EP1281812A1 - Patterned paper - Google Patents
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- Publication number
- EP1281812A1 EP1281812A1 EP01118527A EP01118527A EP1281812A1 EP 1281812 A1 EP1281812 A1 EP 1281812A1 EP 01118527 A EP01118527 A EP 01118527A EP 01118527 A EP01118527 A EP 01118527A EP 1281812 A1 EP1281812 A1 EP 1281812A1
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- EP
- European Patent Office
- Prior art keywords
- paper
- printing
- pattern
- dye solution
- substance
- 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.)
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- MDFFNEOEWAXZRQ-UHFFFAOYSA-N aminyl Chemical group [NH2] MDFFNEOEWAXZRQ-UHFFFAOYSA-N 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- KMGARVOVYXNAOF-UHFFFAOYSA-N benzpiperylone Chemical compound C1CN(C)CCC1N1C(=O)C(CC=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 KMGARVOVYXNAOF-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 235000012745 brilliant blue FCF Nutrition 0.000 description 1
- 239000004161 brilliant blue FCF Substances 0.000 description 1
- OOCMUZJPDXYRFD-UHFFFAOYSA-L calcium;2-dodecylbenzenesulfonate Chemical compound [Ca+2].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O OOCMUZJPDXYRFD-UHFFFAOYSA-L 0.000 description 1
- 235000019241 carbon black Nutrition 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 238000009990 desizing Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- FHIVAFMUCKRCQO-UHFFFAOYSA-N diazinon Chemical compound CCOP(=S)(OCC)OC1=CC(C)=NC(C(C)C)=N1 FHIVAFMUCKRCQO-UHFFFAOYSA-N 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 1
- 239000000982 direct dye Substances 0.000 description 1
- XDBZPHDFHYZHNG-UHFFFAOYSA-L disodium 3-[(5-chloro-2-phenoxyphenyl)diazenyl]-4-hydroxy-5-[(4-methylphenyl)sulfonylamino]naphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].C1=CC(C)=CC=C1S(=O)(=O)NC(C1=C2O)=CC(S([O-])(=O)=O)=CC1=CC(S([O-])(=O)=O)=C2N=NC1=CC(Cl)=CC=C1OC1=CC=CC=C1 XDBZPHDFHYZHNG-UHFFFAOYSA-L 0.000 description 1
- HJORILXJGREZJU-UHFFFAOYSA-L disodium 7-[(5-chloro-2,6-difluoropyrimidin-4-yl)amino]-4-hydroxy-3-[(4-methoxy-2-sulfonatophenyl)diazenyl]naphthalene-2-sulfonate Chemical compound ClC=1C(=NC(=NC1F)F)NC1=CC=C2C(=C(C(=CC2=C1)S(=O)(=O)[O-])N=NC1=C(C=C(C=C1)OC)S(=O)(=O)[O-])O.[Na+].[Na+] HJORILXJGREZJU-UHFFFAOYSA-L 0.000 description 1
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 1
- FPVGTPBMTFTMRT-UHFFFAOYSA-L disodium;2-amino-5-[(4-sulfonatophenyl)diazenyl]benzenesulfonate Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C(N)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 FPVGTPBMTFTMRT-UHFFFAOYSA-L 0.000 description 1
- WJRMGBWBIGOIOF-UHFFFAOYSA-N dodecyl benzenesulfonate;propan-2-amine Chemical compound CC(C)N.CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 WJRMGBWBIGOIOF-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- SFNALCNOMXIBKG-UHFFFAOYSA-N ethylene glycol monododecyl ether Chemical compound CCCCCCCCCCCCOCCO SFNALCNOMXIBKG-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 235000019233 fast yellow AB Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- WTIFIAZWCCBCGE-UUOKFMHZSA-N guanosine 2'-monophosphate Chemical compound C1=2NC(N)=NC(=O)C=2N=CN1[C@@H]1O[C@H](CO)[C@@H](O)[C@H]1OP(O)(O)=O WTIFIAZWCCBCGE-UUOKFMHZSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229920013746 hydrophilic polyethylene oxide Polymers 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- SXQCTESRRZBPHJ-UHFFFAOYSA-M lissamine rhodamine Chemical compound [Na+].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=C(S([O-])(=O)=O)C=C1S([O-])(=O)=O SXQCTESRRZBPHJ-UHFFFAOYSA-M 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- RZRNAYUHWVFMIP-UHFFFAOYSA-N monoelaidin Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- DHZVJRHNESBLAA-UHFFFAOYSA-N n-propan-2-yldodecan-1-amine Chemical compound CCCCCCCCCCCCNC(C)C DHZVJRHNESBLAA-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 125000001117 oleyl group Chemical class [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920006294 polydialkylsiloxane Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005651 polypropylene glycol dimethacrylate Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 235000012752 quinoline yellow Nutrition 0.000 description 1
- FZUOVNMHEAPVBW-UHFFFAOYSA-L quinoline yellow ws Chemical compound [Na+].[Na+].O=C1C2=CC=CC=C2C(=O)C1C1=NC2=C(S([O-])(=O)=O)C=C(S(=O)(=O)[O-])C=C2C=C1 FZUOVNMHEAPVBW-UHFFFAOYSA-L 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical class [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- SLBXZQMMERXQAL-UHFFFAOYSA-M sodium;1-dodecoxy-4-hydroxy-1,4-dioxobutane-2-sulfonate Chemical compound [Na+].CCCCCCCCCCCCOC(=O)C(S(O)(=O)=O)CC([O-])=O SLBXZQMMERXQAL-UHFFFAOYSA-M 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- 229960000943 tartrazine Drugs 0.000 description 1
- 239000010981 turquoise Substances 0.000 description 1
- YXZRCLVVNRLPTP-UHFFFAOYSA-J turquoise blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Cu+2].NC1=NC(Cl)=NC(NC=2C=C(NS(=O)(=O)C3=CC=4C(=C5NC=4NC=4[N-]C(=C6C=CC(=CC6=4)S([O-])(=O)=O)NC=4NC(=C6C=C(C=CC6=4)S([O-])(=O)=O)NC=4[N-]C(=C6C=CC(=CC6=4)S([O-])(=O)=O)N5)C=C3)C(=CC=2)S([O-])(=O)=O)=N1 YXZRCLVVNRLPTP-UHFFFAOYSA-J 0.000 description 1
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 method for producing inconsistently intensely colored paper, as well as after this procedure manufactured paper.
- EP 601 517 white paper is printed in regular or irregular Patterns printed with as little color as possible. The color just penetrates a small amount in the paper. On the low penetration of the Color in the paper becomes more special in the disclosure of EP 601 517 Value, since the paper can then be recycled as white paper should be. Therefore, the color from the paper should come back easily can be removed.
- EP 681 060 describes a method for producing a different colored paper, in the process of manufacturing the Paper cellulose fibers and agglomerations of different thicknesses are used, which are stored on or in the finished paper.
- the differently thick cellulose fibers or agglomerations are dyed in the paper before being put into storage, and are then in the paper pulp, which itself can have a different color.
- EP 439 363 discloses a paper containing a sizing agent contains, or is coated with, thereby better absorption of the Ink is reached when printing on the paper by means of inkjet printing.
- the sizing agent is even on the paper distributed over the entire paper surface in order to achieve an optimal printing result receive.
- EP 518 490 describes ink which is used for inkjet printing, wherein the ink contains an agent which prevents the ink from penetrating into the printed paper relieved.
- EP 439 363 and EP 518 490 have in common that the Penetration of polar liquids such as inkjet inks into it Paper structure and in the paper fibers of glued papers through the appropriate application of sizing agents is facilitated. Neither that However, EP 439 363 and EP 518 490 describe the production patterned papers due to inconsistent coloring of the paper surface.
- the object of the present invention was to have the lowest possible Manufacturing effort a visually appealing paper uneven Get coloring.
- the invention addresses the phenomenon of paper sizing and Possibility of targeting these in preferred areas on the paper web subsequently manipulated by applying suitable substances, advantage.
- Papers are usually sized for the purpose of being excessive Penetration of applied liquids in the paper structure and in to avoid the fibers (blotting paper effect). This will be during the Papermaking is accomplished by adding sizing substances to the aqueous paper pulp before it turns into a paper machine Paper web is formed. The sizing substances are applied to the fibers dejected to the extent that the property of the finished dry Paper is desirable to be able to absorb liquids. This The process is known as internal sizing or mass sizing. The degree to which liquids can be absorbed is reversed proportional to the "internal degree of sizing" of the paper.
- Surface sizing can be used instead of or in addition to mass sizing be performed.
- Film-forming substances are like solutions or dispersions of converted starches, gums and modified Polymers onto the already formed paper web e.g. using size presses applied within the paper machine.
- the surface sizing delivers also a strength contribution for the paper, so that high quality Printing paper often has mass and surface sizing.
- the existence a surface sizing is for the presented invention However, the procedure is not mandatory, paper can also be used, that has no surface sizing.
- step a) the process of producing non-uniformly intense colored paper in step a) applying a dye solution in include the form of a visible image or pattern on paper.
- the manufacturing method according to the invention leads to a paper that is colored throughout, the intensity of the color within the Paper surface is different. Because of the different Intensity of coloring creates an optical effect on the eye appears as a picture or pattern.
- the image or pattern can be in the form of a representative illustration, a fantasy, a lettering, a regular or irregular pattern, a network structure, or one irregular, e.g. statistical distribution of color on paper available.
- the application of the picture or pattern can be done either directly after the Papermaking, i.e. on the still damp paper, or on a previous one made, dried paper take place, the paper then colored over the entire surface using an aqueous dye solution becomes.
- the picture or pattern can be on a running paper web, or on individual sheets of paper can be applied.
- Applying the picture or pattern can be done by any method take place, in particular by means of inkjet printing, offset printing, flexographic printing, Gravure printing, printing with felt or rubber rollers, by spraying or also by hand, the latter method for industrial manufacturing is not suitable.
- Particularly preferred methods of application for the The image or sample is the order using inkjet printing, flexographic printing or Gravure printing.
- the pattern or image is either in the form of a latent image or Pattern or in the form of a visible image or pattern on the paper applied.
- any substance that has this property can be used for inventive methods are used.
- Surfactants used. It can be anionic, cationic, non-ionic or amphoteric surfactants can be used. In addition to the surfactants can be used to prevent the penetration of dyes into to lighten the paper.
- Such substances are, for example, glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monophenyl ether, Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol monobutyl ether.
- Suitable desizing agents can be selected from, for example (1) hydrophilic polydialkylsiloxanes, (2) polyalkylene glycol, (3) Polypropylene oxide-polyethylene oxide copolymers, (4) fatty acid ester modified Compounds of phosphate, sorbitan, glycerin, Polyethylene glycol, sulfosuccinic acids, sulfonic acid or alkylamine, (5) Polyoxyalkylene-modified compounds of sorbitan esters, Fatty amines, alkanolamides, castor oil, fatty acid, fatty alcohol, (6) quaternary alcohol sulfate compounds, (7) fatty imidazolines, (8) polyether modified trisiloxanes and (9) mixtures thereof.
