EP3026175B1 - Paper with high opacity - Google Patents

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Publication number
EP3026175B1
EP3026175B1 EP14195070.9A EP14195070A EP3026175B1 EP 3026175 B1 EP3026175 B1 EP 3026175B1 EP 14195070 A EP14195070 A EP 14195070A EP 3026175 B1 EP3026175 B1 EP 3026175B1
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EP
European Patent Office
Prior art keywords
resin
pigment
paper
decorative
particles
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Application number
EP14195070.9A
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German (de)
French (fr)
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EP3026175A1 (en
Inventor
Marina Skotkin
Andreas Dr. Overberg
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Schoeller Technocell GmbH and Co KG
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Schoeller Technocell GmbH and Co KG
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Application filed by Schoeller Technocell GmbH and Co KG filed Critical Schoeller Technocell GmbH and Co KG
Priority to EP14195070.9A priority Critical patent/EP3026175B1/en
Priority to US14/941,977 priority patent/US9976257B2/en
Priority to JP2015231348A priority patent/JP2016102288A/en
Priority to CN201510849841.4A priority patent/CN105648838A/en
Publication of EP3026175A1 publication Critical patent/EP3026175A1/en
Application granted granted Critical
Publication of EP3026175B1 publication Critical patent/EP3026175B1/en
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    • 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
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • 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
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/69—Water-insoluble compounds, e.g. fillers, pigments modified, e.g. by association with other compositions prior to incorporation in the pulp or paper
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/47—Condensation polymers of aldehydes or ketones
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/47—Condensation polymers of aldehydes or ketones
    • D21H17/49—Condensation polymers of aldehydes or ketones with compounds containing hydrogen bound to nitrogen
    • D21H17/51—Triazines, e.g. melamine
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
    • D21H17/57—Polyureas; Polyurethanes
    • 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
    • D21H17/63—Inorganic compounds
    • 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
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
    • D21H17/74—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic and inorganic material
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • 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
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/26—Agents rendering paper transparent or translucent
    • 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
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/28—Colorants ; Pigments or opacifying agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G7/00—Selection of materials for use in image-receiving members, i.e. for reversal by physical contact; Manufacture thereof
    • G03G7/006—Substrates for image-receiving members; Image-receiving members comprising only one layer
    • G03G7/0066—Inorganic components thereof
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G7/00—Selection of materials for use in image-receiving members, i.e. for reversal by physical contact; Manufacture thereof
    • G03G7/006—Substrates for image-receiving members; Image-receiving members comprising only one layer
    • G03G7/0073—Organic components thereof

