EP1203120A1 - Composition for the impregnation of paper, method for the production thereof, impregnated paper and laminate comprising said impregnated paper - Google Patents

Composition for the impregnation of paper, method for the production thereof, impregnated paper and laminate comprising said impregnated paper

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Publication number
EP1203120A1
EP1203120A1 EP00936879A EP00936879A EP1203120A1 EP 1203120 A1 EP1203120 A1 EP 1203120A1 EP 00936879 A EP00936879 A EP 00936879A EP 00936879 A EP00936879 A EP 00936879A EP 1203120 A1 EP1203120 A1 EP 1203120A1
Authority
EP
European Patent Office
Prior art keywords
paper
composition
impregnated
papers
glyoxal
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP00936879A
Other languages
German (de)
French (fr)
Inventor
Mario Volpatti
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unidur GmbH
Original Assignee
Unidur GmbH
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 Unidur GmbH filed Critical Unidur GmbH
Publication of EP1203120A1 publication Critical patent/EP1203120A1/en
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • B32B29/002—Layered products comprising a layer of paper or cardboard as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
    • D21H17/72—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic material
    • 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
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/18—Paper- or board-based structures for surface covering
    • D21H27/22—Structures being applied on the surface by special manufacturing processes, e.g. in presses
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/028—Paper layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2317/00—Animal or vegetable based
    • B32B2317/20—Starch
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2333/00—Polymers of unsaturated acids or derivatives thereof
    • B32B2333/04—Polymers of esters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2451/00—Decorative or ornamental articles
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/06—Alcohols; Phenols; Ethers; Aldehydes; Ketones; Acetals; Ketals
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/28—Starch
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates

Definitions

  • the present invention relates to a composition which is particularly suitable for impregnating paper.
  • the present invention further relates to a method for producing such a composition, impregnated papers and their use.
  • Impregnated papers are used in many ways to design surfaces. In the furniture industry in particular, such papers are often used to refine surfaces, the papers being able to be single-colored or also being printed with certain decors, for example wood grain. Such papers offer the possibility of inexpensively optically less appealing substrates, such as chipboard, with a more appealing exterior.
  • impregnated papers are used, for example, to design surfaces in the furniture industry, so-called decorative papers, on the one hand they have to meet certain application requirements so that the appropriately coated substrates can be processed, and on the other hand the decorative papers themselves must be easy and inexpensive to manufacture.
  • the decorative papers must first meet certain mechanical requirements. This means that they have to be sufficiently waterproof, have a rigidity or flexibility suitable for processing and also have a suitable core strength.
  • Cleavage behavior means the tendency of the decorative paper to tear beyond the edge of the substrate. The splitting behavior is therefore a measure of how well the decorative paper can be processed.
  • processing steps such. B. sawing drilling milling and the like, the glued film must not fray. Rather, the soaked fiber should break off at the processing edge so that visually appealing results can be obtained.
  • the above-mentioned properties are very significantly influenced by the impregnation of the paper, that is to say the impregnating agent used.
  • the impregnating agent also has a decisive influence on the optical properties, that is to say in particular the depth of color and the level of lacquer of the decorative paper.
  • the compositions used for impregnating decorative papers are free of substances which are potentially harmful to health. It is particularly desirable here that the impregnating agents contain no formaldehyde.
  • compositions for impregnating decorative papers are known, for example, from WO 95/17551.
  • This application proposes aqueous impregnating agents which contain a crosslinkable polymer with a specific
  • this object is achieved by a composition
  • a composition comprising a binder, an aqueous polymer dispersion and glyoxal.
  • composition according to the invention is particularly advantageous since it enables the production of decorative papers with an excellent depth of color and a high level of lacquer.
  • decorative papers produced with the composition according to the invention are particularly stable against splitting without having to accept any loss in flexibility.
  • the compositions according to the present invention are also particularly advantageous in terms of processing technology, since they give very good results even with a low solids content and the paper to be impregnated can easily be impregnated with them. Further advantages and properties of the present invention will become apparent from the following description.
  • compositions according to the invention contain a binder.
  • Conventional binders can be used according to the invention, it being preferred if the binders are water-soluble.
  • water-soluble binders are polyvinyl alcohol, gelatin, cellulose derivatives such as carboxymethyl cellulose, alginates, starch and starch derivatives and mixtures thereof.
  • cellulose derivatives such as carboxymethyl cellulose, alginates, starch and starch derivatives and mixtures thereof.
  • Especially water-soluble starch derivatives and in particular dextrins are preferred. Dextrins have the particular advantage that they are readily water-soluble and do not require any additional measures, such as boiling.
  • compositions according to the invention further contain an aqueous polymer dispersion.
  • the polymer dispersions customary in paper impregnation can also be used here.
  • Dispersions which contain crosslinkable polymers, such as (meth) acrylate polymers and copolymers of (meth) acrylate monomers with suitable comonomers are advantageous.
  • the notation “(meth) acrylates” is intended to make it clear that both methacrylates and acrylates are suitable according to the invention.
  • suitable (meth) acrylate polymers are, for example, styrene (meth) acrylate copolymers, it being possible to use methyl, ethyl, propyl and butyl (meth) acrylates. All those monomers which carry reactive groups, such as amino, hydroxyl or carboxyl groups, which can react with glyoxal are particularly suitable.
  • aqueous polymer dispersion according to the invention can also contain other polymer components, such as polyester or polyurethane components. With these additional components, the properties of the impregnated paper can be adapted even better to the respective requirements.
  • Dispersions based on polyurethane can also be used advantageously for pre-impregnates, since they are characterized by very good smoothness.