- water or alcohol soluble sizing agents from the above-mentioned classes of substances are, for example (1) Poly (oxyalkylene) modifications of (a) sorbitan esters (e.g. alkamuls PSML-4 (poly (oxyethylene) sorbitan monolaurate), Alkamuls PSMO-20 (poly (oxyethylene) sorbitan monooleate), Alkamuls PSTO-20 (poly (oxyethylene) sorbitan trioleate), Alkaril Chemicals); (b) fatty amines (e.g.
- Alkaminox T-2, T-5 (tallow amine oxyethylate), Alkaminox SO-5 (soy amine oxyethylate), Alkaril Chemicals), (Icomeen T-2, Icomeen T-15, ICI Chemicals);
- castor oil e.g. Alkasurf C0-10, Alkasurf CO-25B (castor oil oxyethylate), Alkaril Chemicals
- Alkanolamide e.g. alkamides C-2, C-5 (coconut oil alkanolamide oxyethylates). Alkaril Chemicals
- fatty acids e.g.
- Sorbitan e.g. Alkamuls STO (sorbitan trioleate), Alkamuls SML (sorbitan monolaurate), Alkamuls SMO (Sorbitan Monooleate, Alkaril Chemicals);
- Glycerin compounds e.g. Alkamuls STO (sorbitan trioleate), Alkamuls SML (sorbitan monolaurate), Alkamuls SMO (Sorbitan Monooleate, Alkaril Chemicals);
- Glycerin compounds e.g.
- Alkamuls GMO-45LG glyceryl monooleate
- Alkamuls GDO glyceryl dioleate
- Alkamuls GTO glyceryl trioleate
- D Poly (ethylene glycols) (Alkamuls 600 DO (dioleate), Alkamuls 400-ML (monolaurate), Alkamuls 600 MO (monooleate), Alkamuls 600 DL (dilaurate), Alkamuls 600 DT (Ditalg), Alkaril Chemicals); (e) sulfosuccinic acid (e.g.
- Alkasurf SS-0-75 sodium dioctyl sulfosuccinate
- Alkasurf SS-DA4-HE oxyethylated alcohol sulfosuccinate
- Alkasurf SS-L7DE sodium sulfosuccinate ester from Laurindiethanolamide
- Alkasurf SS-L-HE sodium lauryl sulfosuccinate
- Alkaril Chemicals sulfonic acid
- alkasurf CA calcium dodecylbenzenesulfonate
- Alkasurf IPAM isopropylamine dodecylbenzenesulfonate
- alkylamines e.g. alkamides SDO (Soy diethanolamide), alkamides CDE (coconut diethanolamide), alkamides 2104 (Coconut fatty acid diethanolamide), alkamides CMA (coconut monoethanolamide), Alkamides L9DE (lauryldiethanolamide), alkamides L7Me (laurylmonoethanolamide), Alkamides L1PA (lauryl monoisopropylamide), Alkaril Chemicals); (5) quaternary compounds such as (a) non-polymeric quaternary 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 (a) methanol-soluble Tetronic 150R1, Pluronic L-101, Tetronic 902, Tetronic 25R2 (BASF Corporation), Alkatronic EGE-1 (Alkaril Chemicals); (b) water soluble Tetronic 908, 50R8, 25R8, 904, 90R4, Pluronic F-77, all from BASF Corporation, and Alkatronic EGE 25-2 and PGP 33-8 from Alkaril Chemicals; (7) poly (alkylene glycol) and its Derivatives such as (a) polypropylene glycol (Alkapol PPG 425, Alkapol PPG-4000, Alkaril Chemicals); (b) poly (propylene glycol dimethacrylate), poly (ethylene glycol diacrylate), Poly (ethylene glycol dimethacrylate), poly (ethylene glycol monomethyl ether), Poly
- Preferred sizing agents include linear alcohol oxyethylates (e.g. Alkasurf LA-EP-65, LA-EP-25 and LA-EP-15) available from Alkaril Chemicals, Nonylphenoloxyethylates (e.g. available from Alkaril Chemicals Alkasurf NP-11 and Rexol 130) available from Hart Chemicals, Octylphenoloxyethylate (e.g. Alkasurf available from Alkaril Chemicals OP-12), oleic acid oxyethylates (e.g.
- Alkaril Chemicals Alkasurf 0-14 poly (dimethylsiloxane) -b-poly (propylene oxide) -b-poly (ethylene oxide) copolymers
- poly (dimethylsiloxane) -b-poly (propylene oxide) -b-poly (ethylene oxide) copolymers e.g. available from Alkaril Chemicals Alkasil NEP 73-70
- castor oil oxyethylate e.g. from Alkaril Chemicals available Alkasurf C025B
- cocosimidazoline dicarboxylic acid sodium salts e.g. Alkateric 2C1B available from Alkaril Chemicals
- coconut fatty acid diethanolamide e.g. available from Alkaril Chemicals Alkamide S104.
- the Alkasurf sizing agents are advantageous biodegradable.
- Suitable hydrophobic surfactants are, for example, paper sizing agents such as alkyl succinic anhydride (ASA), alkyl ketene dimer (AKD), as well as polyolefins (e.g. SÜDRANOL 200, Süd Weg Emulsions-Chemie GmbH, Mannheim, Germany), waxes, waxy substances, Metal soaps (stearates), paraffin and paraffin emulsions, fatty acids, Fatty acid (methyl) esters, fatty alcohols, fatty alcohol polyglycol ethers and their sulfates.
- paper sizing agents such as alkyl succinic anhydride (ASA), alkyl ketene dimer (AKD), as well as polyolefins (e.g. SÜDRANOL 200, Süd Weg Emulsions-Chemie GmbH, Mannheim, Germany), waxes, waxy substances, Metal soaps (stearates), paraffin and paraffin emulsions, fatty acids, Fatty acid
- the surfactants When applied to the paper, the surfactants are in the form of solutions, Emulsions or dispersions in addition to the surfactants Can contain auxiliaries. Common auxiliaries are thickeners, such as e.g. Gum arabic, polyacrylates, polymethacrylates, polyvinyl alcohols, Hydroxypropyl cellulose, hydroxyethyl cellulose, polyvinyl pyrrolidone, Polyvinyl ether, starch, polysaccharides, and similar optical brighteners, Brightener-extinguishers, pigments, binders, preservatives and safety chemicals such as fluorescent, phosphorescent or luminescent substances.
- the surfactants are preferably as aqueous or alcoholic solution.
- concentration ranges for the surfactants in the applied Solutions, emulsions or dispersions are 0.01 to 30% by weight, preferably 0.1 to 25% by weight, particularly preferably in the range of 0.2 up to 15% by weight.
- concentrations of thickeners that act as surfactant adjuvants usable are in the range from 0 to 5% by weight, preferably 0.01 to 2.5% by weight, particularly preferably 0.05 to 2.5% by weight of the total Solution, emulsion or dispersion.
- any dye solution can be used.
- An aqueous one is preferred Solution of substantive, basic or acidic dyes used, or Mixtures of these dyes.
- suitable dye solutions are common printer inks, e.g. Anthraquinone, monoazo, disazo, Phthalocyanine, aza (18) annulene and formazan copper complex dyes contain.
- suitable dyes are those such as are mentioned below for the dye solution of the dye bath.
- the concentration ranges of the dyes are 0.1 to 30% by weight, preferably at 1.0 to 20% by weight, particularly preferably at 2.0 to 10% by weight.
- the latent or visible image or pattern can be one-sided or from both sides are applied to the paper so that the finished paper has a color on at least one side, which is more intense or less intense than in the untreated ones Areas of the paper surface (s).
- the paper After applying the latent or visible image or pattern the paper becomes the paper in step (b) using a Dye solution completely colored.
- This coloring is done nationwide either inside or outside the paper machine by applying dye solution (s) to the paper using classic paper coating devices and processes, e.g. size press, Film press, squeegee, blade, roller or spray or through widespread application of a dye solution on the paper with the help suitable printing methods such as inkjet printing, offset printing, flexographic printing, Gravure printing, printing with felt or rubber rollers, by spraying or by dipping the paper in a dye bath.
- This is preferred Dyed paper in an aqueous dye solution.
- the dye solution contains the dyes usually in concentration ranges from 0.1 to 40 % By weight, preferably 0.1 to 35% by weight, very particularly preferably from 0.1 to 30 Wt%.
- concentration of the dye solution can vary depending on the individual desired effect to be achieved (intensity of the later desired Picture) can be set. Any specialist can carry out appropriate tests by simply testing.
- the paper is applied after the latent application or visible image or pattern in an aqueous dye solution immersed, then pressed and dried.
- the dip coloring can with glued or unsized paper webs or sheets be performed. The dip coloring makes it possible to get full Obtain colorations of the highest luminosity. Another advantage of this The method is that even small quantities can be dyed without doing so to work inefficiently.
- the initially latently applied image or pattern appears after coloring the paper in a less intense shade the same color in which all the paper is colored.
- the color intensity of the image that later appears to be "negative” or Pattern by the order quantity and / or composition of the applied hydrophobizing agent can be varied.
- the subsequent coloring of the paper intensifies the Coloring of the previously applied image or pattern, so that also this has a special effect, namely the unevenly intense Coloring of the paper can be achieved. This effect can only be obtained if the paper bearing the visible image is additional is colored.
- aqueous dye solutions can be used to color the paper be used. These can be basic and / or acidic and / or contain substantive dyes. Examples of suitable ones Dye solutions are solutions that contain anthraquinone, monoazo, disazo, Phthalocyanine, aza (18) annulene and formazan copper complex dyes contain. Specific examples of suitable dyes are in EP-A 559 324 on p. 4, lines 25 to 53. These are in particular Triphenodioxazine, Bernacid Red 2BMN; Pontamine Brilliant Bond Blue A; Pontamine; Food black 2; Carodirect Turquoise FBL Supra Conc.
- Duasyn line of "salt-free" Dyes available from Hoechst such as Duasyn Direct Black HEF-SF (Direct Black 168), Duasyn Black RL-SF (Reactive Black 31), Duasyn Direct Yellow 6G-SF VP216 (Direct Yellow 157), Duasyn Brilliant Yellow GL-SF VP220 (Reactive Yellow 37), Duasyn Acid Yellow XX-SF VP413 (Acid Yellow 23), Duasyn Brilliant Red F3B-SF VP218 (Reactive Red 180), Duasyn Rhodamine B-SF VP353 (Acid Red 52), Duasyn Direct Turquoise Blue FRL-SF VP368 (Direct Blue 199), Duasyn Acid Blue AE-SF VP344 (Acid Blue 9), and similar, as well as mixtures of these dyes.
- Duasyn Direct Black HEF-SF Direct Black 168
- Duasyn Black RL-SF Reactive Black
- the concentration of the dye also depends on the manufacturer used color and is not for the present invention limiting.
