EP4577695A1 - Additives for binders and/or fibrous compositions - Google Patents

Additives for binders and/or fibrous compositions

Info

Publication number
EP4577695A1
EP4577695A1 EP23772032.1A EP23772032A EP4577695A1 EP 4577695 A1 EP4577695 A1 EP 4577695A1 EP 23772032 A EP23772032 A EP 23772032A EP 4577695 A1 EP4577695 A1 EP 4577695A1
Authority
EP
European Patent Office
Prior art keywords
composition
monomeric units
alkyl group
alkylene oxide
fibers
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP23772032.1A
Other languages
German (de)
French (fr)
Inventor
Stacy L. ROHDE
Ioan Marcu
Mark W. Wolfinger
Vic Stanislawczyk
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lubrizol Advanced Materials Inc
Original Assignee
Lubrizol Advanced Materials Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lubrizol Advanced Materials Inc filed Critical Lubrizol Advanced Materials Inc
Publication of EP4577695A1 publication Critical patent/EP4577695A1/en
Pending legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
    • D21H17/72—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic material
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/10—Organic non-cellulose fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/36—Inorganic fibres or flakes
    • D21H13/38—Inorganic fibres or flakes siliceous
    • D21H13/40—Inorganic fibres or flakes siliceous vitreous, e.g. mineral wool, glass fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
    • D21H17/375—Poly(meth)acrylamide
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/08—Filter paper

Definitions

  • compositions including fibers, a binder, and an additive, wherein the additive may improve certain properties of the composition and/or reduce the amount of binder needed in the composition.
  • compositions including fibers and a binder may be used in many applications, including in making fibrous substrates, nonwoven mats, and/or papers.
  • the binder may, under certain conditions and/or in certain compositions, migrate to the surface during production of the composition.
  • the binder may migrate to the surface of the paper, and therefore be unevenly distributed through the thickness of the paper. This may result in undesirable physical properties of the paper, which could require the addition of more binder, or other changes to the composition and/or structure, to ensure that the paper meets certain required physical properties.
  • the disclosed technology solves this problem (and possibly others) by at least partially preventing binder migration in the composition during manufacture, via the addition of an additive as described herein.
  • compositions comprising fibers, a binder, and an additive
  • the binder comprises a colloidal dispersion of a polymer comprising 0.1 to 25 percent by weight acid-functionalized monomeric units, based on the total weight of the polymer, wherein the colloidal dispersion of a polymer has a pH of from 5 to 12
  • the additive comprises a water-soluble polymerization reaction product of monomeric units comprising from 5 to 99 weight percent monomeric units represented by at least one of the following general formulas A l or A2, based on the total weight of the additive:
  • R 1 is H, CH3, or C2H5;
  • R 2 is H or a C1-C4 alkyl group;
  • R 3 is a Ci-Ce alkyl group or a Ci-Ce alkylene group;
  • R 4 is H or a C1-C4 alkyl group;
  • R 5 is H or a Ci- C4 alkyl group;
  • R 6 is H, CH3, or C2H5;
  • R 7 is a Ci-Ce alkyl group or a Ci-Ce alkylene group;
  • R 8 is H or a C1-C4 alkyl group; and
  • R 9 is H or a C1-C4 alkyl group.
  • a method of making a fibrous substrate comprising forming fibers and a binder into the fibrous substrate, followed by adding an additive to the fibrous substrate, wherein: the binder comprises a colloidal dispersion of a polymer comprising 0.1 to 25 percent by weight acid-functionalized monomeric units, based on the total weight of the polymer based on the total weight of the polymer, wherein the colloidal dispersion of a polymer has a pH of from 5 to 12; and the additive comprises a water-soluble polymerization reaction product of monomeric units comprising from 5 to 99 weight percent monomeric units represented by at least one of the following general formulas Al or A2, based on the total weight of the additive: wherein, independently for each molecule of the monomeric units represented by at least one of the general formulas Al or A2: R 1 is H, CH3, or C2H5; R 2 is H or a C1-C4 alkyl group; R 3 is a Ci-Ce alkyl group or a Ci-C
  • a method of improving at least one physical property of a fibrous substrate wherein the fibrous substrate comprises fibers and a binder, wherein the method comprises adding an additive to the fibrous substrate, wherein: the binder comprises a colloidal dispersion of a polymer comprising 0.1 to 25 percent by weight acid-functionalized monomeric units, based on the total weight of the polymer based on the total weight of the polymer, wherein the colloidal dispersion of a polymer has a pH of from 5 to 12; and the additive comprises a water-soluble polymerization reaction product of monomeric units comprising from 5 to 99 weight percent monomeric units represented by at least one of the following general formulas Al or A2, based on the total weight of the additive: wherein, independently for each molecule of the monomeric units represented by at least one of the general formulas Al or A2: R 1 is H, CH3, or C2H5; R 2 is H or a C1-C4 alkyl group; R 3 is a C1-C6
  • a method of making a fibrous substrate comprising adding an additive to the fibrous substrate, wherein the additive reduces the amount of binder needed in the fibrous substrate to substantially maintain the physical properties of the fibrous substrate, wherein: the binder comprises a colloidal dispersion of a polymer comprising 0.1 to 25 percent by weight acid- functionalized monomeric units, based on the total weight of the polymer based on the total weight of the polymer, wherein the colloidal dispersion of a polymer has a pH of from 5 to 12; and the additive comprises a water-soluble polymerization reaction product of monomeric units comprising from 5 to 99 weight percent monomeric units represented by at least one of the following general formulas Al or A2, based on the total weight of the additive:
  • R 1 is H, CH3, or C2H5;
  • R 2 is H or a C1-C4 alkyl group;
  • R 3 is a Ci-Ce alkyl group or a Ci-Ce alkylene group;
  • R 4 is H or a C1-C4 alkyl group;
  • R 5 is H or a Ci- C4 alkyl group;
  • R 6 is H, CH3, or C2H5;
  • R 7 is a Ci-Ce alkyl group or a Ci-Ce alkylene group;
  • R 8 is H or a C1-C4 alkyl group; and
  • R 9 is H or a C1-C4 alkyl group.
  • composition of any one of embodiments 1 to 29, wherein the colloidal dispersion of a polymer comprises at least one of acrylic latex, styrene-butadiene resin latex, vinyl chloride copolymer latex, or vinylidene chloride copolymer latex.
  • composition of any one of embodiments 1 to 30, wherein the water-soluble polymerization reaction product of monomeric units comprises from 20 to 95 weight percent monomeric units represented by at least one of the general formulas Al or A2, based on the total weight of the additive.
  • composition of any one of embodiments 1 to 31, wherein the water-soluble polymerization reaction product of monomeric units comprises from 50 to 80 weight percent monomeric units represented by at least one of the general formulas Al or A2, based on the total weight of the additive.
  • composition of any one of embodiments 1 to 32, wherein the water-soluble polymerization reaction product of monomeric units comprises from 1 to 95 weight percent vinyl-group-containing monomeric units different from the monomeric units represented by at least one of the general formulas Al or A2, based on the total weight of the additive.
  • water-soluble polymerization reaction product of monomeric units comprises from 5 to 80 weight percent vinyl-group-containing monomeric units different from the monomeric units represented by at least one of the general formulas Al or A2, based on the total weight of the additive.
  • composition of any one of embodiments 1 to 34, wherein the water-soluble polymerization reaction product of monomeric units comprises from 20 to 50 weight percent vinyl-group-containing monomeric units different from the monomeric units represented by at least one of the general formulas Al or A2, based on the total weight of the additive.
  • composition of any one of embodiments 33 to 35, wherein the vinyl-group- containing monomeric units different from the monomeric units represented by at least one of the general formulas Al or A2 comprise at least one acrylate monomer and/or at least one styrene butadiene monomer.
  • composition of embodiment 36, wherein the at least one acrylate comprises at least one of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, ethylhexyl acrylate, or ethylhexyl methacrylate.
  • composition of embodiment 36, wherein the at least one acrylate comprises at least one monomeric unit represented by the following general formula B: wherein, independently for each molecule of the monomeric unit: R 10 is H, CH3, or C2H5; R 11 is a poly(alkylene oxide) of number average molecular weight of from 88 to 1200 g/mole, wherein the poly(alkylene oxide) is comprised of repeating alkylene oxide units, and wherein each alkylene oxide unit independently has from 2 to 4 carbons; and R 12 is H, a Ci-Cg alkyl group, or a Ci-Cs alkylene group.
  • R 10 is H, CH3, or C2H5
  • R 11 is a poly(alkylene oxide) of number average molecular weight of from 88 to 1200 g/mole, wherein the poly(alkylene oxide) is comprised of repeating alkylene oxide units, and wherein each alkylene oxide unit independently has from 2 to 4 carbons
  • R 12 is H, a Ci
  • composition of embodiment 38, wherein R 11 is a poly(alkylene oxide) of number average molecular weight of from 132 to 1100 g/mole.
  • composition of any one of embodiments 1 to 32, wherein the water-soluble polymerization reaction product of monomeric units comprises from 1 to 95 weight percent monomeric units represented by the following general formula B: wherein, independently for each molecule of the monomeric unit: R 10 is H, CH3, or C2H5; R 11 is a poly(alkylene oxide) of number average molecular weight of from 88 to 1200 g/mole, wherein the poly(alkylene oxide) is comprised of repeating alkylene oxide units, and wherein each alkylene oxide unit independently has from 2 to 4 carbons; and R 12 is H, a Ci-Cs alkyl group, or a Ci-Cs alkylene group.
  • R 10 is H, CH3, or C2H5
  • R 11 is a poly(alkylene oxide) of number average molecular weight of from 88 to 1200 g/mole, wherein the poly(alkylene oxide) is comprised of repeating alkylene oxide units, and wherein each alkylene oxide unit independently has from
  • composition of any one of embodiments 1 to 32, wherein the water-soluble polymerization reaction product of monomeric units comprises from 5 to 80 weight percent monomeric units represented by the following general formula B: wherein, independently for each molecule of the monomeric unit: R 10 is H, CH3, or C2H5; R 11 is a poly(alkylene oxide) of number average molecular weight of from 88 to 1200 g/mole, wherein the poly(alkylene oxide) is comprised of repeating alkylene oxide units, and wherein each alkylene oxide unit independently has from 2 to 4 carbons; and R 12 is H, a Ci-Cs alkyl group, or a Ci-Cs alkylene group.
  • R 10 is H, CH3, or C2H5
  • R 11 is a poly(alkylene oxide) of number average molecular weight of from 88 to 1200 g/mole, wherein the poly(alkylene oxide) is comprised of repeating alkylene oxide units, and wherein each alkylene oxide unit independently has from
  • composition of any one of embodiments 1 to 32, wherein the water-soluble polymerization reaction product of monomeric units comprises from 20 to 50 weight percent monomeric units represented by the following general formula B: wherein, independently for each molecule of the monomeric unit: R 10 is H, CH3, or C2H5; R 11 is a poly(alkylene oxide) of number average molecular weight of from 88 to 1200 g/mole, wherein the poly(alkylene oxide) is comprised of repeating alkylene oxide units, and wherein each alkylene oxide unit independently has from 2 to 4 carbons; and R 12 is H, a Ci-Cs alkyl group, or a Ci-Cs alkylene group.
  • R 10 is H, CH3, or C2H5
  • R 11 is a poly(alkylene oxide) of number average molecular weight of from 88 to 1200 g/mole, wherein the poly(alkylene oxide) is comprised of repeating alkylene oxide units, and wherein each alkylene oxide unit independently has from
  • composition of embodiment 49, wherein the natural fibers comprise cellulosic fibers.
  • a method of making a composition comprising combining, in any order, fibers, a binder, and an additive, wherein: the binder comprises a colloidal dispersion of a polymer comprising 0.1 to 25 percent by weight acid-functionalized monomeric units, based on the total weight of the polymer, wherein the colloidal dispersion of a polymer has a pH of from 5 to 12; and the additive comprises a water-soluble polymerization reaction product of monomeric units comprising from 5 to 99 weight percent monomeric units represented by at least one of the following general formulas Al or A2, based on the total weight of the additive: wherein, independently for each molecule of the monomeric units represented by at least one of the general formulas Al or A2: R 1 is H, CH3, or C2H5; R 2 is H or a C1-C4 alkyl group; R 3 is a Ci-C& alkyl group or a Ci-Ce alkylene group; R 4 is H or a C1-C4 alky
  • a method of making a fibrous substrate comprising forming fibers and a binder into the fibrous substrate, followed by adding an additive to the fibrous substrate, wherein: the binder comprises a colloidal dispersion of a polymer comprising 0.1 to 25 percent by weight acid-functionalized monomeric units, based on the total weight of the polymer, wherein the colloidal dispersion of a polymer has a pH of from 5 to 12; and the additive comprises a water- soluble polymerization reaction product of monomeric units comprising from 5 to 99 weight percent monomeric units represented by at least one of the following general formulas Al or A2, based on the total weight of the additive:
  • composition comprises from 0. 1 to 5 parts of the additive to 100 parts of the binder.
  • colloidal dispersion of a polymer comprises at least one of acrylic latex, styrene-butadiene resin latex, vinyl chloride copolymer latex, or vinylidene chloride copolymer latex.
  • the at least one acrylate comprises at least one of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, ethylhexyl acrylate, or ethylhexyl methacrylate.
  • the at least one acrylate comprises at least one monomeric unit represented by the following general formula B: wherein, independently for each molecule of the monomeric unit: R 10 is H, CH3, or C2H5; R 11 is a poly(alkylene oxide) of number average molecular weight of from 88 to 1200 g/mole, wherein the poly(alkylene oxide) is comprised of repeating alkylene oxide units, and wherein each alkylene oxide unit independently has from 2 to 4 carbons; and R 12 is H, a Ci-Cs alkyl group, or a Ci-Cs alkylene group.
  • R 10 is H, CH3, or C2H5
  • R 11 is a poly(alkylene oxide) of number average molecular weight of from 88 to 1200 g/mole, wherein the poly(alkylene oxide) is comprised of repeating alkylene oxide units, and wherein each alkylene oxide unit independently has from 2 to 4 carbons
  • R 12 is H, a Ci-Cs alkyl group
  • the water-soluble polymerization reaction product of monomeric units comprises from 1 to 95 weight percent monomeric units represented by the following general formula B: wherein, independently for each molecule of the monomeric unit: R 10 is H, CH3, or C2H5; R 11 is a poly(alkylene oxide) of number average molecular weight of from 88 to 1200 g/mole, wherein the poly(alkylene oxide) is comprised of repeating alkylene oxide units, and wherein each alkylene oxide unit independently has from 2 to 4 carbons; and R 12 is H, a Ci-Cs alkyl group, or a Ci-Cs alkylene group.
  • R 10 is H, CH3, or C2H5
  • R 11 is a poly(alkylene oxide) of number average molecular weight of from 88 to 1200 g/mole, wherein the poly(alkylene oxide) is comprised of repeating alkylene oxide units, and wherein each alkylene oxide unit independently has from 2 to 4 carbons
  • R 12 is H,
  • the water-soluble polymerization reaction product of monomeric units comprises from 5 to 80 weight percent monomeric units represented by the following general formula B: wherein, independently for each molecule of the monomeric unit: R 10 is H, CH3, or C2H5; R 11 is a poly(alkylene oxide) of number average molecular weight of from 88 to 1200 g/mole, wherein the poly(alkylene oxide) is comprised of repeating alkylene oxide units, and wherein each alkylene oxide unit independently has from 2 to 4 carbons; and R 12 is H, a Ci-Cs alkyl group, or a Ci-Cs alkylene group.
