EP0013698B1 - Process for the production of reinforced, resin-impregnated sheets by saturation of a fibrous web, and sheets so obtained - Google Patents

Process for the production of reinforced, resin-impregnated sheets by saturation of a fibrous web, and sheets so obtained Download PDF

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Publication number
EP0013698B1
EP0013698B1 EP79104248A EP79104248A EP0013698B1 EP 0013698 B1 EP0013698 B1 EP 0013698B1 EP 79104248 A EP79104248 A EP 79104248A EP 79104248 A EP79104248 A EP 79104248A EP 0013698 B1 EP0013698 B1 EP 0013698B1
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EP
European Patent Office
Prior art keywords
synthetic resin
resin dispersion
linking
resin
acrylic
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Expired
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EP79104248A
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German (de)
French (fr)
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EP0013698A1 (en
Inventor
Helmut Dr. Moroff
Hanns Dr. Bössler
Hans Hauser
Gerhard Ladisich
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Roehm GmbH Darmstadt
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Roehm GmbH Darmstadt
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • 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
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
    • D21H17/45—Nitrogen-containing groups
    • 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
    • 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
    • D21H17/375—Poly(meth)acrylamide
    • 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
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/47—Condensation polymers of aldehydes or ketones
    • D21H17/49—Condensation polymers of aldehydes or ketones with compounds containing hydrogen bound to nitrogen
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/3188—Next to cellulosic
    • Y10T428/31895—Paper or wood
    • Y10T428/31906—Ester, halide or nitrile of addition polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31942—Of aldehyde or ketone condensation product
    • Y10T428/31949—Next to cellulosic
    • Y10T428/31964—Paper
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/259—Coating or impregnation provides protection from radiation [e.g., U.V., visible light, I.R., micscheme-change-itemave, high energy particle, etc.] or heat retention thru radiation absorption
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2631—Coating or impregnation provides heat or fire protection
    • Y10T442/2721—Nitrogen containing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/273—Coating or impregnation provides wear or abrasion resistance

