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EP2816154A1 - Article à revêtement imprégné de résine aux propriétés esthétiques améliorées - Google Patents

Article à revêtement imprégné de résine aux propriétés esthétiques améliorées Download PDF

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Publication number
EP2816154A1
EP2816154A1 EP20130172877 EP13172877A EP2816154A1 EP 2816154 A1 EP2816154 A1 EP 2816154A1 EP 20130172877 EP20130172877 EP 20130172877 EP 13172877 A EP13172877 A EP 13172877A EP 2816154 A1 EP2816154 A1 EP 2816154A1
Authority
EP
European Patent Office
Prior art keywords
reducing agent
pigment
acid
coated article
resin
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.)
Pending
Application number
EP20130172877
Other languages
German (de)
English (en)
Inventor
Ilpo Silventoinen
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.)
Surfactor Germany GmbH
Original Assignee
Surfactor Germany GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Surfactor Germany GmbH filed Critical Surfactor Germany GmbH
Priority to EP20130172877 priority Critical patent/EP2816154A1/fr
Priority to PCT/EP2014/001654 priority patent/WO2014202216A1/fr
Priority to RU2016101224A priority patent/RU2671327C2/ru
Publication of EP2816154A1 publication Critical patent/EP2816154A1/fr
Pending legal-status Critical Current

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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
    • D21H19/00—Coated paper; Coating material
    • D21H19/80—Paper comprising more than one coating
    • D21H19/82—Paper comprising more than one coating superposed
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/47—Condensation polymers of aldehydes or ketones
    • D21H17/48—Condensation polymers of aldehydes or ketones with phenols
    • 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
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/54—Starch
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/28—Colorants ; Pigments or opacifying agents
    • 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

Definitions

  • the present invention relates to a coated article with improved aesthetic properties, a method for preparing said coated article and an ink composition suitable for being applied in said method to produce said article.
  • Resin impregnated papers/films have been used for decades as coatings in the wood working industry.
  • the resin impregnated substrate mostly paper or kraft paper
  • Such coated boards are widely used for various purposes such as concrete shuttering, flooring, building materials and in the furniture or automotive industry.
  • the paper can be printed with such design before being impregnated with the resin.
  • the design can widely vary and can range from simple letters in brand names and company logos via text and pictograms to complex decorative patterns and photographic images (hereinafter referred to in general as "pattern").
  • pattern After being applied to the board, the pattern normally is covered by the resin for impregnation. Hence the aesthetic appearance of the pattern is influenced by the transparency and color of said resin.
  • the color of the resin can cause an unwanted color change of the pattern.
  • the resin further comprises dyes, colorants or pigments such as iron oxide, carbon black.
  • Phenolic resins result from the reaction of phenol and formaldehyde which is either performed under acidic or basic conditions. If a base catalyzed mixture of phenol and formaldehyde contains one or more moles of formaldehyde per mole of phenol it will produce a thermosetting resin ("resole").
  • resole thermosetting resin
  • Such resins have the disadvantage of aging, i.e. they darken when heated or are otherwise cured. The extent of darkening is known to be dependent on the curing or use temperature of the resin and the time of exposure to such temperature.
  • the panels After the manufacturing of panels laminated with impregnated paper the panels are stacked when still hot and they maintain a relatively high temperature for a long time (100°C and reducing gradually). Naturally cooling of panels is not homogenous, i.e. the center of the panel and the center of the stack cool down more slowly. This may result in an unwanted patchy or blotchy surface appearance of the impregnated article.
  • the objective of the present invention thus is to provide a resin impregnated coated article and methods for the manufacture thereof which overcome at least one of the above mentioned disadvantages.
  • a coated article which comprises at least three layers, namely a first layer which is the base layer, a further layer which contains the resin (also called “coating layer”) and a third layer comprising at least one reducing agent.
  • the reducing agent serves to discolor at least parts of the resin.
  • This third layer is also called “extinction layer”.
  • the coated article according to the invention comprises at least three layers, namely
  • the core aspect of the invention is the finding that the reducing agent eliminates at least partially the color of the resin (either the color of the resin itself and/or dyes or pigments contained therein. Therewith the reducing agent is capable of counteracting the darkening of the resin regardless of its cause (e.g. UV-light or heat). In the context of the invention this effect is either called “discoloring", “discolorization” or “elimination of color”.
  • the reducing agent can be added to an ink used for printing a pattern onto the base layer.
  • the inventors could show that this does not have a negative impact on the printing process and the printing quality.
  • established materials, production machines and processes can be applied in the method according to the invention.
  • the at least one reducing agent comes into contact only with parts of the resin layer, namely with those parts of the resin layer which covers the pattern. Only those parts are discolored by the reducing agent and the pattern retains its desired appearance.
  • a particular advantage of this embodiment of the invention is that it allows a spatially selective color elimination of the resin layer.
