EP0889168A2 - Process for making a prepreg, and use of the same for making decorative laminates - Google Patents

Process for making a prepreg, and use of the same for making decorative laminates Download PDF

Info

Publication number
EP0889168A2
EP0889168A2 EP98107656A EP98107656A EP0889168A2 EP 0889168 A2 EP0889168 A2 EP 0889168A2 EP 98107656 A EP98107656 A EP 98107656A EP 98107656 A EP98107656 A EP 98107656A EP 0889168 A2 EP0889168 A2 EP 0889168A2
Authority
EP
European Patent Office
Prior art keywords
acrylic acid
meth
copolymer
dry
base paper
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.)
Granted
Application number
EP98107656A
Other languages
German (de)
French (fr)
Other versions
EP0889168A3 (en
EP0889168B1 (en
Inventor
Horst Matscheko
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.)
Koehler Decor GmbH and Co KG
Original Assignee
Koehler Decor GmbH and Co KG
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
Priority claimed from DE1997128250 external-priority patent/DE19728250C2/en
Application filed by Koehler Decor GmbH and Co KG filed Critical Koehler Decor GmbH and Co KG
Publication of EP0889168A2 publication Critical patent/EP0889168A2/en
Publication of EP0889168A3 publication Critical patent/EP0889168A3/en
Application granted granted Critical
Publication of EP0889168B1 publication Critical patent/EP0889168B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • 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
    • D21H27/26—Structures being applied on the surface by special manufacturing processes, e.g. in presses characterised by the overlay sheet or the top layers of the structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C5/00—Processes for producing special ornamental bodies
    • B44C5/04—Ornamental plaques, e.g. decorative panels, decorative veneers
    • B44C5/043—Ornamental plaques, e.g. decorative panels, decorative veneers containing wooden elements
    • 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
    • D21H17/35—Polyalkenes, e.g. polystyrene
    • 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
    • D21H17/34—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
    • D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
    • D21H17/43—Carboxyl groups or derivatives thereof
    • 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]
    • Y10T428/31725—Of polyamide
    • 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
    • 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
    • Y10T428/31899—Addition polymer of hydrocarbon[s] only
    • Y10T428/31902—Monoethylenically unsaturated
    • 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

Definitions

  • the invention relates to a method for producing a pre-impregnate, with the Process obtained pre-impregnate and its use for the production of decorative composite structures.
  • the invention further relates to those for impregnating the pre-impregnate used impregnation fleet.
  • WO 94/00523 discloses an aqueous impregnation solution with which papers are impregnated which are then used to manufacture laminate panels.
  • the aqueous impregnation solution contains 5 to 90 parts by weight of polyvinyl alcohol to 10 to 95 parts by weight of one Dispersion of an ethyl styrene / acrylate / burylacrylate copolymer.
  • the state of the art has been a pre-impregnation through sales since the late 1980s known that by impregnating a base paper from a cellulose long and Short fiber mixture with an impregnation liquor known under the internal name R20 is obtained.
  • This impregnation liquor contains 15% of a glyoxal / urea precondensate or resin in aqueous solution, 57% of a 50% aqueous dispersion of a copolymer based on n-butyl acrylate and styrene and 28% water.
  • This Preimpregnate has various desirable properties, such as. B.
  • the invention was therefore based on the object of providing a prepreg that all has desirable properties of the pre-impregnate described above, at the same time but shows no tendency to yellowing.
  • this object is achieved with a method which is characterized in that is that a base paper is impregnated with an impregnating liquor which a) a aqueous dispersion based on an acrylic acid ester / styrene copolymer. b) a dry strength agent based on a copolymer of (meth) acrylamide and (meth) acrylic acid and c) contains water, with per part by weight of dry copolymer (Meth) acrylamide and (meth) acrylic acid about 0.3 to 13 parts by weight of dry acrylic acid ester / styrene copolymer be used.
  • pre-impregnate is a term known to the person skilled in the art technicus.
  • the pre-impregnate is, as mentioned above, by impregnating one Obtain base paper with an impregnation liquor. Then it is dried. It lies then in the form of a resin-impregnated fiber material - in technical terms also foil called - before and is brought to the market. Depending on the desired end use it can be modified further.
  • copolymer (Meth) acrylamide and (meth) acrylic acid about 1 to 9 parts by weight, in particular about 3 to 7 parts by weight, acrylic acid ester / styrene copolymer can be used.
  • the latter Area leads to the advantage that it is low in formaldehyde, flexible and resistant to yellowing Product is received.
  • the pH of the impregnation liquor used is preferably in the range of about 4.5 to 8.0, especially in the range of about 5.0 to 5.5.
  • the setting of the desired pH can be adjusted with sodium hydroxide solution and sulfuric or hydrochloric acid. Too high a pH can cause instability of the dispersion, a too low pH can under certain circumstances act fiber damaging.
  • the viscosity (measured according to DIN 53211) of the impregnation liquor should be about 10 to 18 seconds, in particular be about 11 to 14 seconds.
  • the solids content of the impregnation liquor is in the range of about 15 to 50% by weight.
  • a solids content of about 30% by weight is preferred because of this a desirable degree of impregnation of the nonwoven is achieved.
  • the acrylic acid ester of the acrylic acid ester / styrene copolymer can be methyl, Act ethyl, n-butyl, i-butyl and 2-ethylhexyl ester, the use of n-butyl acrylate is preferred.
  • Acronal S 305 D® is one 50% aqueous dispersion of a copolymer based on n-butyl acrylate and styrene.
  • the acrylic acid ester / styrene copolymer is in the form of a film.
  • the Minimum film formation temperature is preferably in the range from about 5 to 70 ° C. especially in the range of about 10 to 30 ° C.
  • the dry strength agent is preferably a copolymer of acrylamide and acrylic acid with an anionic charge. Compared to a dry strength agent Based on a copolymer of methacrylamide and methacrylic acid with an anionic charge the use of a copolymer based on acrylamide and acrylic acid leads to less brittle products.
  • the dry strength agent itself has a solids content of about 15 to 30%, in particular from about 20 to 22%, a pH in the range from about 6.0 to 9.0, a viscosity from about 100 to 300 mPa.s (Brookfield; 20 ° C) and a density of about 1.0 g / ml 20 ° C.
  • the dry strength agent is intended to be used in the pulp in order to to develop properties described below. Because the dry strength agent Forms polymer bridges, it solidifies the paper structure without disturbing the sheet formation or affect the porosity. This means that all mechanical Strength properties of the paper can be improved. Depending on the amount used and paper type, improvements in tear length and burst strength are achieved as well the tear strength and the splitting strength of the paper. This allows, depending on Quality requirements, the use of inexpensive raw materials, a higher ash content of the base paper and the saving of tools. One shows as a side effect significant improvement in retention.
  • Long and short fiber pulps can be used as fiber raw materials.
  • the material input of the pre-impregnated base paper does not differ significantly from that of the Decorative papers.
  • the long fiber content is approximately 0 to 40%, in particular approximately 15 to 30%, the short fiber content about 60 to 100%, in particular about 60 to 85%.
  • the grind of the Base paper is also variable and is between about 18 and 50 ° SR, in particular between 25 and 35 ° SR.
  • the ash content of the base paper depends on the paper used between about 2 to 40%, in particular between about 10 to 30%. The settings in the paper machine, such as. B.
  • property-modifying additives such as. B. pH regulator, Wet and dry strength agents, synthetic resin dispersions, precipitants (fixing agents), Surfactants, dyes, fillers, hardening, viscosity regulation, non-stick and Penetration aids and pigments to add to the impregnation solution.
  • the impregnation of the base paper to the pre-impregnate is done with a paper impregnation system carried out.
  • a paper impregnation system carried out.
  • Machine parts such as unwinding, size press, dryer section, steam humidifier, smoothing value and paperoller rewind.
  • the pre-impregnate can be used either according to the so-called “on-line” or the “off-line” procedure getting produced.
  • "On-line” means that the size press with which the impregnation liquor is applied, arranged in the paper machine, while under To understand “off-line” is that the size press in a separate operation behind or after the paper machine is used. In the latter case, the prepreg is at the end the paper machine not as a finished product but as a semi-finished product. this leads to important parameters such as color, porosity, smoothness and the final basis weight, either reproduced in the laboratory or calculated back from experience Need to become.
  • the impregnation liquor can be applied to one side but also to both sides of the base paper become. If the impregnation liquor is applied to one side, then the training is the surface of the screen side of the base paper is important, for which a control of the Temperature curve of the predrying group of the paper machine is extremely important. At impregnation on both sides, the impregnation can take place completely, d. H. she can in penetrate the entire mass of paper.
  • the total intake amount of impregnation liquor through the base paper depends on the type of base paper, but also that of Pressing off the excess impregnation liquor from the paper web.
  • the pre-impregnate according to the invention has the advantage that the processing products do not turn yellow when applied leads. This is due to the fact that the component of the glyoxal / urea precondensate by a dry strength agent based on a copolymer (Meth) acrylamide and (meth) acrylic acid with a weakly anionic charge was replaced.
  • a dry strength agent based on a copolymer (Meth) acrylamide and (meth) acrylic acid with a weakly anionic charge was replaced.
  • the Dry strength agent is usually used in bulk and physically leads to a fiber consolidation, which improves the dry strength in the end product, not against it the wet strength. This shows that the dry strength agent is only physically fiber adhesive acts and the fiber structure is not solidified by chemical reaction.
  • the pre-impregnate according to the invention can be used for the production of decorative composite structures become.
  • decorative laminates with the invention Pre-impregnated. They are applied using heat and pressure as well as suitable glue systems in presses or laminating plants.
  • chipboard and medium density fibreboard (MDF) on both sides with the coated according to the invention.
  • the pre-impregnate also serves as decor-bearing component.
  • Wood-based materials are also used extensively in the manufacture of furniture of chipboard used. The often unsightly surface of these wood materials and their limited use value require the use of coating materials.
  • the prepreg according to the invention is suitable for this.
  • the invention Foil can have any wood grain or any fancy decor.
  • In the pre-impregnate can be varnished in a further step.
  • transparent paints such as. B. acrylic paints acid-curing, water-soluble and pigmented paints. In addition to the protective function of the lacquer, this gives the pre-impregnate also a corresponding visual impression.
  • a base paper of the following composition was produced: 20% pine sulfate pulp and 80% eucalyptus pulp. The freeness was 31 ° SR (Schopper-Riegler). 30% titanium dioxide and 4% were added (on otro pulp) formaldehyde-free wet strength agent used.
  • This base paper with a weight per unit area of 50 g / m 2 was impregnated on both sides with the impregnating liquor according to the invention in a 7: 1 ratio in a size press, the necessary solids content being set with water.
  • the dispersion alone has poor splitting resistance shows.
  • the dry strength agent alone has insufficient water resistance and tends to poor splitting resistance.
  • the impregnation liquor according to the invention leads to good ones Water resistance and sufficient splitting resistance, as well as formulation 4.
  • the Impregnation liquor 3 according to the invention in contrast to formulation 4, is significantly smaller Yellow shift (db value) after heat treatment.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Paper (AREA)
  • Laminated Bodies (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

