Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B44—DECORATIVE ARTS
  • B44F—SPECIAL DESIGNS OR PICTURES
  • B44F5/00—Designs characterised by irregular areas, e.g. mottled patterns
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B44—DECORATIVE ARTS
  • B44F—SPECIAL DESIGNS OR PICTURES
  • B44F1/00—Designs or pictures characterised by special or unusual light effects
  • B44F1/08—Designs or pictures characterised by special or unusual light effects characterised by colour effects
• • 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
  • D21H27/02—Patterned paper

Definitions

• the present invention relates to a process for the production of nonuniformly intensely colored paper, and the paper produced by this process.
• EP 601 517 white paper is printed in regular or irregular patterns with as little ink as possible.
• the ink penetrates only to a small extent into the paper.
• the disclosure of EP 601 157 attaches particular value to the small penetration of the ink into the paper, since the paper is subsequently to be recyclable as white paper.
• the ink should therefore be capable of being easily removed from the paper.
• EP 681 060 describes a process for the production of a differently colored paper, in which cellulose fibers and agglomerates of different thickness are used in the process for the production of the paper and are deposited on or incorporated into the finished paper.
• the cellulose fibers or agglomerates of different thickness are colored before the deposition on or incorporation into the paper, and are then introduced into the paper pulp, which itself may have a different color.
• the methods used to date for the production of patterned papers are either complicated or slow in the production method or lead to papers which achieve a completely different effect.
• EP 439363 discloses a paper which contains a desizing agent or is coated therewith, with the result that better absorption of the ink during the printing of the paper by means of inkjet printing is achieved.
• the desizing agent is distributed in/on this paper, uniformly over the entire paper surface, in order to obtain an optimum printed copy.
• EP 518 490 describes ink which is used for inkjet printing, the ink containing a composition which facilitates the penetration of the ink into the printed paper.
• EP 439 363 and EP 518 490 are common to the teachings of EP 439 363 and EP 518 490.
• polar liquids such as inkjet inks
• EP 518 490 describes the production of patterned paper by nonuniform coloring of the paper surface.
• the invention makes use of the phenomenon of paper sizing and the possibility of subsequently manipulating this in a specific manner in preferred regions on the paper web by applying suitable substances.
• Papers are as a rule sized for the purpose of avoiding excessive penetration of applied liquids into the paper structure and into the fibers (blotter effect). This is effected during the paper production by adding sizing substances to the aqueous paper fiber slurry before this is shaped into a paper web in the paper machine.
• the sizing substances are deposited on the fibers to the extent to which the property of liquid absorption of the finished dry paper is desired. This process is known as internal sizing or engine sizing.
• the achieved extent of liquid absorption is inversely proportional to the "degree of internal sizing" of the paper.
• Surface sizing can be carried out instead of or in addition to engine sizing.
• film-forming substances such as solutions or dispersions of converted starches, gums and modified polymers, are applied to the already shaped paper web, for example by means of size presses inside the paper machine.
• the surface sizing also contributes to the strength of the paper, so that high-quality printing paper frequently has engine size and surface size.
• the presence of a surface size is, however, not essential for the process according to the invention, and it is also possible to use paper which has no surface size.
• the process for the production of nonuniformly intensely colored paper in step a) may comprise the application of a dye solution in the form of a visible image or pattern to paper.
• the production process according to the invention leads to a paper which is solidly colored, the intensity of the color differing within the paper surface.
• the different intensity of the color results in a visual effect which appears as an image or pattern to the eye.
• the image or pattern may be present in the form of a representative image, an imaginative structure, a signet, a regular or irregular pattern, a net structure or an irregular, for example random, distribution of the color on the paper.
• the image or pattern can be applied either directly after papermaking, i.e. to the still moist paper, or to a previously produced, dried paper, the paper then being solidly colored by means of an aqueous dye solution.
• the image or pattern can be applied to a continuous paper web or to individual paper sheets. Preferably, the image or pattern is applied to a continuous paper web.
