EP1749134B1 - Method of producing decorative paper and decorative laminate comprising such decorative paper - Google Patents

Method of producing decorative paper and decorative laminate comprising such decorative paper Download PDF

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Publication number
EP1749134B1
EP1749134B1 EP05771104A EP05771104A EP1749134B1 EP 1749134 B1 EP1749134 B1 EP 1749134B1 EP 05771104 A EP05771104 A EP 05771104A EP 05771104 A EP05771104 A EP 05771104A EP 1749134 B1 EP1749134 B1 EP 1749134B1
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EP
European Patent Office
Prior art keywords
paper
decorative
resin
process according
decorative paper
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP05771104A
Other languages
German (de)
French (fr)
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EP1749134A1 (en
Inventor
Claude Perrin
Cyril Blois
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
48 Route De Remiremont f-88380 Arches
MUNKSJOE ARCHES
Original Assignee
ArjoWiggins SAS
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Publication date
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Application filed by ArjoWiggins SAS filed Critical ArjoWiggins SAS
Priority to DE602005016102.3T priority Critical patent/DE602005016102C5/en
Priority to PL05771104T priority patent/PL1749134T3/en
Publication of EP1749134A1 publication Critical patent/EP1749134A1/en
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/18—Paper- or board-based structures for surface covering
    • D21H27/22—Structures being applied on the surface by special manufacturing processes, e.g. in presses
    • D21H27/26—Structures being applied on the surface by special manufacturing processes, e.g. in presses characterised by the overlay sheet or the top layers of the structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
    • B41M7/0027—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using protective coatings or layers by lamination or by fusion of the coatings or layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C5/00—Processes for producing special ornamental bodies
    • B44C5/04—Ornamental plaques, e.g. decorative panels, decorative veneers
    • 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
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/22—Addition to the formed paper
    • D21H23/46—Pouring or allowing the fluid to flow in a continuous stream on to the surface, the entire stream being carried away by the paper
    • D21H23/48—Curtain coaters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/38—Coatings with pigments characterised by the pigments
    • D21H19/40—Coatings with pigments characterised by the pigments siliceous, e.g. clays
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/60—Polyalkenylalcohols; Polyalkenylethers; Polyalkenylesters
    • 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
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/22—Addition to the formed paper
    • D21H23/70—Multistep processes; Apparatus for adding one or several substances in portions or in various ways to the paper, not covered by another single group of this main group

