(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)
`
`(19) World Intellectual Property Organization
`International Bureau
`
`(43) International Publication Date
`1 February 2007 (01.02.2007)
`
`PCT
`
`(51) International Patent Classification:
`C08L 5/00 (2006.01)
`C03C 25/32 (2006.01)
`C08L 3/00 (2006.01)
`(21) International Application Number:
`PCT/US2006/028929
`
`26 July 2006 (26.07.2006)
`
`English
`
`English
`
`(22) International Filing Date:
`(25) Filing Language:
`(26) Publication Language:
`(30) Priority Data:
`US
`26 July 2005 (26.07.2005)
`60/702,456
`US
`22 December 2005 (22.12.2005)
`60/743,071
`(71) Applicant (for all designated States except US): KNAUF
`INSULATION GMBH [DE/US]; One Knauf Drive, Shel-
`byville, IN 46176-1496 (US).
`(72) Inventors; and
`(75) Inventors/Applicants (for US only): SWIFT, Brian, Lee
`[US/US]; 2180 East 1000 North, Morristown, IN 46161
`(US). XU, Ruijian [CA/US]; 10521 Patoka Road, Indi
`anapolis, IN 46239 (US). KISSELL, Ronald, E . [US/US];
`5768 State Road 9, Shelbyville, IN 46176-9303 (US).
`Published:
`(74) Agent: ADDISON, Bradford, G.; Barnes & Thornburg — without international search report and to be republished
`upon receipt of that report
`LLP, 11 South Meridian Street, Indianapolis,
`IN 46204
`(US).
`(81) Designated States (unless otherwise indicated, for every
`kind of national protection available): AE, AG, AL, AM,
`
`(10) International Publication Number
`WO 2007/014236 A2
`AT, AU, AZ, BA, BB, BG, BR, BW, BY, BZ, CA, CH, CN,
`CO, CR, CU, CZ, DE, DK, DM, DZ, EC, EE, EG, ES, FI,
`GB, GD, GE, GH, GM, HN, HR, HU, ID, IL, IN, IS, JP,
`KE, KG, KM, KN, KP, KR, KZ, LA, LC, LK, LR, LS, LT,
`LU, LV,LY,MA, MD, MG, MK, MN, MW, MX, MZ, NA,
`NG, NI, NO, NZ, OM, PG, PH, PL, PT, RO, RS, RU, SC,
`SD, SE, SG, SK, SL, SM, SY, TJ, TM, TN, TR, TT, TZ,
`UA, UG, US, UZ, VC, VN, ZA, ZM, ZW
`
`(84) Designated States (unless otherwise indicated, for every
`kind of regional protection available): ARIPO (BW, GH,
`GM, KE, LS, MW, MZ, NA, SD, SL, SZ, TZ, UG, ZM,
`ZW), Eurasian (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM),
`European (AT,BE, BG, CH, CY, CZ, DE, DK, EE, ES, FI,
`FR, GB, GR, HU, IE, IS, IT, LT, LU, LV,MC, NL, PL, PT,
`RO, SE, SI, SK, TR), OAPI (BF, BJ, CF, CG, CI, CM, GA,
`GN, GQ, GW, ML, MR, NE, SN, TD, TG).
`
`Declarations under Rule 4.17:
`— as to the applicant's entitlement to claim the priority of the
`earlier application (Rule 4.17(Hi))
`— of inventor ship (Rule 4.17 (iv))
`
`For two-letter codes and other abbreviations, refer to the "G uid
`ance Notes on Codes and Abbreviations" appearing at the beg in
`ning of each regular issue of the PCT Gazette.
`
`(54) Title: BINDERS AND MATERIALS MADE THEREWITH
`
`AMINE COMPONENT
`
`+
`
`REDUCING SUGAR o r
`Non-carbohydrate
`carbonyl
`comporu ?nt
`
`Proteins/Peptides
`
`(e.g., collagen, casein, gelatin, gluten)
`
`Glucose/Mannose/Galactose
`
`Amino acids (e.g., GIy, Asp, GIu, homoGlu, 7-carboxyGlu)
`
`Fructose/Sorbose/Sedoheptulose
`
`[ + NHj
`
`c • polymeric polycorboxylate
`
`[ + NH3 R1 ]c
`
`polymeric polycarboxylate
`
`[ + NH2 R1 R2 ] x polymeric polycarboxylate
`
`[ + NH 4 ] X monomeric polycarboxylate
`
`[ + NH3 R1]_• monomeric polycarboxylate
`
`[ + NH2 R1 R2 ] x monomeric polycarboxylate
`
`Ribose/Xylose/Arabinose
`
`Ribulose/Arabulose/Xylulose
`
`Sucrose/Dihydroxyacetone/Sfarch
`
`Pyruvaldehyde/Acetaldehyde
`
`Furfural/Crotonaldehyde
`
`Ascorbic acid/Quinone
`
`(57) Abstract: Binders to produce or promote cohesion in non or loosely assembled matter.
`
`MELANOIDINS
`
`PGR2022-00022 - Petitioner’s Exhibit 1006 – Page 1
`
`