Definitions

  • thermoplastic materials By impregnating paper, non-woven fabrics and other fibrous fabrics (textiles) with thermoplastic materials, films can be produced that are characterized by tempered surfaces and improved mechanical properties.
  • plastic-impregnated paper foils decorative foils are used for the surface finishing of wood and other suitable materials.
  • DE-A-2 135 072 recommends a process for producing high-gloss surfaces of decorative papers, in which a decorative base paper is impregnated or coated with a filler-free mixture of a thermoplastic and a self-crosslinking, aqueous dispersion based on acrylate, then dried and coated with a high-gloss polish Calendered roll at a temperature between 120 and 180 ° C.
  • linear polymers with repeating N-methylolamide units and with these groups capable of reaction are suitable, preferably in the form of aqueous dispersions in a mixture with thermosetting aminoplast resins, for impregnating or coating nonwoven fabrics.
  • DE-B-16 19 228 relates to a process for the continuous production of nonwoven or nonwoven fabrics impregnated with polymers and heat-cured under pressure.
  • the substrates are continuously impregnated with a mixture of self-crosslinking group-containing acrylic ester polymers or copolymers and thermosetting polymers, the proportion of thermosetting polymers in the impregnating agent being between 5 and 50 percent by weight, and the impregnated nonwovens or woven fabrics are then continuously cured in a heated calender.
  • Impregnated foils of the type mentioned above should, in order to be suitable as decorative foils, preferably have a closed surface, a high tear resistance, sufficient dimensional stability, high resistance, especially against thermal stress and against solvents, and good adhesiveness.
  • thermoplastic polymer can have a relatively great influence on the quality of the finished film.
  • high-quality reinforced films can be obtained by impregnating raw paper or nonwoven fabric with a mixture which on the one hand contains a commercially available, water-soluble urea resin and, on the other hand, an aqueous synthetic resin dispersion with very finely divided particles, the synthetic resin dispersion in the interest of processability and the surface design of the film is still thermoplastically deformable and uncrosslinked at the start of drying, and the crosslinking with the urea resin is brought about by the further heat treatment.
  • these are aqueous dispersions of polymers which have crosslinkable groups which, however, do not self-crosslink under the conditions to be used.
  • the monomers suitable as building blocks of the synthetic resin dispersions to be used according to the invention therefore have the prerequisite that they can react with added (external) reactive units.
  • Such building blocks accessible to external crosslinking are, for example, monomers containing hydroxyl, amino, amide or carboxyl functions.
  • the polymers or copolymers in question are otherwise prepared, for example, on the basis of vinyl esters of lower carboxylic acids, for example having 2 to 4 carbon atoms, such as vinyl acetate, of butadiene or chlorobutadiene with styrene and / or (meth) acrylate esters.
  • suitable dispersions are composed, for example, of olefins, vinyl chloride, vinylidene chloride, styrene or the mixtures of these monomers with one another or with further modifying comonomers, such as, for example, vinyl ethers.
  • a preferred class of dispersions consists of the esters of acrylic and / or methacrylic acid with e, to C 20 alcohols, preferably with C 1 to C 8 alcohols, preferably esters of alcohols with 1 to 4 C atoms, the main amount of the plastic.
  • acrylic and methacrylic acid for example, come as modifying comonomers accessible to external crosslinking.
  • the acrylic and methacrylamide in question. as well as hydroxy and amino alkyl esters of (meth) acrylic acid, which are represented by the formula wherein A is an optionally branched alkyl radical having 2 to 6 carbon atoms, Z is OH.
  • R represents hydrogen or a methyl radical and R, represents hydrogen or an alkyl radical with 1 to 8 carbon atoms, can be played.
  • the proportion of the above-described monomers accessible to external crosslinking is generally 0.5 to 15% by weight, preferably 2-10% by weight, based on the total polymer.
  • acrylic resin dispersions which are composed of methyl methacrylate, a (meth) acrylic ester of an alcohol having 2 to 8 carbon atoms, methacrylic acid amide and methacrylic acid are preferred.
  • the selection and amount of the (meth) acrylic esters of C 2 -C 8 alcohols depend on the desired flexibility of the reinforced film.
  • the preparation of the dispersions to be used according to the invention is known per se; it can be carried out, for example, in accordance with DE-A-1804159.3.
  • the production process is expediently carried out in such a way that a finely divided polymer, i.e. is obtained with a particle radius below 100 nm.
  • aminoplasts provided as the second component of the impregnation mixture according to the invention for impregnating raw papers or nonwovens are the usual precondensates made from urea-formaldehyde (cf. K. Lindner in “Tenside-Textile Aid-Detergent Raw Materials”, Stuttgart 1964, pp. 244-258 ), of which various types are commercially available.
  • the impregnation mixture according to the invention contains the aqueous synthetic resin dispersion of the type described above and the water-soluble aminoplast resin in comparable proportions, for example in a ratio of 10: 1 to 1:10, preferably about 1: 1, calculated in each case on a dry substrate.
  • the soaking liquors generally contain 25 to 60% by weight of total solid (dry content), preferably 35 to 45% by weight.
  • the base papers or nonwoven fabrics can optionally be pretreated in a suitable manner, for example in the manner recommended in DE-B-17 71 903 by pre-impregnation with a polycationic compound or their addition in the manufacture of the base paper.
  • the impregnation liquor can be applied in a manner known per se, for example by leading the paper or nonwoven web through a trough filled with the liquor * .
  • the webs can also be sufficiently impregnated by roller application, spraying or knife application.
  • the amount of resin to be applied can be conveniently adjusted via the concentration and / or viscosity of the soaking liquor. Depending on the requirements of the field of application and the desired final quality, it is usually between 20-150% by weight, preferably 30-80% by weight of the substrate material.
  • the drying process can be directly connected to the treatment with the drinking liquor.
  • the acrylic resin dispersions can be produced by known processes, for example by the emulsion feed process.
  • part of the monomers can be initially emulsified in an aqueous medium and the remaining part of the monomers can be added to the reaction mixture in the form of an aqueous emulsion as the polymerization progresses.
  • the usual anionic, cationic or non-ionic surfactants can be used as emulsifiers. If polycations have been applied to the paper in accordance with DE-B-1771 903 prior to the impregnation, it is advantageous to work with anionic dispersions.
  • suitable anionic surfactants are the sulfuric acid semiesters of higher alcohols.
  • the commercially available, water-soluble per compounds for example hydrogen peroxide and / or alkali metal or ammonium persulfates, may be used as initiators, if appropriate in combination with reducing components (redox systems).
  • reducing components redox systems
  • the reaction temperatures range between room temperature and the boiling point of the systems.
  • the impregnation with the soaking liquor can be carried out by means of an impregnation unit, in which the continuous paper or fiber web is first pre-impregnated by roller application. To vent the pre-soaked web, it is then passed over a so-called breathing distance (dwell time: several seconds). After the air has been removed from the web in this way, the complete impregnation can be carried out in the immersion bath. The excess liquor is then squeezed or stripped off between rollers or doctor blades, thus achieving the desired dosage of the resin layer. For special cases in which particularly good impregnation or one-sided impregnation is desired, a procedure according to DE-A-25 50 980 using a vacuum suction device is appropriate.
  • the impregnated web is passed through a dryer with one or preferably several drying fields without contact.
  • the transport speed of the train depends on the length of the field or fields and the drying temperature.
  • the drying temperature is generally between 60 and 200 ° C. If there are several dry fields, it is advisable to work with graduated temperatures - starting with the lowest temperature. Jet floating dryers are advantageously used as the non-contact drying system.
  • a Paint application device for painting be attached.
  • a suitable sealable adhesive can also be applied using a suitable device, if necessary in a combined procedure.
  • the finished web can then be cut to the desired format or wound up as a roll.
  • the films produced according to the invention are distinguished by their excellent quality.
  • the closed, smooth surface, high resistance to splitting and tearing, high resistance to light and aging, resistance to aggressive substances, heat resistance, easy maintenance and good adhesion can be emphasized. If a matt or semi-matt surface is desired, suitable matting agents can be easily added to the soaking solution.
  • the mixture is kept at this temperature, 0.4 g of potassium persulfate dissolved in 10 g of water are added and 4 minutes later the addition of a previously prepared emulsion of 480 g of water, 7.3 g of sodium dodecyl sulfate, 1.2 g of potassium persulfate and 471 g of ethyl acrylate is started. 251.2 g methyl methacrylate, 15.7 g methacrylic acid and 47.1 g methacrylamide. After the addition (addition time 4 hours), the mixture is kept at 80 ° C. for 1 hour and then cooled to 25 ° C. A 35% aqueous solution of a condensation product of isononylphenol and ethylene oxide (molar ratio 1 50) is then added within 45 minutes and any small amounts of coagulum formed are filtered off through a fine sieve.
  • Example 2 The procedure is as in Example 1, except that 13.2 g of ethyl acrylate and 1.2 g of 2-hydroxyethyl acrylate are used in the initial charge and 722.2 g of ethyl acrylate and 62.8 g of 2-hydroxyethyl acrylate are used in the feed.
  • Absorbent decorative base paper with a basis weight of 80 g / m 2 is in an impregnation liquor consisting of 500 g of the dispersion described in Example 1, 500 g of urea formaldehyde resin (trade name Kautit 420® *. Solids content 50%), 250 g of water and 2 g of ammonium chloride and 2 g Impregnating agent (weakly sulfated beet oil) impregnated in a watering trough.
  • the impregnation is carried out by placing the base paper on the liquor surface for wetting and then immersing it completely.
  • the impregnated paper is then squeezed between two rubber rollers and dried in a drying cabinet at 140 ° C. for 3 minutes.
  • a medium-hard flexible film with a final weight of 124 g / m 2 , a residual moisture content of 4% and a resin quantity of 42.5% (based on the weight of the base paper) is obtained.
  • Example 4 The procedure is as in Example 4, but the impregnation liquor consists of 700 g of dispersion from Example 2, 300 g of urea formaldehyde resin (50% solids content), 250 g of water and 1.5 g of ammonium chloride and 2 g of the wetting agent described in Example 4.
  • the film produced in this way has a highly flexible character (wrapping film), the amount of resin is 41%, the final weight 112.8 g and the residual moisture 5%.
  • An absorbent base paper basis weight 200 gim 2 , is impregnated and further treated in an impregnation liquor which consists of 1,000 g of the dispersion described in Example 3, 600 g of urea formaldehyde (50% solids content), 1.5 ammonium chloride and 3 g of wetting agent .
  • the end product corresponds to a film that is used as edge banding in the furniture and chipboard industry, it has a resin content of 38%, a residual moisture content of 5% and a final weight of 276 g / m 2 .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
  • Laminated Bodies (AREA)
  • Reinforced Plastic Materials (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Description