• the image or pattern can be applied by any desired method, in particular by ink et printing, offset printing, flexographic printing, gravure printing, printing with felt or rubber rollers, by spraying on or manually, the last method being unsuitable for industrial production.
• Particularly preferred application methods for the image or pattern is application by means of Inkjet printing, flexographic printing or gravure printing.
• the pattern or image is applied either in the form of a latent image or pattern or in the form of a visible image or pattern to the paper.
• a substance which influences the penetration of an aqueous dye solution into the paper at the point at which the substance is applied by either facilitating or reducing the absorption, is applied to the paper.
• Surfactants are preferably used for this purpose.
• Amomc, catiomc, nomomc or amphoteric surfactants may be used.
• substances which facilitate the penetration of dyes into the paper are, for example, glycol ethers, such as ethylene glycol onomethyl ether, ethylene glycol monoethyl ether, ethyl ene glycol onophenyl ether, diethylene glycol monomethyl ether, di ethyl ene glycol onoethyl ether and di ethyl ene glycol monobutyl ether.
• Suitable desizing surfactants can be selected, for example, from (1) hydrophilic polydialkylsiloxanes, (2) polyalkylene glycol, (3) polypropylene oxide/polyethylene oxide copolymers, (4) fatty ester-modified compounds of phosphate, sorbitan, glycerol, polyethylene glycol, sulfosuccimc acids, sulfomc acid or alkylamme, (5) polyoxyalkyl ene -modified compounds of sorbitan esters, fatty amines, alkanol amides, castor oil, fatty acid, fatty alcohol, (6) quaternary alcohol sulfate compounds, (7) fatty imidazolines, (8) polyether -modified t ⁇ siloxanes and (9) mixtures thereof.
• water- or alcohol -soluble desizing agents from the above entioned classes of substances are, for example, (1) poly(oxyalkylene) modifications of (a) sorbitan esters (e.g. Alkamuls PSML-4 (poly(oxyethylene)sorb ⁇ tan monolaurate), Alkamuls PSMO-20 (poly(oxyethyl ene) sorbitan monooleate), Alkamuls PSTO-20 (poly(oxyethyl ene) sorbitan t ⁇ oleate), Alka ⁇ l Chemicals); (b) fatty amines (e.g.
• sorbitan esters e.g. Alkamuls PSML-4 (poly(oxyethylene)sorb ⁇ tan monolaurate), Alkamuls PSMO-20 (poly(oxyethyl ene) sorbitan monooleate), Alkamuls PSTO-20 (poly(oxyethyl ene) sorbitan t ⁇ oleate), Alka ⁇ l Chemical
• Alkammox T-2, T-6 tallow amine oxyethylate), Alkaminox SO-5 (soybean amine oxyethylate), Alka ⁇ l Chemicals), (Ico een T-2, Ico een T-15, ICI Chemicals);
• castor oil e.g. Alkasurf CO- 10, Alkasurf C0-25B (castor oil oxyethylates), Alka ⁇ l Chemicals
• alkanolamide e.g. Alkamide C-2, C-5 (coconut oil alkanol amide oxyethylates), Alka ⁇ l Chemicals
• fatty acids e.g.
• Alkasurf LAN-1, LAN-3, Alkasurf TDA-6, Alkasurf SA-2 linear alcohol oxyethylates
• Alkasurf NP-1, NP-11, Rexol 130 nonyl phenol oxyethylates
• Alkasurf OP-1, OP -12 octyl phenol oxyethylates
• Alkasurf LA-EP-15, Alkasurf LA-EP-25, Alkasurf LA-EP-65 (linear alcohol oxyalkylates));
• hydrophilic pol y( dimethyl si loxanes) such as, for example, (a) poly( dimethyl si loxane) provided with a monocarbinol terminal group (PS556, Petrarch Systems Inc.) and pol y(d ⁇ methyl si loxane) provided with a dicarbinol terminal group (PS555, PS556, Petrarch Systems Inc ); (b) poly(d ⁇ methyls ⁇ loxane)-b-poly
• sorbitan e.g. Alkamuls STO (sorbitan t ⁇ oleate), Alkamuls SML (sorbitan monolaurate), Alkamuls SM0 (sorbitan monooleate), Alka ⁇ l Chemicals
• glycerol compounds e.g.
