WO1993021279A2 - Process for the production of an adhesive for bonding layers of material - Google Patents

Process for the production of an adhesive for bonding layers of material Download PDF

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Publication number
WO1993021279A2
WO1993021279A2 PCT/EP1993/000872 EP9300872W WO9321279A2 WO 1993021279 A2 WO1993021279 A2 WO 1993021279A2 EP 9300872 W EP9300872 W EP 9300872W WO 9321279 A2 WO9321279 A2 WO 9321279A2
Authority
WO
WIPO (PCT)
Prior art keywords
adhesive
concentrate
water
parts
thickener
Prior art date
Application number
PCT/EP1993/000872
Other languages
German (de)
French (fr)
Other versions
WO1993021279A3 (en
Inventor
Jürgen PLÜMER
Leonard Charles Jannusch
Original Assignee
H.B. Fuller Gmbh
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Filing date
Publication date
Application filed by H.B. Fuller Gmbh filed Critical H.B. Fuller Gmbh
Publication of WO1993021279A2 publication Critical patent/WO1993021279A2/en
Publication of WO1993021279A3 publication Critical patent/WO1993021279A3/en

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Classifications

    • 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
    • C09J129/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
    • C09J129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09J129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • 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
    • C09J103/00—Adhesives based on starch, amylose or amylopectin or on their derivatives or degradation products
    • C09J103/04—Starch derivatives
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L31/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
    • C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C08L31/04—Homopolymers or copolymers of vinyl acetate
    • 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
    • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof

Definitions

  • the invention relates to a liquid, water-based adhesive concentrate, in particular with a polyhydroxy compound and / or a polyvinyl ester compound as an adhesive component, and to an adhesive which can be produced, for example, from this concentrate.
  • the invention also relates to a method for producing an adhesive for bonding at least two layers of material, in particular layers of paper, by dilution.
  • the invention further relates to an adhesive concentrate which, inter alia, is suitable for producing such an adhesive.
  • Paper layers in particular tissue paper layers, are usually produced by merging, embossing and laminating two or more paper layers.
  • Conventional production methods are the "nested and bossed” and the "foot to foot” method, which are carried out on machines, for example the PCMC (Paper Converting Machine Company).
  • PCMC Paper Converting Machine Company
  • Known adhesives for layer bonding in Germany have so far been mainly cellulose derivatives, for example cellulose ethers.
  • the adhesive to be processed is normally produced directly by the adhesive processor.
  • a pulverulent cellulose derivative such as methyl cellulose
  • methyl cellulose is stirred into water to produce an up to 10%, preferably 3-5% solution, which is then processed.
  • adhesives based on polyvinyl alcohol are also used. These adhesives contain polyvinyl alcohols in partially saponified form. These are polyvinyl alcohols, which are produced by saponification of polyvinyl acetate. The polyvinyl alcohol ester contains 87-90% PVOH and 10-13% PVAC. These adhesives may not like the corresponding cellulose products will set off a powder by the consumer r but must be obtained from the adhesive manufacturer as a liquid product. This leads to higher costs, which the adhesive consumer has to bear. For economic reasons, some adhesive manufacturers are trying to develop a liquid concentrate based on polyvinyl alcohol. Such concentrates can be diluted by the processor in a ratio up to a maximum of 1: 3 to consumption strength.
  • PVOH adhesive advantages are e.g. in higher adhesive strength with low viscosity and clean machine operation. Disadvantages, however, are the high costs and the sometimes too high adhesive strength when the viscosity is too low.
  • the viscosity of a concentrate should not exceed 30000 mPa »s so that it remains sufficiently easy to handle.
  • the finished, diluted adhesive solution should be sufficiently viscous in order to ensure trouble-free machine operation and sufficient water retention during bonding.
  • Solids contents of preferably 2.5 to 5% (PVOH) and
  • An advantage of the invention is that the adhesive concentrate can be diluted up to a ratio of 1:10 and more. Compared to cellulose derivative solutions, the lengthy production of the adhesive is reduced to a few minutes. The desired higher viscosity for processing can then be set by activating the "latent" thickener contained in the concentrate. Another advantage of the method according to the invention is the possibility of almost any adjustment or regulation of the viscosity of the adhesive after the dilution step. The process thus enables the production of an adhesive with a high dilution ratio and the viscosity required for any processing.
  • the concentrate form of the adhesive is particularly economical, e.g. for export purposes.
  • the adhesive concentrate according to the invention preferably contains a polyhydroxy compound or a polyvinyl ester compound as the adhesive component, and the thickener as the second component, water and optionally plasticizers, such as Dibutyl phthalate and urea as additional components.
  • the urea stabilizes the viscosity of the adhesive concentrate.
  • a partially saponified polyvinyl alcohol or a starch derivative is preferably used as the polyhydroxy component.
  • the thickening agent, the second component is preferably an emulsified, alkali-soluble acrylic acid polymer which contains free acid groups.
  • Natural or synthetic thickeners that can be used according to the invention are used in various technical fields (for example Acrysol ASE- Thickeners, Rohm and Haas Co.). They are used, among other things, to stabilize liquid detergents, floor cleaners and the like, and to increase the viscosity of solvent mixtures or solutions of surface-active substances.
  • This acrylate acid polymer is latent until the addition of an activating reagent, i.e. contained in the adhesive concentrate at a very low degree of viscosity.
  • a base is added to the diluted adhesive solution for activation.
  • any strong base can be used, preferably ammonia or sodium hydroxide.
  • the acrylic acid polymer is neutralized by the base and thus activated, i.e. the adhesive solution becomes more viscous.
  • the viscosity of the adhesive solution is variable and depends, among other things. depends on the setting of the pH value.
  • the method according to the invention enables the production of an adhesive in which the viscosity, solids content and adhesive strength (as required) can be varied.
  • the properties of the adhesive solution can thus be selected by specifying the degree of dilution of the adhesive and the amount of base added, which neutralizes and activates an equivalent amount of acrylic acid polymer.
  • the adhesive solution can subsequently be raised to a higher viscosity, which is necessary, for example, for processing the adhesive.
  • the method according to the invention thus enables the production of an adhesive which, owing to an increased dilution ratio, is less expensive than the conventional adhesives and which avoids the disadvantages of the known adhesives with regard to the processing properties.
  • the desired adhesive properties can be adapted to the respective processing process.
  • the method according to the invention provides an adhesive which e.g. can be used for the production of paper layers, in particular tissue paper layers for household and toilet paper.
  • the adhesive according to the invention contains the following constituents in a preferred embodiment: approx. 10 to 30 parts of partially saponified polyvinyl alcohol esters or optionally derivatized starch acrylate polymers approx. 20 to 35 parts of acrylate thickener
  • An adhesive concentrate 1 is produced with the following composition:
  • Adhesive concentrate 1 22 parts polyvinyl alcohol 32 parts acrylic acid thickener 46 parts water It has a viscosity of approx. 1700 mPa »s.
  • the concentrate is diluted with water in a ratio of 1: 9.
  • the viscosity of the dilution product is approximately 30 mPas.
  • 0.2% base concentrated ammonia solution
  • the viscosity of the ready-to-use adhesive is 350 mPas.
  • An adhesive concentrate 2 is produced with the following composition:
  • Adhesive concentrate 2 26 parts of polyvinyl alcohol
  • An adhesive concentrate 3 is produced with the following composition:
  • the concentrate with a viscosity of approx. 20,000 mPas is diluted with 50% water (2 parts concentrate and 1 part water). After adding 1% ammonia to the mixture, a viscosity of approx. 5000 mPa »s is established.
  • This mixture can be used, for example, in the graphics industry for the longitudinal seam bonding of papers.
  • an Acrysol ASE thickener from Rohm and Haas Co. is used as the acrylic acid thickener.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention relates to a process for producing an adhesive for bonding layers of paper in which an adhesive concentrate is first diluted to 1:10 and then reacted with an activating reagent, especially a base. In addition, the invention relates to an adhesive concentrate which can be used in the production of such an adhesive. The adhesive concentrate contains a polyhydroxy component or polyvinyl ester compound and a thickening agent, especially an acrylic acid polymer. By addition to the diluted adhesive concentrate of a base, the thickening agent is neutralised and becomes active, whereby the viscosity of the adhesive is set and can be adapted to each use. The process of the invention is economical and provides an adhesive with variable viscosity, solid body content and adhesive power. It is used especially in the production of tissue paper layers, particularly domestic and toilet paper.