- the dye solutions can also other additives such as Alcohol, thickeners, wet strength agents, optical brighteners, preservatives, Contain security chemicals, binders and pigments. Aids for the dye solution are in particular gum arabic, Polyacrylate salts, polymethacrylate salts, polyvinyl alcohols, hydroxypropyl cellulose, Hydroxyethyl cellulose, polyvinyl pyrrolidone, polyvinyl ether. Starch, polysaccharides, and the like. Other common additives for inks can also be present. Such common additives are in EP-A 518 490 page 4, line 55 to page 5, line 9.
- a paper with a mass per unit area of 105 g / m 2 is produced on a Fourdrinier paper machine.
- the paper stock composition consists of 80% by weight softwood sulfate pulp and 20% by weight eucalyptus sulfate pulp.
- the paper is glued with resin glue and alum. 1% melamine formaldehyde resin is used as the wet strength agent.
- the paper used in the examples has no surface sizing.
- the percentages of the non-fibrous additives relate to the Fiber content.
- Sheets are taken from the paper so produced, by hand using an application device, e.g. a fineliners (Rotring Rapidograph 0.35 mm diameter), ink tube or one Paintbrushing (example 1) or hydrophobizing (example 2) or both (example 3) substances in the form of handwritten characters be applied.
- an application device e.g. a fineliners (Rotring Rapidograph 0.35 mm diameter), ink tube or one Paintbrushing (example 1) or hydrophobizing (example 2) or both (example 3) substances in the form of handwritten characters be applied.
- a visible image is placed on the Paper applied.
- the sheets thus treated are immersed in dyed a dye solution, then with an absorbent Pressed paper fleece and dried.
Abstract
Description
Die vorliegende Erfindung betrifft ein Verfahren zum Herstellen von uneinheitlich intensiv gefärbtem Papier, sowie das nach diesem Verfahren hergestellte Papier.The present invention relates to a method for producing inconsistently intensely colored paper, as well as after this procedure manufactured paper.
Auch im Zeitalter der elektronischen Datenübertragung besteht allgemein ein Bedarf an optisch ansprechenden Papieren. Daher ist es ein Bestreben der Papierindustrie, Papiere herzustellen, die neben hoher Papierqualität einen ansprechenden optischen Effekt aufweisen.Even in the age of electronic data transmission, there is general a need for visually appealing papers. Therefore, it is an effort the paper industry to manufacture papers that are next to high Paper quality have an attractive optical effect.
In US 4,534,157 wird ein Papier in feuchtem Zustand direkt nach dessen Herstellung als Papierbahn farbig bedruckt, indem Farbe über Farbdüsen auf eine Farbrolle aufgebracht wird, welche die Farbe dann auf das Papier überträgt. Somit wird ein unregelmäßiges, diffuses Muster mit einer über die Papierbahn gleichbleibenden Farbmenge auf ansonsten ungefärbtes Papier aufgebracht.In US 4,534,157 a paper is in the wet state immediately after it Manufacturing as a paper web is printed in color by adding color over color nozzles is applied to a paint roller, which then applies the paint to the Paper transfers. This creates an irregular, diffuse pattern a constant amount of color on the paper web otherwise undyed paper applied.
In EP 601 517 wird weißes Papier in regelmäßigen oder unregelmäßigen Mustern mit möglichst wenig Farbe bedruckt. Die Farbe dringt nur zu einem geringen Anteil in das Papier ein. Auf das geringe Eindringen der Farbe in das Papier wird in der Offenbarung der EP 601 517 besonderer Wert gelegt, da das Papier anschließend als weißes Papier recyclebar sein soll. Daher soll sich die Farbe aus dem Papier leicht wieder entfernen lassen können.In EP 601 517 white paper is printed in regular or irregular Patterns printed with as little color as possible. The color just penetrates a small amount in the paper. On the low penetration of the Color in the paper becomes more special in the disclosure of EP 601 517 Value, since the paper can then be recycled as white paper should be. Therefore, the color from the paper should come back easily can be removed.
Die EP 681 060 beschreibt ein Verfahren zur Herstellung eines unterschiedlich gefärbten Papiers, bei dem im Herstellungsprozeß des Papiers unterschiedlich dicke Zellulosefasern und -agglomerationen verwendet werden, die an oder in das fertige Papier eingelagert werden. Die unterschiedlich dicken Zellulosefasern oder -agglomerationen werden vor der An-/ bzw. Einlagerung in das Papier gefärbt, und werden dann in die Papierpulpe, die selbst eine andere Farbe haben kann, eingebracht.EP 681 060 describes a method for producing a different colored paper, in the process of manufacturing the Paper cellulose fibers and agglomerations of different thicknesses are used, which are stored on or in the finished paper. The differently thick cellulose fibers or agglomerations are dyed in the paper before being put into storage, and are then in the paper pulp, which itself can have a different color.
Die bisher angewendeten Methoden zur Herstellung gemusterter Papiere sind entweder aufwendig oder langsam in der Herstellungmethode, oder führen zu Papieren, die eine völlig andere Effektwirkung erzielen.The previously used methods for the production of patterned papers are either complex or slow to manufacture, or lead to papers that achieve a completely different effect.
In der EP 439 363 ist ein Papier offenbart, das ein Entleimungsmittel enthält, oder damit beschichtet ist, wodurch eine bessere Aufnahme der Tinte beim Bedrucken des Papiers mittels Inkjet-Drucks erreicht wird. Das Entleimungsmittel ist in / auf diesem Papier gleichmäßig auf der gesamten Papierfläche verteilt, um ein optimales Druckergebnis zu erhalten.EP 439 363 discloses a paper containing a sizing agent contains, or is coated with, thereby better absorption of the Ink is reached when printing on the paper by means of inkjet printing. The sizing agent is even on the paper distributed over the entire paper surface in order to achieve an optimal printing result receive.
EP 518 490 beschreibt Tinte, die für den Inkjet-Druck Verwendung findet, wobei die Tinte ein Mittel enthält, die das Eindringen der Tinte in das bedruckte Papier erleichtert.EP 518 490 describes ink which is used for inkjet printing, wherein the ink contains an agent which prevents the ink from penetrating into the printed paper relieved.
Den Lehren von EP 439 363 und EP 518 490 ist gemeinsam, dass das Eindringen von polaren Flüssigkeiten wie Inkjet-Tinten in das Papiergefüge und in die Papierfasern von geleimten Papieren durch die geeignete Anwendung von Entleimungsmitteln erleichtert wird. Weder die EP 439 363 noch die EP 518 490 beschreibt jedoch die Herstellung gemusterter Papiere durch uneinheitliche Färbung der Papieroberfläche.The teachings of EP 439 363 and EP 518 490 have in common that the Penetration of polar liquids such as inkjet inks into it Paper structure and in the paper fibers of glued papers through the appropriate application of sizing agents is facilitated. Neither that However, EP 439 363 and EP 518 490 describe the production patterned papers due to inconsistent coloring of the paper surface.
Aufgabe der vorliegenden Erfindung war es, mit möglichst geringem Herstellungsaufwand ein optisch ansprechendes Papier ungleichmäßiger Färbung zu erhalten.The object of the present invention was to have the lowest possible Manufacturing effort a visually appealing paper uneven Get coloring.
Diese Aufgabe wird gelöst durch ein Verfahren zur Herstellung von
uneinheitlich intensiv gefärbtem Papier, umfassend
Die Erfindung macht sich das Phänomen der Papierleimung und die Möglichkeit, diese gezielt in bevorzugten Bereichen auf der Papierbahn durch Aufbringen von geeigneten Stoffen nachträglich zu manipulieren, zunutze. Papiere sind in der Regel geleimt zu dem Zweck, eine übermäßige Penetration von aufgebrachten Flüssigkeiten in das Papiergefüge und in die Fasern (Löschblatteffekt) zu vermeiden. Dies wird während der Papierherstellung bewirkt durch Hinzufügen von Leimungssubstanzen in den wässrigen Papierfaserbrei bevor dieser in der Papiermaschine zu einer Papierbahn geformt wird. Die Leimungssubstanzen werden auf die Fasern niedergeschlagen in dem Maße, wie die Eigenschaft des fertigen trockenen Papieres erwünscht ist, Flüssigkeiten aufnehmen zu können. Dieses Verfahren ist bekannt als interne Leimung oder Masseleimung. Das erreichte Maß, Flüssigkeiten aufnehmen zu können, ist umgekehrt proportional zum "internen Leimungsgrad" des Papiers.The invention addresses the phenomenon of paper sizing and Possibility of targeting these in preferred areas on the paper web subsequently manipulated by applying suitable substances, advantage. Papers are usually sized for the purpose of being excessive Penetration of applied liquids in the paper structure and in to avoid the fibers (blotting paper effect). This will be during the Papermaking is accomplished by adding sizing substances to the aqueous paper pulp before it turns into a paper machine Paper web is formed. The sizing substances are applied to the fibers dejected to the extent that the property of the finished dry Paper is desirable to be able to absorb liquids. This The process is known as internal sizing or mass sizing. The The degree to which liquids can be absorbed is reversed proportional to the "internal degree of sizing" of the paper.
Oberflächenleimung kann anstatt oder zusätzlich zur Masseleimung durchgeführt werden. Dabei werden filmbildende Substanzen wie Lösungen oder Dispersionen von konvertierten Stärken, Gums und modifizierten Polymeren auf die bereits geformte Papierbahn z.B. mittels Leimpressen innerhalb der Papiermaschine aufgebracht. Die Oberflächenleimung liefert auch einen Festigkeitsbeitrag für das Papier, so daß hochwertiges Druckpapier häufig Masse- und Oberflächenleimung aufweist. Das Vorliegen einer Oberflächenleimung ist für das vorgestellte erfindungsgemäße Verfahren jedoch nicht zwingend, es kann auch Papier verwendet werden, das keine Oberflächenleimung aufweist. Surface sizing can be used instead of or in addition to mass sizing be performed. Film-forming substances are like solutions or dispersions of converted starches, gums and modified Polymers onto the already formed paper web e.g. using size presses applied within the paper machine. The surface sizing delivers also a strength contribution for the paper, so that high quality Printing paper often has mass and surface sizing. The existence a surface sizing is for the presented invention However, the procedure is not mandatory, paper can also be used, that has no surface sizing.
Alternativ kann das Verfahren zur Herstellung von uneinheitlich intensiv gefärbtem Papier in Schritt a) das Auftragen einer Farbstofflösung in Form eines sichtbaren Bildes oder Musters auf Papier umfassen.Alternatively, the process of producing non-uniformly intense colored paper in step a) applying a dye solution in Include the form of a visible image or pattern on paper.
Die bevorzugten Ausführungsformen der Erfindung sind in den Unteransprüchen angegeben.The preferred embodiments of the invention are shown in FIGS Subclaims specified.