  • the color of the resin layer can either be due to the color of the resin itself and/or dyes or pigments contained therein.
  • the pattern can be printed onto the base layer (e.g. the paper) and then the reducing agent is applied onto the printed pattern.
  • the base layer e.g. the paper
  • the reducing agent is applied onto the printed pattern.
  • the extinction layer represents a reservoir for the reducing agent.
  • the discoloring effect according to the invention thus can be maintained over a longer period of time due to continuous diffusion of the reducing agent from the extinction layer to or into the coating layer.
  • the reducing agent is capable of reducing the dye contained in the impregnating resin and thereby discolor it.
  • the reducing agent thus serves as a dye discoloring agent.
  • Agents for discoloring dyes by reduction are for a long time known to the skilled person from waste water treatment in the field of dye manufacturing. Hence the skilled person can select the appropriate reducing agent for the dye in the resin layer which is to be discolored.
  • the coated article consists of the three layers, with the support layer being paper impregnated with a phenolic resin.
  • the paper was printed (for example with a company's logo) with an ink containing a dye discoloring agent before impregnation; therewith forming the extinction layer.
  • This coated article can favourably be laminated onto boards or panels.
  • the base layer according to the invention can be flexible or rigid. Most preferred the base layer is a paper, in particular a kraft paper.
  • the base layer can be applied onto a support layer.
  • the support layer can be selected form the group consisting of cardboard, plywood, chipboard, fibre board, oriented strand board (OSB), glue wood, laminated veneer lumber (LVL), parallel strand lumber (PSL) and oriented strand lumber (OSL).
  • a particularly preferred support is plywood.
  • the reducing agent preferably has a standard electrode potential E 0 between - 150 mVolt and -1500 mvolt.
  • the standard electrode potential of the reducing agent (the dye discoloring agent) has to be more negative than the standard electrode potential of the respective dye.
  • the difference between the standard electrode potentials of the reducing agent and the dye is more than 0.5 Volt, preferably more than 0.75 Volt and more preferably more than 1.0 Volt
  • the reducing agent preferably is selected from the group consisting of reducing sugars, hydrides, organic acids and inorganic salts or a mixture thereof.
  • the reducing agent is selected from the group consisting of dihydroxyacetone, glycoladehyde, glyceraldehyde, erythrose, threose, ribose, arabinose, xylose, lyxose, allose, altrose, glucose, mannose, gulose, idose, galactose, talose, fructose, lactose, maltose, cellobiose, diborane, lithium aluminium hydride, sodium borohydride, lithium borohydride, SnCl 2 , SnF 2 , Sn(OH) 2 , sodium dithionite (Color Index reducing agent 1), thiourea dioxide (Color Index reducing agent 11), sodium hydroxymethanesulfinate (Color Index reducing agent 2), Color Index reducing agent 3, Color Index reducing agent 4, Color Index reducing agent 5, Color Index reducing agent 7, Color Index reducing agent 8, zinc formaldeh
  • reducing agents are fructose, sodium dithionite, tinchloride, iron(II)sulfate, and boronhydride.
  • Fructose is the most preferred reducing agent.
  • the dye in the resin is an organic polycyclic dye, organic monoazo dye, organic diazo dye, organometal complex(e) or an inorganic pigment such as metal oxide or complex.
  • Dyes can be perinone, anthraquinone, azo dye complexes and thioindigoid.
  • the dye in the resin of the coating layer is selected from the group consisting of Acid Yellow 23, Acid Red 18, Acid Yellow 36, Acid Black 194, Direct Red 239, Reactive Red 120, Acid Blue 9, Acid Red 27, Acid Red 51, Direct Blue 199, Direct Red 254, Reactive Red 195, Acid Red 14, Acid Yellow 17, Acid Black 1, Direct Yellow 86, Direct Black 168, Food Black 2.
  • the dye in the coating layer is Acid Black 2 and Direct Red 254.
  • the coated article comprises a coating layer with a dye and a reducing agent in the extinction layer as outlined in the table below.
  • dye and reducing agent are particularly advantageous in order to obtain an effective decolorization in those areas where the coating layer is in direct contact with the extinction layer:
  • Dye in the coating layer Reducing agent of the extinction layer Direct Red 254 SnCl 2 , FeSO 4 , sodium dithionite, fructose Acid black FeSO 4 , fructose Indigo Sodium dithionite, sodium hypochlorite, potassium permanganate
  • Direct Red 80 Sodium borohydride
  • C.I. Disperse Red 60 Sodium borohydride, sodium dithionite
  • Disperse Blue 79 Sodium borohydride, sodium dithionite C.I. Disperse Orange 62 Sodium borohydride, sodium dithionite
  • Non azo-dye such as: Sodium hydroxymethansulfinate Disperse Blue 250, 354, 364 or 366; Solvent Violet 8; Solvent blue 43, Solvent blue 57; Lumogen F Blau 650; Lumogen F Violet 570
  • the reducing agent is part of the ink used for applying a pattern onto the base layer.
