WO1997030118A1 - Resin solutions having enhanced stability - Google Patents

Resin solutions having enhanced stability Download PDF

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Publication number
WO1997030118A1
WO1997030118A1 PCT/US1997/002168 US9702168W WO9730118A1 WO 1997030118 A1 WO1997030118 A1 WO 1997030118A1 US 9702168 W US9702168 W US 9702168W WO 9730118 A1 WO9730118 A1 WO 9730118A1
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WO
WIPO (PCT)
Prior art keywords
resin
resin solution
aminopolyamide
acrylamide
epichlorohydrin
Prior art date
Application number
PCT/US1997/002168
Other languages
French (fr)
Inventor
Richard Underwood
Original Assignee
Callaway Corporation
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 Callaway Corporation filed Critical Callaway Corporation
Priority to AU19565/97A priority Critical patent/AU1956597A/en
Publication of WO1997030118A1 publication Critical patent/WO1997030118A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/24—Homopolymers or copolymers of amides or imides
    • C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/02—Polyamines

Definitions

  • the present invention is directed to the preparation of gly ⁇ oxylated acrylamide-diallyldimethyl ammonium chloride copolymer aqueous resin solutions with improved stability and shelf life.
  • Additives are typically used during paper-making processes to impart strength to paper.
  • papermaking pulps are most conveniently handled as aqueous slurries, so that they can be conveyed, measured, subjected to desired mechanical treat ⁇ ments, and mixed with nonfibrous additives before being delivered to a paper making machine.
  • materials such as mineral pigments are added to the pulp slurries.
  • materials are added to slurries in order to render the resulting paper sheet more resistant to penetration of liquids.
  • additives are delivered to fiber slurries at the wet end of paper machines.
  • Glyoxylated polyacrylamide-diallyldimethyl ammonium chloride copolymer (GPA) resins are known for use as dry strength and temporary wet strength resins for paper.
  • U.S. Patent No. 4,605,702 teaches the preparation of a wet strength additive prepared by glyoxylating an acrylamide copolymer having a molecular weight from about 500 to 6000.
  • the resulting resins have limited shelf stability in aqueous solution and gel after short storage periods, even at non-elevated temperatures. For this reason, the resins are typically supplied in the form of relatively dilute aqueous solutions containing only about 5-10 wt % resin.
  • Aminopolyamide-epichlorohydrin (APAE) resins have been used as wet strength additives for paper.
  • U.S. Patent No. 3,311,594 discloses the preparation of APAE wet strength resins.
  • the resins are prepared by reacting epichlorohydrin with aminopoly- amides, sometimes referred to as polyaminoamides, or polyamino- urylenes containing secondary amino hydrogens.
  • the APAE resins also exhibit storage problems in concentrated form and gel during storage. As such, it has been common practice to dilute the APAE resins to a low solids level to minimize gelation problems.
  • the present invention is directed to an aqueous resin solution containing both (a) an aminopolyamide-epichlorohydrin resin and (b) a glyoxylated acrylamide-diallyldimethyl ammonium chloride resin.
  • the present invention is directed to an aqueous resin solution containing both (a) an aminopolyamide-epichlorohydrin (APAE) resin and (b) a glyoxylated acrylamide-diallyldimethyl ammonium chloride (GPA) resin.
  • the resin solution contains from about 5 to about 25 wt % total resin.
  • the aqueous resin solution functions as a suitable dry strength additive when added to the wet end of a paper machine.
  • the aqueous resin solution also functions as a suitable wet strength additive when added to the wet end of a paper machine.
  • the aminopolyamide-epichlorohydrin resin is prepared by reacting an aminopolyamide and epichlorohydrin in a conventional manner, such as is disclosed in U.S.
  • the resin solution has a viscosity of less than about 150 cp at room temperature for at least 90 days when kept as a solution containing about 13 wt % resin.
  • the aminopolyamide is formed by reacting a carboxylic acid with a polyalkylene polyamine under conditions which produce a water-soluble, long-chain polyamide containing the recurring groups:
  • Dicarboxylic acids useful in preparing the aminopolyamide include saturated aliphatic dicarboxylic acids, preferably containing from about 3 to 8 carbon atoms, such as malonic, succinic, glutaric, adipic, and so on, together with diglycolic acid. Of these, diglycolic acid and the saturated aliphatic dicarboxylic acids having from about 4 to 6 carbon atoms in the molecule, namely, succinic, glutaric, and adipic acids are the most preferred.
  • Blends of two or more dicarboxylic acids may be used, as well as blends which include higher saturated aliphatic dicarboxylic acids such as azelaic and sebatic, as long as the resulting long-chain polyamide is water soluble or at least water dispersible.
  • polyalkylene polyamines such as polyethylene polyamines, polypropylene polyamines, polyoxybutyl- ene polyamines. More specifically, the polyalkylene polyamines of this invention are polyamines containing two primary amine groups and at least one secondary amine group in which the nitrogen atoms are linked together by groups of the formula — c n H 2n— where n is a small integer greater than about 1, and the number of such groups in the molecule ranges from 2 up to about 8, preferably about 2.
  • the nitrogen atoms may be attached to adjacent carbon atoms in the —Cn H 2n— group or to carbon atoms further apart, but not to the same carbon atom.
  • polyamines include but are not limited to diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriam- ine, and the like.