Definitions

  • the invention relates to a paper, in particular a decorative base paper, for applications in which a high opacity of the paper is required, and decorative coating materials produced using the decorative base paper.
  • 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.
  • 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 pad, uniform formation and grammage of the sheet for uniform resin pickup, high lightfastness, high purity and uniformity of color for good reproducibility of the pattern to be printed, high wet strength for smooth impregnation (impregnation), respectively Absorbency to obtain the required resin saturation level, dry strength, which in Umrollvor réellen in the Paper machine and when printing in the printing press is important. Furthermore, the gap strength (strength in the z direction) is of particular importance, since 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.
  • Decorative base papers generally consist of bright white sulphate pulps, predominantly of hardwood pulp, with a high proportion of pigments and fillers, as well as wet strength agents, retention aids and fixatives.
  • Decorative base papers differ from conventional papers due to the much higher filler content and the lack of paper sizing or surface sizing with known sizing agents such as alkylketene dimers.
  • the opacity is one of the most important properties of decorative raw paper. This characterizes the covering capacity with respect to the base.
  • the opacity is caused by light scattering on the pigment particles.
  • pigment particles having a specific size and a narrow size distribution.
  • the light-scattering pigment particles are distributed as uniformly as possible in the medium to be rendered opaque. Clusters of pigment particles reduce light scattering.
  • the US 4,608,401 describes a method for encapsulating titanium dioxide particles with a water-insoluble polymer in an aqueous suspension and the use of the resulting particles in paints.
  • DE 199 61 964 A1 describes a process for preparing an aqueous dispersion of composite particles consisting of a finely divided inorganic solid and a polymer.
  • the described teachings for use in Dekorrohpapieren not be used advantageously because on the one hand the achievable distances between the pigment particles are too low and on the other hand, the pore volume of Dekorrohpapiers is reduced by the soft polymer latex components of these pigment preparations, which adversely affects the impregnation of the base paper.
  • the DE 10 2013 100353 A1 describes a reactive composite of titanium dioxide, a binder and at least one carrier.
  • the support is preferably an inorganic material to which the titania particles are coated with a reactive binder to form the so-called reactive composite.
  • At least 80% by weight of the titanium dioxide particles preferably have a particle size of less than 5 ⁇ m and at least 80% by mass of the carrier particles preferably have a particle size of less than 50 ⁇ m.
  • the entire composite has a particle size of greater than 63 microns.
  • the DE 697 12 421 T2 describes a matte-coated paper having a surface coating containing both organic pigment particles and calcium carbonate particles.
  • the DE 10 2010 051 382 A1 describes the impregnation of a paper with a mixture of thermosetting curing impregnating resin and pigment.
  • the JP 2007 270 388 A describes a matte coated white paper with low gloss that does not cause stains when rubbed with ink, such as another sheet.
  • the surface coating comprises a pigment and an adhesive, for example a urethane resin or (meth) acrylate resin particle.
  • the EP 1 207 233 A2 describes a decorative paper with high opacity with a mixture of two pigments, namely titanium dioxide and talc a certain particle size distribution. The addition of talc is intended to reduce the use of titanium dioxide while maintaining the same opacity of the sheet.
  • the invention is therefore based on the object of producing a decorative base paper with a high opacity and at the same time reduced whiteness and / or color pigment content.
  • a paper in particular a decorative base paper for decorative coating materials, comprising Cellulose fibers and pigment resin particles, wherein the pigment resin particles contain a pigment and a hardening resin and the average particle size of the pigment resin particles is 1 to 30 ⁇ m, wherein the mass ratio of pigment to resin in the pigment resin particles is 1: 1 to 1:10 is.
  • the opacity of the decorative base paper according to the invention is significantly increased compared to a conventional decorative base paper with the same amount of pigment particles in conventional preparation.
  • the invention furthermore relates to a decor paper or decorative film containing such a decorative base paper.
  • the proportion of titanium dioxide in the paper can be significantly reduced while maintaining a uniformly high opacity. It is furthermore surprising that with up to 60% pigment resin parts a high material input can be introduced into the leaf structure, without significantly affecting the desired strength. It appears that the increase in opacity depends on the particle size of the pigment-resin particles.
  • a further advantage of the paper according to the invention is that in the further processing up to 40% impregnation resin can be saved.
  • the decorative base paper according to the invention is neither sized in the mass nor provided with a surface sizing. It contains essentially pulp, pigment and optionally a filler and conventional additives. Common additives may be wet strength agents, retention aids and fixatives.
  • Decorative base papers differ from common papers due to the much higher filler content or pigment content in the paper and the lack of standard paper sizing or surface sizing on paper. A decorative base paper therefore has absorption capacity for an impregnating resin.
  • 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 pigment resin particles contained in the paper of the present invention contain a pigment and a resin.
  • the pigment resin particles have an average particle size of from 1 to 30 .mu.m, preferably from 2 to 10 .mu.m and more preferably from 2 to 5 .mu.m, for example about 3 .mu.m
  • the mass ratio of pigment to resin in the pigment resin particles is 1:10 to 1: 1, preferably 1: 7 to 1: 3.
  • the mass ratio of pigment to resin in the pigment resin particles in the case of using titanium dioxide as a pigment is 1: 1 to 1: 4, preferably about 1: 2.5.
  • any other pigment to resin ratios are also conceivable, as long as the desired high opacity of the decorative base paper is achieved.
  • pigments refers to finely divided inorganic or organic substances which are obtained naturally or synthetically and which are useful for achieving opacity, for coloring purposes or as a filler in paper.
  • Suitable color pigments for the preparation of the pigment resin particles present in the decorative base paper according to the invention are preferably mineral pigments which are used to increase the opacity in paints and coatings, in sheet-like materials such as paper or plastic films.
  • Such pigments may be, for example, kaolins, precipitated calcium carbonate, calcium sulfate, barium sulfate, titanium dioxide, talc, silica, alumina, iron oxide, calcium carbonate in its natural form, such as limestone, marble or dolomite, and mixtures thereof.
  • titanium dioxide is preferred as a white pigment for many applications. This applies in particular to use in decorative base papers.
  • titania used in decorative papers can be usually used.
  • Such titanium dioxides are commercially available and can be used as a rutile or anatase type. Rutile-type titanium dioxides are preferred.
  • Exemplary commercially available titanium dioxides are Ti-Pure® R-796 +, Ti-Pure® R 902 from DuPont, KRONOS 2800 and KRONOS 2305.
  • the particle size of the pigments in the pigment resin particles used according to the invention is in the range from 100 nm to 3 .mu.m, preferably in the range from 200 nm to 1 .mu.m.
  • particle size is understood to mean the diameter of a sphere which is the same volume as the particle.
  • the pigment resin particles contain a substantially cured resin in addition to the pigment.
  • This resin is preferably a thermosetting resin.
  • Substantially cured means that the resin is present in more than 80%, preferably more than 90%, preferably 95%, more preferably more than 99%, in particular 100% cured. Substantially cured also means that the resin does not chemically bond with the cellulosic fibers.
  • suitable thermosetting resins for example, melamine-formaldehyde resins, melamine-urea-formaldehyde resins, phenol-formaldehyde resins, urea resins, polyurethanes and mixtures thereof can be used. But it is also the use of other thermosetting resins conceivable.
  • Urea-formaldehyde resins are particularly preferably used as thermosetting resins, with curing in the preparation of the pigment resin particles being carried out at a pH of from 3 to 6.
  • Commercially available crosslinking agents can also be used to cure the resin.
  • Other suitable polymers as the resin component of the pigment resin particles are those based on polyacrylic or polyacrylomethyl esters, polyvinyl acetate, polyvinyl chloride and mixtures thereof.
  • the preparation of the pigment-resin particles is preferably carried out in such a way that a stable aqueous dispersion of the pigment particles is introduced and this is subsequently mixed with an aqueous preparation of the monomers or oligomers of the resin.
  • concentration of the pigment particles in the dispersion may be 5 to 50% by mass based on the weight of the dispersion.
  • a dispersing aid stabilizer
  • Suitable examples are steric, electrostatic and electrosteric stabilizers.
  • the stabilizer types Byk 154 and Calgon neu are cited here.
  • the dispersion of the pigment particles may contain other additives, such as rheology aids, UV stabilizers, biocides and other additives.
  • the curing of the resin in the aqueous medium is carried out by lowering the pH in the acidic range and possibly an increase in the temperature of the mixture.
  • the thus obtained slurry (dispersion) of pigment resin particles is dried.
  • the drying can be done in a convection oven.
  • the drying temperature may preferably be 95 ° C to 130 ° C.
  • lower and higher temperatures can also be set for drying, as long as the properties of the dispersion are not impaired, in particular as long as there is no change in the color of the dispersion.
  • An essential step in the provision of the pigment resin particles is the adjustment of particle size.
  • the pigment resin particles present after drying in the form of chips are mechanically comminuted for this purpose.
  • the average particle size of the pigment resin particles is less than 5 microns or less than 4 microns, more preferably less than 3 microns.
  • the particle size was measured by laser scattering.
  • the comminution may preferably be carried out in two stages, first a coarse comminution and then grinding to the desired particle size.
  • the mechanical comminution can be carried out by all known comminution methods. Dry or wet grinding with known milling units or a spray drying or fluidized bed drying is preferred. The comminution methods can also be combined or applied one after the other. For example, a fine powder having an average particle size smaller than 50 ⁇ m can be obtained by dry milling. The desired average particle sizes of the pigment resin particles of up to about 3 microns can be adjusted for example by subsequent wet grinding with a drum mill or stirred ball mill.
  • the paper or decorative base paper according to the invention may, in addition to the pigment resin particles, further contain other mineral and non-mineral fillers.
  • Decorative 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 are base papers having a basis weight of 40 to 100 g / m 2 .
  • the decorative base papers are impregnated or impregnated with synthetic resin dispersions customary for this purpose.
  • synthetic resin dispersions customary for this purpose.
  • synthetic resin dispersions include, for example, melamine-formaldehyde resins, melamine-urea-formaldehyde resins, phenol-formaldehyde resins, urea resins, polyurethanes and mixtures thereof or those based on Polyacrylic or Polyacrylmethylestern, polyvinyl acetate, polyvinyl chloride and mixtures thereof.
  • the impregnation can take place in a separate machine passage also in the size press or with a film press in the paper machine.
  • the impregnation or impregnation of the paper with the impregnating resin results in substantially no air pockets in the sheet.
  • the impregnating resin is distributed homogeneously in the sheet.
  • the proportion of the impregnating resin, calculated as solids, in the paper makes up from 10 to 40% by weight, based on the mass of the paper. Because, unlike in a conventional paper or even in a decorative paper in an impregnated paper substantially no air bubbles are present, called a decorative paper as a decorative film.
  • the impregnated papers can still be painted and printed and then applied to a substrate such as a wood panel.
  • Fig. 1 The opacity of the decorative paper after pressing with a pad depending on the amount of titanium dioxide when using a decoration base paper according to the invention with pigment resin particles (A) and außsdekorrohpapiers with the titanium dioxide preparation (C) is shown.
  • Ti-Pure® R-796 + Laminate Grade Titanium Dioxide Pigment, manufacturer DuPont with 158.75 g of deionized water and 1.4 g of Byk 154 (ammonium polyacrylate, Byk Altana) and dispersed with a ULTRA-TURRAX® Model T25 Rotor-Stator Dispersing System for five minutes at 10,000 revolutions per minute (RPM).
  • the dried resin-TiO 2 dispersion is solid and has an area of about 4x750 cm 2 . These chips must be pre-shredded manually before dry grinding. Here, sizes below 3 cm x 3 cm are targeted. Then the chips are dry-ground. For this purpose, the chips are placed in a 3 liter grinding container made of white ceramic (eg zirconium dioxide). In addition, the grinding balls, which are also made of white ceramic, in the container given ([number x ball diameter] 5x4 cm, 12x3 cm, 55x2 cm, 100x1, 5 cm, 165x0,9 cm). After the container has been sealed, it is placed on two rollers with one of the rollers driven by a motor. At a speed of 100 to 150 revolutions / min, the chips are dry-ground for 20 hours.
  • white ceramic eg zirconium dioxide
  • the grinding balls which are also made of white ceramic
  • Ti-Pure® R-796 + Laminate Grade Titanium Dioxide Pigment, manufactured by DuPont a ULTRA-TURRAX® model T25 rotor-stator dispersing system for five minutes dispersed at 10,000 revolutions per minute (rpm), the pH of the dispersion is then adjusted to 8.5 with 10% by weight sodium hydroxide solution.
  • adipic acid diethylenetriaminepichlorohydrin copolymer (Giluton® XP 14, BK Giulini GmbH) as wet strength agent are added to the distributor and the suspension is adjusted to pH 6 with 10% strength sulfuric acid.
  • the titanium dioxide preparations A or C are added (converted about 2 g of pure TiO 2 per sheet) and the suspension mixed with a paddle stirrer for 15 seconds. Thereafter, another 0.95 g of the 1.5% by weight adipic acid diethylenetriaminepichlorohydrin copolymer solution is added and the mixture is mixed for a further 45 seconds.
  • the single batch thus prepared is added to the filling chamber of the sheet former to 2 l of water, made up to 4 l total volume and the sheet forming process is started.
  • the individual sheets A1 to A 4 and from the comparative titanium dioxide dispersion C were prepared.
  • Impregnation and Compression of Inventive and Comparative Decorative Paper Sheets To impregnate the individual sheets, a solution containing 52% by weight of melamine-formaldehyde resin (KAURAMIN® 773 from BASF SE) in water containing 1.6% by weight of wetting agent (Hypersal® VXT 3797 of Surface Specialties Germany) and 0.8% by weight MADURIT® Hardener MH 835 / 70W, available from Ineos Melamines, Germany.
  • the decorative paper sheets are placed on the resin solution until fully soaked for at least 60 seconds and then completely immersed in the resin bath. Excess resin is then doctored off and the sheet dried at 130 ° C for 25 seconds. Thereafter, the sheet is again completely immersed in the resin solution, excess resin is again doctored off and dried at 130 ° C to a residual moisture content of 6 wt .-%.
  • the impregnated decor paper sheets are pressed by the high-pressure process (HPL) at a temperature of 140 ° C and a pressure of 234 bar with a 40x40 cm size plate for 4 minutes and cooled in the press to 60 ° C. Under the sheet to be tested, a much smaller black and a white decor paper sheet for measuring the opacity are pressed in at two different places.
  • HPL high-pressure process
  • the opacity of the decorative paper sheet to be tested is determined by measuring and comparing reflection densities.
  • a white and a black sheet are arranged side by side.
  • the sheet to be tested for opacity is laminated and laminated onto a plate.
  • the reflectance measurements over the white and over the black sheet were made with a Datacolor 600 colorimeter.
  • the reflection density determined over the black sheet was divided by the reflection density obtained over the white sheet, and the result was multiplied by 100.
  • the opacity of the decorative paper is applied after pressing against the surface-related titanium dioxide content.
  • the results of the opacity measurement show that the decorative papers containing the decorative base paper of the invention containing the pigment resin particles (titanium dioxide preparation A), at comparable titanium dioxide content have a significantly higher opacity than the decorative papers containing außsdekorrohpapier with the comparative preparation (titanium dioxide preparation C).
  • a decoration base paper according to the invention a saving of titanium dioxide of at least 50% of the amount can thus be achieved without the opacity of the decor paper deteriorating.

Description

GEBIET DER ERFINDUNGFIELD OF THE INVENTION

Die Erfindung betrifft ein Papier, insbesondere auch ein Dekorrohpapier, für Anwendungen, bei denen eine hohe Opazität des Papiers erforderlich ist, und unter Verwendung des Dekorrohpapiers hergestellte dekorative Beschichtungswerkstoffe.The invention relates to a paper, in particular a decorative base paper, for applications in which a high opacity of the paper is required, and decorative coating materials produced using the decorative base paper.

HINTERGRUND DER ERFINDUNGBACKGROUND OF THE INVENTION

Dekorative Beschichtungswerkstoffe, sogenannte Dekorpapiere oder Dekorfolien, werden vorzugsweise zur Oberflächenbeschichtung bei der Möbelherstellung und im Innenausbau, insbesondere Laminatböden, eingesetzt. Unter Dekorpapier/Dekorfolie versteht man kunstharzgetränkte oder kunstharzgetränkte und oberflächenbehandelte, bedruckte oder unbedruckte Papiere. Dekorpapiere/Dekorfolien werden mit einer Trägerplatte verleimt oder verklebt.Decorative coating materials, so-called decorative papers or decorative films, 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.

Je nach Art des Imprägniervorgangs unterscheidet man zwischen Dekorpapieren/Dekorfolien mit durchimprägniertem Papierkern und sogenannten Vorimprägnaten, bei denen das Papier in der Papiermaschine online oder offline nur teilweise imprägniert wird. Keines der bislang bekannten Vorimprägnate, die formaldehydhaltige duroplastische Harze oder formaldehydarme Bindemittel auf Acrylatbasis enthalten, erfüllt alle an sie gestellten Anforderungen wie gute Bedruckbarkeit, hohe Spaltfestigkeit, gute Verklebbarkeit und gute Lackierbarkeit.Depending on the type of impregnation process, a distinction is made between decorative papers / decorative films with a fully impregnated paper core and so-called prepregs, in which the paper is only partially impregnated in the paper machine online or offline. None of the previously known prepregs containing formaldehyde-containing thermosetting resins or low-formaldehyde binders based on acrylate fulfills all the requirements placed on them, such as good printability, high nip strength, good bondability and good paintability.

