WO2010059699A1 - Adhésifs de crêpage présentant des propriétés de film améliorées - Google Patents

Adhésifs de crêpage présentant des propriétés de film améliorées Download PDF

Info

Publication number
WO2010059699A1
WO2010059699A1 PCT/US2009/064954 US2009064954W WO2010059699A1 WO 2010059699 A1 WO2010059699 A1 WO 2010059699A1 US 2009064954 W US2009064954 W US 2009064954W WO 2010059699 A1 WO2010059699 A1 WO 2010059699A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
acid
polyaminoamide
creping
multifunctional
Prior art date
Application number
PCT/US2009/064954
Other languages
English (en)
Inventor
Vladimir A. Grigoriev
Gary S. Furman
Mingli Wei
Winston Su
Christopher D. Kaley
Bryan M. Schertzer
Original Assignee
Nalco Company
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 Nalco Company filed Critical Nalco Company
Priority to MX2011005194A priority Critical patent/MX2011005194A/es
Priority to EP09756907.3A priority patent/EP2358836B1/fr
Priority to PL09756907T priority patent/PL2358836T3/pl
Priority to CN2009801455016A priority patent/CN102216409B/zh
Priority to CA2740599A priority patent/CA2740599C/fr
Priority to BRPI0916122A priority patent/BRPI0916122B1/pt
Priority to ES09756907.3T priority patent/ES2652468T3/es
Priority to AU2009316690A priority patent/AU2009316690B2/en
Publication of WO2010059699A1 publication Critical patent/WO2010059699A1/fr

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
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/146—Crêping adhesives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/028—Polyamidoamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/028—Polyamidoamines
    • C08G73/0286—Preparatory process from polyamidoamines and epihalohydrins
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J179/00—Adhesives based on 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 C09J161/00 - C09J177/00
    • C09J179/02—Polyamines