Das erfindungsgemäße Herstellungsverfahren führt zu einem Papier, das vollflächig gefärbt ist, wobei die Intensität der Färbung innerhalb der Papieroberfläche unterschiedlich ist. Durch die unterschiedliche Intensität der Färbung wird ein optischer Effekt erzielt, der dem Auge als Bild oder Muster erscheint.The manufacturing method according to the invention leads to a paper that is colored throughout, the intensity of the color within the Paper surface is different. Because of the different Intensity of coloring creates an optical effect on the eye appears as a picture or pattern.
Dabei kann das Bild oder Muster in Form einer darstellenden Abbildung, eines Phantasiegebildes, eines Schriftzugs, eines regelmäßigen oder unregelmäßigen Musters, einer Netzstruktur, oder auch einer unregelmäßigen, z.B. statistischen Verteilung der Farbe auf dem Papier vorliegen.The image or pattern can be in the form of a representative illustration, a fantasy, a lettering, a regular or irregular pattern, a network structure, or one irregular, e.g. statistical distribution of color on paper available.
Das Auftragen des Bildes oder Musters kann entweder direkt nach der Papierherstellung, also auf das noch feuchte Papier, oder auf ein zuvor hergestelltes, getrocknetes Papier erfolgen, wobei das Papier anschließend mittels einer wässrigen Farbstofflösung vollflächig gefärbt wird. Das Bild oder Muster kann auf eine laufende Papierbahn, oder auf einzelne Papierbögen aufgetragen werden. Bevorzugt wird das Bild oder Muster auf eine laufende Papierbahn aufgetragen.The application of the picture or pattern can be done either directly after the Papermaking, i.e. on the still damp paper, or on a previous one made, dried paper take place, the paper then colored over the entire surface using an aqueous dye solution becomes. The picture or pattern can be on a running paper web, or on individual sheets of paper can be applied. The image or is preferred Pattern applied to a running paper web.
Das Auftragen des Bildes oder Musters kann mit jeder beliebigen Methode erfolgen, insbesondere mittels Inkjet-Druck, Offset-Druck, Flexo-Druck, Tiefdruck, Bedrucken mit Filz- oder Gummiwalzen, durch Aufsprühen oder auch per Hand, wobei letztere Methode für die industrielle Fertigung nicht geeignet ist. Besonders bevorzugte Auftragungsmethoden für das Bild oder Muster ist der Auftrag mittels Inkjet- Druck, Flexodruck oder Tiefdruck.Applying the picture or pattern can be done by any method take place, in particular by means of inkjet printing, offset printing, flexographic printing, Gravure printing, printing with felt or rubber rollers, by spraying or also by hand, the latter method for industrial manufacturing is not suitable. Particularly preferred methods of application for the The image or sample is the order using inkjet printing, flexographic printing or Gravure printing.
Das Muster oder Bild wird entweder in Form eines latenten Bildes oder Musters oder in Form eines sichtbaren Bildes oder Musters auf das Papier aufgetragen.The pattern or image is either in the form of a latent image or Pattern or in the form of a visible image or pattern on the paper applied.
Für die Erstellung eines latenten Bildes oder Musters wird auf das Papier ein Stoff aufgetragen, der das Eindringen einer wäßrigen Farbstofflösung in das Papier an der Stelle, an der der Stoff aufgetragen ist, beeinflußt, indem er die Aufnahme entweder erleichtert, oder verringert.To create a latent image or pattern, click on the Paper applied a substance that prevents the penetration of an aqueous Dye solution in the paper at the point where the fabric is affected by either facilitating the absorption, or reduced.
Dies wird dadurch erreicht, dass der mit der Papierleimung erreichte Leimungs- oder Hydrophobierungsgrad durch den aufgetragenen Stoff abgeschwächt (Entleimungsmittel) oder verstärkt (Hydrophobierungsmittel) wird.This is achieved by using paper sizing Degree of sizing or hydrophobization by the applied material weakened (sizing agent) or reinforced (water repellent) becomes.
Jeder Stoff, der diese Eigenschaft aufweist, kann für das erfindungsgemäße Verfahren verwendet werden. Bevorzugt werden hierfür Tenside verwendet. Es können anionische, kationische, nicht-ionische oder amphothere Tenside eingesetzt werden. Zusätzlich zu den Tensiden können Stoffe eingesetzt werden, die das Eindringen von Farbstoffen in das Papier erleichtern. Solche Stoffe sind beispielsweise Glycolether wie Ethylenglycolmonomethylether, Ethylenglycolmonoethylether, Ethylenglycolmonophenylether, Diethylenglycolmonomethylether, Diethylenglycolmonoethylether und Diethylenglycolmonobutylether.Any substance that has this property can be used for inventive methods are used. Are preferred for this Surfactants used. It can be anionic, cationic, non-ionic or amphoteric surfactants can be used. In addition to the surfactants can be used to prevent the penetration of dyes into to lighten the paper. Such substances are, for example, glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monophenyl ether, Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol monobutyl ether.
Geeignete entleimende Tenside können beispielsweise ausgewählt sein aus (1) hydrophilen Polydialkylsiloxanen, (2) Polyalkylenglycol, (3) Polypropylenoxid-Polyethylenoxid-Copolymeren, (4) Fettsäureestermodifizierten Verbindungen von Phosphat, Sorbitan, Glycerin, Polyethylenglycol, Sulfosuccinsäuren, Sulfonsäure oder Alkylamin, (5) Polyoxialkylen-modifizierten Verbindungen von Sorbitanestern, Fettaminen, Alkanolamiden, Rizinusöl, Fettsäure, Fettalkohol, (6) quarternären Alkoholsulfat-Verbindungen, (7) Fettimidazolinen, (8) polyethermodifizierten Trisiloxanen und (9) Mischungen davon.Suitable desizing agents can be selected from, for example (1) hydrophilic polydialkylsiloxanes, (2) polyalkylene glycol, (3) Polypropylene oxide-polyethylene oxide copolymers, (4) fatty acid ester modified Compounds of phosphate, sorbitan, glycerin, Polyethylene glycol, sulfosuccinic acids, sulfonic acid or alkylamine, (5) Polyoxyalkylene-modified compounds of sorbitan esters, Fatty amines, alkanolamides, castor oil, fatty acid, fatty alcohol, (6) quaternary alcohol sulfate compounds, (7) fatty imidazolines, (8) polyether modified trisiloxanes and (9) mixtures thereof.
Spezifische Beispiele für wasser- oder alkohollösliche Entleimungsmittel aus den oben genannten Stoffklassen sind zum Beispiel (1) Poly(oxyalkylen)modifikationen von (a) Sorbitanestern (z.B. Alkamuls PSML-4 (Poly(oxyethylen)sorbitanmonolaurat), Alkamuls PSMO-20 (Poly-(oxyethylen)sorbitanmonooleat), Alkamuls PSTO-20 (Poly(oxyethylen)-sorbitantrioleat), Alkaril Chemicals); (b) Fettamine (z.B. Alkaminox T-2, T-5 (Talgaminoxyethylat), Alkaminox SO-5(Sojaaminoxyethylat), Alkaril Chemicals), (Icomeen T-2, Icomeen T-15, ICI Chemicals); (c) Rizinusöl (z.B. Alkasurf C0-10, Alkasurf CO-25B (Rizinusöloxyethylate), Alkaril Chemicals); (d) Alkanolamid (z.B. Alkamide C-2, C-5 (Koskosnußölalkanolamidoxethylate). Alkaril Chemicals); (e) Fettsäuren (z.B. Alkasurf 075-9, Alkasurf 0-10, Alkasurf 0-14 (Ölsäureoxyethylate), Alkasurf L-14 (Laurinsäureoxyethylate), Alkasurf P-7 (Palmitinsäureoxyethylate) Alkaril Chemicals); (f) Fettsäurealkohol (z.B. Alkasurf LAN-1, LAN-3, Alksasurf TDA-6, Alkasurf SA-2, (lineare Alkoholoxyethylate), Alkasurf NP-1, NP-11, Rexol 130 (Nonylphenoloxyethylate), Alkasurf OP-1, OP-12 (Octylphenoloxyethylate), Alkasurf LA-EP-15, Alkasurf LA-EP-25, Alkasurf LA-EP-65 (lineare Alkoholoxyalkylate)); (2) hydrophile Poly(dimethylsiloxane) wie etwa (a) mit einer Monocarbinolendgruppe versehenes Poly(dimethlysiloxan) (PS558, Petrarch Systems Inc.) und Dicarbinolendgruppe versehenes Poly(dimethylsiloxan) (PS555, PS556, Petrarch Systems Inc.); (b) Poly(dimethylsiloxan)-b-Poly(methylsiloxanalkylenoxid)-Copolymere (PS 073, PS 072, PS 071, Petrarch Systems Inc.), Alkasil HEP 182-280, Alkasil HEP 148-330 (Alkaril Chemicals), nichthydrolysierbare, Si-C-Bindungen enthaltende Copolymere; (c) Poly(dimethylsiloxan)-b-Poly(propylenoxid)-b-Poly(ethylenoxid)-Copolymere (Alkasil NEP 73-70, Alkaril Chemicals) ein hydrolisierbares, Si-0-C-Bindungen enthaltendes Copolymer; (d) polyquaternäre Poly(dimethylsiloxan)-Copolymere (die durch die Additionsreaktion eines α,ω-Wasserstoffpolysiloxans mit olefinische Bindungen enthaltenden Epoxiden und anschließend Umsetzen des Produkts mit einem Diamin erhalten werden können); (3) Fettimidazoline und ihre Derivate wie etwa (a) Alkazine-0 (Oleylderivat); (b) Alkazine TO (Tallölderivate); (c) Alkateric 2C1B (Dicarbonsäurekokosimidazolin-natriumsalz) Alkaril Chemicals; (d) Arzoline-4; (e) Arzoline-215, Baker Chemicals; (4) Fettsäureester von (a) Phosphaten (z.B. Alkaphos B6-56A, Alkaril Chemicals); (b) Sorbitan (z.B. Alkamuls STO (Sorbitantrioleat), Alkamuls SML (Sorbitanmonolaurat), Alkamuls SMO (Sorbitanmonooleat), Alkaril Chemicals); (c) Glycerinverbindungen (z.B. Alkamuls GMO-45LG (Glycerylmonooleat), Alkamuls GDO (Glyceryldioleat), Alkamuls GTO (Glyceryltrioleat); (d) Poly(ethylenglykole) (Alkamuls 600 DO (Dioleat), Alkamuls 400-ML (Monolaurat), Alkamuls 600 MO (Monooleat), Alkamuls 600 DL (Dilaurat), Alkamuls 600 DT (Ditalg), Alkaril Chemicals); (e) Sulfobernsteinsäure (z.B. Alkasurf SS-0-75 (Natriumdioctyl-sulfosuccinat), Alkasurf SS-DA4-HE (oxyethyliertes Alkoholsulfosuccinat), Alkasurf SS-L7DE (Natriumsulfosuccinatester von Laurindiethanolamid), Alkasurf SS-L-HE (Natriumlaurylsulfosuccinat), Alkaril Chemicals); (f) Sulfonsäure (z.B. Alkasurf CA (Calciumdodecylbenzolsulfonat), Alkasurf IPAM (Isopropylamindodecylbenzolsulfonat). Alkaril Chemicals); (g) Alkylamine (z.B. Alkamide SDO (Sojadiethanolamid), Alkamide CDE (Kokosdiethanolamid), Alkamide 2104 (Kokosnußfettsäurediethanolamid), Alkamide CMA (Kokosmonoethanolamid), Alkamide L9DE (Lauryldiethanolamid), Alkamide L7Me (Laurylmonoethanolamid), Alkamide L1PA (Laurylmonoisopropylamid), Alkaril Chemicals); (5) quaternäre Verbindungen wie etwa (a) nicht-polymeres quaternäres Ammoniumethosulfat (z.B. Finquat CT, Cordex T-172, Finetex Corporation); (b) quaternäres Dialkyldimethylmethosulfat (z.B. Alkaquat DHTS (hydrierter Talg)); (c) alkoxyliertes quaternäres Difettmethosulfat (z.B. Alkasurf DAET (Talgderivat)); (d) quaternäres Fettidazolinmethosulfat (z.B. Alkaquat T (Talgderivate), Alkaril Chemicals); (6) wasserlösliche Copolymere lipophilen Poly(propylenoxids) mit hydrophilem Poly-(ethylenoxid) wie etwa (a) methanollösliches Tetronic 150R1, Pluronic L-101, Tetronic 902, Tetronic 25R2 (BASF Corporation), Alkatronic EGE-1 (Alkaril Chemicals); (b) wasserlösliches Tetronic 908, 50R8, 25R8, 904, 90R4, Pluronic F-77, alle von BASF Corporation, und Alkatronic EGE 25-2 und PGP 33-8 von Alkaril Chemicals; (7) Poly(alkylenglykol) und seine Derivate wie etwa (a) Polypropylenglykol (Alkapol PPG 425, Alkapol PPG-4000, Alkaril Chemicals); (b) Poly(propylenglykoldimethacrylat), Poly-(ethylenglykoldiacrylat), Poly(ethylenglykoldimethacrylat), Poly-(ethylenglykolmonomethylether), Poly(ethylenglykoldimethylether), Poly-(ethylenglykoldiglycidylether) (alle von Polysciences); (c) Poly(1,4-oxybutylenglykol) (Scientific Polymer Products) und dergleichen ein.Specific examples of water or alcohol soluble sizing agents from the above-mentioned classes of substances are, for example (1) Poly (oxyalkylene) modifications of (a) sorbitan esters (e.g. alkamuls PSML-4 (poly (oxyethylene) sorbitan monolaurate), Alkamuls PSMO-20 (poly (oxyethylene) sorbitan monooleate), Alkamuls PSTO-20 (poly (oxyethylene) sorbitan trioleate), Alkaril Chemicals); (b) fatty amines (e.g. Alkaminox T-2, T-5 (tallow amine oxyethylate), Alkaminox SO-5 (soy amine oxyethylate), Alkaril Chemicals), (Icomeen T-2, Icomeen T-15, ICI Chemicals); (c) castor oil (e.g. Alkasurf C0-10, Alkasurf CO-25B (castor oil oxyethylate), Alkaril Chemicals); (d) Alkanolamide (e.g. alkamides C-2, C-5 (coconut oil alkanolamide oxyethylates). Alkaril Chemicals); (e) fatty acids (e.g. Alkasurf 075-9, Alkasurf 0-10, Alkasurf 0-14 (oleic acid oxyethylates), Alkasurf L-14 (Lauric acid oxyethylate), Alkasurf P-7 (palmitic acid oxyethylate) Alkaril Chemicals); (f) fatty acid alcohol (e.g. Alkasurf LAN-1, LAN-3, Alksasurf TDA-6, Alkasurf SA-2, (linear alcohol oxyethylates), Alkasurf NP-1, NP-11, Rexol 130 (nonylphenoloxyethylate), Alkasurf OP-1, OP-12 (Octylphenoloxyethylate), Alkasurf LA-EP-15, Alkasurf LA-EP-25, Alkasurf LA-EP-65 (linear alcohol oxyalkylates); (2) hydrophilic Poly (dimethylsiloxanes) such as (a) having a monocarbinol end group provided poly (dimethsiloxane) (PS558, Petrarch Systems Inc.) and Dicarbinol terminated poly (dimethylsiloxane) (PS555, PS556, Petrarch Systems Inc.); (b) Poly (dimethylsiloxane) -b-poly (methylsiloxane alkylene oxide) copolymers (PS 073, PS 072, PS 071, Petrarch Systems Inc.), Alkasil HEP 182-280, Alkasil HEP 148-330 (Alkaril Chemicals), non-hydrolyzable copolymers containing Si-C bonds; (C) Poly (dimethylsiloxane) -b-poly (propylene oxide) -b-poly (ethylene oxide) copolymers, (Alkasil NEP 73-70, Alkaril Chemicals) a hydrolyzable, Si-0-C bonds containing copolymer; (d) polyquaternary poly (dimethylsiloxane) copolymers (by the addition reaction of an α, ω-hydrogen polysiloxane with epoxides containing olefinic bonds and then reacting the product with a diamine can be obtained can); (3) fatty imidazolines and their derivatives such as (a) alkazine-0 (Oleyl derivative); (b) Alkazine TO (tall oil derivatives); (c) Alkateric 2C1B (Dicarboxylic acid cocosimidazoline sodium salt) Alkaril Chemicals; (D) Arzoline-4; (e) Arzoline-215, Baker Chemicals; (4) fatty acid esters of (a) phosphates (e.g. Alkaphos B6-56A, Alkaril Chemicals); (b) Sorbitan (e.g. Alkamuls STO (sorbitan trioleate), Alkamuls SML (sorbitan monolaurate), Alkamuls SMO (Sorbitan Monooleate, Alkaril Chemicals); (C) Glycerin compounds (e.g. Alkamuls GMO-45LG (glyceryl monooleate), Alkamuls GDO (glyceryl dioleate), Alkamuls GTO (glyceryl trioleate); (D) Poly (ethylene glycols) (Alkamuls 600 DO (dioleate), Alkamuls 400-ML (monolaurate), Alkamuls 600 MO (monooleate), Alkamuls 600 DL (dilaurate), Alkamuls 600 DT (Ditalg), Alkaril Chemicals); (e) sulfosuccinic acid (e.g. Alkasurf SS-0-75 (sodium dioctyl sulfosuccinate), Alkasurf SS-DA4-HE (oxyethylated alcohol sulfosuccinate), Alkasurf SS-L7DE (sodium sulfosuccinate ester from Laurindiethanolamide), Alkasurf SS-L-HE (sodium lauryl sulfosuccinate), Alkaril Chemicals); (f) sulfonic acid (e.g. alkasurf CA (calcium dodecylbenzenesulfonate), Alkasurf IPAM (isopropylamine dodecylbenzenesulfonate). Alkaril Chemicals); (g) alkylamines (e.g. alkamides SDO (Soy diethanolamide), alkamides CDE (coconut diethanolamide), alkamides 2104 (Coconut fatty acid diethanolamide), alkamides CMA (coconut monoethanolamide), Alkamides L9DE (lauryldiethanolamide), alkamides L7Me (laurylmonoethanolamide), Alkamides L1PA (lauryl monoisopropylamide), Alkaril Chemicals); (5) quaternary compounds such as (a) non-polymeric quaternary Ammonium ethosulfate (e.g. Finquat CT, Cordex T-172, Finetex Corporation); (b) quaternary dialkyldimethyl methosulfate (e.g. Alkaquat DHTS (hydrogenated tallow)); (c) alkoxylated quaternary difatty methosulfate (e.g. Alkasurf DAET (tallow derivative)); (d) quaternary fatty idazoline methosulfate (e.g. Alkaquat T (tallow derivatives), Alkaril Chemicals); (6) water soluble Copolymers of lipophilic poly (propylene oxide) with hydrophilic poly (ethylene oxide) such as (a) methanol-soluble Tetronic 150R1, Pluronic L-101, Tetronic 902, Tetronic 25R2 (BASF Corporation), Alkatronic EGE-1 (Alkaril Chemicals); (b) water soluble Tetronic 908, 50R8, 25R8, 904, 90R4, Pluronic F-77, all from BASF Corporation, and Alkatronic EGE 25-2 and PGP 33-8 from Alkaril Chemicals; (7) poly (alkylene glycol) and its Derivatives such as (a) polypropylene glycol (Alkapol PPG 425, Alkapol PPG-4000, Alkaril Chemicals); (b) poly (propylene glycol dimethacrylate), poly (ethylene glycol diacrylate), Poly (ethylene glycol dimethacrylate), poly (ethylene glycol monomethyl ether), Poly (ethylene glycol dimethyl ether), poly (ethylene glycol diglycidyl ether) (all from Polysciences); (c) poly (1,4-oxybutylene glycol) (Scientific Polymer Products) and the like.
Bevorzugte Entleimungsmittel schließen lineare Alkoholoxyethylate (z.B. von Alkaril Chemicals erhältliches Alkasurf LA-EP-65, LA-EP-25 und LA-EP-15), Nonylphenoloxyethylate (z.B. von Alkaril Chemicals erhältliches Alkasurf NP-11 und von Hart Chemicals erhältliches Rexol 130), Octylphenoloxyethylate (z.b. von Alkaril Chemicals erhältliches Alkasurf OP-12), Ölsäureoxyethylate (z.B. von Alkaril Chemicals erhältliches Alkasurf 0-14), Poly(dimethylsiloxan)-b-Poly(propylenoxid)-b-Poly-(ethylenoxid)-Copolymere (z.B. von Alkaril Chemicals erhältliches Alkasil NEP 73-70), Rizinusöloxyethylate (z.B. von Alkaril Chemicals erhältliches Alkasurf C025B), Kokosimidazolindicarbonsäurenatriumsalze (z.B. von Alkaril Chemicals erhältliches Alkateric 2C1B) und Kokosnußfettsäurediethanolamid (z.B. von Alkaril Chemicals erhältliches Alkamid S104) ein. Die Alkasurf-Entleimungsmittel sind vorteilhafterweise bioabbaubar.Preferred sizing agents include linear alcohol oxyethylates (e.g. Alkasurf LA-EP-65, LA-EP-25 and LA-EP-15) available from Alkaril Chemicals, Nonylphenoloxyethylates (e.g. available from Alkaril Chemicals Alkasurf NP-11 and Rexol 130) available from Hart Chemicals, Octylphenoloxyethylate (e.g. Alkasurf available from Alkaril Chemicals OP-12), oleic acid oxyethylates (e.g. available from Alkaril Chemicals Alkasurf 0-14), poly (dimethylsiloxane) -b-poly (propylene oxide) -b-poly (ethylene oxide) copolymers (e.g. available from Alkaril Chemicals Alkasil NEP 73-70), castor oil oxyethylate (e.g. from Alkaril Chemicals available Alkasurf C025B), cocosimidazoline dicarboxylic acid sodium salts (e.g. Alkateric 2C1B available from Alkaril Chemicals) and Coconut fatty acid diethanolamide (e.g. available from Alkaril Chemicals Alkamide S104). The Alkasurf sizing agents are advantageous biodegradable.