Für das Aufkleben der Dekorfolien auf Holzwerkstoffe wie Spanplatten oder MDF-Platte werden üblicherweise Harnstoffleime oder Polyvinylacetat (PVAC)-Leime eingesetzt.For gluing the decorative films on wood materials such as chipboard or MDF board usually urea glues or polyvinyl acetate (PVAC) glues are used.

Schichtpressstoffe (High Pressure Laminates) sind Laminate, die durch Verpressen mehrerer imprägnierter, aufeinander geschichteter Papiere entstehen. Der Aufbau dieser Schichtpressstoffe besteht im allgemeinen aus einem höchste Oberflächenbeständigkeit erzeugenden transparenten Auflageblatt (Overlay), einem harzgetränkten Dekorpapier und einem oder mehreren phenolbeharzten Kraftpapieren. Als Unterlage hierfür werden beispielsweise Hartfaser- und Holzspanplatten sowie Sperrholz eingesetzt.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 phenolbeharzten kraft papers. As a basis for this example, hardboard and chipboard and plywood are used.

Bei den nach dem Kurztaktverfahren hergestellten Laminaten (Low Pressure Laminates) wird das mit Kunstharz getränkte Dekorpapier direkt mit einer Unterlage, beispielsweise einer Spanplatte, unter Anwendung eines niedrigen Drucks verpresst.In the case of the laminates (low pressure laminates) produced by the short-cycle method, the decorative paper impregnated with synthetic resin is pressed directly with a base, for example a chipboard, using a low pressure.

Das bei den oben genannten Beschichtungswerkstoffen verwendete Dekorpapier wird weiß oder farbig mit oder ohne zusätzlichen Aufdruck eingesetzt.The decorative paper used in the above-mentioned coating materials is used white or colored with or without additional imprint.

Hinsichtlich der anwendungstechnischen Eigenschaften müssen die als Ausgangsmaterialien dienenden, sogenannten Dekorrohpapiere bestimmte Anforderungen erfüllen. Dazu gehören eine hohe Opazität für eine bessere Abdeckung der Unterlage, gleichmäßige Formation und Grammatur des Blatts für eine gleichmäßige Harzaufnahme, hohe Lichtbeständigkeit, hohe Reinheit und Gleichmäßigkeit der Farbe für gute Reproduzierbarkeit des aufzudruckenden Musters, hohe Nassfestigkeit für eine reibungslose Imprägnierung (Tränkung), entsprechende Saugfähigkeit zur Erlangung des erforderlichen Harzsättigungsgrads, Trockenfestigkeit, die bei Umrollvorgängen in der Papiermaschine und beim Bedrucken in der Druckmaschine wichtig ist. Ferner ist die Spaltfestigkeit (Festigkeit in z-Richtung) von besonderer Bedeutung, da sie ein Maß dafür ist, wie gut sich das Dekorrohpapier verarbeiten lässt. So darf das aufgeleimte Dekorpapier/Dekorfolie bei Bearbeitungsschritten wie Sägen oder Bohren nicht ausfransen.With regard to the performance properties, the so-called decorative base papers serving as starting materials must fulfill certain requirements. These include high opacity for better coverage of the pad, uniform formation and grammage of the sheet for uniform resin pickup, high lightfastness, high purity and uniformity of color for good reproducibility of the pattern to be printed, high wet strength for smooth impregnation (impregnation), respectively Absorbency to obtain the required resin saturation level, dry strength, which in Umrollvorgängen in the Paper machine and when printing in the printing press is important. Furthermore, the gap strength (strength in the z direction) is of particular importance, since 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.

Dekorrohpapiere bestehen im Allgemeinen aus hochweißen Sulfatzellstoffen, überwiegend aus Laubholzzellstoff, mit einem hohen Anteil an Pigmenten und Füllstoffen sowie Nassfestmittel, Retentionsmitteln und Fixiermitteln. Dekorrohpapiere unterscheiden sich von üblichen Papieren durch den sehr viel höheren Füllstoffanteil und das Fehlen einer beim Papier üblichen Masseleimung oder Oberflächenleimung mit bekannten Leimungsmitteln wie Alkylketendimeren.Decorative base papers generally consist of bright white sulphate pulps, predominantly of hardwood pulp, with a high proportion of pigments and fillers, as well as wet strength agents, retention aids and fixatives. Decorative base papers differ from conventional papers due to the much higher filler content and the lack of paper sizing or surface sizing with known sizing agents such as alkylketene dimers.

Die Opazität gehört zu den wichtigsten Eigenschaften des Dekorrohpapiers. Diese kennzeichnet das Abdeckvermögen gegenüber der Unterlage.The opacity is one of the most important properties of decorative raw paper. This characterizes the covering capacity with respect to the base.

Die Opazität wird durch Lichtstreuung an den Pigmentpartikeln verursacht. Für ein hohes Lichtstreuvermögen ist es einerseits vorteilhaft, Pigmentteilchen mit einer bestimmten Größe und einer engen Größenverteilung zu verwenden. Des Weiteren ist es auch vorteilhaft, wenn die lichtstreuenden Pigmentteilchen möglichst gleichmäßig in dem undurchsichtig zu machenden Medium verteilt sind. Zusammenballungen der Pigmentteilchen vermindern die Lichtstreuung.The opacity is caused by light scattering on the pigment particles. On the one hand, for high light scattering power, it is advantageous to use pigment particles having a specific size and a narrow size distribution. Furthermore, it is also advantageous if the light-scattering pigment particles are distributed as uniformly as possible in the medium to be rendered opaque. Clusters of pigment particles reduce light scattering.

Insbesondere beim Einbringen von Pigmenten bei der Papierherstellung beobachtet man aber üblicherweise eine Zusammenballung der Pigmentteilchen mit der Folge, dass es mikroskopische Bereiche im Papier gibt, in denen sehr viele Pigmentteilchen dicht beieinander angeordnet sind. Andere Bereiche im Blatt enthalten dagegen nur wenige Pigmentteilchen, so dass durch solche Bereiche das Licht weitgehend ungehindert und nicht gestreut durchtritt. Aus dieser Ungleichverteilung folgt eine verringerte Opazität des Papiers, die mit einem erhöhten Einsatz des Pigments kompensiert werden muss. Der Pigmentanteil lässt sich aber nicht beliebig erhöhen, da in diesem Fall mit einer Beeinträchtigung der physikalischen Eigenschaften wie Retentionsverhalten der Zellstoffsuspension, Festigkeiten, Lichtechtheit und Harzaufnahme zu rechnen ist.In particular, when introducing pigments into papermaking, however, a conglomeration of the pigment particles is usually observed with the consequence that there are microscopic areas in the paper in which a large number of pigment particles are arranged close to one another. Other areas In contrast, only a few pigment particles are contained in the leaf, so that the light passes through such areas largely unhindered and not scattered. From this unequal distribution follows a reduced opacity of the paper, which must be compensated with an increased use of the pigment. However, the proportion of pigment can not be increased arbitrarily, since in this case is to be expected with a deterioration of the physical properties such as retention behavior of the pulp suspension, strength, light fastness and resin absorption.

Es sind verschiedene Vorschläge gemacht worden, die Gleichverteilung von Pigmentteilchen zu verbessern.Various proposals have been made to improve the uniform distribution of pigment particles.

Die US 4 608 401 beschreibt ein Verfahren zur Verkapselung von Titandioxidteilchen mit einem wasserunlöslichen Polymer in einer wässrigen Suspension und den Einsatz der erhaltenen Teilchen in Anstrichfarben. In der DE 199 61 964 A1 wird ein Verfahren zur Herstellung einer wässrigen Dispersion von Kompositteilchen, bestehend aus einem feinteiligen anorganischen Feststoff und einem Polymerisat, beschrieben. Allerdings sind die beschriebenen Lehren zur Anwendung in Dekorrohpapieren nicht vorteilhaft einsetzbar, weil einerseits die erzielbaren Abstände zwischen den Pigmentteilchen zu gering sind und andererseits das Porenvolumen des Dekorrohpapiers durch die weichen Polymerlatexbestandteile dieser Pigmentzubereitungen verringert wird, was sich nachteilig auf die Imprägnierbarkeit des Rohpapiers auswirkt.The US 4,608,401 describes a method for encapsulating titanium dioxide particles with a water-insoluble polymer in an aqueous suspension and the use of the resulting particles in paints. In the DE 199 61 964 A1 describes a process for preparing an aqueous dispersion of composite particles consisting of a finely divided inorganic solid and a polymer. However, the described teachings for use in Dekorrohpapieren not be used advantageously because on the one hand the achievable distances between the pigment particles are too low and on the other hand, the pore volume of Dekorrohpapiers is reduced by the soft polymer latex components of these pigment preparations, which adversely affects the impregnation of the base paper.

In der GB 487 835 werden Zubereitungen von Farbstoffen und Farbpigmenten mit Melamin-Formaldehyd-Kondensationsprodukten als Bestandteil von Anstrichfarben beschrieben.In the GB 487 835 Preparations of dyes and color pigments are described with melamine-formaldehyde condensation products as a component of paints.

Die DE 10 2013 100353 A1 beschreibt ein reaktives Composite aus Titandioxid, einem Bindemittel und mindestens einem Träger. Der Träger ist vorzugsweise ein anorganisches Material, auf das die Titandioxidteilchen mit einem reaktiven Bindemittel aufgebracht sind, um das sogenannte reaktive Composite zu bilden. Bevorzugt weisen mindestens 80 Masse-% der Titandioxidpartikel eine Korngröße von kleiner 5 µm auf und mindestens 80 Masse-% der Trägerteilchen weisen bevorzugt eine Teilchengröße von kleiner 50 µm auf. Das gesamte Composite weist eine Teilchengröße von größer 63 µm auf.The DE 10 2013 100353 A1 describes a reactive composite of titanium dioxide, a binder and at least one carrier. The support is preferably an inorganic material to which the titania particles are coated with a reactive binder to form the so-called reactive composite. At least 80% by weight of the titanium dioxide particles preferably have a particle size of less than 5 μm and at least 80% by mass of the carrier particles preferably have a particle size of less than 50 μm. The entire composite has a particle size of greater than 63 microns.