`

`BINDERS AND MATERIALS MADE THEREWITH
`
`CROSS REFERENCE TO RELATED APPLICATIONS
`
`This application claims the benefit under 35 U.S.C. § 119 (e) of U.S.
`
`Provisional Application Serial No. 60/702,456, filed July 26, 2005, and U.S.
`
`Provisional Application Serial No. 60/743,071, filed December 22, 2005, the
`
`disclosures of which are hereby incorporated herein by reference.
`
`BACKGROUND
`Binders are useful in fabricating materials from non or loosely
`
`assembled matter. For example, binders enable two or more surfaces to become
`
`united. Binders may be broadly classified into two main groups: organic and
`
`inorganic, with the organic materials being subdivided into those of animal, vegetable,
`
`and synthetic origin. Another way of classifying binders is based upon the chemical
`
`nature of these compounds: (1) protein or protein derivatives; (2) starch, cellulose, or
`
`gums and their derivatives; (3) thermoplastic synthetic resins; (4) thermosetting
`
`synthetic resins; (5) natural resins and bitumens; (6) natural and synthetic rubbers; and
`
`(7) inorganic binders. Binders also may be classified according to the purpose for
`
`which they are used: (1) bonding rigid surfaces, such as, rigid plastics, and metals;
`
`and (2) bonding flexible surfaces, such as, flexible plastics and thin metallic sheets,
`
`among others.
`
`Thermoplastic binders comprise a variety of polymerized materials
`
`such as polyvinyl acetate, polyvinyl butyral, polyvinyl alcohol, and other polyvinyl
`
`resins; polystyrene resins; acrylic and methacrylic acid ester resins; cyanoacrylates;
`
`and various other synthetic resins such as polyisobutylene polyamides, courmarone-
`
`idene products, and silicones. Such thermoplastic binders may have permanent
`
`solubility and fusibility so that they creep under stress and soften when heated. They
`
`are used for the manufacturing various products, for example, tapes.
`
`Thermosetting binders comprise a variety of phenol-aldehyde, urea-
`
`aldehyde, melamine-aldehyde, and other condensation-polymerization materials like
`
`the furane and polyurethane resins. Thermosetting binders may be characterized by
`
`being transformed into insoluble and infusible materials by means of either heat or
`
`PGR2022-00022 - Petitioner’s Exhibit 1006 – Page 2
`
`

`

`catalytic action. Binder compositions containing phenol-, resorcinol-, urea-,
`
`melamine-formaldehyde, phenolfurfuraldehyde, and the like are used for the bonding
`
`of textiles, plastics, rubbers, and many other materials.
`
`As indicated above, binders are useful in fabricating materials from
`
`non or loosely assembled matter. Accordingly, compositions capable of functioning
`
`as a binder are desirable.
`
`SUMMARY
`
`Cured or uncured binders in accordance with an illustrative
`
`embodiment of the present invention may comprise one or more of the following
`
`features or combinations thereof, hi addition, materials in accordance with the
`
`present invention may comprise one or more of the following features or
`
`combinations thereof:
`
`Initially it should be appreciated that the binders of the present
`
`invention may be utilized in a variety of fabrication applications to produce or
`
`promote cohesion in a collection of non or loosely assembled matter. A collection
`
`includes two or more components. The binders produce or promote cohesion in at
`
`least two of the components of the collection. For example, subject binders are
`
`capable of holding a collection of matter together such that the matter adheres in a
`
`manner to resist separation. The binders described herein can be utilized in the
`
`fabrication of any material.
`
`One potential feature of the present binders is that they are
`
`formaldehyde free. Accordingly, the materials the binders are disposed upon may
`
`also be formaldehyde free, (e.g., fiberglass). In addition, the present binders may
`
`have a reduced trimethylamine content as compared to other known binders.
`
`With respect to the present binder's chemical constituents, they may
`
`include ester and/or polyester compounds. The binders may include ester and/or
`
`polyester compounds in combination with a vegetable oil, such as soybean oil.
`
`Furthermore, the binders may include ester and/or polyester compounds in
`
`combination with sodium salts of organic acids. The binders may include sodium
`
`salts of inorganic acids. The binders may also include potassium salts of organic
`
`acids. Moreover, the binders may include potassium salts of inorganic acids. The
`
`PGR2022-00022 - Petitioner’s Exhibit 1006 – Page 3
`
`