  • R 10 is H, CH3, or C2H5
  • R 11 is a poly(alkylene oxide) of number average molecular weight of from 88 to 1200 g/mole, wherein the poly(alkylene oxide) is comprised of repeating alkylene oxide units, and wherein each alkylene oxide unit independently has from 2 to 4 carbons
  • R 12 is H,
  • the indefinite article “a”/“an” is intended to mean one or more than one.
  • the phrase “at least one” means one or more than one of the following terms.
  • “a”/“an” and “at least one” may be used interchangeably.
  • “at least one of A, B or C” means that just one of A, B or C may be included, and any mixture of two or more of A, B and C may be included, in alternative embodiments.
  • the transitional term “comprising,” which is synonymous with “including,” “containing,” or “characterized by,” is inclusive or open-ended and does not exclude additional, un-recited elements or method steps.
  • the polymer comprises 0.1 to 25 (such as 0.1 to 20, 0.1 to 15, 0.1 to 10, 0.1 to 9, 0.1 to 8, 0.1 to 7, 0.1 to 6, 0.1 to 5, 0.1 to 4, 0.1 to 3, 0.1 to 2, 0.1 to 1, 0.1 to 0.5, 0.5 to 25, 0.5 to 20, 0.5 to 15, 0.5 to 10, 0.5 to 9, 0.5 to 8, 0.5 to 7, 0.5 to 6, 0.5 to 5, 0.5 to 4, 0.5 to 3, 0.5 to 2, 0.5 to 1, 1 to 25, 1 to 20, 1 to 15, 1 to 10, 1 to 9, 1 to 8, 1 to 7, 1 to 6,
  • the water-soluble polymerization reaction product of monomeric units comprises from 1 to 95 (such as from 2 to 95, from 3 to 95, from 4 to 95, from 5 to 95, from 10 to 95, from 15 to 95, from 20 to 95, from 25 to 95, from 1 to 90, from 2 to 90, from 3 to 90, from 4 to 90, from 5 to 90, from 10 to 90, from 15 to 90, from 20 to 90, from 25 to 90, from 1 to 85, from 2 to 85, from 3 to 85, from 4 to 85, from 5 to 85, from 10 to 85, from 15 to 85, from 20 to 85, from 25 to 85, from 1 to 80, from 2 to 80, from 3 to 80, from 4 to 80, from 5 to 80, from 10 to 80, from 15 to 80, from 20 to 80, from 25 to 80, from 1 to 70, from 2 to 70, from 3 to 70, from 4 to 70, from 5 to 70, from 10 to 70, from 15 to 70, from 20 to 80, from 25 to 80, from 1 to 70, from 2 to 70, from 3 to
  • R 10 is CH3. In certain embodiments, R 10 is C2H5. In certain embodiments, R 11 is a poly(alkylene oxide) of number average molecular weight of from 88 to 1200 (such as from 132 to 1200, from 88 to 1 100, or from 132 to 1 100) g/mole. Tn certain embodiments, each alkylene oxide unit independently has from 2 to 4 (such as from 2 to 3, from 3 to 4, 2, 3, or 4) carbon atoms.
  • R 12 is H, a Ci-Cs (such as a C1-C7, a Ci-Ce, a C1-C5, a C1-C4, a Ci-C 3 , a C1-C2, a C 2 -C 8 , a C2-C7, a C 2 -C 6 , a C2-C5, a C2-C4, a C 2 -C 3 , a C 3 -Cs, a C 3 -C 7 , a C 3 - Ce, a C 3 -Cs, a C 3 -C4, a C 4 -Cs, a C4-C7, a C4-C6, a C4-C5, a Cs-C 8 , a C5-C7, a C5-C6, a Ce-Cs, a C6-C7, a C7-C8, a Ci, a C2, a C 3 , a C4, a C5,
  • the water-soluble polymerization reaction product of monomeric units comprises from 1 to 95 (such as from 2 to 95, from 3 to 95, from 4 to 95, from 5 to 95, from 10 to 95, from 15 to 95, from 20 to 95, from 25 to 95, from 1 to 90, from 2 to 90, from 3 to 90, from 4 to 90, from 5 to 90, from 10 to 90, from 15 to 90, from 20 to 90, from 25 to 90, from 1 to 85, from 2 to 85, from 3 to 85, from 4 to 85, from 5 to 85, from 10 to 85, from 15 to 85, from 20 to 85, from 25 to 85, from 1 to 80, from 2 to 80, from 3 to 80, from 4 to 80, from 5 to 80, from 10 to 80, from 15 to 80, from 20 to 80, from 25 to 80, from 1 to 70, from 2 to 70, from 3 to 70, from 4 to 70, from 5 to 70, from 10 to 70, from 15 to 70, from 20 to 80, from 25 to 80, from 1 to 70, from 2 to 70, from 3 to
  • R 10 is H or CH3. In certain embodiments, R 10 is H or C2H5. In certain embodiments, R 10 is CH3 or C2H5. In certain embodiments, R 10 is H. In certain embodiments, R 10 is CH3. In certain embodiments, R 10 is C2H5. In certain embodiments, R 11 is a poly(alkylene oxide) of number average molecular weight of from 88 to 1200 (such as from 132 to 1200, from 88 to 1100, or from 132 to 1100) g/mole. In certain embodiments, each alkylene oxide unit independently has from 2 to 4 (such as from 2 to 3, from 3 to 4, 2, 3, or 4) carbon atoms.
  • certain fibrous compositions may suffer from binder migration, which may negatively impact physical properties of the fibrous compositions. It has been found that the additive(s) described herein may reduce or prevent binder migration in at least some fibrous compositions, and thus allow for reduced binder requirements and/or increased physical properties in the fibrous compositions. It is uncertain which physical properties of fibrous compositions may impact binder migration in the fibrous compositions, as it is not observed in all sheet-like fibrous compositions. However, despite these uncertainties, it is possible to directly observe whether binder migration occurs in certain sheet-like fibrous compositions; such methods are known to the industry.
  • this method may not work on certain fabrics, such as fabrics with a certain fiber composition which attracts the dye and/or fabrics that are too thin to visually observe binder migration through the thickness of the fabric. It is believed that it would be readily apparent to a person of ordinary skill in the art whether this method can successfully identify binder migration in a particular fabric after this procedure is conducted on the fabric.
  • Example 1 A polymeric latex was prepared through an emulsion polymerization process run in a 5 liter, 4-neck, spherical reactor fitted with half-moon blade agitator, temperature probe, condenser, and feed ports. The monomer was contained separately in a premixed emulsion vessel and gradually metered to the reactor over 2 hours to reach a steady and controlled reaction rate. Reaction was carried out as a semi-batch in-situ seeded process, where 5 weight % of the pre-emulsified monomer mixture was batch-polymerized to provide a consistent latex particle size. Seed formation temperature was 80 °C, and polymerization temperature was 83.5 °C, at atmospheric pressure.
  • the polymerization was performed in a hood with the reactor submerged in a water bath with controlled temperature. A slight nitrogen purge was applied throughout the reaction.
  • the pre-emulsion content was prepared by mixing 475 grams water (as used in the Examples, the term “water” refers to demineralized water), 30.88 grams of a 45% aqueous solution of Calfax® DB45 surfactant from Pilot Chemical, and subsequently adding the monomers under agitation: 883 grams styrene, 931 grams n-butyl acrylate, 57 grams of 50% aqueous solution of acrylamide, and 57 grams of methacrylic acid.
  • a one-liter reactor was charged with 336 grams of water, 1.68 grams of 0.15% Iron(II) sulfate heptahydrate, and 0.48 grams of 1% tetrasodium ethylenediaminetetraacetic acid (Na4- ETDA), and then was heated to 60 °C under a nitrogen blanket with proper agitation. At 60 °C, Initiator A was added to the reactor. After about 2 minutes, the monomer premix was proportioned to the reaction vessel over a period of 120 minutes, and reductant A was proportioned to the reactor over a period of 150 minutes. After completion of reductant A feed, the temperature of the reaction vessel was maintained at 60 °C for 60 minutes. The reactor was then cooled to 50 °C.
  • Example 4 A blend was prepared by first adjusting the Example 1 polymer latex with a 28% aqueous solution of ammonia to a pH > 9, and then mixing the resulting latex with the Example 2 additive in a weight ratio of 99 to 1.
  • Example 5 A blend was prepared by first adjusting the Example 1 polymer latex with a 95% aqueous solution of 2-amino-2-methyl-l -propanol (AMP-95) to a pH > 9, and then mixing the resulting latex with the Example 2 additive in a weight ratio of 99.5 to 0.5.
  • AMP-95 2-amino-2-methyl-l -propanol
  • Example 6 A blend was prepared by first neutralizing the Example 1 polymer latex with dimethylethanolamine (DMEA) to a pH > 9, and then mixing the resulting latex with the Example 2 additive in a weight ratio of 99.5 to 0.5.
  • DMEA dimethylethanolamine
  • Example 7 A blend was prepared by first neutralizing the Example 1 polymer latex with a 20% aqueous solution of sodium hydroxide to a pH > 9, and then mixing the resulting latex with the Example 2 additive in a weight ratio of 99.5 to 0.5.
  • Example 8 A polymeric latex was prepared and characterized the same way as described in Example 1, where the 57 grams of 50% aqueous solution of acrylamide were replaced by 57 grams of 50% aqueous solution of N-methylolacrylamide.
  • Example 9 A blend is prepared by first neutralizing the Example 8 polymer latex with a 28% aqueous solution of ammonia to a pH > 9, and then mixing the resulting latex with the Example 2 additive in a weight ratio of 99.5 to 0.5.
  • a three-liter reactor was charged with 720 grams of water, 5.6 grams of 0.15% Iron(II) sulfate heptahydrate, and 1.6 grams of 1% tetrasodium ethylenediaminetetraacetic acid (Na4-ETDA), and then was heated to 60 °C under a nitrogen blanket with proper agitation. At 60 °C, Initiator A was added to the reactor. After about 2 minutes, the monomer premix was proportioned to the reaction vessel over a period of 120 minutes, and reductant A was proportioned to the reactor over a period of 150 minutes. After completion of reductant A feed, the temperature of the reaction vessel was maintained at 60 °C for 60 minutes. The reactor was then cooled to 50 °C.
  • Example 11 A blend is prepared by first neutralizing the Example 1 polymer latex with a 28% aqueous solution of ammonia to a pH > 9, and then mixing the resulting latex with the Example 10 additive in a weight ratio of 99.5 to 0.5.
  • Paper properties were evaluated using a Whatman® 3MM CHR chromatography paper substrate, a Whatman® GF/A borosilicate glass substrate, or a spunbond polyester substrate.
  • Whatman® 3 MM CHR is a 100% pure cellulose sheet with no binder.
  • Whatman® GF/A is a 100% borosilicate glass sheet with no binder.
  • the substrate was saturated using a dip and squeeze method where the substrate was placed in a pan containing the diluted saturant. The substrate was removed from the bath and fed through nip rollers to squeeze off any excess material.
  • the sheets were dried on a steam can for one minute at 99 °C.
  • the dry polymer content was controlled at 20% based on the weight of the substrate.
  • the paper was conditioned at 21 °C and 50% relative humidity prior to testing. Paper properties were tested on the as- dried paper and after aging for five-minutes at 149 °C. Glass sheet samples were tested after aging for 2 minutes at 191 °C. Tensile properties were tested according to the Technical Association of the Pulp and Paper Industry (TAPP I) Standard T494 - Tensile properties of paper and paperboard. One-inch wide samples were cut in the cross-machine direction and pulled at twelve inches per minute using a two-inch gauge length. Wet tensile was evaluated after soaking the samples for two minutes in a 1% Triton® X-100 solution. An average of four samples was recorded for each polymer.
  • TAPP I Technical Association of the Pulp and Paper Industry
  • Bursting strength was measured using a Mullen Burst tester. The dry and wet bursting strength were tested according to according to the TAPPI Standard T403 - Bursting Strength of Paper. Wet burst was evaluated after soaking the samples for two minutes in a 1% Triton® X-100 solution. An average of eight samples were used with four wire side up and four felt side up.
  • Stiffness was tested according to TAPPI Standard T543 - Bending resistance of paper (Gurley -type tester). Samples were tested dry and after soaking for two minutes in a 1% Triton® X-100 solution. Samples were tested in the cross-machine direction. Two inch by 2.5 inch samples were tested with the 25 grams weight at the 2 inch from pivot position. An average of eight samples was used for each polymer.

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Abstract

Provided are compositions including fibers, a binder, and an additive, wherein: the binder includes a colloidal dispersion of a polymer comprising 0.1 to 25 percent by weight acid-functionalized monomeric units, based on the total weight of the polymer, wherein the colloidal dispersion of a polymer has a pH of from 5 to 12; and the additive includes a water-soluble polymerization reaction product of monomeric units including from 5 to 99 weight percent monomeric units represented by at least one of the general formulas A1 or A2 as described herein. Related methods and/or uses are also provided.

Description

ADDITIVES FOR BINDERS AND/OR FIBROUS COMPOSITIONS
[00011 The disclosed technology relates to compositions including fibers, a binder, and an additive, wherein the additive may improve certain properties of the composition and/or reduce the amount of binder needed in the composition.
[0002] Compositions including fibers and a binder may be used in many applications, including in making fibrous substrates, nonwoven mats, and/or papers. In certain of these compositions, in which the composition is formed into a sheet-like material, it has been found that the binder may, under certain conditions and/or in certain compositions, migrate to the surface during production of the composition. For example, in making a paper intended for use as a filtration medium, the binder may migrate to the surface of the paper, and therefore be unevenly distributed through the thickness of the paper. This may result in undesirable physical properties of the paper, which could require the addition of more binder, or other changes to the composition and/or structure, to ensure that the paper meets certain required physical properties.
[0003] The disclosed technology solves this problem (and possibly others) by at least partially preventing binder migration in the composition during manufacture, via the addition of an additive as described herein.
[0004] The subject matter disclosed herein provides a composition comprising fibers, a binder, and an additive, wherein: the binder comprises a colloidal dispersion of a polymer comprising 0.1 to 25 percent by weight acid-functionalized monomeric units, based on the total weight of the polymer, wherein the colloidal dispersion of a polymer has a pH of from 5 to 12; and the additive comprises a water-soluble polymerization reaction product of monomeric units comprising from 5 to 99 weight percent monomeric units represented by at least one of the following general formulas A l or A2, based on the total weight of the additive:
wherein, independently for each molecule of the monomeric units represented by at least one of the general formulas Al or A2: R1 is H, CH3, or C2H5; R2 is H or a C1-C4 alkyl group; R3 is a Ci-Ce alkyl group or a Ci-Ce alkylene group; R4 is H or a C1-C4 alkyl group; R5 is H or a Ci- C4 alkyl group; R6 is H, CH3, or C2H5; R7 is a Ci-Ce alkyl group or a Ci-Ce alkylene group; R8 is H or a C1-C4 alkyl group; and R9 is H or a C1-C4 alkyl group.