Die DE 697 12 421 T2 beschreibt ein matt gestrichenes Papier mit einem Oberflächenstrich, der sowohl organische Pigmentteilchen als auch Calciumcarbonatteilchen enthält. Die DE 10 2010 051 382 A1 beschreibt die Imprägnierung eines Papiers mit einem Gemisch aus duroplastisch aushärtendem Imprägnierharz und Pigment. Die JP 2007 270 388 A beschreibt ein matt beschichtetes weißes Papier mit niedrigem Glanz, das nach dem Bedrucken mit Tinte keine Flecken durch Aneinanderreiben, beispielsweise mit einem anderen Blatt, verursacht. Der Oberflächenauftrag umfasst ein Pigment und einen Kleber, beispielsweise ein Urethanharz- oder (Meth)acrylatharzteilchen. Die EP 1 207 233 A2 beschreibt ein Dekorrohpapier mit hoher Opazität mit einem Gemisch aus zwei Pigmenten, nämlich Titandioxid und Talkum einer bestimmten Korngrößenverteilung. Durch den Zusatz von Talkum soll der Einsatz an Titandioxid bei gleichbleibender Opazität des Blatts verringert werden.The DE 697 12 421 T2 describes a matte-coated paper having a surface coating containing both organic pigment particles and calcium carbonate particles. The DE 10 2010 051 382 A1 describes the impregnation of a paper with a mixture of thermosetting curing impregnating resin and pigment. The JP 2007 270 388 A describes a matte coated white paper with low gloss that does not cause stains when rubbed with ink, such as another sheet. The surface coating comprises a pigment and an adhesive, for example a urethane resin or (meth) acrylate resin particle. The EP 1 207 233 A2 describes a decorative paper with high opacity with a mixture of two pigments, namely titanium dioxide and talc a certain particle size distribution. The addition of talc is intended to reduce the use of titanium dioxide while maintaining the same opacity of the sheet.

ZUSAMMENFASSUNG DER ERFINDUNGSUMMARY OF THE INVENTION

Der Erfindung liegt somit die Aufgabe zugrunde ein Dekorrohpapier mit einer hohen Opazität bei gleichzeitig vermindertem Weiß- und/oder Farbpigmentanteil herzustellen.The invention is therefore based on the object of producing a decorative base paper with a high opacity and at the same time reduced whiteness and / or color pigment content.

Gelöst wird diese Aufgabe durch ein Papier, insbesondere ein Dekorrohpapier für dekorative Beschichtungswerkstoffe, umfassend Cellulosefasern und Pigment-Harzteilchen, wobei die Pigment-Harzteilchen ein Pigment und ein härtendes Harz enthalten und die mittlere Teilchengröße der Pigment-Harzteilchen 1 bis 30 µm beträgt, worin das Massenverhältnis Pigment zu Harz in den Pigment-Harzteilchen 1:1 bis 1:10 beträgt.This object is achieved by a paper, in particular a decorative base paper for decorative coating materials, comprising Cellulose fibers and pigment resin particles, wherein the pigment resin particles contain a pigment and a hardening resin and the average particle size of the pigment resin particles is 1 to 30 μm, wherein the mass ratio of pigment to resin in the pigment resin particles is 1: 1 to 1:10 is.

Die Opazität des erfindungsgemäßen Dekorrohpapiers ist deutlich erhöht gegenüber einem herkömmlichen Dekorrohpapier mit gleicher Menge an Pigmentteilchen in herkömmlicher Zubereitung.The opacity of the decorative base paper according to the invention is significantly increased compared to a conventional decorative base paper with the same amount of pigment particles in conventional preparation.

Gegenstand der Erfindung ist ferner ein Dekorpapier oder Dekorfolie, enthaltend ein solches Dekorrohpapier.The invention furthermore relates to a decor paper or decorative film containing such a decorative base paper.

Mit dem erfindungsgemäßen Papier oder Dekorrohpapier kann der Anteil des Titandioxids im Papier unter Erhalt einer gleichmäßig hohen Opazität deutlich gesenkt werden. Überraschend ist ferner, dass mit bis zu 60% Pigment-Harzteilen ein hoher Materialeintrag in die Blattstruktur eingebracht werden kann, ohne die gewünschte Festigkeit wesentlich zu beeinträchtigen. Es hat den Anschein, dass die Steigerung der Opazität von der Teilchengröße der Pigment-Harzteilchen abhängig ist. Ein weiter Vorteil des erfindungsgemäßen Papiers ist, dass bei der Weiterverarbeitung bis zu 40% Imprägnierharz eingespart werden kann.With the paper or decorative base paper according to the invention, the proportion of titanium dioxide in the paper can be significantly reduced while maintaining a uniformly high opacity. It is furthermore surprising that with up to 60% pigment resin parts a high material input can be introduced into the leaf structure, without significantly affecting the desired strength. It appears that the increase in opacity depends on the particle size of the pigment-resin particles. A further advantage of the paper according to the invention is that in the further processing up to 40% impregnation resin can be saved.

DETAILLIERTE BESCHREIBUNG DER ERFINDUNGDETAILED DESCRIPTION OF THE INVENTION

Im Gegensatz zu üblichen Papieren ist das erfindungsgemäße Dekorrohpapier weder in der Masse geleimt noch mit einer Oberflächenleimung versehen. Es enthält im Wesentlichen Zellstoff, Pigment und gegebenenfalls einen Füllstoff und übliche Additive. Übliche Additive können Nassfestmittel, Retentionsmittel und Fixiermittel sein. Dekorrohpapiere unterscheiden sich von üblichen Papieren durch den sehr viel höheren Füllstoffanteil oder Pigmentgehalt im Blatt und das Fehlen einer beim Papier üblichen Masseleimung oder Oberflächenleimung. Ein Dekorrohpapier weist daher Absorptionsfähigkeit für ein Imprägnierharz auf.In contrast to conventional papers, the decorative base paper according to the invention is neither sized in the mass nor provided with a surface sizing. It contains essentially pulp, pigment and optionally a filler and conventional additives. Common additives may be wet strength agents, retention aids and fixatives. Decorative base papers differ from common papers due to the much higher filler content or pigment content in the paper and the lack of standard paper sizing or surface sizing on paper. A decorative base paper therefore has absorption capacity for an impregnating resin.

Als Zellstoffe zur Herstellung der Rohpapiere können Nadelholzzellstoffe (Langfaserzellstoffe) und/oder Laubholzzellstoffe (Kurzfaserzellstoffe) verwendet werden. Auch der Einsatz von Baumwollfasern und Gemische derselben mit den zuvor genannten Zellstoffsorten können verwendet werden. Besonders bevorzugt wird beispielsweise eine Mischung aus Nadelholz-/Laubholz-Zellstoffen im Verhältnis 10:90 bis 90:10, insbesondere 20:80 bis 80:20. Aber auch der Einsatz von 100 Gew.-% Laubholz-Zellstoff hat sich als vorteilhaft erwiesen. Die Mengenangaben beziehen sich auf die Masse der Zellstoffe (atro) .Softwood pulps (long fiber pulps) and / or hardwood pulps (short fiber pulps) can be used as pulps for the production of the base papers. The use of cotton fibers and mixtures thereof with the aforementioned types of pulp can also be used. For example, a mixture of softwood / hardwood pulps in the ratio of 10:90 to 90:10, in particular 20:80 to 80:20, is particularly preferred. But also the use of 100% by weight hardwood pulp has proven to be advantageous. The quantities are based on the mass of the pulps (atro).

Vorzugsweise kann das Zellstoffgemisch einen Anteil an kationisch modifizierten Zellstofffasern von mindestens 5 Gew.-%, bezogen auf das Gewicht des Zellstoffgemischs, enthalten. Als besonders vorteilhaft hat sich ein Anteil von 10 bis 50 Gew.-%, insbesondere 10 bis 20 Gew.-%, des kationisch modifizierten Zellstoffs im Zellstoffgemisch erwiesen. Die kationische Modifizierung der Zellstoffasern kann durch Reaktion der Fasern mit einem Epichlorhydrinharz und einem tertiären Amin erfolgen oder durch Reaktion mit quaternären Ammoniumchloriden wie Chlorhydroxypropyltrimethylammoniumchlorid oder Glycidyltrimethylammoniumchlorid. Kationisch modifizierte Zellstoffe sowie deren Herstellung sind beispielsweise aus DAS PAPIER, Heft 12 (1980) S.575-579 bekannt.Preferably, 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.

Die im erfindungsgemäßen Papier enthaltenen Pigment-Harzteilchen enthalten ein Pigment und ein Harz. Die Pigment-Harzteilchen weisen eine mittlere Teilchengröße von 1 bis 30 µm, vorzugsweise 2 bis 10 µm und besonders bevorzugt 2 bis 5 µm, beispielsweise etwa 3µm aufThe pigment resin particles contained in the paper of the present invention contain a pigment and a resin. The pigment resin particles have an average particle size of from 1 to 30 .mu.m, preferably from 2 to 10 .mu.m and more preferably from 2 to 5 .mu.m, for example about 3 .mu.m

Das Massenverhältnis Pigment zu Harz in den Pigment-Harzteilchen beträgt 1:10 bis 1:1, vorzugsweise 1:7 bis 1:3.Das Massenverhältnis Pigment zu Harz in den Pigment-Harzteilchen im Falle des Einsatzes von Titandioxid als Pigment beträgt 1:1 bis 1:4, vorzugsweise etwa 1:2,5. Denkbar sind jedoch auch beliebige andere Pigment zu Harz-Verhältnisse, solange die gewünschte hohe Opazität des Dekorrohpapiers erreicht wird.The mass ratio of pigment to resin in the pigment resin particles is 1:10 to 1: 1, preferably 1: 7 to 1: 3. The mass ratio of pigment to resin in the pigment resin particles in the case of using titanium dioxide as a pigment is 1: 1 to 1: 4, preferably about 1: 2.5. However, any other pigment to resin ratios are also conceivable, as long as the desired high opacity of the decorative base paper is achieved.