Geeignete hyrophobierende Tenside sind beispielsweise Papierleimungsmittel wie Alkylbernsteinsäureanhydrid (ASA), Alkylketendimer (AKD), sowie Polyolefine (z.B. SÜDRANOL 200, Süddeutsche Emulsions-Chemie GmbH, Mannheim, Deutschland), Wachse, wachsartige Stoffe, Metallseifen (Stearate), Paraffin und Paraffinemulsionen, Fettsäuren, Fettsäure(methyl)ester, Fettalkohole, Fettalkoholpolyglycolether und deren Sulfate.Suitable hydrophobic surfactants are, for example, paper sizing agents such as alkyl succinic anhydride (ASA), alkyl ketene dimer (AKD), as well as polyolefins (e.g. SÜDRANOL 200, Süddeutsche Emulsions-Chemie GmbH, Mannheim, Germany), waxes, waxy substances, Metal soaps (stearates), paraffin and paraffin emulsions, fatty acids, Fatty acid (methyl) esters, fatty alcohols, fatty alcohol polyglycol ethers and their sulfates.
Die Tenside liegen beim Auftragen auf das Papier in Form von Lösungen, Emulsionen oder Dispersionen vor, die neben den Tensiden weitere Hilfsstoffe enthalten können. Übliche Hilfsstoffe sind Verdicker, wie z.B. Gummi arabicum, Polyacrylate, Polymethacrylate, Polyvinylalkohole, Hydroxypropylcellulose, Hydroxyethylcellulose, Polyvinylpyrrolidon, Polyvinylether, Stärke, Polysaccharide, und ähnliche, optische Aufheller, Aufheller-Löscher, Pigmente, Bindemittel, Konservierungsstoffe und Sicherheits-Chemikalien, wie z.B. fluoreszierende, phosphoreszierende oder lumineszierende Stoffe. Bevorzugt liegen die Tenside als wässrige oder alkoholische Lösung vor.When applied to the paper, the surfactants are in the form of solutions, Emulsions or dispersions in addition to the surfactants Can contain auxiliaries. Common auxiliaries are thickeners, such as e.g. Gum arabic, polyacrylates, polymethacrylates, polyvinyl alcohols, Hydroxypropyl cellulose, hydroxyethyl cellulose, polyvinyl pyrrolidone, Polyvinyl ether, starch, polysaccharides, and similar optical brighteners, Brightener-extinguishers, pigments, binders, preservatives and safety chemicals such as fluorescent, phosphorescent or luminescent substances. The surfactants are preferably as aqueous or alcoholic solution.
Die Konzentrationsbereiche für die Tenside in den aufzubringenden Lösungen, Emulsionen oder Dispersionen liegen bei 0,01 bis 30 Gew%, bevorzugt bei 0,1 bis 25 Gew%, besonders bevorzugt im Bereich von 0,2 bis 15 Gew%.The concentration ranges for the surfactants in the applied Solutions, emulsions or dispersions are 0.01 to 30% by weight, preferably 0.1 to 25% by weight, particularly preferably in the range of 0.2 up to 15% by weight.
Die Konzentrationen von Verdickern, die als Tensid-Hilfsstoffe verwendbar sind, liegen im Bereich von 0 bis 5 Gew%, bevorzugt bei 0,01 bis 2,5 Gew%, besonders bevorzugt bei 0,05 bis 2,5 Gew% der gesamten Lösung, Emulsion oder Dispersion.The concentrations of thickeners that act as surfactant adjuvants usable are in the range from 0 to 5% by weight, preferably 0.01 to 2.5% by weight, particularly preferably 0.05 to 2.5% by weight of the total Solution, emulsion or dispersion.
Um einen weiteren besonderen Effekt auf dem fertigen Papier zu erzielen, können auch entleimende und hydrophobierende Tenside nebeneinander auf derselben Papieroberfläche aufgetragen werden.To achieve another special effect on the finished paper, can also have gluing and hydrophobizing surfactants side by side same paper surface.
Für die Erstellung eines sichtbaren Bildes oder Musters kann jede beliebige Farbstofflösung verwendet werden. Bevorzugt wird eine wäßrige Lösung substantiver, basischer oder saurer Farbstoffe verwendet, oder Mischungen dieser Farbstoffe. Beispiele für geeignete Farbstofflösungen sind übliche Druckertinten, die z.B. Anthraquinon-, Monoazo-, Disazo-, Phthalocyanin-, Aza-(18)-Annulen- und Formazan-Kupfer-Komplex-Farbstoffe enthalten. Beispiele für geeignete Farbstoffe sind solche, wie sie weiter unten für die Farbstofflösung des Färbebads genannt sind.Anyone can create a visible image or pattern any dye solution can be used. An aqueous one is preferred Solution of substantive, basic or acidic dyes used, or Mixtures of these dyes. Examples of suitable dye solutions are common printer inks, e.g. Anthraquinone, monoazo, disazo, Phthalocyanine, aza (18) annulene and formazan copper complex dyes contain. Examples of suitable dyes are those such as are mentioned below for the dye solution of the dye bath.
Die Konzentrationsbereiche der Farbstoffe liegen bei 0,1 bis 30 Gew%, bevorzugt bei 1,0 bis 20 Gew% besonders bevorzugt bei 2,0 bis 10 Gew%.The concentration ranges of the dyes are 0.1 to 30% by weight, preferably at 1.0 to 20% by weight, particularly preferably at 2.0 to 10% by weight.
Das latente oder sichtbare Bild oder Muster kann einseitig oder von beiden Seiten auf das Papier aufgetragen werden, so daß das fertiggestellte Papier wenigstens auf einer Seite eine Färbung aufweist, die intensiver, bzw. weniger intensiv ist als in den unbehandelten Bereichen der Papieroberfläche(n).The latent or visible image or pattern can be one-sided or from both sides are applied to the paper so that the finished paper has a color on at least one side, which is more intense or less intense than in the untreated ones Areas of the paper surface (s).
Nach dem Aufbringen des latenten oder sichtbaren Bildes oder Musters auf das Papier wird das Papier in Schritt (b) mit Hilfe einer Farbstofflösung vollständig eingefärbt. Diese Färbung erfolgt flächendeckend entweder innerhalb oder außerhalb der Papiermaschine durch Auftragen von Farbstofflösung(en) auf das Papier mittels klassischer Papierstreichvorrichtungen und -verfahren, wie z.B. Leimpresse, Filmpresse, Rakel, Blade, Walzen oder Sprühen oder durch flächendeckenden Auftrag einer Farbstofflösung auf das Papier mit Hilfe geeigneter Druckmethoden wie Inkjet-Druck, Offset-Druck, Flexo-Druck, Tiefdruck, Bedrucken mit Filz- oder Gummiwalzen, durch Aufsprühen oder durch Tauchfärbung des Papiers in einem Färbebad. Bevorzugt wird das Papier im Tauchverfahren in einer wäßrigen Farbstofflösung gefärbt.After applying the latent or visible image or pattern the paper becomes the paper in step (b) using a Dye solution completely colored. This coloring is done nationwide either inside or outside the paper machine by applying dye solution (s) to the paper using classic paper coating devices and processes, e.g. size press, Film press, squeegee, blade, roller or spray or through widespread application of a dye solution on the paper with the help suitable printing methods such as inkjet printing, offset printing, flexographic printing, Gravure printing, printing with felt or rubber rollers, by spraying or by dipping the paper in a dye bath. This is preferred Dyed paper in an aqueous dye solution.
Jede für diese Zwecke kommerziell erhältliche Farbstofflösung kann in der vorliegenden Erfindung verwendet werden. Die Farbstofflösung enthält die Farbstoffe üblicherweise in Konzentrationsbereichen von 0,1 bis 40 Gew%, bevorzugt 0,1 bis 35 Gew%, ganz besonders bevorzugt von 0,1 bis 30 Gew%. Die Konzentration der Farbstofflösung kann je nach individuell gewünschtem zu erzielendem Effekt (Intensität des später gewünschten Bildes) eingestellt werden. Entsprechende Versuche kann jeder Fachmann durch einfaches Austesten durchführen.Any dye solution commercially available for these purposes can be found in of the present invention. The dye solution contains the dyes usually in concentration ranges from 0.1 to 40 % By weight, preferably 0.1 to 35% by weight, very particularly preferably from 0.1 to 30 Wt%. The concentration of the dye solution can vary depending on the individual desired effect to be achieved (intensity of the later desired Picture) can be set. Any specialist can carry out appropriate tests by simply testing.
Bei dem Tauchverfahren wird das Papier nach dem Auftrag des latenten oder sichtbaren Bildes oder Musters in eine wäßrige Farbstofflösung eingetaucht, anschließend abgepreßt und getrocknet. Die Tauchfärbung kann mit geleimten oder ungeleimten Papierbahnen oder Papierbögen durchgeführt werden. Durch die Tauchfärbung ist es möglich, satte Färbungen höchster Leuchtkraft zu erhalten. Ein weiterer Vorteil dieser Methode ist, daß auch kleine Mengen gefärbt werden können, ohne dabei unrationell zu arbeiten.In the immersion process, the paper is applied after the latent application or visible image or pattern in an aqueous dye solution immersed, then pressed and dried. The dip coloring can with glued or unsized paper webs or sheets be performed. The dip coloring makes it possible to get full Obtain colorations of the highest luminosity. Another advantage of this The method is that even small quantities can be dyed without doing so to work inefficiently.
Wurde vor der Färbung des Papiers ein latentes Bild aufgetragen, so nimmt das Papier während des Färbungsvorganges die Farbe an den vorbehandelten Stellen stärker, bzw. weniger stark an, je nachdem mit welchem Stoff das Papier vorbehandelt wurde.If a latent image was applied before the paper was colored, then so the paper takes on the color during the dyeing process pretreated areas more or less strongly, depending on with which substance the paper has been pretreated with.
Durch die stärkere Annahme der Farbe in Bereichen, die mit einem Entleimungsmittel vorbehandelt wurden, wird ein Papier erhalten, auf dem das zunächst latent aufgetragene Bild oder Muster in einem intensiveren Ton derselben Farbe erscheint, in der das gesamte Papier gefärbt ist. Somit kann die Farbintensität des später als "positiv" erscheinenden Bildes oder Musters durch die Auftragsmenge und / oder Zusammensetzung des aufgetragenen Entleimungsmittels variiert werden.Due to the stronger acceptance of the color in areas with a Sizing agents have been pretreated, a paper is obtained on which the initially latently applied image or pattern in a more intense Tone of the same color appears in which all the paper is colored. Thus, the color intensity of what later appears to be "positive" Image or pattern by the order quantity and / or composition of the applied sizing agent can be varied.
