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EP2158096B1 - Préimprégné - Google Patents

Préimprégné Download PDF

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Publication number
EP2158096B1
EP2158096B1 EP08761274A EP08761274A EP2158096B1 EP 2158096 B1 EP2158096 B1 EP 2158096B1 EP 08761274 A EP08761274 A EP 08761274A EP 08761274 A EP08761274 A EP 08761274A EP 2158096 B1 EP2158096 B1 EP 2158096B1
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EP
European Patent Office
Prior art keywords
weight
paper
molecular weight
mol
molecules
Prior art date
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Application number
EP08761274A
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German (de)
English (en)
Other versions
EP2158096A1 (fr
Inventor
Martina Wicher
Mirko Standke
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.)
Schoeller Technocell GmbH and Co KG
Original Assignee
Technocell Dekor 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
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Application filed by Technocell Dekor GmbH and Co KG filed Critical Technocell Dekor GmbH and Co KG
Priority to PL08761274T priority Critical patent/PL2158096T3/pl
Publication of EP2158096A1 publication Critical patent/EP2158096A1/fr
Application granted granted Critical
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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
    • 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
    • D21H27/20—Flexible structures being applied by the user, e.g. wallpaper
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/28—Starch
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
    • 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/54—Starch
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/58—Polymers or oligomers of diolefins, aromatic vinyl monomers or unsaturated acids 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]
    • Y10T428/31855—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]
    • Y10T428/31971—Of carbohydrate
    • 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]
    • Y10T428/31971—Of carbohydrate
    • Y10T428/31975—Of cellulosic next to another carbohydrate
    • 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]
    • Y10T428/31971—Of carbohydrate
    • Y10T428/31975—Of cellulosic next to another carbohydrate
    • Y10T428/31978—Cellulosic next to another 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]
    • Y10T428/31971—Of carbohydrate
    • Y10T428/31975—Of cellulosic next to another carbohydrate
    • Y10T428/31978—Cellulosic next to another cellulosic
    • Y10T428/31986—Regenerated or modified
    • 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]
    • Y10T428/31971—Of carbohydrate
    • Y10T428/31993—Of paper