Description

Verfahren zur Herstellung eines Klebstoffes für die Verklebunq von Materialla en Process for the production of an adhesive for bonding material layers
Die Erfindung betrifft ein flüssiges Klebstoffkonzentrat auf Wasserbasis, insbesondere mit einer Polyhydroxyverbindung und/oder einer Polyvinylesterverbindung als klebender Kom¬ ponente, sowie einen beispielsweise aus diesem Konzentrat herstellbaren Klebstoff.The invention relates to a liquid, water-based adhesive concentrate, in particular with a polyhydroxy compound and / or a polyvinyl ester compound as an adhesive component, and to an adhesive which can be produced, for example, from this concentrate.
Die Erfindung betrifft außerdem ein Verfahren zur Herstellung eines Klebstoffes für die Verklebung von mindestens zwei Materiallagen, insbesondere Papierlagen, durch Verdünnung.The invention also relates to a method for producing an adhesive for bonding at least two layers of material, in particular layers of paper, by dilution.
Weiterhin betrifft die Erfindung ein Klebstoffkonzentrat, das u.a. zur Erzeugung eines solchen Klebstoffes geeignet ist.The invention further relates to an adhesive concentrate which, inter alia, is suitable for producing such an adhesive.
Die Herstellung von Papierlagen, insbesondere Tissuepapier- lagen, erfolgt gewöhnlich durch Zusammenführung, Prägung und Kaschierung zweier oder mehrerer Papierlagen. Herkömmliche Produktionsmethoden sind das "nested and bossed" und das "foot to foot"-Verfahren, die auf Maschinen, bei¬ spielsweise der PCMC (Papier Converting Machine Company) , durchgeführt werden. Bekannte Klebstoffe für die Lagenver- klebung waren in Deutschland bisher hauptsächlich Zellulose¬ derivate, beispielsweise Zelluloseether.Paper layers, in particular tissue paper layers, are usually produced by merging, embossing and laminating two or more paper layers. Conventional production methods are the "nested and bossed" and the "foot to foot" method, which are carried out on machines, for example the PCMC (Paper Converting Machine Company). Known adhesives for layer bonding in Germany have so far been mainly cellulose derivatives, for example cellulose ethers.
Aus Kostengründen erfolgt die Herstellung des zu verarbei¬ tenden Klebstoffes normalerweise direkt beim Klebstoffver¬ arbeiter. Beispielsweise wird ein pulverförmiges Zellulose¬ derivat wie Methylzellulose in Wasser eingerührt, um eine bis zu 10%ige, vorzugsweise 3-5%ige Lösung herzustellen, die dann verarbeitet wird.For reasons of cost, the adhesive to be processed is normally produced directly by the adhesive processor. For example, a pulverulent cellulose derivative, such as methyl cellulose, is stirred into water to produce an up to 10%, preferably 3-5% solution, which is then processed.
Diese Klebstofflösungen weisen jedoch erhebliche Nachteile während der Verarbeitung auf. Speziell steht dem Einsatz dieser Klebstoffe entgegen, daß diese, infolge eingeschränkter Klebkraft, nicht für jeden Anwendungsbereich geeignet sind. Weiterhin sind solche vom Klebstoffverarbeiter hergestellten Klebstofflösungen nicht immer homogen, da sie zur Klumpen¬ bildung neigen. Darüberhinaus können die hohen Viskositäten dieser Klebstoffe einen unsauberen Maschinenlauf verursachen.However, these adhesive solutions have significant disadvantages during processing. The use of these adhesives is particularly opposed by the fact that, owing to their limited adhesive strength, they are not suitable for every application. Furthermore, such adhesive solutions produced by the adhesive processor are not always homogeneous, since they tend to form lumps. In addition, the high viscosities of these adhesives can cause unclean machine operation.
Neben den Zelluloseklebstoffen werden auch Klebstoffe, die auf Polyvinylalkohol basieren, eingesetzt. Diese Klebstoffe ent¬ halten Polyvinylalkohole in teilverseifter Form. Es handelt sich hierbei um Polyvinylalkohole, die durch Verseifung von Polyvinylacetat hergestellt werden. Der Polyvinylalkoholester enthält 87-90% PVOH und 10-13% PVAC. Diese Klebstoffe können nicht wie die entsprechenden Zelluloseprodukte aus einem Pulver vom Verbraucher selbst angesetzt werde r sondern müssen vom KlebstoffProduzenten als flüssiges Produkt bezogen werden. Dies führt zu höheren Kosten, die der KlebstoffVerbraucher • tragen muß. Aus wirtschaftlichen Gründen haben sich infolge- dessen einige Klebstoffhersteiler darum bemüht, ein flüssiges Konzentrat auf Polyvinylalkoholbasis zu entwickeln. Solche Konzentrate können beim Verarbeiter in einem Verhältnis bis maximal 1:3 auf Verbrauchsstärke verdünnt werden.In addition to cellulose adhesives, adhesives based on polyvinyl alcohol are also used. These adhesives contain polyvinyl alcohols in partially saponified form. These are polyvinyl alcohols, which are produced by saponification of polyvinyl acetate. The polyvinyl alcohol ester contains 87-90% PVOH and 10-13% PVAC. These adhesives may not like the corresponding cellulose products will set off a powder by the consumer r but must be obtained from the adhesive manufacturer as a liquid product. This leads to higher costs, which the adhesive consumer has to bear. For economic reasons, some adhesive manufacturers are trying to develop a liquid concentrate based on polyvinyl alcohol. Such concentrates can be diluted by the processor in a ratio up to a maximum of 1: 3 to consumption strength.