A process for the production of pre-impregnates (prepregs) comprises impregnating base paper with a liquid containing (a) an aqueous dispersion based on an acrylate ester/styrene copolymer (CP1), (b) a dry-strengthener based on a copolymer (CP2) of (meth)acrylamide and (meth)acrylic acid, and (c) water, using 0.3-13 pts. wt. dry CP1 per 1 pt. wt. dry CP2. Also claimed are (i) prepregs obtained by this process and (ii) an impregnating liquid as above.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung eines Vorimprägnats, das mit dem Verfahren erhaltene Vorimprägnat sowie dessen Verwendung zur Herstellung von Dekorverbundgebilden. Ferner betrifft die Erfindung die zum Imprägnieren des Vorimprägnats verwendete Imprägrierflotte.The invention relates to a method for producing a pre-impregnate, with the Process obtained pre-impregnate and its use for the production of decorative composite structures. The invention further relates to those for impregnating the pre-impregnate used impregnation fleet.

Es ist bekannt, daß durch Beschichten von Spanplatten mit imprägnierten Dekorpapieren dekorative Laminate und Möbelteile hergestellt werden können. Eine entscheidende Rolle spielt hierbei das imprägnierte Papier, das durch Imprägnieren eines Rohpapiers mit einer speziellen Imprägnierflotte bzw. einem Imprägnierharz erhalten wird. Dieses imprägnierte Papier wird in diesem Falle als Vorimprägnat bezeichnet und dient in den genannten Anwendungen auch als dekortragende Komponente.It is known that by coating chipboard with impregnated decorative papers decorative laminates and furniture parts can be made. A crucial role plays the impregnated paper, which is made by impregnating a base paper with a special impregnation liquor or an impregnation resin is obtained. This impregnated In this case, paper is referred to as pre-impregnation and serves in the above Applications also as a decorative component.

Ein Verfahren der eingangs beschriebenen Art geht aus der EP 0 223 922 hervor. Dieses Patent beschreibt ein Verfahren zur Herstellung von mit Kunstharzen in Form von Lösungen und Dispersionen imprägnierten Papierbahnen. Als Imprägnierflüssigkeit wird ein Gemisch aus wäßrigen anionischen Copolymerdispersionen auf Basis von Acrylsäure, Acrylsäureester, Acrylnitril, Vinylacetat und/oder Styrol und aus wäßrigen anionischen Lösungen von Copolymerisaten auf Basis von Maleinsäureanhydrid bzw. Maleinsäure mit Styrol, Acrylsäure und Acrylsäureestern verwendet.A method of the type described in the introduction can be found in EP 0 223 922. This Patent describes a process for the production of synthetic resins in the form of solutions and dispersions impregnated paper webs. A mixture is used as the impregnation liquid from aqueous anionic copolymer dispersions based on acrylic acid, acrylic acid ester, Acrylonitrile, vinyl acetate and / or styrene and from aqueous anionic solutions of copolymers based on maleic anhydride or maleic acid with styrene, Acrylic acid and acrylic acid esters are used.

Die WO 94/00523 offenbart eine wäßrige Imprägnierlösung, mit der Papiere imprägniert werden, die dann zur Herstellung von Laminatplatten verwendet werden. Die wäßrige Imprägnierlösung enthalt 5 bis 90 Gew.-Teile Polyvinylalkohol auf 10 bis 95 Gew.-Teile einer Dispersion eines Ethyl-Styrol/Acrylat/Burylacrylat-Copolymers. WO 94/00523 discloses an aqueous impregnation solution with which papers are impregnated which are then used to manufacture laminate panels. The aqueous impregnation solution contains 5 to 90 parts by weight of polyvinyl alcohol to 10 to 95 parts by weight of one Dispersion of an ethyl styrene / acrylate / burylacrylate copolymer.