  • composition according to the invention comprising a binder, an aqueous polymer dispersion and glyoxal, suitably has a viscosity of 10 to 15 seconds at 23 ° C. (measured with a Ford flow cup, 4 mm). This is generally achieved when the
  • the total solids content of the composition according to the invention is in the range from 15 to 45% by weight, preferably 20 to 40% by weight and particularly preferably 22 to 30% by weight.
  • the polymer component can make up 20 to 80% by weight, preferably 40 to 60% by weight and particularly preferably 50 to 60% by weight.
  • the amount of binder based on the dry mass of the composition according to the invention, can be 10 to 50% by weight, preferably 30 to 50% by weight and particularly preferably 35 to 40% by weight.
  • the proportion of the glyoxal in the dry matter of the composition according to the invention can be 2 to 20% by weight, preferably 7 to 15% by weight and very particularly preferably 9 to 12% by weight.
  • compositions according to the invention In addition to the aforementioned constituents of the compositions according to the invention, further constituents can be added, provided that these do not adversely affect the advantageous properties of the compositions according to the invention.
  • pigments or fillers can already be added to the compositions according to the invention.
  • composition according to the invention is suitably produced by first introducing the glyoxal with water. Then the binder is added and finally the polymer dispersion is incorporated.
  • This procedure is very advantageous because the technical glyoxal solutions usually used have a pH of about 2 to 3.5 and are therefore very acidic. If the glyoxal were to be mixed directly with the polymer dispersion, there would be a risk in the case of (meth) acrylate-containing dispersions that the polymer would flocculate and no homogeneous product would be obtained.
  • compositions according to the invention are also very advantageous from an application point of view.
  • the addition of the polymer dispersion as the last component makes it possible, by choosing a suitable polymer dispersion, to adapt the properties of the compositions on site to the individual requirements and in particular to the machines available in each case. At the same time, this procedure significantly improves storage stability.
  • Another advantage that is significant in practice, particularly when using starch and starch derivatives as binders, is that the composition containing glyoxal, water and the respective binder is essentially not subject to fungal attack.
  • compositions according to the invention are particularly suitable for impregnating paper and here in particular for impregnating decorative papers.
  • the papers which can be used are not particularly limited, but papers with an ash content of less than 18% by weight are particularly preferred. It is known that papers with a low ash content are particularly resistant to splitting. Accordingly, papers with an ash content of less than 15% by weight and in particular less than 12% by weight are particularly preferred.
  • the weight per unit area of the papers to be impregnated is not particularly limited; papers with a weight per unit area of 45 to 70 g / m 2 are suitable in any case.
  • the paper can be impregnated with the composition according to the invention by customary methods.
  • the per The amount of paper to be applied per square meter depends on whether post-impregnation or pre-impregnation is carried out.
  • the compositions according to the invention are equally suitable for both procedures.
  • the proportion of impregnation is usually 20 to 24% by weight for pre-impregnates and 25 to 35% by weight for post-impregnates, based on the dry weight of the impregnating agent. According to the invention, this proportion can be significantly reduced. For example, good results with 18% by weight for post-embossing were achieved.
  • the composition according to the invention thus also enables the production of resource-saving and less expensive decorative papers without having to compromise on quality.
  • the paper impregnated in this way can be laminated onto various substrates, such as chipboard, fiberboard and the like, using customary methods. It was found that the papers according to the invention can be glued particularly well, for example using urea glue. This property is of great importance in practice, since good and fast gluing enables high production speeds.
  • Licopol is an aqueous dextrin solution with 50% dry matter available from Südstark GmbH, Schrobenhausen.
  • Acronal S 305 D is an n-butyl acrylate-styrene copolymer available from BASF AG, Ludwigshafen (solids content 50% by weight).
  • the glyoxal used was a 40% by weight aqueous solution.
  • a decorative paper available from Munksjö, Italy, with the number 101465 and a basis weight of 45 g / m 2 at 13% ash content and a porosity of 24 s, measured according to the Gurley method, was impregnated.
  • the impregnation was carried out by soaking the paper in the impregnation solution, wiping off excess impregnation solution and drying at 150 ° C.
  • the impregnating agent content in the impregnated paper was 25 ⁇ 2% by weight and was therefore in the borderline range of pre- and post-impregnates. During the impregnation, it was observed how well the impregnating solution was absorbed by the paper. The results are shown in Table 2.
  • the papers impregnated in this way were then coated with an acid-curable aminoplast lacquer (corresponding to type 9944.61, available from Plantag Chemie, Detmold). Then the papers were dried at 160 ° C. The surface was then examined and the gloss was examined using an Ericsson glossmeter at an angle of 60 ° C. Farther the flexibility of the impregnated and varnished papers by folding was examined. If the paper broke when folded, it was classified as fragile.
  • an acid-curable aminoplast lacquer corresponding to type 9944.61, available from Plantag Chemie, Detmold
  • the splitting strength of the papers was also examined.
  • a sample was adhered to a particle board by means of an aminoplast adhesive, part of the paper protruding beyond the edge of the particle board by at least 20 mm in the cross grain direction.
  • the adhesive temperature was 145 ° C. and the pressure was applied at 10 N / cm for 15 s.
  • the protruding part of the paper was cut at 2 cm intervals, so that 2 x 2 cm protrusions were formed. These supernatants were then quickly pulled towards the edge of the particle board at an angle of 45 °.
  • composition 2 as a standard
  • formulation 4 according to the invention shows unexpectedly good overall properties which cannot be obtained if only two components or only one of the components according to the invention are used. Particularly noteworthy is the high splitting resistance, the good surface gloss and the good flexibility of the papers impregnated according to the invention.