Die Vorteile eines PVOH-Klebstoffes liegen z.B. in höherer Klebkraft bei gleichzeitig niedriger Viskosität und sauberem Maschinenlauf. Nachteilig sind allerdings die hohen Kosten und die teilweise sogar zu hohe Klebkraft bei zu geringer Viskosität. Die Viskosität eines Konzentrates sollte 30000 mPa»s nicht überschreiten, damit es ausreichend leicht handhabbar bleibt. Andererseits sollte die fertige, verdünnte Klebstofflösung ausreichend viskos sein, um so einen störungs¬ freien Maschinenlauf und ausreichend Wasserrückhaltevermögen bei der Verklebung zu gewährleisten. In der Praxis wird mitThe advantages of a PVOH adhesive are e.g. in higher adhesive strength with low viscosity and clean machine operation. Disadvantages, however, are the high costs and the sometimes too high adhesive strength when the viscosity is too low. The viscosity of a concentrate should not exceed 30000 mPa »s so that it remains sufficiently easy to handle. On the other hand, the finished, diluted adhesive solution should be sufficiently viscous in order to ensure trouble-free machine operation and sufficient water retention during bonding. In practice, with
Festkörpergehalten von vorzugsweise 2,5 bis 5 % (PVOH) undSolids contents of preferably 2.5 to 5% (PVOH) and
Viskositäten unter 1000 mPa»s, aber oberhalb 300 mPa»s im fertigen Klebstoff gearbeitet. Gebrauchsfertige Klebstoffe lassen sich aus den bekannten, nur begrenzt verdünnbaren Konzentraten nur unzureichend herstellen.Viscosities below 1000 mPa »s, but above 300 mPa» s worked in the finished adhesive. Ready-to-use adhesives can only be produced inadequately from the known concentrates, which can only be diluted to a limited extent.
Es ist daher eine wesentliche Aufgabe der Erfindung, ein Verfahren zur Herstellung eines Klebstoffes, insbesondere für die Verklebung von Papierlagen, für die Tapetenherstellung, für die Herstellung von Verpackungsmitteln und dergleichen anzugeben, der die genannten Nachteile des Standes der Technik überwindet. Es ist «ine weitere Aufgabe der Erfindung, ein Klebstoffkonzentrat anzugeben, das die' Herstellung eines Klebstoffes der eingangs genannten Art ermöglicht.It is therefore an essential object of the invention to provide a process for the production of an adhesive, in particular for the bonding of paper layers, for the production of wallpaper, for the production of packaging materials and the like, which overcomes the disadvantages of the prior art mentioned. It is a further object of the invention to provide an adhesive concentrate which enables the production of an adhesive of the type mentioned in the introduction.
Insbesondere ist es Aufgabe der Erfindung, ein Klebstoff- konzentrat anzugeben, daß sich ohne störende Viskositäts¬ verluste stärker verdünnen läßt als bekannte Konzentrate. Zur Lösung dieser Aufgabe dienen die Merkmale der unabhängigen Ansprüche; vorteilhafte Ausgestaltungen sind in den zugeord- neten Unteransprüchen definiert.In particular, it is an object of the invention to provide an adhesive concentrate which can be diluted more than known concentrates without interfering viscosity losses. The features of the independent claims serve to solve this problem; advantageous embodiments are in the assigned defined subclaims.
Ein Vorteil der Erfindung liegt darin, daß eine Verdünnung des Klebstoffkonzentrates, bis zu einem Verhältnis von 1:10 und mehr erfolgen kann. Gegenüber Zellulosederivatlösungen ver¬ kürzt sich die langwierige Herstellung des Klebstoffes auf wenige Minuten. Durch die Aktivierung des im Konzentrat ent¬ haltenen "latenten" Verdickungsmittels läßt sich dann die ge¬ wünschte höhere Viskosität zur Verarbeitung einstellen. Ein weiterer Vorteil des erfindungsgemäßen Verfahrens ist die Möglichkeit fast beliebiger Einstellung bzw. Regulierung der Viskosität des Klebstoffes nach dem Verdünnungsschritt. Das Verfahren ermöglicht somit die Herstellung eines Klebstoffes mit einem hohen Verdünnungsverhältnis und der für jedwede Verarbeitung notwendigen Viskosität. Die Konzentratform des Klebstoffes ist besonders wirtschaftlich, z.B. für Export¬ zwecke.An advantage of the invention is that the adhesive concentrate can be diluted up to a ratio of 1:10 and more. Compared to cellulose derivative solutions, the lengthy production of the adhesive is reduced to a few minutes. The desired higher viscosity for processing can then be set by activating the "latent" thickener contained in the concentrate. Another advantage of the method according to the invention is the possibility of almost any adjustment or regulation of the viscosity of the adhesive after the dilution step. The process thus enables the production of an adhesive with a high dilution ratio and the viscosity required for any processing. The concentrate form of the adhesive is particularly economical, e.g. for export purposes.