  • Suitable polyamines for use in this invention also include mixtures and various crude polyamine materials, such as the polyamine mixture obtained by reacting ammonia and ethylene dichloride.
  • a preferred method for preparing the APAE resin entails reacting an aminopolyamide with epichlorohydrin in a mole ratio of epichlorohydrin to free amino groups of about 0.5:1.8, and more preferably 0.5:1.5 in aqueous solution. Still more preferably, the APAE resin is prepared with an aminopolyamide and epichlorohydrin at a molar ratio of about 1:1.3. The temperature may vary from about 45°C to about 100°C. Suitable APAE resins are commercially available and may be obtained from several sources including Callaway Chemical Company, Columbus, GA under the trade name Discostrength® 5800.
  • the GPA resin is prepared by first copolymerizing an acryl ⁇ amide monomer with diallyldimethyl ammonium chloride (DADMAC) in aqueous solution, and then reacting the resulting copolymer with glyoxal, such as is disclosed in U.S. Patent Nos. 3,556,932, and 4,605,702.
  • DMDMAC diallyldimethyl ammonium chloride
  • the subject matter of each patent is incorporated herein by reference.
  • the resin solution has a viscosity of less than about 150 cp, and does not gel at room temperature for at least 14 days when kept as a solution containing about 92 wt % water.
  • Suitable acrylamide monomers for use herein may be any acrylamide, such as acrylamide per se, methacrylamide or the like. Moreover, up to about 10% by weight of the acrylamide comonomers may be replaced by other comonomers copolymerizable with the acrylamide, i.e. acrylic acid, acrylic esters such as ethyl acrylate, methylmethacrylate, acrylonitrile, styrene, vinylbenzene, sulfonic acid, and the like.
  • free radical generating initiators are generally added to an aqueous diallyldimethyl ammonium chloride solution.
  • copolymers containing from about 75 to about 95 wt % acrylamide and from about 5 to 25 wt % diallyldimethyl ammonium chloride Generally, copolymers containing from about 75 to about 95 wt % acrylamide and from about 5 to 25 wt % diallyldimethyl ammonium chloride.
  • the polymerization takes place at a tempera ⁇ ture that is generally between about room temperature and about 100 C C.
  • the resulting AM-DADMAC copolymer has an equivalent molecular weight that is generally in the range from about 500 to 100,000 daltons, preferably about 35,000 to about 50,000 daltons.
  • the mole ratio of the glyoxal to the acrylamide copolymer is preferably between about 2:1 to about 0.5:1. More preferably, the acrylamide-DADMAC copolymer is prepared with an acrylamide copolymer and glyoxal at a mole ratio of about 1:1.
  • the temperatures employed are preferably from about 25 to about 100°C, and the pH during the reaction is preferably kept within the range of about 3.5 to about 10.
  • Suitable GPA resins may be obtained from various sources including Callaway Chemical Company, Columbus, GA under the trade name Discostrength ® 19.
  • the resin solution of the present invention is prepared by mixing a GPA resin solution and an APAE resin solution in suffi ⁇ cient amounts so that the resin solution has a viscosity of less than about 200 cp up to about 21 days after preparation when stored at a maximum temperature of about 30°C, and preferably about 25°C.
  • the GPA/APAE weight ratio to achieve such stability is usually between about 1:3 and about 3:1. However, weight ratios of about 1:5 to about 5:1 can also produce suitable results. It is believed that such weight ratios enhance the stability of the GPA resin and the APAE resin.
  • the resin solutions of this invention may contain up to about 25 wt % total resin.
  • the resin solutions are mixed by methods which produce a substantially homogenous final resin solution. It has been found that mixing the resin solutions by means of a stirring blade produces excellent results.
  • the mixing time for the resin solutions is generally from about 5 minutes to about 1 hour, but factors such as the amount of resins used, the chemical composi ⁇ tion of the resins, the mixing temperatures, the mixing technique utilized, and the like, may influence the actual mixing time.
  • the resin solution is preferably stored at a temperature ranging from room temperature up to about 30°C.
  • EXAMPLE 1 In this Example, the following procedure was used to prepare a series of mixed GPA-APAE resin solutions.
  • a GPA resin solution under the tradename Discostrength® 19 having 8.0 wt % resin solids was obtained from Callaway Chemical Co.
  • An APAE resin solution under the tradename Discostrength® 5,800 having 12.5 wt % resin solids was obtained from Callaway Chemical Co.
  • the APAE resin solution was placed in a mixing vessel equipped with a motor-driven stirrer and thermometer and the GPA resin solution added thereto. The mixtures were stirred until uniform resin solutions were visually produced.
  • the resulting mixed solutions had initial viscosities of about 100 cp.
  • the results are shown in Fig. 1.
  • the mixed resin solution having a GPA/APAE ratio of about 1:1 maintained its viscosity of about 100 cp for more than 21 days.
  • the mixed resin solution having a GPA/APAE ratio of about 2.5:1 maintained its viscosity for about 21 days.
  • the GPA resin solution only maintained a viscosity below 200 cps for 7 days. It gelled in less than 14 days.
  • Example 2 The procedure of Example 1 is repeated with the exception that different amounts of resin solutions are used. Specifi ⁇ cally, two resin solutions are prepared with GPA/APAE weight ratios of 1:2.5, and 1:5 respectively. The stability of each mixed resin solution is observed as in Example 1. The two mixed resin solutions maintain their viscosities for more than 28 days without gelling.