Definitions

  • tissue paper obtains its characteristic properties of softness, bulk, absorbency, and ability to stretch, by a process involving a Yankee Dryer apparatus.
  • tissue paper obtains its characteristic properties of softness, bulk, absorbency, and ability to stretch, by a process involving a Yankee Dryer apparatus.
  • tissuemaking the tissue is fed to the Yankee Dryer apparatus as a wet fiber web.
  • the wet fiber web is largely dewatered at a pressure roll nip where the sheet is transferred to the surface of a Yankee Dryer cylinder.
  • the paper web typically has 35-40% consistency (it is 65-60% water).
  • the sheet is further dried on the hot Yankee Dryer cylinder to 90-97% consistency and removed with a doctor blade.
  • the mechanical action of the blade results in a disruption of the fiber-fiber bonds, which forms a microfold structure that gives the tissue paper its characteristic properties. This process is referred to as creping.
  • the paper web In order to properly crepe a paper web to make soft tissue paper, the paper web has to adhere to the surface of the Yankee dryer cylinder.
  • the doctor blade then forms microfolds by compressing or shortening the paper web in the machine direction while at the same time separating it from the drying cylinder. This adhesion is facilitated by the application of an adhesive to the surface of the dryer cylinder.
  • wet-end furnish components can also contribute to the adhesion that occurs.
  • Yankee adhesives are synthetic polymers such as polyaminoamide-epichlorohydrin resins, polyamine-epichlorohydrin resins, polyvinyl alcohols, polyvinyl acetates, polyacrylamides, polyamines, polyamides, polyvinylpyrrolidones and polyethers.
  • Other natural and derivitized natural polymers may also be employed including starch, guar gum, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and the like.
  • Various low molecular weight compounds, oils and surfactants are used to modify the properties of these adhesives.
  • the tissue industry has a continuing interest in manufacturing premium grade tissues, which are tissues with high levels of softness. Improvements in softness can be obtained by modifying the fiber source, implementing particular forming and drying strategies, creping the fiber sheets, and by using wet-end or topical application of softening agents. Creping the paper sheet when it has a very low sheet moisture level ( ⁇ 3%) is one of the most effective ways of achieving desired levels of high softness. At low moisture levels, the sheet and the coating tend to adhere to each other more strongly which causes the sheet to debond in the Z-direction more efficiently thereby generating greater bulk and softness.
  • At least one embodiment of the invention is directed towards a composition
  • a composition comprising a polyaminoamide epihalohydrin (PAE) resin acidified with at least one multifunctional acid.
  • the acid has at least two functional groups one being a first functional group and one being a second functional group.
  • the first functional group is selected from carboxyl and sulfonyl.
  • the second functional group is selected from carboxyl, sulfonyl, hydroxyl, lactone, phenol, amine, or heterocycle.
  • At least one embodiment of the invention is directed towards a composition having a PAE resin that is prepared by reacting epichlorohydrin with a polyaminoamide prepared by reacting one or more aliphatic or aromatic dicarboxylic acid derivatives with one or more polyalkylene polyamines. This is done in a mole ratio of about 0.8: 1 to about 1.4: 1 with about 0.01 to about 1.8 molar equivalents of epihalohydrin, based on secondary amino groups of the polyaminoamide.
  • the PAE resin can have a weight-average molecular weight of about 10,000 to about 5,000,000 Daltons.
  • the epihalohydrin can be epichlorohydrin.
  • At least one embodiment of the invention is directed towards a composition wherein the PAE resins are prepared by reacting the polyaminoamide with about 0.05 to about 0.8 molar equivalents of epichlorohydrin, based on secondary amino groups of the polyaminoamide.
  • the polyaminoamide can be the reaction product of diethylenetriamine and a dicarboxylic acid derivative selected from adipic acid, glutaric acid, DBE-2 dibasic ester, dimethyl glutarate and dimethyl adipate or a mixture thereof.
  • the PAE resins can be prepared by reacting the polyaminoamide with about 0.1 to about 0.3 molar equivalents of epichlorohydrin, based on secondary amino groups of the polyarainoamide.
  • the PAE resins can also be a terpolymer of adipic acid, diethylenetriamine and epichlorohydrin.
  • At least one embodiment of the invention is directed towards a composition in which at least one multifunctional acid is selected from oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, phthalic, isophthalic, terephthalic, citric, isocitric, aconitic, carballylic, glycolic, lactic, malic, tartaric, gluconic, maleic, f ⁇ maric, ascorbic, aspartic, glutamic, 4-hydroxy-benzoic, 2,4-dihydroxy benzoic, sulfamic, methanesulfonic, 4-toluene sulfonic, xylene sulfonic, phenol sulfonic, and any combination thereof.
  • the first and second functional groups can be different kinds of groups.
  • the molar ratio of multifunctional acid to the PAE polymer secondary amines can be from about 0.01 to about 5. A more preferred ratio is from about 0.1 to about 2. The most preferred ratio is from about 0.2 to about 1.
  • a PAE resin can comprise one or more mineral acids.
  • the mineral acid can be selected from sulfuric, hydrochloric, nitric, phosphoric, boric or hydrofluoric, more preferred from sulfuric or phosphoric, and any combination thereof.
  • the most preferred mineral acid is sulfuric acid.
  • the molar ratio of mineral acid to multifunctional acid can be from about 0.01 to about 99. A more preferred ratio is from about 0.1 to about 1.0. The most preferred ratio from about 0.2 to about 0.5.
  • At least one embodiment of the invention is directed towards an aqueous creping adhesive composition
  • an aqueous creping adhesive composition comprising about 0.01 to about 50 percent by weight of PAE resin and about 99.99 to about 50 weight percent water.
  • the PAE resin is acidified with at least one multifunctional acid having one functional group selected from carboxyl and sulfonyl and at least one more functional group selected from carboxyl, sulfonyl, hydroxyl, lactone, phenol, amine, or heterocycle.
  • the multifunctional acid can be one selected from the list consisting of: citric, glutamic and sulfamic and the adhesive composition has a pH from about 2 to about 9.
  • the aqueous creping composition can further comprise one or more polyols selected from ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, glycerol, 1 ,4-butanediol, diethanolamine, triethanolamine, trimethylolpropane, erythritol, pentaerythritol, dipentaerythritol, arabitol, xylitol, ribitol, mannitol, sorbitol, galactitol, isomalt, maltitol, lactitol.
  • the aqueous creping composition can also comprise one or more phosphate salts selected from monoammonium phosphate, diammonium phosphate, sodium and potassium tripolyphosphate, and phosphate salts formed in situ by adjusting the pH of the creping composition with phosphoric acid, and mixtures thereof.
  • the aqueous composition includes the organic phosphates as described in published US Patent Application Number 2007/0208115.