  • the ink layer thus serves as the extinction layer.
  • the invention also relates to an ink (also called ink composition) comprising at least one coloring agent (dye or a pigment, both here referred to as dye if not otherwise specified) and at least one reducing agent.
  • the dye in the ink preferably is not discolored by the reducing agent, or at least to a lower extent than the dye in the resin.
  • the ink contains 0.5 to 20 % (w/v), preferably 2 to 15 % (w/v), more preferred 7.5 to 12.5 % (w/v) and even more preferred 10 % (w/v) of at least one reducing agent.
  • the composition preferably has a solid content of between 50 wt% and 60 wt%, preferably 55 wt%. In this embodiment especially approximately 10% (w/v) of reducing agent is preferred (e.g. fructose).
  • the binder preferably is casein.
  • the pigment of the ink can be of any color, e.g a black, yellow, orange, red, violet, blue, brown or white pigment, whereby a white pigment is preferred.
  • a non-limiting example of a suitable inorganic black pigment includes carbon black.
  • carbon black pigments include those manufactured by Mitsubishi Chemical Corporation, Japan (such as, e.g., carbon black No. 2300, No. 900, MCF88, No. 33, No. 40, No. 45, No. 52, MA7, MA8, MA100 or No.
  • RAVEN® series manufactured by Columbian Chemicals Company, Marietta, Ga.
  • various carbon black pigments of the REGAL@ series, the MOGUL® series or the MONARCH@ series manufactured by Cabot Corporation, Boston, Mass. (such as, e.g., REGAL@ 400R, REGAL@ 330R, REGAL@ 660R, MOGUL® L, MONARCH@ 700, MONARCH@ 800, MONARCH@ 880, MONARCH@ 900, MONARCH@ 1000, MONARCH@ 1100, MONARCH@ 1300 or MONARCH@ 1400); or various black pigments manufactured by Evonik Degussa Corporation, Parsippany, N.J., (such as, e.
  • inorganic pigments include metal oxides and ceramics, such as the oxides of iron, zinc, cobalt, manganese or nickel.
  • suitable inorganic pigments include those from the Shepherd Color Company (Cincinnati, Ohio) such as Black 10C909A, Black 10P922, Black 1G, Black 20F944, Black 30C933, Black 30C940, Black 30C965, Black 376A, Black 40P925, Black 411 A, Black 430, Black 444, Blue 10F545, Blue 10G511, Blue 10G551, Blue 10K525, Blue 10K579, Blue 211, Blue 212, Blue 214, Blue 30C527, Blue 30C588, Blue 30C591, Blue 385, Blue 40P585, Blue 424, Brown 10C873, Brown 10P835, Brown 10P850, Brown 10P857, Brown 157, Brown 20C819, Green 10K637, Green 187 B, Green 223, Green 260, Green 30C612, Green 30C654, Green 30C678,
  • organic pigments that may be treated accordance with the teachings herein.
  • suitable yellow pigments include C.I. Pigment Yellow 1, C.I. Pigment Yellow 2, C.I. Pigment Yellow 3, C.I. Pigment Yellow 4, C.I. Pigment Yellow 5, C.I. Pigment Yellow 6, C.I. Pigment Yellow 7, C.I. Pigment Yellow 10, C.I. Pigment Yellow 11, C.I. Pigment Yellow 12, C.I. Pigment Yellow 13, C.I. Pigment Yellow 14, C.I. Pigment Yellow 16, C.I. Pigment Yellow 17, C.I.
  • Pigment Yellow 24 C.I. Pigment Yellow 34, C.I. Pigment Yellow 35, C.I. Pigment Yellow 37, C.I. Pigment Yellow 53, C.I. Pigment Yellow 55, C.I. Pigment Yellow 65, C.I. Pigment Yellow 73, C.I. Pigment Yellow 74, C.I. Pigment Yellow 75, C.I. Pigment Yellow 81, C.I. Pigment Yellow 83, C.I. Pigment Yellow 93, C.I. Pigment Yellow 94, C.I. Pigment Yellow 95, C.I. Pigment Yellow 97, C.I. Pigment Yellow 98, C.I. Pigment Yellow 99, C.I. Pigment Yellow 108, C.I. Pigment Yellow 109, C.I.
  • Pigment Yellow 110 C.I. Pigment Yellow 113, C.I. Pigment Yellow 114, C.I. Pigment Yellow 117, C.I. Pigment Yellow 120, C.I. Pigment Yellow 124, C.I. Pigment Yellow 128, C.I. Pigment Yellow 129, C.I. Pigment Yellow 133, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 147, C.I. Pigment Yellow 151, C.I. Pigment Yellow 153, C.I. Pigment Yellow 154, Pigment Yellow 155, C.I. Pigment Yellow 167, C.I. Pigment Yellow 172 or C.I. Pigment Yellow 180.