• Alkamuls GM0-45LG glyceryl monooleate
• Alkamuls GDO glyceryl dioleate
• Alkamuls GT0 glycerol t ⁇ oleate
• poly(ethylene glycol s) Alkamuls 600 DO (dioleate), Alkamuls 400 -ML (monolaurate), Alkamuls 600 MO (monooleate), Alkamuls 600 DL (dilaurate), Alkamuls 600 DT (ditallow), Alka ⁇ l Chemicals);
• sulfosuccimc acid e.g.
• Alkasurf SS-0-75 sodium di octyl sul fosucci nate )
• Alkasurf SS-DA4-HE oxyethylated alcohol sul fosucci nate
• Alkasurf SS-L7DE sodium sul fosucci nate ester of lau ⁇ c acid diethanol amide
• Alkasurf SS-L- HE sodium lauryl sul fosucci nate
• Alka ⁇ l Chemicals sulfomc acid (e.g.
• Alkasurf CA calcium dodecylbenzenesulfonate
• Alkasurf IPAM isopropyl amine dodecylbenzenesulfonate
• Alka ⁇ l Chemicals Alkasurf CA (calcium dodecylbenzenesulfonate), Alkasurf IPAM (isopropyl amine dodecylbenzenesulfonate), Alka ⁇ l Chemicals);
• alkyl amines e.g.
• Alkamide SDO (soybean diethanol amide), Alkamide CDE (coco-diethanol amide) , Alkamide 2104 (coconut fatty acid diethanol amide), Alkamide CMA (coco-monoethanol amide), Alkamide L9DE (lauryl diethanol amide), Alkamide L7Me (lauryl - monoethanol amide), Alkamide L1PA (laurylmonoisopropyl amide), Alka ⁇ l Chemicals); (5) quaternary compounds, such as, for example, (a) nonpolyme ⁇ c quatermzed ammonium ethosulfate (e.g.
• Alkaquat T (tallow derivatives), Alkaril Chemicals), (6) water-soluble copolymers of lipophilic poly(propylene oxide) with hydrophilic poly(ethylene oxide), such as, for example, (a) ethanol -soluble Tetromc 150R1, Pluromc L- 101, Tetromc 902, Tetromc 25R2 (BASF Corporation), Alkatromc EGE-1 (Alka ⁇ l Chemicals); (b) water-soluble Tetromc 908, 50R8, 25R8, 904, 90R4, Pluromc F-77, all from BASF Corporation, and Alkatromc EGE 25-2 and PGP 33-8 from Alkaril Chemicals; (7) poly(alkylene glycol) and its derivatives, such as, for example, (a) polypropylene glycol (Alkapol PPG 425, Alkapol PPG -4000, Alka ⁇ l Chemicals), (b) poly(propylene glycol dimethacrylate) , poly(ethylene glycol diacrylate), poly(ethylene glyco
• Preferred desizing agents include linear alcohol oxyethylates (e g. Alkasurf LA-EP-65, LA-EP-25 and LA-EP-15 obtainable from Alkaril Chemicals), nonylphenol oxyethylates (e.g. Alkasurf NP-11 obtainable from Alka ⁇ l Chemicals and Rexol 130 obtainable from Hart Chemicals), octyl phenol oxyethylates (e.g. Alkasurf OP- 12 obtainable from Alkaril Chemicals), oleic acid oxyethylates (e.g.
• Alkasurf 0-14 obtainable from Alka ⁇ l Chemicals
• pol y di ethyl s 11 oxane
• pol y propyl ene oxi de
• - b - pol y ethyl ene oxide copolymers
• ethyl ene oxide copolymers e.g. Alkasil NEP 73-70 obtainable from Alkaril Chemicals
• castor oil oxyethylates e.g. Alkasurf C025B obtainable from Alka ⁇ l Chemicals
• coco-imidazolmedicarboxylic acid sodium salts e.g.