Definitions

  • the invention relates to prepregs and decorative impregnates or decorative coating materials obtainable therefrom.
  • Decorative coating materials are preferably used for surface coating in the production of furniture and in interior fittings, in particular laminate floors.
  • Decorative paper / decorative film is understood as meaning resin-impregnated or resin-impregnated and surface-treated, printed or unprinted papers.
  • Decorative papers / decorative foils are glued or glued with a carrier plate.
  • urea glues or polyvinyl acetate (PVAC) glues are used for gluing the decorative films on wood materials such as chipboard or MDF board.
  • the bonding of the decorative films is not always guaranteed.
  • High pressure laminates are laminates produced by pressing several impregnated, laminated papers together.
  • the structure of these laminates generally consists of a highest surface resistance generating transparent overlay sheet (overlay), a resin-impregnated decorative paper and one or more phenolbehechen kraft papers.
  • overlay transparent overlay sheet
  • resin-impregnated decorative paper resin-impregnated decorative paper
  • phenolbehechen kraft papers resin-impregnated decorative paper
  • hardboard and chipboard and plywood are used.
  • the decorative paper impregnated with synthetic resin is pressed directly with a base, for example a chipboard, using a low pressure.
  • the decorative paper used in the above-mentioned coating materials is used white or colored with or without additional imprint.
  • the so-called decorative base papers serving as starting materials must fulfill certain requirements. These include high opacity for better coverage of the substrate, uniform formation and grammage of the sheet for uniform resin absorption, high light resistance, high purity and uniformity of color for good reproducibility of the pattern to be printed, high wet strength for a smooth impregnation process, corresponding absorbency to obtain the required resin saturation level, dry strength, which is important in Umrollvorêtn in the paper machine and printing in the printing press. Furthermore, the splitting resistance is of particular importance, as it is a measure of how well the decorative base paper can be processed. For example, the glued decorative paper / decorative foil must not fray during processing steps such as sawing or drilling.
  • the decorative base papers are printed.
  • the so-called rotogravure printing method in which the printed image is transferred to the paper with the aid of several gravure rolls.
  • the individual pressure points should be completely and intensively transferred to the paper surface.
  • the ink penetrates too deeply into the paper texture, reducing color intensity.
  • Prerequisites for a good print image with few defects and high color intensity are as smooth and homogeneous a surface topography as possible and a coordinated ink acceptance behavior of the paper surface.
  • base papers are usually smoothed with so-called soft calenders, sometimes called Janus calenders.
  • This treatment can lead to pinching of the paper surface and thus to its compression, which has a detrimental effect on the resin receptivity.
  • the aforementioned properties are substantially dependent on the impregnation of the decorative base paper, i. influenced by the type of impregnating agent used.
  • the impregnating resin solutions customarily used for the impregnation of decorative base papers are resins based on urea, melamine or phenolic resins and containing formaldehyde and lead to brittle products with poor tear strength and printability.
  • Formaldehyde-free impregnating resin solutions for the impregnation of decorative base paper are also in the EP 0 648 248 A1 and EP 0 739 435 A1 described. These are preferably made of a styrene-acrylic acid ester copolymer and polyvinyl alcohol. However, the paper impregnated with such an impregnating resin solution can still be improved in terms of the splitting strength.
  • the EP 1 176 255 A1 describes starch-containing dispersions as binders for coating papers in order to improve the printability of the papers.
  • the WO 2007/000420 A1 describes starch-containing polymer dispersions with an improved sizing action on alum-containing papers.
  • the EP 0 648 248 B1 describes an aqueous preparation for impregnating a decorative base paper containing a styrene-ethyl acrylate-butyl acrylate copolymer and another binder, which may for example be any starch.
  • the EP 0 739 435 B1 describes a similar impregnating resin formulation with any polymer and a water-soluble binder, which may be starch.
  • WO 01/11139 is a formaldehyde-free composition consisting of a binder, an aqueous Polymer dispersion and glyoxal proposed, which allows the production of splitting resistant decorative papers.
  • the paper impregnated with this composition does not laminate well.
  • the invention is therefore based on the object to provide a formaldehyde-free prepreg, which does not have the disadvantages mentioned above and is characterized in particular by good printability and high nip strength.
  • This object is achieved by a pre-impregnate obtainable by impregnating a base paper with an impregnating resin solution containing at least one polymer latex and at least one modified starch having a molecular weight distribution expressed by a polydispersity index Mw / Mn of 6 to 23.
  • the polydispersity index is usually the ratio of weight and number average molecular weight Mw / Mn. It gives information about the width of the molecular weight distribution curve.
  • the molecular weight distribution of the modified starches was determined by gel permeation chromatography (GPC) in the usual way from the starch manufacturer.
  • GPC gel permeation chromatography
  • the GPC analysis was carried out with a chromatograph with columns Shodex KS.
  • the eluent was 0.05 M NaOH at a flow rate of 1 ml / min.
  • Calibration was done with pullulan standards of known molecular weights.
  • All modified starches used according to the invention are commercially available. These are in particular thermally and oxidatively degraded corn and potato starches.
  • Preimpregnate according to the invention are understood to mean partially impregnated papers.
  • the amount of the impregnating resin is preferably from 10 to 35% by weight, but in particular from 12 to 30% by weight, based on the basis weight of the decorative base paper.