  • At least one embodiment of the invention is directed towards a method of creping a paper web comprising the steps of: a) applying to a rotating creping cylinder an adhesive composition comprising one or more polyaminoaminde epihalohydrin resins acidified with at least one multifunctional acid; b) pressing the paper web against the creping cylinder to effect adhesion of the paper web to the creping cylinder; and c) dislodging the paper web from the creping cylinder with a doctor blade.
  • FIG. 1 is a schematic representation of a Yankee Dryer Apparatus using the novel
  • PAE resin based adhesive PAE resin based adhesive
  • FIG. 2 is a cross sectional image of a cellulose fiber web bound to the surface of a Yankee Dryer Cylinder by the novel PAE resin based adhesive.
  • FIG. 3 is a graph plotting adhesion with temperature. Detailed Description of the Invention
  • FIG.l there is shown a Yankee dryer apparatus (1) upon which the novel polyaminoamide-epichlorohydrin (PAE) resin is used.
  • PAE polyaminoamide-epichlorohydrin
  • Prior Art creping adhesives are based on PAE resins, which are manufactured by crosslinking the polyaminoamide backbone with epichlorohydrin.
  • EP 1109971 and JP 2688950 as well as US Patent Nos.
  • the Yankee dryer apparatus (1) comprises a pressure roll (2) adjacent to a dryer cylinder (3) which is also adjacent to a reel (4).
  • a felt (5) feeds a wet fiber web composed of cellulose fibers (10) from the pressure roll (2) to the dryer cylinder (3).
  • the dryer cylinder (3) then rotates the wet fiber web through a drying hood (6) where the fiber web loses most of its moisture.
  • a creping blade or doctor blade (7) removes the dry fiber web so as to facilitate the paper's absorptiveness and softness.
  • a cleaning blade (8) removes extraneous material and smoothes out the remaining coating.
  • the PAE resin is added by an applier (9). In at least one embodiment the applier is a spray boom.
  • the physical requirements in a Yankee dryer apparatus (1) impose antagonistic properties on any adhesive used in the creping process.
  • the adhesive (11) binds a layer of fiber web (10) to the surface of the Yankee dryer cylinder (3).
  • inorganic contaminants (12), calcium carbonate (13), hemicellulose (15), and cellulose debris (14) are present.
  • the adhesive When the fiber web (10) is first fed to the dryer cylinder (3) the adhesive must be strong enough to resist being washed off the dryer cylinder (3) by the high amounts of moisture present in the fiber web. However once the fiber web is dried, the adhesive must be soft enough to allow the creping blade to easily penetrate the adhesive to properly crepe the fiber web.
  • An adhesive created using a PAE resin with a multifunctional acid possesses these antagonistic properties.
  • a creping adhesive is formed from a PAE resin which is acidified with at least one multifunctional acid having one functional group selected from carboxyl and sulfonyl and at least one more functional group selected from carboxyl, sulfonyl, hydroxyl, lactone, phenol, amine, and heterocycle.
  • multifunctional acids include but are not limited to oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, phthalic, isophthalic, terephthalic, citric, isocitric, aconitic, carballylic, glycolic, lactic, malic, tartaric, gluconic, raaleic, fumaric, ascorbic, aspartic, glutamic, 4-hydroxy-benzoic, 2,4-dihydroxy benzoic, sulfamic, methansulfonic, 4-toluene sulfonic, xylene sulfonic, phenol sulfonic and the like, and any combination thereof.
  • the PAE resin in addition to multifunctional acids, is also formed from one or more mineral acids.
  • Appropriate mineral acids include but are not limited to sulfuric, hydrochloric, nitric, phosphoric, boric, hydrofluoric and the like, and any combination thereof.
  • the mineral acid is sulfuric or phosphoric.
  • the molar ratio of mineral acid to multifunctional acid spans from about 0.01 to 99. In another embodiment, the ratio is about 0.1-1.0. In another embodiment, the ratio is 0.2-0.5.
  • the pH may be adjusted with one or more multifunctional acids or with one or more multifunctional acids and one or more mineral acids or a mixture thereof.
  • the pH is adjusted with citric or sulfamic acids.
  • the pH is adjusted with sulfuric acid first followed by citric acid. Adjusting the pH can be used to modify the resin. Changing the pH can quench the crosslinking reaction, or can stabilize the product in storage, or can affect performance.
  • the pH is adjusted to about 2-8.
  • the pH is adjusted to 3-5.
  • the PAE resins are water soluble, cationic thermosetting resins typically prepared by reacting one or more polyalkylene polyamines containing secondary amine groups and one or more dicarboxylic acid derivatives to form a polyaminoamide and then reacting the polyaminoamide with epihalohydrin to form the PAE resin.
  • the preparation of PAE resins is described, for example, in U.S. Patent No. 6,277,242 and U.S. Published Patent Applications 2005/0217817 and 2007/0151684, and Japanese Patent number JP 2688950B2, all of whose contents are hereby incorporated by reference in their entirety.
  • the polyamides can be made from the condensation polymerization of one or more organic dicarboxylic acid derivatives and one or more polyalkylene polyamines under conditions suitable for forming long-chain polyamides, for example at temperatures higher than about 130 0 C for several hours with removal of water or alcohol byproducts.
  • the resulting polyamide typically has weight average molecular weight of about 500 to about 500,000 Daltons as determined by gel permeation chromatography/multi-angle laser light scattering (GPC/MALLS) and a polymer Brookfield viscosity higher than about 100 cps for a 50% solution at 25 0 C. Water may be added at the end of the polymerization to make an aqueous polymer solution.
  • organic dicarboxylic acid derivative which is capable of reacting with substantially all of the primary amino groups but which is insufficient to react to any significant degree with the secondary amino groups of the polyalkylene polyamine is used.
  • the organic dicarboxylic acid derivative and polyalkylene polyamine are reacted in a molar ratio of about 0.8:1 to about 1.4:1.
  • the organic dicarboxylic acid derivative and the polyalkylene polyamine are reacted in a molar ratio of about 0.9: 1 to about 1.0:0.9.
  • Organic dicarboxylic acid derivatives is aliphatic and aromatic dicarboxylic acids and their corresponding acid chlorides, anhydrides and esters, and mixtures thereof. Esters are preferably C]-C 3 aliphatic esters.
  • the organic dicarboxylic acid derivatives are selected such that the resulting polyamide is water soluble or water dispersible.
  • organic dicarboxylic acids and their derivatives include but are not limited to maleic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebasic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, dimethyl maleate, dimethyl malonate, diethyl malonate, dimethyl succinate, di-isopropyl succinate, dimethyl glutarate, diethyl glutarate, dimethyl adipate, methyl ethyl adipate, dimethyl sebacate, dimethyl phthalate, dimethyl isophthalate, dimethyl terephthalate, dimethyl naphthalenedicarboxylate, dibasic esters (DBE), poly(ethylene glycol) bis(carboxymethyl) ether, succinyl chloride, glutaryl dichloride, adipoyl chloride, sebacoyl chloride
  • Polyalkylene polyamines is organic compounds having two primary amine (-NH 2 ) groups and at least one secondary amine group where the amino nitrogen atoms are linked together by alkylene groups, provided no two nitrogen atoms are attached to the same carbon atoms.