Definitions

  • the invention relates to a method for manufacturing a decorative paper impregnable by a thermosetting resin, having both good printability, especially in inkjet printing, and good resin absorption properties.
  • the invention also relates to such a decorative paper impregnated with a thermosetting resin.
  • the invention finally relates to laminated decorative panels or profiles comprising decorative paper impregnated with thermosetting resin.
  • laminated decorative panels or profiles have been used as materials in homes, commercial and industrial premises.
  • Typical applications of such laminates are floor coverings, particularly flooring-like coatings, furniture coverings, table tops, chairs and the like.
  • the so-called high pressure decorative laminates are produced from a core made of resin-impregnated sheets. These sheets are generally made of kraft paper and have been impregnated with a thermosetting resin, most often a phenolic resin. After impregnating the resin sheets, they are dried, cut, and stacked on top of one another. The number of sheets in the stack depends on the applications and varies between 3 and 9, but can be higher. On the pile of leaves constituting the soul, a decorative paper is then placed, also called decor paper or decorative sheet.
  • Such a decorative sheet is generally a sheet of paper carrying a pattern printed or colored or comprising decorative particles, impregnated with a thermosetting resin, for example melamine-formaldehyde resins, urea-formaldehyde resins, resins benzoguanamine-formaldehyde or unsaturated polyester resins.
  • a thermosetting resin for example melamine-formaldehyde resins, urea-formaldehyde resins, resins benzoguanamine-formaldehyde or unsaturated polyester resins.
  • a so-called "overlay”, patternless and transparent overlay in the final laminate is placed above said decorative sheet to improve the abrasion resistance of the laminate.
  • the pile of impregnated leaves is then placed in a laminating press whose trays are provided with a sheet conferring the surface state to the laminate.
  • the cell is densified by heating, at a temperature of the order of 110 ° C. to 170 ° C., and by pressing, at a pressure of the order of 5.5 MPa to 11 MPa, for approximately 25 to 60 minutes. minutes, to obtain a unitary structure.
  • This structure is then fixed on a base support, for example glued to a panel of agglomerated particles, especially agglomerated wood particles.
  • the so-called low-pressure decorative laminates are produced using only a decorative sheet impregnated with thermosetting resin, and possibly an overlay sheet, which is laminated directly on the base support during a short cycle, the temperature being of the order of 160 at 175 ° C and the pressure of 1.25 MPa at 3 MPa.
  • the decorative paper, or decorative sheet, used for the manufacture of laminates is generally a sheet of paper made on a paper machine.
  • Decorative papers currently marketed are generally free of surface treatment in particular to not alter their impregnation speed.
  • These decorative papers, or decorative sheets, are generally used to confer a particular aesthetic to the laminated supports on which they are affixed, this aesthetics may result from the printing on paper of a decorative pattern.
  • this decorative motif which traditionally consisted of imitating the appearance of a natural material, such as wood or marble, took more diversified forms in view of the demand, so as to adapt to the needs and customer wishes. This increase in the variety of reasons was accompanied by a contrario of a reduction of the quantities to be produced.
  • inkjet printing has proven to be the most more adapted to the needs of the decor papers.
  • inkjet printing also provides higher quality prints.
  • the use of the ink-jet printing principle in the production of decorative papers still faces a major difficulty related to the process of obtaining the laminates themselves.
  • the decor paper is first printed, then impregnated with resin and finally pressed hot with its support at high or low pressure.
  • the impregnation step requires the provision of a decorative paper having a high resistance in the wet state, so as to maintain a sufficient resistance after its total immersion in an aqueous resin, as well as a resin absorption capacity. the largest possible in the shortest possible time. These characteristics are generally obtained by using decorative papers having a very high porosity.
  • the inkjet printing technique is based on the principle of fixing ink on the surface of the print medium, the print medium must therefore, to obtain a clean and high quality, have a limited absorption.
  • Improved decorative papers have already been described by pre-coating the decor paper with a layer comprising ink-fixing particles.
  • These layers are often composed of a mixture of inorganic pigments, such as calcium carbonate, kaolin, silica, and a binder of the starch, casein, latex, polyvinyl alcohol or aminoplast resin type.
  • the patent application EP-A-1044822 discloses a so-called finished sheet, inkjet-printable sheet, formed of a paper coated with an ink-fixing layer. Said paper must be previously smoothed on one side before being coated with said ink fixing layer. This finished sheet is then glued on a panel to make a decorative panel.
  • This type of pre-impregnated paper is not intended for so-called high or low pressure stratified panels.
  • the paper is pre-impregnated before being coated with the ink-fixing layer, so there is no problem of impregnation.
  • a first disadvantage related to the technique of coated coating by a blade is that the excess layer to be deposited before scraping and the mechanical stress of pressure and tension during the contact are hardly applicable to porous and fragile papers such as decor papers . This coating technique causes many breakages during manufacture.
  • a second disadvantage is that the same technique of contact coating causes a partial penetration of the layer in the paper support and, consequently, a strong degradation of the resin absorption capacity by the paper.
  • US 6,517,674 discloses the manufacture of abrasion-resistant papers which can be coated with a layer by a curtain coating process.
  • the invention aims to solve the problems of the prior art decorative laminate papers by providing a manufacturing process conferring said decorative papers both good printability, including inkjet printing, and good absorption properties of thermosetting resin.
  • the object of the invention is to provide a process for producing printable decorative paper, in particular by ink jet printing, and impregnable with a thermosetting resin, to obtain a printable decorative paper impregnated by a resin with an impregnation speed. , determined according to the test described below in the paragraph "DESCRIPTION AND CONDITIONS OF REALIZATION OF TESTS", less than 100 seconds, regardless of its face, and which can be used to manufacture so-called decorative laminates high or low pressure.
  • At least one of the faces of the base decorative paper sheet is applied by curtain coating to at least one ink-fixing layer.
  • the basic decor paper sheet can be smoothed or unsmoothed before being coated with the ink-fixing layer.
  • the decorative paper manufacturing method of the invention has the advantage of producing a decorative paper having similar final characteristics regardless of the smoothness of the paper base.
  • the basic decor paper sheet may have a Bekk satin of the order of 10 to 200 seconds.
  • Said ink-fixing layer preferably comprises at least one hydrophilic binder, in particular a PVA (polyvinyl alcohol).
  • said layer further comprises said hydrophilic binder, a non-hydrophilic polymeric binder in a hydrophilic binder / non-hydrophilic binder ratio of at least 70/30 by dry weight.
  • Non-hydrophilic binders are polymers used in stabilized aqueous dispersion (latex) and customary ink fixing layers or the paper industry.
  • the ink-fixing layer according to the invention is not alkaline so as not to hinder the crosslinking of the thermosetting resin.
  • said ink-fixing layer is free of carbonates and alkaline buffers.
  • the ink-fixing layer according to the invention may comprise coating fillers which are chosen essentially from silicas.
  • the silicas are essentially amorphous precipitated silicas having a specific surface area greater than 100 m 2 / g.
  • said base paper sheet can be stained in bulk and / or on the surface; the color remaining remains visible through said layer in view of its transparency after lamination.
  • the amount of ink-fixing layer deposited on at least one of the faces of said base decorative paper sheet may be between 4 and 20 g / m 2 , in particular between 6 and 15 g / m 2 by dry weight.
  • the curtain coating technique is a pre-dosed coating method used in the photographic industry for more than 20 years. This technology has been developed for photographic films, which require the deposition of many different layers, usually between 8 and 10.
  • the curtain coating process is based on the free flow on a surface from a coating head situated above the surface to be coated at a height of between 10 and 25 cm.
  • the coating head is defined according to the properties of the coating fluid, so as to obtain the most uniform coating film thickness in the direction of the coating. walk or through the machine.
  • Two types of coating heads are generally used: slotted heads and sliding surface heads.
  • curtain coating is the absence of contact between the coating head and the support, unlike blade coating in particular.
  • the Applicant has found that the deposition of the layer being done without any pressure, the penetration of the composition into the support is limited to the simple capillarity of the fibers of the sheet and is therefore minimal. This results in an almost total preservation of the resin absorption capacity of the sheet, in particular on the non-coated face usually used as the contact face during impregnation with the resin.
  • the invention also relates to a process for producing printed decorative paper and impregnable by a thermosetting resin comprising a step of printing, in particular of decorative pattern, of said sheet of printable decor paper coated with at least one ink-fixing layer. of the second step (step b) of the method described above.
  • the process for producing a decorative paper impregnable by a thermosetting resin, for high or low pressure decorative laminate is characterized in that said layer is printed by inkjet printing, in particular in high resolution. ink fixative of the decorative paper obtained at the end of step b.
  • the invention also relates to a decorative paper printed by ink jet printing and impregnable by a thermosetting resin obtained according to this particular case of the method of the invention.
  • the laminate decorative paper obtained by the process of the invention as described above has the characteristic of being printable, in particular by inkjet printing, while retaining good properties of thermosetting resin absorption. .
  • the decorative paper for printable or printed laminate in particular by inkjet printing, and impregnable by a thermosetting resin resulting from the processes described above, is characterized by a speed of impregnation of said resin, determined according to the test described herein. -after paragraph "DESCRIPTION AND CONDITIONS OF REALIZATION OF TESTS”, less than 100 seconds, preferably less than or equal to 65 seconds, regardless of its face.
  • said rate of impregnation of the decorative paper according to the invention is between 40 and 60 seconds.
  • the decorative paper is generally first printed, then impregnated with a heat-stable thermosetting resin, and finally hot pressed with its support at high or low pressure.
  • the invention also relates to a method for producing a decorative paper impregnated with a thermosetting resin, which is characterized in that is impregnated by said thermosetting resin, a printed decorative paper, in particular by jet of ink, obtained according to the method as described above.
  • thermosetting resin is chosen from melamine-formaldehyde resins, urea-formaldehyde resins, benzoguanamine-formaldehyde resins, unsaturated polyester resins and their mixtures.
  • a decorative paper impregnated with partially cross-linked resin is called, in terms of trade, "decorative film” or “decorative film” or “melamine film”.
  • This melamine film contains a resin content preferably between 50 and 55% but may range from 45 to 65%.
  • This step is generally carried out by carrying the decorative paper at temperatures of about 110 to 140 ° C and is controlled, so that the resin during the final lamination of the decorative film flows well into the sheet, by measuring the volatile rate remaining in the movie decor.
  • this decor film then comprises a certain percentage, of the order of 5 to 8%, of volatile products (solvent water of the resin, water resulting from the chemical condensation of the resin, residual formaldehyde, the other products residuals). These volatiles represent the compounds that will be removed during the total crosslinking of the resin, during the lamination of the decor film.
  • the resin once fully thermoset after lamination, will provide surface resistance to the final laminate (abrasion resistance, dirt resistance, water vapor and chemical agents such as solvents, acids and alkalis). bases, etc ).
  • a decorative paper having a non-alkaline ink-fixing layer and obtained according to the printed decorative paper-making process previously described with a thermosetting resin is impregnated and then cross-linked. partially said resin in an acidic medium, the content of volatile compounds being between 5 and 8% by weight of the sheet.
  • the invention relates to a laminated decorative panel or profile, which is characterized in that it comprises as decorative paper, a decorative paper obtained as described above.
  • the basic components of the laminate are kraft sheets impregnated with thermosetting resin and the decorative paper obtained by the process of the invention impregnated with a thermosetting resin.
  • the basic components of the laminate are the support panel as a particleboard and a decorative paper obtained according to the method of the invention impregnated with a thermosetting resin.
  • Comparative Example 1 According to a conventional papermaking process, a smooth, plain white decorative paper having a grammage of 80 g / m 2 , a Gurley porosity of 20 s, a Bekk satin of 20 s, and containing 38% of ash is manufactured. . Such paper is sold by the company ARJOWIGGINS under the trade name ARJOSAVE. This paper is printed as is by inkjet printing on an EPSON® 7600 printer. It is then impregnated with a thermosetting melamine-formaldehyde resin and laminated to form a low pressure laminate board.
  • Comparative Example 2 This same ARJOSAVE white plain decorative paper is coated according to the film coating process with 10 g / m 2 dry weight of a layer C1 composed of 28.6 parts of a binder made of a mixture of an aqueous solution of hydrophilic polyvinyl alcohol (PVA) and a polyvinyl acetate in stabilized aqueous dispersion (said latex), respectively in proportions 85/15 by dry weight, and 100 parts of a calcium carbonate precipitate (PCC) coating.
  • PVA hydrophilic polyvinyl alcohol
  • PCC calcium carbonate precipitate
  • Comparative Example 3 This same ARJOSAVE paper is coated by the blade method with 10 g / m 2 dry weight of a layer C2 composed of 28.6 parts of the binder of Example 2 and 100 parts of a silica coating (amorphous) having an average particle size of 5.3-6.3 ⁇ m and a specific surface area (BET) of 160 m 2 / g.
  • This paper is then, as in the previous examples, printed by inkjet printing on an EPSON® 7600 printer. It is then impregnated with a melamine-formaldehyde thermosetting resin and laminated to form a low pressure laminate panel.
  • a sheet of the same plain white paper marketed by ARJOWIGGINS under the trade name ARJOSAVE is manufactured on a Fourdrinier type paper machine.
  • the sheet after drying has a basis weight of 80 g / m 2 , a porosity
  • Gurley of 20s a satin Bekk of 20s, and contains a rate of ashes of 38%.
  • the paper sheet thus obtained is reeled.
  • this paper is then coated by the curtain coating process on one of its faces by 10 g / m 2 dry weight of a layer C2 identical to that used in Example 3.
  • the paper sheet thus coated on an EPSON® 7600 printer is printed by inkjet printing.
  • the sheet is then impregnated with a melamine-formaldehyde resin in aqueous media.
  • This sheet is laminated to manufacture a low pressure laminate according to the usual operating conditions.
  • Comparative Example 5 (Reference Printing Base): According to a conventional papermaking process, a plain white non-smoothed decorative paper having a grammage of 80 g / m 2 , a Gurley porosity of 20 s, a Bekk satin of 140 is produced. s, and containing 38% ash. Such paper is marketed by ARJOWIGGINS under the trade name ARJOPRINT . This paper is printed as is by inkjet printing on an EPSON® 7600 printer. It is then, as in the previous examples, impregnated with a thermosetting melamine-formaldehyde resin and laminated to form a low-type laminate board. pressure.
  • Comparative Example 6 The same Arjoprint paper is coated according to the blade process with 10 g / m 2 of the layer C2 identical to that used in Example 3. It is then, as in Example 5, printed and impregnated melamine-formaldehyde thermosetting resin and laminated to form a low pressure laminate panel.
  • a sheet of the same plain white paper marketed by ARJOWIGGINS under the trade name ARJOPRINT is manufactured on a Fourdrinier type paper machine.
  • the sheet after drying has a basis weight of 80 g / m 2 , a Gurley porosity of 20 s, a Bekk satin of 140 s, and contains an ash content of 38%.
  • the paper sheet thus obtained is reeled.
  • the paper is coated by the curtain coating process on one of its faces with 10 g / m 2 dry weight of a layer C2 identical to that used in Example 3.
  • the paper sheet thus coated on an EPSON® 7600 printer is printed by inkjet printing.
  • the sheet is then impregnated with a melamine-formaldehyde resin in aqueous media.
  • This sheet is laminated to manufacture a low pressure laminate according to the usual operating conditions.
  • Comparative Example 8 The same ARJOPRINT paper is coated according to the blade process with 10 g / m 2 of a layer C3 composed of 28.6 parts of a polyvinyl acetate in the form of latex and 100 parts of an (amorphous) coating silica having an average particle size of 5.3-6.3 ⁇ m and a BET specific surface area of 160 m 2 / g. It is, as in Example 6, printed and then impregnated with a melamine-formaldehyde thermosetting resin and laminated to form a low pressure laminate panel.
  • Comparative Example 2 shows a high undercuring of the melamine-formaldehyde resin after lamination.
  • Example 8 it will be noted that the use of a layer whose binder contains too much non-hydrophilic binder (latex) causes a blistering phenomenon for the laminate which is unacceptable.
  • the examples show that the invention makes it possible to obtain a decorative paper exhibiting both excellent inkjet printing aptitude and good absorption of the resin, necessary for the subsequent impregnation of this type of paper.
  • non-hydrophilic polymer (of the latex type) mixed with a hydrophilic binder in the coating composition is also possible, in proportions compatible with the impregnation and lamination requirements of the coated sheet. (no blistering)

Abstract

The invention relates to a method of producing decorative paper which is coated with at least one ink-fixing layer, which is printable and which can be impregnated with a thermosetting resin, in order to produce a high- or low-pressure decorative laminate. The inventive method comprises the following steps consisting in: (a) producing a base sheet of decorative paper using paper-making means; and (b) coating at least one of the faces of the base paper sheet with said at least one ink-fixing layer, by means of curtain coating. The invention also relates to high- or low-pressure decorative laminates comprising such decorative paper.