Aus dem Stand der Technik ist seit Ende der 80er Jahre durch Vertrieb ein Vorimprägnat bekannt, das durch Imprägnieren eines Rohpapiers aus einem Cellulose-Lang- und Kurzfasergemisch mit einer, unter der internen Bezeichnung R20 bekannten, Imprägnierflotte erhalten wird. Diese Imprägnierflotte enthält 15% eines Glyoxal/Harnstoff-Vorkondensats bzw. -harzes in wäßriger Lösung, 57% einer 50%-ige wäßrige Dispersion eines Copolymers auf Basis von n-Butylacrylat und Styrol und 28% Wasser. Dieses Vorimprägnat besitzt verschiedene wünschenswerte Eigenschaften, wie z. B. hohe Härte- und Abriebresistenz, hohe Temperaturbeständigkeit, Lichtechtheit, neutrale Eigenfarbe, gute Wasserbeständigkeit sowie gute Beständigkeit gegen Chemikalien, weitgehende Unbrennbarkeit, hohe optische Transparenz, Geruchs- und Geschmacksfreiheit sowie toxikologische Unbedenklichkeit. Insbesondere handelt es sich um ein formaldehydarmes Vorimprägnat. Es ist jedoch beim Zusammentreffen von ungünstigen Temperaturen und Lacksystemen nicht ausreichend stabil gegen Vergilben. Unter Vergilben soll hier nicht eine mangelnde Lichtbeständigkeit verstanden werden, sondern die chemische Reaktion, die aufgrund der eingesetzten Imprägnierflotte stattfindet. Das bekannte Vorimprägnat findet aufgrund dieses Vergilbens im sogenannten "weißen" Bereich geringe Anwendung. Unter "weißen" Bereich versteht der Fachmann helle Laminate bzw. Möbelteile, bei denen ein Vergilben besonders nachteilig zum Tragen kommt.The state of the art has been a pre-impregnation through sales since the late 1980s known that by impregnating a base paper from a cellulose long and Short fiber mixture with an impregnation liquor known under the internal name R20 is obtained. This impregnation liquor contains 15% of a glyoxal / urea precondensate or resin in aqueous solution, 57% of a 50% aqueous dispersion of a copolymer based on n-butyl acrylate and styrene and 28% water. This Preimpregnate has various desirable properties, such as. B. high hardness and Abrasion resistance, high temperature resistance, light fastness, neutral color, good water resistance and good resistance to chemicals, extensive Incombustibility, high optical transparency, odorless and tasteless as well toxicological harmlessness. In particular, it is low in formaldehyde Pre-impregnated. It is however when unfavorable temperatures and Paint systems not sufficiently stable against yellowing. Yellowing is not supposed to be one here lack of lightfastness are understood, but the chemical reaction that due to the impregnation liquor used. The well-known pre-impregnate takes place due to this yellowing in the so-called "white" area little use. Under The specialist understands the "white" area to be light laminates or furniture parts in which a Yellowing is particularly disadvantageous.

Der Erfindung lag daher die Aufgabe zugrunde, ein Vorimprägnat bereitzustellen, daß alle wünschenswerten Eigenschaften des oben beschriebenen Vorimprägnats besitzt, gleichzeitig aber keine Vergilbungsneigung zeigt.The invention was therefore based on the object of providing a prepreg that all has desirable properties of the pre-impregnate described above, at the same time but shows no tendency to yellowing.

Erfindungsgemäß wird diese Aufgabe mit einem Verfahren gelöst, das dadurch gekennzeichnet ist, daß ein Rohpapier mit einer Imprägnierflotte imprägniert wird, die a) eine wäßrige Dispersion auf Basis eines Acrylsäureester/Styrol-Copolymers. b) einen Trockenverfestiger auf Basis eines Copolymerisats aus (Meth-)Acrylamid und (Meth-)Acrylsäure und c) Wasser enthält, wobei pro Gew.-Teil trockenem Copolymerisat aus (Meth-)Acrylamid und (Meth-)Acrylsäure etwa 0,3 bis 13 Gew.-Teile trockenes Acrylsäureester/Styrol-Copolymer eingesetzt werden. According to the invention, this object is achieved with a method which is characterized in that is that a base paper is impregnated with an impregnating liquor which a) a aqueous dispersion based on an acrylic acid ester / styrene copolymer. b) a dry strength agent based on a copolymer of (meth) acrylamide and (meth) acrylic acid and c) contains water, with per part by weight of dry copolymer (Meth) acrylamide and (meth) acrylic acid about 0.3 to 13 parts by weight of dry acrylic acid ester / styrene copolymer be used.

Bei dem Begriff Vorimprägnat handelt es sich um einen dem Fachmann bekannten Terminus technicus. Das Vorimprägnat wird, wie vorstehend erwähnt, durch Imprägnieren eines Rohpapiers mit einer Imprägnierflotte erhalten. Anschließend wird es getrocknet. Es liegt dann in Form eines harzgetränkten Fasermaterials - im Fachsprachgebrauch auch Folie genannt - vor und wird so auf den Markt gebracht. Je nach gewünschter Endverwendung kann es weiter modifiziert werden.The term pre-impregnate is a term known to the person skilled in the art technicus. The pre-impregnate is, as mentioned above, by impregnating one Obtain base paper with an impregnation liquor. Then it is dried. It lies then in the form of a resin-impregnated fiber material - in technical terms also foil called - before and is brought to the market. Depending on the desired end use it can be modified further.

Im Rahmen der Erfindung ist es bevorzugt, daß pro Gew.-Teil Copolymerisat aus (Meth-)Acrylamid und (Meth-)Acrylsäure etwa 1 bis 9 Gew.-Teile, insbesondere etwa 3 bis 7 Gew.-Teile, Acrylsäureester/Styrol-Copolymer eingesetzt werden. Der zuletzt genannte Bereich führt zu dem Vorteil, daß ein formaldehydarmes, flexibles und vergilbungsstabiles Produkt erhalten wird.In the context of the invention it is preferred that per part by weight of copolymer (Meth) acrylamide and (meth) acrylic acid about 1 to 9 parts by weight, in particular about 3 to 7 parts by weight, acrylic acid ester / styrene copolymer can be used. The latter Area leads to the advantage that it is low in formaldehyde, flexible and resistant to yellowing Product is received.

Der pH-Wert der eingesetzten Imprägnierflotte liegt vorzugsweise im Bereich von etwa 4,5 bis 8,0, insbesondere im Bereich von etwa 5,0 bis 5,5. Die Einstellung des gewünschten pH-Wertes kann mit Natronlauge und Schwefel- bzw. Salzsäure erfolgen. Ein zu hoher pH-Wert kann zur Instabilität der Dispersion, ein zu niedriger pH-Wert kann unter Umständen faserschädigend wirken.The pH of the impregnation liquor used is preferably in the range of about 4.5 to 8.0, especially in the range of about 5.0 to 5.5. The setting of the desired pH can be adjusted with sodium hydroxide solution and sulfuric or hydrochloric acid. Too high a pH can cause instability of the dispersion, a too low pH can under certain circumstances act fiber damaging.

Die Viskosität (gemessen nach DIN 53211) der Imprägnierflotte sollte etwa 10 bis 18 sec, insbesondere etwa 11 bis 14 sec betragen.The viscosity (measured according to DIN 53211) of the impregnation liquor should be about 10 to 18 seconds, in particular be about 11 to 14 seconds.

Der Feststoffgehalt der Imprägnierflotte liegt je nach Anwendungsprodukt im Bereich von etwa 15 bis 50 Gew.-%. Ein Feststoffgehalt von etwa 30 Gew.-% ist bevorzugt, da damit ein wünschenswerter Tränkungsgrad des Faservlieses erreicht wird.Depending on the application product, the solids content of the impregnation liquor is in the range of about 15 to 50% by weight. A solids content of about 30% by weight is preferred because of this a desirable degree of impregnation of the nonwoven is achieved.