  • Polyalkylene polyamines include diethylenetriamine (DETA), triethylenetetraamine (TETA), tetraethylenepentaamine (TEPA), dipropylenetriamine, and the like.
  • the PAE resin is formed by reacting polyaminoamide with epichlorohydrin under controlled conditions, hi at least one embodiment the polyaminoamide is diluted with water to a concentration of about 10 to about 50 weight percent, and the solution is cooled below about 25 °C. An amount of epichlorohydrin sufficient to react with the desired amount of the secondary amino groups in the polyaminoamide is then slowly added in the solution. The mixture is then heated at a temperature of about 40 0 C to about 100 0 C until desired viscosity is reached, typically about 2 to about 8 hours.
  • suitable polyaminoamide-epichlorohydrin resins is described in US Patent No. 6,277,242, incorporated herein by reference in its entirety.
  • the epihalohydrin is epichlorohydrin.
  • the mole ratio of epichlorohydrin to secondary nitrogen atoms in the polyaminoamide is less than about 0.5.
  • the polyaminoamide is the reaction product of diethylenetriamine and a dicarboxylic acid derivative selected from adipic acid, glutaric acid, DBE-2 dibasic ester, dimethyl glutarate and dimethyl adipate or a mixture thereof.
  • the adhesive is applied to the surface of a creping cylinder as a dilute aqueous solution.
  • the aqueous solution comprises about 0.01 to about 50 percent of a polyaminoamide-epichlorohydrin resin acidified according to at least one of the above mentioned procedures and about 99.99 to about 50 weight percent water.
  • the reason for such a larger percentage of water in the admixture is in part based on the need to only deposit a very thin layer of adhesive on the creping cylinder.
  • the thin layer is deposited with a spray boom.
  • the adhesive composition of this invention further comprises one or more polyols, one or more phosphate salts or a mixture thereof.
  • polyol is simple water-soluble compositions of matter composed of alkylene groups and up to about six hydroxyl groups in which the alkylene groups are optionally interrupted by one or more O or NH groups.
  • Polyols include but are not limited to ethylene glycol, diethylene glycol, Methylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, glycerol, 1,4-butanediol, diethanolamine, triethanolamine, rrimethylolpropane, erythritol, pentaerythritol, dipentaerythritol, arabitol, xylitol, ribitol, mannitol, sorbitol, galactitol, isomalt, maltitol, lactitol and the like.
  • the polyols are selected from glycerol, ethylene glycol, sorbitol, diethylene glycol, propylene glycol, rrimethylolpropane, polyethylene glycol, diethanolamine, and any combination thereof.
  • Phosphate salts include but are not limited to the sodium, potassium and ammonium salts of orthophosphate, pyrophosphate, metaphosphate, polyphosphate, phosphite and hypophosphite. Phosphate salts also include phosphate salts formed in-situ by adjustment of the pH of the creping composition with phosphoric acid.
  • the phosphate salts are selected from monoammonium phosphate, diammonium phosphate, phosphate salts formed in situ by adjusting the pH of the creping composition with phosphoric acid, and mixtures thereof.
  • the salts include the organic phosphates described in US Published Patent Application 2007/0208115.
  • the amount of polyols and/or phosphate salts in relation to the resin composition on a dry polymer basis typically ranges from about 0.5 to about 100 percent by weight. In at least one embodiment, between about 0.5 to about 20 percent by weight of the polyols and/or phosphate salts are used. It is to be understood that not all of the polyols produce similar results. In certain instances, depending upon the temperature employed, the particular resin composition used and other variables, routine experimentation will be necessary to determine the optimum polyol or phosphate salts to be used, as well as the particular amount to be employed in conjunction with the particular resin composition.
  • a release aid that is also diluted, emulsified or dispersed to aqueous form is applied to the Yankee dryer cylinder along with the polymer adhesive.
  • the release aid interacts with the adhesive materials on the Yankee dryer cylinder surface to avoid excessive coating build-up, to manage the sheet adhesion and to reduce doctor blade wear.
  • Representative release aids include release oils composed of naphthenic, parafflnic, vegetable, mineral or synthetic oil and emulsifying surfactants.
  • the release aid is typically formulated with one or more surfactants such as fatty acids, alkoxylated alcohols, alkoxylated fatty acids, and the like.
  • the release aid may be applied to the creping cylinder before or after the adhesive composition, or may be formulated with the adhesive for application to the creping cylinder.
  • At least some embodiments of the adhesive compositions are formulated with functional additives, which improve the softness of the tissue paper.
  • functional additives include but are not limited to organic quaternary salts having fatty chains of about 12 to about 22 carbon atoms including dialkyl imidazolinium quaternary salts, dialkyl diamidoamine quaternary salts, monoalkyl trimethylammonium quaternary salts, dialkyl dimethylammonium quaternary salts, trialkyl monomethylammonium quaternary salts, ethoxylated quaternary salts, dialkyl and trialkyl ester quaternary salts, and the like.
  • Additional suitable functional additives include polysiloxanes, quaternary silicones, organoreactive polysiloxanes, amino-functional polydimethylsiloxanes, and the like.
  • the spraying applications described above may be further improved by a variety of means, for example by using spraybooms designed for double or triple coverage, by oscillating the sprayboom and by recirculation of the diluted creping aid composition from the outlet of the sprayboom to improve mixing and reduce the possibility of separation.
  • the resin composition is applied according to one, some, or all of the methods and apparatus described in PCT 2004031475 and US Patent Number 7,048,826, the entire contents of which are hereby incorporated by reference in their entirety.
  • the composition, functional additives and/or release aid are applied to the creping cylinder by use of air (or gas) atomization, in addition to or instead of as aqueous solutions.
  • Example 1 Preparation of a representative adhesive composition with multifunctional acid.
  • a 1.5L resin kettle reactor was charged with 326.04 g of a 50% aqueous solution of polyamidoamine and 815.79 g DI water.
  • the solution was mixed at 400 rpm using an overhead stirrer (2.5" 6-blade impeller with 45° pitch).
  • the vessel was purged of oxygen by diffusing nitrogen into the headspace at 0.3 L/min.
  • the solution temperature was raised to 50 0 C and 12.81 g epichlorohydrin were dispensed into the reactor as a single bolus under positive nitrogen pressure.
  • the reaction temperature was maintained at 50 0 C. After 2 h, a sample of the reaction was withdrawn and was transferred to the small sample cup of a Brookfield rheometer.
  • the small sample adapter was held at 25°C by means of a temperature bath.
  • the sample viscosity was measured once the sample temperature had stabilized at 25°C (spindle #18 @ 30 rpm).
  • the solution viscosity was measured hourly until the viscosity had exceeded 12 cPs.