Durch Imprägnierung von Papieren, Faservliesen und anderen faserhaltigen Flächengebilden (Textilien) mit thermoplastischen Kunststoffen können Folien hergestellt werden, die sich durch vergütete Oberflächen und verbesserte mechanische Eigenschaften auszeichnen. In beträchtlichem Umfang werden insbesondere kunststoffimprägnierte Papierfolien (Dekorfolien) zur Oberflächenveredelung von Holz- und anderen geeigneten Werkstoffen verwendet.By impregnating paper, non-woven fabrics and other fibrous fabrics (textiles) with thermoplastic materials, films can be produced that are characterized by tempered surfaces and improved mechanical properties. In particular, plastic-impregnated paper foils (decorative foils) are used for the surface finishing of wood and other suitable materials.

In der DE-A-2 135 072 wird ein Verfahren zur Herstellung hochglänzender Oberflächen von Dekorpapieren empfohlen, bei dem man ein Dekorrohpapier mit einer füllstofffreien Mischung aus einer thermoplastischen und einer selbstvernetzenden, wäßrigen Dispersion auf Acrylatbasis tränkt oder beschichtet, anschließend trocknet und mit einer hochglanzpolierten Walze bei einer Temperatur zwischen 120 und 180 °C kalandriert.DE-A-2 135 072 recommends a process for producing high-gloss surfaces of decorative papers, in which a decorative base paper is impregnated or coated with a filler-free mixture of a thermoplastic and a self-crosslinking, aqueous dispersion based on acrylate, then dried and coated with a high-gloss polish Calendered roll at a temperature between 120 and 180 ° C.

Nach der Lehre der GB-A-998 188 eignen sich lineare Polymerisate mit sich wiederholenden N-Methylolamideinheiten und mit diesen zur Reaktion befähigten Gruppen vorzugsweise in Form wäßriger Dispersionen im Gemisch mit wärmehärtenden Aminoplastharzen zum Imprägnieren bzw. Beschichten von Faservliesen.According to the teaching of GB-A-998 188, linear polymers with repeating N-methylolamide units and with these groups capable of reaction are suitable, preferably in the form of aqueous dispersions in a mixture with thermosetting aminoplast resins, for impregnating or coating nonwoven fabrics.

Die DE-B-16 19 228 hat ein Verfahren zur kontinuierlichen Herstellung von mit Polymeren imprägnierten und unter Druck wärmegehärteten Faservliesen oder -geweben zum Gegenstand. Dabei werden die Substrate mit einem Gemisch aus selbstvernetzenden Gruppen enthaltenden Acrylesterpolymerisaten oder -copolymerisaten und wärmehärtbaren Polymeren, wobei der Anteil an wärmehärtbaren Polymeren im lmprägniermittel zwischen 5 und 50 Gewichtsprozent liegt, kontinuierlich imprägniert und die imprägnierten Vliese oder Gewebe anschließend kontinuierlich in einem beheizten Kalander gehärtet. Imprägnierte Folien der oben genannten Art sollen, um als Dekorfolien geeignet zu sein, möglichst eine geschlossene Oberfläche, eine hohe Weiterreißfestigkeit, ausreichende Formstabilität, hohe Beständigkeit,e insbesondere gegenüber thermischer Beanspruchung und gegenüber Lösungsmitteln und gute Verklebbarkeit aufweisen.DE-B-16 19 228 relates to a process for the continuous production of nonwoven or nonwoven fabrics impregnated with polymers and heat-cured under pressure. The substrates are continuously impregnated with a mixture of self-crosslinking group-containing acrylic ester polymers or copolymers and thermosetting polymers, the proportion of thermosetting polymers in the impregnating agent being between 5 and 50 percent by weight, and the impregnated nonwovens or woven fabrics are then continuously cured in a heated calender. Impregnated foils of the type mentioned above should, in order to be suitable as decorative foils, preferably have a closed surface, a high tear resistance, sufficient dimensional stability, high resistance, especially against thermal stress and against solvents, and good adhesiveness.

Die Verfahren und die Produkte des Standes der Technik können nicht in vollem Umfange befriedigen. So kommt beispielsweise der Frage der Haltbarkeit der Tränkflotten eine nicht zu unterschätzende praktische Bedeutung zu. Zu beachten ist dabei zum Beispiel die Tendenz der Vorkondensate (Harnstoff- und/oder Melaminharze) zur vorzeitigen Kondensation. Dieser Umstand spielt naturgemäß bei höheren Temperaturen, also bei heißer Witterung und in den entsprechenden klimatischen Zonen eine besondere Rolle. Tränkflotten gemäß der vorliegenden Erfindung zeichnen sich hingegen durch eine mehrtägige Lagerfähigkeit auch bei hohen Temperaturen in den Arbeitsräumen aus.The methods and the products of the prior art cannot fully satisfy. For example, the question of the durability of the drinking liquor is of practical importance that should not be underestimated. Note, for example, the tendency of the pre-condensates (urea and / or melamine resins) to condense prematurely. This fact naturally plays a special role at higher temperatures, i.e. in hot weather and in the corresponding climatic zones. Drinking liquors according to the present invention, on the other hand, are characterized by a shelf life of several days even at high temperatures in the workrooms.

