IP Library Granted Patent US 8,163,134
Granted Patent B2
US 8,163,134 · App. 12/562,446 · Granted Apr 24, 2012

Copolymer blend compositions for use to increase paper filler content

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Quick Facts
Patent No.
US 8,163,134
App. No.
12/562,446
Granted
Apr 24, 2012
Kind
B2
Abstract

Methods for making a heterogeneous polymer blend comprising one or more anionic polymers, one or more cationic polymers, and one or more non-ionic polymers, which method comprises (a) adding to a non-neutral solution a first amount of polymerization initiator and one or more anionic or cationic monomers, wherein each monomer has the same charge; (b) adding a second amount of the polymerization initiator and one or more non-ionic monomers; (c) adding a third amount of the polymerization initiator and one or more ionic monomers that are oppositely charged from the monomers of (a); adding stepwise, a fourth amount of the polymerization initiator to react any residual monomer, and (e) neutralizing the resulting polymer blend. Also claimed are heterogeneous polymer blends containing polymers formed from one or more anionic, cationic, and non-ionic monomers, either polymerized in situ or separately and then combined. Also claimed are methods for increasing the filler content of paper or paperboard, which methods comprises (a) combining the heterogeneous polymer blend with a precipitated calcium carbonate filler; (b) combining the resulting mixture with a pulp slurry; and (c) processing the resulting slurry mixture to form a sheet of paper or paperboard. Finally, also claimed are methods of increasing the filler content of paper or paperboard, which method comprises (1) combining either the heterogeneous blend or the precipitated calcium carbonate filler with a pulp slurry, (2) combining the remaining component with the pulp slurry; and (c) processing the resulting pulp slurry mixture to form a sheet of paper or paperboard.

Claims (50)

1. A method of increasing the filler content of a sheet of paper or paperboard, comprising:

(a) combining a heterogeneous polymer blend, comprising:

(i) one or more anionic polymers formed from monomers selected from the group consisting of: (1) acrylic acid, (2) methacrylic acid, (3) styrenesulfonic acid, (4) vinylsulfonic acid, (5) acrylamidomethylpropane sulfonic acid, and (6) mixtures thereof; and

(ii) one or more cationic polymers formed from monomers selected from the group consisting of: (1) diallyldimethylammonium chloride, (2) acryloylethyltrimethyl ammonium chloride (3) methacryloylethyl trimethyl ammonium chloride, (4) acryloylethyltrimethylammonium sulfate (5) methacryloylethyl trimethyl ammonium sulfate, (6) acrylamidopropyltrimethyl ammonium chloride, (7) methacrylamidopropyl trimethyl ammonium chloride, (8) non-quaternized forms of (2)-(7), (9) vinylformamide (subsequently hydrolyzed to vinylamine), and (10) mixtures thereof; and

(iii) one or more non-ionic polymers formed from monomers selected from the group consisting of: (1) acrylamide, (2) methacrylamide, (3) N-alkylacrylamide, (4) vinylformamide, and (5) mixtures thereof;

with a precipitated calcium carbonate filler to form a mixture;

(b) combining the mixture with a pulp slurry; and

(c) processing the resulting pulp slurry mixture to form a sheet of paper or paperboard.

2. The method of claim 1 wherein the precipitated calcium carbonate filler is selected from the group consisting of: (1) clustered acicular-aragonite crystals, (2) clustered scalenohedral-calcite crystals, or (3) mixtures thereof.

3. The method of claim 1 wherein the precipitated calcium carbonate filler has a mean particle diameter from about 2 microns to about 4 microns.

4. A method of increasing the filler content of a sheet of paper or paperboard, comprising

(a) combining either (i) a heterogeneous polymer blend, comprising:

(I) one or more anionic polymers formed from monomers selected from the group consisting of: (1) acrylic acid, (2) methacrylic acid, (3) styrenesulfonic acid, (4) vinylsulfonic acid, (5) acrylamidomethylpropane sulfonic acid, and (6) mixtures thereof; and

(II) one or more cationic polymers formed from monomers selected from the group consisting of: (1) diallyldimethylammonium chloride, (2) acryloylethyltrimethyl ammonium chloride (3) methacryloylethyl trimethyl ammonium chloride, (4) acryloylethyltrimethylammonium sulfate (5) methacryloylethyl trimethyl ammonium sulfate, (6) acrylamidopropyltrimethyl ammonium chloride, (7) methacrylamidopropyl trimethyl ammonium chloride, (8) non-quaternized forms of (2)-(7), (9) vinylformamide (subsequently hydrolyzed to vinylamine), and (10) mixtures thereof; and

(III) one or more non-ionic polymers formed from monomers selected from the group consisting of: (1) acrylamide, (2) methacrylamide, (3) N-alkylacrylamide, (4) vinylformamide, and (5) mixtures thereof;

or (ii) a precipitated calcium carbonate filler with a pulp slurry to form a mixture;

(b) combining the remaining component (i) or (ii) from step (a) with the pulp slurry mixture; and

(c) processing the resulting pulp slurry mixture to form a sheet of paper or paperboard.