  • the impregnating resin solution according to the invention is particularly well suited, since it not only leads to improving the nip strength of the paper impregnated therewith, but also with respect to other properties such as printability, paint level or yellowing good or even better results than the prior art allows.
  • the otherwise usual when using hydrophilic binder problems when laminating (gluing or gluing with the pad) of the impregnated papers do not occur.
  • the impregnating resin solution according to the invention makes it possible to produce prepregs with good laminatability.
  • Another advantage is that the prepreg can be inexpensively manufactured at high machine speeds.
  • the polymer latex may preferably be a styrene copolymer such as a styrene-acrylic acid ester copolymer, a styrene-vinyl acetate copolymer, a styrene-butadiene or a styrene-maleic acid copolymer. But mixtures of these copolymers can be used. Particular preference is given to polymers which have high self-crosslinkability. But not self-crosslinking polymers are suitable.
  • the impregnating resin solution used to prepare the prepreg according to the invention contains an ethyl-free styrene-acrylic ester.
  • the amount ratio of starch / polymer latex in the impregnating resin solution is preferably 80/20 to 20/80, preferably However, a ratio of 45/55 to 65/35 and in particular 50/50 to 60/40, in each case based on the mass of the impregnating resin (atro).
  • the impregnating resin solution contains pigments and / or fillers.
  • the amount of the pigment and / or filler may be from 1 to 30% by weight, in particular from 2 to 20% by weight.
  • the quantity refers to the binder mass (atro).
  • binder is to be understood as meaning the mixture containing the polymer latex and the modified starch.
  • the impregnating resin solution used to prepare the prepregs according to the invention has a total solids content, based on the dry mass, of 9 to 40% by weight, preferably 20 to 35% by weight and particularly preferably 26 to 30% by weight.
  • the starch In the preparation of Tränkharzaims the starch is first applied, which is either cold, that is dissolved at room temperature to at most 60 ° C in water or cooked at about 120 to 145 ° C. In this case, an about 40 to 45% suspension with a pH of about 5 to 6 is generated. In the next step, taking into account the desired solids content and the quantity ratio of starch / latex, the addition of an approximately 50% latex dispersion takes place at a pH of from 5 to 10. In a further step, a pigment or filler addition can take place.
  • the decorative base papers to be impregnated are those which have undergone neither a sizing in the mass nor a surface sizing. They consist essentially of pulps, pigments and fillers and conventional additives. Common additives may be wet strength agents, retention aids and fixatives. Decorative base papers differ from conventional papers due to the much higher filler content or pigment content and the lack of standard paper sizing or surface sizing on paper.
  • the base paper to be impregnated according to the invention may contain a high proportion of a pigment or a filler.
  • the proportion of the filler in the base paper can be up to 55% by weight, in particular 8 to 45% by weight, based on the weight per unit area.
  • Suitable pigments and fillers are, for example, titanium dioxide, talc, zinc sulfide, kaolin, aluminum oxide, calcium carbonate, corundum, aluminum and magnesium silicates or mixtures thereof.
  • Softwood pulps long fiber pulps
  • / or hardwood pulps short fiber pulps
  • the use of cotton fibers and mixtures thereof with the aforementioned types of pulp can also be used.
  • 100% by weight hardwood pulp has proven to be advantageous.
  • the quantities are based on the mass of the pulps (atro).
  • the pulp mixture may contain a proportion of cationically modified pulp fibers of at least 5% by weight, based on the weight of the pulp mixture.
  • a proportion of 10 to 50% by weight, in particular 10 to 20% by weight, of the cationically modified pulp in the pulp mixture has proved to be particularly advantageous.
  • the cationic modification of the pulp fibers can be accomplished by reaction of the fibers with an epichlorohydrin resin and a tertiary amine or by reaction with quaternary ammonium chlorides such as chlorohydroxypropyltrimethylammonium chloride or glycidyltrimethylammonium chloride. Cationically modified pulps and their preparation are for example made THE PAPER, Issue 12 (1980) p.575-579 known.
  • the base papers can be produced on a Fourdrinier paper machine or a Yankee paper machine.
  • the pulp mixture can be ground at a consistency of 2 to 5 wt.% To a freeness of 10 to 45 ° SR.
  • fillers such as titanium dioxide and talc, and wet strength agents can be added and mixed well with the pulp mixture.
  • the resulting thick stock can be diluted to a stock consistency of about 1% and, if necessary, further auxiliaries such as retention aids, defoamers, aluminum sulfate and other auxiliaries mentioned above are mixed.
  • This thin material is fed to the wire section via the headbox of the paper machine.
  • a non-woven fabric is formed and, after dewatering, the base paper is obtained, which is subsequently dried.
  • the basis weights of the papers produced can be 15 to 300 g / m 2 . Particularly suitable However, are base papers with a basis weight of 40 to 100 g / m 2 .
  • the application of the impregnating resin solution to be used according to the invention can be carried out in the paper machine or offline by spraying, impregnating, roller application or brushing (doctor blade). Particularly preferred is an order for size presses or film presses.
  • the impregnation of the impregnated papers is carried out in the usual way with the aid of IR or drum dryers in a temperature range from 120 to 180 ° C. up to a residual moisture content of 2 to 6%.
  • the papers (prepregs) impregnated in this way can be printed and varnished and subsequently laminated by conventional methods to various substrates, for example chipboard or fiberboard.
  • Weight percentages are by weight of the pulp unless otherwise specified. Quantity ratio means ratio of masses or weight ratio.
  • a pulp suspension was prepared by using a pulp mixture of 80% by weight of eucalyptus pulp and 20% by weight of pine sulfate pulp at a pulp density of 5 % to a freeness of 33 ° SR (Schopper-Riegler) was ground. Subsequently, 1.8% by weight of epichlorohydrin resin was added as a wet strength agent. This pulp suspension was adjusted to a pH of 6.5 with aluminum sulfate.