  • the viscosity was then measured in 15 min intervals (between sampling) until the target viscosity of 30 cPs was reached. Once the solution viscosity had reached (or passed) 30 cPs, the reaction was immediately quenched with citric acid until the solution pH reached approximately 3.7 at 50 0 C (52.65 g). The solution was cooled to 30 0 C and the final pH was measured as 3.6.
  • Example 2 Example 2
  • the small sample adapter was held at 25 0 C by means of a temperature bath.
  • the sample viscosity was measured once the sample temperature had stabilized at 25 0 C (spindle #18 @ 30 rpm).
  • the solution viscosity was measured hourly until the viscosity had exceeded 20 cPs.
  • the viscosity was then measured in 15 min intervals (between sampling) until the target viscosity of ⁇ 30 cPs was reached. Once the solution viscosity had reached ⁇ 30 cPs, the reaction was immediately quenched with 123.57 g of a 15% solution of sulfuric acid until the solution pH reached approximately 7.0 at 50 0 C.
  • Example 3 Shear modulus and peel adhesion.
  • the storage shear modulus, G', and the loss shear modulus, G" were determined using a rheometer AR2000 (TA Instruments, New Castle, DE).
  • the adhesion provided by the compositions of this invention was measured by means of a peel adhesion test. This test measures the force required to peel a cotton strip from a heated metal plate.
  • an adhesive composition was neutralized with caustic to pH 7 to accelerate the crosslinking reaction. Then it was applied to the metal panel by means of a #40 coating rod. The adhesive was applied to the panel at about 13% polymer actives.
  • the metal plate was heated to 60°C (this temperature is referred to as the film cure temperature) and, at this point, a wet cotton strip was pressed into the film by means of a 1.9 kg cylindrical roller. The moisture content in the wet strip is about 60%.
  • the metal plate After the strip was applied, the metal plate is placed in a 105 0 C oven for 15 minutes to dry the strip. The metal plate was then clamped in a tensile testing apparatus. One end of the cotton cloth was clamped in the pneumatic grip of the tester and the cloth was peeled from the panel at an angle of 180° and at a constant speed. During the peeling stage, the metal plate was controlled to a temperature of 100 0 C.
  • samples (PAE-I, PAE-2, PAE-3, PAE-4 and PAE-5) are terpolymers of adipic acid, diethyl enetriamine and epichlorohydrin having an epichlorohydrin to secondary amine molar ratio of about 0.20 and an average molecular weight of about 300,000 to 800,000, which are acidified with various acids.
  • Table 1
  • Table 1 shows that PAE made with common mineral acids, sulfuric or hydrochloric, forms films with a very high shear modulus.
  • the shear modulus is lower when phosphoric acid is used, but carboxylic acids, acetic, formic and citric, produce films with significantly lower shear modulus.
  • the shear modulus correlates with the softness of a polymer film. The lower the shear modulus, the softer the film.
  • carboxylic acid for manufacturing PAE adhesive results in much softer adhesive films, which can be beneficial for the creping process at low moisture.
  • citric acid appears to be superior to mineral acids, suggesting that having multiple carboxyl and hydroxyl functions is beneficial for softness of an adhesive film.
  • Example 4 Glass transition temperature (T g ), shear modulus and peel adhesion.
  • a TA 2920 differential scanning calorimeter DSC (TA Instruments, New Castle, DE) is used to measure the glass transition temperature of representative polymer compositions.
  • Polymer samples were prepared by casting films at 105 0 C.
  • the DSC instrument is calibrated with an indium standard.
  • the sample size for DSC analysis is about 10-15 mg.
  • the sample was heated at a heating rate of 10° C/min.
  • the glass transition temperature of polymer was determined from the second scan using a half-height method. Table 2
  • Table 2 demonstrates that multifunctional acids resulted in films having a lower glass transition temperature (T g ) and a lower shear modulus compared to sulfuric acid.
  • T g glass transition temperature
  • a lower glass transition temperature indicates intimate attractive interactions of acids with the polymer chains and correlates with the film softness, which is beneficial for the creping process under low moisture conditions.
  • the use of multifunctional acids such as glutamic, citric and sulfamic has also resulted in higher peel adhesion.
  • Table 3 shows that the use of multifunctional acids to acidify PAE solutions, produce adhesive films that tend to retain more moisture than films of adhesives prepared with mineral acids, sulfuric or phosphoric. Moisture is a very efficient plasticizer for PAE materials. A higher moisture level in the film normally results in a softer film and is correlated with a lower shear modulus in Example 4. Example 6 Effect of acid mixture.
  • Mineral acid could be used in a combination with a multifunctional acid to produce low modulus films.
  • Mineral acids tend to be stronger than multifunctional acids and, therefore, a smaller amount is required to achieve the same product pH. This may be useful when rapid quenching of the crosslinking reaction is desired for a more efficient control over production.
  • mineral acids tend to be less expensive and a partial substitution of multifunctional acid with mineral acid could provide product cost savings.
  • the two or more acids can be charged consecutively in any order or as a mixture.
  • Table 4 shows that, compared to use of a multifunctional acid alone, citric or sulfamic, charging sulfuric acid first followed by a multifunctional acid requires a smaller amount of the total acid to quench the crosslinking reaction and adjust the pH to about 4.
  • complex shear modulus
  • This example demonstrates how peel adhesion of various adhesive compositions is affected by the film cure temperature.
  • the peel test method is the same as in example 3 except the film cure temperature was varied from 60 to 100 0 C.
  • the higher film cure temperature results in a dryer adhesive film before the sheet is applied.
  • a higher film cure temperature and a dryer film represent conditions encountered during low moisture creping. If the film is too dry or is not easily rewettable, it may not be soft enough to interact with the wet cellulose sheet, which is unfavorable for adhesion development.
  • Adhesion of the PAE acidified with citric acid can further be improved by adding a polyol modifier exemplified by glycerol.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paper (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne une composition de matière utilisée pour produire des qualités de souplesse très élevées de papiers minces. La composition de matière comprend une résine de PAE acidifiée par un acide multifonctionnel. L'acide multifonctionnel comprend mais n'est pas limité au carboxyle et au sulfonyle. L'acide comporte un groupe fonctionnel choisi parmi les groupes carboxyle et sulfonyle et un groupe fonctionnel choisi parmi les groupes carboxyle, sulfonyle, hydroxyle, lactone, phénol, amine et hétérocyclique. La résine PAE facilite l'utilisation d'un adhésif dans un appareil « Yankee Dryer » qui est durable lorsque l'adhésif est humide mais reste souple lorsque l'adhésif devient sec. Ces propriétés permettent à l'adhésif d'être puissant et de rester collé à l'appareil de séchage lorsqu'il est humide mais d’être facilement éliminé par la lame de crêpage lorsqu'il est sec.
PCT/US2009/064954 2008-11-18 2009-11-18 Adhésifs de crêpage présentant des propriétés de film améliorées WO2010059699A1 (fr)