Es hat sich herausgestellt, daß die Partikelgröße des thermoplastischen Polymerisats von relativ großem Einfluß auf die Qualität der fertigen Folie sein kann.It has been found that the particle size of the thermoplastic polymer can have a relatively great influence on the quality of the finished film.

Es wurde nun gefunden, daß man hochwertige verstärkte Folien erhalten kann, wenn man Rohpapiere bzw. Faservliese mit einer Mischung tränkt, die einerseits ein handelsübliches, wasserlösliches Harnstoffharz, zum anderen eine wäßrige Kunstharzdispersion mit sehr feinteiligen Partikeln enthält, wobei die Kunstharzdispersion im Interesse der Verarbeitbarkeit und der Oberflächengestaltung der Folie zu Beginn der Trocknung noch thermoplastisch verformbar und unvernetzt vorliegt und die Vernetzung mit dem Harnstoffharz durch die weitere Wärmebehandlung bewirkt wird.It has now been found that high-quality reinforced films can be obtained by impregnating raw paper or nonwoven fabric with a mixture which on the one hand contains a commercially available, water-soluble urea resin and, on the other hand, an aqueous synthetic resin dispersion with very finely divided particles, the synthetic resin dispersion in the interest of processability and the surface design of the film is still thermoplastically deformable and uncrosslinked at the start of drying, and the crosslinking with the urea resin is brought about by the further heat treatment.

Erfindungsgemäß handelt es sich somit um wäßrige Dispersionen von Polymeren, die vernetzungsfähige, jedoch unter den anzuwendenden Bedingungen nicht selbstvernetzende Gruppen aufweisen. Die als Bausteine der erfindungsgemäß zu verwendenden Kunstharzdispersionen geeigneten Monomeren haben demnach zur Voraussetzung, daß sie mit zugesetzten (externen) reaktiven Einheiten reagieren können. Solche der Fremdvernetzung zugänglichen Bausteine sind z.B. Hydroxy-, Amino-, Amid-, bzw. Carboxylfunktionen enthaltende Monomere. Die infrage kommenden Polymerisate bzw. Copolymerisate sind im übrigen beispielsweise auf der Basis von Vinylestern niederer Carbonsäuren, beispielsweise mit 2 bis 4 Kohlenstoffatomen, wie z.B. Vinylacetat, von Butadien bzw. Chlorbutadien mit Styrol und/oder (Meth)acrylatestern hergestellt. Andere geeignete Dispersionen sind z.B. aus Olefinen, Vinylchlorid, Vinylidenchlorid, Styrol oder den Gemischen dieser Monomeren untereinander oder mit weiteren modifizierenden Comonomeren, wie z.B. Vinyläthern aufgebaut. Eine bevorzugte Klasse von Dispersionen besteht aus den Estern der Acryl- und/oder der Methacrylsäure mit e, bis C20-Alkoholen, vorzugsweise mit C1 bis C8-Alkoholen, wobei bevorzugt Ester von Alkoholen mit 1 bis 4 C-Atomen die Hauptmenge des Kunststoffs bilden. Wie bereits ausgeführt, kommen als modifizierende, der Fremdvernetzung zugänglichen Comonomere beispielsweise die Acryl- und die Methacrylsäure. das Acryl- und das Methacrylamid infrage. sowie Hydroxy- und Aminoalkylester der (Meth)acrylsäure, die durch die Formel

Figure imgb0001
worin A für einen gegebenenfalls verzweigten Alkylrest mit 2 bis 6 Kohlenstoffatomen, Z für OH . oder NHR, und R für Wasserstoff oder einen Methylrest und R, für Wasserstoff oder einen Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wiedergegeben werden können. Der Anteil der vorstehend beschriebenen, der Fremdvernetzung zugänglichen Monomeren beträgt in der Regel 0,5 bis 15 Gew.-%, vorzugsweise 2-10 Gew.-%, bezogen auf das Gesamtpolymerisat.According to the invention, these are aqueous dispersions of polymers which have crosslinkable groups which, however, do not self-crosslink under the conditions to be used. The monomers suitable as building blocks of the synthetic resin dispersions to be used according to the invention therefore have the prerequisite that they can react with added (external) reactive units. Such building blocks accessible to external crosslinking are, for example, monomers containing hydroxyl, amino, amide or carboxyl functions. The polymers or copolymers in question are otherwise prepared, for example, on the basis of vinyl esters of lower carboxylic acids, for example having 2 to 4 carbon atoms, such as vinyl acetate, of butadiene or chlorobutadiene with styrene and / or (meth) acrylate esters. Other suitable dispersions are composed, for example, of olefins, vinyl chloride, vinylidene chloride, styrene or the mixtures of these monomers with one another or with further modifying comonomers, such as, for example, vinyl ethers. A preferred class of dispersions consists of the esters of acrylic and / or methacrylic acid with e, to C 20 alcohols, preferably with C 1 to C 8 alcohols, preferably esters of alcohols with 1 to 4 C atoms, the main amount of the plastic. As already stated, acrylic and methacrylic acid, for example, come as modifying comonomers accessible to external crosslinking. the acrylic and methacrylamide in question. as well as hydroxy and amino alkyl esters of (meth) acrylic acid, which are represented by the formula
Figure imgb0001
 wherein A is an optionally branched alkyl radical having 2 to 6 carbon atoms, Z is OH. or NHR, and R represents hydrogen or a methyl radical and R, represents hydrogen or an alkyl radical with 1 to 8 carbon atoms, can be played. The proportion of the above-described monomers accessible to external crosslinking is generally 0.5 to 15% by weight, preferably 2-10% by weight, based on the total polymer.