  • the pulp suspension was added to a mixture of 30% by weight of titanium dioxide and 5% by weight of talc, 0.11% by weight of a retention aid and 0.03% by weight of an antifoam and a decorative base paper having a basis weight of about 50 g / m 2 and an ash content of about 23 wt.%.
  • the weights are based on the weight of the pulp (atro).
  • This base paper was obtained in a size press with an aqueous resin solution of about 25th% solids content, containing modified starch C film 07324 (starch I, table 1) and n-butyl acrylate-styrene copolymer (Acronal ® S 305 D) in a proportion of 80 : 20 impregnated on both sides.
  • modified starch C film 07324 starch I, table 1
  • n-butyl acrylate-styrene copolymer Acronal ® S 305 D
  • the impregnated paper was then dried at a temperature of about 120 ° C to a residual moisture content of 2.5%.
  • the order amount after drying was 10 g / m 2 .
  • the raw paper from Example 1 was purified by size press with an aqueous resin solution containing modified starch I and n-butyl acrylate-styrene copolymer (Acronal ® S 305 D) in a proportion of 60:40, impregnated with three different coating amounts.
  • the solids content of the resin solution was 26% by weight.
  • the impregnated papers were then dried at a temperature of about 120 ° C to a residual moisture content of 2.5%.
  • the application rates after drying were 7 g / m 2 (Example 2A), 10 g / m 2 (Example 2B) and 14 g / m 2 (Example 2C).
  • the raw paper from Example 1 was blended by means of a size press with an aqueous resin solution having a solids content of 27.% Impregnating the modified starch I and n-butyl acrylate-styrene copolymer (Acronal ® S 305 D) in a proportion of 50:50 contains. The impregnated paper was then dried at a temperature of about 120 ° C to a residual moisture content of 2.5%. The order amount after drying was 10 g / m 2 .
  • the raw paper from Example 1 was blended by means of a size press with an aqueous resin solution having a solids content of 25.% Impregnating the modified starch I and n-butyl acrylate-styrene copolymer (Acronal ® S 305 D) in a proportion of 20:80 contains. The impregnated paper was then heated at a temperature of about 120 ° C to a residual moisture content of 2.5%. dried. The order amount after drying was 10 g / m 2 .
  • the raw paper from Example 1 was blended by means of a size press with an aqueous resin solution having a solids content of 25.% Impregnating the modified starch C film 07311 (starch II, s. Table 1) and n-butyl acrylate-styrene copolymer (Acronal ® S 305 D ) in a proportion of 60:40.
  • the impregnated paper was then dried at a temperature of about 120 ° C to a residual moisture content of 2.5%. The order amount after drying was 10 g / m 2 .
  • the raw paper from Example 1 was blended by means of a size press with an aqueous resin solution having a solids content of 25.% Impregnating the modified starch C film 07302 (thickness III, s. Table 1) and n-butyl acrylate-styrene copolymer (Acronal ® S 305 D ) in a proportion of 60:40.
  • the impregnated paper was then dried at a temperature of about 120 ° C to a residual moisture content of 2.5%. The order amount after drying was 10 g / m 2 .
  • the raw paper from Example 1 was purified by size press with an aqueous resin solution containing a modified starch I and a hydrophobized styrene-butyl acrylate copolymer (B Cartacoat ® 641) in a quantitative ratio of 60:40, impregnated.
  • the solids content of the resin solution was 26% by weight.
  • the impregnated paper was then dried at a temperature of about 120 ° C to a residual moisture content of 2.5%. The order amount after drying was 10 g / m 2 .
  • the raw paper from Example 1 was (305 D Acronal ® S) in a quantitative ratio of 60:40 as well as titanium dioxide by means of a size press with an aqueous resin solution containing modified starch I and a styrene-n-butyl acrylate copolymer in an amount of 15 °.% (based on the binder content (atro)), impregnated.
  • the solid content of the resin solution was 28% by weight.
  • the impregnated paper was then dried at a temperature of about 120 ° C to a residual moisture content of 2.5%. The order amount after drying was 10 g / m 2 .
  • the raw paper from Example 1 was purified by size press with an aqueous resin solution containing a dextrin (s. Table 1) and n-butyl acrylate-styrene copolymer (Acronal ® S 305 D) in a proportion of 60:40, impregnated.
  • the solids content of the resin solution was about 26% by weight.
  • the impregnated paper was then dried at a temperature of about 120 ° C to a residual moisture content of 2.5%. The order amount after drying was 10 g / m 2 .
  • Example 1 The base paper of Example 1 was size-pressed with an aqueous resin solution containing modified starch C film 07380 (starch IV, s. Table 1) and styrene-butyl acrylate copolymer (Acronal ® S 305 D) in a proportion of 60:40, impregnated.
  • the solids content of the resin solution was about 26% by weight.
  • the impregnated paper was then dried at a temperature of about 120 ° C to a residual moisture content of 2.5%. The order amount after drying was 10 g / m 2 .
  • the raw paper from Example 1 was purified by size press with an aqueous resin solution containing polyvinyl alcohol (Mowiol ® 4-98) and styrene-butyl acrylate copolymer (Acronal ® S 305 D) is impregnated in a quantitative ratio of 20:80.
  • the solid content of the resin solution was about 27% by weight.
  • the impregnated paper was then dried at a temperature of about 120 ° C to a residual moisture content of 2.5%. The order amount after drying was 10 g / m 2 .
  • the visual rating was according to the reference catalog, grades: 1 (very good) to 6 (very bad)
  • the pre-impregnate samples were coated with an SH coating (SH primer / water-resistant, lacquer with built-in acid hardener) customary for this purpose in an amount of 12 g / m 2 .
  • SH coating SH primer / water-resistant, lacquer with built-in acid hardener
  • the yellowness index was determined according to DIN 6167. It indicates the change in yellowness of a sample under the influence of temperature during a certain period of time. It is the difference between the so-called yellow values ⁇ b of the treated and untreated sample.
  • the b-values were measured with the colorimeter SF 600 (Datacolor) at D65 10 °.
  • the prepregs according to the invention have a higher strength in the z direction and a better printability.
  • the yellowing behavior, especially at higher temperatures, is also improved in the prepregs according to the invention.
  • the paint level is better or comparably good compared to the usual prepregs.

