can be at least partially coated on the surface of the plurality of lignocellulose substrates and/or impregnated within the lignocellulose substrates.
  • the binder in the resinated furnish can be cured to produce a composite lignocellulose product.
  • the lignocellulose substrates can include any one or more of the plant and vegetable materials discussed and described above.
  • the term "lignocellulose” refers to a material that includes lignin and cellulose, hemicellulose, or a combination of cellulose and hemicelluloses.
  • the starting material, from which the lignocellulose substrates can be or can be derived from, can be shaped, reduced, or otherwise formed to the appropriate dimensions by various processes such as hogging, grinding, milling, tearing, shredding, and/or flaking. Other processes for producing the substrates can include skiving, cutting, slicing, and/or sawing.
  • Suitable forms of the lignocellulose substrates can include, but are not limited to, chips, flakes, fibers, powder, shavings, sawdust or dust, veneer or sheets, strands, and/or wafers.
  • substrate when used in conjunction with "lignocellulose” refers to lignocellulose material or lignocellulose containing material having any desired shape, such as, but not limited to, chips, flakes, fibers, powder, shavings, sawdust or dust, veneer or sheets, strands, and/or wafers.
  • Illustrative lignocellulose substrates can be or include, but are not limited to, wood sheets, wood veneers, wood chips, wood fibers, wood flakes, wood strands, wood wafers, wood shavings, wood particles, saw dust, or any combination thereof.
  • Lignocellulose substrates can be or include, but are not limited to, one or more hardwoods, one or more softwoods, a mixture of hardwood and softwood, other plant materials, or any combination thereof.
  • the lignocellulose substrates (material that includes both cellulose and lignin) can include, but is not limited to, straw, hemp, sisal, cotton stalk, wheat, bamboo, sabai grass, rice straw, banana leaves, paper mulberry (i.e., bast fiber), abaca leaves, pineapple leaves, esparto grass leaves, fibers from the genus Hesperaloe in the family Agavaceae jute, salt water reeds, palm fronds, flax, ground nut shells, hardwoods, softwoods, recycled fiberboards such as high density fiberboard, medium density fiberboard, low density fiberboard, oriented strand board, parti cleboard, animal fibers ⁇ e.g., wool, hair), recycled paper products ⁇ e.g., newspapers, cardboard, cereal boxes,
  • Suitable woods can include softwoods and/or hardwoods.
  • Illustrative types of wood can include, but are not limited to, one or more of: alder, almond, apple, ash, aspen, basswood, beech, birch, cedar, cherry, chinaberry, cottonwood, cypress, douglas fir, elm, fir, gum, hackberry, helm, hickory, huiache, jessamine, lenga, maple, mesquite, oak, pear, pecan, pine, poplar, redwood, sassafras, spruce, sycamore, tallow, tepa, walnut, and willow.
  • Illustrative composite lignocellulosic products can be or include, but are not limited to, plywood (e.g., hardwood plywood and/or softwood plywood), oriented strand board (“OSB”), oriented strand lumber (“OSL”), laminated veneer lumber (“LVL”), laminated veneer boards (“LVB”), engineered wood flooring, parti cleboard, fiberboard (e.g., medium density fiberboard (“MDF”) and/or high density fiberboard (“HDF”)), chipboard, flakeboard, or waferboard, other wood and non-wood products.
  • plywood e.g., hardwood plywood and/or softwood plywood
  • OSB oriented strand board
  • OSL oriented strand lumber
  • LDL laminated veneer lumber
  • LLB laminated veneer boards
  • engineered wood flooring parti cleboard
  • fiberboard e.g., medium density fiberboard (“MDF”) and/or high density fiberboard (“HDF”)
  • chipboard e.g., flakeboard, or waferboard, other wood and non-wood products.
  • the lignocellulose substrates can be arranged, positioned, stacked, combined, mixed, or otherwise disposed within a resinated furnish containing one or more binders or adhesives in an uncured configuration of the desired composite product or wood-based product.
  • a plurality of lignocellulose substrates such as multiple wood veneers and/or wood sheets, can be arranged with a binder therebetween to produce a resinated furnish having an uncured configuration of plywood, LVL, LVB, or engineered wood flooring.
  • the plurality of lignocellulose substrates can be strands, chips, flakes, and/or particles that can be arranged with a binder therebetween to produce a resinated furnish having an uncured configuration of OSB, OSL, particleboard, fiberboard, MDF, HDF, chipboard, flakeboard, or waferboard.
  • the lignocellulose substrates can include or contain water on, about, and/or within the substrates.
  • the lignocellulose substrates can have a moisture or water content of about 0.1 wt%, about 1 wt%, about 2 wt%, or about 3 wt% to about 5 wt%, about 7 wt%, about 10 wt%, about 12 wt%, about 15 wt%, about 18 wt%, about 20 wt%, about 25 wt%, about 30 wt%, about 35 wt%, about 40 wt%, or greater, based on a dry weight of the lignocellulose substrate.
  • the lignocellulose substrates can have water content of 0.1 wt% to about 40 wt%, about 1 wt% to about 30 wt%, about 1 wt% to about 20 wt%, about 1 wt% to about 12 wt%, about 1 wt% to about 10 wt%, about 1 wt% to about 8 wt%, about 1 wt% to about 5 wt%, about 3 wt% to about 12 wt%, about 3 wt% to about 8 wt%, or about 5 wt% to about 15 wt%, based on the dry weight of the lignocellulose substrate.
  • the lignocellulose substrates can be fresh, e.g., not treated or dried, or dried and/or treated.
  • the lignocellulose substrates and/or the starting material from which the lignocellulose substrates were derived can be at least partially dried.
  • the lignocellulose substrates can be washed and/or leached with an aqueous medium such as water.