Landscapes

  • Paper (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

The invention relates to a composition which is especially used to impregnate paper, containing a binding agent, an aqueous polymer dispersion and glyoxal. The invention also relates to a method for the production of said composition, in addition to an intermediate produced which can be used in an advantageous manner and which contains glyoxal, water and a binding agent. The inventive compositions are particularly suitable for impregnating paper and can be used to produce decorative paper with improved properties.

Description

ZUSAMMENSETZUNG ZUR IMPRÄGNIERUNG VON PAPIER, VERFAHREN ZU COMPOSITION FOR IMPREGNATING PAPER, METHOD FOR
DEREN HERSTELLUNG, IMPRÄGNIERTES PAPIER UNDTHEIR PRODUCTION, IMPREGNATED PAPER AND
LAMINAT, UMFASSEND DAS IMPRÄGNIERTE PAPIERLAMINATE, COMPREHENSIVE IMPREGNATED PAPER
Die vorliegende Erfindung betrifft eine Zusammensetzung, die sich insbesondere zum Imprägnieren von Papier eignet. Weiter betrifft die vorliegende Erfindung ein Verfahren zur Herstellung einer solchen Zusammensetzung, imprägnierte Papiere und deren Verwendung.The present invention relates to a composition which is particularly suitable for impregnating paper. The present invention further relates to a method for producing such a composition, impregnated papers and their use.
Imprägnierte Papiere finden vielfältige Anwendung zur Gestaltung von Oberflächen. Insbesondere in der Möbelindustrie werden solche Papiere oftmals zur Veredelung von Oberflächen eingesetzt, wobei die Papiere einfarbig sein können oder auch mit bestimmten Dekoren, zum Beispiel Holzmaserungen bedruckt sein können. Solche Papiere bieten die Möglichkeit, kostengünstig optisch weniger ansprechende Substrate, wie zum Beispiel Spanplatten, mit einem ansprechenderen Äußeren zu versehen.Impregnated papers are used in many ways to design surfaces. In the furniture industry in particular, such papers are often used to refine surfaces, the papers being able to be single-colored or also being printed with certain decors, for example wood grain. Such papers offer the possibility of inexpensively optically less appealing substrates, such as chipboard, with a more appealing exterior.
Wenn imprägnierte Papiere zum Beispiel zur Gestaltung von Oberflächen in der Möbelindustrie eingesetzt werden, sogenannte Dekorpapiere, müssen sie zum einen bestimmten anwendungstechnische Anforderungen erfüllen, damit die entsprechend beschichteten Substrate verarbeitet werden können, zum anderen müssen die Dekorpapiere selbst leicht und kostengünstig herstellbar sein.If impregnated papers are used, for example, to design surfaces in the furniture industry, so-called decorative papers, on the one hand they have to meet certain application requirements so that the appropriately coated substrates can be processed, and on the other hand the decorative papers themselves must be easy and inexpensive to manufacture.
Hinsichtlich der anwendungstechnischen Eigenschaften müssen die Dekorpapiere zunächst bestimmte mechanische Anforderungen erfüllen. Das heißt, sie müssen hinreichend wasserfest sein, eine für die Verarbeitung geeignete Steifigkeit bzw. Flexibilität aufweisen und auch eine geeignete Kernfestigkeit zeigen. Insbesondere für die Möbelindustrie ist weiterhin das sogenannte Spaltverhalten von besonderer Bedeutung. Unter Spaltverhalten versteht man die Neigung des Dekorpapiers, über die Substratkante hinaus einzureißen. Das Spaltverhalten ist somit ein Maß dafür, wie gut sich das Dekorpapier verarbeiten läßt . Bei einer Vielzahl von Bearbeitungsschritten, wie z. B. Sägen Bohren Fräsen und dergleichen, darf die aufgeleimte Folie nicht ausfransen. Vielmehr soll die getränkete Faser an der Bearbeitungskante abbrechen, damit optisch ansprechende Ergebnisse erhalten werden können.With regard to the application properties, the decorative papers must first meet certain mechanical requirements. This means that they have to be sufficiently waterproof, have a rigidity or flexibility suitable for processing and also have a suitable core strength. Especially for the furniture industry continues the so-called splitting behavior of particular importance. Cleavage behavior means the tendency of the decorative paper to tear beyond the edge of the substrate. The splitting behavior is therefore a measure of how well the decorative paper can be processed. In a variety of processing steps such. B. sawing drilling milling and the like, the glued film must not fray. Rather, the soaked fiber should break off at the processing edge so that visually appealing results can be obtained.
Die vorgenannten Eigenschaften werden ganz wesentlich von der Imprägnierung des Papiers, also des verwendeten Imprägniermittels beeinflußt . Das Imprägniermittel hat weiterhin einen entscheidenden Einfluß auf die optischen Eigenschaften, das heißt insbesondere die Farbtiefe und den Lackstand des Dekorpapiers.The above-mentioned properties are very significantly influenced by the impregnation of the paper, that is to say the impregnating agent used. The impregnating agent also has a decisive influence on the optical properties, that is to say in particular the depth of color and the level of lacquer of the decorative paper.
Im Hinblick auf die Verwendung in der Möbelindustrie ist in letzter Zeit zunehmend auch darauf zu achten, daß die zur Imprägnierung von Dekorpapieren verwendeten Zusammensetzungen frei von potentiell gesundheitsschädlichen Substanzen sind. Hierbei wird insbesondere angestrebt, daß die Imprägniermittel kein Formaldehyd enthalten.With regard to the use in the furniture industry, it has recently become increasingly important to ensure that the compositions used for impregnating decorative papers are free of substances which are potentially harmful to health. It is particularly desirable here that the impregnating agents contain no formaldehyde.