5. The method of claim 4 wherein the precipitated calcium carbonate filler is selected from the group consisting of: (1) clustered acicular-aragonite crystals, (2) clustered scalenohedral-calcite crystals, and (3) mixtures thereof.

6. The method of claim 4 wherein the precipitated calcium carbonate filler has a mean particle diameter from about 2 microns to about 4 microns.

7. A method of increasing the filler content of a sheet of paper or paperboard, comprising:

(a) combining a heterogeneous polymer blend, comprising:

(i) one or more anionic polymers formed from monomers selected from the group consisting of: (1) acrylic acid, (2) methacrylic acid, (3) styrenesulfonic acid, (4) vinylsulfonic acid, (5) acrylamidomethylpropane sulfonic acid, and (6) mixtures thereof; and

(ii) one or more cationic polymers formed from monomers selected from the group consisting of: (1) diallyldimethylammonium chloride, (2) acryloylethyltrimethyl ammonium chloride (3) methacryloylethyl trimethyl ammonium chloride, (4) acryloylethyltrimethylammonium sulfate (5) methacryloylethyl trimethyl ammonium sulfate, (6) acrylamidopropyltrimethyl ammonium chloride, (7) methacrylamidopropyl trimethyl ammonium chloride, (8) non-quaternized forms of (2)-(7), (9) vinylformamide (subsequently hydrolyzed to vinylamine), and (10) mixtures thereof; and

(iii) one or more non-ionic polymers formed from monomers selected from the group consisting of: (1) acrylamide, (2) methacrylamide, (3) N-alkylacrylamide, (4) vinylformamide, and (5) mixtures thereof; and

(iv) one or more copolymers comprising at least one anionic monomer and at least one non-ionic monomer; and

(v) one or more copolymers comprising at least one cationic monomer and at least one non-ionic monomer;

with a precipitated calcium carbonate filler to form a mixture;

(b) combining the mixture with a pulp slurry; and

(c) processing the resulting pulp slurry mixture to form a sheet of paper or paperboard.

8. The method of claim 7 wherein the precipitated calcium carbonate filler is selected from the group consisting of: (1) clustered acicular-aragonite crystals, (2) clustered scalenohedral-calcite crystals, or (3) mixtures thereof.

9. The method of claim 7 wherein the precipitated calcium carbonate filler has a mean particle diameter from about 2 microns to about 4 microns.

10. A method of increasing the filler content of a sheet of paper or paperboard, comprising

(a) combining either (i) a heterogeneous polymer blend, comprising:

(I) one or more anionic polymers formed from monomers selected from the group consisting of: (1) acrylic acid, (2) methacrylic acid, (3) styrenesulfonic acid, (4) vinylsulfonic acid, (5) acrylamidomethylpropane sulfonic acid, and (6) mixtures thereof; and

(II) one or more cationic polymers formed from monomers selected from the group consisting of: (1) diallyldimethylammonium chloride, (2) acryloylethyltrimethyl ammonium chloride (3) methacryloylethyl trimethyl ammonium chloride, (4) acryloylethyltrimethylammonium sulfate (5) methacryloylethyl trimethyl ammonium sulfate, (6) acrylamidopropyltrimethyl ammonium chloride, (7) methacrylamidopropyl trimethyl ammonium chloride, (8) non-quaternized forms of (2)-(7), (9) vinylformamide (subsequently hydrolyzed to vinylamine), and (10) mixtures thereof; and

(III) one or more non-ionic polymers formed from monomers selected from the group consisting of: (1) acrylamide, (2) methacrylamide, (3) N-alkylacrylamide, (4) vinylformamide, and (5) mixtures thereof; and

(IV) one or more copolymers comprising at least one anionic monomer and at least one non-ionic monomer; and

(V) one or more copolymers comprising at least one cationic monomer and at least one non-ionic monomer;

or (ii) a precipitated calcium carbonate filler with a pulp slurry to form a mixture;

(b) combining the remaining component (i) or (ii) from step (a) with the pulp slurry mixture; and

(c) processing the resulting pulp slurry mixture to form a sheet of paper or paperboard.

11. The method of claim 10 wherein the precipitated calcium carbonate filler is selected from the group consisting of: (1) clustered acicular-aragonite crystals, (2) clustered scalenohedral-calcite crystals, and (3) mixtures thereof.

12. The method of claim 10 wherein the precipitated calcium carbonate filler has a mean particle diameter from about 2 microns to about 4 microns.