`

`described binders may include ester and/or polyester compounds in combination with
`
`a clay additive, such as montmorillonite.
`
`Furthermore, the binders of the present invention may include a
`
`product of a Maillard reaction. For example, see Fig. 2. As shown in Fig. 2 ,
`
`Maillard reactions produce melanoidins, i.e., high molecular weight, furan ring and
`
`nitrogen-containing polymers that vary in structure depending on the reactants and
`
`conditions of their preparation. Melanoidins display a C:N ratio, degree of
`
`unsaturation, and chemical aromaticity that increase with temperature and time of
`
`heating. (See, Ames, J.M. in "The Maillard Browning Reaction - an update,"
`
`Chemistry and Industry (Great Britain), 1988, 7, 558-561, the disclosure of which is
`
`hereby incorporated herein by reference). Accordingly, the subject binders may be
`
`made via a Maillard reaction and thus contain melanoidins. It should be appreciated
`
`that the subject binders may contain melanoidins, or other Maillard reaction products,
`
`which products are generated by a separate process and then simply added to the
`
`composition that makes up the binder. The melanoidins in the binder may be water-
`
`insoluble. Moreover, the binders may be thermoset binders.
`
`The Maillard reactants to produce a melanoidin may include an amine
`
`reactant reacted with a reducing-sugar carbohydrate reactant. For example, an
`
`ammonium salt of a monomelic polycarboxylic acid may be reacted with (i) a
`
`monosaccharide in its aldose or ketose form or (ii) a polysaccharide or (iii) with
`
`combinations thereof. In another variation, an ammonium salt of a polymeric
`
`polycarboxylic acid may be contacted with (i) a monosaccharide in its aldose or
`
`ketose form or (ii) a polysaccharide, or (iii) with combinations thereof. In yet another
`
`variation, an amino acid may be contacted with (i) a monosaccharide in its aldose or
`
`ketose form, or (ii) with a polysaccharide or (iii) with combinations thereof.
`
`Furthermore, a peptide may be contacted with (i) a monosaccharide in its aldose or
`
`ketose form or (ii) with a polysaccharide or (iii) with combinations thereof.
`
`Moreover, a protein may be contacted with (i) a monosaccharide in its aldose or
`
`ketose form or (ii) with a polysaccharide or (iii) with combinations thereof.
`
`It should also be appreciated that the binders of the present invention
`
`may include melanoidins produced in non-sugar variants of Maillard reactions. In
`
`these reactions an amine reactant is contacted with a non-carbohydrate carbonyl
`
`PGR2022-00022 - Petitioner’s Exhibit 1006 – Page 4
`
`

`

`reactant. In one illustrative variation, an ammonium salt of a monomeric
`
`polycarboxylic acid is contacted with a non-carbohydrate carbonyl reactant such as,
`
`pyruvaldehyde, acetaldehyde, crotonaldehyde, 2-furaldehyde, quinone, ascorbic acid,
`
`or the like, or with combinations thereof. In another variation, an ammonium salt of a
`
`polymeric polycarboxylic acid may be contacted with a non-carbohydrate carbonyl
`
`reactant such as, pyruvaldehyde, acetaldehyde, crotonaldehyde, 2-furaldehyde,
`
`quinone, ascorbic acid, or the like, or with combinations thereof. In yet another
`
`illustrative variation, an amino acid may be contacted with a non-carbohydrate
`
`carbonyl reactant such as, pyruvaldehyde, acetaldehyde, crotonaldehyde, 2-
`
`furaldehyde, quinone, ascorbic acid, or the like, or with combinations thereof. In
`
`another illustrative variation, a peptide may be contacted with a non-carbohydrate
`
`carbonyl reactant such as, pyruvaldehyde, acetaldehyde, crotonaldehyde, 2-
`
`furaldehyde, quinone, ascorbic acid, or the like, or with combinations thereof. In still
`
`another illustrative variation, a protein may contacted with a non-carbohydrate
`
`carbonyl reactant such as, pyruvaldehyde, acetaldehyde, crotonaldehyde, 2-
`
`furaldehyde, quinone, ascorbic acid, and the like, or with combinations thereof.
`
`The melanoidins discussed herein may be generated from melanoidin
`
`reactant compounds. These reactant compounds are disposed in an aqueous solution
`
`at an alkaline pH and therefore are not corrosive. That is, the alkaline solution
`
`prevents or inhibits the eating or wearing away of a substance, such as metal, caused
`
`by chemical decomposition brought about by, for example, an acid. The reactant
`
`compounds may include a reducing-sugar carbohydrate reactant and an amine
`
`reactant. In addition, the reactant compounds may include a non-carbohydrate
`
`carbonyl reactant and an amine reactant.
`
`It should also be understood that the binders described herein may be
`
`made from melanoidin reactant compounds themselves. That is, once the Maillard
`
`reactants are mixed, this mixture can function as a binder of the present invention.
`
`These binders may be utilized to fabricate uncured, formaldehyde-free matter, such as
`
`fibrous materials.
`
`In the alternative, a binder made from the reactants of a Maillard
`
`reaction may be cured. These binders may be used to fabricate cured formaldehyde-
`
`PGR2022-00022 - Petitioner’s Exhibit 1006 – Page 5
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`