  • Non-limiting examples of suitable magenta or red or violet organic pigments include C.I. Pigment Red 1, C.I. Pigment Red 2, C.I. Pigment Red 3, C.I. Pigment Red 4, C.I. Pigment Red 5, C.I. Pigment Red 6, C.I. Pigment Red 7, C.I. Pigment Red 8, C.I. Pigment Red 9, C.I. Pigment Red 10, C.I. Pigment Red 11, C.I. Pigment Red 12, C.I. Pigment Red 14, C.I. Pigment Red 15, C.I. Pigment Red 16, C.I. Pigment Red 17, C.I. Pigment Red 18, C.I. Pigment Red 19, C.I. Pigment Red 21, C.I. Pigment Red 22, C.I. Pigment Red 23, C.I.
  • Pigment Red 30 C.I. Pigment Red 31, C.I. Pigment Red 32, C.I. Pigment Red 37, C.I. Pigment Red 38, C.I. Pigment Red 40, C.I. Pigment Red 41, C.I. Pigment Red 42, C.I. Pigment Red 48(Ca), C.I. Pigment Red 48(Mn), C.I. Pigment Red 57(Ca), C.I. Pigment Red 57:1, C.I. Pigment Red 88, C.I. Pigment Red 112, C.I. Pigment Red 114, C.I. Pigment Red 122, C.I. Pigment Red 123, C.I. Pigment Red 144, C.I. Pigment Red 146, C.I.
  • Pigment Violet 19 C.I. Pigment Violet 23, C.I. Pigment Violet 32, C.I. Pigment Violet 33, C.I. Pigment Violet 36, C.I. Pigment Violet 38, C.I. Pigment Violet 43 or C.I. Pigment Violet 50.
  • Non-limiting examples of blue or can organic pigments include C.I. Pigment Blue 1, C.I. Pigment Blue 2, C.I. Pigment Blue 3, C.I. Pigment Blue 15, C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:34, C.I. Pigment Blue 15:4, C.I. Pigment Blue 16, C.I. Pigment Blue 18, C.I. Pigment Blue 22, C.I. Pigment Blue 25, C.I. Pigment Blue 60, C.I. Pigment Blue 65, C.I. Pigment Blue 66, C.I. Vat Blue 4 or C.I. Vat Blue 60.
  • Non-limiting examples of green organic pigments include C.I. Pigment Green 1, C.I. Pigment Green 2, C.I. Pigment Green 4, C.I. Pigment Green 7, C.I. Pigment Green 8, C.I. Pigment Green 10, C.I. Pigment Green 36 or C.I. Pigment Green 45.
  • brown organic pigments include C.I. Pigment Brown 1, C.I. Pigment Brown 5, C.I. Pigment Brown 22, C.I. Pigment Brown 23, C.I. Pigment Brown 25, and C.I. Pigment Brown, C.I. Pigment Brown 41 or C.I. Pigment Brown 42.
  • Non-limiting examples of orange organic pigments include C.I. Pigment Orange 1, C.I. Pigment Orange 2, C.I. Pigment Orange 5, C.I. Pigment Orange 7, C.I. Pigment Orange 13, C.I. Pigment Orange 15, C.I. Pigment Orange 16, C.I. Pigment Orange 17, C.I. Pigment Orange 19, C.I. Pigment Orange 24, C.I. Pigment Orange 34, C.I. Pigment Orange 36, C.I. Pigment Orange 38, C.I. Pigment Orange 40, C.I. Pigment Orange 43 or C.I. Pigment Orange 66.
  • the white pigment of the ink composition can be selected from the group consisting of calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin White, aluminium silicate, diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudo-boehmite, aluminum hydroxide, alumina, modified alumina, lithopone, zeolite, hydrated halloysite, magnesium carbonate, magnesium hydroxide, and mixtures thereof.
  • the white pigment is zinc sulfide, titanium dioxide (including rutile titanium dioxide), or a mixture thereof.
  • the white pigment is titanium dioxide.
  • dye depends on the application and the ink used, whether it is aqueous, solvent based, or hot melt, and on the printer type: flexography, continuous ink jet or drop-on-demand, piezo or thermal ink jet.
  • the dye is suitable for flexography.
  • the solvent can be a water-based solvent.
  • a water-soluble organic solvent can be used having an ability to dissolve a solute and is preferably selected from water-soluble solvents having a smaller vapor pressure than water.
  • water-soluble solvents having a smaller vapor pressure than water.
  • examples thereof include: polyhydric alcohols, such as ethylene glycol, propylene glycol, butanediol, pentanediol, 2-butene-1,4-diol, 2-methyl-2,4-pentanediol, glycerin, 1,2,6-hexanetriol, diethylene glycol, and dipropylene glycol; ketones, such as acetonylacetone; esters, such as y-butyrolactone, diacetin, and triethyl phosphate; lower alkoxy lower alcohols, such as 2-methoxyethanol and 2-ethoxyethanol; furfuryl alcohol; tetrahydrofurfuryl alcohol; and thiodiglycol.