Bei dem Acrylsäureester des Acrylsäureester/Styrol-Copolymers kann es sich um Methyl-, Ethyl-, n-Butyl-, i-Butyl- und 2-Ethylhexylester handeln, wobei der Einsatz von n-Butylacrylat bevorzugt ist. The acrylic acid ester of the acrylic acid ester / styrene copolymer can be methyl, Act ethyl, n-butyl, i-butyl and 2-ethylhexyl ester, the use of n-butyl acrylate is preferred.

Als besonders geeignetes Acrylsäureester/Styrol-Copolymer hat sich das Handelsprodukt Acronal S 305 D® der Firma BASF Aktiengesellschaft erwiesen. Acronal S 305 D® ist eine 50%-ige wäßrige Dispersion eines Copolymers auf Basis von n-Butylacrylat und Styrol.The commercial product has proven to be a particularly suitable acrylic acid ester / styrene copolymer Acronal S 305 D® from BASF Aktiengesellschaft. Acronal S 305 D® is one 50% aqueous dispersion of a copolymer based on n-butyl acrylate and styrene.

Im Vorimprägnat liegt das Acrylsäureester/Styrol-Copolymer in Form eines Films vor. Die Mindestfilmbildungstemperatur liegt vorzugsweise im Bereich von etwa 5 bis 70°C, insbesondere im Bereich von etwa 10 bis 30°C.In the pre-impregnate, the acrylic acid ester / styrene copolymer is in the form of a film. The Minimum film formation temperature is preferably in the range from about 5 to 70 ° C. especially in the range of about 10 to 30 ° C.

Bei dem Trockenverfestiger handelt es sich vorzugsweise um ein Copolymerisat aus Acrylamid und Acrylsäure mit anionischer Ladung. Verglichen mit einem Trockenverfestiger auf Basis eines Copolymerisats aus Methacrylamid und Methacrylsäure mit anionischer Ladung führt der Einsatz eines Copolymerisats auf Basis von Acrylamid und Acrylsäure zu weniger spröden Erzeugnissen.The dry strength agent is preferably a copolymer of acrylamide and acrylic acid with an anionic charge. Compared to a dry strength agent Based on a copolymer of methacrylamide and methacrylic acid with an anionic charge the use of a copolymer based on acrylamide and acrylic acid leads to less brittle products.

Der Trockenverfestiger selbst besitzt einen Feststoffgehalt von etwa 15 bis 30%, insbesondere von etwa 20 bis 22%, einen pH-Wert im Bereich von etwa 6,0 bis 9,0, eine Viskosität von etwa 100 bis 300 mPa.s (Brookfield; 20°C) sowie eine Dichte von etwa 1,0 g/ml bei 20°C.The dry strength agent itself has a solids content of about 15 to 30%, in particular from about 20 to 22%, a pH in the range from about 6.0 to 9.0, a viscosity from about 100 to 300 mPa.s (Brookfield; 20 ° C) and a density of about 1.0 g / ml 20 ° C.

Bestimmungsgemäß soll der Trockenverfestiger in der Papiermasse eingesetzt werden, um nachstehend beschriebene Eigenschaften zu entwickeln. Da der Trockenverfestiger Polymerbrücken ausbildet, verfestigt er das Papiergefüge, ohne die Blattbildung zu stören oder die Porösität zu beeinflussen. Dies bedeutet, daß sämtliche mechanische Festigkeitseigenschaften des Papiers verbessert werden. Abhängig von der Einsatzmenge und der Papierart erreicht man Verbesserungen der Reißlänge und der Berstfestigkeit sowie der Weiterreißfestigkeit und der Spaltfestigkeit des Papiers. Dies erlaubt, je nach Qualitätsanforderungen, den Einsatz preisgünstiger Rohstoffe, einen höheren Aschegehalt des Rohpapiers und die Einsparung von Hilfsmitteln. Als Nebeneffekt zeigt sich eine erhebliche Verbesserung der Retention.The dry strength agent is intended to be used in the pulp in order to to develop properties described below. Because the dry strength agent Forms polymer bridges, it solidifies the paper structure without disturbing the sheet formation or affect the porosity. This means that all mechanical Strength properties of the paper can be improved. Depending on the amount used and paper type, improvements in tear length and burst strength are achieved as well the tear strength and the splitting strength of the paper. This allows, depending on Quality requirements, the use of inexpensive raw materials, a higher ash content of the base paper and the saving of tools. One shows as a side effect significant improvement in retention.

Als Faserrohstoffe können Lang- und Kurzfaserzellstoffe eingesetzt werden. Der Stoffeintrag des Vorimprägnatrohpapiers unterscheidet sich nicht wesentlich von dem der Dekorpapiere. Der Langfaseranteil beträgt etwa 0 bis 40%, insbesondere etwa 15 bis 30%, der Kurzfaseranteil etwa 60 bis 100%, insbesondere etwa 60 bis 85%. Der Mahlgrad des Rohpapiers ist ebenfalls variabel und liegt zwischen etwa 18 und 50 °SR, insbesondere zwischen 25 und 35°SR. Der Aschegehalt des Rohpapiers liegt in Abhängigkeit des jeweils verwendeten Papiers zwischen etwa 2 bis 40%, insbesondere zwischen etwa 10 bis 30%. Die Einstellungen in der Papiermaschine, wie z. B. Geschwindigkeit, Naßpressendruck, Temperaturkurve, Anpreßdruck am Glättzylinder, sind nach Art und Qualität des verwendeten Papiers verschieden und werden im Rahmen der Erfordernisse der Papierherstellung variiert und optimiert. Zur Steuerung von Retention, Nachbruchlasten und pH-Wert werden handelsübliche Produkte, wie Aluminiumsulfat, eingesetzt.Long and short fiber pulps can be used as fiber raw materials. Of the The material input of the pre-impregnated base paper does not differ significantly from that of the Decorative papers. The long fiber content is approximately 0 to 40%, in particular approximately 15 to 30%, the short fiber content about 60 to 100%, in particular about 60 to 85%. The grind of the Base paper is also variable and is between about 18 and 50 ° SR, in particular between 25 and 35 ° SR. The ash content of the base paper depends on the paper used between about 2 to 40%, in particular between about 10 to 30%. The settings in the paper machine, such as. B. speed, wet press pressure, The temperature curve, contact pressure on the Yankee cylinder, are based on the type and quality of the used Papers are different and are within the requirements of papermaking varies and optimizes. To control retention, post-emergence loads and pH commercially available products, such as aluminum sulfate, are used.

In Einzelfällen kann es von Vorteil sein, eigenschaftsmodifizierende Additive, wie z. B. pH-Regulierer, Naß- und Trockenfestmittel, Kunstharzdispersionen, Fällungsmittel (Fixiermittel), Tenside, Farbstoffe, Füllstoffe, Härtungs-, Viskositätsregulierungs-, Antihaft- und Penetrationshilfsmittel sowie Pigmente, der Imprägnierlösung zuzusetzen.In individual cases, it can be advantageous to add property-modifying additives such as. B. pH regulator, Wet and dry strength agents, synthetic resin dispersions, precipitants (fixing agents), Surfactants, dyes, fillers, hardening, viscosity regulation, non-stick and Penetration aids and pigments to add to the impregnation solution.

Die Imprägnierung des Rohpapiers zum Vorimprägnat, wird mit einer Papiertränkungsanlage durchgeführt. Hierbei handelt es sich um eine Anordnung von verschiedenen Maschinenteilen, wie Abrollung, Leimpresse, Trockenpartie, Dampfbefeuchter, Glättwert und Paperoller-Aufwicklung.The impregnation of the base paper to the pre-impregnate is done with a paper impregnation system carried out. This is an arrangement of different ones Machine parts such as unwinding, size press, dryer section, steam humidifier, smoothing value and paperoller rewind.