13. A method of increasing the filler content of a sheet of paper or paperboard by:

(a) combining a poly-diallyldimethylammonium chloride and acrylamide/acrylate copolymer mixture with a precipitated calcium carbonate filler;

(b) combining the resulting mixture from step (a) with a pulp slurry; and

(c) processing the resulting pulp slurry mixture to form a sheet of paper or paperboard.

14. The method of claim 13 wherein the precipitated calcium carbonate filler is selected from the group consisting of; (1) clustered acicular-aragonite crystals, (2) clustered scalenohedral-calcite crystals, and (3) mixtures thereof.

15. The method of claim 13 wherein the precipitated calcium carbonate filler has a mean particle diameter from about 2 microns to about 4 microns.

Assignments (24)
SECURITY INTEREST Recorded Nov 14, 2025
From: CHEM-AQUA, INC.; DIVERSEY, INC.; DIVERSEY TASKI, INC.; INNOVATIVE WATER CARE, LLC; NCH CORPORATION; NCH LIFE SCIENCES LLC; SOLENIS TECHNOLOGIES, L.P.
To: THE BANK OF NEW YORK MELLON TRUST COMPANY, N.A., AS NOTES COLLATERAL AGENT
Reel/Frame 073570/0838 →
RELEASE OF SECURITY INTEREST Recorded Nov 14, 2025
From: THE BANK OF NEW YORK MELLON TRUST COMPANY, N.A., AS NOTES COLLATERAL AGENT
To: BIRKO CORPORATION; DIVERSEY, INC.; DIVERSEY TASKI, INC.; INNOVATIVE WATER CARE, LLC; SOLENIS TECHNOLOGIES, L.P.
Reel/Frame 073564/0864 →
RELEASE OF 2023 NOTES PATENT SECURITY INTERESTS Recorded Oct 10, 2025
From: THE BANK OF NEW YORK MELLON TRUST COMPANY, N.A.
To: BIRKO CORPORATION; DIVERSEY, INC.; DIVERSEY TASKI, INC.; INNOVATIVE WATER CARE, LLC; SOLENIS TECHNOLOGIES, L.P.
Reel/Frame 073074/0198 →
SECURITY AGREEMENT (NOTES) Recorded Oct 10, 2025
From: DIVERSEY, INC.; DIVERSEY TASKI, INC.; INNOVATIVE WATER CARE, LLC; SOLENIS TECHNOLOGIES, L.P.
To: THE BANK OF NEW YORK MELLON TRUST COMPANY, N.A., AS NOTES COLLATERAL AGENT
Reel/Frame 073061/0885 →
SECURITY AGREEMENT (2024 NOTES) Recorded Jun 24, 2024
From: BIRKO CORPORATION; DIVERSEY, INC.; DIVERSEY TASKI, INC.; INNOVATIVE WATER CARE, LLC; SOLENIS TECHNOLOGIES, L.P.
To: THE BANK OF NEW YORK MELLON TRUST COMPANY, N.A., AS NOTES COLLATERAL AGENT
Reel/Frame 067824/0278 →
2023 NOTES PATENT SECURITY AGREEMENT Recorded Jul 7, 2023
From: BIRKO CORPORATION; SOLENIS TECHNOLOGIES, L.P.; INNOVATIVE WATER CARE, LLC; DIVERSEY, INC.; DIVERSEY TASKI, INC.; INNOVATIVE WATER CARE GLOBAL CORPORATION
To: BANK OF NEW YORK MELLON TRUST COMPANY, N.A.
Reel/Frame 064225/0170 →
SECURITY AGREEMENT (NOTES) Recorded Sep 14, 2022
From: SOLENIS TECHNOLOGIES, L.P.; INNOVATIVE WATER CARE, LLC
To: THE BANK OF NEW YORK MELLON TRUST COMPANY, N.A. AS COLLATERAL AGENT
Reel/Frame 061432/0821 →
NOTES SECURITY AGREEMENT Recorded Nov 10, 2021
From: INNOVATIVE WATER CARE, LLC; SOLENIS TECHNOLOGIES, L.P.
To: THE BANK OF NEW YORK MELLON TRUST COMPANY, N.A.
Reel/Frame 058103/0066 →
RELEASE OF SECURITY INTEREST Recorded Nov 10, 2021
From: CREDIT SUISSE AG, CAYMAN ISLANDS BRANCH
To: SOLENIS TECHNOLOGIES, L.P.
Reel/Frame 058856/0724 →