  • polyhydric alcohols such
  • solvents usable herein include not only those that are liquid at room temperature but also those that are solid at room temperature and, when heat melted, can function as a solvent, and those that, when used in combination with an aqueous solution or other solvent(s), can function as a solvent.
  • the amount of the water-soluble organic solvent used may be suitably determined, it is preferably, for example, 5 to 50% by weight based on the total weight of the ink.
  • the ink composition may further comprise an additional organic solvent.
  • additional solvents usable herein include imidazole, methylimidazole, hydroxyimidazole, triazole, nicotinamide, dimethylaminopyridine, ⁇ -caprolactam, 1,3-dimethyl-2-imidazolidinone, lactamide, sulfolane, dimethylsulfoxide, 1,3-propanesultone, methyl carbamate, ethyl carbamate, 1-methylol-5,5-dimethylhydantoin, hydroxyethylpiperazine, piperazine, ethyleneurea, propyleneurea, ethylene carbonate, propylene carbonate, dimethyl sulfoxide, N-methyl-2-pyrrolidinone, 2-pyrrolidinone, acetamide, formamide, dimethylformamide, N-methylformamide, and dimethylacetamide.
  • the addition of the organic solvent can prevent the creation of a precipitation of a precipitation of
  • additives may be added to the ink composition.
  • additives are penetration accelerators, viscosity modifiers, binders, surface tension modifiers, hydrotropy agents, humectants, pH adjustors, antimolds, chelating agents, preservatives, and rust preventives.
  • a specific resistance modifier selected from inorganic salts, such as lithium chloride, sodium chloride, and ammonium chloride.
  • Suitable binders include aqueous dispersions of aromatic or aliphatic polyurethanes, proteins, such as casein or casein derivatives, polyvinyl alcohols or polyvinyl alcohol derivatives, polymers and copolymers of acrylic acid or acrylic acid derivatives, such as, for example, acrylates, poly(vinyl chloride)/poly(vinyl acetate)-copolymer, styrene acrylate polymer, maleic resin, rubber resin, phenolic resin, silicone resin, heat-bodied linseed oil, oligomeric carbohydrates such as dextrin, natural rubber, gum arabic, shellac and cellulose derivatives. Particularily preferred is casein or casein derivatives.
  • the skilled person makes a suitable choice from the binders possible in principle.
  • Penetration accelerators usable herein include: lower alcohols, such as ethanol, isopropanol, butanol, and pentanol; cellosolves, such as ethylene glycol monobutyl ether; carbitols, such as diethylene glycol monobutyl ether, triethylene glycol monobutyl ether glycol ether; and surfactants.
  • Surface tension modifiers usable herein include diethanolamine, triethanolamine, alcohols, such as glycerin and diethylene glycol, and nonionic, cationic, anionic, or amphoteric surfactants.
  • Preferred hydrotropy agents usable herein include urea, alkylureas, ethyleneurea, propyleneurea, thiourea, guanidine acid salts, and tetraalkylammonium halides.
  • Humectants can also affect other properties of the ink composition and the printed images made therefrom, such as viscosity, pH, surface tension, optical density, and print quality.
  • Such humectants typically include ethylene glycol, propylene glycol, diethylene glycols, glycerine, dipropylene glycols, polyethylene glycols, polypropylene glycols, alkane diols, amides, ethers, carboxylic acids, esters, alcohols, organosulfides, organosulfoxides, sulfones, alcohol derivatives, 3-pyrrolidone, ether derivatives, amino alcohols, and ketones.
  • the amount of a particular additive will vary depending on a variety of factors including the molecular weight of the pigment or dye, the viscosity, the amount of any salt added, as well as the nature of the pigment or dye.
  • the ink composition according to the invention comprises or consists of: 5 to 20 % (w/w) binder 5 to 25 % (w/w) dye/pigment 1 to 15 % (w/w) one or more additives (optionally) 0.5 to 20 % (w/w) reducing agent
  • the solvent can be e.g. water or alcohol or a mixture thereof.
  • the ink composition as above contains 5 to 15 % (w/w), more preferred approximately 10 % (w/w).
  • the binder preferably is casein and the reducing agent is a reducing sugar, most preferred fructose.
  • the ink composition comprises or consists of: 30 - 70 % (w/w) dye/pigments 2 - 30 % (w/w) more particularily 5 - 20 wt % binder 1 - 3 % (w/w) one or more additives (optionally) 0.5 to 20 % (w/w) reducing agent
  • the solvent can be e.g. water or alcohol or a mixture thereof.
  • the ink composition as above can contain e.g. 5 to 15 % (w/w), more preferred approximately 10 % (w/w).