Für die Zwecke der Erfindung versteht man unter dem Begriff Pigmente feinteilige anorganische oder organische Stoffe, die natürlich oder synthetisch gewonnen werden und zum Erreichen von Opazität, zu Farbgebungszwecken oder als Füllstoff im Papier verwendbar sind.For the purposes of the invention, the term pigments refers to finely divided inorganic or organic substances which are obtained naturally or synthetically and which are useful for achieving opacity, for coloring purposes or as a filler in paper.

Geeignete Farbpigmente zur Herstellung der im erfindungsgemäßen Dekorrohpapier enthaltenen Pigment-Harzteilchen sind vorzugsweise mineralische Pigmente, die zur Erhöhung der Opazität in Anstrichen und Beschichtungen, in blattförmigen Materialien wie Papier oder Kunststofffolien eingesetzt werden.Suitable color pigments for the preparation of the pigment resin particles present in the decorative base paper according to the invention are preferably mineral pigments which are used to increase the opacity in paints and coatings, in sheet-like materials such as paper or plastic films.

Solche Pigmente können beispielsweise Kaoline, gefälltes Calciumcarbonat, Calciumsulfat, Bariumsulfat, Titandioxid, Talkum, Silica, Aluminiumoxid, Eisenoxid, Calciumcarbonat in seiner natürlichen Form, wie Kalkstein, Marmor oder Dolomitstein, und deren Gemische sein.Such pigments may be, for example, kaolins, precipitated calcium carbonate, calcium sulfate, barium sulfate, titanium dioxide, talc, silica, alumina, iron oxide, calcium carbonate in its natural form, such as limestone, marble or dolomite, and mixtures thereof.

Wegen der hohen Deckkraft und Opazität wird Titandioxid als Weißpigment für viele Anwendungen bevorzugt. Dies gilt insbesondere für den Einsatz in Dekorrohpapieren. Als Titandioxid zur Herstellung der im erfindungsgemäßen Dekorrohpapier enthaltenen Pigment-Harzteilchen kann üblicherweise in Dekorpapieren verwendetes Titandioxid eingesetzt werden. Solche Titandioxide sind im Handel erhältlich und können als Rutil- oder Anatas-Typ verwendet werden. Titandioxide vom Rutil-Typ sind bevorzugt. Beispielhafte im Handel erhältlichen Titandioxide sind Ti-Pure® R-796+, Ti-Pure® R 902 von DuPont, KRONOS 2800 und KRONOS 2305.Because of the high hiding power and opacity, titanium dioxide is preferred as a white pigment for many applications. This applies in particular to use in decorative base papers. As the titanium dioxide for producing the pigment resin particles contained in the decorative paper according to the present invention, titania used in decorative papers can be usually used. Such titanium dioxides are commercially available and can be used as a rutile or anatase type. Rutile-type titanium dioxides are preferred. Exemplary commercially available titanium dioxides are Ti-Pure® R-796 +, Ti-Pure® R 902 from DuPont, KRONOS 2800 and KRONOS 2305.

Die Teilchengröße der Pigmente in den erfindungsgemäß eingesetzten Pigment-Harzteilchen liegt im Bereich von 100 nm bis 3 µm, bevorzugt im Bereich 200 nm bis 1 µm. Für die Fälle, in denen die Pigmentpartikel eine nichtsphärische Form aufweisen, wird unter "Teilchengröße" der Durchmesser einer mit dem Teilchen volumengleichen Kugel verstanden.The particle size of the pigments in the pigment resin particles used according to the invention is in the range from 100 nm to 3 .mu.m, preferably in the range from 200 nm to 1 .mu.m. For the cases in which the pigment particles have a non-spherical shape, "particle size" is understood to mean the diameter of a sphere which is the same volume as the particle.

Die Pigment-Harzteilchen enthalten neben dem Pigment ein im Wesentlichen ausgehärtetes Harz. Dieses Harz ist vorzugsweise ein duroplastisches Harz. Im Wesentlichen ausgehärtet bedeutet, dass das Harz zu mehr als 80%, vorzugsweise zu mehr als 90%, bevorzugt zu 95%, besonders bevorzugt zu mehr als 99%, insbesondere zu 100% ausgehärtet vorliegt. Im Wesentlichen ausgehärtet bedeutet auch, dass das Harz keine chemische Bindung mit den Cellulosefasern eingeht. Als geeignete duroplastische Harze können beispielsweise Melamin-Formaldehyd-Harze, Melamin-Harnstoff-Formaldehyd-Harze, Phenol-Formaldehyd-Harze, Harnstoffharze, Polyurethane und deren Gemische eingesetzt werden. Es ist aber auch der Einsatz anderer duroplastischer Harze denkbar. Besonders bevorzugt werden als duroplastische Harze Harnstoff-Formaldehyd-Harze eingesetzt, wobei eine Aushärtung bei der Herstellung der Pigment-Harzteilchen bei einem pH-Wert von 3 bis 6 durchgeführt wird. Es können auch handelsübliche Vernetzungsmittel zur Aushärtung des Harzes eingesetzt werden. Weitere geeignete Polymere als Harzbestandteil der Pigment-Harzteilchen sind solche auf der Basis von Polyacryl- oder Polyacrylmethylestern, Polyvinylacetat, Polyvinylchlorid und deren Gemische.The pigment resin particles contain a substantially cured resin in addition to the pigment. This resin is preferably a thermosetting resin. Substantially cured means that the resin is present in more than 80%, preferably more than 90%, preferably 95%, more preferably more than 99%, in particular 100% cured. Substantially cured also means that the resin does not chemically bond with the cellulosic fibers. As suitable thermosetting resins, for example, melamine-formaldehyde resins, melamine-urea-formaldehyde resins, phenol-formaldehyde resins, urea resins, polyurethanes and mixtures thereof can be used. But it is also the use of other thermosetting resins conceivable. Urea-formaldehyde resins are particularly preferably used as thermosetting resins, with curing in the preparation of the pigment resin particles being carried out at a pH of from 3 to 6. Commercially available crosslinking agents can also be used to cure the resin. Other suitable polymers as the resin component of the pigment resin particles are those based on polyacrylic or polyacrylomethyl esters, polyvinyl acetate, polyvinyl chloride and mixtures thereof.

Die Herstellung der Pigment-Harzteilchen erfolgt vorzugsweise derart, dass eine stabile wässrige Dispersion der Pigmentteilchen vorgelegt und diese anschließend mit einer wässrigen Zubereitung der Monomere oder Oligomere des Harzes versetzt wird. Die Konzentration der Pigmentteilchen in der Dispersion kann 5 bis 50 Masse-%, bezogen auf das Gewicht der Dispersion betragen. Zur Stabilisierung der Dispersion der Pigmentteilchen kann ein Dispergierhilfsmittel (Stabilisator) zugesetzt werden. Geeignet sind beispielsweise sterische, elektrostatische sowie elektrosterische Stabilisatoren. Beispielhaft seien hier die Stabilisatortypen Byk 154 und Calgon neu, angeführt. Neben dem Stabilisator kann die Dispersion der Pigmentteilchen weitere Additive enthalten, wie Rheologiehilfsmittel, UV-Stabilisatoren, Biozide und weitere Additive.The preparation of the pigment-resin particles is preferably carried out in such a way that a stable aqueous dispersion of the pigment particles is introduced and this is subsequently mixed with an aqueous preparation of the monomers or oligomers of the resin. The concentration of the pigment particles in the dispersion may be 5 to 50% by mass based on the weight of the dispersion. To stabilize the dispersion of the pigment particles, a dispersing aid (stabilizer) can be added. Suitable examples are steric, electrostatic and electrosteric stabilizers. By way of example, the stabilizer types Byk 154 and Calgon neu are cited here. In addition to the stabilizer, the dispersion of the pigment particles may contain other additives, such as rheology aids, UV stabilizers, biocides and other additives.

Die Aushärtung des Harzes im wässrigen Medium erfolgt durch die Absenkung des pH-Werts in den sauren Bereich und ggf. eine Erhöhung der Temperatur des Gemischs. Die so erhaltene Aufschlämmung (Dispersion) von Pigment-Harzteilchen wird getrocknet. Die Trocknung kann in einem Umluftofen erfolgen. Die Trocknungstemperatur kann vorzugsweise 95°C bis 130°C betragen. Es können jedoch auch niedrigere und höhere Temperaturen zur Trocknung eingestellt werden, solange die Eigenschaften der Dispersion nicht beeinträchtigt werden, insbesondere solange es nicht zu einer Farbveränderung der Dispersion kommt.The curing of the resin in the aqueous medium is carried out by lowering the pH in the acidic range and possibly an increase in the temperature of the mixture. The thus obtained slurry (dispersion) of pigment resin particles is dried. The drying can be done in a convection oven. The drying temperature may preferably be 95 ° C to 130 ° C. However, lower and higher temperatures can also be set for drying, as long as the properties of the dispersion are not impaired, in particular as long as there is no change in the color of the dispersion.

Ein wesentlicher Schritt in der Bereitstellung der Pigment-Harzteilchen ist die Einstellung der Teilchengröße. Die nach der Trocknung in Form von Chips vorliegenden Pigment-Harzteilchen werden dazu mechanisch zerkleinert. Vorzugsweise ist die mittlere Teilchengröße der Pigment-Harzteilchen kleiner als 5 µm oder kleiner als 4 µm, besonders bevorzugt kleiner als 3 µm. Gemessen wurde die Teilchengröße durch Laserstreuung. Die Zerkleinerung kann vorzugsweise in zwei Stufen erfolgen, zunächst eine Grobzerkleinerung und anschließend ein Mahlen auf die gewünschte Teilchengröße.An essential step in the provision of the pigment resin particles is the adjustment of particle size. The pigment resin particles present after drying in the form of chips are mechanically comminuted for this purpose. Preferably, the average particle size of the pigment resin particles is less than 5 microns or less than 4 microns, more preferably less than 3 microns. The particle size was measured by laser scattering. The comminution may preferably be carried out in two stages, first a coarse comminution and then grinding to the desired particle size.