• Alkate ⁇ c 2C1B obtainable from Alkaril Chemicals
• coconut fatty acid diethanol amide e.g. Alkamid S104 obtainable from Alka ⁇ l Chemicals.
• the Alkasurf desizing agents are advantageously biodegradable. Suitable surfactants imparting water repel lency are, for example, paper sizes, such as al ylsuccimc anhydride (ASA), alkylketene dimer (AKD) and polyolefins (e.g.
• SUDRANOL 200 Suddeutsche Emulsions-Cheime GmbH, Mannheim, Germany
• waxes wax-like substances
• metal soaps stearates
• paraffin and paraffin emulsions fatty acids, fatty acid (methyl) esters, fatty alcohols, fatty alcohol polyglycol ethers and the sul fates thereof.
• the surfactants are present in the form of solutions, emulsions or dispersions, which further may contain soluble dyes as mentioned below, and/or further auxiliaries in addition to surfactants.
• auxiliaries are thickeners, such as, for example, gum arable, polyacrylates, polymethacrylates, polyvinyl alcohols, hydroxypropylcellulose, hydroxyethylcellulose, polyvinylpyrrol idone, polyvinyl ether, starch, polysaccha ⁇ des and the like, optical b ⁇ ghteners, b ⁇ ghtener quenchers, pigments (dying or non-dying pigments, including pigments with a metallic effect or metals), binders, preservatives and safety chemicals, such as, for example, fluorescent, phosphorescent or luminescent substances.
• the surfactants are preferably present as an aqueous or alcoholic solution.
• concentration ranges for the surfactants in the solutions, emulsions or dispersions to be applied are 0.01 to 30# by weight, preferably 0.1 to 25# by weight, particularly preferably in the range from 0.2 to 15# by weight.
• concentrations of the thickeners which can be used as surfactant auxiliaries are in the range from 0 to 5# by weight, preferably 0.01 to 2.5# by weight, particularly preferably 0.05 to 25% by weight, of the total solution, emulsion or dispersion.
• desizing and water repellency-imparting surfactants may also be applied side by side on the same paper surface.
• Any desired dye solution can be used for creating a visible image or pattern.
• suitable dye solutions are customary printing inks which contain, for example, anthraquinone-, monoazo-, diazo-, phthalocyanine- , aza- (18) -annul ene- and for azan-copper complex dyes.
• suitable dyes are those mentioned further below for the dye solution of the dyeing bath, including dyes containing or based on pigments as mentioned below.
• the concentration ranges of the dyes are 0.1 to 30* by weight, preferably 1.0 to 20* by weight, particularly preferably 2.0 to 10* by weight.
• the latent or visible image or pattern can be applied to one side or both sides of the paper so that the finished paper has, at least on one side, a color which is more intense or less intense than in the untreated regions of the paper surface(s).
• the paper is solidly colored in step (b) with the aid of a dye solution.
• This coloring is effected so as to cover the whole area, either inside or outside the paper machine, by applying dye solution(s) to the paper by means of classical paper coating apparatuses and processes, such as, for example, a size press, film press, knife coater, blade, rolls or spraying, or by application of a dye solution to the total surface of the paper with the aid of suitable printing methods, such as inkjet printing, offset printing, flexographic printing, gravure printing or printing by means of felt or rubber rollers, by spraying on or by tub coloring of the paper in a dyeing bath. It is preferable to color the paper by the dip process in an aqueous dye solution.
• the dye solution usually contains the dyes in concentration ranges of 0.1 to 40* by weight, preferably 0.1 to 35* by weight, very particularly preferably 0.1 to 30* by weight.
• concentration of the dye solution can be established according to the individually desired effect to be achieved (intensity of the subsequently desired image). Corresponding experiments can be carried out by any person skilled in the art by simple testing.
• the paper is immersed in an aqueous dye solution after application of the latent or visible image or pattern and is then pressed off and dried.