Abstract

The performance stability and shelf life of an aqueous resin solution of a glyoxylated acrylamide-diallyldimethyl ammonium chloride copolymer is improved by incorporating therein an aminopolyamide-epichlorohydrin resin.

Description

RESIN SOLUTIONS HAVING ENHANCED STABILITY
FIELD OF THE INVENTION
The present invention is directed to the preparation of gly¬ oxylated acrylamide-diallyldimethyl ammonium chloride copolymer aqueous resin solutions with improved stability and shelf life.
BACKGROUND OF THE INVENTION
Additives are typically used during paper-making processes to impart strength to paper. During the stock-preparation step of papermaking processes, for instance, papermaking pulps are most conveniently handled as aqueous slurries, so that they can be conveyed, measured, subjected to desired mechanical treat¬ ments, and mixed with nonfibrous additives before being delivered to a paper making machine. During filling and loading stages of papermaking processes, materials such as mineral pigments are added to the pulp slurries. During sizing, materials are added to slurries in order to render the resulting paper sheet more resistant to penetration of liquids. During continuous sheet forming steps of papermaking processes, additives are delivered to fiber slurries at the wet end of paper machines.
Glyoxylated polyacrylamide-diallyldimethyl ammonium chloride copolymer (GPA) resins are known for use as dry strength and temporary wet strength resins for paper. U.S. Patent No. 4,605,702, for instance, teaches the preparation of a wet strength additive prepared by glyoxylating an acrylamide copolymer having a molecular weight from about 500 to 6000. The resulting resins have limited shelf stability in aqueous solution and gel after short storage periods, even at non-elevated temperatures. For this reason, the resins are typically supplied in the form of relatively dilute aqueous solutions containing only about 5-10 wt % resin.
Aminopolyamide-epichlorohydrin (APAE) resins have been used as wet strength additives for paper. U.S. Patent No. 3,311,594, discloses the preparation of APAE wet strength resins. The resins are prepared by reacting epichlorohydrin with aminopoly- amides, sometimes referred to as polyaminoamides, or polyamino- urylenes containing secondary amino hydrogens. The APAE resins also exhibit storage problems in concentrated form and gel during storage. As such, it has been common practice to dilute the APAE resins to a low solids level to minimize gelation problems.
Despite the relatively poor stability of the GPA and APAE resins individually, it has been unexpectedly found that a resin solution which contains both the APAE and GPA resins has signif¬ icantly increased stability and extended shelf life, as compared to the stability of the GPA and APAE resins individually.
SUMMARY OF THE INVENTION
The present invention is directed to an aqueous resin solution containing both (a) an aminopolyamide-epichlorohydrin resin and (b) a glyoxylated acrylamide-diallyldimethyl ammonium chloride resin.
DESCRIPTION OF THE DRAWINGS
Fig. 1 is a stability graph of aqueous resin solutions con¬ taining varying amounts of aminopolyamide-epichlorohydrin and glyoxylated acrylamide-diallyldimethyl ammonium chloride resins as compared to the stability of aminopolyamide-epichlorohydrin and glyoxylated acrylamide-diallyldimethyl ammonium chloride resins individually.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention is directed to an aqueous resin solution containing both (a) an aminopolyamide-epichlorohydrin (APAE) resin and (b) a glyoxylated acrylamide-diallyldimethyl ammonium chloride (GPA) resin. The resin solution contains from about 5 to about 25 wt % total resin. The aqueous resin solution functions as a suitable dry strength additive when added to the wet end of a paper machine. The aqueous resin solution also functions as a suitable wet strength additive when added to the wet end of a paper machine. The aminopolyamide-epichlorohydrin resin is prepared by reacting an aminopolyamide and epichlorohydrin in a conventional manner, such as is disclosed in U.S. Patent Nos. 3,197,427, 3,442,754, and 3,311,594, the subject matter of each patent is incorporated herein by reference. The resin solution has a viscosity of less than about 150 cp at room temperature for at least 90 days when kept as a solution containing about 13 wt % resin.