Formaldehyd-freie Zusammensetzungen zur Imprägnierung von Dekorpapieren sind zum Beispiel aus der WO 95/17551 bekannt. Diese Anmeldung schlägt wäßrige Imprägniermittel vor, die ein vernetzbares Polymer mit einer bestimmtenFormaldehyde-free compositions for impregnating decorative papers are known, for example, from WO 95/17551. This application proposes aqueous impregnating agents which contain a crosslinkable polymer with a specific
Glasübergangstemperatur und ein Bindemittel enthalten. Diese Formaldehyd-freien Zusammensetzungen nach dem Stand der Technik liefern bereits brauchbare Ergebnisse, allerdings sind sie insbesondere im Hinblick auf das Spaltverhalten damit hergestellter Dekorpapiere noch verbesserungsfähig. Das gleiche gilt auch für die von der Südstärke GmbH, Schrobenhausen, vorgeschlagenen Imprägniermittel auf der Basis von Dextrin und einer Polymerdispersion.Glass transition temperature and a binder included. These formaldehyde-free compositions according to the prior art already provide usable results, but they can still be improved, in particular with regard to the splitting behavior of decorative papers produced therewith. The same also applies to the impregnating agents based on dextrin and a polymer dispersion proposed by Südstark GmbH, Schrobenhausen.
Aufgabe der vorliegenden Erfindung ist es daher, eine Formaldehyd-freie Zusammensetzung, insbesondere zum Imprägnieren von Papier, bereitzustellen, die die vorgenannten Eigenschaften bestmöglich in sich vereint und insbesondere die Herstellung von besonders spaltbeständigen Dekorpapieren ermöglicht.It is therefore an object of the present invention to provide a formaldehyde-free composition, in particular for impregnating paper, which optimally combines the abovementioned properties and in particular enables the production of particularly gap-resistant decorative papers.
Diese Aufgabe wird erfindungsgemäß durch eine Zusammensetzung, enthaltend ein Bindemittel, eine wäßrige Polymerdispersion und Glyoxal, gelöst.According to the invention, this object is achieved by a composition comprising a binder, an aqueous polymer dispersion and glyoxal.
Es hat sich gezeigt, daß die erfindungsgemäße Zusammensetzung besonders vorteilhaft ist, da sie die Herstellung von Dekorpapieren mit hervorragender Farbtiefe und hohem Lackstand ermöglicht. Gleichzeitig sind die mit der erfindungsgemäßen Zusammensetzung hergestellten Dekorpapiere besonders spaltstabil, ohne daß Einbußen hinsichtlich der Flexibilität hingenommen werden müßten. Auch in verarbeitungstechnischer Hinsicht sind die Zusammensetzungen gemäß der vorliegenden Erfindung besonders vorteilhaft, da sie sehr gute Ergebnisse auch bei geringem Feststoffgehalt liefern und das zu imprägnierende Papier leicht mit ihnen getränkt werden kann. Weitere Vorteile und Eigenschaften der vorliegende Erfindung werden aus der folgenden Beschreibung deutlich.It has been shown that the composition according to the invention is particularly advantageous since it enables the production of decorative papers with an excellent depth of color and a high level of lacquer. At the same time, the decorative papers produced with the composition according to the invention are particularly stable against splitting without having to accept any loss in flexibility. The compositions according to the present invention are also particularly advantageous in terms of processing technology, since they give very good results even with a low solids content and the paper to be impregnated can easily be impregnated with them. Further advantages and properties of the present invention will become apparent from the following description.
Die erfindungsgemäßen Zusammensetzungen enthalten ein Bindemittel . Als Bindemittel können erfindungsgemäß übliche Bindemittel eingesetzt werden, wobei es bevorzugt ist, wenn die Bindemittel wasserlöslich sind. Beispiele für solche wasserlöslichen Bindemittel sind Polyvinylalkohol, Gelatine, Cellulosederivate, wie etwa Carboxymethylcellulose, Alginate, Stärke und Stärkederivate und Mischungen davon. Besonders bevorzugt sind wasserlösliche Stärkederivate und hier insbesondere Dextrine. Dextrine haben den besonderen Vorteil, daß sie ohne weiteres wasserlöslich sind und keine zusätzlichen Maßnahmen, wie etwa Aufkochen, erfordern.The compositions according to the invention contain a binder. Conventional binders can be used according to the invention, it being preferred if the binders are water-soluble. Examples of such water-soluble binders are polyvinyl alcohol, gelatin, cellulose derivatives such as carboxymethyl cellulose, alginates, starch and starch derivatives and mixtures thereof. Especially water-soluble starch derivatives and in particular dextrins are preferred. Dextrins have the particular advantage that they are readily water-soluble and do not require any additional measures, such as boiling.