Description

L'invention concerne un procédé de fabrication d'un papier décoratif imprégnable par une résine thermodurcissable, présentant à la fois une bonne imprimabilité, notamment en impression jet d'encre, et de bonnes propriétés d'absorption de résine. L'invention concerne également un tel papier décoratif imprégné d'une résine thermodurcissable. L'invention concerne enfin les panneaux ou profilés décoratifs stratifiés comportant le papier décoratif imprégné de résine thermodurcissable.The invention relates to a method for manufacturing a decorative paper impregnable by a thermosetting resin, having both good printability, especially in inkjet printing, and good resin absorption properties. The invention also relates to such a decorative paper impregnated with a thermosetting resin. The invention finally relates to laminated decorative panels or profiles comprising decorative paper impregnated with thermosetting resin.

Depuis de nombreuses années, on emploie des panneaux ou profilés décoratifs stratifiés (encore appelés « stratifiés ») comme matériaux dans les habitations et les locaux commerciaux et industriels. Des applications typiques de tels stratifiés sont les revêtements de sols, en particulier les revêtements imitant le parquet, les revêtements des meubles, des dessus de table, des chaises et autres.For many years, laminated decorative panels or profiles have been used as materials in homes, commercial and industrial premises. Typical applications of such laminates are floor coverings, particularly flooring-like coatings, furniture coverings, table tops, chairs and the like.

Il existe deux grandes sortes de « stratifiés » décoratifs: les « stratifiés » dits haute pression et les « stratifiés » dits basse pression.There are two main types of decorative "laminates": so-called high-pressure "laminates" and so-called "low-pressure" laminates.

On produit les stratifiés décoratifs dits haute pression à partir d'une âme constituée de feuilles imprégnées de résine. Ces feuilles sont généralement en papier kraft et ont été imprégnées d'une résine thermodurcissable, le plus souvent d'une résine phénolique. Après avoir imprégné les feuilles de résine, on les sèche, on les découpe, puis on les empile les unes sur les autres. Le nombre de feuilles dans la pile dépend des applications et varie entre 3 et 9, mais peut être supérieur. Sur la pile de feuilles constituant l'âme, on place ensuite un papier décoratif, appelé aussi papier décor ou feuille décorative. Une telle feuille décorative est en général une feuille de papier portant un motif imprimé ou de couleur ou comportant des particules décoratives, imprégnée d'une résine thermodurcissable, par exemple des résines de mélamine-formaldéhyde, des résines d'urée-formaldéhyde, des résines de benzoguanamine-formaldéhyde ou des résines de polyester insaturé.The so-called high pressure decorative laminates are produced from a core made of resin-impregnated sheets. These sheets are generally made of kraft paper and have been impregnated with a thermosetting resin, most often a phenolic resin. After impregnating the resin sheets, they are dried, cut, and stacked on top of one another. The number of sheets in the stack depends on the applications and varies between 3 and 9, but can be higher. On the pile of leaves constituting the soul, a decorative paper is then placed, also called decor paper or decorative sheet. Such a decorative sheet is generally a sheet of paper carrying a pattern printed or colored or comprising decorative particles, impregnated with a thermosetting resin, for example melamine-formaldehyde resins, urea-formaldehyde resins, resins benzoguanamine-formaldehyde or unsaturated polyester resins.

En général, on place au-dessus de ladite feuille décorative, une feuille protectrice de recouvrement, dite "overlay", dépourvue de motif et transparente dans le stratifié final, pour améliorer la résistance à l'abrasion du stratifié. La pile de feuilles imprégnées est ensuite placée dans une presse à stratifier dont les plateaux sont munis d'une tôle conférant l'état de surface au stratifié. Puis, on densifie la pile par chauffage, à une température de l'ordre de 110°C à 170°C, et par pressage, à une pression de l'ordre de 5,5 MPa à 11 MPa, pendant environ 25 à 60 minutes, pour obtenir une structure unitaire. On fixe ensuite cette structure sur un support de base, par exemple on la colle sur un panneau de particules agglomérées, notamment de particules de bois agglomérées.In general, a so-called "overlay", patternless and transparent overlay in the final laminate is placed above said decorative sheet to improve the abrasion resistance of the laminate. The pile of impregnated leaves is then placed in a laminating press whose trays are provided with a sheet conferring the surface state to the laminate. Then, the cell is densified by heating, at a temperature of the order of 110 ° C. to 170 ° C., and by pressing, at a pressure of the order of 5.5 MPa to 11 MPa, for approximately 25 to 60 minutes. minutes, to obtain a unitary structure. This structure is then fixed on a base support, for example glued to a panel of agglomerated particles, especially agglomerated wood particles.

On produit les stratifiés décoratifs dits basse pression en utilisant uniquement une feuille décorative imprégnée de résine thermodurcissable, et éventuellement une feuille overlay, que l'on stratifie directement sur le support de base pendant un cycle court, la température étant de l'ordre de 160 à 175°C et la pression de 1,25 MPa à 3 MPa.The so-called low-pressure decorative laminates are produced using only a decorative sheet impregnated with thermosetting resin, and possibly an overlay sheet, which is laminated directly on the base support during a short cycle, the temperature being of the order of 160 at 175 ° C and the pressure of 1.25 MPa at 3 MPa.

Le papier décoratif, ou feuille décorative, utilisé pour la fabrication de stratifiés est en général une feuille de papier réalisée sur une machine à papier. Les papiers décoratifs actuellement commercialisés sont généralement exempts de traitement de surface afin notamment de ne pas altérer leur vitesse d'imprégnation.The decorative paper, or decorative sheet, used for the manufacture of laminates is generally a sheet of paper made on a paper machine. Decorative papers currently marketed are generally free of surface treatment in particular to not alter their impregnation speed.

Ces papiers décoratifs, ou feuilles décoratives, sont généralement utilisés pour conférer une esthétique particulière aux supports stratifiés sur lesquels ils sont apposés, cette esthétique pouvant résulter de l'impression sur le papier d'un motif décoratif.These decorative papers, or decorative sheets, are generally used to confer a particular aesthetic to the laminated supports on which they are affixed, this aesthetics may result from the printing on paper of a decorative pattern.

Or, ce motif décoratif, qui consistait traditionnellement à imiter l'aspect d'un matériau naturel, comme du bois ou du marbre, a pris des formes plus diversifiées compte-tenu de la demande, de manière à s'adapter aux besoins et aux souhaits du client. Cet accroissement dans la variété des motifs s'est accompagné a contrario d'une réduction des quantités à produire.However, this decorative motif, which traditionally consisted of imitating the appearance of a natural material, such as wood or marble, took more diversified forms in view of the demand, so as to adapt to the needs and customer wishes. This increase in the variety of reasons was accompanied by a contrario of a reduction of the quantities to be produced.

Ce phénomène de personnalisation des décors et de production en petite série n'a pas été sans conséquence sur les difficultés rencontrées par les fabricants de papiers décoratifs. En effet, pour des productions de motifs simples en grande série, les techniques d'impression telles que l'héliogravure présentaient l'avantage d'imprimer sur grande laize à des cadences élevées. Or, ce procédé d'impression ne s'avère pas rentable pour des petites séries, de plus, le rendu d'impression obtenu n'est pas suffisant pour des motifs complexes qui exige une haute résolution.This phenomenon of personalization of the sets and production in small series has not been without consequence on the difficulties met by the manufacturers of decorative papers. Indeed, for mass production of simple patterns, printing techniques such as gravure printing had the advantage of printing on large width at high rates. However, this printing process is not profitable for small series, moreover, the print result obtained is not sufficient for complex reasons that requires a high resolution.

Parmi les techniques d'impression suffisamment souples pour fabriquer de petites quantités à la demande, l'impression par jet d'encre s'est avérée être la technique la plus adaptée aux besoins des papiers décors. Outre la simplicité de son principe de fonctionnement et ses coûts de production relativement faibles, l'impression par jet d'encre permet également d'obtenir des impressions de meilleure qualité. Toutefois, l'utilisation du principe d'impression par jet d'encre dans la fabrication de papiers décors reste confrontée à une difficulté majeure liée au procédé d'obtention des stratifiés eux-mêmes.Among printing techniques that are flexible enough to make small quantities on demand, inkjet printing has proven to be the most more adapted to the needs of the decor papers. In addition to the simplicity of its operating principle and its relatively low production costs, inkjet printing also provides higher quality prints. However, the use of the ink-jet printing principle in the production of decorative papers still faces a major difficulty related to the process of obtaining the laminates themselves.

Dans le processus classique de fabrication des stratifiés, le papier décor est d'abord imprimé, puis imprégné de résine et finalement pressé à chaud avec son support à haute ou basse pression. L'étape d'imprégnation nécessite de disposer d'un papier décoratif possédant une résistance élevée à l'état humide, de manière à conserver une tenue suffisante après son immersion totale dans une résine aqueuse, ainsi qu'une capacité d'absorption de résine la plus importante possible dans le temps le plus court possible. Ces caractéristiques sont généralement obtenues en utilisant des papiers décoratifs possédant une porosité très importante.In the conventional process of manufacturing laminates, the decor paper is first printed, then impregnated with resin and finally pressed hot with its support at high or low pressure. The impregnation step requires the provision of a decorative paper having a high resistance in the wet state, so as to maintain a sufficient resistance after its total immersion in an aqueous resin, as well as a resin absorption capacity. the largest possible in the shortest possible time. These characteristics are generally obtained by using decorative papers having a very high porosity.

Or, la technique d'impression par jet d'encre repose sur le principe d'une fixation d'encre à la surface du support à imprimer, le support à imprimer doit donc, pour obtenir une impression nette et de haute qualité, avoir une absorption limitée.However, the inkjet printing technique is based on the principle of fixing ink on the surface of the print medium, the print medium must therefore, to obtain a clean and high quality, have a limited absorption.