[0005] Also provided is a method of making a composition comprising combining, in any order, fibers, a binder, and an additive, wherein: the binder comprises a colloidal dispersion of a polymer comprising 0.1 to 25 percent by weight acid-functionalized monomeric units, based on the total weight of the polymer based on the total weight of the polymer, wherein the colloidal dispersion of a polymer has a pH of from 5 to 12; and the additive comprises a water- soluble polymerization reaction product of monomeric units comprising from 5 to 99 weight percent monomeric units represented by at least one of the following general formulas Al or A2, based on the total weight of the additive: wherein, independently for each molecule of the monomeric units represented by at least one of the general formulas Al or A2: R1 is H, CH3, or C2H5; R2 is H or a C1-C4 alkyl group; R3 is a Ci-Ce alkyl group or a Ci-Ce alkylene group; R4 is H or a C1-C4 alkyl group; R5 is H or a Ci- C4 alkyl group; R6 is H, CH3, or C2H5; R7 is a Ci-Ce alkyl group or a Ci-Ce alkylene group; R8 is H or a C1-C4 alkyl group; and R9 is H or a C1-C4 alkyl group.
[00061 Also provided is a method of making a fibrous substrate comprising forming fibers and a binder into the fibrous substrate, followed by adding an additive to the fibrous substrate, wherein: the binder comprises a colloidal dispersion of a polymer comprising 0.1 to 25 percent by weight acid-functionalized monomeric units, based on the total weight of the polymer based on the total weight of the polymer, wherein the colloidal dispersion of a polymer has a pH of from 5 to 12; and the additive comprises a water-soluble polymerization reaction product of monomeric units comprising from 5 to 99 weight percent monomeric units represented by at least one of the following general formulas Al or A2, based on the total weight of the additive: wherein, independently for each molecule of the monomeric units represented by at least one of the general formulas Al or A2: R1 is H, CH3, or C2H5; R2 is H or a C1-C4 alkyl group; R3 is a Ci-Ce alkyl group or a Ci-Ce alkylene group; R4 is H or a C1-C4 alkyl group; R5 is H or a Ci- C4 alkyl group; R6 is H, CH3, or C2H5; R7 is a Ci-Ce alkyl group or a Ci-Ce alkylene group; R8 is H or a C1-C4 alkyl group; and R9 is H or a C1-C4 alkyl group.
[0007] Also provided is a method of improving at least one physical property of a fibrous substrate, wherein the fibrous substrate comprises fibers and a binder, wherein the method comprises adding an additive to the fibrous substrate, wherein: the binder comprises a colloidal dispersion of a polymer comprising 0.1 to 25 percent by weight acid-functionalized monomeric units, based on the total weight of the polymer based on the total weight of the polymer, wherein the colloidal dispersion of a polymer has a pH of from 5 to 12; and the additive comprises a water-soluble polymerization reaction product of monomeric units comprising from 5 to 99 weight percent monomeric units represented by at least one of the following general formulas Al or A2, based on the total weight of the additive: wherein, independently for each molecule of the monomeric units represented by at least one of the general formulas Al or A2: R1 is H, CH3, or C2H5; R2 is H or a C1-C4 alkyl group; R3 is a C1-C6 alkyl group or a C1-C6 alkylene group; R4 is H or a C1-C4 alkyl group; R5 is H or a Ci- C4 alkyl group; R6 is H, CH3, or C2H5; R7 is a Ci-Ce alkyl group or a Ci-Ce alkylene group; R8 is H or a C1-C4 alkyl group; and R9 is H or a C1-C4 alkyl group.
[0008] Also provided is a method of making a fibrous substrate, wherein the fibrous substrate comprises fibers and a binder, the method comprising adding an additive to the fibrous substrate, wherein the additive reduces the amount of binder needed in the fibrous substrate to substantially maintain the physical properties of the fibrous substrate, wherein: the binder comprises a colloidal dispersion of a polymer comprising 0.1 to 25 percent by weight acid- functionalized monomeric units, based on the total weight of the polymer based on the total weight of the polymer, wherein the colloidal dispersion of a polymer has a pH of from 5 to 12; and the additive comprises a water-soluble polymerization reaction product of monomeric units comprising from 5 to 99 weight percent monomeric units represented by at least one of the following general formulas Al or A2, based on the total weight of the additive:
wherein, independently for each molecule of the monomeric units represented by at least one of the general formulas Al or A2: R1 is H, CH3, or C2H5; R2 is H or a C1-C4 alkyl group; R3 is a Ci-Ce alkyl group or a Ci-Ce alkylene group; R4 is H or a C1-C4 alkyl group; R5 is H or a Ci- C4 alkyl group; R6 is H, CH3, or C2H5; R7 is a Ci-Ce alkyl group or a Ci-Ce alkylene group; R8 is H or a C1-C4 alkyl group; and R9 is H or a C1-C4 alkyl group.
[0009] The following embodiments of the present subject matter are contemplated:
[0010] 1. A composition comprising fibers, a binder, and an additive, wherein: the binder comprises a colloidal dispersion of a polymer comprising 0.1 to 25 percent by weight acid- functionalized monomeric units, based on the total weight of the polymer, wherein the colloidal dispersion of a polymer has a pH of from 5 to 12; and the additive comprises a water-soluble polymerization reaction product of monomeric units comprising from 5 to 99 weight percent monomeric units represented by at least one of the following general formulas Al or A2, based on the total weight of the additive: wherein, independently for each molecule of the monomeric units represented by at least one of the general formulas Al or A2: R1 is H, CH3, or C2H5; R2 is H or a C1-C4 alkyl group; R3 is a Ci-Ce alkyl group or a Ci-Ce alkylene group; R4 is H or a C1-C4 alkyl group; R5 is H or a Ci- C4 alkyl group; R6 is H, CH3, or C2H5; R7 is a Ci-Ce alkyl group or a Ci-Ce alkylene group; R8 is H or a C1-C4 alkyl group; and R9 is H or a C1-C4 alkyl group.
[00111 2. The composition of embodiment 1, wherein, independently for each molecule of the monomeric units represented by at least one of the general formulas Al or A2: R1 is H or CH3; R2 is H or CH3; R4 is H or CH3; R5 is H or CH3; R6 is H or CH3; R8 is H or CH3; and R9 is H or CH3.
[0012] 3. The composition of either embodiment 1 or embodiment 2, wherein, independently for each molecule of the monomeric units represented by at least one of the general formulas Al or A2: R3 is a C1-C4 alkyl group or a C1-C4 alkylene group; and R7 is a Ci- C4 alkyl group or a C1-C4 alkylene group.
[0013] 4. The composition of any one of embodiments 1 to 3, wherein, independently for each molecule of the monomeric units represented by at least one of the general formulas Al or A2: R1 is CH3; R2 is H; R3 is C3H6; R4 is CH3; R5 is CH3; R6 is CH3; R7 is C3He; R8 is CH3; and R9 is CH3.
[0014] 5. The composition of any one of embodiments 1 to 4, wherein the binder is present in the composition in an amount of from 5 to 60 percent by weight, based on the total dry weight of the composition.
[0015] 6. The composition of any one of embodiments 1 to 5, wherein the binder is present in the composition in an amount of from 5 to 40 percent by weight, based on the total dry weight of the composition.
[0016] 7. The composition of any one of embodiments 1 to 6, wherein the binder is present in the composition in an amount of from 5 to 30 percent by weight, based on the total dry weight of the composition.
[0017] 8. The composition of any one of embodiments 1 to 7, wherein the binder is present in the composition in an amount of from 5 to 25 percent by weight, based on the total dry weight of the composition.
[0018] 9. The composition of any one of embodiments 1 to 8, wherein the binder is present in the composition in an amount of from 10 to 60 percent by weight, based on the total dry weight of the composition. [0019] 10. The composition of any one of embodiments 1 to 9, wherein the binder is present in the composition in an amount of from 10 to 40 percent by weight, based on the total dry weight of the composition.
[0020] 11. The composition of any one of embodiments 1 to 10, wherein the binder is present in the composition in an amount of from 10 to 30 percent by weight, based on the total dry weight of the composition.
[0021] 12. The composition of any one of embodiments 1 to 11, wherein the binder is present in the composition in an amount of from 10 to 25 percent by weight, based on the total dry weight of the composition.
[0022] 13. The composition of any one of embodiments 1 to 12, wherein the composition comprises from 0.01 to 30 parts of the additive to 100 parts of the binder.
[0023] 14. The composition of any one of embodiments 1 to 13, wherein the composition comprises from 0.01 to 25 parts of the additive to 100 parts of the binder.
[0024] 15. The composition of any one of embodiments 1 to 14, wherein the composition comprises from 0.05 to 20 parts of the additive to 100 parts of the binder.
[0025] 16. The composition of any one of embodiments 1 to 15, wherein the composition comprises from 0.05 to 10 parts of the additive to 100 parts of the binder.
[0026] 17. The composition of any one of embodiments 1 to 16, wherein the composition comprises from 0.1 to 20 parts of the additive to 100 parts of the binder.
[0027] 18. The composition of any one of embodiments 1 to 17, wherein the composition comprises from 0.1 to 10 parts of the additive to 100 parts of the binder.
[0028] 19. The composition of any one of embodiments 1 to 18, wherein the composition comprises from 0.1 to 5 parts of the additive to 100 parts of the binder.
[0029] 20. The composition of any one of embodiments 1 to 19, wherein the composition comprises from 0. 1 to 2.5 parts of the additive to 100 parts of the binder.
[0030] 21. The composition of any one of embodiments 1 to 20, wherein the composition comprises from 0.2 to 5 parts of the additive to 100 parts of the binder.
[0031] 22. The composition of any one of embodiments 1 to 21, wherein the composition comprises from 0.2 to 2.5 parts of the additive to 100 parts of the binder. [0032] 23. The composition of any one of embodiments 1 to 22, wherein the polymer comprises 0.5 to 10 percent by weight acid-functionalized monomeric units, based on the total weight of the polymer.
[0033] 24. The composition of any one of embodiments 1 to 23, wherein the polymer comprises 1 to 5 percent by weight acid-functionalized monomeric units, based on the total weight of the polymer.
[0034] 25. The composition of any one of embodiments 1 to 24, wherein the colloidal dispersion of a polymer has a pH of from 7 to 12.
[0035] 26. The composition of any one of embodiments 1 to 25, wherein the colloidal dispersion of a polymer has a pH of from 7 to 10.
[0036] 27. The composition of any one of embodiments 1 to 26, wherein the colloidal dispersion of a polymer has a pH of from 7 to 9.
[0037] 28. The composition of any one of embodiments 1 to 27, wherein the colloidal dispersion of a polymer has a pH of from 7.5 to 9.
[0038] 29. The composition of any one of embodiments 1 to 28, wherein the colloidal dispersion of a polymer has a pH of from 8 to 9.
[0039] 30. The composition of any one of embodiments 1 to 29, wherein the colloidal dispersion of a polymer comprises at least one of acrylic latex, styrene-butadiene resin latex, vinyl chloride copolymer latex, or vinylidene chloride copolymer latex.
[0040] 31. The composition of any one of embodiments 1 to 30, wherein the water-soluble polymerization reaction product of monomeric units comprises from 20 to 95 weight percent monomeric units represented by at least one of the general formulas Al or A2, based on the total weight of the additive.
[0041] 32. The composition of any one of embodiments 1 to 31, wherein the water-soluble polymerization reaction product of monomeric units comprises from 50 to 80 weight percent monomeric units represented by at least one of the general formulas Al or A2, based on the total weight of the additive.
[0042] 33. The composition of any one of embodiments 1 to 32, wherein the water-soluble polymerization reaction product of monomeric units comprises from 1 to 95 weight percent vinyl-group-containing monomeric units different from the monomeric units represented by at least one of the general formulas Al or A2, based on the total weight of the additive. [0043] 34. The composition of any one of embodiments 1 to 33, wherein the water-soluble polymerization reaction product of monomeric units comprises from 5 to 80 weight percent vinyl-group-containing monomeric units different from the monomeric units represented by at least one of the general formulas Al or A2, based on the total weight of the additive.
[0044] 35. The composition of any one of embodiments 1 to 34, wherein the water-soluble polymerization reaction product of monomeric units comprises from 20 to 50 weight percent vinyl-group-containing monomeric units different from the monomeric units represented by at least one of the general formulas Al or A2, based on the total weight of the additive.
[0045] 36. The composition of any one of embodiments 33 to 35, wherein the vinyl-group- containing monomeric units different from the monomeric units represented by at least one of the general formulas Al or A2 comprise at least one acrylate monomer and/or at least one styrene butadiene monomer.
[0046] 37. The composition of embodiment 36, wherein the at least one acrylate comprises at least one of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, ethylhexyl acrylate, or ethylhexyl methacrylate.
[0047] 38. The composition of embodiment 36, wherein the at least one acrylate comprises at least one monomeric unit represented by the following general formula B: wherein, independently for each molecule of the monomeric unit: R10 is H, CH3, or C2H5; R11 is a poly(alkylene oxide) of number average molecular weight of from 88 to 1200 g/mole, wherein the poly(alkylene oxide) is comprised of repeating alkylene oxide units, and wherein each alkylene oxide unit independently has from 2 to 4 carbons; and R12 is H, a Ci-Cg alkyl group, or a Ci-Cs alkylene group.
[0048] 39. The composition of embodiment 38, wherein R11 is a poly(alkylene oxide) of number average molecular weight of from 132 to 1100 g/mole. [0049] 40. The composition of either embodiment 38 or embodiment 39, wherein at least
90 weight percent of the alkylene oxide units of the poly(alkylene oxide) have 2 carbons, based on the total weight of the poly(alkylene oxide).
[0050] 41. The composition of any one of embodiments 38 to 40, wherein R12 is H, CH3, or C2H5.
[0051] 42. The composition of any one of embodiments 1 to 32, wherein the water-soluble polymerization reaction product of monomeric units comprises from 1 to 95 weight percent monomeric units represented by the following general formula B: wherein, independently for each molecule of the monomeric unit: R10 is H, CH3, or C2H5; R11 is a poly(alkylene oxide) of number average molecular weight of from 88 to 1200 g/mole, wherein the poly(alkylene oxide) is comprised of repeating alkylene oxide units, and wherein each alkylene oxide unit independently has from 2 to 4 carbons; and R12 is H, a Ci-Cs alkyl group, or a Ci-Cs alkylene group.