  • the resinated furnish and/or the composite product can include about 5 wt%, about 10 wt%, about 15 wt%, about 20 wt%, about 25 wt%, about 30 wt%, or about 35 wt% to about 40 wt%, about 45 wt%, about 50 wt%, about 55 wt%, about 60 wt%, about 65 wt%, about 70 wt%, about 75 wt%, about 80 wt%, about 85 wt%, about 90 wt%, about 95 wt%, about 97 wt%, about 98 wt%, or about 99 wt% of the plurality of substrates, based on a dried weight of the plurality of substrates and the combined solids weight of the aldehyde-based resin and the blocked isocyanate.
  • the composite product can include about 1 wt%, about 3 wt%, about 5 wt%, about 7 wt%, or about 10 wt% to about 12 wt%, about 15 wt% about 17 wt%, about 20 wt%, about 23 wt%, or about 25 wt% of the cured binder, based on a combined weight of the cured binder and the plurality of substrates.
  • the resinated furnish can be heated in air.
  • the resinated furnish can be heated in an inert atmosphere or substantially an inert atmosphere such as nitrogen. If the resinated furnish is heated in a substantially inert atmosphere, the amount of oxygen can be less than 5 mol%, less than 3 mol%, less than 1 mol%, less than 0.5 mol%, or less than 0.1 mol% oxygen relative to the balance of gases in the inert atmosphere.
  • Suitable inert gases can include, but are not limited to, nitrogen, argon, helium, or a mixture thereof.
  • the binder can be cured by heating the binder. Heating the binder, the resinated furnish, or any other mixture that includes the binder can cause or promote the unblocking or removal of the aryloxy group contained in the second urethane group of the blocked isocyanate and can cause or promote the at least partial curing of the binder to produce the composite product.
  • the terms "curing,” “cured,” “at least partially curing,” “at least partially cured,” and similar terms refer to the structural and/or morphological change that occurs in the mixture, such as by covalent chemical reaction (crosslinking), ionic interaction or clustering, phase transformation or inversion, and/or hydrogen bonding when the is subjected to conditions sufficient, e.g., sufficiently heated, to cause the properties of a flexible, porous substrate, such as a nonwoven mat or fiberglass mat and/or a rigid or semirigid substrate, such as a carbon fiber structure, to which an effective amount of the binder has been applied, to be altered.
  • crosslinking covalent chemical reaction
  • ionic interaction or clustering phase transformation or inversion
  • hydrogen bonding when the is subjected to conditions sufficient, e.g., sufficiently heated, to cause the properties of a flexible, porous substrate, such as a nonwoven mat or fiberglass mat and/or a rigid or semirigid substrate, such as a carbon fiber structure, to which an effective amount of the bin
  • the binder or the resinated furnish can include a blocked isocyanate that can release MDI or other isocyanate therefrom upon being heated to an elevated temperature (e.g., about 100°C to about 200°C). Once released, the MDI or other isocyanate can react with the aldehyde-based resin (e.g., PF, MF, MUF, and/or UF).
  • the binder can be partially cured or fully cured. A partially cured binder can be capable of undergoing additional structural and/or morphological change whereas a fully cured binder would not be capable of undergoing additional structural and/or morphological change.
  • the resinated furnish or any other mixture that includes the binder can be heated to a temperature of about 50°C to about 300°C for about 1 second to about 60 min to cure the binder and produce the composite product.
  • the resinated furnish or any other mixture that includes the binder can be heated to a temperature of about 60°C, about 80°C, about 100°C, about 140°C, about 160°C, about 170°C, about 180°C, or about 190°C to about 200°C, about 210°C, about 230°C, about 240°C, about 250°C, about 260°C, about 270°C, about 280°C, about 290°C, about 300°C, or greater for about 1 second, about 2 seconds, about 3 seconds, about 4 seconds, about 5 seconds, about 6 seconds, about 7 seconds, about 8 seconds, about 9 seconds, or about 10 seconds to about 30 seconds, about 1 minute, about 2 minutes, about 3 minutes, about 5 minutes, about 10 minutes, about 20 minutes, about 30 minutes, about
  • the resinated furnish can be heated in air.
  • the resinated furnish can be heated in an inert atmosphere or substantially an inert atmosphere such as nitrogen. If the resinated furnish is heated in a substantially inert atmosphere, the amount of oxygen can be less than 5 mol%, less than 3 mol%, less than 1 mol%, less than 0.5 mol%, or less than 0.1 mol% oxygen relative to the balance of gases in the inert atmosphere.
  • Suitable inert gases can include, but are not limited to, nitrogen, argon, helium, or a mixture thereof.
  • a composite product containing a cured binder that, prior to curing, included the aldehyde-based resin and the blocked isocyanate can have greater flexibility, e.g., modulus of rupture (MOR), as compared to a composite product containing a cured binder that, prior to curing, included the same aldehyde-based resin, but not the blocked isocyanate.
  • MOR modulus of rupture
  • a composite product containing a cured binder that, prior to curing, included the aldehyde-based resin and the blocked isocyanate can have greater dry tensile strength, as compared to a composite product containing a cured binder that, prior to curing, included the same aldehyde-based resin, but not the blocked isocyanate.
  • composite glass fiber or "fiberglass" products made with the binder can have an average dry tensile strength of about 475 N/3", about 490 N/3", about 500 N/3", about 505 N/3", about 510 N/3", or about 515 N/3" to about 520 N/3", about 525 N/3", about 530 N/3", about 540 N/3", about 550 N/3", about 560 N/3", about 570 N/3", about 580 N/3", about 590 N/3", about 600 N/3", about 610 N/3", about 620 N/3", about 630 N/3", about 640 N/3", about 650 N/3", about 660 N/3", about 670 N/3", about 680 N/3", about 690 N/3", about 700 N/3", about 710 N/3", about 720 N/3", about 730 N/3", about 740 N/3", about 750 N/3", or greater, as measured according to TAPPI/ ANSI T 1009 om-10.