On a déjà décrit des papiers décoratifs améliorés par une enduction préalable du papier décor avec une couche comprenant des particules fixatrices d'encre. Ces couches sont souvent composées d'un mélange de pigments minéraux, tels que le carbonate de calcium, le kaolin, la silice, et d'un liant de type amidon, caséine, latex, alcool polyvinylique ou résine aminoplaste.Improved decorative papers have already been described by pre-coating the decor paper with a layer comprising ink-fixing particles. These layers are often composed of a mixture of inorganic pigments, such as calcium carbonate, kaolin, silica, and a binder of the starch, casein, latex, polyvinyl alcohol or aminoplast resin type.

La demande de brevet EP-A-054405 concerne l'amélioration de l'imprimabilité des papiers décoratifs, toutefois l'impression par jet d'encre n'est pas spécifiquement visée. Ce document décrit des papiers couchés avec une couche pigmentée classiquement connue en impression-écriture, mais afin de maintenir une certaine capacité d'absorption de résine par le papier, le poids de couche ne doit pas être supérieur à 10 g/m2 et le poids recommandé est compris entre 2,5 et 3 g/m2.The patent application EP-A-054405 Improving the printability of decorative papers, however, inkjet printing is not specifically targeted. This document describes coated papers with a pigmented layer conventionally known in print-writing, but in order to maintain a certain capacity of resin absorption by the paper, the weight of the layer must not be greater than 10 g / m 2 and the recommended weight is between 2.5 and 3 g / m 2 .

La demande de brevet EP-A-1044822 décrit une feuille décorative dite feuille finie, imprimable par jet d'encre, formée d'un papier revêtu d'une couche fixatrice d'encre. Ledit papier doit être préalablement lissé sur une face avant d'être revêtu de ladite couche fixatrice d'encre. Cette feuille finie est ensuite collée sur un panneau pour faire un panneau décoratif. Ce type de papier pré-imprégné n'est pas destiné aux panneaux stratifiés dits haute ou basse pression. De plus, le papier est pré-imprégné avant d'être revêtu de la couche fixatrice d'encre, il n'y a donc pas de problème d'imprégnation.The patent application EP-A-1044822 discloses a so-called finished sheet, inkjet-printable sheet, formed of a paper coated with an ink-fixing layer. Said paper must be previously smoothed on one side before being coated with said ink fixing layer. This finished sheet is then glued on a panel to make a decorative panel. This type of pre-impregnated paper is not intended for so-called high or low pressure stratified panels. In addition, the paper is pre-impregnated before being coated with the ink-fixing layer, so there is no problem of impregnation.

Bien que le rendu d'impression des papiers décoratifs soit sensiblement amélioré, il subsiste de nombreux inconvénients liés à leur procédé de fabrication, et notamment liés aux techniques d'enduction.Although the rendering of decorative papers is substantially improved, there are still many drawbacks related to their manufacturing process, and in particular related to coating techniques.

Un premier inconvénient lié à la technique d'enduction par couchage par lame est que l'excès de couche à déposer avant raclage et les contraintes mécaniques de pression et de tension lors du contact sont difficilement applicables à des papiers poreux et fragiles comme les papiers décors. Cette technique d'enduction entraîne de nombreuses casses lors de la fabrication. Un second inconvénient est que la technique mème d'enduction par contact entraîne une pénétration partielle de la couche dans le support papier et, en conséquence, une forte dégradation de la capacité d'absorption de résine par le papier.A first disadvantage related to the technique of coated coating by a blade is that the excess layer to be deposited before scraping and the mechanical stress of pressure and tension during the contact are hardly applicable to porous and fragile papers such as decor papers . This coating technique causes many breakages during manufacture. A second disadvantage is that the same technique of contact coating causes a partial penetration of the layer in the paper support and, consequently, a strong degradation of the resin absorption capacity by the paper.

Comme l'état de la technique le révèle, la fabrication de papier décoratif ayant unpoids de couche relativement élevé et/ou conservant une capacité d'absorption de résine élevée pour fabriquer des stratifiés haute ou basse pression, présente de nombreuses difficultés.As is known from the state of the art, the production of decorative paper having a relatively high layer weight and / or maintaining a high resin absorption capacity for making high or low pressure laminates presents many difficulties.

US 5,773,093 , JP 03 353 925 , JP 2002/274009 et JP 10 114 142 décrivent des procédés de fabrication de papiers pouvant être imprimés par impression jet d'encre et mettant en oeuvre un procédé de couchage à rideau. US 5,773,093 , JP 03 353 925 , JP 2002/274009 and JP 10 114 142 disclose methods of making paper that can be printed by inkjet printing and embodying a curtain coating process.

US 6,517,674 décrit la fabrication de papiers résistants à l'abrasion pouvant être revêtus d'une couche par un procédé de couchage à rideau. US 6,517,674 discloses the manufacture of abrasion-resistant papers which can be coated with a layer by a curtain coating process.

L'invention vise à résoudre les problèmes de l'art antérieur des papiers décoratifs pour stratifiés en proposant un procédé de fabrication conférant auxdits papiers décoratifs à la fois une bonne imprimabilité, notamment en impression jet d'encre, et de bonnes propriétés d'absorption de résine thermodurcissable.The invention aims to solve the problems of the prior art decorative laminate papers by providing a manufacturing process conferring said decorative papers both good printability, including inkjet printing, and good absorption properties of thermosetting resin.

Le but de l'invention est de fournir un procédé de fabrication de papier décoratif imprimable, notamment par impression jet d'encre, et imprégnable par une résine thermodurcissable, pour obtenir un papier décoratif imprimable, imprégnable par une résine avec une vitesse d'imprégnation, déterminée selon le test décrit ci-après dans le paragraphe « DESCRIPTION ET CONDITIONS DE REALISATION DES TESTS », inférieure à 100 secondes, quelle que soit sa face, et qui puise être utilisé pour fabriquer des stratifiés décoratifs dits haute ou basse pression.The object of the invention is to provide a process for producing printable decorative paper, in particular by ink jet printing, and impregnable with a thermosetting resin, to obtain a printable decorative paper impregnated by a resin with an impregnation speed. , determined according to the test described below in the paragraph "DESCRIPTION AND CONDITIONS OF REALIZATION OF TESTS", less than 100 seconds, regardless of its face, and which can be used to manufacture so-called decorative laminates high or low pressure.

L'invention a donc pour objet un procédé de fabrication d'un papier décoratif revêtu d'au moins une couche fixatrice d'encre, imprimable et imprégnable par une résine thermodurcissable, pour stratifié décoratif haute ou basse pression, comportant les étapes suivantes :

  1. a. on fabrique une feuille de papier décor de base par voie papetière , puis
  2. b. on enduit, par un couchage à rideau, au moins une des faces de ladite feuille de papier décor de base par au moins ladite couche fixatrice d'encre. Selon le procédé de fabrication de papier décoratif de l'invention, dans une première étape, on fabrique une feuille de papier décor de base par voie papetière sur une machine à papier à partir d'une dispersion à base de fibres de cellulose, et éventuellement de fibres synthétiques, en milieu aqueux, les fibres de cellulose se répartissant en poids, en général, de 40 à 100 %, de préférence 80 à 100 %, en fibres courtes et de 0 à 60 %, de préférence 0 à 20 %, en fibres longues. La dispersion comporte de préférence 0,2 à 2,5 % en poids sec par rapport à la feuille d'un agent de résistance humide, plus préférentiellement de 0,4 à 0,8 %. La dispersion peut également comporter de 5 à 50 % en poids sec par rapport à la feuille de particules décoratives telles que des pigments iridiscents par exemple, de colorants pigmentaires
ou organiques ou de charges opacifiantes comme le dioxyde de titane, notamment de type rutile, ladite charge opacifiante comme le dioxyde de titane étant en quantité de préférence d'au moins 15%, en général, comprise entre environ 15 à 40 % par rapport au poids de la feuille.The invention therefore relates to a process for producing a decorative paper coated with at least one ink-fixing layer, printable and impregnable by a thermosetting resin, for high or low pressure decorative laminate, comprising the following steps:
  1. at. a basic sheet of paper is made by papermaking, then
  2. b. at least one of the faces of said base decorative paper sheet is coated by a curtain coating with at least said ink-fixing layer. According to the decorative paper manufacturing method of the invention, in a first step, a base paper paper is prepared by papermaking on a paper machine from a dispersion based on cellulose fibers, and optionally synthetic fibers, in an aqueous medium, the cellulose fibers being distributed in weight, in general, from 40 to 100%, preferably 80 to 100%, short fibers and 0 to 60%, preferably 0 to 20%, in long fibers. The dispersion preferably comprises 0.2 to 2.5% by dry weight relative to the sheet of a wet strength agent, more preferably from 0.4 to 0.8%. The dispersion may also comprise from 5 to 50% by dry weight relative to the sheet of decorative particles such as iridiscent pigments, for example, pigment dyes
or organic or opacifying fillers such as titanium dioxide, especially of rutile type, said opacifying filler such as titanium dioxide being in an amount preferably of at least 15%, generally between about 15 to 40% relative to the weight of the leaf.

Selon le procédé de l'invention, dans une deuxième étape, on applique par un couchage à rideau sur au moins une des faces de la feuille de papier décor de base au moins une couche fixatrice d'encre.According to the process of the invention, in a second step, at least one of the faces of the base decorative paper sheet is applied by curtain coating to at least one ink-fixing layer.

Selon l'invention, la feuille de papier décor de base peut être lissée ou non lissée avant d'être revêtue de la couche fixatrice d'encre. En effet, le procédé de fabrication de papier décoratif de l'invention présente l'avantage de produire un papier décor présentant des caractéristiques finales similaires quel que soit le lissé de la base papier.According to the invention, the basic decor paper sheet can be smoothed or unsmoothed before being coated with the ink-fixing layer. Indeed, the decorative paper manufacturing method of the invention has the advantage of producing a decorative paper having similar final characteristics regardless of the smoothness of the paper base.