Die mechanische Zerkleinerung kann durch alle bekannten Zerkleinerungsverfahren erfolgen. Bevorzugt wird Trocken- oder Nassmahlung mit bekannten Mahlaggregaten oder aSprühtrocknung oder Wirbelschichttrockung. Die Zerkleinerungsverfahren können auch kombiniert oder nacheinander angewendet werden. Beispielsweise kann ein feines Pulver mit einer mittleren Teilchengröße von kleiner als 50 µm durch Trockenmahlung gewonnen werden. Die gewünschten mittleren Teilchengrößen der Pigment-Harzteilchen von bis zu etwa 3 µm können beispielsweise durch anschließende Nassmahlung mit einer Trommelmühle oder Rührwerkskugelmühle eingestellt werden.The mechanical comminution can be carried out by all known comminution methods. Dry or wet grinding with known milling units or a spray drying or fluidized bed drying is preferred. The comminution methods can also be combined or applied one after the other. For example, a fine powder having an average particle size smaller than 50 μm can be obtained by dry milling. The desired average particle sizes of the pigment resin particles of up to about 3 microns can be adjusted for example by subsequent wet grinding with a drum mill or stirred ball mill.

Es kann auch daran gedacht werden, das Pigment, insbesondere Titandioxid, in einer Zubereitung, beispielsweise einer Lösung oder Dispersion, der zu härtenden Harzbestandteile zu dispergieren.It may also be considered to disperse the pigment, in particular titanium dioxide, in a preparation, for example a solution or dispersion, of the resin constituents to be cured.

Das erfindungsgemäße Papier oder Dekorrohpapier kann neben den Pigment-Harzteilchen ferner weitere mineralische und nicht mineralische Füllstoffe enthalten.The paper or decorative base paper according to the invention may, in addition to the pigment resin particles, further contain other mineral and non-mineral fillers.

Dekorrohpapiere können auf einer Fourdrinier-Papiermaschine oder einer Yankee-Papiermaschine hergestellt werden. Dazu kann das Zellstoffgemisch bei einer Stoffdichte von 2 bis 5 Gew.-% bis zu einem Mahlgrad von 10 bis 45°SR gemahlen werden. In einer Mischbütte können die Füllstoffe wie Titandioxid und Talkum, und Nassfestmittel zugesetzt und mit dem Zellstoffgemisch gut vermischt werden. Der so erhaltene Dickstoff kann bis zu einer Stoffdichte von etwa 1 % verdünnt und soweit erforderlich weitere Hilfsstoffe wie Retentionsmittel, Entschäumer, Aluminiumsulfat und andere zuvor genannte Hilfsstoffe zugemischt werden. Dieser Dünnstoff wird über den Stoffauflauf der Papiermaschine auf die Siebpartie geführt. Es wird ein Faservlies gebildet und nach Entwässerung das Rohpapier erhalten, welches anschließend noch getrocknet wird. Die Flächengewichte der erzeugten Papiere können 15 bis 300 g/m2 betragen. Insbesondere geeignet sind jedoch Rohpapiere mit einem Flächengewicht von 40 bis 100 g/m2.Decorative base papers can be produced on a Fourdrinier paper machine or a Yankee paper machine. For this purpose, the pulp mixture can be ground at a consistency of 2 to 5 wt .-% to a freeness of 10 to 45 ° SR. In a mixing vessel, 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 . However, particularly suitable are base papers having a basis weight of 40 to 100 g / m 2 .

Zur Herstellung von Dekorpapieren oder Dekorfolien werden die Dekorrohpapiere mit für diesen Zweck üblichen Kunstharzdispersionen imprägniert oder getränkt. Diese umfassen beispielsweise Melamin-Formaldehyd-Harze, Melamin-Harnstoff-Formaldehyd-Harze, Phenol-Formaldehyd-Harze, Harnstoffharze, Polyurethane und deren Gemische oder solche auf der Basis von Polyacryl- oder Polyacrylmethylestern, Polyvinylacetat, Polyvinylchlorid und deren Gemische.To produce decorative papers or decorative films, the decorative base papers are impregnated or impregnated with synthetic resin dispersions customary for this purpose. These include, for example, melamine-formaldehyde resins, melamine-urea-formaldehyde resins, phenol-formaldehyde resins, urea resins, polyurethanes and mixtures thereof or those based on Polyacrylic or Polyacrylmethylestern, polyvinyl acetate, polyvinyl chloride and mixtures thereof.

Die Imprägnierung kann in einem getrennten Maschinendurchgang auch in der Leimpresse oder mit einer Filmpresse in der Papiermaschine erfolgen. Die Imprägnierung oder Tränkung des Papiers mit dem Imprägnierharz führt dazu, dass im Blatt im Wesentlichen keine Lufteinschlüsse mehr vorhanden sind. Das Imprägnierharz ist homogen im Blatt verteilt. Der Anteil des Imprägnierharzes, berechnet als Feststoff, im Papier macht 10 bis 40 Gew.-%, bezogen auf die Masse des Papiers aus. Weil anders als in einem üblichen Papier oder auch in einem Dekorrohpapier in einem imprägnierten Papier im Wesentlichen keine Lufteinschlüsse mehr vorhanden sind, bezeichnet man ein Dekorpapier auch als Dekorfolie.The impregnation can take place in a separate machine passage also in the size press or with a film press in the paper machine. The impregnation or impregnation of the paper with the impregnating resin results in substantially no air pockets in the sheet. The impregnating resin is distributed homogeneously in the sheet. The proportion of the impregnating resin, calculated as solids, in the paper makes up from 10 to 40% by weight, based on the mass of the paper. Because, unlike in a conventional paper or even in a decorative paper in an impregnated paper substantially no air bubbles are present, called a decorative paper as a decorative film.

Nach Trocknung können die getränkten Papiere noch lackiert und bedruckt werden und anschließend auf ein Substrat wie eine Holzplatte aufgebracht werden.After drying, the impregnated papers can still be painted and printed and then applied to a substrate such as a wood panel.

In der Fig. 1 wird die Opazität des Dekorpapiers nach Verpressen mit einer Unterlage in Abhängigkeit von der Titandioxidmenge bei Verwendung eines erfindungsgemäßen Dekorrohpapiers mit Pigment-Harzteilchen (A) und eines Vergleichsdekorrohpapiers mit der Titandioxidzubereitung (C) gezeigt.In the Fig. 1 The opacity of the decorative paper after pressing with a pad depending on the amount of titanium dioxide when using a decoration base paper according to the invention with pigment resin particles (A) and a Vergleichsdekorrohpapiers with the titanium dioxide preparation (C) is shown.

Die Erfindung wird durch die folgenden Beispiele weiter erläutert.The invention is further illustrated by the following examples.

BEISPIELEEXAMPLES Beispiel 1 - Herstellung der Pigment-Harzteilchen (A) Example 1 - Preparation of Pigment Resin Particles (A)

Herstellung der TiO 2 -Dispersion - Es werden 91,25 g Titandioxid (Ti-Pure® R-796+ Laminate Grade Titanium Dioxide Pigment, Hersteller DuPont) mit 158,75 g VE-Wasser und 1,4 g Byk 154 (Ammoniumpolyacrylat, Hersteller Byk Altana) vermischt und mit einem Rotor-Stator-Dispergiersystem ULTRA-TURRAX® Modell T25 fünf Minuten lang bei 10.000 Umdrehungen pro Minute (U/min) dispergiert. Preparation of the TiO 2 Dispersion - 91.25 g of titanium dioxide (Ti-Pure® R-796 + Laminate Grade Titanium Dioxide Pigment, manufacturer DuPont) with 158.75 g of deionized water and 1.4 g of Byk 154 (ammonium polyacrylate, Byk Altana) and dispersed with a ULTRA-TURRAX® Model T25 Rotor-Stator Dispersing System for five minutes at 10,000 revolutions per minute (RPM).

Herstellung der Harz-TiO 2 -Dispersion - Es werden 387,6 g Harz (Kaurit® 210, Hersteller BASF SE) und 212,4 g der im Schritt 1 hergestellten Titandioxiddispersion zusammengemischt (entspricht einem Verhältnis TiO2 (Feststoff):Harz (Feststoff) von 1:2,5) und mit dem ULTRA-TURRAX® Modell T25 fünf Minuten lang bei 10.000 Umdrehungen pro Minute (U/min) dispergiert. Dabei wird der pH-Wert der Dispersion mit einer 10 %igen Schwefelsäure auf 5 gesenkt. Preparation of the Resin-TiO 2 Dispersion - 387.6 g of resin (Kaurit® 210, manufacturer BASF SE) and 212.4 g of the titanium dioxide dispersion prepared in step 1 are mixed together (corresponds to a ratio TiO 2 (solid): resin (solid ) of 1: 2.5) and dispersed with the ULTRA-TURRAX® Model T25 for five minutes at 10,000 revolutions per minute (RPM). The pH of the dispersion is lowered to 5 with a 10% strength sulfuric acid.

Trocknung der Harz-TiO 2 -Dispersion - Die 500 g Harz-TiO2-Dispersion werden zu gleichen Anteilen (125 g) in vier handelsübliche Silikonschalen gegeben, die eine Fläche von 750 cm2 aufweisen. Anschließend werden die Schalen mit dem Inhalt in einen Laborumlufttrockner (WTC-Binder) gestellt und eine Stunde lang bei 95°C getrocknet, anschließend eine weitere halbe Stunde bei 130°C. Danach können die Schälchen aus dem Trockner herausgenommen werden. Drying of the TiO 2 Resin Dispersion - The 500 g of resin-TiO 2 dispersion are added in equal proportions (125 g) to four commercially available silicone shells having an area of 750 cm 2 . The trays are then placed with the contents in a laboratory air dryer (WTC binder) and dried for one hour at 95 ° C, then another half hour at 130 ° C. Thereafter, the bowls can be removed from the dryer.