[0052] 43. The composition of any one of embodiments 1 to 32, wherein the water-soluble polymerization reaction product of monomeric units comprises from 5 to 80 weight percent monomeric units represented by the following general formula B: wherein, independently for each molecule of the monomeric unit: R10 is H, CH3, or C2H5; R11 is a poly(alkylene oxide) of number average molecular weight of from 88 to 1200 g/mole, wherein the poly(alkylene oxide) is comprised of repeating alkylene oxide units, and wherein each alkylene oxide unit independently has from 2 to 4 carbons; and R12 is H, a Ci-Cs alkyl group, or a Ci-Cs alkylene group. [0053] 44. The composition of any one of embodiments 1 to 32, wherein the water-soluble polymerization reaction product of monomeric units comprises from 20 to 50 weight percent monomeric units represented by the following general formula B: wherein, independently for each molecule of the monomeric unit: R10 is H, CH3, or C2H5; R11 is a poly(alkylene oxide) of number average molecular weight of from 88 to 1200 g/mole, wherein the poly(alkylene oxide) is comprised of repeating alkylene oxide units, and wherein each alkylene oxide unit independently has from 2 to 4 carbons; and R12 is H, a Ci-Cs alkyl group, or a Ci-Cs alkylene group.
[0054] 45. The composition of any one of embodiments 42 to 44, wherein R11 is a poly(alkylene oxide) of number average molecular weight of from 132 to 1100 g/mole.
[0055] 46. The composition of any one of embodiments 42 to 45, wherein at least 90 weight percent of the alkylene oxide units of the poly(alkylene oxide) have 2 carbons, based on the total weight of the poly(alkylene oxide).
[0056] 47. The composition of any one of embodiments 42 to 46, wherein R12 is H, CH3, or C2H5.
[0057] 48. The composition of any one of embodiments 1 to 47, wherein the fibers comprises at least one of natural fibers, glass fibers, or synthetic fibers.
[0058] 49. The composition of any one of embodiments 1 to 48, wherein the fibers comprise natural fibers.
[0059] 50. The composition of embodiment 49, wherein the natural fibers comprise cellulosic fibers.
[0060] 51. The composition of either embodiment 49 or 50, wherein the fibers further comprise at least one additional type of fibers other than the natural fibers.
[0061] 52. The composition of embodiment 51, wherein the at least one additional type of fibers comprises at least one of glass fibers or synthetic fibers. [0062] 53. A fibrous substrate comprising the composition of any one of embodiments 1 to
52 formed into a substrate.
[0063] 54. A method of making a composition comprising combining, in any order, fibers, a binder, and an additive, wherein: the binder comprises a colloidal dispersion of a polymer comprising 0.1 to 25 percent by weight acid-functionalized monomeric units, based on the total weight of the polymer, wherein the colloidal dispersion of a polymer has a pH of from 5 to 12; and the additive comprises a water-soluble polymerization reaction product of monomeric units comprising from 5 to 99 weight percent monomeric units represented by at least one of the following general formulas Al or A2, based on the total weight of the additive: wherein, independently for each molecule of the monomeric units represented by at least one of the general formulas Al or A2: R1 is H, CH3, or C2H5; R2 is H or a C1-C4 alkyl group; R3 is a Ci-C& alkyl group or a Ci-Ce alkylene group; R4 is H or a C1-C4 alkyl group; R5 is H or a Ci- C4 alkyl group; R6 is H, CH3, or C2H5; R7 is a Ci-Ce alkyl group or a Ci-Ce alkylene group; R8 is H or a C1-C4 alkyl group; and R9 is H or a C1-C4 alkyl group.
[0064] 55. A method of making a fibrous substrate comprising forming fibers and a binder into the fibrous substrate, followed by adding an additive to the fibrous substrate, wherein: the binder comprises a colloidal dispersion of a polymer comprising 0.1 to 25 percent by weight acid-functionalized monomeric units, based on the total weight of the polymer, wherein the colloidal dispersion of a polymer has a pH of from 5 to 12; and the additive comprises a water- soluble polymerization reaction product of monomeric units comprising from 5 to 99 weight percent monomeric units represented by at least one of the following general formulas Al or A2, based on the total weight of the additive:
wherein, independently for each molecule of the monomeric units represented by at least one of the general formulas Al or A2: R1 is H, CH3, or C2H5; R2 is H or a C1-C4 alkyl group; R3 is a Ci-Ce alkyl group or a Ci-Ce alkylene group; R4 is H or a C1-C4 alkyl group; R5 is H or a Ci- C4 alkyl group; R6 is H, CH3, or C2H5; R7 is a Ci-Ce alkyl group or a Ci-Ce alkylene group; R8 is H or a C1-C4 alkyl group; and R9 is H or a C1-C4 alkyl group.
[0065] 56. A method of improving at least one physical property of a fibrous substrate, wherein the fibrous substrate comprises fibers and a binder, wherein the method comprises adding an additive to the fibrous substrate, wherein: the binder comprises a colloidal dispersion of a polymer comprising 0.1 to 25 percent by weight acid-functionalized monomeric units, based on the total weight of the polymer, wherein the colloidal dispersion of a polymer has a pH of from 5 to 12; and the additive comprises a water-soluble polymerization reaction product of monomeric units comprising from 5 to 99 weight percent monomeric units represented by at least one of the following general formulas Al or A2, based on the total weight of the additive: wherein, independently for each molecule of the monomeric units represented by at least one of the general formulas Al or A2: R1 is H, CH3, or C2H5; R2 is H or a C1-C4 alkyl group; R3 is a Ci-Ce alkyl group or a Ci-Ce alkylene group; R4 is H or a C1-C4 alkyl group; R5 is H or a Ci- C4 alkyl group; R6 is H, CH3, or C2H5; R7 is a Ci-Ce alkyl group or a Ci-Ce alkylene group; R8 is H or a C1-C4 alkyl group; and R9 is H or a C1-C4 alkyl group.
[00661 57. A method of making a fibrous substrate, wherein the fibrous substrate comprises fibers and a binder, the method comprising adding an additive to the fibrous substrate, wherein the additive reduces the amount of binder needed in the fibrous substrate to substantially maintain the physical properties of the fibrous substrate, wherein: the binder comprises a colloidal dispersion of a polymer comprising 0.1 to 25 percent by weight acid-functionalized monomeric units, based on the total weight of the polymer, wherein the colloidal dispersion of a polymer has a pH of from 5 to 12; and the additive comprises a water-soluble polymerization reaction product of monomeric units comprising from 5 to 99 weight percent monomeric units represented by at least one of the following general formulas Al or A2, based on the total weight of the additive: wherein, independently for each molecule of the monomeric units represented by at least one of the general formulas Al or A2: R1 is H, CH3, or C2H5; R2 is H or a C1-C4 alkyl group; R3 is a Ci-Ce alkyl group or a Ci-Ce alkylene group; R4 is H or a C1-C4 alkyl group; R5 is H or a Ci- C4 alkyl group; R6 is H, CH3, or C2H5; R7 is a Ci-Ce alkyl group or a Ci-Ce alkylene group; R8 is H or a C1-C4 alkyl group; and R9 is H or a C1-C4 alkyl group.
[0067] 58. The method of any one of embodiments 54 to 57, wherein independently for each molecule of the monomeric units represented by at least one of the general formulas Al or A2: R1 is H or CH3; R2 is H or CH3; R4 is H or CH3; R5 is H or CH3; R6 is H or CH3; R8 is H or CH3; and R9 is H or CH3.
[0068] 59. The method of any one of embodiments 54 to 58, wherein, independently for each molecule of the monomeric units represented by at least one of the general formulas Al or A2: R3 is a C1-C4 alkyl group or a C1-C4 alkylene group; and R7 is a C1-C4 alkyl group or a C1-C4 alkylene group.
[00691 60. The method of any one of embodiments 54 to 59, wherein, independently for each molecule of the monomeric units represented by at least one of the general formulas Al or A2: R1 is CH3; R2 is H; R3 is C3H6; R4 is CH3; R5 is CH3; R6 is CH3; R7 is C3B; R8 is CH3; and R9 is CH3.
[0070] 61. The method of any one of embodiments 54 to 60, wherein the binder is present in the composition in an amount of from 5 to 60 percent by weight, based on the total dry weight of the composition.
[0071] 62. The method of any one of embodiments 54 to 61, wherein the binder is present in the composition in an amount of from 5 to 40 percent by weight, based on the total dry weight of the composition.
[0072] 63. The method of any one of embodiments 54 to 62, wherein the binder is present in the composition in an amount of from 5 to 30 percent by weight, based on the total dry weight of the composition.
[0073] 64. The method of any one of embodiments 54 to 63, wherein the binder is present in the composition in an amount of from 5 to 25 percent by weight, based on the total dry weight of the composition.
[0074] 65. The method of any one of embodiments 54 to 64, wherein the binder is present in the composition in an amount of from 10 to 60 percent by weight, based on the total dry weight of the composition.
[00751 66. The method of any one of embodiments 54 to 65, wherein the binder is present in the composition in an amount of from 10 to 40 percent by weight, based on the total dry weight of the composition.
[0076] 67. The method of any one of embodiments 54 to 66, wherein the binder is present in the composition in an amount of from 10 to 30 percent by weight, based on the total dry weight of the composition.
[0077] 68. The method of any one of embodiments 54 to 67, wherein the binder is present in the composition in an amount of from 10 to 25 percent by weight, based on the total dry weight of the composition. [0078] 69. The method of any one of embodiments 54 to 68, wherein the composition comprises from 0.01 to 30 parts of the additive to 100 parts of the binder.
[0079] 70. The method of any one of embodiments 54 to 69, wherein the composition comprises from 0.01 to 25 parts of the additive to 100 parts of the binder.
[0080] 71. The method of any one of embodiments 54 to 70, wherein the composition comprises from 0.05 to 20 parts of the additive to 100 parts of the binder.
[0081] 72. The method of any one of embodiments 54 to 71, wherein the composition comprises from 0.05 to 10 parts of the additive to 100 parts of the binder.
[0082] 73. The method of any one of embodiments 54 to 72, wherein the composition comprises from 0.1 to 20 parts of the additive to 100 parts of the binder.
[0083] 74. The method of any one of embodiments 54 to 73, wherein the composition comprises from 0.1 to 10 parts of the additive to 100 parts of the binder.
[0084] 75. The method of any one of embodiments 54 to 74, wherein the composition comprises from 0. 1 to 5 parts of the additive to 100 parts of the binder.
[0085] 76. The method of any one of embodiments 54 to 75, wherein the composition comprises from 0.1 to 2.5 parts of the additive to 100 parts of the binder.
[0086] 77. The method of any one of embodiments 54 to 76, wherein the composition comprises from 0.2 to 5 parts of the additive to 100 parts of the binder.
[0087] 78. The method of any one of embodiments 54 to 77, wherein the composition comprises from 0.2 to 2.5 parts of the additive to 100 parts of the binder.
[0088] 79. The method of any one of embodiments 54 to 78, wherein the polymer comprises
0.5 to 10 percent by weight acid-functionalized monomeric units, based on the total weight of the polymer.
[0089] 80. The method of any one of embodiments 54 to 79, wherein the polymer comprises
1 to 5 percent by weight acid-functionalized monomeric units, based on the total weight of the polymer.
[0090] 81. The method of any one of embodiments 54 to 80, wherein the colloidal dispersion of a polymer has a pH of from 7 to 12.
[0091] 82. The method of any one of embodiments 54 to 81, wherein the colloidal dispersion of a polymer has a pH of from 7 to 10. [0092] 83. The method of any one of embodiments 54 to 82, wherein the colloidal dispersion of a polymer has a pH of from 7 to 9.
[0093] 84. The method of any one of embodiments 54 to 83, wherein the colloidal dispersion of a polymer has a pH of from 7.5 to 9.
[0094] 85. The method of any one of embodiments 54 to 84, wherein the colloidal dispersion of a polymer has a pH of from 8 to 9.
[0095] 86. The method of any one of embodiments 54 to 85, wherein the colloidal dispersion of a polymer comprises at least one of acrylic latex, styrene-butadiene resin latex, vinyl chloride copolymer latex, or vinylidene chloride copolymer latex.
[0096] 87. The method of any one of embodiments 54 to 86, wherein the water-soluble polymerization reaction product of monomeric units comprises from 20 to 95 weight percent monomeric units represented by at least one of the general formulas Al or A2, based on the total weight of the additive.
[0097] 88. The method of any one of embodiments 54 to 87, wherein the water-soluble polymerization reaction product of monomeric units comprises from 50 to 80 weight percent monomeric units represented by at least one of the general formulas Al or A2, based on the total weight of the additive.
[0098] 89. The method of any one of embodiments 54 to 88, wherein the water-soluble polymerization reaction product of monomeric units comprises from 1 to 95 weight percent vinyl-group-containing monomeric units different from the monomeric units represented by at least one of the general formulas Al or A2, based on the total weight of the additive.
[0099] 90. The method of any one of embodiments 54 to 89, wherein the water-soluble polymerization reaction product of monomeric units comprises from 5 to 80 weight percent vinyl-group-containing monomeric units different from the monomeric units represented by at least one of the general formulas A l or A2, based on the total weight of the additive.
[0100] 91. The method of any one of embodiments 54 to 90, wherein the water-soluble polymerization reaction product of monomeric units comprises from 20 to 50 weight percent vinyl-group-containing monomeric units different from the monomeric units represented by at least one of the general formulas Al or A2, based on the total weight of the additive.
[0101] 92. The method of any one of embodiments 89 to 91, wherein the vinyl-group- containing monomeric units different from the monomeric units represented by at least one of the general formulas Al or A2 comprise at least one acrylate monomer and/or at least one styrene butadiene monomer.
[01021 93. The method of embodiment 92, wherein the at least one acrylate comprises at least one of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, ethylhexyl acrylate, or ethylhexyl methacrylate.
[0103] 94. The method of embodiment 92, wherein the at least one acrylate comprises at least one monomeric unit represented by the following general formula B: wherein, independently for each molecule of the monomeric unit: R10 is H, CH3, or C2H5; R11 is a poly(alkylene oxide) of number average molecular weight of from 88 to 1200 g/mole, wherein the poly(alkylene oxide) is comprised of repeating alkylene oxide units, and wherein each alkylene oxide unit independently has from 2 to 4 carbons; and R12 is H, a Ci-Cs alkyl group, or a Ci-Cs alkylene group.
[0104] 95. The method of embodiment 94, wherein R11 is a poly(alkylene oxide) of number average molecular weight of from 132 to 1100 g/mole.
[0105] 96. The method of either embodiment 94 or embodiment 95, wherein at least 90 weight percent of the alkylene oxide units of the poly(alkylene oxide) have 2 carbons, based on the total weight of the poly(alkylene oxide).
[0106] 97. The method of any one of embodiments 94 to 96, wherein R12 is H, CH3, or
C2H5.
[0107] 98. The method of any one of embodiments 54 to 88, wherein the water-soluble polymerization reaction product of monomeric units comprises from 1 to 95 weight percent monomeric units represented by the following general formula B: wherein, independently for each molecule of the monomeric unit: R10 is H, CH3, or C2H5; R11 is a poly(alkylene oxide) of number average molecular weight of from 88 to 1200 g/mole, wherein the poly(alkylene oxide) is comprised of repeating alkylene oxide units, and wherein each alkylene oxide unit independently has from 2 to 4 carbons; and R12 is H, a Ci-Cs alkyl group, or a Ci-Cs alkylene group.