Bevorzugt sind beispielsweise Acrylharzdispersionen, die aus Methylmethacrylat, einem (Meth)acrylester eines Alkohols mit 2 bis 8 Kohlenstoffatomen, Methacrylsäureamid und Methacrylsäure aufgebaut sind. Auswahl und Menge der (Meth)-Acrylester von C2-C8-Alkoholen richten sich nach der gewünschten Flexibilität der verstärkten Folie.For example, acrylic resin dispersions which are composed of methyl methacrylate, a (meth) acrylic ester of an alcohol having 2 to 8 carbon atoms, methacrylic acid amide and methacrylic acid are preferred. The selection and amount of the (meth) acrylic esters of C 2 -C 8 alcohols depend on the desired flexibility of the reinforced film.

Die Herstellung der erfindungsgemäß zu verwendenden Dispersionen ist an sich bekannt, sie kann beispielsweise in Anlehnung an die DE-A-1804159.3 vorgenommen werden. Zweckmäßigerweise wird das Herstellungsverfahren in der Weise durchgeführt, daß ein feinteiliges Polymerisat, d.h. mit einem Teilchenradius unter 100 nm erhalten wird.The preparation of the dispersions to be used according to the invention is known per se; it can be carried out, for example, in accordance with DE-A-1804159.3. The production process is expediently carried out in such a way that a finely divided polymer, i.e. is obtained with a particle radius below 100 nm.

Die als zweite Komponente der erfindungsgemäßen Tränkmischung zum Tränken von Rohpapieren bzw. Faservliesen vorgesehenen Aminoplaste sind die üblichen Vorkondensate aus Harnstoff-Formaldehyd (vgl. K. Lindner in « Tenside-Textilhilfsmittel-Waschrohstoffe • , wissenschaftliche Verlagsgesellschaft, Stuttgart 1964, S. 244-258), von denen verschiedene Typen im Handel erhältlich sind.The aminoplasts provided as the second component of the impregnation mixture according to the invention for impregnating raw papers or nonwovens are the usual precondensates made from urea-formaldehyde (cf. K. Lindner in “Tenside-Textile Aid-Detergent Raw Materials”, Wissenschaftliche Verlagsgesellschaft, Stuttgart 1964, pp. 244-258 ), of which various types are commercially available.

Als Substrate der Tränkung kommen handelsübliche Dekorrohpapiere mit den üblichen Flächengewichten von 30-400 g/m2 infrage. Die erfindungsgemäße Tränkmischung enthält die wäßrige Kunstharzdispersion der vorstehend beschriebenen Art und das wasserlösliche Aminoplastharz in vergleichbaren Mengenanteilen, beispielsweise im Verhältnis 10 : 1 bis 1 : 10, vorzugsweise etwa 1 : 1, berechnet jeweils auf Trockensubstrat. Die Tränkflotten enthalten in der Regel 25 bis 60 Gew.-% an Gesamtfeststoff (Trockengehalt), vorzugsweise 35 bis 45 Gew.-%.Commercially available decorative base papers with the usual basis weights of 30-400 g / m 2 are suitable as substrates for the impregnation. The impregnation mixture according to the invention contains the aqueous synthetic resin dispersion of the type described above and the water-soluble aminoplast resin in comparable proportions, for example in a ratio of 10: 1 to 1:10, preferably about 1: 1, calculated in each case on a dry substrate. The soaking liquors generally contain 25 to 60% by weight of total solid (dry content), preferably 35 to 45% by weight.

Vor dem Aufbringen der Dispersion können die Rohpapiere bzw. Faservliese gegebenenfalls in geeigneter Weise vorbehandelt sein, beispielsweise nach der in der DE-B-17 71 903 empfohlenen Art durch Vorimprägnierung mit einer polykationischen Verbindung oder deren Zugabe bei der Rohpapierherstellung.Before the dispersion is applied, the base papers or nonwoven fabrics can optionally be pretreated in a suitable manner, for example in the manner recommended in DE-B-17 71 903 by pre-impregnation with a polycationic compound or their addition in the manufacture of the base paper.

Das Aufbringen der Tränkflotte kann in an sich bekannter Weise erfolgen, beispielsweise indem man die Papier- oder Faservliesbahn durch einen mit der Flotte* gefüllten Trog führt. Auch durch Walzenantrag, Aufsprühen oder Aufrakeln können die Bahnen ausreichend getränkt werden. Die aufzubringende Harzmenge läßt sich dabei über die Konzentration und/oder Viskosität der Tränkflotte bequem einstellen. Sie liegt in Abhängigkeit von den Erfordernissen des Anwendungsgebiets und der gewünschten Endqualität, gewöhnlich zwischen 20-150 Gew.-%,
vorzugsweise 30-80 Gew.-% des Substratmaterials. Die Trocknung kann unmittelbar an die Behandlung mit der Tränkflotte angeschlossen werden.The impregnation liquor can be applied in a manner known per se, for example by leading the paper or nonwoven web through a trough filled with the liquor * . The webs can also be sufficiently impregnated by roller application, spraying or knife application. The amount of resin to be applied can be conveniently adjusted via the concentration and / or viscosity of the soaking liquor. Depending on the requirements of the field of application and the desired final quality, it is usually between 20-150% by weight,
preferably 30-80% by weight of the substrate material. The drying process can be directly connected to the treatment with the drinking liquor.