Trockenmahlung der Chips - Die getrocknete Harz-TiO2-Dispersion ist fest und hat eine Fläche von etwa 4x750 cm2. Diese Chips müssen vor der Trockenvermahlung manuell vorzerkleinert werden. Dabei werden Größen unter 3 cm x 3 cm angezielt. Anschließend werden die Chips trockenvermahlen. Dazu werden in einen 3 Liter Mahlbehälter aus weißer Keramik (z.B. Zirkondioxid) die Chips gegeben. Zudem werden die Mahlkugeln, die ebenfalls aus weißer Keramik hergestellt sind, in den Behälter gegeben ([AnzahlxKugeldurchmesser] 5x4 cm, 12x3 cm, 55x2 cm, 100x1, 5 cm, 165x0,9 cm). Nachdem der Behälter dicht verschlossen wurde, wird dieser auf zwei Walzen gestellt, wobei eine der Walzen motorgetrieben ist. Bei einer Drehzahl von 100 bis 150 Umdrehungen/Min werden die Chips 20 Stunden lang trockenvermahlen. Dry Milling of the Chips - The dried resin-TiO 2 dispersion is solid and has an area of about 4x750 cm 2 . These chips must be pre-shredded manually before dry grinding. Here, sizes below 3 cm x 3 cm are targeted. Then the chips are dry-ground. For this purpose, the chips are placed in a 3 liter grinding container made of white ceramic (eg zirconium dioxide). In addition, the grinding balls, which are also made of white ceramic, in the container given ([number x ball diameter] 5x4 cm, 12x3 cm, 55x2 cm, 100x1, 5 cm, 165x0,9 cm). After the container has been sealed, it is placed on two rollers with one of the rollers driven by a motor. At a speed of 100 to 150 revolutions / min, the chips are dry-ground for 20 hours.

Nassmahlung des Pulvers - Das nach der Trockenvermahlung erhaltene Pulver ist mit einer mittleren Teilchengröße von 10 bis 20 µm noch nicht fein genug. Daher muss es feiner vermahlen werden. Die geschieht in der Nassvermahlung. Dazu werden 125 g des Kompositpulvers und 400 g VE-Wasser mit dem ULTRA-TURRAX® Modell T25 fünf Minuten lang bei 10.000 Umdrehungen pro Minute (U/min) dispergiert. Diese Dispersion wird anschließend in einer Rührwerkskugelmühle (MiniCer, Netzsch GmbH; komplette Zirkondioxidausstattung, Mahlkörper 0,7 bis 0,9 mm (140 ml), 3.600 Umdrehungen/Min) eine Stunde lang vermahlen. Dabei werden mittlere Teilchengrößen von 2 bis 3 µm erzielt. Wet grinding of the powder - The powder obtained after dry milling is not yet fine enough with an average particle size of 10 to 20 μm. Therefore, it must be finely ground. This happens in the wet grinding. For this purpose, 125 g of the composite powder and 400 g of deionized water are dispersed with the ULTRA-TURRAX® Model T25 for five minutes at 10,000 revolutions per minute (rpm). This dispersion is then ground for one hour in a stirred ball mill (MiniCer, Netzsch GmbH, complete zirconium dioxide equipment, grinding body 0.7 to 0.9 mm (140 ml), 3,600 revolutions / min). In this case, average particle sizes of 2 to 3 microns are achieved.

Vergleichsbeispiel 1 - Ansatz einer üblich in der Dekorindustrie verwendeten Titandioxiddispersion (C) Comparative Example 1 Approach of a Titanium Dioxide Dispersion Commonly Used in the Decorative Industry (C)

Es werden 91,25 g Titandioxid (Ti-Pure® R-796+ Laminate Grade Titanium Dioxide Pigment, Hersteller DuPont) mit 158,75 g VE-Wasser vermischt und mit einem Rotor-Stator-Dispergiersystem ULTRA-TURRAX® Modell T25 fünf Minuten lang bei 10.000 Umdrehungen pro Minute (U/min) dispergiert, der pH-Wert der Dispersion wird anschließend mit 10 Gew.-% Natriumhydroxidlösung auf 8,5 eingestellt.91.25 g of titanium dioxide (Ti-Pure® R-796 + Laminate Grade Titanium Dioxide Pigment, manufactured by DuPont) are mixed with 158.75 g of deionized water and mixed with a ULTRA-TURRAX® model T25 rotor-stator dispersing system for five minutes dispersed at 10,000 revolutions per minute (rpm), the pH of the dispersion is then adjusted to 8.5 with 10% by weight sodium hydroxide solution.

Herstellung der erfindungsgemäßen und Vergleichsdekorrohpapiere - 50 g Eukalyptuszellstoff (25g Cacia von Portucel-Empresa Produtora de Pasta e Papel, 25g Aracruz von Fibria Celulose SA) werden in einem Dreiliter-Dispergiergefäß mit 1,5 Litern Wasser aufgefüllt, so dass eine Stoffdichte von etwa 3 % eingestellt wird. Mit einem Labordissolver und einer Dispergierscheibe (Durchmesser 50 mm) wird der Zellstoff bei 3700 U/min 30 Minuten lang aufgeschlagen. Anschließend wird der entstandene Zellstoffbrei in ein Verteilergerät gefüllt und mit Wasser auf 8 Liter Gesamtmenge aufgefüllt, so dass eine Stoffdichte von etwa 1 % erhalten wird. In den Verteiler wird zusätzlich 25 g einer 1,5 Gew.-%igen Lösung eines Adipinsäurediethylentriaminepichlorhydrin-Copolymers (Giluton® XP 14, BK Giulini GmbH) als Nassfestmittel gegeben und die Suspension mit 10%iger Schwefelsäure auf pH 6 eingestellt. Preparation of the Inventive and Comparative Decor Raw Papers - 50 g eucalyptus pulp (25 g Cacia from Portucel-Empresa Produtora de Pasta e Papel, 25 g Aracruz from Fibria Celulose SA) are filled in a three-liter dispersing vessel with 1.5 liters of water, so that a consistency of about 3% is set. Using a laboratory dissolver and a dispersing disc (diameter 50 mm), the pulp is whipped at 3700 rpm for 30 minutes. Subsequently, the resulting pulp is filled in a distributor and filled with water to 8 liters total, so that a consistency of about 1% is obtained. In addition, 25 g of a 1.5% strength by weight solution of adipic acid diethylenetriaminepichlorohydrin copolymer (Giluton® XP 14, BK Giulini GmbH) as wet strength agent are added to the distributor and the suspension is adjusted to pH 6 with 10% strength sulfuric acid.

Aus der so hergestellten Zellstoffsuspension werden zur Erzeugung von Dekorrohpapierblättern am Blattbildner (Hersteller ERNST HAAGE Apparatebau) Einzelansätze in folgender Weise hergestellt.From the pulp suspension produced in this way individual formulations are produced in the following manner to produce decorative base paper sheets on the sheet former (manufacturer ERNST HAAGE Apparatebau).

Zu je 300 g der Zellstoffsuspension werden die Titandioxid-Zubereitungen A oder C zugegeben (umgerechnet etwa 2 g reines TiO2 pro Blatt) und die Suspension mit einem Flügelrührer 15 Sekunden lang durchmischt. Danach werden weitere 0,95 g der 1,5 Gew.-% Adipinsäurediethylentriaminepichlorhydrincopolymer-Lösung zugesetzt und weitere 45 Sekunden lang durchmischt.To each 300 g of the pulp suspension, the titanium dioxide preparations A or C are added (converted about 2 g of pure TiO 2 per sheet) and the suspension mixed with a paddle stirrer for 15 seconds. Thereafter, another 0.95 g of the 1.5% by weight adipic acid diethylenetriaminepichlorohydrin copolymer solution is added and the mixture is mixed for a further 45 seconds.

Der so hergestellte Einzelansatz wird in die Füllkammer des Blattbildners zu 2 l Wasser gegeben, auf 4 l Gesamtvolumen aufgefüllt und der Blattbildungsprozess wird gestartet.The single batch thus prepared is added to the filling chamber of the sheet former to 2 l of water, made up to 4 l total volume and the sheet forming process is started.

Unter Verwendung der erfindungsgemäßen Pigment-Harzteilchen (Titandioxid-Zubereitung A) wurden so die Einzelblätter A1 bis A 4 und aus der Vergleichs-Titandioxiddispersion C die Einzelblätter C1 bis C8 hergestellt.Using the pigment resin particles of the invention (titanium dioxide preparation A), the individual sheets A1 to A 4 and from the comparative titanium dioxide dispersion C, the individual sheets C1 to C8 were prepared.

Tränken und Verpressen der erfindungsgemäßen und Vergleichs-Dekorrohpapierblätter - Zum Tränken der Einzelblätter wird eine Lösung mit 52 Gew.-% Melamin-Formaldehydharz (KAURAMIN® 773 der BASF SE) in Wasser verwendet, der 1,6 Gew.-% Netzmittel (Hypersal® VXT 3797 der Surface Specialities Germany) und 0,8 Gew.-% MADURIT®-Härter MH 835/70W, erhältlich von Ineos Melamines, Deutschland zugesetzt wird. Impregnation and Compression of Inventive and Comparative Decorative Paper Sheets - To impregnate the individual sheets, a solution containing 52% by weight of melamine-formaldehyde resin (KAURAMIN® 773 from BASF SE) in water containing 1.6% by weight of wetting agent (Hypersal® VXT 3797 of Surface Specialties Germany) and 0.8% by weight MADURIT® Hardener MH 835 / 70W, available from Ineos Melamines, Germany.

Die Dekorrohpapierblätter werden bis zur völligen Durchtränkung, mindestens aber 60 Sekunden lang auf die Harzlösung aufgelegt und anschließend komplett ins Harzbad getaucht. Überschüssiges Harz wird danach abgerakelt und das Blatt 25 Sekunden bei 130°C getrocknet. Danach wird das Blatt nochmals komplett in die Harzlösung getaucht, überschüssiges Harz wieder abgerakelt und bei 130°C bis zu einer Restfeuchte von 6 Gew.-% getrocknet.The decorative paper sheets are placed on the resin solution until fully soaked for at least 60 seconds and then completely immersed in the resin bath. Excess resin is then doctored off and the sheet dried at 130 ° C for 25 seconds. Thereafter, the sheet is again completely immersed in the resin solution, excess resin is again doctored off and dried at 130 ° C to a residual moisture content of 6 wt .-%.