TERM LOAN PATENT SECURITY AGREEMENT Recorded Nov 10, 2021
From: INNOVATIVE WATER CARE, LLC; SOLENIS TECHNOLOGIES, L.P.
To: GOLDMAN SACHS BANK USA
Reel/Frame 058102/0407 →
ABL PATENT SECURITY AGREEMENT Recorded Nov 10, 2021
From: INNOVATIVE WATER CARE, LLC; SOLENIS TECHNOLOGIES, L.P.
To: BANK OF AMERICA, N.A.
Reel/Frame 058102/0122 →
RELEASE OF SECURITY INTEREST Recorded Nov 10, 2021
From: CITIBANK, N.A.
To: SOLENIS TECHNOLOGIES, L.P.
Reel/Frame 058848/0636 →
FIRST LIEN NOTICE AND CONFIRMATION OF GRANT OF SECURITY INTEREST IN PATENTS Recorded Jul 20, 2018
From: SOLENIS TECHNOLOGIES, L.P.
To: CITIBANK, N.A., COLLATERAL AGENT
Reel/Frame 046595/0241 →
SECOND LIEN NOTICE AND CONFIRMATION OF GRANT OF SECURITY INTEREST IN PATENTS Recorded Jul 20, 2018
From: SOLENIS TECHNOLOGIES, L.P.
To: CREDIT SUISSE AG, CAYMAN ISLANDS BRANCH, AS COLLATERAL AGENT
Reel/Frame 046629/0213 →
INTELLECTUAL PROPERTY FIRST LIEN SECURITY AGREEMENT RELEASE Recorded Jul 20, 2018
From: CREDIT SUISSE AG, CAYMAN ISLANDS BRANCH, AS COLLATERAL AGENT
To: SOLENIS TECHNOLOGIES, L.P.
Reel/Frame 046594/0252 →
INTELLECTUAL PROPERTY SECOND LIEN SECURITY AGREEMENT RELEASE Recorded Jul 20, 2018
From: BANK OF AMERICA, N.A., AS COLLATERAL AGENT
To: SOLENIS TECHNOLOGIES, L.P.
Reel/Frame 047058/0800 →
NOTICE AND CONFIRMATION OF GRANT OF SECURITY INTEREST IN PATENTS (FIRST LIEN) Recorded Aug 14, 2014
From: SOLENIS TECHNOLOGIES, L.P.
To: CREDIT SUISSE AG, CAYMAN ISLANDS BRANCH, AS COLLATERAL AGENT
Reel/Frame 033535/0806 →
NOTICE AND CONFIRMATION OF GRANT OF SECURITY INTEREST IN PATENTS (SECOND LIEN) Recorded Aug 14, 2014
From: SOLENIS TECHNOLOGIES, L.P.
To: BANK OF AMERICA, N.A., AS COLLATERAL AGENT
Reel/Frame 033535/0847 →
U.S. ASSIGNMENT OF PATENTS Recorded Aug 4, 2014
From: HERCULES INCORPORATED
To: SOLENIS TECHNOLOGIES, L.P.
Reel/Frame 033470/0922 →
CORRECTIVE ASSIGNMENT TO CORRECT THE ASSIGNOR NAME PREVIOUSLY RECORDED ON REEL 032908 FRAME 0946. ASSIGNOR(S) HEREBY CONFIRMS THE SECURITY INTEREST. Recorded May 19, 2014
From: MINERALS TECHNOLOGIES INC.; SPECIALTY MINERALS (MICHIGAN) INC.
To: JPMORGAN CHASE BANK, N.A., AS ADMINISTRATIVE AGENT
Reel/Frame 032922/0127 →
SECURITY INTEREST Recorded May 15, 2014
From: MINERAL TECHNOLOGIES INC.; SPECIALTY MINERALS (MICHIGAN) INC.
To: JPMORGAN CHASE BANK, N.A., AS ADMINISTRATIVE AGENT
Reel/Frame 032908/0946 →
RELEASE OF PATENT SECURITY AGREEMENT Recorded Mar 18, 2013
From: THE BANK OF NOVA SCOTIA
To: ASHLAND LICENSING AND INTELLECTUAL PROPERTY LLC; AQUALON COMPANY; ISP INVESTMENTS INC.; HERCULES INCORPORATED
Reel/Frame 030025/0320 →
SECURITY AGREEMENT Recorded Sep 16, 2011
From: ASHLAND LICENSING AND INTELLECTUAL PROPERTY LLC; HERCULES INCORPORATED; AQUALON COMPANY; ISP INVESTMENT INC.
To: THE BANK OF NOVA SCOTIA, AS ADMINISTRATIVE AGENT
Reel/Frame 026918/0052 →
RELEASE OF PATENT SECURITY AGREEMENT Recorded Sep 15, 2011
From: BANK OF AMERICA, N.A.
To: ASHLAND, INC.; ASHLAND LICENSING AND INTELLECTUAL PROPERTY LLC; AQUALON COMPANY; HERCULES INCORPORATED
Reel/Frame 026927/0247 →