  • TAPPI/ ANSI T 1009 om-10 The test method “TAPPI/ ANSI T 1009 om-10" that can be used to measure the average dry tensile strength of the fibrous composite products and other materials refers to the Technical Association of the Pulp and Paper Industry (TAPPI) and Approved American National Standard (ANSI) test method - Tensile Strength and Elongation at Break for Fiber Glass Mats, TAPPI/ ANSI T 1009 om-10 test method, using a 7.62 cm (3 in) sample size of the fibrous composite product or other sample..
  • composite fiberglass products made with the binder can have an average Elmendorf tear resistance or tear strength of about 4 N, about 4.2 N, about 4.4 N, about 4.6 N, about 4.8 N, or about 5 N to about 5.2 N, about 5.4 N, about 5.6 N, about 5.8 N, about 6 N, about 6.2 N, about 6.4 N, about 6.6 N, about 6.8 N, or about 7 N, as measured according to T 1006 sp-15.
  • the T 1006 sp-16 test method that can be used to measure the average Elmendorf tear resistance or tear strength refers to the Technical Association of the Pulp and Paper Industry (TAPPI) test method - Testing of fiber glass mats: use of modified TAPPI procedures for sampling and lot acceptance, stiffness, tear resistance, and thickness, T 1006 sp-15 test method, using a 1,600-g pendulum.
  • TAPPI Pulp and Paper Industry
  • the average Elmendorf tear resistance or tear strength can be measured with a Thwing- Albert Pro Tear (1,600 g pendulum).
  • the instrument can be leveled and calibrated before testing.
  • Test samples can be cut to a width of 63 mm (2.48 in.) in the tearing direction and a length of about 75 mm (3 in.).
  • the samples can be long enough to be held by the full width of each sample clamp.
  • the test samples can be placed in the clamps of the tester while ensuring that the bottom of each sample rests squarely on the bottom of the sample clamps.
  • the sample can be aligned with the front edge of the pendulum clamp. Any excess material can be allowed to hang over the rear of the stationary clamp. The clamps were then closed.
  • the cutter handle can be pressed all the way down to cut a 20 mm (0.79 in) slit in the sample.
  • the "test" key of the instrument can be pressed and the pendulum can be allowed to make one full swing in the tearing direction.
  • the pendulum can be stopped on the return swing and gently lowered until the pendulum rested against the pendulum stop,
  • the average dry tensile strength values and the average Elmendorf tear resistance or tear strength values can be measured on fiber mats or fiber webs that were composed of randomly oriented glass fibers.
  • the fiber mats or fiber webs did not have a machine direction and a cross-direction, but instead generally had the same fiber orientation from any direction or angle, which was a random, non-woven orientation.
  • An aqueous slurry of the glass fibers was poured onto a synthetic mat that allowed the water to run off, but retained the glass fibers in a random orientation as a fiber mat or web.
  • the average dry tensile strength values and the average Elmendorf tear resistance or tear strength values can be considered as a total dry tensile strength or total Elmendorf tear strength value that would correspond to an average of the machine direction and the cross-direction values measured for fiber mats or fiber webs made on a large scale process that have a machine direction and a cross-direction.
  • composite fiberglass products made with the binder can have a basis weight ("BW") of about 0.68 kg/9.29 m 2 (about 1.5 lbs/100 ft 2 ), about 0.70 kg/9.29 m 2 (about 1.55 lbs/100 ft 2 ), or about 0.73 kg/9.29 m 2 (about 1.6 lbs/100 ft 2 ) to about 0.75 kg/9.29 m 2 (about 1.65 lbs/100 ft 2 ), about 0.76 kg/9.29 m 2 (about 1.67 lbs/100 ft 2 ), about 0.76 kg/9.29 m 2 (about 1.68 lbs/100 ft 2 ), about 0.77 kg/9.29 m 2 (about 1.69 lbs/100 ft 2 ), about 0.77 kg/9.29 m 2 (about 1.7 lbs/100 ft 2 ), about 0.79 kg/9.29 m 2 (about 1.75 lbs/100 ft 2 ), about 0.82 kg/9.29 m 2 (BW) of about 0.68
  • composite fiberglass products made with the binder can have a percent of hot-wet retention ("% HW") of about 50%, about 55%, or about 60%> to about 65%>, about 70%), about 75%, about 80%>, or greater.
  • the percent of hot-wet retention can be determined as the amount of dry tensile strength retained after immersing a sample in an 80°C water bath for 10 minutes.
  • composite fiberglass products made with the binder can have a percent loss on ignition ("%> LOI") of about 12%, about 12.5%, about 13%> to about 13.5%), about 14%, about 14.5%, or about 15%> to about 15.5%, about 16%>, about 17%), about 18%), about 19%, about 20%, about 21%, or greater.
  • the percent loss of ignition can be determined for each value by taking the ratio of a sample weight after 30 minutes at 650°C relative to the original sample weight.
  • composite fiberglass products made with the binder can have a dry tensile number ("DTN") of about 3.5, about 3.6, about 3.7, about 3.8, about 3.9, about 4, about 4.1, about 4.2, about 4.3, about 4.4, or about 4.5 to about 4.6, about 4.7, about 4.8, about 4.9, about 5, about 5.1, about 5.2, about 5.3, about 5.4, or about 5.5 to about 5.6, about 5.7, about 5.8, about 5.9, about 6, or greater.