Die erfindungsgemäßen Zusammensetzungen enthalten weiter eine wäßrige Polymerdispersion. Auch hier können die bei der Papierimprägnierung üblichen Polymerdispersionen eingesetzt werden. Vorteilhaft sind Dispersionen, die vernetzbare Polymere enthalten, wie etwa (Meth) acrylatpolymere und Copolymere von (Meth) acrylatmonomeren mit geeigneten Comonomeren. Mit der Schreibweise " (Meth) acrylate" soll verdeutlich werden, daß erfindungsgemäß sowohl Methacrylate als auch Acrylate geeignet sind. Beispiele für geeignete (Meth) acrylatpolymere sind zum Beispiel Styrol (Meth) acrylat- Copolymere, wobei Methyl-, Ethyl-, Propyl- und Butyl- (Meth) acrylate verwendet werden können. Besonders geeignet sind all jene Monomere, die reaktive Gruppen, wie Amino-, Hydroxyl- oder Carboxylgruppen tragen, die mit Glyoxal reagieren können.The compositions according to the invention further contain an aqueous polymer dispersion. The polymer dispersions customary in paper impregnation can also be used here. Dispersions which contain crosslinkable polymers, such as (meth) acrylate polymers and copolymers of (meth) acrylate monomers with suitable comonomers, are advantageous. The notation “(meth) acrylates” is intended to make it clear that both methacrylates and acrylates are suitable according to the invention. Examples of suitable (meth) acrylate polymers are, for example, styrene (meth) acrylate copolymers, it being possible to use methyl, ethyl, propyl and butyl (meth) acrylates. All those monomers which carry reactive groups, such as amino, hydroxyl or carboxyl groups, which can react with glyoxal are particularly suitable.
Darüber hinaus kann die wäßrige Polymerdispersion erfindungsgemäß auch weitere Polymerkomponenten enthalten, wie zum Beispiel Polyester- oder Polyurethankomponenten. Mit diesen zusätzlichen Komponenten lassen sich die Eigenschaften des imprägnierten Papiers den jeweiligen Anforderungen noch besser anpassen.In addition, the aqueous polymer dispersion according to the invention can also contain other polymer components, such as polyester or polyurethane components. With these additional components, the properties of the impregnated paper can be adapted even better to the respective requirements.
Insbesondere für Vorimpregnate können auch Dispersionen auf Polyurethanbasis vorteilhaft verwendet werden, da diese sich durch eine sehr gute Glättebildung auszeichnen.Dispersions based on polyurethane can also be used advantageously for pre-impregnates, since they are characterized by very good smoothness.
Geeigneterweise hat die erfindungsgemäße Zusammensetzung, enthaltend ein Bindemittel, eine wäßrige Polymerdispersion und Glyoxal eine Viskosität von 10 bis 15 Sekunden bei 23°C (gemessen mit eine Ford Auslaufbecher, 4mm) . Dies wird im allgemeinen erreicht, wenn derThe composition according to the invention, comprising a binder, an aqueous polymer dispersion and glyoxal, suitably has a viscosity of 10 to 15 seconds at 23 ° C. (measured with a Ford flow cup, 4 mm). This is generally achieved when the
Gesamtfeststoffgehalt der erfindungsgemäßen Zusammensetzung bezogen auf die Trockenmasse im Bereich von 15 bis 45 Gew.-%, bevorzugt 20 bis 40 Gew.-% und insbesondere bevorzugt 22 bis 30 Gew.-% beträgt.The total solids content of the composition according to the invention, based on the dry matter, is in the range from 15 to 45% by weight, preferably 20 to 40% by weight and particularly preferably 22 to 30% by weight.
Bezogen auf die Trockenmasse der erfindungsgemäßen Zusammensetzung kann die Polymerkomponente 20 bis 80 Gew.-%, bevorzugt 40 bis 60 Gew.-% und insbesondere bevorzugt 50 bis 60 Gew.-% ausmachen. Die Menge an Bindemittel, bezogen auf die Trockenmasse der erfindungsgemäßen Zusammensetzung, kann 10 bis 50 Gew.-%, bevorzugt 30 bis 50 Gew.-% und insbesondere bevorzugt 35 bis 40 Gew.-% betragen. Der Anteil des Glyoxals an der Trockenmasse der erfindungsgemäßen Zusammensetzung kann 2 bis 20 Gew.-%, bevorzugt 7 bis 15 Gew.-% und ganz besonders bevorzugt 9 bis 12 Gew.-% betragen.Based on the dry mass of the composition according to the invention, the polymer component can make up 20 to 80% by weight, preferably 40 to 60% by weight and particularly preferably 50 to 60% by weight. The amount of binder, based on the dry mass of the composition according to the invention, can be 10 to 50% by weight, preferably 30 to 50% by weight and particularly preferably 35 to 40% by weight. The proportion of the glyoxal in the dry matter of the composition according to the invention can be 2 to 20% by weight, preferably 7 to 15% by weight and very particularly preferably 9 to 12% by weight.
Zusätzlich zu den vorgenannten Bestandteilen der erfindungsgemäßen Zusammensetzungen können weitere Bestandteile hinzugefügt werden, soweit diese die vorteilhaften Eigenschaften der erfindungsgemäßen Zusammensetzungen nicht nachteilig beeinflussen. Beispielsweise können den erfindungsgemäßen Zusammensetzungen bereits Pigmente oder Füllstoffe zugesetzt werden.In addition to the aforementioned constituents of the compositions according to the invention, further constituents can be added, provided that these do not adversely affect the advantageous properties of the compositions according to the invention. For example, pigments or fillers can already be added to the compositions according to the invention.