  • the binder preferably is casein and the reducing agent is a reducing sugar, most preferred fructose.
  • the ink composition comprises or consists of: 2 - 6 % (w/w) dye, preferably an acid or direct dye 5 - 15 % (w/w) humectant 0.2 - 0.8 % (w/w) a first additive, e.g. surface tension modifier, such as triethanolamine 0.05 - 0.2 % (w/w) one or more further additives, e.g. a preservative or biocide. 0.5 to 20 % (w/w) reducing agent
  • the solvent can be water or an organic solvent, such as N-methyl-2-pyrrolidone or a mixture thereof.
  • the ink composition as above can contain e.g. 5 to 15 % (w/w), more preferred approximately 10 % (w/w).
  • the binder preferably is casein and the reducing agent is a reducing sugar, most preferred fructose.
  • the ink composition comprises or consists of: 2 - 6 % (w/w) dye/pigment 5 - 15 % (w/w) one or more additives 2.5 - 7.5 % (w/w) binder, e.g. an poly(vinyl chloride)/poly(vinyl acetate)-copolymer 0.5 to 20 % (w/w) reducing agent
  • the solvent can be non-aqueous, e.g. methyl ethyl ketone
  • the ink composition as above can contain e.g. 5 to 15 % (w/w), more preferred approximately 10 % (w/w).
  • the binder preferably is casein and the reducing agent is a reducing sugar, most preferred fructose.
  • Ink compositions are generally known to the person skilled in the art, e.g. from “ Industrial Dyes” 2003, K. Hunger (editor), Wiley-VCH, chapter 5.6 “Ink dyes ", the disclosure of which is expressively incorporated herein by reference, or WO 2006/005513 A1 .
  • the reducing agent can be admixed and/or dispered with/in the commonly known ink compositions.
  • the resin can be selected from the group consisting of phenol-formaldehyde resins, amino resins such as urea-formaldehyde and melamine formaldehyde resins, epoxy resins, vinylester resins and polyester resins or mixtures thereof.
  • the resin contains phenolic resins.
  • the resin in the coating layer consists of phenolic resin only.
  • the resins may be modified or unmodified resins.
  • the amino resins may be modified e.g. by glycol, caprolactam, acetoguanamine, benzoguanamine or p-toluene-sulphonamide, by alkylation or etherification.
  • the phenol-formaldehyde resins may be modified e.g. by urea, melamine, lignin, resorcinol, modified phenols, cresols, bisphenols or other equivalent compounds. Any amino and phenolic resins known to the skilled person may be used as the amino and phenolic resins.
  • any solvent in which the resin is soluble may be used as the solvent for the resin.
  • the resin containing coating composition (also called “resin composition”) forming the coating layer can comprise between about 0.01 and about 5 wt%, more preferably between about 0.02 and about 3 wt%, and most preferably, about 1 wt% of dye
  • a preferred dosage for direct red 254 is 0.2 wt% and acid black 2 is 1.5 wt%. Possible and preferred dyes have been mentioned supra.
  • the coating composition can further comprise additives, e.g. waxes, surfactants, softeners, hardeners, wetting agents, anti-foam agents, diluents and/or alkalis.
  • Preferred hardeners are sulfamic acid, ethanol amine hydrochloride, triethanol ammonium sulfate or hardener combinations such as morpholine / p-toluene sulfonic acid, N-methyl ethanol amine / SO 2 or N-methyl ethanol amine / ethanol amine / SO 2 .
  • the hardeners may be added to the impregnating procedure in amounts of 0.1 to 3 % by weight.
  • Surface-active agents can, for example, be ethoxylated fatty acids or alkyl phenol ethoxylates, which may be used in amounts between 0.2 and 1.0% by weight.
  • Typical separating agents can be wax emulsions in amounts between 0.2 and 2.0% by weight.
  • Possible anti-foaming agents may be weakly foaming special surfactant combinations in amounts between 0.1 and 1.0 % by weight.
  • the flow values of the resin compositions can range from 2 to 20% and preferably from 4 to 8% which can be achieved by employing modifiers.
  • modifiers can be, but are not restricted to, di- and polyols, polyether diols and alkoxylated alcohols.
  • the alkoxylated alcohols comprise methoxylated, ethoxylated and propoxylated alcohols, diols and polyols.
  • Preferred compounds belong to the group of C 2 to C 12 diols, such as 1,4-butane diol, 1,5-pentane diol and 1,6-hexane diol. These diols preferably can be added in an amount of 8 to 20 weight parts per 100 parts resin.
  • an ammonium salt can be added to the resin composition, in particular containing a phenolic resin.
  • Preferred ammonium salts include ammonium aluminium hexafluoride, ammonium borone hexafluoride, ammonium chloride, ammonium phosphate and ammonium citrate.
  • Suitable ammonium-containing stabilisers are disclosed in US 5,110,320 the disclosure of which is hereby incorporated in its entirety.