  • composite fiberglass products made with the binder can have an average dry tensile strength of about 475 N/3" to about 750 N/3", an average Elmendorf tear resistance or tear strength of about 4 N to about 7 N, a basis weight ("BW") of about 0.68 kg/9.29 m 2 (about 1.5 lbs/100 ft 2 ) to about 0.91 kg/9.29 m 2 (about 2 lbs/100 ft 2 ), a percent of hot-wet retention of about 50% to about 80%, a percent loss on ignition of about 12% to about 20%), and a dry tensile number of about 3.5 to about 6.
  • BW basis weight
  • composite fiberglass products made with the binder can have an average dry tensile strength of about 500 N/3" to about 700 N/3", an average Elmendorf tear resistance or tear strength of about 4 N to about 6.5 N, a basis weight ("BW") of about 0.75 kg/9.29 m 2 (about 1.65 lbs/100 ft 2 ) to about 0.82 kg/9.29 m 2 (about 1.8 lbs/100 ft 2 ), a percent of hot-wet retention of about 50% to about 70%, a percent loss on ignition of about 14.5% to about 16.5%, and a dry tensile number of about 4.3 to about 5.8.
  • BW basis weight
  • Composite lignocellulose products in the shape or form of a panel, sheet, board, veneer, or the like can be in the form of a rectangular prism that includes six outer surfaces, e.g., three pairs of oppositely facing surfaces.
  • the first pair of oppositely facing surfaces of the composite product can include a first or "top” surface and an opposing second or “bottom” surface.
  • the second and third pairs of oppositely facing surfaces of the composite product can be referred to as the "side surfaces” that have a surface area less than the surface area of the first and second surfaces.
  • composite products in the shape or form of a panel, sheet, board, or the like can have an average thickness, where the average thickness is the length or distance between the first and second surfaces.
  • the amount or length of time the resinated furnish can be heated can be about 5 seconds per millimeter (s/mm), about 10 s/mm, about 12 s/mm, or about 15 s/mm to about 17 s/mm, about 19 s/mm, about 21 s/mm, about 23 s/mm, about 25 s/mm, about 27 s/mm, about 30 s/mm, about 35 s/mm, about 40 s/mm, about 50 s/mm, or about 60 s/mm, where the length refers to the average thickness of the composite product.
  • the resinated furnish can be heated for a time of about 5 s/mm to about 60 s/mm, about 10 s/mm to about 45 s/mm, about 15 s/mm to about 40 s/mm, about 5 s/mm to about 25 s/mm, about 8 s/mm to about 20 s/mm, about 14 s/mm to about 18 s/mm, where the length refers to the average thickness of the composite product.
  • the resinated furnish can be heated for a time less than 120 s/mm, less than 100 s/mm, less than 90 s/mm, less than 80 s/mm, less than 70 s/mm, less than 60 s/mm, less than 50 s/mm, less than 40 s/mm, less than 30 s/mm, less than 25 s/mm, less than 20 s/mm, less than 18 s/mm, less than 15 s/mm, or less than 12 s/mm, where the length refers to the average thickness of the composite product.
  • a composite product in the form of a panel, sheet, board, or the like and having an average thickness of about 15 mm and subjected to a total heating time of about 4 minutes would correspond to heating the resinated furnish for about 16 s/mm.
  • the resinated furnish can be heated to a temperature of about 100°C to about 300°C, about 100°C to about 250°C, about 100°C to about 200°C, about 100°C to about 170°C, about 140°C to about 170°C, or about 160°C to about 170°C for a time of about 10 s/mm to about 30 s/mm, about 13 s/mm to about 19 s/mm, about 15 s/mm to about 40 s/mm, or about 8 s/mm to about 50 s/mm.
  • Pressure can optionally be applied to the resinated furnish before, during, and/or after the resinated furnish is heated to produce the composite product.
  • the desired composite product shape or structure is a panel, sheet, board, or the like
  • an amount of the resinated furnish sufficient to produce a composite product of the desired size can be transported, directed, placed, introduced, disposed, or otherwise located within a press capable of pressing the resinated furnish before the resinated furnish is heated and/or when the resinated furnish is heated.
  • the press can be an open press or a closed press.
  • an open press can be used to press the resinated furnish when the resinated furnish is heated, e.g., to a temperature of about 100°C to about 300°C or about 100°C to about 250°C.
  • the resinated furnish can be extruded through a die (extrusion process) and heated to produce the composite product.
  • the resinated furnish can be pressed under a pressure of about 0.5 MPa, about 1 MPa, about 3 MPa, or about 5 MPa to about 7 MPa, about 9 MPa, about 11 MPa, about 13 MPa, about 15 MPa, or about 20 MPa.
  • Illustrative open presses can be as discussed and described in U. S. Patent Nos.
  • Suitable, commercially available, open presses can include, but are not limited to, the CONTIROLL® press available from Siempelkamp, GmbH and the CPS press available from Dieffenbacher, GmbH.
  • the resinated furnish can be pressed when heated to produce the composite product.
  • the resinated furnish can be heated to a temperature of at least 100°C to about 250°C and can be pressed to a pressure of about 0.8 MPa to about 2 MPa for about 1 min to about 20 min to produce the composite product.
  • the resinated furnish can be heated to a temperature of about 100°C to about 300°C, about 100°C to about 200°C, about 100°C to about 160°C, about 120°C to about 160°C, or about 140°C to about 160°C and can be pressed to a pressure of about 1 MPa to about 2 MPa or about 1.5 MPa to about 2 MPa for about 2 min, about 3 min, about 5 min, or about 8 min to about 10 min, about 15 min, about 18 min, or about 20 min to produce the composite product.
  • the resinated furnish can be heated to a temperature of about 100°C to about 300°C and can be pressed to a pressure of about 0.5 MPa to about 15 MPa for about 0.1 min to about 30 min to at least partially cure the binder and produce the composite product.
  • a composite lignocellulose product containing a cured binder that, prior to curing, included the aldehyde-based resin and the blocked isocyanate can have greater flexibility (e.g., modulus of rupture (MOR)) as compared to a composite lignocellulose product containing a cured binder that, prior to curing included the same aldehyde based-resin, but not the blocked isocyanate.