[0108] 99. The method of any one of embodiments 54 to 88, wherein the water-soluble polymerization reaction product of monomeric units comprises from 5 to 80 weight percent monomeric units represented by the following general formula B: wherein, independently for each molecule of the monomeric unit: R10 is H, CH3, or C2H5; R11 is a poly(alkylene oxide) of number average molecular weight of from 88 to 1200 g/mole, wherein the poly(alkylene oxide) is comprised of repeating alkylene oxide units, and wherein each alkylene oxide unit independently has from 2 to 4 carbons; and R12 is H, a Ci-Cs alkyl group, or a Ci-Cs alkylene group.
[0109] 100. The method of any one of embodiments 54 to 88, wherein the water- soluble polymerization reaction product of monomeric units comprises from 20 to 50 weight percent monomeric units represented by the following general formula B: wherein, independently for each molecule of the monomeric unit: R10 is H, CH3, or C2H5; R11 is a poly(alkylene oxide) of number average molecular weight of from 88 to 1200 g/mole, wherein the poly(alkylene oxide) is comprised of repeating alkylene oxide units, and wherein each alkylene oxide unit independently has from 2 to 4 carbons; and R12 is H, a Ci-Cs alkyl group, or a Ci-Cs alkylene group. [0110] 101. The method of any one of embodiments 98 to 100, wherein R11 is a poly(alkylene oxide) of number average molecular weight of from 132 to 1100 g/mole.
[0111] 102. The method of any one of embodiments 98 to 101, wherein at least 90 weight percent of the alkylene oxide units of the poly(alkylene oxide) have 2 carbons, based on the total weight of the poly(alkylene oxide).
[0112] 103. The method of any one of embodiments 98 to 102, wherein R12 is H,
CH3, or C2H5.
[0113] 104. The method of any one of embodiments 54 to 103, wherein the fibers comprises at least one of natural fibers, glass fibers, or synthetic fibers.
[0114] 105. The method of any one of embodiments 54 to 104, wherein the fibers comprise natural fibers.
[0115] 106. The method of embodiment 105, wherein the natural fibers comprise cellulosic fibers.
[0116] 107. The method of either embodiment 105 or 106, wherein the fibers further comprise at least one additional type of fibers other than the natural fibers.
[0117] 108. The composition of embodiment 107, wherein the at least one additional type of fibers comprises at least one of glass fibers or synthetic fibers.
[0118] Various features and embodiments of the present subject matter will be described below by way of non-limiting illustration.
[0119] It is known that some of the materials described herein may interact in the final formulation, so that the components of the final formulation may be different from those that are initially added. The products formed thereby, including the products formed upon employing the composition of the present subject matter in its intended use, may not be susceptible of easy description. Nevertheless, all such modifications and reaction products are included within the scope of the present subject matter; the present subject matter encompasses the composition prepared by admixing the components described herein.
[0120] As used herein, the indefinite article “a”/“an” is intended to mean one or more than one. As used herein, the phrase “at least one” means one or more than one of the following terms. Thus, “a”/“an” and “at least one” may be used interchangeably. For example “at least one of A, B or C” means that just one of A, B or C may be included, and any mixture of two or more of A, B and C may be included, in alternative embodiments. [0121] As used herein, the transitional term “comprising,” which is synonymous with “including,” “containing,” or “characterized by,” is inclusive or open-ended and does not exclude additional, un-recited elements or method steps. However, in each recitation of “comprising” herein, it is intended that the term also encompass, as alternative embodiments, the phrases “consisting essentially of’ and “consisting of,” where “consisting of’ excludes any element or step not specified and “consisting essentially of’ permits the inclusion of additional un-recited elements or steps that do not materially affect the essential or basic and novel characteristics of the composition or method under consideration.
[0122] Provided is a composition comprising fibers, a binder, and an additive, wherein: the binder comprises a colloidal dispersion of a polymer comprising 0.1 to 25 percent by weight acid-functionalized monomeric units, based on the total weight of the polymer, wherein the colloidal dispersion of a polymer has a pH of from 5 to 12; and the additive comprises a water- soluble polymerization reaction product of monomeric units comprising from 5 to 99 weight percent monomeric units represented by at least one of the following general formulas Al or A2, based on the total weight of the additive: wherein, independently for each molecule of the monomeric units represented by at least one of the general formulas Al or A2: R1 is H, CH3, or C2H5; R2 is H or a C1-C4 alkyl group; R3 is a Ci-Ce alkyl group or a Ci-Ce alkylene group; R4 is H or a C1-C4 alkyl group; R5 is H or a Ci- C4 alkyl group; R6 is H, CH3, or C2H5; R7 is a Ci-Ce alkyl group or a Ci-Ce alkylene group; R8 is H or a C1-C4 alkyl group; and R9 is H or a C1-C4 alkyl group.
[0123] Additives similar to the additives described herein are disclosed in WO 2020/068889 Al, referred to therein as polyamine additives; various descriptions and/or embodiments of such polyamine additives may apply to embodiments of the additives described herein, as would be apparent to a person of ordinary skill in the art. The polyamine additives described in WO 2020/068889 Al were not described as having usefulness in compositions comprising fibers, however, which was newly discovered as described herein.
[0124] In certain embodiments, R1 is H or CH3. In certain embodiments, R1 is H or C2H5. In certain embodiments, R1 is CH3 or C2H5. In certain embodiments, R1 is H. In certain embodiments, R1 is CH3. In certain embodiments, R1 is C2H5.
[0125] In certain embodiments, R2 is H or a C1-C4 (such as a C1-C3, a C1-C2, C2-C4, a C2- C3, C3-C4, a Ci, a C2, a C3, or a C4) alkyl group.
[0126] In certain embodiments, R3 is a Ci-Ce (such as a C1-C5, a C1-C4, a C1-C3, a C1-C2, a C2-C6, a C2-C5, a C2-C4, a C2-C3, a C3-C6, a C3-C5, a C3-C4, a C4-C6, a C4-C5, a Cs-Ce, a Ci, a C2, a C3, a C4, a C5, or a Ce) alkyl group or a Ci-Ce (such as a C1-C5, a C1-C4, a C1-C3, a C1-C2, a C2-C6, a C2-C5, a C2-C4, a C2-C3, a C3-C6, a C3-C5, a C3-C4, a C4-C6, a C4-C5, a C5-C6, a Ci, a C2, a C3, a C4, a C5, or a Ce) alkylene group.
[0127] In certain embodiments, R4 is H or a C1-C4 (such as a C1-C3, a C1-C2, C2-C4, a C2- C3, C3-C4, a Ci, a C2, a C3, or a C4) alkyl group.
[0128] In certain embodiments, R5 is H or a C1-C4 (such as a C1-C3, a C1-C2, C2-C4, a C2- C3, C3-C4, a Ci, a C2, a C3, or a C4) alkyl group.
[0129] In certain embodiments, R6 is H or CH3. In certain embodiments, R6 is H or C2H5. In certain embodiments, R6 is CH3 or C2H5. In certain embodiments, R6 is H. In certain embodiments, R6 is CH3. In certain embodiments, R6 is C2H5.
[0130] In certain embodiments, R7 is a Ci-Ce (such as a C1-C5, a C1-C4, a C1-C3, a C1-C2, a C2-C6, a C2-C5, a C2-C4, a C2-C3, a C3-C6, a C3-C5, a C3-C4, a C4-Ce, a C4-C5, a C5-C6, a Ci, a C2, a C3, a C4, a C5, or a Ce) alkyl group or a Ci-Ce (such as a C1-C5, a C1-C4, a C1-C3, a C1-C2, a C2-C6, a C2-C5, a C2-C4, a C2-C3, a C3-C6, a C3-C5, a C3-C4, a C4-C6, a C4-C5, a C5-C6, a Ci, a C2, a C3, a C4, a C5, or a Ce) alkylene group.
[0131] In certain embodiments, R8 is H or a C1-C4 (such as a C1-C3, a C1-C2, C2-C4, a C2- C3, C3-C4, a Ci, a C2, a C3, or a C4) alkyl group.
[0132] In certain embodiments, R9 is H or a C1-C4 (such as a C1-C3, a C1-C2, C2-C4, a C2- C3, C3-C4, a Ci, a C2, a C3, or a C4) alkyl group.
[0133] In certain embodiments, the binder is present in the composition in an amount of from 5 to 60 (such as from 5 to 55, from 5 to 50, from 5 to 45, from 5 to 40, from 5 to 35, from 5 to 30, from 5 to 25, from 5 to 20, from 5 to 15, from 5 to 10, from 10 to 60, from 10 to 55, from 10 to 50, from 10 to 45, from 10 to 40, from 10 to 35, from 10 to 30, from 10 to 25, from 10 to 20, from 10 to 15, from 15 to 60, from 15 to 55, from 15 to 50, from 15 to 45, from 15 to 40, from 15 to 35, from 15 to 30, from 15 to 25, from 15 to 20, from 20 to 60, from 20 to 55, from 20 to 50, from 20 to 45, from 20 to 40, from 20 to 35, from 20 to 30, from 20 to 25, from 25 to 60, from 25 to 55, from 25 to 50, from 25 to 45, from 25 to 40, from 25 to 35, from 25 to 30, from 30 to 60, from 30 to 55, from 30 to 50, from 30 to 45, from 30 to 40, from 30 to 35, from 35 to 60, from 35 to 55, from 35 to 50, from 35 to 45, from 35 to 40, from 40 to 60, from 40 to 55, from 40 to 50, from 40 to 45, from 45 to 60, from 45 to 55, from 45 to 50, from 50 to 60, from 50 to 55, or from 55 to 60) percent by weight, based on the total dry weight of the composition.
[0134] As used herein, the term “dry weight” means the weight of a composition not including water and/or solvent (if any).
[0135] In certain embodiments, the composition comprises from 0.01 to 30 (such as from 0.01 to 25, from 0.01 to 20, from 0.01 to 15, from 0.01 to 10, from 0.01 to 5, from 0.01 to 4, from 0.01 to 3, from 0.01 to 2.5, from 0.01 to 2, from 0.01 to 1.5, from 0.01 to 1, from 0.01 to 0.5, from 0.01 to 0.4, from 0.01 to 0.3, from 0.01 to 0.2, from 0.01 to 0.1, from 0.01 to 0.05, from 0.05 to 30, from 0.05 to 25, from 0.05 to 20, from 0.05 to 15, from 0.05 to 10, from 0.05 to 5, from 0.05 to 4, from 0.05 to 3, from 0.05 to 2.5, from 0.05 to 2, from 0.05 to 1.5, from 0.05 to 1, from 0.05 to 0.5, from 0.05 to 0.4, from 0.05 to 0.3, from 0.05 to 0.2, from 0.05 to 0.1, from 0.1 to 30, from 0.1 to 25, from 0.1 to 20, from 0.1 to 15, from 0.1 to 10, from 0.1 to 5, from 0.1 to 4, from 0.1 to 3, from 0.1 to 2.5, from 0.1 to 2, from 0.1 to 1.5, from 0.1 to 1, from 0.1 to 0.5, from 0.1 to 0.4, from 0.1 to 0.3, from 0.1 to 0.2, from 0.2 to 30, from 0.2 to 25, from 0.2 to 20, from 0.2 to 15, from 0.2 to 10, from 0.2 to 5, from 0.2 to 4, from 0.2 to 3, from 0.2 to 2.5, from 0.2 to 2, from 0.2 to 1.5, from 0.2 to 1, from 0.2 to 0.5, from 0.2 to 0.4, from 0.2 to 0.3, from 0.3 to 30, from 0.3 to 25, from 0.3 to 20, from 0.3 to 15, from 0.3 to 10, from 0.3 to 5, from 0.3 to 4, from 0.3 to 3, from 0.3 to 2.5, from 0.3 to 2, from 0.3 to 1.5, from 0.3 to 1, from 0.3 to 0.5, from 0.3 to 0.4, from 0.4 to 30, from 0.4 to 25, from 0.4 to 20, from 0.4 to 15, from 0.4 to 10, from 0.4 to 5, from 0.4 to 4, from 0.4 to 3, from 0.4 to 2.5, from 0.4 to 2, from 0.4 to 1.5, from 0.4 to 1, from 0.4 to 0.5, from 0.5 to 30, from 0.5 to 25, from 0.5 to 20, from 0.5 to 15, from 0.5 to 10, from 0.5 to 5, from 0 5 to 4, from 0.5 to 3, from 0.5 to 2.5, from 0.5 to 2, from 0.5 to 1 .5, from 0.5 to 1 , from 1 to 30, from 1 to 25, from 1 to 20, from 1 to 15, from 1 to 10, from 1 to 5, from 1 to 4, from 1 to 3, from 1 to 2.5, from 1 to 2, from 1 to 1.5, from 1.5 to 30, from 1.5 to 25, from 1.5 to 20, from 1.5 to 15, from 1.5 to 10, from 1.5 to 5, from 1.5 to 4, from 1.5 to 3, from 1.5 to 2.5, from 1.5 to 2, from 2 to 30, from 2 to 25, from 2 to 20, from 2 to 15, from 2 to 10, from 2 to 5, from 2 to 4, from 2 to 3, from 2 to 2.5, from 2.5 to 30, from 2.5 to 25, from 2.5 to 20, from 2.5 to 15, from 2.5 to 10, from 2.5 to 5, from 2.5 to
4, from 2.5 to 3, from 3 to 30, from 3 to 25, from 3 to 20, from 3 to 15, from 3 to 10, from 3 to
5, from 3 to 4, from 4 to 30, from 4 to 25, from 4 to 20, from 4 to 15, from 4 to 10, from 4 to 5, from 5 to 30, from 5 to 25, from 5 to 20, from 5 to 15, from 5 to 10, from 10 to 30, from 10 to 25, from 10 to 20, from 10 to 15, from 15 to 30, from 15 to 25, from 15 to 20, from 20 to 30, from 20 to 25, or from 25 to 30) parts of the additive to 100 parts of the binder. In this context, parts of the additive and parts of the binder are considered on a “dry” basis, i.e., not including water and/or solvent (if any).
[0136] The term “colloidal dispersion” when used in the context of the colloidal dispersion of a polymer described herein, means that the polymer is dispersed and stable within the continuous phase of the dispersion, as would be understood by a person of ordinary skill in the art.
[0137] In certain embodiments, the polymer comprises 0.1 to 25 (such as 0.1 to 20, 0.1 to 15, 0.1 to 10, 0.1 to 9, 0.1 to 8, 0.1 to 7, 0.1 to 6, 0.1 to 5, 0.1 to 4, 0.1 to 3, 0.1 to 2, 0.1 to 1, 0.1 to 0.5, 0.5 to 25, 0.5 to 20, 0.5 to 15, 0.5 to 10, 0.5 to 9, 0.5 to 8, 0.5 to 7, 0.5 to 6, 0.5 to 5, 0.5 to 4, 0.5 to 3, 0.5 to 2, 0.5 to 1, 1 to 25, 1 to 20, 1 to 15, 1 to 10, 1 to 9, 1 to 8, 1 to 7, 1 to 6,
1 to 5, 1 to 4, 1 to 3, 1 to 2, 2 to 25, 2 to 20, 2 to 15, 2 to 10, 2 to 9, 2 to 8, 2 to 7, 2 to 6, 2 to 5,
2 to 4, 2 to 3, 3 to 25, 3 to 20, 3 to 15, 3 to 10, 3 to 9, 3 to 8, 3 to 7, 3 to 6, 3 to 5, 3 to 4, 4 to 25, 4 to 20, 4 to 15, 4 to 10, 4 to 9, 4 to 8, 4 to 7, 4 to 6, 4 to 5, 5 to 25, 5 to 20, 5 to 15, 5 to 10, 5 to 9, 5 to 8, 5 to 7, 5 to 6, 6 to 25, 6 to 20, 6 to 15, 6 to 10, 6 to 9, 6 to 8, 6 to 7, 7 to 25, 7 to 20, 7 to 15, 7 to 10, 7 to 9, 7 to 8, 8 to 25, 8 to 20, 8 to 15, 8 to 10, 8 to 9, 9 to 25, 9 to 20, 9 to 15, 9 to 10, 10 to 25, 10 to 20, 10 to 15, 15 to 25, 15 to 20, or 20 to 25) percent by weight acid- functionalized monomeric units, based on the total weight of the polymer.