Wurde vor der Färbung des Papiers ein Hydrophobierungsmittel aufgetragen, erscheint das zunächst latent aufgetragene Bild oder Muster nach der Färbung des Papiers in einem weniger intensiven Farbton derselben Farbe, in dem das gesamte Papier gefärbt ist. Auch hier kann die Farbintensität des später als "negativ" erscheinenden Bildes oder Musters durch die Auftragsmenge und / oder Zusammensetzung des aufgetragenen Hydrophobierungsmittels variiert werden.Became a water repellent before staining the paper applied, the initially latently applied image or pattern appears after coloring the paper in a less intense shade the same color in which all the paper is colored. Here too the color intensity of the image that later appears to be "negative" or Pattern by the order quantity and / or composition of the applied hydrophobizing agent can be varied.
Zur Herstellung des latenten Bildes können auch entleimende und hydrophobierende Stoffe nebeneinander auf derselben Papieroberfläche aufgetragen werden, so daß das fertiggestellte Papier sowohl "positive", als auch "negative" Bilder oder Muster aufweist.To produce the latent image, gluing and Hydrophobic substances side by side on the same paper surface applied so that the finished paper is both "positive", as well as "negative" images or patterns.
Um einen der bislang beschriebenen Effekte zu erzielen, muß die Färbung des Papiers zwingend nach dem Auftragen des die Farbaufnahme beeinflussenden Stoffes erfolgen.In order to achieve one of the effects described so far, the coloring must of the paper is mandatory after applying the color picture influencing substance.
Wird vor der Färbung des Papiers ein sichtbares Bild oder Muster aufgetragen, intensiviert die anschließende Färbung des Papiers die Färbung des zuvor aufgebrachten Bildes oder Musters, so daß auch hierdurch ein besonderer Effekt, nämlich die ungleichmäßig intensive Färbung des Papiers erzielt werden kann. Dieser Effekt läßt sich nur erhalten, wenn das das sichtbare Bilde tragende Papier zusätzlich gefärbt wird.Becomes a visible image or pattern before coloring the paper applied, the subsequent coloring of the paper intensifies the Coloring of the previously applied image or pattern, so that also this has a special effect, namely the unevenly intense Coloring of the paper can be achieved. This effect can only be obtained if the paper bearing the visible image is additional is colored.
Für die Färbung des Papiers können übliche wässrige Farbstofflösungen verwendet werden. Diese können basische und / oder saure und / oder substantive Farbstoffe enthalten. Beispiele für geeignete Farbstofflösungen sind Lösungen, die Anthraquinon-, Monoazo-, Disazo-, Phthalocyanin-, Aza-(18)-Annulen- und Formazan-Kupfer-Komplex-Farbstoffe enthalten. Spezifische Beispiele für geeignete Farbstoffe sind in EP-A 559 324 auf S. 4, Zeilen 25 bis 53 aufgeführt. Dies sind insbesondere Triphenodioxazine, Bernacid Red 2BMN; Pontamine Brilliant Bond Blue A; Pontamine; Food Black 2; Carodirect Turquoise FBL Supra Conc. (Direct Blue 199), erhältlich von Carolina Color and Chemical; Special Fast Turquoise 8GL Liquid (Direct Blue 86), erhältlich von Mobay Chemical; Intrabond Liquid Turquoise GLL (Direct Blue 86), erhältlich von Crompton and Knowles; Cibracron Brilliant Red 38-A (Reactive Red 4), erhältlich von Aldrich Chemical; Drimarene Brilliant Red X-2B (Reactive Red 56), erhältlich von Pylam, Inc.; Levafix Brilliant Red E-4B, erhältlich von Mobay Chemical; Levafix Brilliant Red E-6BA, erhältlich von Mobay Chemical; Procion Red H8B (Reactive Red 31), erhältlich von ICI America; Pylam Certified D&C Red #28 (Acid Red 92), erhältlich von Pylam; Direct Brill Pink B Ground Crude, erhältlich von Crompton & Knowles; Cartasol Gelb GTF, erhältlich von Sandoz, Inc.; Tartrazine Extra Conc. (FD&C Gelb #5, Acid Yellow 23), erhältlich von Sandoz; Carodirect Yellow RL (Direct Yellow 86), erhältlich von Carolina Color and Chemical; Cartasol Yellow GTF Liquid Special 110, erhältlich von Sandoz, Inc.; D&C Yellow #10 (Acid Yellow 3), erhältlich von Tricon; Yellow Shade 16948, erhältlich von Tricon, Basacid Black X34, erhältlich von BASF, Carta Black 2GT, erhältlich von Sandoz, Inc.; Direct Brilliant Pink B (Crompton-Knolls); Kayanol Red 3BL (Nippon Kayaku Company); Levanol Brilliant Red 3BW (Mobay Chemical Company); Levaderm Lemon Yellow (Mobay Chemical Company); Spirit Fast Yellow 3G; Sirius Supra Yellow GD 167; Cartasol Brilliant Yellow 4GF (Sandoz); Pergasol Yellow CGP (Ciba-Geigy); Dermacarbon 2GT (Sandoz); Pyrazol Black BG (ICI); Morfast Black Conc A (Morton-Thiokol); Diazol Black RN Quad (ICI); Luxol Blue MBSN (Morton-Thiokol); Sevron Blue 5GMF (ICI); Basacid Blue 750 (BASF); Bernacid Red, erhältlich von Berncolors, Poughkeepsie, NY; Pontamine Brilliant Bond Blue; Berncolor A. Y. 34; Telon Fast Yellow 4GL-175; BASF Basacid Black SE 0228; die Pro-Jet Serien erhältlich von ICI, einschließlich 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 (direkt Black 168), Pro-Jet Yellow 1-G (Direct Yellow 132), Aminyl Brilliant Red F-B, erhältlich von Sumitomo Chemical Co. (Japan), die Duasyn Linie von "Salz-freien" Farbstoffen erhältlich von Hoechst, wie 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 Türkisblau FRL-SF VP368 (Direct Blue 199), Duasyn Acid Blue AE-SF VP344 (Acid Blue 9), und ähnliche, sowie Mischungen dieser Farbstoffe.Common aqueous dye solutions can be used to color the paper be used. These can be basic and / or acidic and / or contain substantive dyes. Examples of suitable ones Dye solutions are solutions that contain anthraquinone, monoazo, disazo, Phthalocyanine, aza (18) annulene and formazan copper complex dyes contain. Specific examples of suitable dyes are in EP-A 559 324 on p. 4, lines 25 to 53. These are in particular Triphenodioxazine, Bernacid Red 2BMN; Pontamine Brilliant Bond Blue A; Pontamine; Food black 2; Carodirect Turquoise FBL Supra Conc. (Direct Blue 199), available from Carolina Color and Chemical; Special Fast Turquoise 8GL Liquid (Direct Blue 86) available from Mobay Chemical; Intrabond Liquid Turquoise GLL (Direct Blue 86) available from Crompton and Knowles; Cibracron Brilliant Red 38-A (Reactive Red 4) available from Aldrich Chemical; Drimarene Brilliant Red X-2B (Reactive Red 56), available from Pylam, Inc .; Levafix Brilliant Red E-4B, available from Mobay Chemical; Levafix Brilliant Red E-6BA, available from Mobay Chemical; Procion Red H8B (Reactive Red 31) available from ICI America; Pylam Certified D&C Red # 28 (Acid Red 92), available from Pylam; Direct Brill Pink B Ground Crude, available from Crompton &Knowles; Cartasol Yellow GTF available from Sandoz, Inc .; Tartrazine Extra Conc. (FD&C yellow # 5, Acid Yellow 23) available from Sandoz; Carodirect Yellow RL (Direct Yellow 86), available from Carolina Color and Chemical; Cartasol Yellow GTF Liquid Special 110, available from Sandoz, Inc .; D&C Yellow # 10 (Acid Yellow 3) available from Tricon; Yellow Shade 16948 available from Tricon, Basacid Black X34, available from BASF, Carta Black 2GT, available from Sandoz, Inc .; Direct Brilliant Pink B (Crompton-Knolls); Kayanol Red 3BL (Nippon Kayaku Company); Levanol Brilliant Red 3BW (Mobay Chemical Company); Levaderm Lemon Yellow (Mobay Chemical Company); Spirit Fast Yellow 3G; Sirius Supra Yellow GD 167; Cartasol Brilliant Yellow 4GF (Sandoz); Pergasol Yellow CGP (Ciba-Geigy); Dermacarbon 2GT (Sandoz); Pyrazole black BG (ICI); Morfast Black Conc A (Morton-Thiokol); Diazol Black RN Quad (ICI); Luxol Blue MBSN (Morton-Thiokol); Sevron Blue 5GMF (ICI); Basacid Blue 750 (BASF); Bernacid Red, available from Berncolors, Poughkeepsie, NY; Pontamine Brilliant Bond Blue; Berncolor A.Y. 34; Telon Fast Yellow 4GL-175; BASF Basacid Black SE 0228; the Pro-Jet series available from ICI, including Pro-Jet Yellow I (Direct Yellow 86), Pro-Jet Magenta I (Acid Red 249), Pro-Jet Cyan I (Direct Blue 199), Pro-Jet Black I (Direct Black 168), Pro-Jet Yellow 1-G (Direct Yellow 132), Aminyl Brilliant Red F-B, available from Sumitomo Chemical Co. (Japan), the Duasyn line of "salt-free" Dyes available from Hoechst, such as Duasyn Direct Black HEF-SF (Direct Black 168), Duasyn Black RL-SF (Reactive Black 31), Duasyn Direct Yellow 6G-SF VP216 (Direct Yellow 157), Duasyn Brilliant Yellow GL-SF VP220 (Reactive Yellow 37), Duasyn Acid Yellow XX-SF VP413 (Acid Yellow 23), Duasyn Brilliant Red F3B-SF VP218 (Reactive Red 180), Duasyn Rhodamine B-SF VP353 (Acid Red 52), Duasyn Direct Turquoise Blue FRL-SF VP368 (Direct Blue 199), Duasyn Acid Blue AE-SF VP344 (Acid Blue 9), and similar, as well as mixtures of these dyes.
Die Konzentration des Farbstoffs hängt je nach Hersteller auch von der verwendeten Farbe ab und ist für die vorliegende Erfindung nicht limitierend.The concentration of the dye also depends on the manufacturer used color and is not for the present invention limiting.