`

`firee matter, such as, fibrous compositions. These compositions are water-resistant
`
`and, as indicated above, include water-insoluble melanoidins.
`
`It should b e appreciated that the binders described herein may be used
`
`in manufacturing products from a collection of non or loosely assembled matter. For
`
`example, these binders may b e employed to fabricate fiber products. These products
`
`may be made from woven or nonwoven fibers. The fibers can be heat-resistant or non
`
`heat-resistant fibers or combinations thereof, hi one illustrative embodiment, the
`
`binders are used to bind glass fibers to make fiberglass.
`
`In another illustrative
`
`embodiment, the binders are used to make cellulosic compositions. With respect to
`
`cellulosic compositions,
`
`the binders may be used to bind cellulosic matter to fabricate,
`
`for example, wood fiber board which has desirable physical properties (e.g.,
`
`mechanical strength).
`
`One embodiment of the invention is directed to a method for
`
`manufacturing products from a collection of non-or loosely assembled matter. One
`
`example of using this method is in the fabrication of fiberglass. However, as
`
`indicated above this method can be utilized in the fabrication of any material, as long
`
`as the method produces or promotes cohesion when utilized. The method may
`
`include contacting the fibers with a thermally-curable, aqueous binder. The binder
`
`may include (i) an ammonium salt of a polycarboxylic acid reactant and (ii) a
`
`reducing-sugar carbohydrate reactant. These two reactants are melanoidin reactants
`
`(i.e., these reactants produce melanoidins when reacted under conditions to initiate a
`
`Maillard reaction.) The method can further include removing water from the binder
`
`in contact with the fibers (i.e., the binder is dehydrated). The method can also include
`
`curing the binder in contact with the glass fibers (e.g., thermally curing the binder).
`
`Another example of utilizing this method is in the fabrication of
`
`cellulosic materials. The method may include contacting the cellulosic material (e.g.,
`
`cellulose fibers) with a thermally-curable, aqueous binder. The binder may include (i)
`
`an ammonium salt of a polycarboxylic acid reactant and (ii) a reducing-sugar
`
`carbohydrate reactant. As indicated above, these two reactants are melanoidin
`
`reactant compounds. The method can also include removing water from the binder in
`
`contact with the cellulosic material. As before, the method can also include curing the
`
`binder (e.g., thermal curing).
`
`PGR2022-00022 - Petitioner’s Exhibit 1006 – Page 6
`
`