Das erfindungsgemäße Klebstoffkonzentrat enthält vorzugsweise eine Polyhydroxyverbindung bzw. eine Polyvinylesterverbindung als klebende Komponente, sowie das Verdickungsmitel als zweite Komponente, Wasser sowie ggf. Weichmacher wie z.B. Dibutyl- phthalat und Harnstoff als Zusatzkomponente. Der Harnstoff bewirkt eine Stabiliserung der Viskosität des Klebstoffkon- zentrateε.The adhesive concentrate according to the invention preferably contains a polyhydroxy compound or a polyvinyl ester compound as the adhesive component, and the thickener as the second component, water and optionally plasticizers, such as Dibutyl phthalate and urea as additional components. The urea stabilizes the viscosity of the adhesive concentrate.
Bevorzugt wird ein teilverseifter Polyvinylalkohol oder ein Stärkederivat als Polyhydroxykomponente eingesetzt. Das Verdickungsmittel, die zweite Komponente, ist vorzugsweise ein emulgiertes, alkalilösliches Acrylsäurepolymer, welches freie Säuregruppen enthält.A partially saponified polyvinyl alcohol or a starch derivative is preferably used as the polyhydroxy component. The thickening agent, the second component, is preferably an emulsified, alkali-soluble acrylic acid polymer which contains free acid groups.
Natürliche oder synthetische Verdickungsmittel, die sich erfindungsgemäß verwenden lassen, werden in verschiedenen technischen Bereichen eingesetzt (z.B. Acrysol ASE- Thickeners, Rohm and Haas Co.). Sie werden u.a. zur Stabiliserung von Flüssigwaschmitteln, Fußbodenreinigern und dergleichen, sowie zur Erhöhung der Viskosität von Lösungs¬ mittelgemischen oder Lösungen oberflächenaktiver Substanzen verwendet.Natural or synthetic thickeners that can be used according to the invention are used in various technical fields (for example Acrysol ASE- Thickeners, Rohm and Haas Co.). They are used, among other things, to stabilize liquid detergents, floor cleaners and the like, and to increase the viscosity of solvent mixtures or solutions of surface-active substances.
Dieses Acrylatsäurepolymer ist bis zur Zugabe eines akti¬ vierenden Reagens latent, d.h. bei sehr geringem Viskositäts¬ grad im Klebstoffkonzentrat enthalten.This acrylate acid polymer is latent until the addition of an activating reagent, i.e. contained in the adhesive concentrate at a very low degree of viscosity.
Zur Aktivierung wird der verdünnten Klebstofflösung eine Base zugesetzt. Grundsätzlich kann jede starke Base verwendet werden, wobei vorzugsweise Ammoniak oder Natriumhydroxyd zum Einsatz kommen. Das Acrylsäurepolymer wird durch die Base neutralisiert und damit aktiviert, d.h. die Klebstofflösung wird viskoser. Die Viskosität der Klebstofflösung ist variabel und hängt u.a. von der Einstellung des PH-Wertes ab. Das er¬ findungsgemäße Verfahren ermöglicht die Herstellung eines Klebstoffes, in dem Viskosität, Festkörpergehalt und Klebkraft (nach Bedarf) variiert werden können.A base is added to the diluted adhesive solution for activation. In principle, any strong base can be used, preferably ammonia or sodium hydroxide. The acrylic acid polymer is neutralized by the base and thus activated, i.e. the adhesive solution becomes more viscous. The viscosity of the adhesive solution is variable and depends, among other things. depends on the setting of the pH value. The method according to the invention enables the production of an adhesive in which the viscosity, solids content and adhesive strength (as required) can be varied.
Bei der Tissueherstellung werden hervorragende Verklebungs- ergebnisse bei Festkörpergehalten von 1,5 bis 4% erhalten. Für andere Anwendungen können Festkörpergehalte von bis zu 40% vorgesehen werden.In the tissue production, excellent gluing results are obtained with solids contents of 1.5 to 4%. Solids contents of up to 40% can be provided for other applications.
Die Eigenschaften der Klebstofflösung sind damit wählbar durch Festlegung des Verdünnungsgrades des Klebstoffes und der Menge der zugesetzten Base, die eine äquivalente Menge an Acryl¬ säurepolymer neutralisiert und aktiviert. Damit kann die Kleb¬ stofflösung nach entsprechender Verdünnung nachträglich auf eine höhere Viskosität angehoben werden, die beispielsweise zur Verarbeitung des Klebstoffes notwendig ist. Das erfindungsgemäße Verfahren ermöglicht somit die Her¬ stellung eines Klebstoffes, der infolge eines erhöhten Ver¬ dünnungsverhältnisses kostengünstiger ist als die her¬ kömmlichen Klebstoffe, und der die Nachteile der bekannten Klebstoffe hinsichtlich der Verarbeitungseigenschaften vermeidet.The properties of the adhesive solution can thus be selected by specifying the degree of dilution of the adhesive and the amount of base added, which neutralizes and activates an equivalent amount of acrylic acid polymer. Thus, after appropriate dilution, the adhesive solution can subsequently be raised to a higher viscosity, which is necessary, for example, for processing the adhesive. The method according to the invention thus enables the production of an adhesive which, owing to an increased dilution ratio, is less expensive than the conventional adhesives and which avoids the disadvantages of the known adhesives with regard to the processing properties.
