IP Library Granted Patent US 7,943,705
Granted Patent B2
US 7,943,705 · App. 12/016,494 · Granted May 17, 2011

Creping adhesives made from amine-terminated polyamidoamines

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Quick Facts
Patent No.
US 7,943,705
App. No.
12/016,494
Granted
May 17, 2011
Kind
B2
Abstract

Polyamidoamine (PAE) resins are prepared from polyamidoamine made with excess amine, which are reacted with a specifically defined amount of difunctional crosslinker. The amount of difunctional crosslinker used is based on the polyamidoamine amine number and reduced specific viscosity (RSV). The PAE resin is prepared by first synthesizing a polyamidoamine from a polyamine and a polycarboxylic acid or polycarboxylic acid derivative, wherein the polyamine is present in a molar excess, said molar excess being from about 1.02 to 2.00, then reacting the polyamidoamine with difunctional crosslinker, wherein the weight % of difunctional crosslinker to polyamidoamine solids is no more than about 0.308(amine number/RSV)—9.18 or 385(amine number/RSV)—5.20, wherein the amine number is expressed as the milliequivalents of amine per gram of polyamidoamine solids and the RSV is the reduced specific viscosity measured at 2% concentration in 1M NH 4 Cl expressed in deciliters per gram. PAE resins prepared according to this process can by used in creping adhesives, which are used to manufacture a variety of paper articles, such as facial tissue, bath tissue, wipes, paper towels, paper napkins, filter papers, and coffee filters.

Claims (17)

1. A process for preparing a polyamidoamine-epichlorohydrin resin comprising the steps of:

(1) reacting a polycarboxylic acid or a polycarboxylic acid derivative with an excess of a polyamine to form a polyamidoamine; and

(2) reacting the polyamidoamine of (1) with epichlorohydrin to form a polyamidoamine-epichlorohydrin resin;

wherein the molar ratio of said polyamine to said polycarboxylic acid is in the range of from 1.02:1 to 1.48:1; and

wherein the weight percent of epichlorohydrin to polyamidoamine in step (2) is from 3.85% to 47%, and

the maximum weight ratio of epichlorohydrin to the solids of polyamidoamine used in step (2) is no greater than about the calculated result of the mathematical expression [0.308-(amine number/RSV)—9.18], wherein said amine number is expressed as the milliequivalents of amine per gram of polyamidoamine solids and said RSV is the reduced specific viscosity measured at 2% concentration in 1 M NH 4 Cl expressed in deciliters per gram.

2. The process of claim 1 , wherein the reaction between said polyamidoamine and said epichlorohydrin is conducted in an aqueous media.

3. The process of claim 1 , wherein said polycarboxylic acid is selected from the group consisting of malonic acid, glutaric acid, adipic acid, azelaic acid, citric acid, tricarballylic acid (1,2,3-propanetricarboxylic acid), 1,2,3,4-butanetetracarboxylic acid, nitrilotriacetic acid, N,N,N′,N′-ethylenediaminetetraacetate, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2,4-benzenetricarboxylic acid (trimellitic acid), 1,2,4,5-benzenetetracarboxylic acid (pyromellitic acid), and mixtures thereof.

4. The process of claim 1 , wherein said polycarboxylic acid derivative is selected from the group consisting of dimethyl adipate, dimethyl malonate, diethyl malonate, dimethyl succinate, dimethyl glutarate, diethyl glutarate, succinic anhydride, maleic anhydride, N,N,N′,N′-ethylenediaminetetraacetate dianhydride, phthalic anhydride, mellitic anhydride, pyromellitic anhydride, adipoyl chloride, glutaryl chloride, sebacoyl chloride, and mixtures thereof.

5. The process of claim 1 , wherein said polyamine is selected from the group consisting of polyethylene polyamines, polypropylene polyamines, polybutylene polyamines, polypentylene polyamines, polyhexylene polyamines, and mixtures thereof.

6. The process of claim 1 , wherein said polyamine is selected from the group consisting of diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), dipropylenetriamine (DPTA), bis-hexamethylenetriamine (BHMT), N-methylbis(aminopropyl)amine (MBAPA), aminoethyl-piperazine (AEP), and mixtures thereof.

7. The process of claim 1 , wherein the weight ratio of said epichlorohydrin to the solids of said polyamidoamine is about 60 to 100% of the calculated maximum weight ratio of epichlorohydrin to the solids of saidpolyamidoamine.

8. The process of claim 1 , wherein said polycarboxylic acid derivative is adipic acid or dimethyl glutarate and said polyamine is diethylenetriamine (DETA).

9. A polyamidoamine-epichlorohydrin resin prepared by the process of claim 1 .

10. A creping adhesive comprising the polyamidoamine-epichlorohydrin resin of claim 9 .

11. An article comprising the creping adhesive of claim 10 wherein said article is selected from the group consisting of facial tissue, bath tissue, wipes, paper towels, paper napkins, filter papers, and coffee filters.

12. An article comprising the polyamidoamine-epichlorohydrin resin of claim 9 wherein said article is selected from the group consisting of facial tissue, bath tissue, wipes, paper towels, paper napkins, filter papers, and coffee filters.

Assignments (25)
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 →
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 →
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 (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 →
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: CREDIT SUISSE AG, CAYMAN ISLANDS BRANCH
To: SOLENIS TECHNOLOGIES, L.P.
Reel/Frame 058856/0724 →
RELEASE OF SECURITY INTEREST Recorded Nov 10, 2021
From: CITIBANK, N.A.
To: SOLENIS TECHNOLOGIES, L.P.
Reel/Frame 058848/0636 →
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 →
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 →
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 →
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 →
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 →
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 →
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 →
U.S. ASSIGNMENT OF PATENTS Recorded Aug 4, 2014
From: HERCULES INCORPORATED
To: SOLENIS TECHNOLOGIES, L.P.
Reel/Frame 033470/0922 →
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 →
SECURITY AGREEMENT Recorded Apr 14, 2010
From: ASHLAND LICENSING AND INTELLECTUAL PROPERTY LLC; AQUALON COMPANY; HERCULES INCORPORATED
To: BANK OF AMERICA, N.A., AS ADMINISTRATIVE AGENT
Reel/Frame 024225/0289 →
RELEASE OF SECURITY INTEREST Recorded Apr 13, 2010
From: BANK OF AMERICA, N.A., AS COLLATERAL AGENT
To: ASHLAND LICENSING AND INTELLECTUAL PROPERTY LLC; AQUALON COMPANY; HERCULES INCORPORATED
Reel/Frame 024218/0928 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 25, 2008
From: ALLEN, ANTHONY J.
To: HERCULES INCORPORATED
Reel/Frame 021152/0703 →