Die Farbstofflösungen können darüber hinaus weitere Zusätze, wie Alkohol, Verdicker, Naßfestmittel, optische Aufheller, Konservierungsstoffe, Sicherheitschemikalien, Bindemittel und Pigmente enthalten. Hilfsmittel für die Farbstofflösung sind insbesondre Gummi arabicum, Polyacrylatsalze, Polymethacrylatsalze, Polyvinylalkohole, Hydroxypropylcellulose, Hydroxyethylcellulose, Polyvinylpyrrolidon, Polyvinylether. Stärke, Polysaccharide, und dergleichen. Weitere übliche Additive für Tinten können ebenfalls zugegen sein. Solche üblichen Zusätze sind in EP-A 518 490 Seite 4, Zeile 55 bis Seite 5, Zeile 9 genannt.The dye solutions can also other additives such as Alcohol, thickeners, wet strength agents, optical brighteners, preservatives, Contain security chemicals, binders and pigments. Aids for the dye solution are in particular gum arabic, Polyacrylate salts, polymethacrylate salts, polyvinyl alcohols, hydroxypropyl cellulose, Hydroxyethyl cellulose, polyvinyl pyrrolidone, polyvinyl ether. Starch, polysaccharides, and the like. Other common additives for inks can also be present. Such common additives are in EP-A 518 490 page 4, line 55 to page 5, line 9.
Das erfindungsgemäße Verfahren soll durch die folgenden Beispiele näher erläutert werden, ohne daß die Erfindung auf die hier gezeigten Ausführungsbeispiele beschränkt werden soll. The process according to the invention is illustrated by the following examples are explained without the invention to those shown here Embodiments should be limited.
Auf einer Langsiebpapiermaschine wird ein Papier mit einer flächenbezogenen Masse von 105 g/m2 hergestellt. Die Papierstoffzusammensetzung besteht aus 80 Gew.-% Nadelholzsulfatzellstoff, und 20 Gew.-% Eukalyptussulfatzellstoff. Die Papierleimung erfolgt mit Harzleim und Alaun. Als Naßfestmittel wird 1% Melaminformaldehydharz eingesetzt. Das in den Beispielen verwendete Papier weist keine Oberflächenleimung auf.A paper with a mass per unit area of 105 g / m 2 is produced on a Fourdrinier paper machine. The paper stock composition consists of 80% by weight softwood sulfate pulp and 20% by weight eucalyptus sulfate pulp. The paper is glued with resin glue and alum. 1% melamine formaldehyde resin is used as the wet strength agent. The paper used in the examples has no surface sizing.
Die Prozentangaben der nicht faserigen Zusätze beziehen sich auf den Faserstoffanteil. Dem so hergestellten Papier werden Bögen entnommen, auf die von Hand mit Hilfe eines Auftragsgerätes, z.B. eines Fineliners (Rotring Rapidograph 0,35 mm Durchmesser), Tuscherohrs oder eines Pinsels entleimende (Beispiel 1) bzw. hydrophobierende (Beispiel 2) oder beide (Beispiel 3) Stoffe in Form von handschriftlichen Zeichen aufgetragen werden. In Beispiel 4 wird ein sichtbares Bild auf das Papier aufgetragen. Die so behandelten Bögen werden durch Eintauchen in eine Farbstofflösung gefärbt, anschließend mit einem saugfähigen Papiervlies abgepreßt und getrocknet.The percentages of the non-fibrous additives relate to the Fiber content. Sheets are taken from the paper so produced, by hand using an application device, e.g. a fineliners (Rotring Rapidograph 0.35 mm diameter), ink tube or one Paintbrushing (example 1) or hydrophobizing (example 2) or both (example 3) substances in the form of handwritten characters be applied. In Example 4, a visible image is placed on the Paper applied. The sheets thus treated are immersed in dyed a dye solution, then with an absorbent Pressed paper fleece and dried.
Auftragen eines latenten Bildes mit einem Entleimungsmittel :
Auftragen eines latenten Bildes mit einem Hydrophobierungsmittel :
Simultanes Auftragen eines latenten Bildes / Musters mit sowohl einem
Hydrophobierungsmittel, wie auch einem Entleimungsmittel :
Auftragen eines sichtbaren Bildes vor Tauchfärbung :
Claims (13)
Priority Applications (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE50102060T DE50102060D1 (en) | 2001-08-01 | 2001-08-01 | Patterned paper |
| AT01118527T ATE264942T1 (en) | 2001-08-01 | 2001-08-01 | PATTERNED PAPER |
| ES01118527T ES2217066T3 (en) | 2001-08-01 | 2001-08-01 | PAPER WITH REASONS. |
| DK01118527T DK1281812T3 (en) | 2001-08-01 | 2001-08-01 | Patterned paper |
| EP01118527A EP1281812B9 (en) | 2001-08-01 | 2001-08-01 | Patterned paper |
| US10/483,271 US20040182532A1 (en) | 2001-08-01 | 2002-07-27 | Patterned paper |
| CA002454291A CA2454291A1 (en) | 2001-08-01 | 2002-07-27 | Patterned paper |
| JP2003517369A JP2005523388A (en) | 2001-08-01 | 2002-07-27 | Pattern paper |
| CNB028152360A CN1289756C (en) | 2001-08-01 | 2002-07-27 | Patterned paper |
| PCT/EP2002/008404 WO2003012202A1 (en) | 2001-08-01 | 2002-07-27 | Patterned paper |
| HK05103342A HK1070674A1 (en) | 2001-08-01 | 2005-04-19 | Patterned paper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP01118527A EP1281812B9 (en) | 2001-08-01 | 2001-08-01 | Patterned paper |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP1281812A1 true EP1281812A1 (en) | 2003-02-05 |
| EP1281812B1 EP1281812B1 (en) | 2004-04-21 |
| EP1281812B9 EP1281812B9 (en) | 2004-11-17 |
Family
ID=8178209
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP01118527A Expired - Lifetime EP1281812B9 (en) | 2001-08-01 | 2001-08-01 | Patterned paper |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US20040182532A1 (en) |
| EP (1) | EP1281812B9 (en) |
| JP (1) | JP2005523388A (en) |
| CN (1) | CN1289756C (en) |
| AT (1) | ATE264942T1 (en) |
| CA (1) | CA2454291A1 (en) |
| DE (1) | DE50102060D1 (en) |
| DK (1) | DK1281812T3 (en) |
| ES (1) | ES2217066T3 (en) |
| HK (1) | HK1070674A1 (en) |
| WO (1) | WO2003012202A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7591926B2 (en) * | 2003-01-15 | 2009-09-22 | M-Real Oyj | Process for production on nonuniformly intensely colored paper and paper obtainable by such process |
| EP2213791A1 (en) * | 2009-01-30 | 2010-08-04 | Büttenpapierfabrik Gmund GmbH & Co. KG | Office paper |
| CN110593000A (en) * | 2019-08-13 | 2019-12-20 | 山西大学 | Water-induced color development material and preparation method thereof |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1522629A1 (en) * | 2003-10-08 | 2005-04-13 | M-real Oyj | Coated paper for printing |
| EP1844945A1 (en) * | 2006-04-13 | 2007-10-17 | M-real Oyj | Process of applying interference pigments onto a substrate |
| EP2038478B1 (en) * | 2006-06-27 | 2012-04-11 | Basf Se | Method for finishing paper and paper products |
| EP2689067A4 (en) | 2011-03-25 | 2014-11-12 | Nanopaper Llc | Volatile debonder formulations for papermaking |
| CA2854903A1 (en) | 2011-11-09 | 2013-05-16 | Nanopaper, Llc | Bulk and stiffness enhancement in papermaking |
| CN103469694B (en) * | 2013-09-02 | 2016-08-17 | 金红叶纸业集团有限公司 | Paper making equipment and papermaking process |
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| DE359588C (en) * | 1919-02-15 | 1922-09-23 | Albrecht Blomberg | Process for the production of patterned paper and patterned, non-woven fabrics |
| US1481567A (en) * | 1921-05-19 | 1924-01-22 | Marvellum Company | Ornamental paper and process of preparing same |
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-
2001
- 2001-08-01 DE DE50102060T patent/DE50102060D1/en not_active Expired - Lifetime
- 2001-08-01 EP EP01118527A patent/EP1281812B9/en not_active Expired - Lifetime
- 2001-08-01 DK DK01118527T patent/DK1281812T3/en active
- 2001-08-01 AT AT01118527T patent/ATE264942T1/en active
- 2001-08-01 ES ES01118527T patent/ES2217066T3/en not_active Expired - Lifetime
-
2002
- 2002-07-27 CA CA002454291A patent/CA2454291A1/en not_active Abandoned
- 2002-07-27 CN CNB028152360A patent/CN1289756C/en not_active Expired - Fee Related
- 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
- 2002-07-27 JP JP2003517369A patent/JP2005523388A/en active Pending
-
2005
- 2005-04-19 HK HK05103342A patent/HK1070674A1/en not_active IP Right Cessation
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| DE296412C (en) * | ||||
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| DE296089C (en) * | ||||
| DE359588C (en) * | 1919-02-15 | 1922-09-23 | Albrecht Blomberg | Process for the production of patterned paper and patterned, non-woven fabrics |
| US1481567A (en) * | 1921-05-19 | 1924-01-22 | Marvellum Company | Ornamental paper and process of preparing same |
| DE580903C (en) * | 1927-03-20 | 1933-07-18 | I G Farbenindustrie Akt Ges | Process for dyeing paper webs on the paper machine |
| DE581032C (en) * | 1928-03-30 | 1933-07-22 | I G Farbenindustrie Akt Ges | Process for coloring paper or other material webs |
| US2180387A (en) * | 1937-09-23 | 1939-11-21 | George La Monte & Son | Ornamentally coloring paper |
| US4543157A (en) * | 1983-11-14 | 1985-09-24 | James River Pepperell, Inc. | Method and apparatus for the manufacture of variegated paper webs |
| EP0439363A1 (en) * | 1990-01-25 | 1991-07-31 | Xerox Corporation | Treated papers |
| EP0518490A1 (en) * | 1991-05-16 | 1992-12-16 | Xerox Corporation | Ink jet compositions containing desizing agents |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7591926B2 (en) * | 2003-01-15 | 2009-09-22 | M-Real Oyj | Process for production on nonuniformly intensely colored paper and paper obtainable by such process |
| EP2213791A1 (en) * | 2009-01-30 | 2010-08-04 | Büttenpapierfabrik Gmund GmbH & Co. KG | Office paper |
| CN110593000A (en) * | 2019-08-13 | 2019-12-20 | 山西大学 | Water-induced color development material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| DK1281812T3 (en) | 2004-08-16 |
| EP1281812B1 (en) | 2004-04-21 |
| CN1289756C (en) | 2006-12-13 |
| CN1539043A (en) | 2004-10-20 |
| HK1070674A1 (en) | 2005-06-24 |
| ATE264942T1 (en) | 2004-05-15 |
| CA2454291A1 (en) | 2003-02-13 |
| DE50102060D1 (en) | 2004-05-27 |
| JP2005523388A (en) | 2005-08-04 |
| WO2003012202A1 (en) | 2003-02-13 |
| EP1281812B9 (en) | 2004-11-17 |
| US20040182532A1 (en) | 2004-09-23 |
| ES2217066T3 (en) | 2004-11-01 |
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