Priority Applications (8)

Application Number Priority Date Filing Date Title
MX2011005194A MX2011005194A (es) 2008-11-18 2009-11-18 Adhesivos de plisado con propiedades de pelicula mejoradas.
EP09756907.3A EP2358836B1 (fr) 2008-11-18 2009-11-18 Adhésifs de crêpage présentant des propriétés de film améliorées
PL09756907T PL2358836T3 (pl) 2008-11-18 2009-11-18 Kleje krepujące o ulepszonych właściwościach powlekania
CN2009801455016A CN102216409B (zh) 2008-11-18 2009-11-18 具有改善的膜性能的起绉粘结剂
CA2740599A CA2740599C (fr) 2008-11-18 2009-11-18 Adhesifs de crepage presentant des proprietes de film ameliorees
BRPI0916122A BRPI0916122B1 (pt) 2008-11-18 2009-11-18 ''composição de adesivos para crepagem e método de crepagem''
ES09756907.3T ES2652468T3 (es) 2008-11-18 2009-11-18 Adhesivos de crepado con propiedades de película mejoradas
AU2009316690A AU2009316690B2 (en) 2008-11-18 2009-11-18 Creping adhesives with improved film properties

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US12/273,217 US8444812B2 (en) 2008-11-18 2008-11-18 Creping adhesives with improved film properties
US12/273,217 2008-11-18

Publications (1)

Publication Number Publication Date
WO2010059699A1 true WO2010059699A1 (fr) 2010-05-27

Family

ID=41531600

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2009/064954 WO2010059699A1 (fr) 2008-11-18 2009-11-18 Adhésifs de crêpage présentant des propriétés de film améliorées

Country Status (10)

Country Link
US (1) US8444812B2 (fr)
EP (1) EP2358836B1 (fr)
CN (1) CN102216409B (fr)
AU (1) AU2009316690B2 (fr)
BR (1) BRPI0916122B1 (fr)
CA (1) CA2740599C (fr)
ES (1) ES2652468T3 (fr)
MX (1) MX2011005194A (fr)
PL (1) PL2358836T3 (fr)
WO (1) WO2010059699A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013019526A1 (fr) * 2011-08-01 2013-02-07 Buckman Laboratories International, Inc. Procédés de crêpage utilisant des compositions adhésives de crêpage au ph modifié
US8444812B2 (en) * 2008-11-18 2013-05-21 Nalco Company Creping adhesives with improved film properties