- * (enthaltend die Dispersion und das Kondensationsharz)- * (containing the dispersion and the condensation resin)

Wie bereits ausgeführt, können die Acrylharzdispersionen nach bekannten Verfahren, beispielsweise nach dem Emulsionszulaufverfahren hergestellt werden.As already stated, the acrylic resin dispersions can be produced by known processes, for example by the emulsion feed process.

Dabei kann beispielsweise ein Teil der Monomeren in wäßrigem Medium emulgiert vorgelegt und der restliche Teil der Monomeren in Form einer wäßrigen Emulsion mit fortschreitender Polymerisation dem Reaktionsansatz zugefügt werden. Als Emulgatoren können die üblichen anionischen, kationischen bzw. nicht-ionischen Tenside benutzt werden. Falls Polykationen vor der Tränkung entsprechend DE-B-1771 903 auf das Papier aufgebracht worden sind, sollte vorteilhaft mit anionischen Dispersionen gearbeitet werden. Als anionische Tenside bieten sich beispielsweise die Schwefelsäurehalbester von höheren Alkoholen an. Als Initiatoren können beispielsweise die handelsüblichen, wasserlöslichen Perverbindungen angewendet werden, beispielsweise Wasserstoffperoxid und/oder Alkali- bzw. Ammoniumpersulfate, gegebenenfalls in Kombination mit reduzierenden Komponenten (Redoxsysteme). Die Reaktionstemperaturen bewegen sich je nach Initiator und Monomeren zwischen Raumtemperatur und dem Siedepunkt der Systeme.For example, part of the monomers can be initially emulsified in an aqueous medium and the remaining part of the monomers can be added to the reaction mixture in the form of an aqueous emulsion as the polymerization progresses. The usual anionic, cationic or non-ionic surfactants can be used as emulsifiers. If polycations have been applied to the paper in accordance with DE-B-1771 903 prior to the impregnation, it is advantageous to work with anionic dispersions. Examples of suitable anionic surfactants are the sulfuric acid semiesters of higher alcohols. The commercially available, water-soluble per compounds, for example hydrogen peroxide and / or alkali metal or ammonium persulfates, may be used as initiators, if appropriate in combination with reducing components (redox systems). Depending on the initiator and monomers, the reaction temperatures range between room temperature and the boiling point of the systems.

Die Imprägnierung mit der Tränkflotte kann gemäß einer besonders bewährten Ausführungsform mittels eines Imprägnierwerks vorgenommen werden, in dem die durchlaufende Papier- bzw. Faserbahn zunächst durch Walzenauftrag vorimprägniert wird. Zum Entlüften der vorgetränkten Bahn wird diese dann über eine sogenannte Atemstrecke (Verweilzeit : mehrere Sekunden) geführt. Nachdem auf diese Weise die Luft aus der Bahn entfernt wurde, kann die Vollimprägnierung im Tauchbad vorgenommen werden. Anschließend wird die überschüssige Flotte zwischen Walzen oder Rakeln abgequetscht bzw. abgestreift und damit die gewünschte Dosierung der Harzauflage erreicht. Für spezielle Fälle, bei denen eine besonders gute Durchimprägnierung bzw. einseitige Imprägnierung angestrebt wird, bietet sich ein Vorgehen gemäß DE-A-25 50 980 unter Verwendung einer Vakuumsaugeinrichtyng an. Von der Tränkeinrichtung aus wird die getränkte Bahn berührungsfrei durch einen Trockner mit einem oder vorzugsweise mehreren Trockenfeldern geführt. Die Transportgeschwindigkeit der Bahn richtet sich nach der Länge des bzw. der Felder sowie der Trockentemperatur. Im allgemeinen liegt die Trockentemperatur zwischen 60 und 200 °C. Bei mehreren Trockenfeldern wird zweckmäßig mit abgestuften Temperaturen - anfangend mit der niedrigsten Temperatur - gearbeitet. Als berührungsfreie Trocknungsanlage werden vorteilhaft Düsenschwebetrockner verwendet. Anschließend an oder zwischengeschaltet in der Trockenstrecke kann eine Lackauftragsvorrichtung zur Lackierung angebracht sein. Darüber hinaus kann auch der Auftrag eines geeigneten siegelbaren Klebers mittels einer geeigneten Vorrichtung erfolgen, gegebenenfalls in kombiniertem Vorgehen.According to a particularly proven embodiment, the impregnation with the soaking liquor can be carried out by means of an impregnation unit, in which the continuous paper or fiber web is first pre-impregnated by roller application. To vent the pre-soaked web, it is then passed over a so-called breathing distance (dwell time: several seconds). After the air has been removed from the web in this way, the complete impregnation can be carried out in the immersion bath. The excess liquor is then squeezed or stripped off between rollers or doctor blades, thus achieving the desired dosage of the resin layer. For special cases in which particularly good impregnation or one-sided impregnation is desired, a procedure according to DE-A-25 50 980 using a vacuum suction device is appropriate. From the impregnation device, the impregnated web is passed through a dryer with one or preferably several drying fields without contact. The transport speed of the train depends on the length of the field or fields and the drying temperature. The drying temperature is generally between 60 and 200 ° C. If there are several dry fields, it is advisable to work with graduated temperatures - starting with the lowest temperature. Jet floating dryers are advantageously used as the non-contact drying system. Subsequent to or interposed in the drying section, a Paint application device for painting be attached. In addition, a suitable sealable adhesive can also be applied using a suitable device, if necessary in a combined procedure.

Die fertiggestellte Bahn kann direkt anschließend auf das gewünschte Format zugeschnitten oder als Rolle aufgewickelt werden.The finished web can then be cut to the desired format or wound up as a roll.