  • Particularly preferred stabilizers are ammonium aluminum hexafluorid, ammonium boron hexafluorid, ammonium chloride, ammonium phosphate and ammonium citrate.
  • a formaldehyde-phenol resin is used for preparing the coating layer.
  • F formaldehyde
  • P phenol
  • two classes of PF resin can be synthesized: resoles (resols) and novolaks (novolacs).
  • Resoles are synthesized under basic conditions with excess formaldehyde (i.e. F/P>1); novolaks are synthesized under acidic conditions with excess phenol (i.e. F/P ⁇ 1).
  • this resin is a novolak.
  • a novolak is a phenoloc resin which is not inherently reactive. It is prepared by reacting phenol with formaldehyde under acidic conditions at a formaldehyde/phenol molar ratio of below 1:1, in particular at a molar ratio from 0.75 to 0.85:1. This can result in a linear polymer of molecular weight of 1000 to 1500. Further cross-linking can take place by the addition of more formaldehyde, usually in the form of hexamine.
  • the resin is a resol which is formed from the base catalysed reaction of phenol and formaldehyde and requires an excess of formaldehyde. For solution resin, they are reacted to a low molecular weight of 300 to 700, so that the polymer is still soluble. Further heating will cause condensation reactions and result in a high molecular weight cross-linked polymer.
  • the resol resin used for the coating layer has a molar ratio of formaldehyde to phenol from 1.6 to 2.5 and/or an alkalinity between 1.5 and 3%.
  • the resol can contain commonly known additives such as e.g. urea or glycols.
  • the base layer favourably is paper, most preferred a kraft paper.
  • the paper can have a weight of 20 to 150 g/m 2 , preferably of 30 to 80 g/m 2 .
  • the impregnated paper can then be attached under pressure and heat to a panel or board in order to provide a coated board or coated panel.
  • the board or panel serves as a support layer.
  • Possible support layers to be coated with an impregnated paper according to the invention are plywood, chipboard, fibre board, oriented strand board (OSB), glue wood, laminated veneer lumber (LVL), parallel strand lumber (PSL) and oriented strand lumber (OSL).
  • the most preferred embodiment is plywood panel.
  • the coated board or panel can be applied in the wood working industry, in particular in construction industry for concrete shuttering.
  • the coated article comprises the following structures; preferably it consists of such structures:
  • the coated article comprises at least or consists of four layers: the support layer, the paper, the extinction layer formed by the printed ink and the coating layer.
  • the extinction layer is in contact with the coating layer.
  • an ink composition containing a first dye or pigment and one or more reducing agents is suggested for discoloring a second dye in a resin composition, whereas the first dye or pigment is not or less affected by said reducing agent.
  • the colorant of the ink does not substantially interfere with the reducing agent(s) in the ink.
  • the reducing agent is still capable of reducing the colorant which is present in the coating layer.
  • the impregnation of the base layer can be performed with conventional techniques known to the skilled person, e.g. using baths, rollers, doctor blades, air knife, metering roll, doctor bars, or others.
  • the resin compositions can be applied in one or more steps with drying and/or partial curing between the application stages.
  • coated articles according to the invention are described with the following illustrative figures and examples, which should not be interpreted in order to limit the scope of protection.
  • the kraft paper is printed using the ink WM1A-002H (Woodline, Flint Group, Finland) having a viscosity of 14 s (measured according DIN 4) which equals a viscosity of approx. 28 mPas.
  • the application rate of the liquid ink is approx. 11 g/m 2 .
  • a commonly known printing ink (such as e.g. known from WO2006/005513 A1 , see above) was modified in order to arrive at the present invention by addition of 5, 10 and 15%, respectively, of fructose as reduction agent. The fructose was dissolved into the ink by mixing. The modified ink was used to print a pattern (company logo) on 80 g/m2 natural kraft paper.
  • the printed kraft paper was saturated with water-based phenolic resol resin containing a molar ratio of formaldehyde to phenol from 1.6 to 2.5 having an alkalinity of 1.5 to 3% and dried to have a volatile matter content of 8% (5 min at 160°C).
  • Resin contained red and black dyes to give resin and impregnated paper a deep reddish brown colour.