• Tub coloring can be carried out using sized or unsized paper webs or paper sheets. By means of tub coloring, it is possible to obtain rich colors of very high luminous power. A further advantage of this method is that even small amounts can be colored without operating inefficiently.
• the paper absorbs the color to a greater or lesser extent in the pretreated areas during the coloring process, depending on the substance with which the paper was pretreated.
• the image or pattern initially applied in latent form appears, after the coloring of the paper, in a less intense hue of the same color in which the entire paper is colored.
• the color intensity of the image or pattern subsequently appearing as "negative” can be varied by the applied amount and/or composition of the water repellent applied.
• the latent image it is also possible to apply desizing and water-repellent substances side by side on the same paper surface, so that the finished paper has both "positive” and “negative” images or patterns.
• the subsequent coloring of the paper intensifies the color of the previously applied image or pattern, so that a special effect, namely the nonuniformly intense coloring of the paper, can also be achieved thereby. This effect can be obtained only if the paper carrying the visible image is additionally colored.
• Customary aqueous dye solutions can be used for coloring the paper. These may contain basic and/or acidic and/or substantive dyes. Examples of suitable dye solutions are solutions which contain anthraquinone- , monoazo-, diazo-, phthalocyamne- , aza- (l ⁇ )-annulene- and for azan-copper complex dyes. Specific examples of suitable dyes are mentioned in EP-A 559 324, on page 4, lines 25 to 53. These are in particular t ⁇ phenodioxazmes, Bernacid Red 2BMN; Pontamine Brilliant Bond Blue A; Ponta ⁇ ne; Food Black 2; Carodirect Turquoise FBL Supra Cone.
• Pro- Jet series obtainable from ICI, including Pro- Jet Gelb I (Direct Yellow 86), Pro- Jet Magenta I (Acid Red 249), Pro-Jet Cyan I (Direct Blue 199), Pro- Jet Schwarz I (Direct Black 168), Pro- Jet Yellow 1-G (Direct Yellow 132), Aminyl Brilliant Red F-B, obtainable from Sumitomo Chemical Co.
• Duasyn line of "salt-free" dyes obtainable from Hoechst, such as Duasyn Direct Schwarz HEF-SF (Direct Black 168), Duasyn Schwarz RL-SF (Reactive Black 31), Duasyn Direct Gelb 6G-SF VP216 (Direct Yellow 157), Duasyn Brilliant Gelb GL-SF VP220 (Reactive Yellow 37), Duasyn Acid Yellow XX-SF VP413 (Acid Yellow 23), Duasyn Brilliant Rot F3B-SF VP218 (Reactive Red 180), Duasyn Rhodamine B-SF VP353 (Acid Red 52), Duasyn Direct Turkisblau FRL-SF VP368 (Direct Blue 199), Duasyn Acid Blue AE-SF VP344 (Acid Blue 9), and the like, and mixtures of these dyes.
• Duasyn Direct Schwarz HEF-SF Direct Black 168
• Duasyn Schwarz RL-SF Reactive
• dyes which contain or are based on pigments (dying or non-dying pigment), including pigments with metallic effect, or metals.
• the concentration of the dye depends on the manufacturer and also on the color used and is not limiting for the present invention.
• the dye solutions can moreover contain further additives, such as alcohol, thickeners, wet-strength agents, optical brighteners, preservatives, safety chemicals, binders and pigments (dyes or non-dying pigments, like for example calcium carbonate).
• Auxiliaries for the dye solution are in particular gum arabic, polyacrylate salts, pol methacrylate salts, polyvinyl alcohols, hydroxypropyl eel 1 ul ose, hydroxyethyl eel 1 ul ose, polyvinyl pyrrol i - done, polyvinyl ether, starch, polysaccharides and the like. Further customary additives for inks may likewise be present. Such customary additives are mentioned in EP-A 518 490, page 4, line 55, to page 5, line 9.
• a paper having a basis weight of 105 g/m 2 is produced on a Fourdrinier machine.