En particulier, la feuille de papier décor de base peut présenter un satinage Bekk de l'ordre de 10 à 200 secondes.In particular, the basic decor paper sheet may have a Bekk satin of the order of 10 to 200 seconds.

Ladite couche fixatrice d'encre comporte de préférence au moins un liant hydrophile, en particulier un PVA (alcool polyvinylique). Selon un cas particulier de l'invention, ladite couche comporte en plus dudit liant hydrophile, un liant polymère non-hydrophile dans un ratio liant hydrophile/liant non-hydrophile d'au moins 70/30 en poids sec. Les liants non-hydrophiles sont des polymères utilisés en dispersion aqueuse stabilisées (latex) et usuels des couches fixatrices d'encre ou du domaine papetier.Said ink-fixing layer preferably comprises at least one hydrophilic binder, in particular a PVA (polyvinyl alcohol). According to a particular case of the invention, said layer further comprises said hydrophilic binder, a non-hydrophilic polymeric binder in a hydrophilic binder / non-hydrophilic binder ratio of at least 70/30 by dry weight. Non-hydrophilic binders are polymers used in stabilized aqueous dispersion (latex) and customary ink fixing layers or the paper industry.

De préférence, la couche fixatrice d'encre selon l'invention n'est pas alcaline afin de ne pas gêner la réticulation de la résine thermodurcissable. En particulier, ladite couche fixatrice d'encre est exempte de carbonates et de tampons alcalins.Preferably, the ink-fixing layer according to the invention is not alkaline so as not to hinder the crosslinking of the thermosetting resin. In particular, said ink-fixing layer is free of carbonates and alkaline buffers.

La couche fixatrice d'encre selon l'invention peut comporter des charges de couchage qui sont choisies essentiellement parmi les silices. De préférence, les silices sont essentiellement des silices amorphes de précipitation ayant une surface spécifique supérieure à 100m2/g.The ink-fixing layer according to the invention may comprise coating fillers which are chosen essentially from silicas. Preferably, the silicas are essentially amorphous precipitated silicas having a specific surface area greater than 100 m 2 / g.

Dans le cas particulier de l'invention où les charges de couchage de la couche fixatrice d'encre sont transparentes ou translucides, notamment des silices amorphes, ladite feuille de papier de base peut être colorée en masse et/ou en surface; la coloration restant maintenue visible à travers ladite couche compte-tenu de sa transparence après stratification.In the particular case of the invention where the coating charges of the ink-fixing layer are transparent or translucent, in particular amorphous silicas, said base paper sheet can be stained in bulk and / or on the surface; the color remaining remains visible through said layer in view of its transparency after lamination.

La quantité de couche fixatrice d'encre déposée sur au moins une des faces de ladite feuille de papier décor de base peut être comprise entre 4 et 20 g/m2, en particulier entre 6 et 15 g/m2 en poids sec.The amount of ink-fixing layer deposited on at least one of the faces of said base decorative paper sheet may be between 4 and 20 g / m 2 , in particular between 6 and 15 g / m 2 by dry weight.

La technique du couchage à rideau est une méthode de couchage pré-dosée, utilisée dans l'industrie photographique depuis plus de 20 ans. Cette technologie a été développée pour les films photographiques, qui nécessitent le dépôt de nombreuses couches différentes, généralement entre 8 et 10.The curtain coating technique is a pre-dosed coating method used in the photographic industry for more than 20 years. This technology has been developed for photographic films, which require the deposition of many different layers, usually between 8 and 10.

Le procédé de couchage à rideau est basé sur l'écoulement libre sur une surface à partir d'une tête de couchage située au-dessus de la surface à enduire à une hauteur variant entre 10 et 25 cm.The curtain coating process is based on the free flow on a surface from a coating head situated above the surface to be coated at a height of between 10 and 25 cm.

La tête de couchage est définie selon les propriétés du fluide de couchage, de façon à obtenir une épaisseur de film de couchage la plus uniforme possible dans le sens marche ou travers de la machine. Il est généralement utilisé deux types de têtes de couchage : les têtes à fentes et les têtes à surface de glissement.The coating head is defined according to the properties of the coating fluid, so as to obtain the most uniform coating film thickness in the direction of the coating. walk or through the machine. Two types of coating heads are generally used: slotted heads and sliding surface heads.

Un autre avantage du couchage à rideau est l'absence de contact entre la tête de couchage et le support, contrairement au couchage par lame notamment.Another advantage of the curtain coating is the absence of contact between the coating head and the support, unlike blade coating in particular.

Le pré-dosage de la quantité de matière à déposer et l'absence totale de contact, donc de contraintes mécaniques, lors de ce dépôt permettent un couchage plus aisé de la feuille de papier décoratif aux vitesses d'une coucheuse industrielle, en particulier à des vitesses supérieures à 400 m/mn.The pre-metering of the quantity of material to be deposited and the total absence of contact, and therefore of mechanical stresses, during this deposition make it easier to coat the decorative paper sheet at the speeds of an industrial coater, in particular to speeds above 400 m / min.

Par ailleurs, la Demanderesse a constaté que le dépôt de la couche se faisant sans aucune pression, la pénétration de la composition dans le support se limite à la simple capillarité des fibres de la feuille et est donc minimale. Il s'ensuit une conservation presque totale de la capacité d'absorption de résine de la feuille, en particulier sur la face non couchée habituellement utilisée comme face de contact lors de l'imprégnation par la résine.Furthermore, the Applicant has found that the deposition of the layer being done without any pressure, the penetration of the composition into the support is limited to the simple capillarity of the fibers of the sheet and is therefore minimal. This results in an almost total preservation of the resin absorption capacity of the sheet, in particular on the non-coated face usually used as the contact face during impregnation with the resin.

L'invention concerne également un procédé de fabrication de papier décoratif imprimé et imprégnable par une résine thermodurcissable comprenant une étape d'impression, notamment de motif décoratif, de ladite feuille de papier décor imprimable revêtue d'au moins une couche fixatrice d'encre issue de la deuxième étape (étape b) du procédé décrit précédemment. En particulier, le procédé de fabrication d'un papier décoratif imprimé, imprégnable par une résine thermodurcissable, pour stratifié décoratif haute ou basse pression, se caractérise en ce qu'on imprime par impression jet d'encre, notamment en haute résolution, ladite couche fixatrice d'encre du papier décoratif obtenu à l'issue de l'étape b.The invention also relates to a process for producing printed decorative paper and impregnable by a thermosetting resin comprising a step of printing, in particular of decorative pattern, of said sheet of printable decor paper coated with at least one ink-fixing layer. of the second step (step b) of the method described above. In particular, the process for producing a decorative paper impregnable by a thermosetting resin, for high or low pressure decorative laminate, is characterized in that said layer is printed by inkjet printing, in particular in high resolution. ink fixative of the decorative paper obtained at the end of step b.

De ce fait, l'invention concerne aussi un papier décoratif imprimé par impression jet d'encre et imprégnable par une résine thermodurcissable obtenu selon ce cas particulier du procédé de l'invention.Therefore, the invention also relates to a decorative paper printed by ink jet printing and impregnable by a thermosetting resin obtained according to this particular case of the method of the invention.

Selon l'invention, le papier décoratif pour stratifié obtenu par le procédé de l'invention tel que décrit précédemment présente la caractéristique d'être imprimable, notamment par impression jet d'encre, tout en conservant de bonnes propriétés d'absorption de résine thermodurcissable.According to the invention, the laminate decorative paper obtained by the process of the invention as described above has the characteristic of being printable, in particular by inkjet printing, while retaining good properties of thermosetting resin absorption. .

En effet, le papier décoratif pour stratifié imprimable ou imprimé, notamment par impression jet d'encre, et imprégnable par une résine thermodurcissable issu des procédés décrits précédemment, se caractérise par une vitesse d'imprégnation de ladite résine, déterminée selon le test décrit ci-après au paragraphe « DESCRIPTION ET CONDITIONS DE REALISATION DES TESTS », inférieure à 100 secondes, de préférence inférieure ou égale à 65 secondes, quelle que soit sa face.Indeed, the decorative paper for printable or printed laminate, in particular by inkjet printing, and impregnable by a thermosetting resin resulting from the processes described above, is characterized by a speed of impregnation of said resin, determined according to the test described herein. -after paragraph "DESCRIPTION AND CONDITIONS OF REALIZATION OF TESTS", less than 100 seconds, preferably less than or equal to 65 seconds, regardless of its face.

En particulier, ladite vitesse d'imprégnation du papier décoratif selon l'invention est comprise entre 40 et 60 secondes.In particular, said rate of impregnation of the decorative paper according to the invention is between 40 and 60 seconds.

Comme décrit précédemment, lors de la fabrication des stratifiés, le papier décor est en général d'abord imprimé, puis imprégné d'une résine thermodurcissable stable thermiquement, et finalement pressé à chaud avec son support à haute ou basse pression.As described previously, during the manufacture of the laminates, the decorative paper is generally first printed, then impregnated with a heat-stable thermosetting resin, and finally hot pressed with its support at high or low pressure.

En conséquence, l'invention concerne aussi un procédé de fabrication d'un papier décoratif imprégné d'une résine thermodurcissable, qui se caractérise en ce que l'on imprègne, par ladite résine thermodurcissable, un papier décoratif imprimé, en particulier par jet d'encre, obtenu selon le procédé tel que décrit précédemment.Accordingly, the invention also relates to a method for producing a decorative paper impregnated with a thermosetting resin, which is characterized in that is impregnated by said thermosetting resin, a printed decorative paper, in particular by jet of ink, obtained according to the method as described above.

En particulier, la résine thermodurcissable est choisie parmi les résines mélamine-formaldéhyde, les résines urée-formaldéhyde, les résines benzoguanamine-formaldéhyde, les résines de polyester insaturé et leurs mélanges.In particular, the thermosetting resin is chosen from melamine-formaldehyde resins, urea-formaldehyde resins, benzoguanamine-formaldehyde resins, unsaturated polyester resins and their mixtures.