  • MOR modulus of rupture
  • the composite lignocellulose product can have a modulus of rupture of about 12.4 MPa, about 12.8 MPa, about 13.1 MPa, about 13.4 MPa, about 13.8 MPa, about 14.1 MPa, or about 14.5 MPa to about 14.8 MPa, about 15.2 MPa, about 15.5 MPa, about 15.9 MPa, about 16.2 MPa, about 16.5 MPa, about 16.9 MPa, or about 17.2 MPa.
  • the modulus of rupture can be measured according to ASTM D 1037- 12- Standard Test Methods for Evaluating Properties of Wood-Base Fiber and Particle Panel Materials.
  • a first handsheet study was carried out for three comparative examples (C1-C3) and two inventive examples (Ex. 1 and 2).
  • the aldehyde-based resin was an aqueous urea- formaldehyde resin that had a molar ratio of formaldehyde to urea of about 2: 1, a solids content of about 60 wt%, a pH of about 7.8-8.2, and a viscosity of about 130 cps to about 250 cps at a temperature of about 25°C.
  • the styrene maleic anhydride (SMA) copolymer had a weight average molecular weight of about 120,000, a solids content of about 13 wt%, a pH of about 10.6, and a maleic content of about 22 wt% to about 23 wt%.
  • a first blocked isocyanate was BAYHYDUR ® BL XP 2706 (2706), had a NCO content of about 8.2% and a solids content of about 38 wt% to about 42 wt% in water, and was used as acquired from Covestro.
  • the blocked isocyanate B was BAYHYDUR ® BL 5335 (5335), had a NCO content of about 7.1% and a solids content of about 34 wt% to about 36 wt% in a mixture of water/MPA/xylene at a weight ratio of about 56:4.5:4.5, and was used as acquired from Covestro.
  • the glass fibers were wet chopped strands that had a length of about 31.75 mm and a diameter of k.
  • the conditions of the first handsheet study were as follows.
  • the binders were diluted to approximately 11 wt% solids with polyacrylamide (PAA) white water and the diluted binders were applied to non-woven fiberglass mats.
  • Four handsheets (about 26.7 cm x about 26.7 cm) were made for each example. Each set was tested for dry and wet tensile strength on a Thwing- Albert tensile tester (0-200 kg load cell), Elmendorf tear strength on a Thwing- Albert Pro Tear (1600 g pendulum).
  • the targeted average basis weight was about 1.70 lbs/100 ft 2
  • targeted glass moisture was about 12.4 wt%
  • the targeted average loss on ignition (LOI) was about 15.5 wt%.
  • the binder coated fibers were cured at a temperature of 205°C for about 70 seconds.
  • the results are shown in Table 2 below.
  • the UF resin had a solids content of about 60%.
  • the "%solids" of the SMA, the 5335 blocked isocyanate, and the 2706 blocked isocyanate shown in Tables 1 and 2 below are based on the UF resin solids.
  • Ex. 2 had a statistically higher dry tensile strength as compared to C1-C3 and Ex. 1.
  • the % Hot-wet retention (%HW) for C2 was statistically different as compared to CI, C3, Ex. 1, and Ex. 2.
  • the average tear strength for all examples was statistically equal.
  • Ex. 4 had a statistically higher dry tensile strength in comparison to C4, C5 and Ex. 3.
  • the % Hot-wet retention (%HW) for C6 and Ex. 4 was statistically lower than C4, C5, and Ex. 3.
  • the average tear strength for all examples was statistically equal.
  • the results from Examples I and II show the binder is compatible with polyacrylamide white water.
  • the aldehyde-based resin was an aqueous urea- formaldehyde resin that had a molar ratio of formaldehyde to urea of about 2.25: 1, a solids content of about 56 wt%, a pH of about 7.3-7.8, and a viscosity of about 110 cps to about 220 cps at a temperature of about 25°C.
  • the blocked isocyanate was BAYHYDUR ® BL XP 2706 (2706) that had a NCO content of about 8.2% and a solids content of about 40 wt% in water, and was used as acquired from Covestro.
  • the glass fibers were wet chopped strands that had a length of about 31.75 mm and a diameter of k.
  • the conditions of the third handsheet study were as follows. Dilutions were made to approximately 11 wt% solids with amine oxide (AO) white water and the diluted binders were applied to non-woven fiberglass mats. Four handsheets (about 26.7 cm x about 26.7 cm) were made for each example. Each set was tested for dry and wet tensile strength on a Thwing- Albert tensile tester (0-200 kg load cell) and Elmendorf tear strength on a Thwing-Albert Pro Tear (1600 g pendulum). The targeted average basis weight was about 1.70 lbs/100 ft 2 , targeted glass moisture was about 12.4 wt%, and the targeted average loss on ignition (LOI) was about 15.5 wt%.
  • AO amine oxide
  • the binder coated fibers were cured at a temperature of 270°C for about 10 seconds.
  • the UF resin had a solids content of about 56% and the "%solids" of the 2706 blocked isocyanate shown in Table 3 below is based on the UF resin solids. The results are shown in Table 3 below.
  • a fourth handsheet study was carried out for a comparative example (C8) and three inventive examples (Ex. 7, 8, and 9).
  • the aldehyde-based resin was an aqueous urea- formaldehyde resin that had a molar ratio of formaldehyde to urea of about 2.25: 1, a solids content of about 56 wt%, a pH of about 7.3-7.8, and a viscosity of about 110 cps to about 220 cps.
  • the styrene maleic anhydride (SMA) copolymer had a weight average molecular weight of about 120,000, a solids content of about 13 wt%, a pH of about 10.6, and a maleic content of about 22 wt% to about 23 wt%.