  • the prepared film was pressed in a hot press on 9 mm birch plywood using pressing parameters of 5 min, 135°C and 18 kg/cm 2 pressure. Visual evaluation of pressed samples gave the following results:

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Laminated Bodies (AREA)
  • Paper (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP20130172877 2013-06-19 2013-06-19 Article à revêtement imprégné de résine aux propriétés esthétiques améliorées Pending EP2816154A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP20130172877 EP2816154A1 (fr) 2013-06-19 2013-06-19 Article à revêtement imprégné de résine aux propriétés esthétiques améliorées
PCT/EP2014/001654 WO2014202216A1 (fr) 2013-06-19 2014-06-18 Article revêtu imprégné de résine ayant des propriétés esthétiques améliorées
RU2016101224A RU2671327C2 (ru) 2013-06-19 2014-06-18 Пропитанное смолой покрытое изделие с улучшенными эстетическими свойствами

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109322211A (zh) * 2018-09-28 2019-02-12 东莞市贝辉装饰材料有限公司 矽片胺醛树脂胶水、可以净味的胶膜纸及制备方法
EP4155340A1 (fr) * 2021-09-23 2023-03-29 Borealis AG Décoloration de polyoléfines à l'état fondu

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GB1114944A (en) * 1965-04-29 1968-05-22 Du Pont Stilbene-azo and stilbene-azoxy dyes and their preparation
US3952119A (en) * 1972-07-12 1976-04-20 Th. Goldschmidt Ag Process for coloring absorptive, rough surface paper
EP0442218A2 (fr) * 1990-02-13 1991-08-21 Minnesota Mining And Manufacturing Company Produits abrasifs liés par une résine phénolique à couleur stabilisée basique
WO2000022232A1 (fr) * 1998-10-14 2000-04-20 The Mead Corporation Application de colorants dans la partie humide d'une machine a papier
EP1323863A1 (fr) * 2001-12-27 2003-07-02 Ricoh Company, Ltd. Feuille composite, son procédé de fabrication, et feuille d'étiquettes autocollantes
EP1464484A1 (fr) * 2001-12-10 2004-10-06 Dai Nippon Printing Co., Ltd. Papier decoratif
WO2008112652A1 (fr) * 2007-03-09 2008-09-18 Ecology Coatings, Inc. Surface souple ayant une composition imperméable durcissable aux uv
US20100189931A1 (en) * 2007-06-25 2010-07-29 Van Der Zwan Rijk Ink-jet-printable decorative paper
EP2213466A1 (fr) * 2007-11-19 2010-08-04 Nippon Paper Industries Co., Ltd. Papier d'impression à jet d'encre
US20110008619A1 (en) * 2009-06-01 2011-01-13 Polymer Ventures, Inc. Polyol Coatings, Articles, and Methods

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DE102004033237A1 (de) 2004-07-08 2006-02-09 Basf Drucksysteme Gmbh Verfahren zur Herstellung von Dekor-Laminaten mit Synchronporen sowie dazu geeignete Druckfarbe
FI20050172A7 (fi) * 2005-02-15 2006-08-16 Dynea Chemicals Oy Pinnoite, menetelmä sen valmistamiseksi ja pinnoitteen käyttö

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Publication number Priority date Publication date Assignee Title
GB1114944A (en) * 1965-04-29 1968-05-22 Du Pont Stilbene-azo and stilbene-azoxy dyes and their preparation
US3952119A (en) * 1972-07-12 1976-04-20 Th. Goldschmidt Ag Process for coloring absorptive, rough surface paper
EP0442218A2 (fr) * 1990-02-13 1991-08-21 Minnesota Mining And Manufacturing Company Produits abrasifs liés par une résine phénolique à couleur stabilisée basique
WO2000022232A1 (fr) * 1998-10-14 2000-04-20 The Mead Corporation Application de colorants dans la partie humide d'une machine a papier
EP1464484A1 (fr) * 2001-12-10 2004-10-06 Dai Nippon Printing Co., Ltd. Papier decoratif
EP1323863A1 (fr) * 2001-12-27 2003-07-02 Ricoh Company, Ltd. Feuille composite, son procédé de fabrication, et feuille d'étiquettes autocollantes
WO2008112652A1 (fr) * 2007-03-09 2008-09-18 Ecology Coatings, Inc. Surface souple ayant une composition imperméable durcissable aux uv
US20100189931A1 (en) * 2007-06-25 2010-07-29 Van Der Zwan Rijk Ink-jet-printable decorative paper
EP2213466A1 (fr) * 2007-11-19 2010-08-04 Nippon Paper Industries Co., Ltd. Papier d'impression à jet d'encre
US20110008619A1 (en) * 2009-06-01 2011-01-13 Polymer Ventures, Inc. Polyol Coatings, Articles, and Methods

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109322211A (zh) * 2018-09-28 2019-02-12 东莞市贝辉装饰材料有限公司 矽片胺醛树脂胶水、可以净味的胶膜纸及制备方法
CN109322211B (zh) * 2018-09-28 2021-07-30 东莞市贝辉装饰材料有限公司 矽片胺醛树脂胶水、可以净味的胶膜纸及制备方法
EP4155340A1 (fr) * 2021-09-23 2023-03-29 Borealis AG Décoloration de polyoléfines à l'état fondu

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RU2016101224A (ru) 2017-07-24
WO2014202216A1 (fr) 2014-12-24
RU2671327C2 (ru) 2018-10-30
RU2016101224A3 (fr) 2018-04-03

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