Das Vorimprägnat kann sowohl nach der sogenannten "on-line"- als auch nach der "off-line"-Verfahrensweise hergestellt werden. "On-line" bedeutet, daß die Leimpresse, mit der die Imprägnierflotte aufgetragen wird, in der Papiermaschine angeordnet ist, während unter "off-line" zu verstehen ist, daß die Leimpresse in einem separaten Arbeitsgang hinter bzw. nach der Papiermaschine eingesetzt wird. Im letzteren Fall liegt das Vorimprägnat am Ende der Papiermaschine nicht als Fertigprodukt sondern als Halbfertigprodukt vor. Dies führt dazu, daß wichtige Parameter, wie Farbe, Porösität, Glätte und das endgültige Flächengewicht, entweder im Labor nachgestellt oder aus der Erfahrung heraus zurückgerechnet werden müssen.The pre-impregnate can be used either according to the so-called "on-line" or the "off-line" procedure getting produced. "On-line" means that the size press with which the impregnation liquor is applied, arranged in the paper machine, while under To understand "off-line" is that the size press in a separate operation behind or after the paper machine is used. In the latter case, the prepreg is at the end the paper machine not as a finished product but as a semi-finished product. this leads to important parameters such as color, porosity, smoothness and the final basis weight, either reproduced in the laboratory or calculated back from experience Need to become.

Die Imprägnierflotte kann auf eine Seite aber auch auf beide Seiten des Rohpapiers aufgebracht werden. Wird die Imprägnierflotte auf eine Seite aufgetragen, dann ist die Ausbildung der Oberfläche der Siebseite des Rohpapiers von Bedeutung, wozu eine Steuerung der Temperaturkurve der Vortrockengruppe der Papiermaschine äußerst wichtig ist. Bei beidseitiger Imprägnierung kann die Imprägnierung vollständig erfolgen, d. h. sie kann in die gesamten Papiermasse eindringen. Die gesamte Aufnahmemenge an Imprägnierflotte durch das Rohpapier richtet sich nach der Art des Rohpapiers, aber auch nach der des Abpressens der überschüssigen Imprägnierflotte von der Papierbahn. Rahmenbedingungen für die Menge an in das Rohpapier eingebrachter Imprägnierflotte sind etwa 15 bis 30% Harzanteil, vorzugsweise etwa 18 bis 27% Harzanteil, bei beidseitiger Imprägnierung, wobei eine Vollimprägnierung nicht vorliegt. In der Mitte liegt demzufolge eine geringere Konzentration als im Oberflächenbereich vor.The impregnation liquor can be applied to one side but also to both sides of the base paper become. If the impregnation liquor is applied to one side, then the training is the surface of the screen side of the base paper is important, for which a control of the Temperature curve of the predrying group of the paper machine is extremely important. At impregnation on both sides, the impregnation can take place completely, d. H. she can in penetrate the entire mass of paper. The total intake amount of impregnation liquor through the base paper depends on the type of base paper, but also that of Pressing off the excess impregnation liquor from the paper web. Framework for the amount of the impregnation liquor introduced into the base paper, about 15 to 30% Resin content, preferably about 18 to 27% resin content, with impregnation on both sides, but there is no full impregnation. There is therefore a lower one in the middle Concentration than in the surface area.

Gegenüber dem eingangs geschilderten Vorimprägnat besitzt das erfindungsgemäße Vorimprägnat den Vorteil, daß es beim Anwenden nicht zu einem Vergilben der Weiterverarbeitungsprodukte führt. Dies geht darauf zurück, daß der Bestandteil des Glyoxal/Harnstoff-Vorkondensates durch einen Trockenverfestiger auf Basis eines Copolymerisats aus (Meth)acrylamid und (Meth)acrylsäure mit schwach anionischer Ladung ersetzt wurde. Der Trockenverfestiger wird üblicherweise in der Masse eingesetzt und führt physikalisch zu einer Faserverfestigung, die im Endprodukt die Trockenfestigkeit verbessert, nicht dagegen die Naßfestigkeit. Dies zeigt, daß der Trockenverfestiger nur physikalisch faserverklebend wirkt und das Fasergefüge nicht durch chemische Reaktion verfestigt wird.Compared to the pre-impregnate described above, the pre-impregnate according to the invention has the advantage that the processing products do not turn yellow when applied leads. This is due to the fact that the component of the glyoxal / urea precondensate by a dry strength agent based on a copolymer (Meth) acrylamide and (meth) acrylic acid with a weakly anionic charge was replaced. Of the Dry strength agent is usually used in bulk and physically leads to a fiber consolidation, which improves the dry strength in the end product, not against it the wet strength. This shows that the dry strength agent is only physically fiber adhesive acts and the fiber structure is not solidified by chemical reaction.

Das erfindungsgemäße Vorimprägnat kann zur Herstellung von Dekorverbundgebilden verwendet werden. So können beispielsweise dekorative Laminate mit dem erfindungsgemäßen Vorimprägnat hergestellt werden. Sie werden unter Anwendung von Wärme und Druck sowie geeigneten Leimsystemen in Pressen bzw. Kaschieranlagen hergestellt. Insbesondere werden Spanplatten und mitteldichte Faserplatten (MDF-Platten) beidseitig mit dem erfindungsgemäßen Vorimprägnat beschichtet. Das Vorimprägnat dient auch als dekortragende Komponente.The pre-impregnate according to the invention can be used for the production of decorative composite structures become. For example, decorative laminates with the invention Pre-impregnated. They are applied using heat and pressure as well as suitable glue systems in presses or laminating plants. Especially chipboard and medium density fibreboard (MDF) on both sides with the coated according to the invention. The pre-impregnate also serves as decor-bearing component.

Auch bei der Herstellung von Möbeln werden in großem Umfang Holzwerkstoffe auf Basis von Spanplatten eingesetzt. Die optisch oft unansehnliche Oberfläche dieser Holzwerkstoffe und deren eingeschränkter Gebrauchswert erfordern den Einsatz von Beschichtungsmaterialien. Hierzu bietet sich das erfindungsgemäße Vorimprägnat an. Die erfindungsgemäße Folie kann jede beliebige Holzmaserung oder jedes beliebige Phantasiedekor besitzen. In einen, weiteren Arbeitsgang kann das Vorimprägnat lackiert werden. Zum Einsatz kommen insbesondere Transparentlacke, wie z. B. Acrylatlacke säurehärtende, wasserlösliche und pigmentierte Lacke. Neben der Schutzfunktion des Lacks verleiht dieser den, Vorimprägnat auch einen entsprechenden optischen Eindruck.Wood-based materials are also used extensively in the manufacture of furniture of chipboard used. The often unsightly surface of these wood materials and their limited use value require the use of coating materials. The prepreg according to the invention is suitable for this. The invention Foil can have any wood grain or any fancy decor. In the pre-impregnate can be varnished in a further step. Are used in particular transparent paints, such as. B. acrylic paints acid-curing, water-soluble and pigmented paints. In addition to the protective function of the lacquer, this gives the pre-impregnate also a corresponding visual impression.

Nachfolgend wird die Erfindung anhand von Beispielen noch näher erläutert:The invention is explained in more detail below with the aid of examples:

Beispielexample

Erfindungsgemäß wurde ein Rohpapier folgender Zusammensetzung hergestellt: 20% Kiefersulfat-Zellstoff und 80% Eukalyptuszellstoff. Der Mahlgrad betrug 31°SR (Schopper-Riegler). Als Zusätze wurden (auf otro Zellstoff) 30% Titandioxid und 4% formaldehydfreies Naßfestmittel eingesetzt.According to the invention, a base paper of the following composition was produced: 20% pine sulfate pulp and 80% eucalyptus pulp. The freeness was 31 ° SR (Schopper-Riegler). 30% titanium dioxide and 4% were added (on otro pulp) formaldehyde-free wet strength agent used.