Une fois imprégné de résine, le papier décoratif est chauffé, la résine est partiellement réticulée (thermodurcie) afin qu'elle ne soit plus dans un état collant et que la feuille soit manipulable. Un papier décoratif imprégné de résine partiellement réticulée est appelé, en termes de métier, "film décor" ou "film décoratif" ou encore "film mélaminé". Ce film mélaminé contient un taux de résine de préférence compris entre 50 et 55% mais pouvant aller de 45 à 65%.Once impregnated with resin, the decorative paper is heated, the resin is partially crosslinked (thermoset) so that it is no longer in a sticky state and that the sheet is manipulable. A decorative paper impregnated with partially cross-linked resin is called, in terms of trade, "decorative film" or "decorative film" or "melamine film". This melamine film contains a resin content preferably between 50 and 55% but may range from 45 to 65%.

Cette étape est généralement réalisée en portant le papier décoratif à des températures d'environ 110 à 140 °C et est contrôlée, de façon à ce que la résine lors de la stratification finale du film décor flue correctement dans la feuille, par la mesure du taux de volatils restant dans le film décor. En effet ce film décor comporte alors un certain pourcentage, de l'ordre de 5 à 8 %, de produits volatils (eau solvant de la résine, eau résultant de la condensation chimique de la résine, le formaldéhyde résiduel, les autres produits résiduels ..). Ces volatils représentent les composés qui seront éliminés lors de la réticulation totale de la résine, pendant la stratification du film décor.This step is generally carried out by carrying the decorative paper at temperatures of about 110 to 140 ° C and is controlled, so that the resin during the final lamination of the decorative film flows well into the sheet, by measuring the volatile rate remaining in the movie decor. Indeed, this decor film then comprises a certain percentage, of the order of 5 to 8%, of volatile products (solvent water of the resin, water resulting from the chemical condensation of the resin, residual formaldehyde, the other products residuals). These volatiles represent the compounds that will be removed during the total crosslinking of the resin, during the lamination of the decor film.

La résine, une fois totalement thennodurcie, après stratification, apportera de la résistance de surface au stratifié final (résistance à l'abrasion, résistance à la salissure, à la vapeur d'eau et aux agents chimiques comme les solvants, les acides et les bases, etc... ).The resin, once fully thermoset after lamination, will provide surface resistance to the final laminate (abrasion resistance, dirt resistance, water vapor and chemical agents such as solvents, acids and alkalis). bases, etc ...).

Selon un cas particulier du procédé de fabrication de papier décoratif imprégné de résine, on imprègne un papier décoratif ayant une couche fixatrice d'encre non alcaline et obtenu selon le procédé de fabrication de papier décoratif imprimé précédemment décrit avec une résine thermodurcissable, puis on réticule partiellement ladite résine en milieu acide, le taux de composés volatils étant compris entre 5 et 8 % en poids de la feuille.According to a particular case of the method for manufacturing resin-impregnated decorative paper, a decorative paper having a non-alkaline ink-fixing layer and obtained according to the printed decorative paper-making process previously described with a thermosetting resin, is impregnated and then cross-linked. partially said resin in an acidic medium, the content of volatile compounds being between 5 and 8% by weight of the sheet.

L'invention concerne enfin un panneau ou profilé décoratif stratifié, qui se caractérise par le fait qu'il comporte comme papier décoratif, un papier décoratif obtenu tel que décrit précédemment.Finally, the invention relates to a laminated decorative panel or profile, which is characterized in that it comprises as decorative paper, a decorative paper obtained as described above.

Dans le cas d'un stratifié dit haute pression, les composants de base du stratifié sont les feuilles kraft imprégnées de résine thermodurcissable et le papier décoratif obtenu selon le procédé de l'invention imprégné d'une résine thermodurcissable.In the case of so-called high pressure laminate, the basic components of the laminate are kraft sheets impregnated with thermosetting resin and the decorative paper obtained by the process of the invention impregnated with a thermosetting resin.

Dans le cas d'un stratifié basse pression, les composants de base du stratifié sont le panneau support comme un panneau de particules agglomérées et un papier décoratif obtenu selon le procédé de l'invention imprégné d'une résine thermodurcissable.In the case of a low-pressure laminate, the basic components of the laminate are the support panel as a particleboard and a decorative paper obtained according to the method of the invention impregnated with a thermosetting resin.

Les exemples non limitatifs suivants permettront de mieux comprendre l'invention.The following nonlimiting examples will make it possible to better understand the invention.

EXEMPLES DE REALISATION :EXAMPLES OF REALIZATION:

Exemple comparatif 1: Selon un procédé papetier usuel, on fabrique un papier décoratif uni blanc, bien lissé, ayant un grammage de 80 g/m2, une porosité Gurley de 20 s, un satinage Bekk de 20s , et contenant 38 % de cendres. Un tel papier est commercialisé par la société ARJOWIGGINS sous le nom commercial ARJOSAVE. Ce papier est imprimé en l'état par impression jet d'encre sur une imprimante EPSON® 7600. Il est ensuite imprégné d'une résine thermodurcissable de mélamine-formaldéhyde et stratifié pour former un panneau stratifié de type basse pression. Comparative Example 1: According to a conventional papermaking process, a smooth, plain white decorative paper having a grammage of 80 g / m 2 , a Gurley porosity of 20 s, a Bekk satin of 20 s, and containing 38% of ash is manufactured. . Such paper is sold by the company ARJOWIGGINS under the trade name ARJOSAVE. This paper is printed as is by inkjet printing on an EPSON® 7600 printer. It is then impregnated with a thermosetting melamine-formaldehyde resin and laminated to form a low pressure laminate board.

Exemple comparatif 2 : Ce même papier décoratif uni blanc ARJOSAVE est couché selon le procédé de couchage à lame avec 10 g/m2 en poids sec d'une couche C1 composée de 28,6 parts d'un liant fait d'un mélange d'une solution aqueuse d'alcool polyvinylique (PVA) hydrophile et d'un poly(acétate de vinyle) en dispersion aqueuse stabilisée (dit latex), respectivement en proportions 85/15 en poids sec, et 100 parts d'un carbonate de calcium précipité (PCC) de couchage. Ce papier est imprimé par impression jet d'encre sur une imprimante EPSON® 7600. Il est ensuite, comme dans l'exemple 1, imprégné d'une résine thermodurcissable mélamine-formaldéhyde et stratifié pour former un panneau stratifié basse pression. Comparative Example 2: This same ARJOSAVE white plain decorative paper is coated according to the film coating process with 10 g / m 2 dry weight of a layer C1 composed of 28.6 parts of a binder made of a mixture of an aqueous solution of hydrophilic polyvinyl alcohol (PVA) and a polyvinyl acetate in stabilized aqueous dispersion (said latex), respectively in proportions 85/15 by dry weight, and 100 parts of a calcium carbonate precipitate (PCC) coating. This paper is printed by inkjet printing on an EPSON® 7600 printer. It is then, as in Example 1, impregnated with a melamine-formaldehyde thermosetting resin and laminated to form a low pressure laminate board.

Exemple comparatif 3: Ce même papier ARJOSAVE est couché par le procédé à lame avec 10 g/m2 en poids sec d'une couche C2 composée de 28,6 parts du liant de l'exemple 2 et de 100 parts d'une silice de couchage (amorphe) ayant une taille moyenne de particules de 5,3-6,3 µm et une surface spécifique (BET) de 160m2/g. Ce papier est alors, comme dans les exemples précédents, imprimé par impression jet d'encre sur une imprimante EPSON® 7600. Il est ensuite imprégné d'une résine thermodurcissable mélamine-formaldéhyde et stratifié pour former un panneau stratifié basse pression. Comparative Example 3: This same ARJOSAVE paper is coated by the blade method with 10 g / m 2 dry weight of a layer C2 composed of 28.6 parts of the binder of Example 2 and 100 parts of a silica coating (amorphous) having an average particle size of 5.3-6.3 μm and a specific surface area (BET) of 160 m 2 / g. This paper is then, as in the previous examples, printed by inkjet printing on an EPSON® 7600 printer. It is then impregnated with a melamine-formaldehyde thermosetting resin and laminated to form a low pressure laminate panel.

Exemple 4 selon l'invention :Example 4 according to the invention

On fabrique une feuille de ce même papier uni blanc commercialisé par la société ARJOWIGGINS sous le nom commercial ARJOSAVE sur une machine à papier de type Fourdrinier. La feuille après séchage a un grammage de 80 g/m2, une porositéA sheet of the same plain white paper marketed by ARJOWIGGINS under the trade name ARJOSAVE is manufactured on a Fourdrinier type paper machine. The sheet after drying has a basis weight of 80 g / m 2 , a porosity

Gurley de 20 s, un satinage Bekk de 20 s, et contient un taux de cendres de 38 %.Gurley of 20s, a satin Bekk of 20s, and contains a rate of ashes of 38%.

On bobine la feuille de papier ainsi obtenue.The paper sheet thus obtained is reeled.

Dans une deuxième étape, ce papier est ensuite couché par le procédé de couchage à rideau sur une de ses faces de 10 g/m2 en poids sec d'une couche C2 identique à celle utilisée dans l'exemple 3.In a second step, this paper is then coated by the curtain coating process on one of its faces by 10 g / m 2 dry weight of a layer C2 identical to that used in Example 3.

On imprime par impression jet d'encre la feuille de papier ainsi couchée sur une imprimante EPSON® 7600.The paper sheet thus coated on an EPSON® 7600 printer is printed by inkjet printing.

On imprègne ensuite la feuille avec une résine mélamine-formaldéhyde en milieux aqueux.The sheet is then impregnated with a melamine-formaldehyde resin in aqueous media.