Die erfindungsgemäß erzeugten Folien zeichnen sich durch eine hervorragende Qualität aus. Hervorzuheben ist ihre gesch!ossene, glatte Oberfläche, hohe Spalt- und Weiterreißfestigkeit, hohe Licht- und Alterungsbeständigkeit, Beständigkeit gegenüber aggressiven Stoffen, Hitzebeständigkeit, leichte Pflegbarkeit und gute Verklebbarkeit. Falls eine matte oder halb matte Oberfläche gewünscht wird, lassen sich in die Tränkflotte ohne Schwierigkeit geeignete Mattierungsmittel aufnehmen.The films produced according to the invention are distinguished by their excellent quality. The closed, smooth surface, high resistance to splitting and tearing, high resistance to light and aging, resistance to aggressive substances, heat resistance, easy maintenance and good adhesion can be emphasized. If a matt or semi-matt surface is desired, suitable matting agents can be easily added to the soaking solution.

Beispiel 1example 1

In einem Witt'schen Topf mit Rührer, Rückflußkühler, Innenthermometer und Tropftrichter werden 310 g Wasser. 0,6 g Na-Dodecylsulfat. 9 g Äthylacrylat, 4,8 g Methylmethacrylat, 0.3 g Methacrylsäure und 0,9 g Methacrylamid emulgiert und auf 80 °C erhitzt. Man hält bei dieser Temperatur, gibt 0,4 g Kaliumpersulfat gelöst in 10 g Wasser und beginnt 4 Minuten später mit der Zugabe einer vorher bereiteten Emulsion aus 480 g Wasser, 7,3 g Na-Dodecylsulfat, 1.2 g Kaliumpersulfat, 471 g Äthylacrylat, 251,2 g Methylmethacrylat, 15,7 g Methacrylsäure und 47,1 g Methacrylamid. Nach der Zugabe (Zugabezeit 4 Std.) hält man noch 1 Std. auf 80 °C und kühlt dann auf 25 °C ab. Danach gibt man innerhalb 45 Minuten eine 35 %ige wäßrige Lösung eines Kondensationsproduktes aus Isononylphenol und Äthylenoxid (Molverhältnis 1 50) zu und filtriert etwa entstandene geringe Koagulatmengen über ein feines Sieb ab.310 g of water are placed in a Witt pot with stirrer, reflux condenser, internal thermometer and dropping funnel. 0.6 g Na dodecyl sulfate. Emulsified 9 g of ethyl acrylate, 4.8 g of methyl methacrylate, 0.3 g of methacrylic acid and 0.9 g of methacrylamide and heated to 80 ° C. The mixture is kept at this temperature, 0.4 g of potassium persulfate dissolved in 10 g of water are added and 4 minutes later the addition of a previously prepared emulsion of 480 g of water, 7.3 g of sodium dodecyl sulfate, 1.2 g of potassium persulfate and 471 g of ethyl acrylate is started. 251.2 g methyl methacrylate, 15.7 g methacrylic acid and 47.1 g methacrylamide. After the addition (addition time 4 hours), the mixture is kept at 80 ° C. for 1 hour and then cooled to 25 ° C. A 35% aqueous solution of a condensation product of isononylphenol and ethylene oxide (molar ratio 1 50) is then added within 45 minutes and any small amounts of coagulum formed are filtered off through a fine sieve.

Beispiel 2Example 2

Man verfährt wie in Beispiel 1, setzt jedoch in der Vorlage 13,2 g Äthylacrylat und 1,2 g 2-Hydroxyäthylacrylat und im Zulauf 722,2 g Äthylacrylat und 62,8 g 2-Hydroxyäthylacrylat ein.The procedure is as in Example 1, except that 13.2 g of ethyl acrylate and 1.2 g of 2-hydroxyethyl acrylate are used in the initial charge and 722.2 g of ethyl acrylate and 62.8 g of 2-hydroxyethyl acrylate are used in the feed.

Beispiel 3Example 3

Im Witt'schen Topf werden 440 g Wasser und 11,2 g Na-Dodecylsulfat und 0,56 g Kaliumpersulfat auf 80 °C erhitzt. Dann wird bei dieser Temperatur innerhalb 4 Std. eine Emulsion aus 672 g Wasser, 1,68 g Na-Dodecylsulfat, 1,68 g Kaliumpersulfat, 240 g Butylacrylat, 211,4 g Methylmethacrylat, 4,8 g Methacrylsäure und 24 g Methacrylamid zugegeben. Man hält noch 1 Std. bei dieser Temperatur. kühlt ab und filtriert über ein feines Sieb.440 g of water and 11.2 g of sodium dodecyl sulfate and 0.56 g of potassium persulfate are heated to 80 ° C. in the Witt pot. An emulsion of 672 g of water, 1.68 g of sodium dodecyl sulfate, 1.68 g of potassium persulfate, 240 g of butyl acrylate, 211.4 g of methyl methacrylate, 4.8 g of methacrylic acid and 24 g of methacrylamide is then added at this temperature within 4 hours . The mixture is kept at this temperature for 1 hour. cools and filters through a fine sieve.

Beispiel 4Example 4

Saugfähiges Dekorrohpapier mit einem Flächengewicht von 80 g/m2 wird in einer Imprägnierflotte bestehend aus 500 g der in Beispiel 1 beschriebenen Dispersion, 500 g Harnstoffformaldehydharz (Handelsbezeichnung Kautit 420® *. Feststoffgehalt 50 %), 250 g Wasser sowie 2 g Ammoniumchlorid und 2 g Netzmittel (schwach sulfatiertes Rüböl) in einer Tränkwanne imprägniert.Absorbent decorative base paper with a basis weight of 80 g / m 2 is in an impregnation liquor consisting of 500 g of the dispersion described in Example 1, 500 g of urea formaldehyde resin (trade name Kautit 420® *. Solids content 50%), 250 g of water and 2 g of ammonium chloride and 2 g Impregnating agent (weakly sulfated beet oil) impregnated in a watering trough.