[0138] In certain embodiments, the colloidal dispersion of a polymer has a pH of from 5 to 12 (such as from 5.5 to 12, from 6 to 12, from 6.5 to 12, from 7 to 12, from 7.5 to 12, from 8 to 12, from 8.5 to 12, from 5 to 11.5, from 5.5 to 11.5, from 6 to 11 5, from 6.5 to 11.5, from 7 to 11 .5, from 7.5 to 1 1 .5, from 8 to 11 5, from 8.5 to 1 1 .5, from 5 to 11 , from 5.5 to 1 1 , from 6 to 11, from 6.5 to 11, from 7 to 11, from 7.5 to 11, from 8 to 11, from 8.5 to 11, from 5 to 10.5, from 5.5 to 10.5, from 6 to 10.5, from 6.5 to 10.5, from 7 to 10.5, from 7.5 to 10.5, from 8 to
10.5, from 8.5 to 10.5, from 5 to 10, from 5.5 to 10, from 6 to 10, from 6.5 to 10, from 7 to 10, from 7.5 to 10, from 8 to 10, from 8.5 to 10, from 5 to 9.5, from 5.5 to 9.5, from 6 to 9.5, from 6.5 to 9.5, from 7 to 9.5, from 7.5 to 9.5, from 8 to 9.5, from 8.5 to 9.5, from 5 to 9, from 5.5 to 9, from 6 to 9, from 6.5 to 9, from 7 to 9, from 7.5 to 9, from 8 to 9, or from 8.5 to 9).
[0139] In certain embodiments, the colloidal dispersion of a polymer comprises at least one of acrylic latex, styrene-butadiene resin latex, vinyl chloride copolymer latex, or vinylidene chloride copolymer latex.
[0140] In certain embodiments, the water-soluble polymerization reaction product of monomeric units comprises from 5 to 99 (such as from 10 to 99, from 15 to 99, from 20 to 99, from 30 to 99, from 40 to 99, from 50 to 99, from 60 to 99, from 70 to 99, from 5 to 98, from 10 to 98, from 15 to 98, from 20 to 98, from 30 to 98, from 40 to 98, from 50 to 98, from 60 to 98, from 70 to 98, from 5 to 97, from 10 to 97, from 15 to 97, from 20 to 97, from 30 to 97, from 40 to 97, from 50 to 97, from 60 to 97, from 70 to 97, from 5 to 96, from 10 to 96, from 15 to 96, from 20 to 96, from 30 to 96, from 40 to 96, from 50 to 96, from 60 to 96, from 70 to 96, from 5 to 95, from 10 to 95, from 15 to 95, from 20 to 95, from 30 to 95, from 40 to 95, from 50 to 95, from 60 to 95, from 70 to 95, from 5 to 90, from 10 to 90, from 15 to 90, from 20 to 90, from 30 to 90, from 40 to 90, from 50 to 90, from 60 to 90, from 70 to 90, from 5 to 85, from 10 to 85, from 15 to 85, from 20 to 85, from 30 to 85, from 40 to 85, from 50 to 85, from 60 to 85, from 70 to 85, from 5 to 80, from 10 to 80, from 15 to 80, from 20 to 80, from 30 to 80, from 40 to 80, from 50 to 80, from 60 to 80, from 70 to 80, from 5 to 75, from 10 to 75, from 15 to 75, from 20 to 75, from 30 to 75, from 40 to 75, from 50 to 75, from 60 to 75, or from 70 to 75) weight percent monomeric units represented by at least one of the general formulas Al or A2, based on the total weight of the additive.
[0141] In certain embodiments, the water-soluble polymerization reaction product of monomeric units comprises from 1 to 95 (such as from 2 to 95, from 3 to 95, from 4 to 95, from 5 to 95, from 10 to 95, from 15 to 95, from 20 to 95, from 25 to 95, from 1 to 90, from 2 to 90, from 3 to 90, from 4 to 90, from 5 to 90, from 10 to 90, from 15 to 90, from 20 to 90, from 25 to 90, from 1 to 85, from 2 to 85, from 3 to 85, from 4 to 85, from 5 to 85, from 10 to 85, from 15 to 85, from 20 to 85, from 25 to 85, from 1 to 80, from 2 to 80, from 3 to 80, from 4 to 80, from 5 to 80, from 10 to 80, from 15 to 80, from 20 to 80, from 25 to 80, from 1 to 70, from 2 to 70, from 3 to 70, from 4 to 70, from 5 to 70, from 10 to 70, from 15 to 70, from 20 to 70, from 25 to 70, from 1 to 60, from 2 to 60, from 3 to 60, from 4 to 60, from 5 to 60, from 10 to 60, from 15 to 60, from 20 to 60, from 25 to 60, from 1 to 50, from 2 to 50, from 3 to 50, from 4 to 50, from 5 to 50, from 10 to 50, from 15 to 50, from 20 to 50, from 25 to 50, from 1 to 40, from 2 to 40, from 3 to 40, from 4 to 40, from 5 to 40, from 10 to 40, from 15 to 40, from 20 to 40, from 25 to 40, from 1 to 30, from 2 to 30, from 3 to 30, from 4 to 30, from 5 to 30, from 10 to 30, from 15 to 30, from 20 to 30, or from 25 to 30) weight percent vinyl-group-containing monomeric units different from the monomeric units represented by at least one of the general formulas Al or A2.
[0142] In certain embodiments, the vinyl-group-containing monomeric units different from the monomeric units represented by at least one of the general formulas Al or A2 comprise at least one acrylate monomer and/or at least one styrene butadiene monomer. In certain embodiments, the at least one acrylate (i.e., the at least one acrylate monomer) comprises at least one of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, ethylhexyl acrylate, or ethylhexyl methacrylate. In certain embodiments, the at least one acrylate (i.e., the at least one acrylate monomer) comprises at least one monomeric unit represented by the following general formula B: wherein, independently for each molecule of the monomeric unit: R10 is H, CH3, or C2H5; R11 is a poly(alkylene oxide), wherein the poly(alkylene oxide) is comprised of repeating alkylene oxide units; and R12 is H, a Ci-Cs alkyl group, or a Ci-Cs alkylene group. In certain embodiments, R10 is H or CH3. In certain embodiments, R10 is H or C2H5. In certain embodiments, R10 is CH3 or C2H5. In certain embodiments, R10 is H. In certain embodiments, R10 is CH3. In certain embodiments, R10 is C2H5. In certain embodiments, R11 is a poly(alkylene oxide) of number average molecular weight of from 88 to 1200 (such as from 132 to 1200, from 88 to 1 100, or from 132 to 1 100) g/mole. Tn certain embodiments, each alkylene oxide unit independently has from 2 to 4 (such as from 2 to 3, from 3 to 4, 2, 3, or 4) carbon atoms. In certain embodiments, at least 5 (such as at least 10, at least 15, at least 20, at least 25, at least 30, at least 35, at least 40, at least 45, at least 50, at least 55, at least 60, at least 65, at least 70, at least 75, at least 80, at least 85, at least 90, or at least 95) weight percent of the alkylene oxide units of the poly(alkylene oxide) have 2 carbon atoms, based on the total weight of the poly(alkylene oxide). In certain embodiments, from 5 to 100 (such as from 5 to 95, from 5 to 90, from 5 to 85, from 5 to 80, from 5 to 75, from 5 to 70, from 5 to 65, from 5 to 60, from 5 to 55, from 5 to 50, from 5 to 45, from 5 to 40, from 5 to 35, from 5 to 30, from 5 to 25, from 5 to 20, from 5 to 15, from 5 to 10, from 10 to 100, from 10 to 95, from 10 to 90, from 10 to 85, from 10 to 80, from 10 to 75, from 10 to 70, from 10 to 65, from 10 to 60, from 10 to 55, from 10 to 50, from 10 to 45, from 10 to 40, from 10 to 35, from 10 to 30, from 10 to 25, from 10 to 20, from 10 to 15, from 15 to 100, from 15 to 95, from 15 to 90, from 15 to 85, from 15 to 80, from 15 to 75, from 15 to 70, from 15 to 65, from 15 to 60, from 15 to 55, from 15 to 50, from 15 to 45, from 15 to 40, from 15 to 35, from 15 to 30, from 15 to 25, from 15 to 20, from 20 to 100, from 20 to 95, from 20 to 90, from 20 to 85, from 20 to 80, from 20 to 75, from 20 to 70, from 20 to 65, from 20 to 60, from 20 to 55, from 20 to 50, from 20 to 45, from 20 to 40, from 20 to 35, from 20 to 30, from 20 to 25, from 25 to 100, from 25 to 95, from 25 to 90, from 25 to 85, from 25 to 80, from 25 to 75, from 25 to 70, from 25 to 65, from 25 to 60, from 25 to 55, from 25 to 50, from 25 to 45, from 25 to 40, from 25 to 35, from 25 to 30, from 30 to 100, from 30 to 95, from 30 to 90, from 30 to 85, from 30 to 80, from 30 to 75, from 30 to 70, from 30 to 65, from 30 to 60, from 30 to 55, from 30 to 50, from 30 to 45, from 30 to 40, from 30 to 35, from 35 to 100, from 35 to 95, from 35 to 90, from 35 to 85, from 35 to 80, from 35 to 75, from 35 to 70, from 35 to 65, from 35 to 60, from 35 to 55, from 35 to 50, from 35 to 45, from 35 to 40, from 40 to 100, from 40 to 95, from 40 to 90, from 40 to 85, from 40 to 80, from 40 to 75, from 40 to 70, from 40 to 65, from 40 to 60, from 40 to 55, from 40 to 50, from 40 to 45, from 45 to 100, from 45 to 95, from 45 to 90, from 45 to 85, from 45 to 80, from 45 to 75, from 45 to 70, from 45 to 65, from 45 to 60, from 45 to 55, from 45 to 50, from 50 to 100, from 50 to 95, from 50 to 90, from 50 to 85, from 50 to 80, from 50 to 75, from 50 to 70, from 50 to 65, from 50 to 60, from 50 to 55, from 55 to 100, from 55 to 95, from 55 to 90, from 55 to 85, from 55 to 80, from 55 to 75, from 55 to 70, from 55 to 65, from 55 to 60, from 60 to 100, from 60 to 95, from 60 to 90, from 60 to 85, from 60 to 80, from 60 to 75, from 60 to 70, from 60 to 65, from 65 to 100, from 65 to 95, from 65 to 90, from 65 to 85, from 65 to 80, from 65 to 75, from 65 to 70, from 70 to 100, from 70 to 95, from 70 to 90, from 70 to 85, from 70 to 80, from 70 to 75, from 75 to 100, from 75 to 95, from 75 to 90, from 75 to 85, from 75 to 80, from 80 to 100, from 80 to 95, from 80 to 90, from 80 to 85, from 85 to 100, from 85 to 95, from 85 to 90, from 90 to 100, from 90 to 85, or from 95 to 100) weight percent of the alkylene oxide units of the poly(alkylene oxide) have 2 carbon atoms, based on the total weight of the poly(alkylene oxide). In certain embodiments, R12 is H, a Ci-Cs (such as a C1-C7, a Ci-Ce, a C1-C5, a C1-C4, a Ci-C3, a C1-C2, a C2-C8, a C2-C7, a C2-C6, a C2-C5, a C2-C4, a C2-C3, a C3-Cs, a C3-C7, a C3- Ce, a C3-Cs, a C3-C4, a C4-Cs, a C4-C7, a C4-C6, a C4-C5, a Cs-C8, a C5-C7, a C5-C6, a Ce-Cs, a C6-C7, a C7-C8, a Ci, a C2, a C3, a C4, a C5, a Ce, a C7, or a Cs) alkyl group, or a Ci-Cs (such as a C1-C7, a C1-C.6, a Ci-C5, a C1-C4, a Ci-C3, a C1-C2, a C2-C8, a C2-C7, a C2-C6, a C2-C5, a C2- C4, a C2-C3, a C3-C8, a C3-C7, a C3-C6, a C3-C5, a C3-C4, a C4-C8, a C4-C7, a C4-C6, a C4-C5, a Cs-Cs, a C5-C7, a Cs-Ce, a Cs-Cs, a C6-C7, a C7-C8, a Ci, a C2, a C3, a C4, a C5, a Cs, a C7, or a Cs) alkylene group. In certain embodiments, R12 is H, CH3, or C2H5.