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

Abstract

L'invention concerne un préimprégné qui peut être obtenu par imprégnation d'un papier de base pour décoration avec une solution de résine d'imprégnation qui contient au moins un latex polymère et au moins un amidon modifié avec une répartition de poids moléculaire spécifique.

Claims (10)

  1. Préimprégné, qui est obtenu par imprégnation d'un papier décoratif brut avec une solution de résine imprégnatrice, caractérisé en ce que la solution de résine imprégnatrice contient au moins un latex polymère et au moins un amidon modifié avec une répartition spécifique du poids moléculaire, sachant que le poids moléculaire des molécules d'amidon se répartissent de la manière suivante :
    - 6 % en poids au maximum de molécules d'un poids moléculaire de 0 à 1.000 g / mol,
    - 5 à 20 % en poids de molécules d'un poids moléculaire de 1.000 à 5.000 g / mol,
    - 20 à 40 % en poids de molécules d'un poids moléculaire de 5.000 à 25.000 g / mol,
    - 20 à 45 % en poids de molécules d'un poids moléculaire de 25.000 à 200.000 g / mol,
    - 5 à 22 % en poids de molécules d'un poids moléculaire de 200.000 à 1.000.000 g / mol,
    - 0,5 à 5 % en poids de molécules d'un poids moléculaire de plus de 1.000.000 g / mol,
  2. Préimprégné selon la revendication 1, caractérisé en ce que latex polymère est un copolymère styrol-(méth)acrylique d'ester.
  3. Préimprégné selon revendication 1 ou 2, caractérisé en ce que le latex polymère est un styrol-Butylacrylate.
  4. Préimprégné selon l'une des revendications 1 à 3, caractérisé en ce que le rapport quantitatif d'amidon / latex polymère est de 20 / 80 à 80 / 20 par rapport à la masse de la résine imprégnatrice (atro).
  5. Préimprégné selon la revendication 4, caractérisé en ce que le rapport quantitatif est de 45 / 55 à 65 / 35 par rapport à la masse de la résine imprégnatrice (atro).
  6. Préimprégné selon l'une des revendications 1 à 5, caractérisé en ce que la solution de résigne imprégnatrice contient 1 à 30 % en poids d'un pigment et / ou d'une charge, par rapport à la masse du liant (atro).
  7. Préimprégné selon la revendication 6, caractérisé en ce que le pigment peut être des dioxydes de titane, du caolin, de la bentonite et / ou de carbonate de calcium.
  8. Préimprégné selon l'une des revendications 1 à 7, caractérisé en ce que la solution de résine imprégnatrice présente une teneur en matière solide de 9 à 40 % en poids.
  9. Préimprégné selon l'une des revendications 1 à 8, caractérisé en ce que la quantité de résine imprégnatrice est de 10 à 35 % de la masse au mètre carré du papier décoratif brut.
  10. Papier décoratif ou matériau de revêtement décoratif, obtenu à partir d'un préimprégné selon l'une des revendications 1 à 9.
EP08761274A 2007-06-28 2008-06-20 Préimprégné Active EP2158096B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL08761274T PL2158096T3 (pl) 2007-06-28 2008-06-20 Preimpregnat