On stratifie cette feuille pour fabriquer un stratifié basse pression selon les conditions opératoires usuelles.This sheet is laminated to manufacture a low pressure laminate according to the usual operating conditions.

Exemple comparatif 5 (Référence Base d'impression) : Selon un procédé papetier usuel, on fabrique un papier décoratif uni blanc, non lissé, ayant un grammage de 80 g/m2, une porosité Gurley de 20 s, un satinage Bekk de 140 s, et contenant 38 % de cendres. Un tel papier est commercialisé par la société ARJOWIGGINS sous le nom commercial ARJOPRINT. Ce papier est imprimé en l'état par impression jet d'encre sur une imprimante EPSON® 7600. Il est ensuite, comme aux exemples précédents, imprégné d'une résine thermodurcissable de mélamine-formaldéhyde et stratifié pour former un panneau stratifié de type basse pression. Comparative Example 5 (Reference Printing Base): According to a conventional papermaking process, a plain white non-smoothed decorative paper having a grammage of 80 g / m 2 , a Gurley porosity of 20 s, a Bekk satin of 140 is produced. s, and containing 38% ash. Such paper is marketed by ARJOWIGGINS under the trade name ARJOPRINT . This paper is printed as is by inkjet printing on an EPSON® 7600 printer. It is then, as in the previous examples, impregnated with a thermosetting melamine-formaldehyde resin and laminated to form a low-type laminate board. pressure.

Exemple comparatif 6 : Ce même papier ARJOPRINT est couché selon le procédé à lame avec 10 g/m2 de la couche C2 identique à celle utilisée dans l'exemple 3. Il est ensuite, comme à l'exemple 5, imprimé puis imprégné d'une résine thermodurcissable mélamine-formaldéhyde et stratifié pour former un panneau stratifié basse pression. Comparative Example 6: The same Arjoprint paper is coated according to the blade process with 10 g / m 2 of the layer C2 identical to that used in Example 3. It is then, as in Example 5, printed and impregnated melamine-formaldehyde thermosetting resin and laminated to form a low pressure laminate panel.

Exemple 7 selon l'invention :Example 7 according to the invention

On fabrique une feuille de ce même papier uni blanc commercialisé par la société ARJOWIGGINS sous le nom commercial ARJOPRINT sur une machine à papier de type Fourdrinier. La feuille après séchage a un grammage de 80 g/m2, une porosité Gurley de 20 s, un satinage Bekk de 140 s, et contient un taux de cendres de 38 %.A sheet of the same plain white paper marketed by ARJOWIGGINS under the trade name ARJOPRINT is manufactured on a Fourdrinier type paper machine. The sheet after drying has a basis weight of 80 g / m 2 , a Gurley porosity of 20 s, a Bekk satin of 140 s, and contains an ash content of 38%.

On bobine la feuille de papier ainsi obtenue.The paper sheet thus obtained is reeled.

Dans une deuxième étape, le papier est couché par le procédé de couchage à rideau sur une de ses faces avec 10 g/m2 en poids sec d'une couche C2 identique à celle utilisée dans l'exemple 3.In a second step, the paper is coated by the curtain coating process on one of its faces with 10 g / m 2 dry weight of a layer C2 identical to that used in Example 3.

On imprime par impression jet d'encre la feuille de papier ainsi couchée sur une imprimante EPSON® 7600.The paper sheet thus coated on an EPSON® 7600 printer is printed by inkjet printing.

On imprègne ensuite la feuille avec une résine mélamine-formaldéhyde en milieux aqueux.The sheet is then impregnated with a melamine-formaldehyde resin in aqueous media.

On stratifie cette feuille pour fabriquer un stratifié basse pression selon les conditions opératoires usuelles.This sheet is laminated to manufacture a low pressure laminate according to the usual operating conditions.

Exemple comparatif 8 : Ce même papier ARJOPRINT est couché selon le procédé à lame avec 10 g/m2 d'une couche C3 composée de 28,6 parts d'un poly(acétate de vinyle) sous forme de latex et de 100 parts d'une silice de couchage (amorphe) ayant une taille moyenne de particules 5,3-6,3 µm et une surface spécifique BET de 160m2/g. Il est, comme à l'exemple 6, imprimé puis imprégné d'une résine thermodurcissable mélamine-formaldéhyde et stratifié pour former un panneau stratifié basse pression. Comparative Example 8: The same ARJOPRINT paper is coated according to the blade process with 10 g / m 2 of a layer C3 composed of 28.6 parts of a polyvinyl acetate in the form of latex and 100 parts of an (amorphous) coating silica having an average particle size of 5.3-6.3 μm and a BET specific surface area of 160 m 2 / g. It is, as in Example 6, printed and then impregnated with a melamine-formaldehyde thermosetting resin and laminated to form a low pressure laminate panel.

Les papiers selon ces exemples sont testés selon les tests décrits ci-après et les résultats sont mentionnés dans le tableau 1.Papers according to these examples are tested according to the tests described below and the results are shown in Table 1.

RESULTATS :RESULTS:

Comme on peut le voir dans le tableau 1, tous les papiers couchés -représentés par les exemples comparatifs 2, 3, 6 et 8 et les exemples 4 et 7 selon l'invention- présentent une amélioration très sensible de l'intensité d'encre par rapport aux papiers décoratifs de référence non couchés, représentés à l'exemple comparatif 1 pour le cas d'un papier lissé et à l'exemple comparatif 5 pour le cas d'un papier non lissé.As can be seen in Table 1, all coated papers -represented by Comparative Examples 2, 3, 6 and 8 and Examples 4 and 7 according to the invention-show a very significant improvement in ink intensity. relative to the uncoated reference decorative papers, represented in Comparative Example 1 for the case of a smoothed paper and Comparative Example 5 for the case of a non-smoothed paper.

On peut constater au vu des résultats présentés dans le tableau 1 que les exemples comparatifs 2, 3, 6 et 8 de papiers couchés ont un comportement très éloigné des exemples comparatif 1 et 5 de papiers de référence non couchés en terme de capacité d'absorption de la résine.It can be seen from the results presented in Table 1 that Comparative Examples 2, 3, 6 and 8 of coated papers have a behavior far removed from Comparative Examples 1 and 5 of uncoated reference papers in terms of absorption capacity. of the resin.

Il convient de noter que parmi tous les essais d'enduction, l'exemple comparatif 2 présente une forte sous-cuisson de la résine mélamine-formaldéhyde après stratification.It should be noted that among all the coating tests, Comparative Example 2 shows a high undercuring of the melamine-formaldehyde resin after lamination.

D'après l'exemple 8, on notera que l'utilisation d'une couche dont le liant contient trop de liant non-hydrophile (latex) entraîne un phénomène de cloquage pour le stratifié qui est inacceptable.According to Example 8, it will be noted that the use of a layer whose binder contains too much non-hydrophilic binder (latex) causes a blistering phenomenon for the laminate which is unacceptable.

Les exemples montrent que l'invention permet d'obtenir un papier décoratif présentant à la fois une excellente aptitude à l'impression jet d'encre et une bonne absorption de la résine, nécessaire à l'imprégnation ultérieure de ce type de papier.The examples show that the invention makes it possible to obtain a decorative paper exhibiting both excellent inkjet printing aptitude and good absorption of the resin, necessary for the subsequent impregnation of this type of paper.

Le résultat de ces essais montre par ailleurs que les papiers décoratifs issus du procédé de fabrication de papier décoratif selon l'invention (exemples 4 et 7) réalisés aussi bien sur un support lissé Arjosave que non lissé Arjoprint, présentent à la fois une bonne aptitude à l'impression jet d'encre et une bonne absorption de résine selon le test décrit ci-après.The result of these tests shows, moreover, that the decorative papers resulting from the process for the production of decorative paper according to the invention (Examples 4 and 7) carried out both on an Arjosave smoothed and a non-smoothed Arjoprint support, exhibit both a good aptitude to inkjet printing and good resin absorption according to the test described hereinafter.

Par ailleurs, l'utilisation de polymère non-hydrophile (de type latex) en mélange avec un liant hydrophile dans la composition de couchage s'avère également possible, dans des proportions compatibles avec les exigences d'imprégnation et de stratification de la feuille couchée (absence de cloquage).Moreover, the use of non-hydrophilic polymer (of the latex type) mixed with a hydrophilic binder in the coating composition is also possible, in proportions compatible with the impregnation and lamination requirements of the coated sheet. (no blistering)

DESCRIPTION ET CONDITIONS DE REALISATION DES TESTS:DESCRIPTION AND CONDITIONS OF REALIZATION OF THE TESTS:

  • Le grammage des feuilles est déterminé selon la norme ISO 536 après conditionnement selon la norme ISO 187. Il s'agit du grammage de la feuille traitée par ladite composition pigmentée mais avant imprégnation de la résine.The grammage of the sheets is determined according to ISO 536 after conditioning according to ISO 187. This is the grammage of the sheet treated by said pigmented composition but before impregnation of the resin.
  • La perméabilité à l'air, méthode porosité Gurley, est déterminée selon la norme ISO 5636-5R (1990).The air permeability, Gurley porosity method, is determined according to ISO 5636-5R (1990).
  • La vitesse d'imprégnation est caractérisée par la détermination du temps de pénétration de la résine thermodurcissable à travers la feuille, ce temps est déterminé de la façon suivante :The rate of impregnation is characterized by the determination of the penetration time of the thermosetting resin through the sheet, this time is determined as follows:
  • on prépare une solution de résine à 56 % en poids en dissolvant de la résine mélamine-formaldéhyde MADURIT MW550 en poudre dans de l'eau distillée chauffée vers 45°C. On ajuste sa viscosité telle qu'elle soit de l'ordre de 100 mPas (cps) vers 20° C sur viscosimètre Brookfield mesurée à 100 tours/min - Arbre N° 2,a 56% by weight resin solution is prepared by dissolving powdered MADURIT MW550 melamine-formaldehyde resin in distilled water heated to 45 ° C. Its viscosity is adjusted such that it is of the order of 100 mPas (cps) at 20 ° C. on a Brookfield viscometer measured at 100 revolutions / min.
  • on détermine comme suit le temps d'imprégnation d'une feuille de papier:
    • on découpe deux échantillons en carré (10 x 10 cm) par essai ; pour tester chaque face, on repère la face,
    • on remplit un verre de montre de résine,
    • on dépose le carré de papier sur la surface de la résine, la face à tester en contact avec celle-ci, et on déclenche le chronomètre en même temps,
    • on note le temps du transpercement total qui donne le temps de pénétration de la résine.
    the impregnation time of a sheet of paper is determined as follows:
    • two square samples (10 x 10 cm) are cut per test; to test each face, we find the face,
    • we fill a glass of resin watch,
    • depositing the square of paper on the surface of the resin, the face to be tested in contact therewith, and the stopwatch is started at the same time,
    • we note the time of the total piercing which gives the penetration time of the resin.