`

`One way of using the binders is to bind glass fibers together such that
`
`they become organized into a fiberglass mat. The mat of fiberglass may be processed
`
`to form one of several types of fiberglass materials, such as fiberglass insulation. In
`
`one example, the fiberglass material may have glass fibers present in the range from
`
`about 80% to about 99% by weight. The uncured binder may function to hold the
`
`glass fibers together. The cured binder may function to hold the glass fibers together.
`
`hi addition, a fibrous product is described that includes a binder in
`
`contact with cellulose fibers, such as those in a mat of wood shavings or sawdust.
`
`The mat may be processed to form one of several types of wood fiber board products.
`
`In one variation, the binder is uncured. hi this variation, the uncured binder may
`
`function to hold the cellulosic fibers together, hi the alternative, the cured binder may
`
`function to hold the cellulosic fibers together.
`
`Additional features of the present invention will become apparent to
`
`those skilled in the art upon consideration of the following detailed description of
`
`illustrative embodiments exemplifying the best mode of carrying out the invention as
`
`presently perceived.
`
`BRIEF DESCRIPTION OF THE DRAWINGS
`
`Fig. 1 shows a number of illustrative reactants for producing
`
`melanoidins;
`
`Fig. 2 illustrates a Maillard reaction schematic when reacting a
`
`reducing sugar with an amino compound;
`
`Fig. 3 shows the FT-IR spectrum of an illustrative embodiment of a
`
`dried binder of the present disclosure;
`
`Fig. 4 shows the FT-IR spectrum of an illustrative embodiment of a
`
`cured binder of the present disclosure;
`
`Fig. 5 shows the 650 0F hot surface performance of a fiberglass pipe
`
`insulation material fabricated with an illustrative embodiment of a binder of the
`
`present disclosure;
`Fig. 6 shows the 1000 0F hot surface performance of a fiberglass pipe
`
`insulation material fabricated with an illustrative embodiment of a binder of the
`
`PGR2022-00022 - Petitioner’s Exhibit 1006 – Page 7
`
`

`

`present disclosure.
`
`DETAILED DESCRIPTION
`
`While the invention is susceptible to various modifications and
`
`alternative forms, specific embodiments will herein be described in detail. It should
`
`be understood, however, that there is no intent to limit the invention to the particular
`
`forms described, but on the contrary, the intention is to cover all modifications,
`
`equivalents, and alternatives falling within the spirit and scope of the invention.
`
`As used herein, the phrase "formaldehyde-free" means that a binder or
`
`a material that incorporates a binder liberates less than about 1 ppm formaldehyde as a
`
`result of drying and/or curing. The 1 ppm is based on the weight of sample being
`
`measured for formaldehyde release.
`
`Cured indicates that the binder has been exposed to conditions to so as
`
`to initiate a chemical change. Examples of these chemical changes include, but are
`
`not limited to, (i) covalent bonding, (ii) hydrogen bonding of binder components, and
`
`chemically cross-linking the polymers and/or oligomers in the binder. These changes
`
`may increase the binder's durability and solvent resistance as compared to the
`
`uncured binder. Curing a binder may result in the formation of a thermoset material.
`
`Furthermore, curing may include the generation of melanoidins. These melanoidins
`
`may be generated from a Maillard reaction from melanoidin reactant compounds,
`
`i
`
`addition, a cured binder may result in an increase in adhesion between the matter in a
`
`collection as compared to an uncured binder. Curing can be initiated by, for example,
`
`heat, electromagnetic radiation or, electron beams.
`
`In a situation where the chemical change in the binder results in the
`
`release of water, e.g., polymerization and cross-linking, a cure can be determined by
`
`the amount of water released above that would occur from drying alone. The
`
`techniques used to measure the amount of water released during drying as compared
`
`to when a binder is cured, are well known in the art.
`
`In accordance with the above paragraph, an uncured binder is one that
`
`has not been cured.
`
`As used herein, the term "alkaline" indicates a solution having a pH
`
`that is greater than or equal to about 7. For example, the pH of the solution can be
`
`PGR2022-00022 - Petitioner’s Exhibit 1006 – Page 8
`
`