Families Citing this family (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8911592B2 (en) * 2002-10-07 2014-12-16 Georgia-Pacific Consumer Products Lp Multi-ply absorbent sheet of cellulosic fibers
US9266301B2 (en) * 2005-06-30 2016-02-23 Nalco Company Method to adhere and dislodge crepe paper
US8753478B2 (en) * 2005-12-29 2014-06-17 Nalco Company Creping adhesives comprising blends of high and low molecular weight resins
US8066847B2 (en) * 2005-12-29 2011-11-29 Nalco Corporation Creping adhesives comprising blends of polyaminoamide epihalolhydrin resins and polyamides
WO2008131071A1 (fr) * 2007-04-17 2008-10-30 Kemira Chemicals Inc. Adhésifs en polyamidoamine acidifiée, procédé de fabrication de ceux-ci et utilisation de ceux-ci pour des applications de crêpage et de liaison de couches
US8652610B2 (en) * 2008-12-19 2014-02-18 Kimberly-Clark Worldwide, Inc. Water-dispersible creping materials
US9086057B2 (en) * 2010-01-21 2015-07-21 The Abell Foundation, Inc. Ocean thermal energy conversion cold water pipe
EP4273372A3 (fr) 2010-01-21 2024-01-24 The Abell Foundation Inc. Centrale de conversion d'énergie thermique marine
US8899043B2 (en) * 2010-01-21 2014-12-02 The Abell Foundation, Inc. Ocean thermal energy conversion plant
US20120247697A1 (en) 2011-03-29 2012-10-04 Kemira Oyj Polyamine Polyamidoamine Epihaloohydrin Compositions and Processes for Preparing and Using the Same
PL2761083T3 (pl) 2011-09-30 2017-12-29 Kemira Oyj Papier i sposoby wytwarzania papieru
US20130126113A1 (en) * 2011-11-22 2013-05-23 Buckman Laboratories International, Inc. Control Of Wet Strength Resin Fouling Of Paper-Making Felt
US9777434B2 (en) * 2011-12-22 2017-10-03 Kemira Dyj Compositions and methods of making paper products
CN104204308A (zh) * 2012-02-29 2014-12-10 日立金属株式会社 低熔点的电镀铝用镀液的调制方法、电镀铝用镀液、铝箔的制造方法、以及降低电镀铝用镀液的熔点的方法
CN103233388B (zh) * 2013-04-26 2015-03-25 浙江师范大学 一种聚酰胺环氧氯丙烷树脂起皱剥离剂及其制备方法
US9656914B2 (en) 2013-05-01 2017-05-23 Ecolab Usa Inc. Rheology modifying agents for slurries
US9410288B2 (en) 2013-08-08 2016-08-09 Ecolab Usa Inc. Use of nanocrystaline cellulose and polymer grafted nanocrystaline cellulose for increasing retention in papermaking process
US9303360B2 (en) 2013-08-08 2016-04-05 Ecolab Usa Inc. Use of nanocrystaline cellulose and polymer grafted nanocrystaline cellulose for increasing retention in papermaking process
US9034145B2 (en) 2013-08-08 2015-05-19 Ecolab Usa Inc. Use of nanocrystaline cellulose and polymer grafted nanocrystaline cellulose for increasing retention, wet strength, and dry strength in papermaking process
US9567708B2 (en) 2014-01-16 2017-02-14 Ecolab Usa Inc. Wet end chemicals for dry end strength in paper
US9834730B2 (en) 2014-01-23 2017-12-05 Ecolab Usa Inc. Use of emulsion polymers to flocculate solids in organic liquids
JP5938079B2 (ja) * 2014-09-30 2016-06-22 大王製紙株式会社 プライ接着糊及び衛生薄葉紙の製造方法
WO2017066540A1 (fr) 2015-10-15 2017-04-20 Ecolab Usa Inc. Cellulose nanocristalline et cellulose nanocristalline greffée avec un polymère comme agents de modification de la rhéologie pour suspensions d'oxyde de magnésium et de chaux
CA3057327A1 (fr) 2017-03-21 2018-09-27 Solenis Technologies, L.P. Composition et procede de production d'un papier crepe, et papier crepe resultant de ceux-ci
US10731063B2 (en) 2017-05-19 2020-08-04 Ecolab Usa Inc. Use of boronic acid-functionalized polymers as Yankee coating adhesives
CN110997593B (zh) 2017-07-17 2023-01-24 埃科莱布美国股份有限公司 使浆料的流变性改性的方法
CN108914689A (zh) * 2017-10-11 2018-11-30 天津中天精科科技有限公司 一种生活用纸纸浆脱模剂及其制备工艺
US20230065043A1 (en) * 2021-08-26 2023-03-02 Valmet Aktiebolag Method of applying a wear-resistant coating on a yankee drying cylinder
US20230064090A1 (en) * 2021-08-26 2023-03-02 Valmet Aktiebolag Method of applying a wear-resistant coating on a yankee drying cylinder, such coatings and yankee cylinders with such coatings
US20230243102A1 (en) * 2022-01-31 2023-08-03 Solenis Technologies, L.P. Composition for improving softness of tissue and/or towel products

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6277242B1 (en) * 2000-02-28 2001-08-21 Calgon Corporation Creping adhesive containing an admixture of PAE resins
WO2005098130A2 (fr) * 2004-04-05 2005-10-20 Nalco Company Resine avec resistance au mouille stable
US20080257507A1 (en) * 2007-04-17 2008-10-23 Campbell Clayton J Acidified polyamidoamine adhesives, method of manufacture, and use for creping and ply bond applications