Les tests suivants sont réalisés sur un panneau de particules sur lequel le film décor (feuille imprégnée de résine) a été stratifié :

  • Le test au graphite est réalisé comme suit : on mélange du graphite en poudre avec une huile de façon à former une pâte. On étale cette pâte sur la face apparente du film décor. On nettoie ensuite le panneau avec une éponge humide imprégnée d'un détergent. On compare la surface nettoyée avec une échelle témoin. L'échelle va de 1 à 6, la plus basse note étant 1.
The following tests are performed on a particle board on which the decorative film (resin impregnated sheet) has been laminated:
  • The graphite test is carried out as follows: graphite powder is mixed with an oil so as to form a paste. This paste is spread on the apparent face of the decor film. The panel is then cleaned with a damp sponge impregnated with a detergent. The cleaned surface is compared with a control scale. The scale goes from 1 to 6, the lowest rating being 1.

Ce test au graphite permet d'apprécier la porosité du film décor après stratification et donc sa résistance à la salissure. Cette caractéristique dépend de plusieurs paramètres dont le taux de volatils dans la résine, la stratification, la feuille décorative. TABLEAU 1 : Procédé de couchage Rendu en impression Imprégnation de la résine Stratification Observations Transpercement total (secondes) face couchée/face non couchée Porosité (test au graphite) Cuisson de la résine (°C) Aspect du panneau Exemple comparatif 1 - Très pâle 8 / 6 3,5 3 Bon Exemple comparatif 2 Lame Bonne > 240 / 15 4 4,5 Mat Exemple comparatif 3 Lame Bonne > 240 / 13 4,5 2,5 Bon Invention Exemple 4 Rideau Bonne 65 / 7 4 2,5 Bon Exemple comparatif 5 - Très pâle 6/6 4,5 3 Bon Exemple comparatif 6 Lame Bonne > 240 / 10 5 2,5 Bon Invention Exemple 7 Rideau Bonne 40/8 4 2,5 Bon Exemple comparatif 8 Lame Bonne > 240 / 13 4 2,5 Assez nombreuses cloques This graphite test makes it possible to assess the porosity of the decorative film after lamination and thus its resistance to soiling. This characteristic depends on several parameters including the rate of volatiles in the resin, the stratification, the decorative sheet. <u> TABLE 1: </ u> Sleeping process Printed rendering Impregnation of the resin Stratification observations Total piercing (seconds) lying face / non-recumbent face Porosity (graphite test) Resin baking (° C) Panel appearance Comparative Example 1 - Very pale 8/6 3.5 3 Well Comparative Example 2 Blade good > 240/15 4 4.5 Mast Comparative Example 3 Blade good > 240/13 4.5 2.5 Well Invention Example 4 Curtain good 65/7 4 2.5 Well Comparative Example 5 - Very pale 6/6 4.5 3 Well Comparative Example 6 Blade good > 240/10 5 2.5 Well Invention Example 7 Curtain good 40/8 4 2.5 Well Comparative Example 8 Blade good > 240/13 4 2.5 Quite a lot of blisters

Claims (17)

  1. Process for the manufacture of a decorative paper coated with at least one ink fixative layer that is printable and impregnatable with thermosetting resin for a high or low pressure decorative laminate, comprising the following steps:
    a. a base sheet of decorative paper is produced by a papermaking process and then
    b. at least one of the faces of the said base sheet of paper is coated with at least the said ink fixative layer by curtain coating.
  2. Process according to Claim 1, characterized in that the said ink fixative layer is printable by inkjet printing.
  3. Process according to either of Claims 1 and 2, characterized in that the ink fixative layer contains at least one hydrophilic binder.
  4. Process according to Claim 3, characterized in that the said layer contains a non-hydrophilic polymeric binder in addition to the said hydrophilic binder, in a ratio of hydrophilic binder to non-hydrophilic binder of at least 70/30 in dry weight.
  5. Process according to Claim 3 or Claim 4, characterized in that the hydrophilic binder is a polyvinyl alcohol (PVA).
  6. Process according to any one of Claims 1 to 5, characterized in that the layer is not alkaline and in particular contains no carbonates or alkaline buffers.
  7. Process according to any one of the preceding claims, characterized in that the layer contains coating fillers chosen substantially among the silicas.
  8. Process according to Claim 7, characterized in that the said silicas are substantially amorphous precipitated silicas.
  9. Process according to any one of Claims 1 to 8, characterized in that the amount of layer deposited is between 4 and 20 g/m2 in dry weight and in particular between 6 and 15 g/m2.
  10. Process according to any one of Claims 1 to 9, characterized in that the said process comprises a step of printing in particular a decorative motif on the sheet of paper coated with at least an ink fixative layer produced by step b of the said process.
  11. Process according to Claim 10, characterized in that the said ink fixative layer is printed by inkjet printing, in particular with high resolution.
  12. Decorative paper printable or printed in particular by inkjet printing and impregnatable with thermosetting resin, obtained by the decorative paper manufacturing process defined in Claims 1 to 11.
  13. Decorative paper printable or printed and impregnatable with thermosetting resin, as defined in Claims 1 to 12, characterized in that it has a resin impregnation speed on either face of less than 100 seconds, the said speed being characterized by determination of the time taken by the thermosetting resin to penetrate through the sheet, such time being determined in the following manner:
    a resin solution of 56% by weight is prepared by dissolving a
    melamine-formaldehyde resin powder with the trade name Madurit MW550 in distilled water heated to 45°C; its viscosity is adjusted so that it is of the order of 100 mPas at 20°C when measured on a Brookfield viscosimeter at 100 rpm, Shaft No. 2,
    and the impregnation time of a sheet of paper is determined as follows:
    two square 10 x 10 cm specimens are cut out for each test; to test each face, the face is marked,
    a watch-glass is filled with resin,
    the square of paper is placed on the surface of the resin with the face to be tested in contact with the resin, and the chronometer is started at the same moment,
    the total soak-through time is noted, thus giving the resin penetration time.
  14. Paper according to Claim 13, characterized in that the said impregnation time is less than or equal to 65 seconds.
  15. Process for the manufacture of an impregnated decorative paper for decorative laminates, characterized in that a printed decorative paper as defined in Claims 12 to 14 is impregnated with a thermosetting resin.
  16. Process according to Claim 15, characterized in that the thermosetting resin is chosen among the melamine-formaldehyde resins, the urea-formaldehyde resins, the benzoguanamine-formaldehyde resins, and the unsaturated polyester resins, and mixtures thereof.
  17. High or low pressure laminated decorative panel or moulding characterized in that it comprises as decorative paper, a decorative paper as obtained or defined in Claims 10 to 16.
EP05771104A 2004-05-13 2005-05-13 Method of producing decorative paper and decorative laminate comprising such decorative paper Active EP1749134B1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE602005016102.3T DE602005016102C5 (en) 2004-05-13 2005-05-13 PROCESS FOR PREPARING DECORPAPER AND DECORLAMINATE WITH SUCH A DECORATIVE PAPER
PL05771104T PL1749134T3 (en) 2004-05-13 2005-05-13 Method of producing decorative paper and decorative laminate comprising such decorative paper

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0405205A FR2870265B1 (en) 2004-05-13 2004-05-13 DECORATIVE PAPER AND DECORATIVE LAMINATE COMPRISING THE SAME
PCT/FR2005/001203 WO2005116337A1 (en) 2004-05-13 2005-05-13 Method of producing decorative paper and decorative laminate comprising such decorative paper

Publications (2)

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EP1749134A1 EP1749134A1 (en) 2007-02-07
EP1749134B1 true EP1749134B1 (en) 2009-08-19

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Country Status (11)

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US (1) US9567713B2 (en)
EP (1) EP1749134B1 (en)
CN (1) CN1973089B (en)
AT (1) ATE440177T1 (en)
CA (1) CA2564505C (en)
DE (1) DE602005016102C5 (en)
ES (1) ES2330867T3 (en)
FR (1) FR2870265B1 (en)
PL (1) PL1749134T3 (en)
PT (1) PT1749134E (en)
WO (1) WO2005116337A1 (en)

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Also Published As

Publication number Publication date
DE602005016102C5 (en) 2015-12-10
DE602005016102D1 (en) 2009-10-01
CN1973089A (en) 2007-05-30
FR2870265A1 (en) 2005-11-18
FR2870265B1 (en) 2006-07-14
CN1973089B (en) 2012-06-13
CA2564505C (en) 2013-12-31
PT1749134E (en) 2009-10-29
CA2564505A1 (en) 2005-12-08
ATE440177T1 (en) 2009-09-15
ES2330867T3 (en) 2009-12-16
US20080090032A1 (en) 2008-04-17
PL1749134T3 (en) 2010-01-29
US9567713B2 (en) 2017-02-14
WO2005116337A1 (en) 2005-12-08
EP1749134A1 (en) 2007-02-07

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