* (Eingetragenes Warenzeichen der BASF) * (Registered trademark of BASF)

Die Imprägnierung erfolgt, indem man das Rohpapier zur Benetzung auf die Flottenoberfläche auflegt und anschließend zur vollständigen Durchtränkung taucht. Im Anschluß daran wird das imprägnierte Papier zwischen 2 Gummiwalzen abgequetscht und im Trockenschrank bei 140 °C 3 Min. getrocknet.The impregnation is carried out by placing the base paper on the liquor surface for wetting and then immersing it completely. The impregnated paper is then squeezed between two rubber rollers and dried in a drying cabinet at 140 ° C. for 3 minutes.

Man erhält eine mittelharte flexible Folie mit einem Endgewicht von 124 g/m2, einer Restfeuchte von 4 % und einer Beharzungsmenge von 42,5 % (bez. auf Rohpapiergewicht).A medium-hard flexible film with a final weight of 124 g / m 2 , a residual moisture content of 4% and a resin quantity of 42.5% (based on the weight of the base paper) is obtained.

Beispiel 5Example 5

Man verfährt wie in Beispiel 4, die Imprägnierflotte besteht jedoch aus 700 g Dispersion von Beispiel 2, 300 g Harnstofformaldehydharz (50 % Feststoffgehalt), 250 g Wasser sowie 1,5 g Ammoniumchlorid und 2 g des in Beispiel 4 beschriebenen Netzmittels. Die so hergestellte Folie hat hochflexiblen Charakter (Ummantelungsfolie), die Beharzungsmenge beträgt 41 %, das Endgewicht 112,8 g und die Restfeuchte 5%.The procedure is as in Example 4, but the impregnation liquor consists of 700 g of dispersion from Example 2, 300 g of urea formaldehyde resin (50% solids content), 250 g of water and 1.5 g of ammonium chloride and 2 g of the wetting agent described in Example 4. The film produced in this way has a highly flexible character (wrapping film), the amount of resin is 41%, the final weight 112.8 g and the residual moisture 5%.

Beispiel 6Example 6

Ein saugfähiges Rohpapier, Flächengewicht 200 gim2 wird in einer Imprägnierflotte, welche aus 1 000 g der in Beispiel 3 beschriebenen Dispersion, 600 g Harnstofformaldehyd (50 % Feststoffgehalt), 1,5 Ammoniumchiorid sowie 3 g Netzmittel besteht, wie vorstehend beschrieben imprägniert und weiterbehandelt.An absorbent base paper, basis weight 200 gim 2 , is impregnated and further treated in an impregnation liquor which consists of 1,000 g of the dispersion described in Example 3, 600 g of urea formaldehyde (50% solids content), 1.5 ammonium chloride and 3 g of wetting agent .

Das Endprodukt entspricht einer Folie, welche als Kantenumleimer in der Möbel- und Spanplattenindustrie Verwendung findet, es hat einen Beharzungsanteil von 38 %, eine Restfeuchte von 5 % und ein Endgewicht von 276 g/m2.The end product corresponds to a film that is used as edge banding in the furniture and chipboard industry, it has a resin content of 38%, a residual moisture content of 5% and a final weight of 276 g / m 2 .

Claims (8)

1. Process for the preparation of reinforced films (finishing films) by impregnating fibrous flat materials such as backing papers, non-woven fabrics and the like with water-soluble aminoplast resin and an aqueous synthetic resin dispersion and subsequently drying them by heat treatment, characterized in that urea resin is used as the water-soluble aminoplast resin and in that the synthetic resin dispersion consists of finely divided particles and, owing to its content of groups capable of heterogeneous cross-linking, is still thermoplastically deformable and uncrosslinked at the start of the drying operation and the heterogeneous cross-linking is brought about by the continuing heat treatment.
2. Process as claimed in claim 1, characterized in that the aqueous synthetic resin dispersion used is one which contains hydroxy, amino, amide or carboxyl functions as groups capable of heterogeneous cross-linking.
3. Process as claimed in claims 1 and 2, characterized in that the aqueous synthetic resin dispersion used is the copolymer of (meth)acrylic acid esters with acrylic or methacrylic acid, acrylamide or methacrylamide, a hydroxy- and/ or aminoalkyl ester of formula
Figure imgb0003
wherein R represents hydrogen or a methyl group, A represents an optionally branched alkyl group with 2 to 6 carbon atoms, Z represents a substituent OH or NHR, located at the alkyl group and R, represents an alkyl group with 1 to 8 carbon atoms or hydrogen, as comonomers.
4. Process as claimed in claim 3, characterized in that the proportion of the monomers capable of heterogeneous cross-linking is between 0.5 and 15 % by weight, preferably between 2 and 10 % by weight, based on the total polymer.
5. Process as claimed in claims 3 and 4, characterised in that the copolymer of methyl methacrylate, (meth)acrylic esters of C2 to C8 alcohols, methacrylamide and methacrylic acid is used as the synthetic resin dispersion.
6. Process as claimed in claims 1 to 5, characterized in that the radius of the particles in the synthetic resin dispersion is < 100 nm.
7. Process as claimed in claims 1 to 6, characterized in that drying is effected by heat treatment at between 80 and 180 °C, preferably at 100-150°C.
8. Reinforced films (finishing films) prepared using the process as claimed in claims 1 to 7.
EP79104248A 1979-01-27 1979-10-31 Process for the production of reinforced, resin-impregnated sheets by saturation of a fibrous web, and sheets so obtained Expired EP0013698B1 (en)

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DE19792903172 DE2903172A1 (en) 1979-01-27 1979-01-27 METHOD FOR PRODUCING PLASTIC-IMPREGNATED PAPERS, FIBER FLEECE AND THE LIKE

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DE2903172A1 (en) 1980-08-07
JPH0154477B2 (en) 1989-11-20
DE2903172C2 (en) 1990-04-19
JPS55103373A (en) 1980-08-07
EP0013698A1 (en) 1980-08-06
US4324832A (en) 1982-04-13

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