Die getränkten Dekorpapierbögen werden nach dem Hochdruckverfahren (HPL) bei einer Temperatur von 140°C und einen Pressdruck von 234 bar mit einer Schichtstoffplatte von 40x40 cm Größe 4 Minuten lang verpresst und in der Presse auf 60°C abgekühlt. Unter das zu prüfende Blatt werden dabei an zwei verschiedenen Stellen ein wesentlich kleinerer schwarzer und ein weißer Dekorpapierbogen zur Messung der Opazität mit verpresst.The impregnated decor paper sheets are pressed by the high-pressure process (HPL) at a temperature of 140 ° C and a pressure of 234 bar with a 40x40 cm size plate for 4 minutes and cooled in the press to 60 ° C. Under the sheet to be tested, a much smaller black and a white decor paper sheet for measuring the opacity are pressed in at two different places.

Die Opazität des zu prüfenden Dekorpapierblatts wird ermittelt, in dem Reflexionsdichten gemessen und verglichen werden. Dazu werden ein weißes und ein schwarzes Blatt nebeneinander angeordnet. Darüber wird das auf Opazität zu prüfende Blatt auflaminiert und auf eine Platte aufkaschiert. Die Reflexionsdichtemessungen über dem weißen und über dem schwarzen Blatt erfolgten mit einem Farbmessgerät Datacolor 600. Die über dem schwarzen Blatt ermittelte Reflexionsdichte wurde durch die über dem weißen Blatt ermittelte Reflexionsdichte geteilt und das Ergebnis mit 100 multipliziert wird.The opacity of the decorative paper sheet to be tested is determined by measuring and comparing reflection densities. For this purpose, a white and a black sheet are arranged side by side. In addition, the sheet to be tested for opacity is laminated and laminated onto a plate. The reflectance measurements over the white and over the black sheet were made with a Datacolor 600 colorimeter. The reflection density determined over the black sheet was divided by the reflection density obtained over the white sheet, and the result was multiplied by 100.

Das Flächengewicht (ermittelt nach EN ISO 536) der erhaltenen Blätter, deren Aschegehalt und die erzielte Opazität sind in nachstehender Tabelle zusammengestellt, wobei der Aschegehalt (DIN 54370) gleichgesetzt werden kann mit der Menge Titandioxid, die bezogen auf das Blattgewicht oder die Blattfläche enthalten ist. Tabelle 1: Versuchsergebnisse Blatt Blattgewicht [g/m2] Aschegehalt [%] Aschegehalt [g/m2] Opazität [%] A1 74,2 6,4 4,8 66,9 A2 87,9 10,1 8,9 81,4 A3 93,5 12,2 11,4 86,8 A4 105 14,5 15,2 90,9 C1 79,5 21,6 17,2 79,63 C2 82 24,6 20,2 82,2 C3 85,7 26,3 22,6 83,31 C4 86 28,4 24,4 85,82 C5 86 28,7 24,7 85,81 C6 89,4 31,9 28,6 87,23 C7 92,2 30,3 27,9 88,04 C8 94,7 34 32,2 89,87 The basis weight (determined according to EN ISO 536) of the resulting leaves, their ash content and the achieved opacity are summarized in the table below, wherein the ash content (DIN 54370) can be equated with the amount of titanium dioxide, which is based on the sheet weight or the leaf area , Table 1: Test results sheet Leaf weight [g / m 2 ] Ash content [%] Ash content [g / m 2 ] Opacity [%] A1 74.2 6.4 4.8 66.9 A2 87.9 10.1 8.9 81.4 A3 93.5 12.2 11.4 86.8 A4 105 14.5 15.2 90.9 C1 79.5 21.6 17.2 79.63 C2 82 24.6 20.2 82.2 C3 85.7 26.3 22.6 83.31 C4 86 28.4 24.4 85.82 C5 86 28.7 24.7 85.81 C6 89.4 31.9 28.6 87.23 C7 92.2 30.3 27.9 88.04 C8 94.7 34 32.2 89.87

In Abbildung 1 ist die Opazität des Dekorpapiers nach Verpressen gegen den flächenbezogenen Titandioxidgehalt aufgetragen. Die Ergebnisse der Opazitätsmessung zeigen, dass die Dekorpapiere, die das erfindungsgemäße Dekorrohpapier mit den Pigment-Harzteilchen (Titandioxidzubereitung A) enthalten, bei vergleichbarem Titandioxidgehalt eine deutlich höhere Opazität aufweisen als die Dekorpapiere, die ein Vergleichsdekorrohpapier mit der Vergleichszubereitung (Titandioxidzubereitung C) enthalten. Durch die Verwendung eines erfindungsgemäßen Dekorrohpapiers kann somit eine Einsparung von Titandioxid von mindestens 50% der Menge erreicht werden, ohne dass sich die Opazität des Dekorpapiers verschlechtert.In illustration 1 the opacity of the decorative paper is applied after pressing against the surface-related titanium dioxide content. The results of the opacity measurement show that the decorative papers containing the decorative base paper of the invention containing the pigment resin particles (titanium dioxide preparation A), at comparable titanium dioxide content have a significantly higher opacity than the decorative papers containing a Vergleichsdekorrohpapier with the comparative preparation (titanium dioxide preparation C). By using a decoration base paper according to the invention, a saving of titanium dioxide of at least 50% of the amount can thus be achieved without the opacity of the decor paper deteriorating.

Claims (10)

  1. Paper for decorative coating materials, containing cellulose fibres and pigment resin particles, characterised in that the pigment resin particles contain a carrier-free pigment and a cured resin and the average particle size of the pigment resin particles is 1 to 30 µm, whereby the mass ratio of pigment to resin in the pigment resin particles is 1:1 to 1:10.
  2. Paper according to claim 1, characterised in that the paper is a decorative base paper.
  3. Paper according to claim 1 or 2, characterised in that the pigment resin particles have an average particle size of approximately 3 µm.
  4. Paper according to claim 3, characterised in that the mass ratio of pigment to resin in the pigment-resin particles is 1:1.5 to 1:4.
  5. Paper according to any one of claims 1 to 4, characterised in that the pigment is selected from kaolin, calcium carbonate, calcium sulphate, barium sulphate, titanium dioxide, talc, silica, alumina, iron oxide, calcium carbonate in its natural form, such as limestone, marble or dolomite stone, and their mixtures.
  6. Paper according to claim 5, characterised in that the pigment is titanium dioxide.
  7. Paper according to any one of claims 1 to 6, characterised in that the volume ratio of titanium dioxide to resin in the pigment resin particles is 1:7 to 1:3.
  8. Paper according to any one of claims 1 to 7, characterised in that the resin is selected from melamine-formaldehyde resin, melamine-urea-formaldehyde resin, urea resin, urea-formaldehyde resin and phenol-formaldehyde resin and mixtures thereof.
  9. Paper according to claim 8, characterised in that the resin is a urea resin.
  10. Decorative paper or decorative film containing a paper for decorative coating materials according to any one of claims 1 to 9.
EP14195070.9A 2014-11-27 2014-11-27 Paper with high opacity Active EP3026175B1 (en)

Priority Applications (4)

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EP14195070.9A EP3026175B1 (en) 2014-11-27 2014-11-27 Paper with high opacity
US14/941,977 US9976257B2 (en) 2014-11-27 2015-11-16 Paper with high covering power
JP2015231348A JP2016102288A (en) 2014-11-27 2015-11-27 Paper with high covering power
CN201510849841.4A CN105648838A (en) 2014-11-27 2015-11-27 Paper with high opacity

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DE3020854A1 (en) * 1980-06-02 1981-12-10 Lentia GmbH Chem. u. pharm. Erzeugnisse - Industriebedarf, 8000 München FILLER FOR PAPER, CARDBOARD OR CARDBOARD
US4608401A (en) 1982-09-02 1986-08-26 Union Carbide Corporation Method of encapsulating finely divided solid particles
US4495245A (en) * 1983-07-14 1985-01-22 E. I. Du Pont De Nemours And Company Inorganic fillers modified with vinyl alcohol polymer and cationic melamine-formaldehyde resin
JPS61133218A (en) * 1984-12-04 1986-06-20 Mitsui Toatsu Chem Inc Production of loading material for paper
US4895759A (en) * 1988-03-18 1990-01-23 Ppg Industries, Inc. Saturating grade paper
JPH04370297A (en) * 1990-11-15 1992-12-22 Mitsui Toatsu Chem Inc Cationic composite particle for paper, its production and use therof
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FR2685704B1 (en) * 1991-12-30 2002-06-14 Rhone Poulenc Chimie NOVEL TITANIUM DIOXIDE PARTICLES, THEIR USE AS OPACIFYING PIGMENTS FOR PAPER AND PAPER LAMINATES.
DE69712421T2 (en) * 1996-02-29 2002-12-05 Oji Paper Co MATERIAL COATED PAPER AND METHOD FOR PRODUCING SIENER
DE19961964A1 (en) 1999-12-22 2001-06-28 Basf Ag Aqueous dispersion of a polymer and fine particulate inorganic particles, useful as an adhesive, is prepared by a radical aquoeus emulsion polymerization in the presence of the dispersed particles.
DE10057294C5 (en) * 2000-11-17 2005-06-30 Technocell Dekor Gmbh & Co. Kg Decorative paper with high opacity, as well as decorative paper or decorative foil
JP2007270388A (en) * 2006-03-31 2007-10-18 Oji Paper Co Ltd Printing mat coated paper
DE102010051382A1 (en) * 2010-11-16 2012-05-16 Dekor-Kunststoffe Gmbh Producing printable base layer useful for producing printed decorative layer for laminate, comprises providing base paper for forming recoverable paper web, applying mixture of thermosetting resin material and pigments, and drying paper web
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US9976257B2 (en) 2018-05-22
EP3026175A1 (en) 2016-06-01
JP2016102288A (en) 2016-06-02
CN105648838A (en) 2016-06-08
US20160153147A1 (en) 2016-06-02

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