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DE102007030102.4A DE102007030102B4 (de) 2007-06-28 2007-06-28 Vorimprägnat
PCT/EP2008/057870 WO2009000769A1 (fr) 2007-06-28 2008-06-20 Préimprégné

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EP2158096A1 EP2158096A1 (fr) 2010-03-03
EP2158096B1 true EP2158096B1 (fr) 2012-02-08

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US (1) US8349464B2 (fr)
EP (1) EP2158096B1 (fr)
JP (1) JP2010531376A (fr)
CN (1) CN101743132B (fr)
AR (1) AR067037A1 (fr)
AT (1) ATE544614T1 (fr)
BR (1) BRPI0813753A2 (fr)
CA (1) CA2692288C (fr)
CL (1) CL2008001931A1 (fr)
DE (1) DE102007030102B4 (fr)
ES (1) ES2382085T3 (fr)
PL (1) PL2158096T3 (fr)
PT (1) PT2158096E (fr)
RU (1) RU2431572C1 (fr)
WO (1) WO2009000769A1 (fr)

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DE102013114420A1 (de) 2012-12-23 2014-06-26 Michael Jokiel Imprägnierflotte zur Imprägnierung eines Rohpapieres
DE202013009496U1 (de) 2013-10-24 2013-11-14 Samtastic Products GmbH Mehrschichtige dekorative Kunststoffbahn bzw. -platte
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DE202014003058U1 (de) * 2014-04-10 2014-05-06 Schoeller Technocell Gmbh & Co. Kg Verbundkörper mit einer dekorativen Oberfläche, einer elektrisch leitfähigen Struktur und einer elektronischen Schaltung
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CN107211543B (zh) 2014-10-10 2020-08-18 得利乐公司 具有嵌入式导电材料的装饰性多层表面材料，由此制成的固体表面，制备这种表面材料的方法及其用途
RU2677150C1 (ru) * 2015-02-04 2019-01-15 Альстром-Мунксьё Деттинген Гмбх Композиция и способ получения предварительно пропитанной декоративной бумаги-основы, содержащей биополимерные наночастицы
PT3040476T (pt) * 2015-07-10 2018-07-30 SWISS KRONO Tec AG Material laminado para o revestimento de um material derivado da madeira na forma de painel e processo para a produção do material laminado
JP2018531328A (ja) * 2015-08-14 2018-10-25 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 紙および板紙用の水性表面処理組成物
CN106337317B (zh) * 2016-08-31 2018-02-23 浙江大盛新材料股份有限公司 一种环保装饰原纸制造方法
CN106283823B (zh) * 2016-08-31 2017-09-19 浙江大盛新材料股份有限公司 一种防龟裂装饰原纸的制造方法
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Publication number Publication date
DE102007030102A1 (de) 2009-01-02
DE102007030102B4 (de) 2019-10-31
ES2382085T3 (es) 2012-06-05
CL2008001931A1 (es) 2010-01-22
WO2009000769A1 (fr) 2008-12-31
AR067037A1 (es) 2009-09-30
JP2010531376A (ja) 2010-09-24
CN101743132B (zh) 2013-04-10
PT2158096E (pt) 2012-05-17
RU2431572C1 (ru) 2011-10-20
CA2692288C (fr) 2013-09-24
EP2158096A1 (fr) 2010-03-03
US20100183890A1 (en) 2010-07-22
BRPI0813753A2 (pt) 2014-12-30
US8349464B2 (en) 2013-01-08
ATE544614T1 (de) 2012-02-15
PL2158096T3 (pl) 2013-01-31
CN101743132A (zh) 2010-06-16
CA2692288A1 (fr) 2008-12-31

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