So können die gewünschten Klebstoffeigenschaften dem jeweiligen Verarbeitungsprozeß angepaßt werden.In this way, the desired adhesive properties can be adapted to the respective processing process.
Das erfindungsgemäße Verfahren liefert einen Klebstoff, der z.B. zur Herstellung von Papierlagen, insbesondere Tissue- papierlagen für Haushalts- und Toilettenpapier, eingesetzt werden kann. Der erfindungsgemäße Klebstoff enthält für eine solche Anwendung in einer bevorzugten Ausführungs orm die folgenden Bestandteile: ca. 10 bis 30 Teile teilverseifter Polyvinylalkoholester oder gegebenenfalls derivatisierte Stärkeacrylatpolymere ca. 20 bis 35 Teile AcrylatverdickerThe method according to the invention provides an adhesive which e.g. can be used for the production of paper layers, in particular tissue paper layers for household and toilet paper. For such an application, the adhesive according to the invention contains the following constituents in a preferred embodiment: approx. 10 to 30 parts of partially saponified polyvinyl alcohol esters or optionally derivatized starch acrylate polymers approx. 20 to 35 parts of acrylate thickener
0 bis 2 Teile übliche Zusätze, insbesondere Harnstoff0 to 2 parts of common additives, especially urea
Rest Wasser.Rest of water.
Die folgenden Ausführungsbeispiele erläutern die Erfindung, ohne sie jedoch einzuschränken.The following exemplary embodiments explain the invention without, however, restricting it.
Ausführuncrsbeispiel 1:Example 1:
Ein Klebstoffkonzentrat 1 wird mit folgender Zusammensetzung hergestellt:An adhesive concentrate 1 is produced with the following composition:
Klebsto fkonzentrat 1: 22 Teile Polyvinylalkohol 32 Teile Acrylεäureverdicker 46 Teile Wasser Es hat eine Viskosität von ca. 1700 mPa»s. Das Konzentrat wird mit Wasser in einem Verhältnis von 1:9 verdünnt. Die Viskosität des Verdünnungsproduktes beträgt ca. 30 mPa«s. Nach Zugabe von 0,2 % Base (konzentrierte Ammoniaklösung) (bezogen auf 100 Teile Konzentrat) beträgt die Viskosität des verar¬ beitungsfertigen Klebstoffes 350 mPa»s.Adhesive concentrate 1: 22 parts polyvinyl alcohol 32 parts acrylic acid thickener 46 parts water It has a viscosity of approx. 1700 mPa »s. The concentrate is diluted with water in a ratio of 1: 9. The viscosity of the dilution product is approximately 30 mPas. After addition of 0.2% base (concentrated ammonia solution) (based on 100 parts of concentrate), the viscosity of the ready-to-use adhesive is 350 mPas.
Ausführungsbeispiel 2:Example 2:
Ein Klebstoffkonzentrat 2 wird mit folgender Zusammensetzung hergestellt:An adhesive concentrate 2 is produced with the following composition:
Klebstoffkonzentrat 2: 26 Teile PolyvinylalkoholAdhesive concentrate 2: 26 parts of polyvinyl alcohol
2 Teile Harnstoff 33 Teile Acrylsäureverdicker 39 Teile Wasser2 parts urea 33 parts acrylic acid thickener 39 parts water
Mit einer Viskosität von ca. 5000 mPa»s wird mit Wasser in einem Verhältnis von 1:7 verdünnt. Die Viskosität des Kleb¬ stoffes nach diesem Verdünnungsschritt beträgt ca. 40 mPa»s. Nach Zugabe von 0,2% Base (konzentrierte NH4 - Lsg) (bezogen auf 100 Teile Konzentrat) als aktivierendes Reagens beträgt die Viskosität des fertigen Klebstoffes 1100 mPa»s.With a viscosity of approx. 5000 mPa »s is diluted with water in a ratio of 1: 7. The viscosity of the adhesive after this dilution step is approximately 40 mPas. After adding 0.2% base (concentrated NH 4 solution) (based on 100 parts of concentrate) as the activating reagent, the viscosity of the finished adhesive is 1100 mPa »s.
Ausführungsbeispiel 3:Example 3:
Ein Klebstoffkonzentrat 3 wird mit folgender Zusammensetzung hergestellt:An adhesive concentrate 3 is produced with the following composition:
Konzentrat 3:Concentrate 3:
75 Teile PVAC-Dispersion 50%ig75 parts of PVAC dispersion 50%
13 Teile Dibutylphthalat13 parts of dibutyl phthalate
5 Teile Acrylsäureverdicker5 parts of acrylic acid thickener
7 Teile Wasser. - a7 parts water. - a
Das Konzentrat mit einer Viskosität von ca. 20000 mPa»s wird mit 50% Wasser verdünnt (2 Teile Konzentrat und 1 Teil Wasser) . nach Zugabe von 1% Ammoniak auf die Mischung stellt sich eine Viskosität von ca. 5000 mPa»s ein. Diese Mischung kann beispielsweise in der graphischen Industrie für die Längsnahtverklebung von Papieren eingesetzt werden.The concentrate with a viscosity of approx. 20,000 mPas is diluted with 50% water (2 parts concentrate and 1 part water). after adding 1% ammonia to the mixture, a viscosity of approx. 5000 mPa »s is established. This mixture can be used, for example, in the graphics industry for the longitudinal seam bonding of papers.
In allen Ausführungsbeispielen wird als Acrylsäureverdicker ein Acrysol ASE-Verdicker von Rohm and Haas Co. verwendet. In all of the exemplary embodiments, an Acrysol ASE thickener from Rohm and Haas Co. is used as the acrylic acid thickener.