The aminopolyamide is formed by reacting a carboxylic acid with a polyalkylene polyamine under conditions which produce a water-soluble, long-chain polyamide containing the recurring groups:
—NH(CnH2nHN)χ—CORCO— wherein n and x are each 2 or more and R is the divalent, organic radical of the dicarboxylic acid. Dicarboxylic acids useful in preparing the aminopolyamide include saturated aliphatic dicarboxylic acids, preferably containing from about 3 to 8 carbon atoms, such as malonic, succinic, glutaric, adipic, and so on, together with diglycolic acid. Of these, diglycolic acid and the saturated aliphatic dicarboxylic acids having from about 4 to 6 carbon atoms in the molecule, namely, succinic, glutaric, and adipic acids are the most preferred. Blends of two or more dicarboxylic acids may be used, as well as blends which include higher saturated aliphatic dicarboxylic acids such as azelaic and sebatic, as long as the resulting long-chain polyamide is water soluble or at least water dispersible.
Useful polyamines include polyalkylene polyamines such as polyethylene polyamines, polypropylene polyamines, polyoxybutyl- ene polyamines. More specifically, the polyalkylene polyamines of this invention are polyamines containing two primary amine groups and at least one secondary amine group in which the nitrogen atoms are linked together by groups of the formula — cnH2n— where n is a small integer greater than about 1, and the number of such groups in the molecule ranges from 2 up to about 8, preferably about 2. The nitrogen atoms may be attached to adjacent carbon atoms in the —CnH2n— group or to carbon atoms further apart, but not to the same carbon atom. Specific polyamines include but are not limited to diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriam- ine, and the like. Suitable polyamines for use in this invention also include mixtures and various crude polyamine materials, such as the polyamine mixture obtained by reacting ammonia and ethylene dichloride.
A preferred method for preparing the APAE resin entails reacting an aminopolyamide with epichlorohydrin in a mole ratio of epichlorohydrin to free amino groups of about 0.5:1.8, and more preferably 0.5:1.5 in aqueous solution. Still more preferably, the APAE resin is prepared with an aminopolyamide and epichlorohydrin at a molar ratio of about 1:1.3. The temperature may vary from about 45°C to about 100°C. Suitable APAE resins are commercially available and may be obtained from several sources including Callaway Chemical Company, Columbus, GA under the trade name Discostrength® 5800.
The GPA resin is prepared by first copolymerizing an acryl¬ amide monomer with diallyldimethyl ammonium chloride (DADMAC) in aqueous solution, and then reacting the resulting copolymer with glyoxal, such as is disclosed in U.S. Patent Nos. 3,556,932, and 4,605,702. The subject matter of each patent is incorporated herein by reference. The resin solution has a viscosity of less than about 150 cp, and does not gel at room temperature for at least 14 days when kept as a solution containing about 92 wt % water.
Suitable acrylamide monomers for use herein may be any acrylamide, such as acrylamide per se, methacrylamide or the like. Moreover, up to about 10% by weight of the acrylamide comonomers may be replaced by other comonomers copolymerizable with the acrylamide, i.e. acrylic acid, acrylic esters such as ethyl acrylate, methylmethacrylate, acrylonitrile, styrene, vinylbenzene, sulfonic acid, and the like. In polymerizing the acrylamide with the diallyldimethyl ammonium chloride, free radical generating initiators are generally added to an aqueous diallyldimethyl ammonium chloride solution. Generally, copolymers containing from about 75 to about 95 wt % acrylamide and from about 5 to 25 wt % diallyldimethyl ammonium chloride. The polymerization takes place at a tempera¬ ture that is generally between about room temperature and about 100CC. The resulting AM-DADMAC copolymer has an equivalent molecular weight that is generally in the range from about 500 to 100,000 daltons, preferably about 35,000 to about 50,000 daltons.