Family Cites Families (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3058873A (en) * 1958-09-10 1962-10-16 Hercules Powder Co Ltd Manufacture of paper having improved wet strength
US4501640A (en) * 1983-10-18 1985-02-26 Kimberly-Clark Corporation Creping adhesives containing polyvinyl alcohol and cationic polyamide resins
JP2688950B2 (ja) 1988-11-02 1997-12-10 日本ピー・エム・シー株式会社 クレープ助剤の製造法
US5171795A (en) 1990-08-01 1992-12-15 Hercules Incorporated Process for the production of improved polyaminopolyamide epichlorohydrin resins
US5338807A (en) * 1991-12-23 1994-08-16 Hercules Incorporated Synthesis of creping aids based on polyamides containing methyl bis(3-aminopropylamine)
US5382323A (en) * 1993-01-08 1995-01-17 Nalco Chemical Company Cross-linked poly(aminoamides) as yankee dryer adhesives
US5529665A (en) * 1994-08-08 1996-06-25 Kimberly-Clark Corporation Method for making soft tissue using cationic silicones
NZ286384A (en) * 1995-04-25 1998-05-27 Hercules Inc Process and composition for creping paper to give desired texture, where the composition comprises polyamine/epihalohydrin resin adhesive and a plasticizer
DE69603539T2 (de) * 1995-05-18 2000-01-13 Fort James Corp., Richmond Neue adhesive Zusammensetzungen zum Kreppen, Verfahren zum Kreppen und gekrepptes fibröses Gewebe
US6689250B1 (en) * 1995-05-18 2004-02-10 Fort James Corporation Crosslinkable creping adhesive formulations
US6280571B1 (en) 1998-08-17 2001-08-28 Hercules Incorporated Stabilizer for creping adhesives
AU770346B2 (en) * 1999-11-24 2004-02-19 Hercules Incorporated Creping adhesives
US6465602B2 (en) * 2000-01-20 2002-10-15 Kimberly-Clark Worldwide, Inc. Modified condensation polymers having azetidinium groups and containing polysiloxane moieties
US6562194B1 (en) * 2000-03-30 2003-05-13 Calgon Corporation Method of creping paper webs
US20030114631A1 (en) * 2001-03-12 2003-06-19 Walton Cynthia D. Resins acting as wet strength agents and creping aids and processes for preparing and using the same
US20040060675A1 (en) * 2002-09-30 2004-04-01 Archer Sammy L. Method for targeted application of performance enhancing materials to a creping cylinder
US6949167B2 (en) * 2002-12-19 2005-09-27 Kimberly-Clark Worldwide, Inc. Tissue products having uniformly deposited hydrophobic additives and controlled wettability
US6908983B2 (en) * 2003-04-01 2005-06-21 Hercules Corporation Synthesis of high solids resins from amine terminated polyamides
US7291695B2 (en) * 2004-04-05 2007-11-06 Nalco Company Stable wet strength resin
US7718035B2 (en) * 2005-03-15 2010-05-18 Georgia-Pacific Consumer Products Lp Phosphoric acid quenched creping adhesive
US8066847B2 (en) 2005-12-29 2011-11-29 Nalco Corporation Creping adhesives comprising blends of polyaminoamide epihalolhydrin resins and polyamides
US8753478B2 (en) * 2005-12-29 2014-06-17 Nalco Company Creping adhesives comprising blends of high and low molecular weight resins
US8084525B2 (en) 2006-03-06 2011-12-27 Nalco Company Use of organophosphorus compounds as creping aids
US7744722B1 (en) * 2006-06-15 2010-06-29 Clearwater Specialties, LLC Methods for creping paper
CN100465374C (zh) * 2006-10-19 2009-03-04 上海东升新材料有限公司 一种环氧聚酰胺树脂湿强剂及其制备方法
US8021518B2 (en) * 2006-11-30 2011-09-20 Nalco Company Method of applying a super-absorbent composition to tissue or towel substrates
PL2121806T3 (pl) * 2007-01-19 2015-08-31 Solenis Tech Cayman Lp Sposób wytwarzania środków adhezyjnych do krepowania wytworzonych z poliamidoamin zakończonych grupą aminową
US8444812B2 (en) * 2008-11-18 2013-05-21 Nalco Company Creping adhesives with improved film properties

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6277242B1 (en) * 2000-02-28 2001-08-21 Calgon Corporation Creping adhesive containing an admixture of PAE resins
WO2005098130A2 (fr) * 2004-04-05 2005-10-20 Nalco Company Resine avec resistance au mouille stable
US20080257507A1 (en) * 2007-04-17 2008-10-23 Campbell Clayton J Acidified polyamidoamine adhesives, method of manufacture, and use for creping and ply bond applications

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8444812B2 (en) * 2008-11-18 2013-05-21 Nalco Company Creping adhesives with improved film properties
WO2013019526A1 (fr) * 2011-08-01 2013-02-07 Buckman Laboratories International, Inc. Procédés de crêpage utilisant des compositions adhésives de crêpage au ph modifié
US8568562B2 (en) 2011-08-01 2013-10-29 Buckman Laboratories International, Inc. Creping methods using pH-modified creping adhesive compositions
AU2012290432B2 (en) * 2011-08-01 2015-05-14 Buckman Laboratories International, Inc. Creping methods using pH-modified creping adhesive compositions

Also Published As

Publication number Publication date
AU2009316690A1 (en) 2010-05-27
CN102216409A (zh) 2011-10-12
CA2740599A1 (fr) 2010-05-27
PL2358836T3 (pl) 2018-05-30
AU2009316690B2 (en) 2014-12-04
ES2652468T3 (es) 2018-02-02
US20100122785A1 (en) 2010-05-20
CA2740599C (fr) 2015-09-01
MX2011005194A (es) 2011-08-15
BRPI0916122A2 (pt) 2015-11-03
BRPI0916122B1 (pt) 2019-02-05
CN102216409B (zh) 2013-12-25
US8444812B2 (en) 2013-05-21
EP2358836A1 (fr) 2011-08-24
EP2358836B1 (fr) 2017-10-04

Similar Documents

Publication Publication Date Title
AU2009316690B2 (en) Creping adhesives with improved film properties
US8066847B2 (en) Creping adhesives comprising blends of polyaminoamide epihalolhydrin resins and polyamides
CA2613882C (fr) Polymeres de vinylamine/vinylformamide modifies utilises comme adhesifs de crepage
EP2222811B1 (fr) Adhésifs de crêpage comprenant des mélanges de résines de haut et de bas poids moléculaires
EP2521814B1 (fr) Agent de modification amélioré pour des revêtements pour cylindres yankee

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200980145501.6

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09756907

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2740599

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 2009316690

Country of ref document: AU

WWE Wipo information: entry into national phase

Ref document number: MX/A/2011/005194

Country of ref document: MX

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2009316690

Country of ref document: AU

Date of ref document: 20091118

Kind code of ref document: A

REEP Request for entry into the european phase

Ref document number: 2009756907

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2009756907

Country of ref document: EP

ENP Entry into the national phase

Ref document number: PI0916122

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20110513