[0143] In certain embodiments, the water-soluble polymerization reaction product of monomeric units comprises from 1 to 95 (such as from 2 to 95, from 3 to 95, from 4 to 95, from 5 to 95, from 10 to 95, from 15 to 95, from 20 to 95, from 25 to 95, from 1 to 90, from 2 to 90, from 3 to 90, from 4 to 90, from 5 to 90, from 10 to 90, from 15 to 90, from 20 to 90, from 25 to 90, from 1 to 85, from 2 to 85, from 3 to 85, from 4 to 85, from 5 to 85, from 10 to 85, from 15 to 85, from 20 to 85, from 25 to 85, from 1 to 80, from 2 to 80, from 3 to 80, from 4 to 80, from 5 to 80, from 10 to 80, from 15 to 80, from 20 to 80, from 25 to 80, from 1 to 70, from 2 to 70, from 3 to 70, from 4 to 70, from 5 to 70, from 10 to 70, from 15 to 70, from 20 to 70, from 25 to 70, from 1 to 60, from 2 to 60, from 3 to 60, from 4 to 60, from 5 to 60, from 10 to 60, from 15 to 60, from 20 to 60, from 25 to 60, from 1 to 50, from 2 to 50, from 3 to 50, from 4 to 50, from 5 to 50, from 10 to 50, from 15 to 50, from 20 to 50, from 25 to 50, from 1 to 40, from 2 to 40, from 3 to 40, from 4 to 40, from 5 to 40, from 10 to 40, from 15 to 40, from 20 to 40, from 25 to 40, from 1 to 30, from 2 to 30, from 3 to 30, from 4 to 30, from 5 to 30, from 10 to 30, from 15 to 30, from 20 to 30, or from 25 to 30) weight percent monomeric units represented by the following general formula B: wherein, independently for each molecule of the monomeric unit: R10 is H, CH3, or C2H5; R11 is a poly(alkylene oxide), wherein the poly(alkylene oxide) is comprised of repeating alkylene oxide units; and R12 is H, a Ci-Cs alkyl group, or a Ci-Cs alkylene group. In certain embodiments, R10 is H or CH3. In certain embodiments, R10 is H or C2H5. In certain embodiments, R10 is CH3 or C2H5. In certain embodiments, R10 is H. In certain embodiments, R10 is CH3. In certain embodiments, R10 is C2H5. In certain embodiments, R11 is a poly(alkylene oxide) of number average molecular weight of from 88 to 1200 (such as from 132 to 1200, from 88 to 1100, or from 132 to 1100) g/mole. In certain embodiments, each alkylene oxide unit independently has from 2 to 4 (such as from 2 to 3, from 3 to 4, 2, 3, or 4) carbon atoms. In certain embodiments, at least 5 (such as at least 10, at least 15, at least 20, at least 25, at least 30, at least 35, at least 40, at least 45, at least 50, at least 55, at least 60, at least 65, at least 70, at least 75, at least 80, at least 85, at least 90, or at least 95) weight percent of the alkylene oxide units of the poly(alkylene oxide) have 2 carbon atoms, based on the total weight of the poly(alkylene oxide). In certain embodiments, from 5 to 100 (such as from 5 to 95, from 5 to 90, from 5 to 85, from 5 to 80, from 5 to 75, from 5 to 70, from 5 to 65, from 5 to 60, from 5 to 55, from 5 to 50, from 5 to 45, from 5 to 40, from 5 to 35, from 5 to 30, from 5 to 25, from 5 to 20, from 5 to 15, from 5 to 10, from 10 to 100, from 10 to 95, from 10 to 90, from 10 to 85, from 10 to 80, from 10 to 75, from 10 to 70, from 10 to 65, from 10 to 60, from 10 to 55, from 10 to 50, from 10 to 45, from 10 to 40, from 10 to 35, from 10 to 30, from 10 to 25, from 10 to 20, from 10 to 15, from 15 to 100, from 15 to 95, from 15 to 90, from 15 to 85, from 15 to 80, from 15 to 75, from 15 to 70, from 15 to 65, from 15 to 60, from 15 to 55, from 15 to 50, from 15 to 45, from 15 to 40, from 15 to 35, from 15 to 30, from 15 to 25, from 15 to 20, from 20 to 100, from 20 to 95, from 20 to 90, from 20 to 85, from 20 to 80, from 20 to 75, from 20 to 70, from 20 to 65, from 20 to 60, from 20 to 55, from 20 to 50, from 20 to 45, from 20 to 40, from 20 to 35, from 20 to 30, from 20 to 25, from 25 to 100, from 25 to 95, from 25 to 90, from 25 to 85, from 25 to 80, from 25 to 75, from 25 to 70, from 25 to 65, from 25 to 60, from 25 to 55, from 25 to 50, from 25 to 45, from 25 to 40, from 25 to 35, from 25 to 30, from 30 to 100, from 30 to 95, from 30 to 90, from 30 to 85, from 30 to 80, from 30 to 75, from 30 to 70, from 30 to 65, from 30 to 60, from 30 to 55, from 30 to 50, from 30 to 45, from 30 to 40, from 30 to 35, from 35 to 100, from 35 to 95, from 35 to 90, from 35 to 85, from 35 to 80, from 35 to 75, from 35 to 70, from 35 to 65, from 35 to 60, from 35 to 55, from 35 to 50, from 35 to 45, from 35 to 40, from 40 to 100, from 40 to 95, from 40 to 90, from 40 to 85, from 40 to 80, from 40 to 75, from 40 to 70, from 40 to 65, from 40 to 60, from 40 to 55, from 40 to 50, from 40 to 45, from 45 to 100, from 45 to 95, from 45 to 90, from 45 to 85, from 45 to 80, from 45 to 75, from 45 to 70, from 45 to 65, from 45 to 60, from 45 to 55, from 45 to 50, from 50 to 100, from 50 to 95, from 50 to 90, from 50 to 85, from 50 to 80, from 50 to 75, from 50 to 70, from 50 to 65, from 50 to 60, from 50 to 55, from 55 to 100, from 55 to 95, from 55 to 90, from 55 to 85, from 55 to 80, from 55 to 75, from 55 to 70, from 55 to 65, from 55 to 60, from 60 to 100, from 60 to 95, from 60 to 90, from 60 to 85, from 60 to 80, from 60 to 75, from 60 to 70, from 60 to 65, from 65 to 100, from 65 to 95, from 65 to 90, from 65 to 85, from 65 to 80, from 65 to 75, from 65 to 70, from 70 to 100, from 70 to 95, from 70 to 90, from 70 to 85, from 70 to 80, from 70 to 75, from 75 to 100, from 75 to 95, from 75 to 90, from 75 to 85, from 75 to 80, from 80 to 100, from 80 to 95, from 80 to 90, from 80 to 85, from 85 to 100, from 85 to 95, from 85 to 90, from 90 to 100, from 90 to 85, or from 95 to 100) weight percent of the alkylene oxide units of the poly(alkylene oxide) have 2 carbon atoms, based on the total weight of the poly(alkylene oxide). In certain embodiments, R12 is H, a Ci-Cs (such as a C1-C7, a Ci-Ce, a C1-C5, a C1-C4, a Ci-C3, a C1-C2, a C2-C8, a C2-C7, a C2-C6, a C2-C5, a C2-C4, a C2-C3, a C3-C8, a C3-C7, a C3- Ce, a C -C5, a C3-C4, a C4-C8, a C4-C7, a C4-C6, a C4-C5, a Cs-C8, a C5-C7, a C5-C6, a Ce-C8, a C6-C7, a C7-C8, a Ci, a C2, a C3, a C4, a C5, a Ce, a C7, or a C8) alkyl group, or a Ci-C8 (such as a C1-C7, a Ci-C6, a C1-C5, a C1-C4, a Ci-C3, a C1-C2, a C2-C8, a C2-C7, a C2-C6, a C2-C5, a C2- C4, a C2-C3, a C3-C8, a C3-C7, a C3-C6, a C3-C5, a C3-C4, a C4-C8, a C4-C7, a C4-C6, a C4-C5, a Cs-C8, a C5-C7, a Cs-Cg, a Ce-C8, a Ce-C?, a C?-C8, a Ci, a C2, a C3, a C4, a C5, a Ce, a C7, or a C8) alkylene group. In certain embodiments, R12 is H, CH3, or C2H5.
[0144] In certain embodiments, the fibers comprise at least one of natural fibers, glass fibers, or synthetic fibers. In certain embodiments, the fibers comprise natural fibers. In certain embodiments, the natural fibers comprise cellulosic fibers. In certain embodiments, the fibers further comprise at least one additional type of fibers other than the natural fibers. In certain embodiments, the at least one additional type of fibers comprises at least one of glass fibers or synthetic fibers. There are many types of fibers known to be used for the applications described herein, and it is anticipated that the subject matter disclosed herein should have wide applicability to various types of fibers which may be used in the compositions described herein. [0145] Also provided are fibrous substrates comprising the compositions described herein. [0146] Further provided are various methods of making and/or using the compositions described above, as follows. In addition to the methods described below, analogous uses of the compositions described herein are also contemplated, and should be considered to be disclosed herein as would be understood by a person of skill in the art, based on the descriptions of the methods provided below.
[0147] In certain embodiments, provided is a method of making the compositions described above, the method comprising combining, in any order, fibers, a binder, and an additive, features of which are described in detail above.
[0148] In certain embodiments, provided is a method of making a fibrous substrate comprising forming fibers and a binder into the fibrous substrate, followed by adding an additive to the fibrous substrate. The fibers, binder, and additive used to make the fibrous substrate, as well as the composition form by combining them, are described in detail above. [0149] In certain embodiments, the fibers and binder may be combined together, followed by adding the additive at any point during manufacture of the composition. For example, the fibers and binder may be combined in a slurry and used to lay down a fibrous web including the fibers and the binder, followed by addition of the additive prior to diying/curing of the fibrous web; the additive may be added at any point during further processing of the fibrous web, so long as it is added prior to the binder drying/curing within the fibrous web.
[0150] In certain embodiments, the fibers may be formed into a slurry and laid down in a fibrous web, followed by addition of the binder and additive. In these embodiments, the binder and additive could be added to the fibrous web separately or together.
[0151] In certain embodiments, the fibers, binder, and additive may be combined together to form a slurry which is then used to lay down a fibrous web.
[0152] Fibrous webs, nonwoven fibrous materials, and/or papers are made according to various methods, as is known to those of skill in the art, and as such it would be apparent to a person of skill in the art after reading this disclosure at which point during a particular manufacturing process it may be most expeditious to add the additive, and any testing needed in order to make such a determination would be relatively simple to accomplish according to known procedures.
[0153] In certain embodiments, provided is a method of improving at least one physical property of a fibrous substrate, wherein the fibrous substrate comprises fibers and a binder, wherein the method comprises adding an additive to the fibrous substrate. The fibers, binder, and additive used to make the fibrous substrate, as well as the composition form by combining them, are described in detail above.
[0154] In certain embodiments, provided is a method of making a fibrous substrate, wherein the fibrous substrate comprises fibers and a binder, the method comprising adding an additive to the fibrous substrate, wherein the additive reduces the amount of binder needed in the fibrous substrate to substantially maintain the physical properties of the fibrous substrate. The fibers, binder, and additive used to make the fibrous substrate, as well as the composition formed by combining them, are described in detail above. By “substantially maintain the physical properties of the fibrous substrate”, what is meant that the physical properties of the fibrous substrate are such that the fibrous substrate would still meet the requirements of a particular use to which the fibrous substrate may be put.
[0155] As mentioned above, certain fibrous compositions may suffer from binder migration, which may negatively impact physical properties of the fibrous compositions. It has been found that the additive(s) described herein may reduce or prevent binder migration in at least some fibrous compositions, and thus allow for reduced binder requirements and/or increased physical properties in the fibrous compositions. It is uncertain which physical properties of fibrous compositions may impact binder migration in the fibrous compositions, as it is not observed in all sheet-like fibrous compositions. However, despite these uncertainties, it is possible to directly observe whether binder migration occurs in certain sheet-like fibrous compositions; such methods are known to the industry. For example, the following procedure may be used to visually observe binder migration in some sheet-like fibrous compositions (referred to in the remainder of this paragraph as “fabric” for ease of understanding): (1) prepare a dye bath that is 1% DuPont Fiber ID Stain #4 and 99% water, with sufficient volume such that there is greater than 20 parts solution to 1 part of fabric to be tested; (2) bring the dye bath to a boil; (3) place the fabric into the boiling dye bath and leave for 5-10 minutes; (4) remove the fabric from the dye bath, rinse thoroughly with water, and dry; (5) evaluate with high- powered microscopy - binder migration is indicated by differential staining through the thickness of the fabric. It should be noted that this method may not work on certain fabrics, such as fabrics with a certain fiber composition which attracts the dye and/or fabrics that are too thin to visually observe binder migration through the thickness of the fabric. It is believed that it would be readily apparent to a person of ordinary skill in the art whether this method can successfully identify binder migration in a particular fabric after this procedure is conducted on the fabric.
[0156] Examples
[0157] The subject matter disclosed herein may be better understood with reference to the following examples, which are set forth merely to further illustrate the subject matter disclosed herein. The illustrative examples should not be construed as limiting the subject matter in any manner.
[0158] Example Preparation
[0159] Example 1 : A polymeric latex was prepared through an emulsion polymerization process run in a 5 liter, 4-neck, spherical reactor fitted with half-moon blade agitator, temperature probe, condenser, and feed ports. The monomer was contained separately in a premixed emulsion vessel and gradually metered to the reactor over 2 hours to reach a steady and controlled reaction rate. Reaction was carried out as a semi-batch in-situ seeded process, where 5 weight % of the pre-emulsified monomer mixture was batch-polymerized to provide a consistent latex particle size. Seed formation temperature was 80 °C, and polymerization temperature was 83.5 °C, at atmospheric pressure. The polymerization was performed in a hood with the reactor submerged in a water bath with controlled temperature. A slight nitrogen purge was applied throughout the reaction. The pre-emulsion content was prepared by mixing 475 grams water (as used in the Examples, the term “water” refers to demineralized water), 30.88 grams of a 45% aqueous solution of Calfax® DB45 surfactant from Pilot Chemical, and subsequently adding the monomers under agitation: 883 grams styrene, 931 grams n-butyl acrylate, 57 grams of 50% aqueous solution of acrylamide, and 57 grams of methacrylic acid. The reactor content was prepared by mixing 1045 grams of water with 4.75 grams of a 45% aqueous solution of Calfax® DB45. The reactor content was heated to 80 °C, and the in-situ seed, consisting of 5 weight % of the pre-emulsion (130 88 grams) was quickly added to the reactor. After the temperature stabilized, a solution consisting of 1 .9 grams sodium persulfate and 38 grams water was added to the reaction mass. The seed formation reaction was allowed to occur for 15 minutes, then the temperature was set to 83.5 °C, and the pre-emulsion feed into the reactor was started and continued for 120 minutes at a constant rate. Thirty minutes after the start of pre-emulsion feed, the metering of an initiator solution consisting of 2.57 grams sodium persulfate and 133 grams water into the reactor was started and continued for 120 minutes. After the completion of the metered initiator feed, the temperature was maintained at 83.5 °C for 60 more minutes, then the reactor was cooled to 65 °C and a redox initiator was added consisting of 28.5 grams water, 4.07 grams of a 70% aqueous solution of t-butyl hydroperoxide, and 1.9 grams of a 30% aqueous solution of sodium dodecyl sulfate, followed by an aqueous solution consisting of 19 grams water and 1.43 grams of erythorbic acid. Another identical redox initiator was added to the reactor 30 minutes after the first one. Sixty minutes after the last redox initiator addition, the reactor was cooled to 40 °C, and the reaction product was filtered through a 150-micron nylon mesh filter.
[0160] Example 2: An additive was prepared through a free radical solution copolymerization process, as follows. The monomer composition was 70 DMAPMA:30 MPEG350 MA. An aqueous polymer was prepared as follows. A monomer premix was made by mixing 120 grams of water, 84 grams of dimethylaminopropyl methacrylamide (DMAPMA), and 36 grams of polyethylene glycol methacrylate (MPEG 350MA). Initiator A was made by mixing 1.37 grams of 70% t-butyl hydrogen peroxide (TBHP) in 4.8 grams of water. Reductant A was prepared by dissolving 0.96 grams of erythorbic acid in 24 grams of water. A one-liter reactor was charged with 336 grams of water, 1.68 grams of 0.15% Iron(II) sulfate heptahydrate, and 0.48 grams of 1% tetrasodium ethylenediaminetetraacetic acid (Na4- ETDA), and then was heated to 60 °C under a nitrogen blanket with proper agitation. At 60 °C, Initiator A was added to the reactor. After about 2 minutes, the monomer premix was proportioned to the reaction vessel over a period of 120 minutes, and reductant A was proportioned to the reactor over a period of 150 minutes. After completion of reductant A feed, the temperature of the reaction vessel was maintained at 60 °C for 60 minutes. The reactor was then cooled to 50 °C. A solution of 0.43 grams of 70% TBHP and 0.04 grams of 30% sodium lauryl sulfate (SLS) in 6 grams of water was added to the reactor. After 5 minutes, a solution of 0.25 grams of erythorbic acid in 6 grams of water was added to the reactor. The reactor was maintained at 50 °C. After 30 minutes, a solution of 0.43 grams of 70% TBHP and 0 04 grams of 30% sodium lauryl sulfate (SLS) in 6 grams of water was added to the reactor. After 5 minutes, a solution of 0.25 grams of erythorbic acid in 6 grams of water was added to the reactor. The reactor was maintained at 50 °C for about 30 minutes. Then, the reactor was cooled to the room temperature. The polymer had a pH 10.5, solids 22.4%, viscosity 120 cps. [0161] Example 3: A blend was prepared by first adjusting the Example 1 polymer latex with a 28% aqueous solution of ammonia to a pH > 9, and then mixing the resulting latex with the Example 2 additive in a weight ratio of 99.5 to 0.5.