In reacting the resulting acrylamide-DADMAC copolymer and the glyoxal, the mole ratio of the glyoxal to the acrylamide copolymer is preferably between about 2:1 to about 0.5:1. More preferably, the acrylamide-DADMAC copolymer is prepared with an acrylamide copolymer and glyoxal at a mole ratio of about 1:1. The temperatures employed are preferably from about 25 to about 100°C, and the pH during the reaction is preferably kept within the range of about 3.5 to about 10. Suitable GPA resins may be obtained from various sources including Callaway Chemical Company, Columbus, GA under the trade name Discostrength® 19.
The resin solution of the present invention is prepared by mixing a GPA resin solution and an APAE resin solution in suffi¬ cient amounts so that the resin solution has a viscosity of less than about 200 cp up to about 21 days after preparation when stored at a maximum temperature of about 30°C, and preferably about 25°C. The GPA/APAE weight ratio to achieve such stability is usually between about 1:3 and about 3:1. However, weight ratios of about 1:5 to about 5:1 can also produce suitable results. It is believed that such weight ratios enhance the stability of the GPA resin and the APAE resin. The resin solutions of this invention may contain up to about 25 wt % total resin. Preferably they contain from about 5 to about 15 wt % total resin, more preferably from about 7 to about 12 wt % total resin. The resin solutions are mixed by methods which produce a substantially homogenous final resin solution. It has been found that mixing the resin solutions by means of a stirring blade produces excellent results. The mixing time for the resin solutions is generally from about 5 minutes to about 1 hour, but factors such as the amount of resins used, the chemical composi¬ tion of the resins, the mixing temperatures, the mixing technique utilized, and the like, may influence the actual mixing time. The resin solution is preferably stored at a temperature ranging from room temperature up to about 30°C.
The following examples illustrate the invention described herein. All parts and percents are by weight unless otherwise specified.
EXAMPLE 1 In this Example, the following procedure was used to prepare a series of mixed GPA-APAE resin solutions. A GPA resin solution under the tradename Discostrength® 19 having 8.0 wt % resin solids was obtained from Callaway Chemical Co. An APAE resin solution under the tradename Discostrength® 5,800 having 12.5 wt % resin solids was obtained from Callaway Chemical Co. The APAE resin solution was placed in a mixing vessel equipped with a motor-driven stirrer and thermometer and the GPA resin solution added thereto. The mixtures were stirred until uniform resin solutions were visually produced. The resulting mixed solutions had initial viscosities of about 100 cp.
By following this procedure, three resin solutions were pre¬ pared having GPA/APAE weight ratios of 1:1, 2.5:1, and 5:1 respectively. The stability of each mixed resin solution as well as of the individual GPA and APAE solutions was evaluated at room temperature weekly by measuring the viscosity of each with a Brookfield viscometer until gelation occurred.
The results are shown in Fig. 1. The mixed resin solution having a GPA/APAE ratio of about 1:1 maintained its viscosity of about 100 cp for more than 21 days.
The mixed resin solution having a GPA/APAE ratio of about 2.5:1 maintained its viscosity for about 21 days.
The mixed resin solution having a GPA/APAE ratio of about 5:1 maintained a viscosity of less than 200 cps for 14 days and did not become a gel until 21 days after preparation.
The GPA resin solution only maintained a viscosity below 200 cps for 7 days. It gelled in less than 14 days.
The APAE resin solution maintained a viscosity below 200 cps for 21 days.
EXAMPLE 2 The procedure of Example 1 is repeated with the exception that different amounts of resin solutions are used. Specifi¬ cally, two resin solutions are prepared with GPA/APAE weight ratios of 1:2.5, and 1:5 respectively. The stability of each mixed resin solution is observed as in Example 1. The two mixed resin solutions maintain their viscosities for more than 28 days without gelling.