Die erfindungsgemäße Zusammensetzung wird geeigneterweise hergestellt, indem zunächst das Glyoxal mit Wasser vorgelegt wird. Dann wird das Bindemittel zugegeben und schließlich die Polymerdispersion eingearbeitet. Diese Vorgehensweise ist sehr vorteilhaft, weil die üblicherweise zum Einsatz kommenden technischen Glyoxallösungen einen pH-Wert von etwa 2 bis 3,5 aufweisen und somit sehr sauer sind. Würde man das Glyoxal direkt mit der Polymerdispersion vermischen, so bestünde jedenfalls im Falle von (meth) acrylathaltigen Dispersionen die Gefahr, daß das Polymer ausflockt und kein homogenes Produkt erhalten wird. Zum Einarbeiten der Polymerdispersion insbesondere im Fall von (Meth) acrylat- haltigen Dispersionen ist es daher ratsam, eine Mischung enthaltend Wasser, Bindemittel und Glyoxal vorzulegen, deren pH größer als 6 ist und vorteilhafterweise im neutralen Bereich, das heißt zwischen pH 6 und 8, liegt.The composition according to the invention is suitably produced by first introducing the glyoxal with water. Then the binder is added and finally the polymer dispersion is incorporated. This procedure is very advantageous because the technical glyoxal solutions usually used have a pH of about 2 to 3.5 and are therefore very acidic. If the glyoxal were to be mixed directly with the polymer dispersion, there would be a risk in the case of (meth) acrylate-containing dispersions that the polymer would flocculate and no homogeneous product would be obtained. To incorporate the polymer dispersion, especially in the case of (meth) acrylate containing dispersions, it is therefore advisable to submit a mixture containing water, binder and glyoxal, the pH of which is greater than 6 and advantageously in the neutral range, that is to say between pH 6 and 8.
Die vorgenannte Art und Weise zur Herstellung der erfindungsgemäßen Zusammensetzungen ist auch aus anwendungstechnischer Hinsicht sehr vorteilhaft. Das Hinzufügen der Polymerdispersion als letzte Komponente ermöglicht es, durch Wahl einer geeigneten Polymerdispersion die Eigenschaften der Zusammensetzungen vor Ort auf die individuellen Bedürfnisse und insbesondere auf die jeweils zur Verfügung stehenden Maschinen abzustellen. Gleichzeitig wird durch diese Vorgehensweise die Lagerstabilität deutlich verbessert. Ein weiterer in der Praxis bedeutender Vorteil insbesondere bei der Verwendung von Stärke und Stärkederivaten als Bindemittel besteht darin, daß die Zusammensetzung, enthaltend Glyoxal, Wasser und das jeweilige Bindemittel, im wesentlichen keinem Pilzbefall unterliegt.The above-mentioned way of producing the compositions according to the invention is also very advantageous from an application point of view. The addition of the polymer dispersion as the last component makes it possible, by choosing a suitable polymer dispersion, to adapt the properties of the compositions on site to the individual requirements and in particular to the machines available in each case. At the same time, this procedure significantly improves storage stability. Another advantage that is significant in practice, particularly when using starch and starch derivatives as binders, is that the composition containing glyoxal, water and the respective binder is essentially not subject to fungal attack.
Die erfindungsgemäßen Zusammensetzungen eignen sich wie erwähnt insbesondere zum Imprägnieren von Papier und hier insbesondere zum Imprägnieren von Dekorpapieren. Die dabei verwendbaren Papiere sind nicht besonders beschränkt, allerdings sind Papiere mit einem Aschegehalt von weniger als 18 Gew.-% besonders bevorzugt. Es ist bekannt, daß Papiere mit einem geringen Aschegehalt besonders spaltfest sind. Dementsprechend sind Papiere mit einem Aschegehalt von weniger als 15 Gew.-% und insbesondere weniger als 12 Gew.-% besonders bevorzugt .As mentioned, the compositions according to the invention are particularly suitable for impregnating paper and here in particular for impregnating decorative papers. The papers which can be used are not particularly limited, but papers with an ash content of less than 18% by weight are particularly preferred. It is known that papers with a low ash content are particularly resistant to splitting. Accordingly, papers with an ash content of less than 15% by weight and in particular less than 12% by weight are particularly preferred.
Das Flächengewicht der zu imprägnierenden Papiere ist nicht besonders beschränkt, geeignet sind in jedem Fall Papiere mit einem Flächengewicht von 45 bis 70 g/m2.The weight per unit area of the papers to be impregnated is not particularly limited; papers with a weight per unit area of 45 to 70 g / m 2 are suitable in any case.
Das Papier kann mit der erfindungsgemäßen Zusammensetzung nach üblichen Verfahren getränkt werden. Die dabei pro Quadratmeter Papier aufzubringende Menge hängt davon ab, ob eine Nachimprägnierung oder eine Vorimprägnierung durchgeführt wird. Für beide Vorgehensweisen eignen sich die erfindungsgemäßen Zusammensetzungen gleichermaßen.The paper can be impregnated with the composition according to the invention by customary methods. The per The amount of paper to be applied per square meter depends on whether post-impregnation or pre-impregnation is carried out. The compositions according to the invention are equally suitable for both procedures.
Üblicherweise beträgt der Anteil der Imprägnierung bei Vorimprägnaten 20 bis 24 Gew.-% und bei Nachimprägnaten 25 bis 35 Gew.-% bezogen auf die Trockenmasse des Iprägniermittels. Erfindungsgemäß kann dieser Anteil deutlich vermindert werden. So wurden beispielsweise gute Ergebnisse mit 18 Gew.-% für Nachiprägnate erzielt. Die erfindungsgemäße Zusammensetzung ermöglicht somit auch die Herstellung von recourcenschonenden und preisgünstigeren Dekorpapieren, ohne dabei Abstriche bei der Qualität machen zu müssen.The proportion of impregnation is usually 20 to 24% by weight for pre-impregnates and 25 to 35% by weight for post-impregnates, based on the dry weight of the impregnating agent. According to the invention, this proportion can be significantly reduced. For example, good results with 18% by weight for post-embossing were achieved. The composition according to the invention thus also enables the production of resource-saving and less expensive decorative papers without having to compromise on quality.