  • the blocked isocyanate was BAYHYDUR ® BL XP 2706 (2706), had a NCO content of about 8.2% and a solids content of about 40 wt% in water, and was used as acquired from Covestro.
  • the glass fibers were wet chopped strands that had a length of about 31.75 mm and a diameter of k.
  • the conditions of the fourth handsheet study were as follows. Dilutions were made to approximately 1 1 wt% solids with amine oxide white water and the diluted binders were applied to non-woven fiberglass mats. Four handsheets (about 26.7 cm x about 26.7 cm) were made for each example. Each set was tested for dry and wet tensile strength on a Thwing- Albert tensile tester (0-200 kg load cell) and Elmendorf tear strength on a Thwing-Albert Pro Tear (1600 g pendulum). The targeted average basis weight was about 1.70 lbs/100 ft 2 , targeted glass moisture was about 12.4 wt%, and the targeted average loss on ignition (LOI) was about 15.5 wt%.
  • LOI targeted average loss on ignition
  • the binder coated fibers were cured at a temperature of 270 °C for about 10 second.
  • the UF resin had a solids content of about 56% and the "%solids" of the 2706 blocked isocyanate and the SMA shown in Table 4 below is based on the UF resin solids. The results are shown in Table 4 below.
  • a fifth handsheet study was carried out one comparative example (C9) and two inventive examples (Ex. 10 and 11) that repeated the fourth handsheet study. Accordingly, all of the materials and conditions used were the same as in Example IV. The results are shown in Table 5 below.
  • % LOI Percent loss of ignition
  • % HW Percent hot-wet retention
  • BW basis weight
  • LOI loss of ignition
  • %HW percent hot-wet retention
  • Embodiments of the present disclosure further relate to any one or more of the following paragraphs:
  • a binder comprising: an aldehyde-based resin; a solvent; and a blocked isocyanate having a diisocyanate base structure with a first urethane group and a second urethane group, wherein the first urethane group comprises a polyoxyalkylene group, and wherein the second urethane group comprises an aryloxy group.
  • a process for making a composite product comprising: combining a plurality of fibers and a binder comprising an aldehyde-based resin, a solvent, and a blocked isocyanate to produce resin coated fibers, wherein the blocked isocyanate has a diisocyanate base structure with a first urethane group and a second urethane group, wherein the first urethane group comprises a polyoxyalkylene group, and wherein the second urethane group comprises an aryloxy group; and at least partially curing the binder in the resin coated fibers to produce a composite product.
  • the binder comprises about 20 wt% to about 50 wt% of the aldehyde-based resin, about 30 wt% to about 70 wt% of the solvent, and about 1 wt% to about 40 wt% of the blocked isocyanate, based on a combined weight of the solvent, a solids weight of the aldehyde-based resin, and a solids weight of the blocked isocyanate.
  • polyalkylene glycol comprises an oxymethylene unit, an oxyethylene unit, an oxypropylene unit, an oxybutylene unit, isomers thereof, or any mixture thereof.
  • the polyalkylene glycol comprises a compound having the chemical formula: H[-OR 1 -] n OR 2 , and wherein each R 1 is a C1-C5 alkylene, R 2 is hydrogen or a C1-C20 alkyl, and n is a number of 1 to about 100.
  • each R 1 is methylene, ethylene, propylene, or butylene
  • R 2 is hydrogen, methyl, ethyl, propyl, or butyl
  • n is a number of 5 to about 50.
  • each R 1 is propylene and n is a number of about 10 to about 40.
  • each R 3 is a C1-C5 alkyl, and x is 0, 1, or 2.
  • each R 3 is methyl, ethyl, propyl, butyl, isomers thereof, or halogen substitutes thereof; and x is 1 or 2.
  • OR 4 is the polyoxyalkylene group and has the chemical formula: [-OR 1 -] n OR 2 , wherein each R 1 is a C1-C5 alkyl ene; R 2 is hydrogen or a C1-C20 alkyl, and n is a number of 1 to about 100, and R 5 , R 6 , R 7 , R 8 , and R 9 are independently hydrogen or a C1-C5 alkyl.
  • each R 1 is a C1-C4 alkylene; n is a number of 5 to about 50; R 5 , R 6 , R 8 , and R 9 are hydrogen; and R 7 is methyl, ethyl, propyl, or butyl.
  • a binder comprising: an aldehyde-based resin; a solvent; and about 10 wt% to about 60 wt% of a blocked isocyanate, based on a combined solids weight of the aldehyde- based resin and the blocked isocyanate, wherein the blocked isocyanate has the chemical formula:
  • OR 4 is a polyoxyalkylene group
  • R 5 , R 6 , R 7 , R 8 , and R 9 are independently hydrogen or a C1-C5 alkyl.
  • a composite product comprising: a plurality of lignocellulose substrates; and an at least partially cured binder, wherein prior to curing, the binder comprises: an aldehyde-based resin, and a blocked isocyanate having a diisocyanate base structure with a first urethane group and a second urethane group, wherein the first urethane group comprises a polyoxyalkylene group, and wherein the second urethane group comprises an aryloxy group.
  • the binder further comprises a solvent, and wherein the binder comprises about 1 wt% to about 40 wt% of the blocked isocyanate, about 20 wt% to about 50 wt% of the aldehyde-based resin, and about 30 wt% to about 70 wt% of the solvent, based on a combined weight of the solvent, a solids weight of the aldehyde-based resin, and a solids weight of the blocked isocyanate.
  • the binder further comprises a solvent, and wherein the solvent comprises an alkanol, an aromatic alcohol, and water.