Dieses Rohpapier mit einem Flächengewicht von 50 g/m2 wurde mit der erfindungsgemäßen Imprägnierflotte in Verhältnis 7:1 in einer Leimpresse beidseitig imprägniert, wobei mit Wasser der notwendige Feststoffgehalt eingestellt wurde. Eigenschaften Imprägniertes Rohpapier Rezeptur 1 2 3 4 Wasserfestigkeit in Ordnung schlecht gut gut Spaltfestigkeit schlecht schlecht in Ordnung in Ordnung Farbdifferenz dL -0,6 -0,4 -0,6 -2,2 Cie Lab da -0,2 -0,1 -0,1 0,4 db 2,9 1,4 1,5 6,2 dE 3,0 1,5 1,6 6,6 This base paper with a weight per unit area of 50 g / m 2 was impregnated on both sides with the impregnating liquor according to the invention in a 7: 1 ratio in a size press, the necessary solids content being set with water. characteristics Impregnated base paper Recipe 1 2nd 3rd 4th Water resistance okay bad Good Good Gap resistance bad bad okay okay Color difference dL -0.6 -0.4 -0.6 -2.2 Cie Lab there -0.2 -0.1 -0.1 0.4 db 2.9 1.4 1.5 6.2 dE 3.0 1.5 1.6 6.6

Daraus ergeben sich dann die Farbdifferenzen dL (Helligkeitsverschiebung), da (Rot-Grünverschiebung) db (Blau-Gelbverschiebung) und dE (Gesamtfarbverschiebung) der hitzebehandelten zur unbehandelten Folie.This then results in the color differences dL (brightness shift), since (red-green shift) db (blue-yellow shift) and dE (total color shift) of heat-treated to untreated film.

Rezepturen:Recipes:

  • 1.) Dispersion allein (Acrylsäureester/Styrol-Copolymer), verdünnt auf 30% Feststoffgehalt.1.) Dispersion alone (acrylic acid ester / styrene copolymer), diluted to 30% Solids content.
  • 2.) Trockenverfestiger allein (Acrylamid/Acrylsäure), verdünnt 10% Feststoffgehalt.2.) Dry strength agent alone (acrylamide / acrylic acid), diluted 10% solids content.
  • 3.) Erfindungsgemäße Imprägnierflotte, bestehend aus Dispersion (Rezept 1) und Trockenverfestiger (Rezept 2) im Verhältnis 7:1, verdünnt mit Wasser auf 30% Feststoffgehalt.3.) Impregnation liquor according to the invention, consisting of dispersion (recipe 1) and Dry hardener (recipe 2) in a ratio of 7: 1, diluted with water to 30% Solids content.
  • 4.) Rezeptur mit Glyoxal/Harnstoffharz und Dispersion.4.) Recipe with glyoxal / urea resin and dispersion.

    • Aus obiger Tabelle ist ersichtlich, daß die Dispersion allein eine schlechte Spaltfestigkeit zeigt. Der Trockenverfestiger allein bildet eine zu geringe Wasserfestigkeit aus und neigt zu schlechter Spaltfestigkeit. Die erfindungsgemäße Imprägnierflotte führt zu guter Wasserfestigkeit und genügender Spaltfestigkeit, ebenso wie Rezeptur 4. Jedoch zeigt die erfindungsgemäße Imprägnierflotte 3 im Gegensatz zur Rezeptur 4 eine deutlich geringere Gelbverschiebung (db-Wert) nach der Hitzebehandlung.From the table above it can be seen that the dispersion alone has poor splitting resistance shows. The dry strength agent alone has insufficient water resistance and tends to poor splitting resistance. The impregnation liquor according to the invention leads to good ones Water resistance and sufficient splitting resistance, as well as formulation 4. However, the Impregnation liquor 3 according to the invention, in contrast to formulation 4, is significantly smaller Yellow shift (db value) after heat treatment.

    Claims (15)

    Verfahren zur Herstellung eines Vorimprägnats, dadurch gekennzeichnet, daß ein Rohpapier mit einer Imprägnierflotte imprägniert wird, die a) eine wäßrige Dispersion auf Basis eines Acrylsäureester/Styrol-Copolymers, b) einen Trockenverfestiger auf Basis eines Copolymerisats aus (Meth-)Acrylamid und (Meth-)Acrylsäure und c) Wasser enthält, wobei pro Gew.-Teil trockenem Copolymerisat aus (Meth-)Acrylamid und (Meth-)Acrylsäure etwa 0,3 bis 13 Gew.-Teile trockenes Acrylsäureester/Styrol-Copolymer eingesetzt werden.Process for producing a pre-impregnate, characterized in that a base paper is impregnated with an impregnating liquor which a) is an aqueous dispersion based an acrylic acid ester / styrene copolymer, b) a dry strength agent based on a Contains copolymer of (meth) acrylamide and (meth) acrylic acid and c) water, wherein per part by weight of dry copolymer of (meth) acrylamide and (meth) acrylic acid, for example 0.3 to 13 parts by weight of dry acrylic acid ester / styrene copolymer can be used. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß pro Gew.-Teil trockenem Copolymerisat aus (Meth-)Acrylamid und (Meth-)Acrylsäure etwa 1 bis 9 Gew.-Teile, insbesondere etwa 3 bis 7 Gew.-Teile, trockenes Acrylsäureester/Styrol-Copolymer eingesetzt werden.A method according to claim 1, characterized in that dry per part by weight Copolymer of (meth) acrylamide and (meth) acrylic acid about 1 to 9 parts by weight, especially about 3 to 7 parts by weight, dry acrylic acid ester / styrene copolymer be used. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß der pH-Wert der Imprägnierflotte auf etwa 4,5 bis 8,0, insbesondere auf etwa 5,0 bis 5,5, eingestellt wird.A method according to claim 1 or 2, characterized in that the pH of the impregnation liquor is set to about 4.5 to 8.0, in particular to about 5.0 to 5.5. Verfahren nach einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, daß die Viskosität der Imprägnierflotte auf etwa 10 bis 18 sec, insbesondere auf etwa 11 bis 14 sec, eingestellt wird.Method according to one of the preceding claims, characterized in that the viscosity of the impregnation liquor to about 10 to 18 seconds, in particular to about 11 to 14 sec. Verfahren nach einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, daß der Feststoffgehalt der Imprägnierflotte auf etwa 15 bis 50 Gew.-%, insbesondere auf etwa 25 bis 35 Gew.-%, eingestellt wird.Method according to one of the preceding claims, characterized in that the solids content of the impregnation liquor to about 15 to 50 wt .-%, in particular to about 25 to 35 wt .-%, is set. Verfahren nach mindestens einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, daß als Acrylsäureester n-Butylacrylat eingesetzt wird. Method according to at least one of the preceding claims, characterized in that that n-butyl acrylate is used as the acrylic acid ester. Verfahren nach mindestens einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, daß als Trockenverfestiger ein Copolymerisat aus Acrylamid und Acrylsäure eingesetzt wird.Method according to at least one of the preceding claims, characterized in that that a copolymer of acrylamide and acrylic acid is used as a dry strength agent becomes. Verfahren nach einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, daß als Rohpapier ein Zellstoffasergemisch aus 0-40% Langfaser und 60-100% Kurzfaser eingesetzt wird.Method according to one of the preceding claims, characterized in that as raw paper a cellulose fiber mixture of 0-40% long fiber and 60-100% short fiber is used. Verfahren nach mindestens einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, daß der Mahlgrad des Rohpapiers auf etwa 18 bis 50°SR, insbesondere auf etwa 25 bis 35°SR, eingestellt wird.Method according to at least one of the preceding claims, characterized in that that the degree of grinding of the base paper to about 18 to 50 ° SR, in particular to about 25 to 35 ° SR, is set. Verfahren nach mindestens einem der vorangegangenen Ansprüche, dadurch gekennzeichnet, daß der Langfaseranteil des Rohpapiers auf etwa 0 bis 40%, insbesondere auf etwa 15 bis 30%, und der Kurzfaseranteil des Rohpapiers auf etwa 60 bis 100%, insbesondere auf etwa 70 bis 85% eingestellt wird.Method according to at least one of the preceding claims, characterized in that that the long fiber content of the base paper to about 0 to 40%, in particular to about 15 to 30%, and the short fiber content of the base paper to about 60 to 100%, in particular is set to about 70 to 85%. Vorimprägnat erhältlich gemäß dem Verfahren nach mindestens einem der vorangegangenen Ansprüche.Pre-impregnate obtainable according to the method according to at least one of the preceding Expectations. Verwendung des Vorimprägnats nach Anspruch 11 zur Herstellung von Dekorverbundgebilden.Use of the pre-impregnate according to claim 11 for the production of decorative composite structures. Verwendung nach Anspruch 12 zur Herstellung von dekorativen Laminaten.Use according to claim 12 for the production of decorative laminates. Verwendung nach Anspruch 12 zur Herstellung von Möbelteilen, insbesondere auf Basis von Spanplatten.Use according to claim 12 for the production of furniture parts, in particular based of chipboard. Imprägnierflotte, wie in einem der Ansprüche 1 bis 7 definiert.Impregnation liquor as defined in any one of claims 1 to 7.
    EP98107656A 1997-07-02 1998-04-27 Process for making a prepreg, and use of the same for making decorative laminates Expired - Lifetime EP0889168B1 (en)