Claims

What is Claimed is:
1. An aqueous resin solution characterized by a mixture of (a) an aminopolyamide-epichlorohydrin resin and (b) a glyoxylated acrylamide-diallyldimethyl ammonium chloride resin and the mixed resin solution contains from about 5 to about 25 wt % total resin.
2. The resin solution of Claim 1, characterized in that the aminopolyamide-epichlorohydrin resin and the glyoxylated acrylamide-diallyldimethyl ammonium chloride resin are present at a weight ratio of about 1:5 to about 5:1.
3. The resin solution of Claim 1, characterized in that the aminopolyamide-epichlorohydrin resin and the glyoxylated acrylamide-diallyldimethyl ammonium chloride resin are present in a weight ratio of about 1:1.
4. The resin solution of Claim 1, characterized in that the resin solution has a viscosity of less than about 200 cp for at least 21 days after preparation when stored at a temperature of less than about 30°C.
5. The resin solution of Claim 1, characterized in that the glyoxylated acrylamide-diallyldimethyl ammonium resin is prepared with an acrylamide copolymer and glyoxal at a mole ratio of about 1:1.
6. The resin solution of Claim 1, characterized in that the aminopolyamide-epichlorohydrin resin is prepared with an aminopolyamide and epichlorohydrin at a mole ratio of about 1:1.3.
PCT/US1997/002168 1996-02-16 1997-02-11 Resin solutions having enhanced stability WO1997030118A1 (en)