`

`less than or equal
`
`to about 10. In addition,
`
`the solution may have a pH from about 7
`
`to about 10, or from about 8 to about 10, or from about 9 to about 10.
`
`A s used herein,
`
`the term "ammonium"
`
`includes, but is not limited to,
`
`1TMH4, K H3R 1, and TSIH2R 1R 2, where R 1 and R 2 are each independently
`4TSJH2R 1R 2, and where R 1 and R 2 are selected from alkyl, cycloalkyl,
`alkenyl,
`cycloalkenyl
`, heterocyclyl
`, aryl, and heteroaryl.
`
`selected in
`
`The term "alkyl" refers to a saturated monovalent
`
`chain of carbon
`
`atoms, which may b e optionally branched;
`
`the term "cycloalkyl"
`
`refers to a
`
`monovalent
`
`chain of carbon atoms, a portion of which forms a ring;
`
`the term
`
`"alkenyl" refers to an unsaturated monovalent chain of carbon atoms including at least
`
`one double bond, which may b e optionally branched;
`
`the term "cycloalkenyl"
`
`refers
`
`to an unsaturated monovalent
`
`chain of carbon atoms, a portion of which forms a ring;
`
`the term "heterocyclyl"
`
`refers to a monovalent chain of carbon and heteroatoms,
`
`wherein the heteroatoms
`
`are selected from nitrogen, oxygen, and sulfur, a portion of
`
`which,
`
`including at least one heteroatom,
`
`form a ring;
`
`the term "aryl" refers to an
`
`aromatic mono or polycyclic
`
`ring of carbon atoms, such as phenyl, naphthyl, and the
`
`like; and the term "heteroaryl"
`
`refers to an aromatic mono or polycyclic ring of
`
`carbon atoms and at least one heteroatom selected from nitrogen, oxygen, and sulfur,
`
`such as pyridinyl, pyrimidinyl,
`
`indolyl, benzoxazolyl,
`
`and the like.
`
`It is to b e
`
`understood that each of alkyl, cycloalkyl, alkenyl, cycloalkenyl,
`
`and heterocyclyl may
`
`b e optionally substituted with independently selected groups such as alkyl, haloalkyl,
`
`hydroxyalkyl,
`
`aminoalkyl,
`
`carboxylic acid and derivatives
`
`thereof,
`
`including esters,
`
`amides, and nitriles, hydroxy, alkoxy, acyloxy, amino, alkyl and dialkylamino,
`
`acylamino,
`
`thio, and the like, and combinations
`
`thereof.
`
`It is further to b e understood
`
`that each of aryl and heteroaryl may b e optionally substituted with one or more
`
`independently
`
`selected substituents,
`
`such as halo, hydroxy, amino, alkyl or
`
`dialkylamino,
`
`alkoxy, alkylsulfonyl,
`
`cyano, nitro, and the like.
`
`A s used herein,
`
`the term "polycarboxylic
`
`acid" indicates a
`
`dicarboxylic,
`
`tricarboxylic,
`
`tetracarboxylic,
`
`pentacarboxylic,
`
`and like monomelic
`
`polycarboxylic
`
`acids, and anhydrides, and combinations
`
`thereof, as well as polymeric
`
`polycarboxylic
`
`acids, anhydrides,
`
`copolymers, and combinations
`
`thereof.
`
`In one
`
`aspect, the polycarboxylic
`
`acid ammonium salt reactant
`
`is sufficiently non- volatile to
`
`PGR2022-00022 - Petitioner’s Exhibit 1006 – Page 9
`
`

`

`maximize its ability to remain available for reaction with the carbohydrate reactant of
`
`a Maillard reaction (discussed below). In another aspect, the polycarboxylic acid
`
`ammonium salt reactant may be substituted with other chemical functional groups.
`
`Illustratively, a monomeric polycarboxylic acid may be a dicarboxylic
`
`acid, including, but not limited to, unsaturated aliphatic dicarboxylic acids, saturated
`
`aliphatic dicarboxylic acids, aromatic dicarboxylic acids, unsaturated cyclic
`
`dicarboxylic acids, saturated cyclic dicarboxylic acids, hydroxy-substituted
`
`derivatives thereof, and the like. Or, illustratively, the polycarboxylic acid(s) itself
`
`may be a tricarboxylic acid, including, but not limited to, unsaturated aliphatic
`
`tricarboxylic acids, saturated aliphatic tricarboxylic acids, aromatic tricarboxylic
`
`acids, unsaturated cyclic tricarboxylic acids, saturated cyclic tricarboxylic acids,
`
`hydroxy-substituted derivatives thereof, and the like. It is appreciated that any such
`
`polycarboxylic acids may be optionally substituted, such as with hydroxy, halo, alkyl,
`
`alkoxy, and the like. In one variation, the polycarboxylic acid is the saturated
`
`aliphatic tricarboxylic acid, citric acid. Other suitable polycarboxylic acids are
`
`contemplated to include, but are not limited to, aconitic acid, adipic acid, azelaic acid,
`
`butane tetracarboxylic acid dihydride, butane tricarboxylic acid, chlorendic acid,
`
`citraconic acid, dicyclopentadiene-maleic acid adducts, diethylenetriamine
`
`pentaacetic acid, adducts of dipentene and maleic acid, ethylenediamine tetraacetic
`
`acid (EDTA), fully maleated rosin, maleated tall-oil fatty acids, fumaric acid, glutaric
`
`acid, isophthalic acid, itaconic acid, maleated rosin oxidized with potassium peroxide
`
`to alcohol then carboxylic acid, maleic acid, malic acid, mesaconic acid, biphenol A
`
`or bisphenol F reacted via the KOLBE-Schmidt reaction with carbon dioxide to
`
`introduce 3-4 carboxyl groups, oxalic acid, phthalic acid, sebacic acid, succinic acid,
`
`tartaric acid, terephthalic acid, tetrabromophthalic acid, tetrachlorophthalic acid,
`
`tetrahydrophthalic acid, trimellitic acid, trimesic acid, and the like, and anhydrides,
`
`and combinations thereof.
`
`Illustratively, a polymeric polycarboxylic acid may be an acid, for
`
`example, polyacrylic acid, polymethacrylic acid, polymaleic acid, and like polymeric
`
`polycarboxylic acids, copolymers thereof, anhydrides thereof, and mixtures thereof.
`
`Examples of commercially available polyacrylic acids include AQUASET-529
`
`(Rohm & Haas, Philadelphia, PA, USA), CRITERION 2000 (Kemira, Helsinki,
`
`PGR2022-00022 - Petitioner’s Exhibit 1006 – Page 10
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`