• the paper stock composition consists of 80* by weight of softwood sul fate pulp and 20* by weight of eucalyptus sul fate pulp.
• the paper sizing is carried out using rosin size and alum. 1* of melamine/formaldehyde resin is used as the wet- strength agent.
• the paper used in the example has no surface size.
• the stated percentages of the nonfibrous additives are based on the fiber content.
• Sheets are taken from the paper thus produced, and desizing (example 1) or water-repellent (example 2) or both (example 3) substances are applied in the form of handwritten characters to said sheets manually with the aid of an application apparatus, for example a Fineliner (Rotring Rapidograph 0.35 mm diameter), reed pen or brush.
• an application apparatus for example a Fineliner (Rotring Rapidograph 0.35 mm diameter), reed pen or brush.
• a visible image is applied to the paper.
• the sheets treated in this manner are colored by dipping in a dye solution, then pressed off with an absorptive paper mat and dried.
• a 02* strength by weight aqueous solution of a polyether-modified t ⁇ si loxane (TEGOPREN 5847) is applied as described above to a paper sheet.
• the subsequent coloring is effected by dipping the ) paper sheet into a 1.0* strength by weight aqueous Cartasol Blau 3RF solution (Sandoz Chemikalien AG, Basle/Cla ⁇ ant (Deutschland) GmbH, Lorrach).
• the latent handwritten characters are very clearly visible and appear positive and in an intense hue in the same color in which the entire paper is colored.
• a 5.0* strength by weight aqueous dispersion of a polyethylene wax (SUDRAN0L 200) is applied as described above to a paper sheet.
• the subsequent coloring is effected by dipping the paper sheet into a 1 0* strength by weight aqueous Cartasol Blau 3RF solution (Sandoz Chemikalien AG, Basle/Cla ⁇ ant (Deutschland) GmbH, Lorrach).
• the latent handwritten characters are very clearly visible and appear negative and in a less intense hue in the same color in which the entire paper is colored.
• a 0 2* strength by weight aqueous solution of a polyether-modified t ⁇ si loxane (TEGR0PEN 5847, Goldschmidt AG, Essen, Germany) and a 5.0* strength by weight aqueous dispersion of a polyethylene wax (SUDRANOL 200, Sud Weg Emulsions-Chemie GmbH, Mannheim, Germany) are applied simultaneously, but not overlapping, as described above to a paper sheet.
• the subsequent coloring is effected by dipping into a 1.0* strength by weight Cartasol Blau 3RF solution (Sandoz Chemikalien AG, Basle/Cla ⁇ ant (Deutschland) GmbH, Lorrach).
• Cartasol Blau 3RF solution Cartasol Blau 3RF solution
• a blue inkjet imprint in the form of a net pattern is applied to a paper sheet by means of a commercial printer (Hewlett Packard DeskJet 870Cxi using the HP 51641A printer cartridge.
• the subsequent tub coloring of the printed paper sheet in a 1.0* strength by weight aqueous Cartasol Blau 3RF solution makes the imprinted pattern very clearly visible. The pattern appears positive and in a more intense hue in the same color in which the entire paper is colored.

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• Paper (AREA)
• Laminated Bodies (AREA)
• Ink Jet (AREA)

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• 2001
  • 2001-08-01 ES ES01118527T patent/ES2217066T3/es not_active Expired - Lifetime
  • 2001-08-01 AT AT01118527T patent/ATE264942T1/de active
  • 2001-08-01 DK DK01118527T patent/DK1281812T3/da active
  • 2001-08-01 DE DE50102060T patent/DE50102060D1/de not_active Expired - Lifetime
  • 2001-08-01 EP EP01118527A patent/EP1281812B9/de not_active Expired - Lifetime
• 2002
  • 2002-07-27 JP JP2003517369A patent/JP2005523388A/ja active Pending
  • 2002-07-27 US US10/483,271 patent/US20040182532A1/en not_active Abandoned
  • 2002-07-27 WO PCT/EP2002/008404 patent/WO2003012202A1/en active Search and Examination
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• 2005
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