Das so imprägnierte Papier läßt sich nach üblichen Verfahren auf verschiedene Substrate, wie etwa Spanplatten, Faserplatten und dergleichen aufkaschieren. Dabei wurde gefunden, daß sich die erfindungsgemäßen Papiere besonders gut verleimen lassen, wobei zum Beispiel Harnstoffleime zum Einsatz kommen können. Diese Eigenschaft ist in der Praxis von großer Bedeutung, da eine gute und schnelle Verleimung hohe Produktionsgeschwindigkeiten ermöglicht .The paper impregnated in this way can be laminated onto various substrates, such as chipboard, fiberboard and the like, using customary methods. It was found that the papers according to the invention can be glued particularly well, for example using urea glue. This property is of great importance in practice, since good and fast gluing enables high production speeds.
BeispieleExamples
Zur Verdeutlichung der Vorteile der vorliegenden Erfindung wurden die folgenden sechs Zusammensetzungen verglichen, die alle auf 30 Gew.-% Feststoffgehalt eingestellt wurden.To demonstrate the advantages of the present invention, the following six compositions were compared, all of which were adjusted to 30 wt% solids.
Tabelle 1Table 1
Licopol ist eine wäßrige Dextrinlösung mit 50 % Trockensubstanz erhältlich von Südstärke GmbH, Schrobenhausen. Acronal S 305 D ist ein n-Butylacrylat- Styrolcopolymer erhältlich von BASF AG, Ludwigshafen (Feststoffgehalt 50 Gew.-%). Das eingesetzte Glyoxal war eine 40 Gew.-% wäßrige Lösung.Licopol is an aqueous dextrin solution with 50% dry matter available from Südstark GmbH, Schrobenhausen. Acronal S 305 D is an n-butyl acrylate-styrene copolymer available from BASF AG, Ludwigshafen (solids content 50% by weight). The glyoxal used was a 40% by weight aqueous solution.
Mit diesen Zusammensetzung wurde ein Dekorpapier, erhältlich von Munksjö, Italien, mit der Nummer 101465 und einem Flächengewicht von 45 g/m2 bei 13 % Aschegehalt und einer Porosität von 24 s, gemessen nach der Gurley-Methode, imprägniert. Die Imprägnierung erfolgte durch Tränken des Papiers in der Imprägnierlösung, Abstreifen überschüssiger Impragnierlösung und Trocknen bei 150°C.With this composition, a decorative paper, available from Munksjö, Italy, with the number 101465 and a basis weight of 45 g / m 2 at 13% ash content and a porosity of 24 s, measured according to the Gurley method, was impregnated. The impregnation was carried out by soaking the paper in the impregnation solution, wiping off excess impregnation solution and drying at 150 ° C.
Danach betrug der Gehalt an Imprägniermittel in dem imprägnierten Papier 25 ± 2 Gew.-% und lag damit im Grenzbereich von Vor- und Nachimprägnaten. Während der Tränkung wurde beobachtet, wie gut die Impragnierlösung vom Papier aufgenommen wurde. Die Ergebnisse sind in Tabelle 2 angegeben.Thereafter, the impregnating agent content in the impregnated paper was 25 ± 2% by weight and was therefore in the borderline range of pre- and post-impregnates. During the impregnation, it was observed how well the impregnating solution was absorbed by the paper. The results are shown in Table 2.
Anschließend wurden die so imprägnierten Papiere mit einem säurehärtbaren Aminoplastlack (entsprechend Typ 9944.61, erhältlich von Plantag Chemie, Detmold) lackiert. Dann wurden die Papiere bei 160°C getrocknet. Anschließend wurde die Oberfläche untersucht und der Glanz mit einem Ericsson Glossmeter unter einem Winkel von 60°C untersucht. Weiterhin wurde die Flexibilität der imprägnierten und lackierten Papiere durch Falten untersucht . Wenn das Papier beim Falten brach, wurde es als brüchig eingestuft.The papers impregnated in this way were then coated with an acid-curable aminoplast lacquer (corresponding to type 9944.61, available from Plantag Chemie, Detmold). Then the papers were dried at 160 ° C. The surface was then examined and the gloss was examined using an Ericsson glossmeter at an angle of 60 ° C. Farther the flexibility of the impregnated and varnished papers by folding was examined. If the paper broke when folded, it was classified as fragile.
Weiterhin wurde die Farbe des Papiers relativ zur Probe Nr. 2 bestimmt. Diese Messungen wurden mit einem Datacolor Spectrophotometer bei 10°, das heißt, der normalen Betrachtereinstellung, untersucht .Furthermore, the color of the paper was determined relative to sample No. 2. These measurements were examined with a Datacolor Spectrophotometer at 10 °, that is, the normal viewer setting.