  • [00156] 28 The composite product according to paragraph 27, wherein the alkanol comprises isopropanol and the aromatic alcohol comprises free phenol, and wherein the solvent comprises: about 50 wt% to about 85 wt% of the alkanol, about 10 wt% to about 40 wt% of the aromatic alcohol, and about 0.1 wt% to about 15 wt% of the water, based on a combined weight of the alkanol, the aromatic alcohol, and the water.
  • the solvent comprises: about 50 wt% to about 85 wt% of the alkanol, about 10 wt% to about 40 wt% of the aromatic alcohol, and about 0.1 wt% to about 15 wt% of the water, based on a combined weight of the alkanol, the aromatic alcohol, and the water.
  • each R 1 is methylene, ethylene, propylene, or butylene
  • R 2 is hydrogen, methyl, ethyl, propyl, or butyl
  • n is a number of 5 to about 50.
  • each R 3 is methyl, ethyl, propyl, butyl, isomers thereof, or halogen substitutes thereof, and x is 1 or 2.
  • OR 4 is the polyoxyalkylene group and has the chemical formula: [-OR 1 -] n OR 2 , wherein each R 1 is a C1-C5 alkylene, R 2 is hydrogen or a C1-C20 alkyl, and n is a number of 1 to about 100, and wherein R 5 , R 6 , R 7 , R 8 , and R 9 are independently hydrogen or a C1-C5 alkyl. [00165] 37.
  • each R 1 is a C1-C4 alkylene, n is a number of 5 to about 50, R 5 , R 6 , R 8 , and R 9 are hydrogen; and R 7 is methyl, ethyl, propyl, or butyl.
  • a resinated furnish comprising: a plurality of lignocellulose substrates; and a binder disposed on at least a portion of each of the lignocellulose substrates, wherein the binder comprises: an aldehyde-based resin, and a blocked isocyanate having a diisocyanate base structure with a first urethane group and a second urethane group, wherein the first urethane group comprises a polyoxyalkylene group, and wherein the second urethane group comprises an aryloxy group.
  • the first urethane group is a reaction product between a first isocyanate group on the diisocyanate base structure and a polyalkylene glycol
  • the polyalkylene glycol comprises an oxymethylene unit, an oxyethylene unit, an oxypropylene unit, an oxybutylene unit, isomers thereof, or any mixture thereof
  • the second urethane group is a reaction product between a second isocyanate group on the diisocyanate base structure and a phenolic compound
  • the phenolic compound comprises a compound having the chemical formula: HOC6H x R 3 (5- X ), wherein each R 3 is a substituted or unsubstituted linear, branched, cyclic, heterocyclic, or aromatic hydrocarbyl group, and x is 0, 1, 2, 3, 4, or 5.
  • a process for producing a composite product comprising: combining a plurality of lignocellulose substrates and a binder comprising an aldehyde-based resin and a blocked isocyanate to produce a resinated furnish, wherein the blocked isocyanate has a diisocyanate base structure with a first urethane group and a second urethane group, wherein the first urethane group comprises a polyoxyalkylene group, and wherein the second urethane group comprises an aryloxy group; and at least partially curing the binder in the resinated furnish to produce the composite product.
  • the lignocellulose substrates comprise wood sheets, wood veneers, wood strands, wood particles, wood chips, or any combination thereof, and wherein the resinated furnish is heated to a temperature of about 100°C to about 300°C and pressed to a pressure of about 0.5 MPa to about 15 MPa for about 0.1 min to about 30 min to at least partially cure the binder and produce the composite product.
  • the binder comprises about 5 wt% to about 60 wt% of the blocked isocyanate, based on a combined solids weight of the aldehyde-based resin and the blocked isocyanate.
  • [00173] 45 The resinated furnish or the process according to any one of paragraphs 38 to 44, wherein the binder further comprises a solvent, and wherein the binder comprises about 1 wt% to about 40 wt% of the blocked isocyanate, about 20 wt% to about 50 wt% of the aldehyde- based resin, and about 30 wt% to about 70 wt% of the solvent, based on a combined weight of the solvent, a solids weight of the aldehyde-based resin, and a solids weight of the blocked isocyanate.
  • [00175] 47 The resinated furnish or the process according to paragraph 46, wherein the alkanol comprises isopropanol and the aromatic alcohol comprises free phenol, and wherein the solvent comprises: about 50 wt% to about 85 wt% of the alkanol, about 10 wt% to about 40 wt% of the aromatic alcohol, and about 0.1 wt% to about 15 wt% of the water, based on a combined weight of the alkanol, the aromatic alcohol, and the water.
  • each R 1 is methylene, ethylene, propylene, or butylene
  • R 2 is hydrogen, methyl, ethyl, propyl, or butyl
  • n is a number of 5 to about 50.
  • each R 3 is methyl, ethyl, propyl, butyl, isomers thereof, or halogen substitutes thereof, and x is 1 or 2.
  • OR 4 is the polyoxyalkylene group and has the chemical formula: [-OR 1 -] n OR 2 , wherein each R 1 is a C1-C5 alkylene, R 2 is hydrogen or a C1-C20 alkyl, and n is a number of 1 to about 100, and wherein R 5 , R 6 , R 7 , R 8 , and R 9 are independently hydrogen or a C1-C5 alkyl.
  • each R 1 is a C1-C4 alkylene
  • n is a number of 5 to about 50
  • R 5 , R 6 , R 8 , and R 9 are hydrogen
  • R 7 is methyl, ethyl, propyl, or butyl.
  • a process for making a composite product comprising: combining a plurality of substrates and a binder comprising an aldehyde-based resin and a blocked isocyanate to produce a resinated furnish, wherein the blocked isocyanate has a diisocyanate base structure with a first urethane group and a second urethane group, wherein the first urethane group comprises a polyoxyalkylene group, and wherein the second urethane group comprises an aryloxy group; and curing the binder in the resinated furnish to produce the composite product.