[0162] Example 4: A blend was prepared by first adjusting the Example 1 polymer latex with a 28% aqueous solution of ammonia to a pH > 9, and then mixing the resulting latex with the Example 2 additive in a weight ratio of 99 to 1.
[0163] Example 5: A blend was prepared by first adjusting the Example 1 polymer latex with a 95% aqueous solution of 2-amino-2-methyl-l -propanol (AMP-95) to a pH > 9, and then mixing the resulting latex with the Example 2 additive in a weight ratio of 99.5 to 0.5.
[0164] Example 6: A blend was prepared by first neutralizing the Example 1 polymer latex with dimethylethanolamine (DMEA) to a pH > 9, and then mixing the resulting latex with the Example 2 additive in a weight ratio of 99.5 to 0.5.
[0165] Example 7 : A blend was prepared by first neutralizing the Example 1 polymer latex with a 20% aqueous solution of sodium hydroxide to a pH > 9, and then mixing the resulting latex with the Example 2 additive in a weight ratio of 99.5 to 0.5.
[0166] Example 8: A polymeric latex was prepared and characterized the same way as described in Example 1, where the 57 grams of 50% aqueous solution of acrylamide were replaced by 57 grams of 50% aqueous solution of N-methylolacrylamide.
[0167] Example 9: A blend is prepared by first neutralizing the Example 8 polymer latex with a 28% aqueous solution of ammonia to a pH > 9, and then mixing the resulting latex with the Example 2 additive in a weight ratio of 99.5 to 0.5.
[0168] Example 10: An additive was prepared through a free radical solution copolymerization process, as follows. The monomer composition was 94 DMAPMA:6 MMA. An aqueous polymer was prepared as follows. A monomer premix was made by mixing 400 grams of water, 376 grams of dimethylaminopropyl methacrylamide (DMAPMA) and 24 grams of methyl methacrylate (MMA). Initiator A was made by mixing 4.57 grams of 70% t-butyl hydrogen peroxide (TBHP) in 16 grams of water. Reductant A was prepared by dissolving 3.2 grams of erythorbic acid in 80 grams of water. A three-liter reactor was charged with 720 grams of water, 5.6 grams of 0.15% Iron(II) sulfate heptahydrate, and 1.6 grams of 1% tetrasodium ethylenediaminetetraacetic acid (Na4-ETDA), and then was heated to 60 °C under a nitrogen blanket with proper agitation. At 60 °C, Initiator A was added to the reactor. After about 2 minutes, the monomer premix was proportioned to the reaction vessel over a period of 120 minutes, and reductant A was proportioned to the reactor over a period of 150 minutes. After completion of reductant A feed, the temperature of the reaction vessel was maintained at 60 °C for 60 minutes. The reactor was then cooled to 50 °C. A solution of 1.43 grams of 70% TBHP and 0.13 grams of 30% sodium lauryl sulfate (SLS) in 20 grams of water was added to the reactor. After 5 minutes, a solution of 0.84 grams of erythorbic acid in 20 grams of water was added to the reactor. The reactor was maintained at 50 °C. After 30 minutes, a solution of 1.43 grams of 70% TBHP and 0.13 grams of 30% sodium lauryl sulfate (SLS) in 20 grams of water was added to the reactor. After 5 minutes, a solution of 0.84 grams of erythorbic acid in 20 grams of water was added to the reactor. The reactor was maintained at 50 °C for about 30 minutes. Then, the reactor was cooled to the room temperature. The polymer had a pH 10.7, solids 22.6%, viscosity 270 cps.
[0169] Example 11: A blend is prepared by first neutralizing the Example 1 polymer latex with a 28% aqueous solution of ammonia to a pH > 9, and then mixing the resulting latex with the Example 10 additive in a weight ratio of 99.5 to 0.5.
[0170] Paper Saturation and Evaluation
[0171] Paper properties were evaluated using a Whatman® 3MM CHR chromatography paper substrate, a Whatman® GF/A borosilicate glass substrate, or a spunbond polyester substrate. Whatman® 3 MM CHR is a 100% pure cellulose sheet with no binder. Whatman® GF/A is a 100% borosilicate glass sheet with no binder. The substrate was saturated using a dip and squeeze method where the substrate was placed in a pan containing the diluted saturant. The substrate was removed from the bath and fed through nip rollers to squeeze off any excess material. The sheets were dried on a steam can for one minute at 99 °C. The dry polymer content was controlled at 20% based on the weight of the substrate. The paper was conditioned at 21 °C and 50% relative humidity prior to testing. Paper properties were tested on the as- dried paper and after aging for five-minutes at 149 °C. Glass sheet samples were tested after aging for 2 minutes at 191 °C. Tensile properties were tested according to the Technical Association of the Pulp and Paper Industry (TAPP I) Standard T494 - Tensile properties of paper and paperboard. One-inch wide samples were cut in the cross-machine direction and pulled at twelve inches per minute using a two-inch gauge length. Wet tensile was evaluated after soaking the samples for two minutes in a 1% Triton® X-100 solution. An average of four samples was recorded for each polymer.
[0172] Bursting strength was measured using a Mullen Burst tester. The dry and wet bursting strength were tested according to according to the TAPPI Standard T403 - Bursting Strength of Paper. Wet burst was evaluated after soaking the samples for two minutes in a 1% Triton® X-100 solution. An average of eight samples were used with four wire side up and four felt side up.
[0173] Stiffness was tested according to TAPPI Standard T543 - Bending resistance of paper (Gurley -type tester). Samples were tested dry and after soaking for two minutes in a 1% Triton® X-100 solution. Samples were tested in the cross-machine direction. Two inch by 2.5 inch samples were tested with the 25 grams weight at the 2 inch from pivot position. An average of eight samples was used for each polymer.
[0174] Results
[0175] Whatman® 3MM CHR chromatography paper substrates were used to evaluate the example materials described above, using the binder content (weight percent based on total weight of the composition), cure temperature (°F), and time (minutes) as shown in Table 1A, with results of certain evaluations (described above) shown in Table IB.
Table 1 A
Table IB [0176] Whatman® 3 MM CHR chromatography paper substrates were used to evaluate the example materials described above, using the binder content (weight percent based on total weight of the composition), cure temperature (°F), and time (minutes) as shown in Table 2A, with results of certain evaluations (described above) shown in Table 2B. Table 2A
Table 2B [01771 Whatman® GF/A borosilicate glass substrates were used to evaluate the example materials described above, using the binder content (weight percent based on total weight of the composition), cure temperature (°F), and time (minutes), with results of certain evaluations (described above), as shown in Table 3.
Table 3
[0178] Spunbond polyester substrates were used to evaluate the example materials described above, using the binder content (weight percent based on total weight of the composition), cure temperature (°F), and time (minutes), with results of certain evaluations (described above), as shown in Table 4.
Table 4
[0179] Except in the Examples, or where otherwise explicitly indicated or required by context, all numerical quantities in this description specifying amounts of materials, reaction conditions, molecular weights, number of carbon atoms, and the like, are to be understood as modified by the word “about”. As used herein, the term “about” means that a value of a given quantity is within ±20% of the stated value. In other embodiments, the value is within ±15% of the stated value. In other embodiments, the value is within ±10% of the stated value. In other embodiments, the value is within ±5% of the stated value. In other embodiments, the value is within ±2.5% of the stated value. In other embodiments, the value is within ±1% of the stated value. In other embodiments, the value is within a range of the explicitly-described value which would be understood by those of ordinary skill, based on the disclosures provided herein, to perform substantially similarly to compositions including the literal amounts described herein.
[0180] It is to be understood that the upper and lower amount, range, and ratio limits set forth herein may be independently combined, and that any amount within a disclosed range is contemplated to provide a minimum or maximum of a narrower range in alternative embodiments (with the proviso, of course, that the minimum amount of a range must be lower than the maximum amount of the same range). Similarly, the ranges and amounts for each element of the subject matter disclosed herein may be used together with ranges or amounts for any of the other elements.
[0181] While certain representative embodiments and details have been shown for the purpose of illustrating the subject matter disclosed herein, it will be apparent to those skilled in this art that various changes and modifications may be made therein without departing from the scope of the subject matter. Tn this regard, the scope of the invention is to be limited only by the following claims.

Claims

What is claimed is:
1. A composition comprising fibers, a binder, and an additive, wherein: the binder comprises a colloidal dispersion of a polymer comprising 0.1 to 25 percent by weight acid-functionalized monomeric units, based on the total weight of the polymer, wherein the colloidal dispersion of a polymer has a pH of from 5 to 12; and the additive comprises a water-soluble polymerization reaction product of monomeric units comprising from 5 to 99 weight percent monomeric units represented by at least one of the following general formulas Al or A2, based on the total weight of the additive: wherein, independently for each molecule of the monomeric units represented by at least one of the general formulas Al or A2: R1 is H, CH3, or C2H5; R2 is H or a C1-C4 alkyl group; R3 is a Ci-Ce alkyl group or a Ci-Ce alkylene group; R4 is H or a C1-C4 alkyl group; R5 is H or a Ci- C4 alkyl group; R6 is H, CH3, or C2H5; R7 is a Ci-Ce alkyl group or a Ci-Ce alkylene group; R8 is H or a C1-C4 alkyl group; and R9 is H or a C1-C4 alkyl group.
2. The composition of claim 1, wherein, independently for each molecule of the monomeric units represented by at least one of the general formulas Al or A2: R1 is H or CH3; R2 is H or CH3; R4 is H or CH3; R5 is H or CH3; R6 is H or CH3; R8 is H or CH3; and R9 is H or CH3.
3. The composition of either claim 1 or claim 2, wherein, independently for each molecule of the monomeric units represented by at least one of the general formulas Al or A2: R3 is a C1-C4 alkyl group or a C1-C4 alkylene group; and R7 is a C1-C4 alkyl group or a C1-C4 alkylene group.
4. The composition of any one of claims 1 to 3, wherein the binder is present in the composition in an amount of from 5 to 60 percent by weight, based on the total dry weight of the composition.
5. The composition of any one of claims 1 to 4, wherein the composition comprises from 0.01 to 30 parts of the additive to 100 parts of the binder.
6. The composition of any one of claims 1 to 5, wherein the polymer comprises 0.5 to 10 percent by weight acid-functionalized monomeric units, based on the total weight of the polymer.
7. The composition of any one of claims 1 to 6, wherein the colloidal dispersion of a polymer has a pH of from 7 to 12.
8. The composition of any one of claims 1 to 7, wherein the colloidal dispersion of a polymer comprises at least one of acrylic latex, styrene-butadiene resin latex, vinyl chloride copolymer latex, or vinylidene chloride copolymer latex.
9. The composition of any one of claims 1 to 8, wherein the water-soluble polymerization reaction product of monomeric units comprises from 20 to 95 weight percent monomeric units represented by at least one of the general formulas Al or A2, based on the total weight of the additive.
10. The composition of any one of claims 1 to 9, wherein the water-soluble polymerization reaction product of monomeric units comprises from 1 to 95 weight percent vinyl-group- containing monomeric units different from the monomeric units represented by at least one of the general formulas Al or A2, based on the total weight of the additive.
11. The composition of claim 10, wherein the vinyl -group-containing monomeric units different from the monomeric units represented by at least one of the general formulas Al or A2 comprise at least one acrylate monomer and/or at least one styrene butadiene monomer.
12. The composition of claim 11, wherein the at least one acrylate comprises at least one of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, ethylhexyl acrylate, or ethylhexyl methacrylate.
13. The composition of claim 11, wherein the at least one acrylate comprises at least one monomeric unit represented by the following general formula B: wherein, independently for each molecule of the monomeric unit: R10 is H, CH3, or C2H5; R11 is a poly(alkylene oxide) of number average molecular weight of from 88 to 1200 g/mole, wherein the poly(alkylene oxide) is comprised of repeating alkylene oxide units, and wherein each alkylene oxide unit independently has from 2 to 4 carbons; and R12 is H, a Ci-Cs alkyl group, or a Ci-Cs alkylene group.
14. The composition of claim 13, wherein R11 is a poly(alkylene oxide) of number average molecular weight of from 132 to 1100 g/mole.
15. The composition of either claim 13 or claim 14, wherein at least 90 weight percent of the alkylene oxide units of the poly(alkylene oxide) have 2 carbons, based on the total weight of the poly(alkylene oxide).
16. The composition of any one of claims 13 to 15, wherein R12 is H, CH3, or C2H5.
17. The composition of any one of claims 1 to 9, wherein the water-soluble polymerization reaction product of monomeric units comprises from 1 to 95 weight percent monomeric units represented by the following general formula B : wherein, independently for each molecule of the monomeric unit: R10 is H, CH3, or C2H5; R11 is a poly(alkylene oxide) of number average molecular weight of from 88 to 1200 g/mole, wherein the poly(alkylene oxide) is comprised of repeating alkylene oxide units, and wherein each alkylene oxide unit independently has from 2 to 4 carbons; and R12 is H, a Ci-Cs alkyl group, or a Ci-Cs alkylene group.
18. The composition of claim 17, wherein R11 is a poly(alkylene oxide) of number average molecular weight of from 132 to 1100 g/mole.
19. The composition of either claim 16 or claim 17, wherein at least 90 weight percent of the alkylene oxide units of the poly(alkylene oxide) have 2 carbons, based on the total weight of the poly(alkylene oxide).
20. The composition of any one of claims 17 to 19, wherein R12 is H, CH3, or C2H5.
21. The composition of any one of claims 1 to 20, wherein the fibers comprises at least one of natural fibers, glass fibers, or synthetic fibers.
22. The composition of any one of claims 1 to 21 , wherein the fibers comprise natural fibers.
23. The composition of claim 22, wherein the natural fibers comprise cellulosic fibers.
24. The composition of either claim 22 or 23, wherein the fibers further comprise at least one additional type of fibers other than the natural fibers.
25. The composition of claim 24, wherein the at least one additional type of fibers comprises at least one of glass fibers or synthetic fibers.
26. A fibrous substrate comprising the composition of any one of claims 1 to 25 formed into a substrate.
27. A method of making the composition of any one of claims 1 to 25, the method comprising combining, in any order, the fibers, the binder, and the additive.
28. A method of making the fibrous substrate of claim 26, the method comprising forming the fibers and the binder into the fibrous substrate, followed by adding the additive to the fibrous substrate.
EP23772032.1A 2022-08-24 2023-08-23 Additives for binders and/or fibrous compositions Pending EP4577695A1 (en)

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