Claims

- 3-Ansprüche - 3 claims
1. Flüssiges Klebstoffkonzentrat auf Wasserbasis, insbesondere mit einer Polyhydroxyverbindung bzw. einer Polyvinylesterverbindung als klebender Komponente, dadurch gekennzeichnet/ daß das Klebstoffkonzentrat ein Verdickungsmittel ent¬ hält, das bei Zugabe eines aktivierenden Reagens eine Viskositätserhöhung bewirkt.1. A liquid adhesive concentrate water-based, particularly with a polyhydroxy compound or a Polyvinylesterverbindung as adhesive component, characterized in / that the adhesive concentrate maintains a thickener ent, which causes an increase in viscosity upon addition of an activating reagent.
2. Klebstoffkonzentrat nach Anspruch 1, dadurch gekennzeichnet, daß die Polyhydroxyverbindung ein Polyvinylalkohol- derivat und/oder ein Stärkederivat umfaßt.2. Adhesive concentrate according to claim 1, characterized in that the polyhydroxy compound comprises a polyvinyl alcohol derivative and / or a starch derivative.
3. Klebstoffkonzentrat nach Anspruch 2, dadurch gekennzeichnet, daß das Polyvinylalkoholderivat ein teilverseifter PVOH- (Ester) ist. 3. Adhesive concentrate according to claim 2, characterized in that the polyvinyl alcohol derivative is a partially saponified PVOH (ester).
4. Klebstoffkonzentrat nach Anspruch 3, dadurch gekennzeichnet, daß der teilverseifte Polyvinylalkoholester folgende Zusammensetzung aufweist: a) 10-13% PVAC b) 87-90% PVOH4. Adhesive concentrate according to claim 3, characterized in that the partially saponified polyvinyl alcohol ester has the following composition: a) 10-13% PVAC b) 87-90% PVOH
5. Klebsto fkonzentrat nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß das Verdickungsmittel ein emulgiertes, alkalilös¬ liches (Meth)acrylsäurepolymer oder -copoly er ist.5. Adhesive concentrate according to one of claims 1 to 4, characterized in that the thickener is an emulsified, alkali-soluble (meth) acrylic acid polymer or copoly er.
6. Klebstoffkonzentrat nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß das aktivierende Reagens eine Base, vorzugsweise Ammoniak oder Natronlauge, ist.6. Adhesive concentrate according to one of claims 1 to 5, characterized in that the activating reagent is a base, preferably ammonia or sodium hydroxide solution.
7. Klebsto fkonzentrat nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß das Klebstoffkonzentrat folgende Bestandteile enthält: ca. 10 bis 30 Teile teilverseifter Polyvinylalkoholester oder ggf. derivatisierte Stärkeacrylatpolymere ca. 20 bis 35 Teile Acrylatverdicker ca. 25 bis 70 Teile Wasser ca. 0 bis 2 Teile übliche Zusätze, insbesondere7. Adhesive concentrate according to one of claims 1 to 6, characterized in that the adhesive concentrate contains the following components: about 10 to 30 parts of partially saponified polyvinyl alcohol ester or possibly derivatized starch acrylate polymers about 20 to 35 parts of acrylate thickener about 25 to 70 parts of water approx 0 to 2 parts of common additives, in particular
Harnstoffurea
Rest Wasser.Rest of water.
8. Klebstoffkonzentrat nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß das Konzentrat eine Weichmacherkomponente, vorzugsweise Dibutylphthalat, enthält. - II -8. Adhesive concentrate according to one of the preceding claims, characterized in that the concentrate contains a plasticizer component, preferably dibutyl phthalate. - II -
9. Klebstoffkonzentrat nach Anspruch 8, dadurch gekennzeichnet, daß das Konzentrat enthält: ca. 50-90 Teile Polyvinylacetat-Dispersion mit einem9. adhesive concentrate according to claim 8, characterized in that the concentrate contains: about 50-90 parts of polyvinyl acetate dispersion with a
PVAC-Gehalt von 30-70% ca. 10-20 Teile Weichmacher ca. 5 Teile Acrylsäureverdicker ca. 5-10 Teile Wasser.PVAC content of 30-70% approx. 10-20 parts plasticizer approx. 5 parts acrylic acid thickener approx. 5-10 parts water.
10. Klebstoff auf Wasserbasis, insbesondere zur Verklebung von Tissuepapierlagen, für die Tapetenherstellung, für Verpackungsmittel und dergleichen, herstellbar durch Verdünnen eines Konzentrats gemäß einem der Ansprüche 1 bis 9 mit Wasser, insbesondere im Verhältnis bis ca. 1:15, der folgende Bestandteile enthält: teilverseifter Polyvinylalkohol oder Polyvinyl- ester - wenigstens teilweise neutralisiertes (Meth)acryl- säure(co)polymer ggf. Harnstoff und/oder andere übliche Zusätze ggf. Weichmacher Rest Wasser.10. Water-based adhesive, in particular for bonding tissue paper layers, for wallpaper production, for packaging and the like, can be produced by diluting a concentrate according to one of claims 1 to 9 with water, in particular in a ratio of up to about 1:15, which contains the following constituents : partially saponified polyvinyl alcohol or polyvinyl ester - at least partially neutralized (meth) acrylic acid (co) polymer, optionally urea and / or other customary additives, if necessary plasticizer, remainder water.