    Applications Claiming Priority (2)

    Application Number Priority Date Filing Date Title
    DE19728250 1997-07-02
    DE1997128250 DE19728250C2 (en) 1997-07-02 1997-07-02 Process for producing a pre-impregnate, the pre-impregnate obtained therewith and its use for the production of decorative composite structures

    Publications (3)

    Publication Number Publication Date
    EP0889168A2 true EP0889168A2 (en) 1999-01-07
    EP0889168A3 EP0889168A3 (en) 2000-03-01
    EP0889168B1 EP0889168B1 (en) 2005-06-29

    Family

    ID=7834415

    Family Applications (1)

    Application Number Title Priority Date Filing Date
    EP98107656A Expired - Lifetime EP0889168B1 (en) 1997-07-02 1998-04-27 Process for making a prepreg, and use of the same for making decorative laminates

    Country Status (7)

    Country Link
    US (2) US6113987A (en)
    EP (1) EP0889168B1 (en)
    BR (1) BR9802621B1 (en)
    CA (1) CA2240011C (en)
    CZ (1) CZ292989B6 (en)
    DE (1) DE19758479C2 (en)
    PL (1) PL196113B1 (en)

    Cited By (8)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    WO2001011139A1 (en) * 1999-06-11 2001-02-15 Unidur Gmbh Composition for the impregnation of paper, method for the production thereof, impregnated paper and laminate comprising said impregnated paper
    WO2001077438A1 (en) * 2000-04-05 2001-10-18 Basf Aktiengesellschaft Polymer dispersion for impregnating paper
    WO2007082819A1 (en) * 2006-01-13 2007-07-26 Basf Se Use of an aqueous polymer composition for impregnating raw paper
    DE102008041296A1 (en) 2007-08-22 2009-03-19 Basf Se Aqueous impregnating agent, useful for impregnating raw or glued papers, comprises an urea derivative and an emulsion polymer, where the emulsion polymer contains ethylenically unsaturated monomer containing e.g. epoxide group
    CN102837554A (en) * 2011-06-22 2012-12-26 舍尔勒尔电子元件两合公司 Prepreg
    EP2589499A1 (en) * 2010-06-30 2013-05-08 Flooring Technologies Ltd. Primed panel made of wooden material
    DE102013114420A1 (en) 2012-12-23 2014-06-26 Michael Jokiel Impregnated paper comprises base paper which is impregnated on one side with water-based impregnating solution comprising e.g. aqueous dispersion of styrene-ethyl-butyl acrylate copolymer and aqueous dispersion of styrene-acrylate copolymer
    WO2014177258A1 (en) * 2013-05-03 2014-11-06 Schattdecor Ag Method for producing a printable single or multi-layered material web as well as a material web produced in this manner and an associated installation for producing such a material web

    Families Citing this family (4)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    WO1999024292A1 (en) 1997-11-11 1999-05-20 Giok Djien Go Retainer device with shoulder arrester for transport systems
    DE10134302C1 (en) * 2001-07-14 2002-12-12 Technocell Dekor Gmbh & Co Kg Pre-impregnate obtained by impregnation of crude paper with a thermally hardenable formaldehyde-free resin useful in the production of decorative impregnates or coatings, and surface treatment of printed and unprinted papers
    EP2843129B2 (en) * 2013-08-30 2023-06-07 Saint-Gobain Placo Reinforced gypsum board having improved fire resistance
    CN110791997B (en) * 2019-11-22 2020-08-04 山东华沙新材料有限公司 Back coating for anti-slip coating on back surface of paper for coating abrasive tool and method for preparing paper for coating abrasive tool by using back coating

    Citations (6)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    DE2854491A1 (en) * 1978-12-16 1980-06-26 Bayer Ag METHOD FOR PRODUCING COPOLYMER DISPERSIONS
    DE2903172A1 (en) * 1979-01-27 1980-08-07 Roehm Gmbh METHOD FOR PRODUCING PLASTIC-IMPREGNATED PAPERS, FIBER FLEECE AND THE LIKE
    US4294873A (en) * 1979-01-27 1981-10-13 Basf Aktiengesellschaft Manufacture of paper having a high dry strength and a low wet strength
    EP0223922A1 (en) * 1985-11-21 1987-06-03 Kämmerer Gmbh Process for producing paper webs impregnated with synthetic resins in a soluble or dispersed form
    WO1994000523A1 (en) * 1992-06-22 1994-01-06 Gebrueder Buhl Papierfabriken Gmbh Aqueous impregnating composition
    WO1997008384A1 (en) * 1995-08-25 1997-03-06 Cytec Technology Corp. Methods and agents for improving paper printability and strength

    Family Cites Families (4)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    DE223922C (en)
    JPS5182011A (en) * 1974-12-24 1976-07-19 Nippon Synthetic Chem Ind KAMINOHYOMENKOTAKUFUYOHOHO
    JPS61207697A (en) * 1985-03-13 1986-09-16 日本カ−リツト株式会社 Surface processing agent of paper
    US5851684A (en) 1992-06-22 1998-12-22 Arjo Wiggins Deutschland Gmbh Decorative sheets used in the production of laminated panels