  • a resinated furnish comprising: a plurality of substrates, and a binder comprising an aldehyde-based resin and a blocked isocyanate, wherein the blocked isocyanate has a diisocyanate base structure with a first urethane group and a second urethane group, wherein the first urethane group comprises a polyoxyalkylene group, and wherein the second urethane group comprises an aryloxy group.
  • a composite product comprising: a plurality of substrates; and a cured binder, wherein, prior to curing, the binder comprises an aldehyde-based resin and a blocked isocyanate, wherein the blocked isocyanate has a diisocyanate base structure with a first urethane group and a second urethane group, wherein the first urethane group comprises a polyoxyalkylene group, and wherein the second urethane group comprises an aryloxy group.
  • [00193] 65 The process, the resinated furnish, or the composite product according to any one of paragraphs 57 to 63, wherein the binder comprises about 3 wt% to about 17 wt% of the blocked isocyanate, based on a combined solids weight of the aldehyde-based resin and the blocked isocyanate.
  • [00194] 66 The process, the resinated furnish, or the composite product according to any one of paragraphs 57 to 63, wherein the binder comprises about 5 wt% to about 15 wt% of the blocked isocyanate, based on a combined solids weight of the aldehyde-based resin and the blocked isocyanate.
  • [00203] 75 The process, the resinated furnish, or the composite product according to any one of paragraphs 69 to 73, wherein the binder comprises about 70 wt% to about 99 wt% of the aldehyde-based resin, about 1 wt% to about 30 wt% of the blocked isocyanate, and about 10 wt% to about 95 wt% of the solvent, wherein all weight percent values are based on a combined solids weight of the aldehyde-based resin and the blocked isocyanate.
  • the phenolic compound comprises a compound having the chemical formula: HOC6HxR 3 (5-x), and wherein each R 3 is a substituted or unsubstituted linear, branched, cyclic, heterocyclic, or aromatic hydrocarbyl group, and x is 0, 1, 2, 3, 4, or 5.
  • each R 3 is a C1-C5 alkyl, and x is 0, 1, or 2.
  • OR 4 is the polyoxyalkylene group and has the chemical formula: [-OR 1 -] n OR 2 , wherein each R 1 is a C1-C5 alkylene; R 2 is hydrogen or a C1-C20 alkyl, and n is a number of 1 to about 100, and R 5 , R 6 , R 7 , R 8 , and R 9 are independently hydrogen or a C1-C5 alkyl. [00223] 95.
  • each R 1 is a C1-C4 alkylene
  • n is a number of 5 to about 50
  • R 5 , R 6 , R 8 , and R 9 are hydrogen
  • R 7 is methyl, ethyl, propyl, or butyl.
  • the fiberglass mat has a basis weight of about 1.5 lbs/100 ft 2 to about 2 lbs/100 ft 2 .
  • the fiberglass mat has a percent of hot-wet retention of about 50% to about 80%.
  • a binder comprising an aldehyde-based resin and a blocked isocyanate, wherein the blocked isocyanate has a diisocyanate base structure with a first urethane group and a second urethane group, wherein the first urethane group comprises a polyoxyalkylene group, and wherein the second urethane group comprises an aryloxy group.
  • aldehyde-based resin comprises a urea-formaldehyde resin, a melamine-formaldehyde resin, a melamine-urea- formaldehyde resin, or a mixture thereof.
  • polyalkylene glycol comprises an oxymethylene unit, an oxyethylene unit, an oxypropylene unit, an oxybutylene unit, isomers thereof, or a mixture thereof.
  • polyalkylene glycol comprises a compound having the chemical formula: H[-OR 1 -] n OR 2 , and wherein each R 1 is a C1-C5 alkylene, R 2 is hydrogen or a C1-C20 alkyl, and n is a number of 1 to about 100.
  • each R 1 is methylene, ethylene, propylene, or butylene
  • R 2 is hydrogen, methyl, ethyl, propyl, or butyl
  • n is a number of 5 to about 50.
  • each R 1 is propylene and n is a number of about 10 to about 40.
  • each R 3 is a C1-C5 alkyl, and x is 0, 1, or 2.
  • each R 3 is methyl, ethyl, propyl, butyl, isomers thereof, or halogen substitutes thereof, and x is 1 or 2.
  • OR 4 is the polyoxyalkylene group and has the chemical formula: [-OR 1 -] n OR 2 , wherein each R 1 is a C1-C5 alkyl ene; R 2 is hydrogen or a C1-C20 alkyl, and n is a number of 1 to about 100, and R 5 , R 6 , R 7 , R 8 , and R 9 are independently hydrogen or a C1-C5 alkyl.
  • each R 1 is a C1-C4 alkylene; n is a number of 5 to about 50; R 5 , R 6 , R 8 , and R 9 are hydrogen; and R 7 is methyl, ethyl, propyl, or butyl.
  • binder according to any one of paragraphs 122 to 143, wherein the binder further comprises a copolymer comprising one or more vinyl aromatic derived units and at least one of maleic anhydride and maleic acid.

Abstract

L'invention porte sur des procédés de fabrication de produits composites à l'aide d'un liant, sur des pâtes résinées qui comprennent le liant et sur des produits composites fabriqués avec le liant. Dans certains exemples, le procédé de fabrication d'un produit composite peut comprendre la combinaison d'une pluralité de substrats et d'un liant qui comprend une résine à base d'aldéhyde et un isocyanate bloqué afin de produire une pâte résinée. L'isocyanate bloqué peut présenter une structure de base de diisocyanate présentant un premier groupe uréthane et un deuxième groupe uréthane. Le premier groupe uréthane peut comprendre un groupe polyoxyalkylène. Le deuxième groupe uréthane peut comprendre un groupe aryloxy. Le procédé peut également comprendre le durcissement du liant dans la pâte résinée pour produire le produit composite.
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