11. Verfahren zur Herstellung eines Klebstoffes für die Verklebung von mindestens zwei Materiallagen, insbesondere Papierlagen, durch Verdünnung eines Kleb¬ stoffkonzentrats, auf Wasserbasis, insbesondere mit einer Polyhydroxyverbindung bzw. einer Polyvinylester¬ verbindung als klebender Komponente dadurch gekennzeichnet, daß das Klebstoffkonzentrat, welches ein latentes11. A process for producing an adhesive for bonding at least two layers of material, in particular paper, by diluting an adhesive concentrate, water-based, in particular with a polyhydroxy compound or a polyvinyl ester compound as an adhesive component, characterized in that the adhesive concentrate, which is a latent
Verdickungsmittel enthält, auf Verbrauchskonzentration verdünnt und das Verdickungsmittel durch Zugabe eines aktivierenden Reagens zur Viskositätserhöhung aktiviert wird. Contains thickener, diluted to consumption concentration and the thickener is activated by adding an activating reagent to increase the viscosity.
12. Verfahren nach Anspruch 11, dadurch gekennzeichnet, daß das Klebstoffkonzentrat mit Wasser in einem Verhältnis von bis zu über 1:10, vorzugsweise 1:5 bis 1:15, verdünnt wird.12. The method according to claim 11, characterized in that the adhesive concentrate is diluted with water in a ratio of up to over 1:10, preferably 1: 5 to 1:15.
13. Verfahren nach einem der Ansprüche 11 oder 12, dadurch gekennzeichnet, daß die Polyhydroxykomponente ein teilverseifter Polyvinylalkohol oder ein Stärkederivat ist.13. The method according to any one of claims 11 or 12, characterized in that the polyhydroxy component is a partially saponified polyvinyl alcohol or a starch derivative.
14. Verfahren nach einem der Ansprüche 11 bis 13, dadurch gekennzeichnet, daß der Klebstoff Zusatzkömponenten wie Harnstoff und/oder Weichmacher enthält.14. The method according to any one of claims 11 to 13, characterized in that the adhesive contains additional components such as urea and / or plasticizers.
15. Verfahren nach einem der Ansprüche 11 bis 14, dadurch gekennzeichnet, daß das Verdickungsmittel ein alkalilösliches und emulgiertes (Meth)acrylsäurepolymer ist, welches bei wenigstens teilweiser Neutralisation eine Viskositäts¬ erhöhung bewirkt.15. The method according to any one of claims 11 to 14, characterized in that the thickener is an alkali-soluble and emulsified (meth) acrylic acid polymer, which causes an increase in viscosity with at least partial neutralization.
16. Verfahren nach einem der Ansprüche 11 bis 15, dadurch gekennzeichnet, daß das aktivierende Reagens eine Base, insbesondere Ammoniak oder Natronlauge, ist.16. The method according to any one of claims 11 to 15, characterized in that the activating reagent is a base, in particular ammonia or sodium hydroxide solution.
17. Verfahren nach einem der Ansprüche 11 bis 16, dadurch gekennzeichnet, daß die Zugabe des aktivierenden Reagens nach der Verdünnung des Klebstoffkonzentrates erfolgt. - J 3 -17. The method according to any one of claims 11 to 16, characterized in that the addition of the activating reagent takes place after the dilution of the adhesive concentrate. - J 3 -
18. Verfahren nach einem der Ansprüche 11 bis 17, dadurch gekennzeichnet, daß die Viskosität des Klebstoffes durch Mengenwahl bei der Umsetzung des Verdickungsmittel mit der Base eingestellt oder reguliert wird.18. The method according to any one of claims 11 to 17, characterized in that the viscosity of the adhesive is adjusted or regulated by quantity selection in the implementation of the thickener with the base.
19. Verwendung des Klebstoffes gemäß einem der Ansprüche 1 bis 10, insbesondere bei einem Verfahren gemäß einem der Ansprüche 11 bis 18, zur Verklebung von zwei- oder mehr¬ lagigen Tissuepapieren, insbesondere saugfähigen Haushalts- und Toilettenpapieren; zur Verklebung von Papier in der graphischen Industrie oder zur Verklebung von Papier, Karton, Pappe und dergleichen bei der Herstellung von Verpackungen. 19. Use of the adhesive according to one of claims 1 to 10, in particular in a method according to one of claims 11 to 18, for the adhesive bonding of two- or multi-layer tissue papers, in particular absorbent household and toilet papers; for gluing paper in the graphics industry or for gluing paper, cardboard, cardboard and the like in the manufacture of packaging.
PCT/EP1993/000872 1992-04-10 1993-04-08 Process for the production of an adhesive for bonding layers of material WO1993021279A2 (en)