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`Finland, Europe), NFl (H.B. Fuller, St. Paul, MN, USA), and SOKALAN (BASF,
`
`Ludwigshafen, Germany, Europe). With respect to SOKALAN, this is a water-
`
`soluble polyacrylic copolymer of acrylic acid and maleic acid, having a molecular
`
`weight of approximately 4000. AQUASET- 529 is a composition containing
`
`polyacrylic acid cross-linked with glycerol, also containing sodium hypophosphite as
`
`a catalyst. CRITERION 2000 is an acidic solution of a partial salt of polyacrylic acid,
`
`having a molecular weight of approximately 2000. With respect to NFl, this is a
`
`copolymer containing carboxylic acid functionality and hydroxy functionality, as well
`
`as units with neither functionality; NFl also contains chain transfer agents, such as
`
`sodium hypophosphite or organophosphate catalysts.
`
`Further, compositions including polymeric polycarboxylic acids are
`
`also contemplated to be useful in preparing the binders described herein, such as those
`
`compositions described in U.S. Patents Nos. 5,318,990, 5,661,213, 6,136,916, and
`
`6,331,350, the disclosures of which are hereby incorporated herein by reference. In
`
`particular, in U.S. Patents Nos. 5,318,990 and 6,331,350 an aqueous solution of a
`
`polymeric polycarboxylic acid, a polyol, and a catalyst is described.
`
`As described in U.S. Patents Nos. 5,318,990 and 6,331,350, the
`
`polymeric polycarboxylic acid comprises an organic polymer or oligomer containing
`
`more than one pendant carboxy group. The polymeric polycarboxylic acid may be a
`
`homopolymer or copolymer prepared from unsaturated carboxylic acids including, but
`
`not necessarily limited to, acrylic acid, methacrylic acid, crotonic acid, isocrotonic
`
`acid, maleic acid, cinnamic acid, 2-methylmaleic acid, itaconic acid, 2-methylitaconic
`
`acid,
`
`,j6-methyleneglutaric acid, and the like. Alternatively, the polymeric
`
`polycarboxylic acid may be prepared from unsaturated anhydrides including, but not
`
`necessarily limited to, maleic anhydride, itaconic anhydride, acrylic anhydride,
`
`methacrylic anhydride, and the like, as well as mixtures thereof. Methods for
`
`polymerizing these acids and anhydrides are well-known in the chemical art. The
`
`polymeric polycarboxylic acid may additionally comprise a copolymer of one or more
`
`of the aforementioned unsaturated carboxylic acids or anhydrides and one or more
`
`vinyl compounds including, but not necessarily limited to, styrene,
`
`-methylstyrene,
`
`acrylonitrile, methacrylonitrile, methyl acrylate, ethyl acrylate, n-butyl acrylate,
`
`isobutyl acrylate, methyl methacrylate, n-butyl methacrylate, isobutyl methacrylate,
`
`PGR2022-00022 - Petitioner’s Exhibit 1006 – Page 11
`
`