    Patent Citations (6)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    DE2854491A1 (en) * 1978-12-16 1980-06-26 Bayer Ag METHOD FOR PRODUCING COPOLYMER DISPERSIONS
    DE2903172A1 (en) * 1979-01-27 1980-08-07 Roehm Gmbh METHOD FOR PRODUCING PLASTIC-IMPREGNATED PAPERS, FIBER FLEECE AND THE LIKE
    US4294873A (en) * 1979-01-27 1981-10-13 Basf Aktiengesellschaft Manufacture of paper having a high dry strength and a low wet strength
    EP0223922A1 (en) * 1985-11-21 1987-06-03 Kämmerer Gmbh Process for producing paper webs impregnated with synthetic resins in a soluble or dispersed form
    WO1994000523A1 (en) * 1992-06-22 1994-01-06 Gebrueder Buhl Papierfabriken Gmbh Aqueous impregnating composition
    WO1997008384A1 (en) * 1995-08-25 1997-03-06 Cytec Technology Corp. Methods and agents for improving paper printability and strength

    Cited By (10)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    WO2001011139A1 (en) * 1999-06-11 2001-02-15 Unidur Gmbh Composition for the impregnation of paper, method for the production thereof, impregnated paper and laminate comprising said impregnated paper
    WO2001077438A1 (en) * 2000-04-05 2001-10-18 Basf Aktiengesellschaft Polymer dispersion for impregnating paper
    US6767646B2 (en) 2000-04-05 2004-07-27 Basf Aktiengesellschaft Polymer dispersion for impregnating paper
    WO2007082819A1 (en) * 2006-01-13 2007-07-26 Basf Se Use of an aqueous polymer composition for impregnating raw paper
    DE102008041296A1 (en) 2007-08-22 2009-03-19 Basf Se Aqueous impregnating agent, useful for impregnating raw or glued papers, comprises an urea derivative and an emulsion polymer, where the emulsion polymer contains ethylenically unsaturated monomer containing e.g. epoxide group
    EP2589499A1 (en) * 2010-06-30 2013-05-08 Flooring Technologies Ltd. Primed panel made of wooden material
    CN102837554A (en) * 2011-06-22 2012-12-26 舍尔勒尔电子元件两合公司 Prepreg
    DE102013114420A1 (en) 2012-12-23 2014-06-26 Michael Jokiel Impregnated paper comprises base paper which is impregnated on one side with water-based impregnating solution comprising e.g. aqueous dispersion of styrene-ethyl-butyl acrylate copolymer and aqueous dispersion of styrene-acrylate copolymer
    WO2014177258A1 (en) * 2013-05-03 2014-11-06 Schattdecor Ag Method for producing a printable single or multi-layered material web as well as a material web produced in this manner and an associated installation for producing such a material web
    RU2661211C2 (en) * 2013-05-03 2018-07-13 Шаттдекор Аг Suitable for printing one- or multi-layer material manufacturing method, and also a material web manufactured by this method and the appropriate plant for such materials manufacturing

    Also Published As

    Publication number Publication date
    BR9802621A (en) 1999-12-28
    EP0889168A3 (en) 2000-03-01
    CA2240011C (en) 2006-09-19
    CA2240011A1 (en) 1999-01-02
    CZ145498A3 (en) 1999-01-13
    PL196113B1 (en) 2007-12-31
    US6113987A (en) 2000-09-05
    US6312827B1 (en) 2001-11-06
    DE19758479C2 (en) 2002-07-11
    DE19758479A1 (en) 1999-01-07
    EP0889168B1 (en) 2005-06-29
    PL327120A1 (en) 1999-01-04
    CZ292989B6 (en) 2004-01-14
    BR9802621B1 (en) 2008-11-18

    Similar Documents

    Publication Publication Date Title
    EP1407079B1 (en) Prepreg
    DE102007030102B4 (en) prepreg
    DE19728250C2 (en) Process for producing a pre-impregnate, the pre-impregnate obtained therewith and its use for the production of decorative composite structures
    DE19758479C2 (en) impregnating
    DE2348571A1 (en) LAMINATES AND METHODS FOR THEIR PRODUCTION
    DE3541187C2 (en) Process for producing a paper web impregnated with synthetic resins and their use
    WO2005118718A1 (en) Method for producing coated substrates
    EP2537682B1 (en) Prepreg
    EP0870872B1 (en) One-side impregnated printing paper support
    DE10307966C5 (en) Preimpregnate and process for its preparation
    EP3754109B1 (en) Pre-impregnate with improved flatness
    DE19715268A1 (en) Laminating sheet, e.g. for chipboard laminates
    EP0002044B1 (en) Impregnation agent for cellulosic fibrous materials
    DE19946151B4 (en) Process for the preparation of a prepreg, the prepreg prepared therefrom and its use
    DE102013114420A1 (en) Impregnated paper comprises base paper which is impregnated on one side with water-based impregnating solution comprising e.g. aqueous dispersion of styrene-ethyl-butyl acrylate copolymer and aqueous dispersion of styrene-acrylate copolymer
    DE1446609B1 (en) Process for the production of plastic-containing papers by adding plastic dispersions to the fiber material prior to sheet formation
    DE102004026481A1 (en) Production of coated substrates with a 3-dimensional structured surface, e.g. furniture parts, involves press-coating with melamine resin-impregnated paper containing synthetic polymer fibres
    DE2500164B2 (en) LAMINATE FOR THE SURFACE FINISHING OF WOOD-BASED PANELS
    DE102004026480A1 (en) Production of coated substrates with a 3-dimensional structured surface, e.g. furniture parts, involves press-coating with melamine resin-impregnated paper containing synthetic polymer fibres

    Legal Events

    Date Code Title Description
    PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

    Free format text: ORIGINAL CODE: 0009012

    AK Designated contracting states

    Kind code of ref document: A2

    Designated state(s): FR GB IT SE

    AX Request for extension of the european patent

    Free format text: AL;LT;LV;MK;RO;SI

    PUAL Search report despatched

    Free format text: ORIGINAL CODE: 0009013

    AK Designated contracting states

    Kind code of ref document: A3

    Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

    AX Request for extension of the european patent

    Free format text: AL;LT;LV;MK;RO;SI

    17P Request for examination filed

    Effective date: 20000714

    AKX Designation fees paid

    Free format text: FR GB IT SE

    17Q First examination report despatched

    Effective date: 20030612

    REG Reference to a national code

    Ref country code: DE

    Ref legal event code: 8566

    GRAP Despatch of communication of intention to grant a patent

    Free format text: ORIGINAL CODE: EPIDOSNIGR1

    GRAS Grant fee paid

    Free format text: ORIGINAL CODE: EPIDOSNIGR3

    GRAA (expected) grant

    Free format text: ORIGINAL CODE: 0009210

    AK Designated contracting states

    Kind code of ref document: B1

    Designated state(s): FR GB IT SE

    REG Reference to a national code

    Ref country code: GB

    Ref legal event code: FG4D

    Free format text: NOT ENGLISH

    GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

    Effective date: 20050629

    REG Reference to a national code

    Ref country code: SE

    Ref legal event code: TRGR

    ET Fr: translation filed
    PLBE No opposition filed within time limit

    Free format text: ORIGINAL CODE: 0009261

    STAA Information on the status of an ep patent application or granted ep patent

    Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

    26N No opposition filed

    Effective date: 20060330

    REG Reference to a national code

    Ref country code: FR

    Ref legal event code: PLFP

    Year of fee payment: 19

    REG Reference to a national code

    Ref country code: FR

    Ref legal event code: PLFP

    Year of fee payment: 20

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: GB

    Payment date: 20170426

    Year of fee payment: 20

    Ref country code: FR

    Payment date: 20170428

    Year of fee payment: 20

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: IT

    Payment date: 20170420

    Year of fee payment: 20

    Ref country code: SE

    Payment date: 20170427

    Year of fee payment: 20

    REG Reference to a national code

    Ref country code: GB

    Ref legal event code: PE20

    Expiry date: 20180426

    REG Reference to a national code

    Ref country code: SE

    Ref legal event code: EUG

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: GB

    Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

    Effective date: 20180426