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AU19565/97A AU1956597A (en) 1996-02-16 1997-02-11 Resin solutions having enhanced stability

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US60129796A 1996-02-16 1996-02-16
US08/601,297 1996-02-16

Publications (1)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5976196A (en) * 1998-06-15 1999-11-02 Callaway Corporation Process for preparing a dyed textile fabric wherein the dyed fabric is coated with a mixture of resins
WO2004061235A1 (en) * 2002-12-20 2004-07-22 Kimberly-Clark Worldwide, Inc. Bicomponent strengthening system for paper
US7034087B2 (en) * 2004-08-17 2006-04-25 Georgia-Pacific Resins, Inc. Aldehyde scavengers for preparing temporary wet strength resins with longer shelf life
US7488403B2 (en) 2004-08-17 2009-02-10 Cornel Hagiopol Blends of glyoxalated polyacrylamides and paper strengthening agents
US7897013B2 (en) 2004-08-17 2011-03-01 Georgia-Pacific Chemicals Llc Blends of glyoxalated polyacrylamides and paper strengthening agents

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3556932A (en) * 1965-07-12 1971-01-19 American Cyanamid Co Water-soluble,ionic,glyoxylated,vinylamide,wet-strength resin and paper made therewith
GB1561727A (en) * 1975-11-20 1980-02-27 Basf Ag Comprising water-soluble acrylamides polymers and water-soluble resinous amine condensation products
EP0278336A2 (en) * 1987-02-11 1988-08-17 Wolff Walsrode Aktiengesellschaft Agents for paper production
EP0662542A1 (en) * 1993-12-31 1995-07-12 Hercules Incorporated Composition for the manufacture of wet strengthened paper

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3556932A (en) * 1965-07-12 1971-01-19 American Cyanamid Co Water-soluble,ionic,glyoxylated,vinylamide,wet-strength resin and paper made therewith
GB1561727A (en) * 1975-11-20 1980-02-27 Basf Ag Comprising water-soluble acrylamides polymers and water-soluble resinous amine condensation products
EP0278336A2 (en) * 1987-02-11 1988-08-17 Wolff Walsrode Aktiengesellschaft Agents for paper production
EP0662542A1 (en) * 1993-12-31 1995-07-12 Hercules Incorporated Composition for the manufacture of wet strengthened paper

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5976196A (en) * 1998-06-15 1999-11-02 Callaway Corporation Process for preparing a dyed textile fabric wherein the dyed fabric is coated with a mixture of resins
WO2004061235A1 (en) * 2002-12-20 2004-07-22 Kimberly-Clark Worldwide, Inc. Bicomponent strengthening system for paper
KR101029658B1 (en) * 2002-12-20 2011-04-15 킴벌리-클라크 월드와이드, 인크. Bicomponent Strengthening System for Paper
US7034087B2 (en) * 2004-08-17 2006-04-25 Georgia-Pacific Resins, Inc. Aldehyde scavengers for preparing temporary wet strength resins with longer shelf life
US7488403B2 (en) 2004-08-17 2009-02-10 Cornel Hagiopol Blends of glyoxalated polyacrylamides and paper strengthening agents
US7897013B2 (en) 2004-08-17 2011-03-01 Georgia-Pacific Chemicals Llc Blends of glyoxalated polyacrylamides and paper strengthening agents

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AU1956597A (en) 1997-09-02
AR005741A1 (en) 1999-07-14
ZA971186B (en) 1997-08-25
ID18934A (en) 1998-05-20

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