`

`glycidyl methacrylate, vinyl methyl ether, vinyl acetate, and the like. Methods for
`
`preparing these copolymers are well-known in the art. The polymeric polycarboxylic
`
`acids may comprise homopolymers and copolymers of polyacrylic acid. The
`
`molecular weight of the polymeric polycarboxylic acid, and in particular polyacrylic
`
`acid polymer, may be is less than 10000, less than 5000, or about 3000 or less. For
`
`example, the molecular weight may be 2000.
`
`As described in U.S. Patents Nos. 5,318,990 and 6,331,350, the polyol
`
`(in a composition including a polymeric polycarboxylic acid) contains at least two
`
`hydroxyl groups. The polyol should be sufficiently nonvolatile such that it will
`
`substantially remain available for reaction with the polymeric polycarboxylic acid in
`
`the composition during heating and curing operations. The polyol may be a
`
`compound with a molecular weight less than about 1000 bearing at least two hydroxyl
`
`groups such as, ethylene glycol, glycerol, pentaerythritol, trimethylol propane,
`
`sorbitol, sucrose, glucose, resorcinol, catechol, pyrogallol, glycollated ureas, 1,4-
`
`cyclohexane diol, diethanolamine, triethanolamine, and certain reactive polyols, for
`example, /3-hydroxyalkylamides such as, for example, bis[N,N-di(b -
`hydroxyethyl)]adipamide, or it may be an addition polymer containing at least two
`
`hydroxyl groups such as, polyvinyl alcohol, partially hydrolyzed polyvinyl acetate,
`
`and homopolymers or copolymers of hydroxyethyl(meth)acrylate,
`
`hydroxypropyl(meth)acrylate, and the like.
`
`As described in U.S. Patents Nos. 5,318,990 and 6,331,350, the
`
`catalyst (in a composition including a polymeric polycarboxylic acid) is a
`
`phosphorous-containing accelerator which may be a compound with a molecular
`
`weight less than about 1000 such as, an alkali metal polyphosphate, an alkali metal
`
`dihydrogen phosphate, a polyphosphoric acid, and an alkyl phosphinic acid or it may
`
`be an oligomer or polymer bearing phosphorous-containing groups, for example,
`
`addition polymers of acrylic and/or maleic acids formed in the presence of sodium
`
`hypophosphite, addition polymers prepared from ethylenically unsaturated monomers
`
`in the presence of phosphorous salt chain transfer agents or terminators, and addition
`
`polymers containing acid-functional monomer residues, for example, copolymerized
`
`phosphoethyl methacrylate, and like phosphonic acid esters, and copolymerized vinyl
`
`sulfonic acid monomers, and their salts. The phosphorous-containing accelerator may
`
`PGR2022-00022 - Petitioner’s Exhibit 1006 – Page 12
`
`

`

`be used at a level of from about 1% to about 40%, by weight based on the combined
`
`weight of the polymeric polycarboxylic acid and the polyol. A level of phosphorous-
`
`containing accelerator of from about 2.5% to about 10%, by weight based on the
`
`combined weight of the polymeric polycarboxylic acid and the polyol may be used.
`
`Examples of such catalysts include, but are not limited to, sodium hypophosphite,
`
`sodium phosphite, potassium phosphite, disodium pyrophosphate, tetrasodium
`
`pyrophosphate, sodium tripolyphosphate, sodium hexametaphosphate, potassium
`
`phosphate, potassium polymetaphosphate, potassium polyphosphate, potassium
`
`tripolyphosphate, sodium trimetaphosphate, and sodium tetrametaphosphate, as well
`
`as mixtures thereof.
`
`Compositions including polymeric polycarboxylic acids described in
`
`U.S. Patents Nos. 5,661,213 and 6,136,916 that are contemplated to be useful in
`
`preparing the binders described herein comprise an aqueous solution of a polymeric
`
`polycarboxylic acid, a polyol containing at least two hydroxyl groups, and a
`
`phosphorous-containing accelerator, wherein the ratio of the number of equivalents of
`
`carboxylic acid groups, to the number of equivalents of hydroxyl groups is from about
`
`1:0.01 to about 1:3
`
`As disclosed in U.S. Patents Nos. 5,661,213 and 6,136,916, the
`
`polymeric polycarboxylic acid may be, a polyester containing at least two carboxylic
`
`acid groups or an addition polymer or oligomer containing at least two copolymerized
`
`carboxylic acid-functional monomers. The polymeric polycarboxylic acid is
`
`preferably an addition polymer formed from at least one ethylenically unsaturated
`
`monomer. The addition polymer may be in the form of a solution of the addition
`
`polymer in an aqueous medium such as, an alkali-soluble resin which has been
`
`solubilized in a basic medium; in the form of an aqueous dispersion, for example, an
`
`emulsion-polymerized dispersion; or in the form of an aqueous suspension. The
`
`addition polymer must contain at least two carboxylic acid groups, anhydride groups,
`
`or salts thereof. Ethylenically unsaturated carboxylic acids such as, methacrylic acid,
`
`acrylic acid, crotonic acid, fumaric acid, maleic acid, 2-methyl maleic acid, itaconic
`
`acid, 2-methyl itaconic acid,
`
`,jS-methylene glutaric acid, monoalkyl maleates, and
`
`monoalkyl