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DE4212133A DE4212133A1 (en) 1992-04-10 1992-04-10 Process for the production of an adhesive for the bonding of material layers
DEP4212133.7 1992-04-10

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WO1993021279A3 WO1993021279A3 (en) 1994-01-06

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997011226A1 (en) * 1995-09-06 1997-03-27 The Procter & Gamble Company Paper product comprising adhesively joined plies
US5858554A (en) * 1995-08-25 1999-01-12 The Procter & Gamble Company Paper product comprising adhesively joined plies
US7348378B2 (en) 2003-12-18 2008-03-25 3M Innovative Properties Company Adhesive

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005062293A1 (en) * 2005-12-24 2007-06-28 Pci Augsburg Gmbh Aqueous adhesive formulation for laying floor or wall coverings on an alkaline base, shows an acidic pH and contains polymeric binder, water, resin, filler, other additives and at least one alkali-activated thickener

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1594071A1 (en) * 1963-08-12 1970-10-01 Kurashiki Rayon Co Polyvinyl alcohol adhesives
EP0022550A1 (en) * 1979-07-13 1981-01-21 Hoechst Aktiengesellschaft Adhesive made from polyvinyl alcohol, and its use
US4424291A (en) * 1980-12-11 1984-01-03 National Starch And Chemical Corporation Corrugating adhesive composition and paperboard product produced therewith
JPH0720598A (en) * 1993-06-04 1995-01-24 Minnesota Mining & Mfg Co <3M> Optothermographic material which is sensitive to electromagnetic beam in red region of electromagnetic spectrum and which is transparent to electromagnetic beam in ultraviolet region of electromagnetic beam

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1594071A1 (en) * 1963-08-12 1970-10-01 Kurashiki Rayon Co Polyvinyl alcohol adhesives
EP0022550A1 (en) * 1979-07-13 1981-01-21 Hoechst Aktiengesellschaft Adhesive made from polyvinyl alcohol, and its use
US4424291A (en) * 1980-12-11 1984-01-03 National Starch And Chemical Corporation Corrugating adhesive composition and paperboard product produced therewith
JPH0720598A (en) * 1993-06-04 1995-01-24 Minnesota Mining & Mfg Co <3M> Optothermographic material which is sensitive to electromagnetic beam in red region of electromagnetic spectrum and which is transparent to electromagnetic beam in ultraviolet region of electromagnetic beam

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 74, no. 14, 5. April 1971, Columbus, Ohio, US; abstract no. 65034m, IMOTO,SABURO 'water-resistant adhesives' Seite 45 ;Spalte 1 ; & JP,A,7 020 598 (KURASHIKI RAYON) 13. Juli 1970 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5858554A (en) * 1995-08-25 1999-01-12 The Procter & Gamble Company Paper product comprising adhesively joined plies
WO1997011226A1 (en) * 1995-09-06 1997-03-27 The Procter & Gamble Company Paper product comprising adhesively joined plies
US7348378B2 (en) 2003-12-18 2008-03-25 3M Innovative Properties Company Adhesive
US7560507B2 (en) 2003-12-18 2009-07-14 3M Innovative Properties Company Adhesive

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WO1993021279A3 (en) 1994-01-06
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