Nach dem Imprägnieren und Lackieren wurde ferner die Spaltfestigkeit der Papiere untersucht. Dazu wurde eine Probe mittels eines Aminoplast-Klebstoffes auf eine Spanplatte flächig aufgeklebt, wobei ein Teil des Papieres über die Kante der Spanplatte um mindestens 20 mm in der cross grain Richtung hinausragte. Die Klebetemperatur betrug 145°C und es wurde 15 s mit 10 N/cm angedrückt. Nach dem Aufkleben wurde der überstehende Teil des Papiers in 2 cm Abständen eingeschnitten, so daß 2 x 2 cm große Überstände entstanden. Diese Überstände wurden dann unter einem Winkel von 45° rasch in Richtung der Kante der Spanplatte gezogen. Dieser Test wurde sowohl direkt nach der Imprägnierung, also zu einem Zeitpunkt, zu dem die Temperatur etwa 90°C betrug, und nach dem Abkühlen auf Raumtemperatur durchgeführt. Die dabei entstehenden Einrisse in dem mit dem Substrat verbundenen Teil des Papiers wurden von der Kante aus gemessen. After impregnation and varnishing, the splitting strength of the papers was also examined. For this purpose, a sample was adhered to a particle board by means of an aminoplast adhesive, part of the paper protruding beyond the edge of the particle board by at least 20 mm in the cross grain direction. The adhesive temperature was 145 ° C. and the pressure was applied at 10 N / cm for 15 s. After gluing, the protruding part of the paper was cut at 2 cm intervals, so that 2 x 2 cm protrusions were formed. These supernatants were then quickly pulled towards the edge of the particle board at an angle of 45 °. This test was carried out both immediately after the impregnation, that is to say at a point in time at which the temperature was approximately 90 ° C., and after cooling to room temperature. The resulting tears in the part of the paper connected to the substrate were measured from the edge.
Tabelle 2Table 2
1) Zusammensetzung 2 als Standart 1) Composition 2 as a standard
Die vorstehenden Ergebnisse zeigen, daß die erfindungsgemäße Formulierung 4 unerwartet gute Gesamteigenschaften zeigt, die nicht erhalten werden können, wenn nur zwei Komponenten oder nur eine der erfindungsgemäßen Komponenten verwendet werden. Hervorzuheben ist insbesondere die hohe Spaltfestigkeit, der gute Oberflächenglanz und die gute Flexibilität der erfindungsgemäß imprägnierten Papiere. The above results show that formulation 4 according to the invention shows unexpectedly good overall properties which cannot be obtained if only two components or only one of the components according to the invention are used. Particularly noteworthy is the high splitting resistance, the good surface gloss and the good flexibility of the papers impregnated according to the invention.

Claims

P A T E N T AN S P R Ü C H E PATENT TO SPEECH
1. Zusammensetzung, insbesondere zum Imprägnieren von Papier, enthaltend ein Bindemittel, eine wäßrige Polymerdispersion und Glyoxal.1. Composition, in particular for impregnating paper, containing a binder, an aqueous polymer dispersion and glyoxal.
2. Zusammensetzung gemäß Anspruch 1, bei der das Bindemittel Stärke und/oder Stärkederivate enthält .2. The composition of claim 1, wherein the binder contains starch and / or starch derivatives.
3. Zusammensetzung gemäß Anspruch 2, bei der das Bindemittel Dextrin enthält.3. The composition of claim 2, wherein the binder contains dextrin.
4. Zusammensetzung gemäß einem der Ansprüche 1 bis 3, bei der die wäßrige Polymerdispersion wenigstens ein (Meth) acrylatpolymer enthält .4. The composition according to any one of claims 1 to 3, wherein the aqueous polymer dispersion contains at least one (meth) acrylate polymer.
5. Verfahren zur Herstellung einer Zusammensetzung gemäß einem der vorstehenden Ansprüche, bei dem das Glyoxal mit Wasser vorgelegt, das Bindemittel zugegeben und die erhaltene Mischung schließlich mit der Polymerdispersion versetzt wird.5. A process for the preparation of a composition according to any one of the preceding claims, in which the glyoxal is initially charged with water, the binder is added, and the mixture obtained is finally mixed with the polymer dispersion.
6. Zusammensetzung zur Verwendung in einem Verfahren nach Anspruch 5, enthaltend Glyoxal, Wasser und ein Bindemittel .6. A composition for use in a process according to claim 5, containing glyoxal, water and a binder.
7. Verfahren zum Imprägnieren von Papier, umfassend das Aufbringen einer Zusammensetzung gemäß einem der Ansprüche 1 bis 4 auf ein Papiersubstrat .7. A method for impregnating paper, comprising applying a composition according to any one of claims 1 to 4 to a paper substrate.
8. Imprägniertes Papier, erhältlich nach dem Verfahren gemäß Anspruch 7. 8. Impregnated paper, obtainable by the process according to claim 7.
9. Verwendung eines imprägniertes Papier gemäß Anspruch 8 zur Gestaltung von Oberflächen.9. Use of an impregnated paper according to claim 8 for the design of surfaces.
10. Laminat, umfassend ein imprägniertes Papier gemäß Anspruch 8 und ein Substrat . 10. Laminate comprising an impregnated paper according to claim 8 and a substrate.
EP00936879A 1999-06-11 2000-06-13 Composition for the impregnation of paper, method for the production thereof, impregnated paper and laminate comprising said impregnated paper Withdrawn EP1203120A1 (en)

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US20050019569A1 (en) * 2003-07-25 2005-01-27 Weyerhaeuser Company Glyoxal crosslinked cellulosic fibers having improved brightness and color
DE102007030102B4 (en) 2007-06-28 2019-10-31 Schoeller Technocell Gmbh & Co. Kg prepreg
AU2008337508B2 (en) 2007-12-17 2012-03-15 Technocell Dekor Gmbh & Co. Kg Compressible decorative paper impregnating agent which can be printed by the inkjet method
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ES2385766T3 (en) * 2008-04-03 2012-07-31 Basf Se Coating or agglutination formulations of paper and methods for making and using them
US8613834B2 (en) * 2008-04-03 2013-12-24 Basf Se Paper coating or binding formulations and methods of making and using same
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